Title of Invention

SPIROPIPERIDINE DERIVATIVES COMPOUND OF FORMULA I' FOR CONTROLLING PESTS

Abstract The use of a compound of formula I, Y is a single bond, C=0, C=S or S(0)m where m is 0, 1 or 2; the ring represented by T is a 5 or 6 membered heteroaromatic and R1,R2,R3,R8 and Ra are specified organic groups and p is 0, 1, 2, 3, 4, 5 or 6; p+q is 0, 1, 2, 3, 4, 5 or 6; or salts or N-oxides thereof or compositions containing them in controlling insects, acarines, nematodes or mollusks; novel compounds are also provided.
Full Text

SPIROPIPERIDINE DERIVATIVES FOR CONTROLLING PESTS
The present invention relates to hetero-spiroindoline derivatives to processes for preparing them to insecticidal acaricidal molluscicidal and nematicidal compositions comprising them and to methods of using them to combat and control insect acarine mollusc and nematode pests.
Aza-spiroindolines with pharmaceutical properties are disclosed in for example WO02/94825 and WO00/27845. Synthetic routes to selected compounds are described for instance in Bioorganic & Medicinal Chemistry Letters (1995) 5 1875 and Tetrahedron Letters (2001) 42 999.
It has now surprisingly been found that certain hetero-spiroindolines have insecticidal properties.
The present invention therefore provides a method of combating and controlling insects acarines nematodes or molluscs which comprises applying to a pest to a locus of a pest or to a plant susceptible to attack by a pest an insecticidally acaricidally nematicidally or molluscicidally effective amount of a compound of formula (I);

wherein Y is a single bond C=0 C=S or S(0)m where m is 0 1 or 2;
R1 is hydrogen optionally substituted alkyl optionally substituted alkoxycarbonyl optionally substituted alkylcarbonyl aminocarbonyl optionally substituted alkylarninocarbonyl optionally substituted dialkylaminocarbonyl optionally substituted aryl optionally substituted heteroaryl optionally substituted alkoxy optionally substituted

aryloxy optionally substituted heteroaryloxy optionally substituted heterocyclyloxy cyano optionally substituted alkenyl optionally substituted alkynyl optionally substituted cycloalkyl optionally substituted cycloalkenyl/formyl optionally substituted heterocyclyl optionally substituted alkylthto NO or NR13R14 where R13 and R14 are independently hydrogen COR15 optionally substituted alkyl optionally substituted aryl optionally substituted heteroaryl optionally substituted heterocyclyl or R13 and R14 together with the N atom to which they are attached form a group -N=C(R16)-NRI7R18; R15 is H optionally substituted alkyl optionally substituted alkoxy optionally substituted aryl optionally substituted aryloxy optionally substituted heteroaryl optionally substituted heteroaryloxy or NR19R2o; R16 R17 and R18 are each independently H or lower alkyl; R19 and R20 are
independently optionally substituted alkyl optionally substituted aryl or optionally substituted heteroaryl;
R2 and R3 are independently hydrogen halogen cyano optionally substituted alkyl optionally substituted alkoxy or optionally substituted aryl; the ring

is a 5 or 6 membered heteroaromatic ring;
each R4 is independently halogen nitro cyano optionally substituted C1-8 alkyl optionally substituted C2-6 alkenyl optionally substituted C2-6 alkynyl optionally substituted alkoxycarbonyl optionally substituted alkylcarbonyl optionally substituted alkylaminocarbonyl optionally substituted dialkylaminocarbonyl optionally substituted C3-7 cycloalkyl optionally substituted aryl optionally substituted heteroaryl optionally substituted heterocyclyl optionally substituted alkoxy optionally substituted aryloxy optionally substituted heteroaryloxy optionally substituted alkylthio or R21R22N where R21 and R22 are independently hydrogen C1-8 alkyl C3-7 cycloalkyl C3-6 alkenyl C3-6 alkynyl C3-7 cycloalkyl(C1-4)alkyl C2-6 haloalkyl C1-6 alkoxy(C1-6)alkyl C1-6 alkoxycarbonyl or R21 and R22 together with the N atom to which they are attached form a five six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O N or S and which may be optionally substituted by one or two C1-6 alkyl groups or 2

6 or 7 membered carbocyclic or heterocyclic ring which may be optionally substituted by halogen; n is 0 1 2 or 3;
each Ra is independently hydrogen halogen hydroxy cyano optionally substituted C1--g alkyl optionally substituted C2-6 alkcnyl optionally substituted C2-6 alkynyl optionally substituted alkoxycarbonyl optionally substituted alkylcarbonyl optionally substituted alkylaminocarbonyl optionally substituted dialkylaminocarbonyl optionally substituted C3-7 cycloalkyl optionally substituted aryl optionally substituted heteroaryl optionally substituted heterocyclyl optionally substituted alkoxy optionally substituted aryloxy optionally substituted heteroaryloxy optionally substituted alkylthio optionally substituted arylthio or R23R24N where R23 and R24 are independently hydrogen C1-6 alkyl C3-7 cycloalkyl C3-6 alkenyl C3-6 alkynyl C3-7 cycIoalkyI(C1-4)alkyl C2-6 haloalkyl C1-6 alkoxy(C1-6)alkyl C1-6 alkoxycarbonyl or R23 and R24 together with the N atom to which they are attached form a five six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O N or S and which may be optionally substituted by one or two C1-6 alkyl groups or two Ra groups attached to the same carbon atom are =0 or two Ra groups attached to adjacent carbon atoms form a bond or two Ra groups together with the carbon atom to which they are attached form a three- to seven-membered ring that may be saturated or unsaturated and that may contain one or two hetero atoms selected from the group consisting of N O and S and which may be optionally substituted by one or two C1-6 alkyl groups; or two Ra groups together form a group -CH2- -CH=CH- or -CH2CH2; p is 0 1 2 3 4 5 or 6; q is 0 1 2 3 4 5 or 6 provided that p+q is 1 2 3 4 5 or 6;
R8 is optionally substituted alkyl optionally substituted alkenyl optionally substituted alkynyl optionally substituted cycloalkyl optionally substituted aryl optionally substituted alkoxy optionally substituted aryloxy optionally substituted alkoxycarbonyl optionally substituted alkylcarbonyl or optionally substituted alkenylcarbonyl; or salts or N-oxides thereof.
The compounds of formula (I) may exist in different geometric or optical isomers or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
Each alkyl moiety either alone or as part of a larger group (such as alkoxy alkoxycarbonyl alkylcarbonyl alkylaminocarbonyl dialkylaminocarbonyl) is a straight or branched chain and is for example methyl ethyl n-propyl n-butyl n-pentyl n-hexyl iso-

propyl n-butyl sec-butyl iso-butyl tert-butyl or neo-pentyl. The alkyl groups are suitably C1 to C12 alkyl groups but are preferably C1-C10 more preferably C1-Cg even more preferably preferably C1-C6 and most preferably C1-C4 alkyl groups.
When present the optional substituents on an alkyl moiety (alone or as part of a larger group such as alkoxy alkoxycarbonyl alkylcarbonyl alkylaminocarbonyl dialkylaminocarbonyl) include one or more of halogen nitro cyano NCS- C3-7 cycloalkyl (itself optionally substituted with C1-6 alkyl or halogen) C5-7 cycloalkenyl (itself optionally
substituted with C1-6 alkyl or halogen) hydroxy C1-10 alkoxy C1-10 alkoxy(C].io)alkoxy tri(C1-4)alkylsilyl(C1-6)alkoxy C1-6 alkoxycarbonyl(C1-10)alkoxy C1-10 haloalkoxy aiyl(C|-4)-alkoxy (where the aryl group is optionally substituted) C3-7 cycloalkyloxy (where the cycloalkyl group is optionally substituted with C1-6 alkyl or halogen) C2-10 alkenyloxy C2-10 alkynyloxy SH C1-10alkylthio C1-10 haloalkylthio aryl(C1-4)alkylthio (where the aryl group is optionally substituted) C3-7 cycloalkylthio (where the cycloalkyl group is optionally substituted with C1-6 alkyl or halogen) tri(C1-4)aIkylsiIyl(C1-6)alkylthio arylthio (where the aryl group is optionally substituted) C1-6 alkylsulfonyl C1-6 haloalkylsulfonyl C1-6 alkylsulfinyl C1-6 haloalkylsulfinyl arylsulfonyl (where the aryl group may be optionally substituted) tri(C1-4)alkylsilyl aryldi(C1-4)a1kylsilyl (C1-4)alkyldiarylsilyl triarylsilyl C1-10alkylcarbonyl HO2C C1-10alkoxycarbonyl aminocarbonyl C1--6 alkylaminocarbonyl di(C1-^ alkyl)aminocarbonyl N-(C1-3 alkyl)-N-(C1-3 alkoxy)aminocarbonyl C\-e alkylcarbonyloxy arylcarbonyloxy (where the aryl group is optionally substituted) di(C1-6)alkylaminocarbonyloxy oximes such as =NOalkyl =NOhaloalkyl and -NOaryl (itself optionally substituted) aryl (itself optionally substituted) heteroaryl (itself optionally substituted) heterocyclyl (itself optionally substituted with C1-6 alkyl or halogen) aryloxy (where the aryl group is optionally substituted) heteroaryloxy (where the heteroaryl group is optionally substituted) heterocyclyloxy (where the heterocyclyl group is optionally substituted with C1-6 alkyl or halogen) amino C1-6 alkylamino di(C1-6)alkylamino C1-6 alkylcarbonylamino N-(C1-r6)alkylcarbonyl-N-(C1-6)alkylamino C2-6 alkenylcarbonyl C2-6 alkynylcarbonyl C3-6 alkenyloxycarbonyl C3-6 alkynyloxycarbonyl aryloxycarbonyl (where the aryl group is optionally substituted) and arylcarbonyl (where the aryl group is optionally substituted).

Alkenyl and alkynyl moieties can be in the form of straight or branched chains and the alkenyl moieties where appropriate can be of either the (E)- or (Z)-configuration. Examples are vinyl ally! and propargyl.
- When present the optional substituents on alkenyl or alkynyl include those optional substituents given above for an alkyl moiety.
In the context of this specification acyl is optionally substituted C1-6 alkylcarbonyl (for example acetyl) optionally substituted C2-6 alkenylcarbonyl optionally substituted C2-6 alkynylcarbonyl optionally substituted arylcarbonyl (for example benzoyl) or optionally substituted heteroarylcarbonyl.
Halogen is fluorine chlorine bromine or iodine.
Haloalkyl groups are alkyl groups which are substituted with one or more of the same of different halogen atoms and are for example CF3 CF2C1 CF3CH2 or CHF2CH2.
In the context of the present specification the terms "arylM and "aromatic ring system" refer to ring systems which may be mono- bi- or tricyclic. Examples of such rings include phenyl naphthalenyl anthracenyl indenyl or phenanthrenyl. A preferred aryl group is phenyl. In addition the terms "heteroaryl" "heteroaromatic ring" or "heteroaromatic ring system" refer to an aromatic ring system containing at least one heteroatom and consisting either of a single ring or of two or more fused rings. Preferably single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen oxygen and sulphur. Examples of such groups include furyl thienyl pyrrolyl pyrazolyl imidazolyl 1 2 3-triazolyl 1 2 4-triazolyl oxazolyl isoxazolyl thiazolyl isothiazolyl 1 2 3-oxadiazolyl 1 2 4-oxadiazoIyl 1 3 4-oxadiazolyl 1 2 5-oxadiazolyl 1 2 3-thiadiazolyl 1 2 4-thiadiazolyl 1 3 4-thiadiazolyl 1 2 5-thiadiazolyI pyridyl pyrimidinyl pyridazinyl pyrazinyl 1 2 3-triazinyl 1 2 4-triazinyl 1 3 5-triazinyl benzofuryl benzisofuryl benzothienyl benzisothienyl indolyl isoindolyl indazolyl benzothiazoly! benzisothiazolyl benzoxazolyl benzisoxazolyl benzimidazolyl 2 1 3-benzoxadiazole quinolinyl isoquinolinyl cinnolinyl phthalazinyl quinazolinyl quinoxalinyl naphthyridinyl benzotriazinyl purinyl pteridinyl and indolizinyl. Preferred examples of heteroaromatic radicals include pyridyl pyrimidyl triazinyl thienyl fury! oxazolyl isoxazolyl 2 1 3-benzoxadiazole and thiazolyl.

The terms heterocycle and heterocyclyl refer to a non-aromatic ring containing up to 10 atoms including one or more (preferably one or two) heteroatoms selected from O S and N. Examples of such rings include 1 3-dioxolane tetrahydrofuran and morpholine.
When present the optional substituents on heterocyclyl include C6 alkyl and C1-6 haloalkyl as well as those optional substituents given above for an alkyl moiety.
Cycloalkyl includes cyclopropyl cyclopentyl and cyclohexyl.
Cycloalkenyl includes cyclopentenyl and cyclohexenyl.
When present the optional substituents on cycloalkyl or cycloalkenyl include C1.3 alkyl as well as those optional substituents given above for an alkyl moiety.
Carbocyclic rings include aryl cycloalkyl and cycloalkenyl groups.
When present the optional substituents on aryl or heteroaryl are selected independently from halogen nitro cyano NCS- C1-6 alkyl C1-6 haloalkyl C1-6 alkoxy-(C1-6)alkyl C2-6 alkenyl C2-6 haloalkenyl C2-6 alkynyl C3-7 cycloalkyl (itself optionally substituted with C1-e alkyl or halogen) C5-7 cycloalkenyl (itself optionally substituted with C1-6 alkyl or halogen) hydroxy C1-10alkoxy C1-10alkoxy(C1-10)alkoxy tri(CM)alkyI-silyl(Ci.6)alkoxy C1-6 alkoxycarbonyl(C1-10)alkoxy C1-10haloalkoxy aryl(C1-4)alkoxy (where the aryl group is optionally substituted with halogen or C1-6 alkyl) C3-7 cycloalkyloxy (where the cycloalkyl group is optionally substituted with C1-6 alkyl or halogen) C2-10 alkenyloxy C2-10 alkynyloxy .SH C1-10alkylthio C1-10haloalkylthio aryl(C1-4)alkylthio C3-7 cycloalkylthio (where the cycloalkyl group is optionally substituted with C1-6 alkyl or halogen) tri(C1-4)-alkylsilyl(Ci.6)alkylthio arylthio C1-6 alkylsulfonyl C1-6 haloalkylsulfonyl C1-6alkylsulfinyl C1-6 haloalkylsulfmyl arylsulfonyl tri(CM)alkylsilyl aryldi(CM)-alkylsilyl (C1-6)alkyldiarylsilyl triarylsilyl C1-10alkylcarbonyl H02C C1-10alkoxycarbonyl aminocarbonyl C1-6 alkylaminocarbonyl di(C1-6 alkyl)-aminocarbonyl N-(C1-3 alkyl)-N-(C1-3 alkoxy)aminocarbonyl C1-6 alkylcarbonyloxy arylcarbonyloxy di(C1-6)alkylamino«carbonyloxy aryl (itself optionally substituted with C1--6 alkyl or halogen) heteroaryl (itself optionally substituted with C1-6 alkyl or halogen) heterocyclyl (itself optionally substituted with C1-6 alkyl or halogen) aryloxy (where the aryl group is optionally substituted with C1-6 alkyl or halogen) heteroaryloxy (where the heteroaryl group is optionally substituted with C1-6 alkyl or halogen) heterocyclyloxy (where the heterocyclyl group is optionally substituted with C1-6 alkyl or halogen) amino C1-6 alkylamino di(C1-6 )alkylamino C1-6 alkylcarbonylamino N-(C1-6)alkylcarbonyl-N-(C1-6)alkylamino

arylcarbonyl (where the aryl group is itself optionally substituted with halogen or C1-6 alkyl) or two adjacent positions on an aryl or heteroaryl system may be cyclised to form a 5 6 or 7 membered carbocyclic or heterocyclic ring itself optionally substituted with halogen or C1-o alkyl. Further substituents for aryl or heteroaryl include aryl caibonyl amino (where the aryl group is substituted by C1--6 alkyl or halogen) (C1-6alkyloxycarbonylamino (C1-6)aIkyloxycarbonyl-N-(Ci.6)alkylamino) aryloxycarbonylamino (where the aryl group is substituted by C1-6 alkyl or halogen) aryloxycarbonyl N-(C1-6)alkylamino (where the aryl group is substituted by C1-6 alkyl or halogen) arylsulphonylamino (where the aryl group is substituted by C1-6 alkyl or halogen) arylsulphonyl-N-(C1-6)alkylamino (where the aryl group is substituted by C1-c alkyl or halogen) aryl-N-(C1-6)alkylamino (where the aryl group is substituted by C1-.e alkyl or halogen) arylamino (where the aryl group is substituted by C1-6 alkyl or halogen) heteroaryl amino (where the heteroaryl group is substituted by C]-6 alkyl or halogen) heterocyclylamino (where the heterocyclyl group is substituted by C\.^ alkyl or halogen) aminocarbonylamino C1-6alkylaminocarbonyl amino di(C]^)alkylaminocarbonyl amino arylaminocarbonyl amino where the aryl group is substituted by C1-e alkyl or halogen) aryl-N-(C1-6)alkylaminocarbonylamino where the aryl group is substituted by C1-.6 alkyl or halogen) C1-6aIkylaminocarbonyl-N-(C1-6)alkyl amino; di(d^)alkylaminocarbonyl-N-fCt^alkvl amino. arvlaminocarhnnvl-N-CC!i For substituted phenyl moieties heterocyclyl and heteroaryl groups it is preferred that one or more substituents are independently selected from halogen C1-.6 alkyl C1-6 haloalkyl C1-6 alkoxy(C1-6)alkyl C1--6 alkoxy C1-6 haloalkoxy C1-6 alkylthio C\* haloalkylthio C1-6 alkylsulfinyl C1-6 haloalkylsulfinyl C1-6 alkylsulfonyl Q-6 haloalkylsulfonyl C2-6 alkenyl C2.6 haloalkenyl C2.6 alkynyl C3-7 cycloalkyl nitro cyano CO2H alkylcarbonyl C1-6 alkoxycarbonyl R25R26N or R27R28NC(0); wherein R25 R26 R27 and R28 are independently hydrogen or C1.6 alkyl. Further preferred substituents are aryl and heteroaryl groups.
Haloalkenyl groups are alkenyl groups which are substituted with one or more of the same or different halogen atoms.
It is to be understood that dialkylamino substituents include those where the dialkyl groups together with the N atom to which they are attached form a five six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from

O N or S and which is optionally substituted by one or two independently selected (C1-6)alkyl groups. When heterocyclic rings are formed by joining two groups on an N atom the resulting rings are suitably pyrrolidine piperidine thiomorpholine and morpholine each of which may be substituted by one or two independently selected (CM) alkyl groups.
Preferably the optional substituents on an alkyl moiety include one or more of halogen nitro cyano HO2C C1-10alkoxy (itself optionally substituted by C1-10alkoxy) aryl(C1-4)alkoxy C1-10alkylthio C1-10alkylcarbonyl C1-10 alkoxycarbonyl CM alkylaminocarbonyl di(C1-.6 alkyl)aminocarbonyl (CM)alkylcarbonyloxy optionally substituted phenyl heteroaryl aryloxy arylcarbonyloxy heteroaryloxy heterocyclyl heterocyclyloxy C3-7 cycloalkyl (itself optionally substituted with (C1-6)alkyl or halogen) C3-7cycloalkyloxy C5-7 cycloalkenyl CM alkylsulfonyl CM alkylsulfinyl tri(CM)alkylsilyl tri(C1-4)alkylsilyl(Ci.6)alkoxy aryldi(C1-6)alkylsilyl (CM)alkyldiarylsilyl and triarylsilyl.
Preferably the optional substituents on alkenyl or alkynyl include one or more of halogen aryl and C3-7 cycloalkyl.
A preferred optional substituent for heterocyclyl is C 1.6 alkyl.
Preferably the optional substituents for cycloalkyl include halogen cyano and C1-3 alkyl.
Preferably the optional substituents for cycloalkenyl include C1-3 alkyl halogen and cyano.
Preferably Y is a single bond C=0 or S(0)m where m is 0 1 or 2.
More preferably Y is a single bond C=0 or SO2.
Yet more preferably Y is a single bond or C=0.
Most preferably Y is C=0.
Preferably R1 is hydrogen Cue alkyl Cue cyanoalkyl CM haloalkyl C3-7 cycloalkyl(C1-4)alkyl CM alkoxy(C}.6)alkyl heteroaryl(C1-6)alkyl (wherein the heteroaryl group maybe optionally substituted by halo nitro cyano CM alkyl CM haloalkyl CM alkoxy CM haloalkoxy Cu alkylsulfonyl CM alkylsulfinyl CM alkylthio Cu alkoxycarbonyl C1-6 alkylcarbonylamino arylcarbonyl or two adjacent positions on the heteroaryl system may be cyclised to form a 5 6 or 7 membered carbocyclic or heterocyclic ring itself optionally substituted with halogen) aryl(C1-6)alkyl (wherein the aryl group may be optionally substituted by halo nitro cyano C1-6 alkyl CM haloalkyl CM alkoxy CM haloalkoxy C^ alkylsulfonyl CM alkylsulfinyl CM alkylthio CM alkoxycarbonyl CM

alkylcarbonylamino arylcarbonyl or two adjacent positions on the aryl system may be cyclised to form a 5 6 or 7 membered carbocyclic or heterocyclic ring itself optionally substituted with halogen) CM alkylcarbonylamino(C1-6)alkyl aryl (which may be optionally substituted by halo nitro cyano CM alkyl CM haloalkyt CM alkoxy C1-6 haloalkoxy CM alkylsulfonyl CM alkylsulfinyl CM alkylthio C1-6 alkoxycarbonyl CM alkylcarbonylamino arylcarbonyl or two adjacent positions on the aryl system may be cyclised to form a 5 6 or 7 membered carbocyclic or heterocyclic ring itself optionally substituted with halogen) heteroaryl (which may be optionally substituted by halo nitro cyano CM alkyl CM haloalkyl CM alkoxy CM haloalkoxy CM alkylsulfonyl CM alkylsulfinyl CM alkylthio CM alkoxycarbonyl CM alkylcarbonylamino arylcarbonyl or two adjacent positions on the heteroaryl system may be cyclised to form a 5 6 or 7 membered carbocyclic or heterocyclic ring itself optionally substituted with halogen) CM alkoxy CM haloalkoxy phenoxy (wherein the phenyl group is optionally substituted by halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino) heteroaryloxy (optionally substituted by halo nitro cyano CM alkyl C1-6 haloalkyl CM alkoxy or CM haloalkoxy) heterocyclyloxy (optionally substituted by halo CM alkyl CM haloalkyl CM alkoxy or C1-6 haloalkoxy) cyano C2-6 alkenyl C2-6 alkynyl C3-6 cycloalkyl C5-7 cycloalkenyh heterocyclyl (optionally substituted by halo nitro. cyano. CM alkyl. C1-6 haloalkyl CM alkoxy or CM haloalkoxy) CM alkylthio CM haloalkylthio or NR 3R14 where R13 and R14 are independently hydrogen CM alkyl CM haloalkyl CM alkoxy(C1-. 6)alkyl phenyl (which may be optionally substituted by halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino dialkylamino or CM alkoxycarbonyl) phenyl (C1-6)alkyl (wherein the phenyl group may be optionally substituted by halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino dialkylamino CM alkylsulfonyl CM alkoxycarbonyl or two adjacent positions on the phenyl ring may be cyclised to form a 5 6 or 7 membered carbocyclic or heterocyclic ring itself optionally substituted with halogen) heteroaryl (CM)alkyl (wherein the heteroaryl group may be optionally substituted by halo nitro cyano CM alkyl CM haloalkyl CM alkoxy CM haloalkoxy CM alkylsulfonyl CM alkylsulfinyl CM alkylthio CM alkoxycarbonyl CM alkylcarbonylamino arylcarbonyl or two adjacent positions on the heteroaryl system may be cyclised to form a 5 6 or 7 membered carbocyclic or heterocyclic ring itself optionally substituted with halogen) or heteroaryl (which may be optionally

substituted by halo nitro cyano CM alkyl CM haloalkyl CM alkoxy or CM haloalkoxy C1-4 alkoxycarbonyl C1-6 alkylcarbonylamino phenyloxycarbonylamino (wherein the phenyl group is optionally substituted by halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO^atyl" heteroaryl amino or dialkylamino) aSftino CM alkylamino or phenylamino (wherein the phenyl group is optionally substituted halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino)). More preferably R1 is CM alkyl CM haloalkyl CM alkoxy(CM)alkyl heteroaryl(C1- 3)alkyl (wherein the heteroaryl group may be optionally substituted by halo nitro cyano CM alkyl Cue haloalkyl CM alkoxy CM haloalkoxy CM alkylsulfonyl CM alkoxycarbonyl or two adjacent positions on the heteroaryl system may be cyclised to form a 5 6 or 7 membered carbocyclic or heterocyclic ring itself optionally substituted with halogen) phenyl(C1-3)alkyl (wherein the phenyl group may be optionally substituted by halogen CM alkyl CM alkoxy CM haloalkyl haloalkoxy CN NO2 aryl heteroaryl amino dialkylamino CM alkylsulfonyl CM alkoxycarbonyl or two adjacent positions on the phenyl ring may be cyclised to form a 5 6 or 7 membered carbocyclic or heterocyclic ring itself optionally substituted with halogen) phenyl (which may be optionally substituted by halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino dialkylamino CM alkylsulfonyl CM alkoxycarbonyl or two adjacent positions on the phenyl ring may be cyclised to form a 5 6 or 7 membered carbocyclic or heterocyclic ring itself optionally substituted with halogen) heteroaryl (which may be optionally substituted by halo nitro cyano CM alkyl CM haloalkyl CM alkoxy CM haloalkoxy CM alkylsulfonyl CM alkoxycarbonyl or two adjacent positions on the heteroaryl system may be cyclised to form a 5 6 or 7 membered carbocyclic or heterocyclic ring itself optionally substituted with halogen) CM alkoxy CM haloalkoxy C2-6 alkenyl heterocyclyl (optionally substituted by halo cyano CM alkyl CM haloalkyl CM alkoxy or CM haloalkoxy) CM alkylthio CM haloalkylthio or NR13R14 where R13 and R14 are independently hydrogen CM alkyl or CM haloalkyl CM alkoxy(C1-6)alkyl C2-6 alkylcarbonyl phenylcarbonyl (where the phenyl is optionally substituted by halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino) phenyl(C1-3)aIkyl (wherein the phenyl group may be optionally substituted by halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN N02 aryl heteroaryl amino dialkylamino CM alkylsulfonyl CM alkoxycarbonyl or two adjacent positions on the phenyl ring may be

cyclised to form a 5 6 or 7 membered carbocyclic or heterocyclic ring itself optionally substituted with halogen) or heteroaryl(C1-3)alkyl (wherein the heteroaryl group may be optionally substituted by halo nitro cyano C1-6 alkyl C]-6 haloalkyl C1-6 alkoxy C1-6 haloalkoxy alkylsulfonyl C1-6 alkylsulfmyl C1-e alkylthio Cue alkoxycarbonyl C1--6 alkylcarbonylamino arylcarbonyl or two adjacent positions on the heteroaryl system may be cyclised to form a 5 6 or 7 membered carbocyclic or heterocyclic ring itself optionally substituted with halogen).
Even more preferably R1 is Q-e alkyl Q-6 haloalkyl heteroaryl(C1-3)alkyl (wherein the heteroaryl group may be optionally substituted by halo cyano C1-* alkyl C1-6 haloalkyl and where the heteroaryl group is a thiazole pyridine pyrimidine pyrazine or pyridazine ring) heteroaryl (optionally substituted by halo cyano C1-6 alkyl C1-6 haloalkyl and where the heteroaryl group is a pyridine pyrimidine 2 1 3-benzoxadiazole pyrazine or.pyridazine ring) C1-6 alkoxy C1-6 alkoxy(C1-6)alkyl C1-6 alkylamino C1-6 alkoxy(C1-)alkylamino or heteroaryl(C|_3)alkylamino (wherein the heteroaryl group may be optionally substituted by halo cyano CC1-6 alkyl C1-6 haloalkyl and where the heteroaryl group is a thiazole pyridine pyrimidine pyrazine or pyridazine ring).
Most preferably R1 is pyridyl (optionally substituted by halo C1-3 alkyl or C1-3 haloalkyl) especially halo-substituted pyridyl.
It is preferred that R2 and R3 are independently hydrogen C1-6 alkyl C1-6 haloalkyl C1.6 alkoxy or cyano.
More preferably R2 and R3 are independently hydrogen halogen C1-2 alkyl C1-2 haloalkyl C1-2 alkoxy cyano.
Even more preferably R arid R are independently hydrogen or CM alkyl.
Yet more preferably R and R are independently hydrogen or methyl.
Most preferably R2 and R3 are both hydrogen.
Preferably each R4 is independently halogen cyano C1-g alkyl C1-g haloalkyl C1-6 cyanoalkyl Ci* alkoxy(C1-^)alkyl C3-7 cycloalkyl(C1-6)alkyl Cs-e cycloalkenyl(C1-6)alkyl C3.6 alkenyloxy(Ci.6)alkyl C3^ alkynyloxy(C1-6)alkyl aryloxy(C1-6)alkyl C1-e carboxyalkyl C1-6 alkylcarbonyl(C1-6)alkyl C2-6 alkenylcarbonyl(C1-6)alkyl C2-6 alkynylcarbonyl(C]-6)-alkyl CM alkoxycarbonyl(C1-6)alkyl C3-6 alkenyloxycarbonyl(C1-6)alkyl C3-6 alkynyloxycarbonyl(C1-6)alkyl aryloxycarbonyl(C1-6)alkyl C1-6 alkylthio(C1-6)alkyl C1-$ alkylsulfinyl(C1-6)alkyl C1-.6 alkylsulfonyl(C1-6)a!kyl aminocarbonyl(C1-6)alkyl Ci.6

alkylaminocarbonyl(C1-6)alkyI di(Ci.6)alkylaminocarbonyl(C1-6)alkyl phenyl(C1-4)alkyl (wherein the phenyl group is optionally substituted by halogen CM alkyl CM alkoxy C1-4 haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino) 'Tieteroaryl(C1-4)aIkyl (wherein tfreTieteroaryl groupls optionally substituted By halo nitro cyano CM alkyl CM haloalkyl CM alkoxy or CM haloalkoxy) heterocyclyl(CM)alkyl (wherein the heterocyclyl group is optionally substituted by halo nitro cyano CM alkyl CM haloalkyl CM alkoxy or CM haloalkoxy) C2-6 alkenyl aminocarbonyl(C2-6)alkenyl CM alkylaminocarbonyl(C2-6)alkenyl di(C 1 ^)alkylaminocarbonyl(C2-6)alkenyl phenyl(C2-4)-alkenyl (wherein the phenyl group is optionally substituted by halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino) C2-6 alkynyl trimethylsilyl(C2-G)alkynyI aminocarbonyl(C2-6)alkynyl Ct-6 alkylaminocarbonyl(C2^)alkynyl di(C1-6)alkylaminocarbonyl(C2-6)alkynyl;C1-6 alkpxycarbonyl C3-7 cycloalkyl C3-7 halocycloalkyl C3-7 cyanocycloalkyl C1-3 alkyl(C3-7)-cycloalkyl C1-3 alkyl(C3-7)halocycloalkyl phenyl (optionally substituted by halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino) heteroaryl (optionally substituted by halo nitro cyano Cue alkyl CM haloalkyl CM alkoxy or CM haloalkoxy) heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo nitro cyano Cue alkyl CM haloalkyl CM alkoxy or Cue haloalkoxy) or 2 adjacent groups R4 together with the carbon atoms to which they are attached form a 4 5 6 or 7 membered carbocylic or heterocyclic ring which may be optionally substituted by halogen CM alkoxy CM haloalkoxy phenoxy (optionally substituted by halo nitro cyano CM alkyl CM haloalkyl CM alkoxy or CM haloalkoxy) heteroaryloxy (optionally substituted by halo nitro cyano CM alkyl CM haloalkyl CM alkoxy or CM haloalkoxy) CM alkylthio or R19R20N where R19 and R20 are independently hydrogen CM alkyl C3-7 cycloalkyl C3-6 alkenyl C3-6 alkynyl C2-6 haloalkyl CM alkoxycarbonyl or R19 and R20 together with the N atom to which they are attached form a five six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O N or S and which may be optionally substituted by one or two CM alkyl groups; n is 0 1 2 or 3.
More preferably each R4 is independently halogen cyano CM alkyl CM haloalkyl CM cyanoalkyl CM alkoxy(C].6)alkyl C2-6 alkynyl trimethylsilyl(C2-6)alkynyl CM * alkoxycarbonyl C3-7 cycloalkyl C1-3 alkyl (C3-7) cycloalkyl phenyl (optionally substituted by

halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino) heterocyclyl (optionally substituted by halo nitro cyano CM alkyl Ci* haloalkyl CM alkoxy or C1-6 haloalkoxy) CM alkoxy CM haloalkoxy phenoxy -(optionally substituted by halogen XM alkylfCM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino) heteroaryloxy (optionally substituted by halo nitro cyano CM alkyl CM haloalkyl CM alkoxy or C1-3 haloalkoxy) di(Ci. g)alkylamino or 2 adjacent groups R4 together with the carbon atoms to which they are attached form a 4 5 6 or 7 membered carbocylic or heterocyclic ring which may be optionally substituted by halogen; n is 0 1 2 or 3.
Even more preferably each R4 is independently halogen cyano CM alkyl CM haloalkyl CM cyanoalkyl CM alkoxy(C1-6)alkyl C2-6 alkynyl heterocyclyl (optionally substituted by CM alkyl) CM alkoxy CM haloalkoxy phenoxy (optionally substituted by halo cyano CM alkyl or CM haloalkyl) heteroaryloxy (optionally substituted by halo cyano CM alkyl or CM haloalkyl) di(CM)alkylamino or 2 adjacent groups R4 together with the carbon atoms to which they are attached form a 4 5 6 or 7 membered carbocylic or heterocyclic ring which may be optionally substituted by halogen; n is 0 1 2 or 3.
Yet more preferably each R4 is independently fluoro chloro bromo cyano CM alkvl. C1-A haloalkvL C1-d cvanoalkvl or C1-* alkoxvfC1-itallcvl: n is 0. 1 or 2.
Most preferably each R4 is independently fluoro chloro bromo CM alkyl or CM haloalkyl; n is I or 2.
Preferably R8 is C1-10alkyl C1-10haloalkyl aryl(CM)alkyl (wherein the aryl group is optionally substituted by halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino) heteroaryl(CM)alkyl (wherein the heteroaryl group is optionally substituted by halogen C]-4 alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino) arylcarbonyl-(CM)alkyl (wherein the aryl group may be optionally substituted by halogen C\^ alkyl CM alkoxy C1-4 haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino and the alkyl group may be optionally substituted by aryl) C2-8 alkenyl C2-8 haloalkenyl aryl(C2^)-alkenyl (wherein the aryl group is optionally substituted halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino CM alkoxycarbonyl or two adjacent substituents can cyclise to form a 5 6 or 7 membered carbocyclic or heterocyclic ring) heteroaryl(C2^)-alkenyl (wherein the heteroaryl group is

optionally substituted halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino CM alkoxycarbonyl or two adjacent substituents can cyclise to form a 5 6 or 7 membered carbocyclic or heterocyclic ring) C2-6 alkynyCphenyl(C2-6)alkynyl (wherein thepKeriyl group is optionally substituted by Halogen alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino) C3-7 cycloalkyl CM alkoxycarbonyl C1-6 alkylcarbonyl C1-6 haloalkylcaibonyl or aryl(C2-6)alkenylcarbonyl (wherein the aryl group may be optionally substituted halogen CM alkyl C1-C6 alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino) or -C(R5l)(R52)-[CR53=CR 54]z-R55 where z is 1 or 2 R51 and R52 are each independently H halo or C1-2 alkyl R53 and R54 are each independently H halogen CM alkyl or CM haloalkyl and R55 is optionally substituted aryl or optionally substituted heteroaryl.
More preferably R is phenyl(CM)alkyl (wherein the phenyl group is optionally substituted by halogen CM alkyl C\^ alkoxy CM haloalkyl CM haloalkoxy CN NC>2 aryl heteroaryl amino or dialkylamino) heteroaryl(C1-6)alkyl (wherein the heteroaryl group is optionally substituted halogen CM alkyl CM alkoxy CM haloalkyl C1-6j haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino) phenyl(C2-6)alkenyl (wherein the phenyl group is optionally substituted by halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino) heteroaryl(C2-6)alkenyl (wherein the heteroaryl group is optionally substituted by halogen CM alkyl CM alkoxy CM haloalkyl C\-A haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino) or phenyl(C2-6)alkynyl (wherein the phenyl group is optionally substituted by halogen CM alkyl CM alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino or -C(R5 )(R52)-[CR53=CR54]z-R55 where 2 is 1 or 2 R51 and R52 are each independently H halo or C1-2 alkyl R53 and R54 are each independently H halogen CM alkyl or CM haloalkyl and R55 is optionally substituted aryl or optionally substituted heteroaryl.
Most preferably R8 is -C(R51)(R52)-[CR53=CR54]z-R55 where z is 1 or 2 preferably 1 R5IandR52 are each independently H halo or C]-2 alkyl R53 and R54 are each independently H halogen CM alkyl or CM haloalkyl and R55 is phenyl substituted by halogen CM alkyl C1-4 alkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino or heteroaryl substituted by halogen CM alkyl CM alkoxy CM haloalkyl C\. 4 haloalkoxy CN NO2 aryl heteroaryl amino or dialkylamino.

R51 and R52 are preferably hydrogen.
R53 and R54 are preferably hydrogen or halogen especially hydrogen. R55 is preferably phenyl substituted with one to three substituents selected from halogen CM alkyl C^jjkoxy CM haloalkyl CM haloalkoxy CN NO2 aryl heteroaryl amino or; „ dialkylamino.
It is preferred that the ring

a 5 or 6 membered heteroaromatic ring wherein the ring members are each independently CH S N NR4 O or CR4 provided that at least one ring member is other than CH or CR4 and that there are no more than one O or S atoms present in the ring. More preferably the ring

is a pyridine pyrimidine pyrazine pyridazine triazine furan thiophene pyrrole imidazole pyrazole oxazole thiazole isoxazole isothiazole [l 2 3]triazole [l 2 3]oxadiazole or [l 2 3]thiadiazole.
Preferably each Ra is independently hydrogen halo cyano C1-.3 alkyl hydroxy or two Ra groups together with the carbon atom to which they are attached form a carbonyl group
More preferably each Ra is independently hydrogen fluoro methyl hydroxy or two Ra groups together with the carbon atom to which they are attached form a carbonyl group
Most preferably each Ra is hydrogen.
Preferably p is 1 2 or 3 and q is 1 2 or 3 and p+q is 3 4 or 5.
More preferably p is 1 or 2 and q is 2.
Most preferably p and q are both 2.
One group of preferred compounds of formula (I) are those where Yis C(O) and R1 is NR 3R14 where R13 and R14 are as defined above.

Certain compounds of formula I are novel. One group of novel compounds is that of formula I*
wherein Y is CO C=S;
R1 is hydrogen optionally substituted alkyl optionally substituted alkoxycarbonyl optionally substituted alkylcarbonyl aminocarbonyl optionally substituted alkylaminocarbonyl optionally substituted dialkylaminocarbonyl optionally substituted aryl optionally substituted heteroaryl optionally substituted alkoxy optionally substituted aryloxy optionally substituted heteroaryloxy optionally substituted heterocyclyloxy cyano optionally substituted alkenyl optionally substituted alkynyl optionally substituted cycloalkyl optionally substituted cycloalkenyl formyl optionally substituted heterocyclyl optionally substituted alkylthio NO or NRI3R14 where R13 and R14 are independently hydrogen COR15 optionally substituted alkyl optionally substituted aryl optionally substituted heteroaryl optionally substituted heterocyclyl or R13 and R14 together with the N atom to which they are attached form a group -N=C(RI6)-NRI7R18; R15 is H optionally substituted alkyl optionally substituted alkoxy optionally substituted aryl optionally substituted aryloxy optionally substituted heteroaryl optionally substituted heteroaryloxy or NRI9R20; R 6 R17 and R18 are each independently H or lower alkyl; R19 and R20 are independently optionally substituted alkyl optionally substituted aryl or optionally substituted heteroaryl;
R2 and R3 are independently hydrogen halogen cyano optionally substituted alkyl optionally substituted alkoxy or optionally substituted aryl;
the ring

- -
is a 5 or 6 membered heteroaromatic ring;
each R4 is independently halogen nitro cyano optionally substituted C1-g alkyl optionally substituted C2.6 alkenyl optionally substituted C2-6 alkynyl optionally substituted alkoxycarbonyl optionally substituted alkylcarbonyl optionally substituted alkylaminocarbonyl optionally substituted dialkylaminocarbonyl optionally substituted C3-7 cycloalkyl optionally substituted aryl optionally substituted heteroaryl optionally substituted heterocyclyl optionally substituted alkoxy optionally substituted aryloxy optionally substituted heteroaryloxy optionally substituted alkylthio or R21R22N where R21 and R22 are independently hydrogen C1-g alkyl C3-7 cycloalkyl C3-6 alkenyl C3-6 alkynyl C3-7 cycloalkyl(C1-4)alkyl C2-6 haloalkyl CM alkoxy(C1-6)alkyl CM alkoxycarbonyl orR21 and R22 together with the N atom to which they are attached form'a five six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O N or S and which may be optionally substituted by one or two C1-6 alkyl groups or 2 adjacent groups R4 together with the carbon atoms to which they are attached form a 4 5 6 or 7 membered carbocyclic or heterocyclic ring which may be optionally substituted by halogen; n is 0 1 2 or 3;
each Ra is independently hydrogen halogen hydroxy cyano optionally substituted C1-.g alkyl optionally substituted C2-6 alkenyl optionally substituted C2-6 alkynyl optionally substituted alkoxycarbonyl optionally substituted alkylcarbonyl optionally substituted alkylaminocarbonyl optionally substituted dialkylaminocarbonyl optionally substituted C3-7 cycloalkyl optionally substituted aryl optionally substituted heteroaryl optionally substituted heterocyclyl optionally substituted alkoxy optionally substituted aryloxy optionally substituted heteroaryloxy optionally substituted alkylthio optionally substituted arylthio or R23R24N where R23 and R24 are independently hydrogen C1-g alkyl C3-7 cycloalkyl C3-6 alkenyl C3.6 alkynyl C3-7 cycloalkyl(C1-4)alkyl C2-6 haloalkyl CM alkoxy(C1-6)alkyl CM alkoxycarbonyl or R23 and R24 together with the N atom to which they are attached form a five six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O N or S and which may be optionally substituted by

two Ra groups attached to adjacent carbon atoms form a bond or two Ra groups together with the carbon atom to which they are attached form a three- to seven-membered ring that may be saturated or unsaturated and that may contain one or two hetero atoms selected from the group consisting of N 0 and S and which may be optionally substituted by one or two C1--6 alkyl groups; or two Ra groups together form a group -CH2- -CH=CH- or -CH2CH2;
p is 0 1 2 3 4 5 or 6; q is 0 1 2 3 4 5 or 6 provided that p+q is 1 2 3 4 5 or 6;
R is optionally substituted alkyl optionally substituted alkenyl optionally substituted alkynyl optionally substituted cycloalkyl optionally substituted aryl optionally substituted alkoxy optionally substituted aryloxy optionally substituted alkoxycarbonyl optionally substituted alkylcarbonyl or optionally substituted alkenylcarbonyl; or salts or N-oxides thereof.
The compounds in Tables I- DCCLXVII below illustrate the compounds of the" invention.
Table I provides 575 compounds of formula la





































wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R40 are given in Table 1.
Table III provides 575 compounds of formula Ic
wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c
are given in Table 1.
Table IV provides 575 compounds of formula Id

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.

Table V provides 575 compounds of formula Ie

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table VI provides 575 compounds of formula If

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table VII provides 575 compounds of formula Ig


wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table VIII provides 575 compounds of formula Ih

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR* and the values of R8 R4a R4b and R4c are given in Table 1.
Table IX provides 575 compounds of formula Ii


wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table X provides 575 compounds of formula Ij

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XI provides 575 compounds of formula Ik

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XII provides 575 compounds of formula II
i

wherein Tl is N T2 is CR4a T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XIII provides 575 compounds of formula Im

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XIV provides 575 compounds of formula In

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XV provides 575 compounds of formula Io


wherein Tl is N T2 is CR4a T3is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XVI provides 575 compounds of formula Ip

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c
are given in Table 1.
Table XVII provides 575 compounds of formula Iq

wherein Tl is N T2 is CR4a T3is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XVm provides 575 compounds of formula Ir


wherein Tl is N T2 is CR4a T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XIX provides 575 compounds of formula Is

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XX provides 575 compounds of formula It


wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4* are given in Table 1.
Table XXI provides 575 compounds of formula Iu

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4cand the values of R8 R4a R4b and R4c are given in Table I.
Table XXII provides 575 compounds of formula Iv


wherein Tl is N T2 is CR4a? T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XXII] provides 575 compounds of formula Iw

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the-values of R8 R4a R4b and R4c are given in Table 1.
Table XXIV provides 575 compounds of formula Ix

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XXV provides 575 compounds of formula Iy


wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XXVI provides 575 compounds of formula Iz

wherein Tl is N T2 is CR4i\ T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XXVII provides 575 compounds of formula Iaa

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c ) are given in Table 1.
Table XXVIII provides 575 compounds of formula lab


wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XXIX provides 575 compounds of formula lac

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XXX provides 575 compounds of formula lad

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XXXI provides 575 compounds of formula Iae


wherein Tl is N T2 is CR4a T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XXXII provides 575 compounds of formula laf

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XXXIII provides 575 compounds of formula lag

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XXXIV provides 575 compounds of formula Iah


wherein Tl is N T2 is CR4a T3 is CR4a T4 is CR40 and the values of R8 R4a R4b and R4c are given in Table 1.
Table XXXV provides 575 compounds of formula Iai

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XXXVI provides 575 compounds of formula Iaj


wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XXXVII provides 575 compounds of formula Iak

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR40 and the values of R8 R4a R4b and R4c are given in Table 1.
Table XXXVIII provides 575 compounds of formula Ial

wherein Tl is N T2 is CR4a T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R40 are given in Table 1.
Table XXXK provides 575 compounds of formula lam


wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XLX provides 575 compounds of formula Ian

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XLI provides 575 compounds of formula Iao

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.

Table XLII provides 575 compounds of formula lap

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XLHI provides 575 compounds of formula Iaq

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR^ and the values of R8 R4a R4b and R4c are given in Table 1.
Table XLIV provides 575 compounds of formula Iar

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XLV provides 575 compounds of formula las


wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XLV provides 575 compounds of formula lat

wherein Tl is N T2 is CR4a T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XLVII provides 575 compounds of formula Iau

wherein Tl is N T2 is CR4a T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table XLVIH provides 575 compounds of formula lav


therein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c ire given in Table 1.
Table IL provides 575 compounds of formula law
(law) wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table L provides 575 compounds of formula lax

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table LI provides 575 compounds of formula lay


wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table LII provides 575 compounds of formula Iaz

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table LIU provides 575 compounds of formula Iba

wherein Tl is N T2 is CR4a T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table LIV provides 575 compounds of formula Ibb


wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table LV provides 575 compounds of formula Ibc
wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table LVI provides 575 compounds of formula Ibd

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R40 are given in Table 1.
Table LVI1 provides 575 compounds of formula Ibe


wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table LVIII provides 575 compounds of formula Ibf

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table LIX provides 575 compounds of formula Ibg

wherein Tl is N T2 is CR4a T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table LX provides 575 compounds of formula Ibh


wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R* are given in Table 1.
Table LXI provides 575 compounds of formula Ibi

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table LXII provides 575 compounds of formula Ibj

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table I.
Table LXIQ provides 575 compounds of formula Ibk


wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table LXIV provides 575 compounds of formula Ibl

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table LXV provides 575 compounds of formula Ibm


wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table LXVI provides 575 compounds of formula Ibn

wherein Tl is N T2 is CR4a T3 is CR4b T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table LXVII provides 575 compounds of formula Ibo

wherein Tl is N T2 is CR4a T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CI provides 575 compounds of formula la wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CI1 provides 575 compounds of formula lb wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. i Table CHI provides 575 compounds of formula Ic wherein Tl is CR4a T2 is N T3 is CR4a T4 is CR* and the values of R8; R4a R4b and R4c are given in Table 1. Table CIV provides 575 compounds of formula Id wherein Tl is CR4b T2 is N T3 is CR*3 T4 is CR4c and the values of R8 R4a R4b and R4* are given in Table 1.

Table CV provides 575 compounds of formula Ie wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CVT provides 575 compounds of formula If wherein Tl is CR4h T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CVII provides 575 compounds of formula lg wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR* and the values of R8 R4a R4b and R4c are given in Table 1. Table CVIII provides 575 compounds of formula Ih wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CIX provides 575 compounds of formula Ii wherein Tl is CR4a T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CX provides 575 compounds of formula Tj wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CXI provides 575 compounds of formula Ik wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CXH provides 575 compounds of formula II wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CXD3 provides 575 compounds of formula Im wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CXIV provides 575 compounds of formula In wherein Tl is CR4a T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CXV provides 575 compounds of formula Io wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CXVI provides 575 compounds of formula Ip wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CXVTC provides 575 compounds of formula Iq wherein Tl is CR4a T2 is N T3 is CR4a T4 is CR* and the values of R8 R4a R4b and R4c are given in Table 1. Table CXVm provides 575 compounds of formula Ir wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CXIX provides 575 compounds of formula Is wherein Tl is CR4b T2 is N T3 is CR4a ) T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXX provides 575 compounds of formula It wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.

Table CXXI provides 575 compounds of formula lu wherein Tl is CR4b T2 is N T3 is CR4a
T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXXII provides 575 compounds of formula Iv wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXXIII provides 575 compounds of formula Iw wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXXTV provides 575 compounds of formula Ix wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXXV provides 575 compounds of formula Iy wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXXVI provides 575 compounds of formula Iz wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXXVII provides 575 compounds of formula Iaa wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXXVIII provides 575 compounds of formula lab wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXXIX provides 575 compounds of formula lac wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4cand the values of R8: R4a R4b and R4care given in Table 1
Table CXXX provides 575 compounds of formula lad wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXXXI provides 575 compounds of formula Iae wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR40 and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXXXH provides 575 compounds of formula Iaf wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXXXIII provides 575 compounds of formula lag wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR40 and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXXXIV provides 575 compounds of formula Iah wherein Tl is CR4a T2 is N T3 is
CR4a T4 is CR* and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXXXV provides 575 compounds of formula Iai wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXXXVI provides 575 compounds of formula Iaj wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR40 and the values of R8 R4a R4b and R4c are given in Table 1.

Table CXXXVII provides 575 compounds of formula Iak wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXXXVIH provides 575 compounds of formula Ial wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R87R4a R4b and R4c are given in Table 1.
Table CXXXK provides 575 compounds of formula lam wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4* and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXL provides 575 compounds of formula Ian wherein Tl is CR4b T2 is N T3 is CR4a
T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXLI provides 575 compounds of formula Iao wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR* and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXLII provides 575 compounds of formula lap wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXLIII provides 575 compounds of formula Iaq wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXLTV provides 575 compounds of formula Iar wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXLV provides 575 compounds of formula las wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXLVI provides 575 compounds of formula Iat wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are giv.en in Table 1.
Table CXLVI1 provides 575 compounds of formula Iau wherein Tl is CR4a T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CXLVIII provides 575 compounds of formula lav wherein Tl is CR4b T2 is N T3 is
CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CIL provides 575 compounds of formula law wherein Tl is CR4b T2 is N T3 is CR4a
T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CL provides 575 compounds of formula lax wherein Tl is CR4b T2 is N T3 is CR4a
T4 is CR4C and the values of R8 R4a R4b and R4c are given in Table 1.
Table CLI provides 575 compounds of formula wherein Tl is CR4b T2 is N T3 is CR4a T4
is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CLI1 provides 575 compounds of formula Iaz wherein Tl is CR4b T2 is N T3 is CR4a
T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.

Table CLIII provides 575 compounds of formula Iba wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CLIV provides 575 compounds of formula Ibb wherein Tl is CR4b T2 is N T3 is CR4YT4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CLV provides 575 compounds of formula Ibc wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CLVI provides 575 compounds of formula Ibd wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CLVD provides 575 compounds of formula Ibe wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CLVTII provides 575 compounds of formula Ibf wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CLIX provides 575 compounds of formula Ibg wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CLX provides 575 compounds of formula Ibh wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CLXI provides 575 compounds of formula Ibi wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table !. Table CLXD provides 575 compounds of formula Ibj wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R40 are given in Table 1. Table CLXm provides 575 compounds of formula Ibk wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CLXIV provides 575 compounds of formula Ibl wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CLXV provides 575 compounds of formula Ibm wherein Tl is CR4b T2 is N T3 is CR4a T4 is CR* and the values of R8 R4a R4b and R4c are given in Table 1. Table CLXVI provides 575 compounds of formula Ibn wherein Tl is CR4a T2 is N T3 is CR4a T4 is CR4c and the values of R8 R4" R4b and R40 are given in Table 1. Table CLXVTI provides 575 compounds of formula Ibo wherein Tl is CR4b T2 is N T3 is i CR4a T4 is CR4c and the values of R8 R4a R4b and R40 are given in Table 1.
Table CCI provides 575 compounds of formula la wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.

Table CCI1 provides 575 compounds of formula lb wherein Tl is CR4b T2 is CR4a T3 is N
T4 is CR4t and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCIII provides 575 compounds of formula Ic wherein Tl is CR4b T2 is CR4a T3 is N
T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCIV provides 575 compounds of formula Id wherein Tl is CR4b T2.is CR4a T3 is N
T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCV provides 575 compounds of formula Ie wherein Tl is CR4a T2 is CR4a T3 is N
T4 is CR4cand the values of R8 R4a R4b and R4c are given in Table 1.
Table CCVI provides 575 compounds of formula If wherein Tl is CR4b T2 is CR4a T3 is N
T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCVII provides 575 compounds of formula Ig wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCVIII provides 575 compounds of formula Ih wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCIX provides 575 compounds of formula Ii wherein Tl is CR4b T2 is CR4a T3 is N
T4 is CR* and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCX provides 575 compounds of formula Ij wherein Tl is CR4a T2 is CR4a T3 is N
T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXI provides 575 compounds of formula Be wherein Tl is CR4b T2 is CR4a T3 is N
T4 is CR4c and the values of R8 R4a R4b and R40 are given in Table 1.
Table CCXII provides 575 compounds of formula II wherein Tl is CR4b T2 is CR4a T3 is N
T4 is CR4c and the values of R8 R4a R4b and R40 are given in Table 1.
Table CCXIII provides 575 compounds of formula Im wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R40 are given in Table 1.
Table CCXIV provides 575 compounds of formula In wherein Tl is CR4a T2 is CR4a T3 is
N T4 is CRAc and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXV provides 575 compounds of formula Io wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXVI provides 575 compounds of formula Ip wherein Tl is CR4a T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXVD provides 575 compounds of formula Iq wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.

Table CCXVIII provides 575 compounds of formula Ir wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXIX provides 575 compounds of formula Is wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXX provides 575 compounds of formula It wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXXI provides 575 compounds of formula Iu wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXXII provides 575 compounds of formula Iv wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXXIII provides 575 compounds of formula Iw wherein Tl is CR4b T2 is CR4a T3
is N T4 is CR4* and the values of R8 R4a R4b and R4* are given in Table 1.
Table CCXXIV provides 575 compounds of formula Ix wherein Tl is CR4b T2 is CR4a T3
is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXXV provides 575 compounds of formula Iy wherein Tl is CR4a T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXXVI provides 575 compounds of formula Iz wherein Tl is CR4b T2 is CR4a T3
is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXXV1I provides 575 compounds of formula Iaa wherein Tl is CR4b T2 is CR4a T3
is N T4 is CR4c and the values of R8 R4a R4b and R4* are given in Table 1.
Table CCXXV1II provides 575 compounds of formula lab wherein Tl is CR4b T2 is CR4a
T3 is N T4 is CR40 and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXXIX provides 575 compounds of formula lac wherein Tl is CR4b T2 is CR4a T3
is N T4 is CR4c and the values of R8 R4a R4b and R4* are given in Table 1.
Table CCXXX provides 575 compounds of formula lad wherein Tl is CR4b T2 is CR4a T3
is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXXXI provides 575 compounds of formula Iae wherein Tl is CR4b T2 is CR4a T3
is N T4 is CR40 and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXXXE provides 575 compounds of formula Iaf wherein Tl is CR4a T2 is CR4a T3
is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCXXXIII provides 575 compounds of formula lag wherein Tl is CR4b T2 is CR4a
T3 is N T4 is CR4cand the values of R8 R4a R4b and R4c are given in Table 1.

Table CCXXXIV provides 575 compounds of formula Iah wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CCXXXV provides 575 compounds of formula lai wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CCXXXVI provides 575 compounds of formula Iaj wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR4cand the values of R8 R4a R4b and R4c are given in Table 1. Table CCXXXVII provides 575 compounds of formula Iak wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CCXXXVm provides 575 compounds of formula Ial wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR4cand the values of R8 R4a R4b and R4c are given in Table 1. Table CCXXXIX provides 575 compounds of formula lam wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CCXL provides 575 compounds of formula Ian wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CCXLI provides 575 compounds of formula Iao wherein Tl is CR4a T2 is CR4a T3 is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CCXLII provides 575 compounds of formula lap wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CCXLU1 provides 575 compounds of formula Iaq wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR40 and the values of R8 R4a R4b and R4c are given in Table 1. Table CCXLIV provides 575 compounds of formula Iar wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. Table CCXLV provides 575 compounds of formula las wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1. • Table CCXLV1 provides 575 compounds of formula Iat wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR4* and the values of R8 R4a R4b and R4c are given in Table 1. Table CCXLVn provides 575 compounds of formula Iau wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR4* and the values of R8 R4a R4b and R4c are given in Table 1. Table CCXLVni provides 575 compounds of formula lav wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR4* and the values of R8 R4* R4b and R41 are given in Table 1. Table CCIL provides 575 compounds of formula law wherein Tl is CR4b T2 is CR4a T3 is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.

Table CCL provides 575 compounds of formula lax wherein Tl is CR4b T2 is CR4a T3 is N
T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCLI provides 575 compounds of formula wherein Tl is CR4a T2 is CR4a T3 is N
T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCLII provides 575 compounds of formula Iaz wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4cand the values of R8 R4a R4b and R4c are given in Table 1.
Table CCLIII provides 575 compounds of formula Iba wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCLIV provides 575 compounds of formula Ibb wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCLV provides 575 compounds of formula Ibc wherein Tl is CR4a T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCLVI provides 575 compounds of formula Ibd wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCLVII provides 575 compounds of formula Ibe wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCLVIII provides 575 compounds of formula Ibf wherein Tl is CR4b T2 is CR4a T3
is N. T4 is CR^and the values of R8 R4a. R4b and R4c an» piv*n in Tabl* 1.
Table CCLIX provides 575 compounds of formula Ibg wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCLX provides 575 compounds of formula Ibh wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCLXI provides 575 compounds of formula Ibi wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR46 and the values of R8 R4a R4b and R40 are given in Table 1.
Table CCLXTI provides 575 compounds of formula Ibj wherein Tl is CR4b T2 is CR4a T3 is
N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCLXDI provides 575 compounds of formula Ibk wherein Tl is CR4b T2 is CR4a T3
is N T4 is CR* and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCLXIV provides 575 compounds of formula Ibl wherein Tl is CR4b T2 is CR4a T3
is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCLXV provides 575 compounds of formula Ibm wherein Tl is CR4b T2 is CR4a T3
is N T4 is CR* and the values of R8 R4a R4b and R4c are given in Table 1.

Table CCLXVI provides 575 compounds of formula Ibn wherein Tl is CR4b T2 is CR4a T3
is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCLXVII provides 575 compounds of formula Ibo wherein Tl is CR4b T2 is CR4a T3
is N T4 is CR4c and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCI provides 575 compounds of formula la wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCII provides 575 compounds of formula lb wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCIII provides 575 compounds of formula Ic wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCIV provides 575 compounds of formula Id wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCV provides 575 compounds of formula Ie wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCVI provides 575 compounds of formula If wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCVII provides 575 compounds of formula Ig wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCVIH provides 575 compounds of formula Ih wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCIX provides 575 compounds of formula li wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCX provides 575 compounds of formula Ij wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXI provides 575 compounds of formula Dc wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXII provides 575 compounds of formula II wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R40 are given in Table 1.
Table CCCXIII provides 575 compounds of formula Im wherein Tl is CR4c T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXIV provides 575 compounds of formula In wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.

Table CCCXV provides 575 compounds of formula Io wherein Tl is CR4c T2 is CR4a T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1. Table CCCXVI provides 575 compounds of formula Ip wherein Tl is CR4* T2 is CR4a T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1. Table CCCXVII provides 575 compounds of formula Iq wherein Tl is CR4c T2 is CR4a T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1. Table CCCXVU1 provides 575 compounds of formula Ir wherein Tl is CR4c T2 is CR4a T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1. Table CCCXIX provides 575 compounds of formula Is wherein Tl is CR4c T2 is CR4a T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1. Table CCCXX provides 575 compounds of formula It wherein Tl is CR4c T2 is CR4a T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1. Table CCCXXI provides 575 compounds of formula Iu wherein Tl is CR4c T2 is CR4a T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1. Table CCCXXII provides 575 compounds of formula Iv wherein Tl is CR4c T2 is CR4a T3 is CR4a T4 is N and the values of R8 R4a R4b and R4c are given in Table 1. Table CCCXXIII provides 575 compounds of formula Iw wherein Tl is CR4c T2 is CR4a T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1. Table CCCXXIV provides 575 compounds of formula Ix wherein Tl is CR4c T2 is CR4a T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1. Table CCCXXV provides 575 compounds of formula Iy wherein Tl is CR4c T2 is CR4a T3 is CR4a T4 is N and the values of R8 R4a R4b and R46 are given in Table 1. Table CCCXXVI provides 575 compounds of formula Iz wherein Tl is CR4c T2 is CR4a T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1. Table CCCXXVD provides 575 compounds of formula Iaa wherein Tl is CR4c T2 is CR4a T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1. Table CCCXXVHI provides 575 compounds of formula lab wherein Tl is CR4c T2 is CR4a T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1. Table CCCXXIX provides 575 compounds of formula lac wherein Tl is CR4c T2 is CR4a > T3 is CR4a T4 is N and the values of R8 R4a R4b and R40 are given in Table 1.
Table CCCXXX provides 575 compounds of formula lad wherein Tl is CR4c T2 is CR4a T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.

Table CCCXXXI provides 575 compounds of formula Iae wherein Tl is CR4c T2 is CR4a
T3 is CR4b T4 is N and the values of R8 R4 R4b and R4c are given in Table 1.
Table CCCXXXII provides 575 compounds of formula Iaf wherein Tl is CR4c T2 is CR4a
T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXXXIII provides 575 compounds of formula lag wherein Tl is CR4c T2 is CR4a
T3 is CR4 T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXXXTV provides 575 compounds of formula Iah wherein Tl is CR4c T2 is CR4a
T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXXXV provides 575 compounds of formula Iai wherein Tl is CR4c T2 is CR4a
T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXXXVI provides 575 compounds of formula Iaj wherein Tl is CR4c T2 is CR4a
T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXXXVII provides 575 compounds of formula Iak wherein Tl is CR4c T2 is CR4a
T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXXXVIII provides 575 compounds of formula Ial wherein Tl is CR4° T2 is CR4a
T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXXXDX provides 575 compounds of formula lam wherein Tl is CR4c T2 is CR4a
T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXL provides 575 compounds of formula Ian wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXLI provides 575 compounds of formula Iao wherein Tl is CR4c T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXLII provides 575 compounds of formula lap wherein Tl is CR4c T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4* are given in Table 1.
Table CCCXLIII provides 575 compounds of formula Iaq wherein Tl is CR4c T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXLTV provides 575 compounds of formula Iar wherein Tl is CR4c T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXLV provides 575 compounds of formula las wherein Tl is CR4c T2 is CR4a T3
is CR4a T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXLVI provides 575 compounds of formula Iat wherein Tl is CR4c T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.

Table CCCXLVII provides 575 compounds of formula Iau wherein Tl is CR4c T2 is CR4a
T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCXLVID provides 575 compounds of formula lav wherein Tl is CR4c T2 is CR4a
T3 is CR4b T4 is N and the values of R\ R4a R4b and.R4c are given in Table 1.
Table CCCIL provides 575 compounds of formula law wherein Tl is CR40 T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCL provides 575 compounds of formula lax wherein Tl is CR40 T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCLI provides 575 compounds of formula wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R40 are given in Table 1.
Table CCCLII provides 575 compounds of formula Iaz wherein Tl is CR4c T2 is CR4a T3 is
CR4b T4 is N and the values of R8 R4a R4b and R40 are given in Table 1.
Table CCCLIII provides 575 compounds of formula Iba wherein Tl is CR4c T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCLIV provides 575 compounds of formula Ibb wherein Tl is CR4c T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCLV provides 575 compounds of formula Ibc wherein Tl is CR4c T2 is CR4a T3 is
CR4b. T4 is N and the values of R8. R4a. R4b and R4c are Piven in Table 1
Table CCCLVI provides 575 compounds of formula Ibd wherein Tl is CR40 T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCLVII provides 575 compounds of formula Ibe wherein Tl is CR4c T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCLV1II provides 575 compounds of formula Ibf wherein Tl is CR4c T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCLIX provides 575 compounds of formula Ibg wherein Tl is CR4c T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCLX provides 575 compounds of formula Ibh wherein Tl is CR4c T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCLXI provides 575 compounds of formula Ibi wherein Tl is CR4c T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCLXII provides 575 compounds of formula Ibj wherein Tl is CR4c T2 is CR4a T3
is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.

Table CCCLXIII provides 575 compounds of formula Ibk wherein Tl is CR4c T2 is CR4a
T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCLXIV provides 575 compounds of formula Ibl wherein Tl is CR4c T2 is CR4a T3
s CR4Vf4 is N and the values of R8 R4a R4b and R*c are given in Table 1.
Table CCCLXV provides 575 compounds of formula Ibm wherein Tl is CR4c T2 is CR4a
T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCLXVI provides 575 compounds of formula Ibn wherein Tl is CR4c T2 is CR4a
T3 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CCCLXVII provides 575 compounds of formula Ibo wherein Tl is CR4c T2 is CR4a
13 is CR4b T4 is N and the values of R8 R4a R4b and R4c are given in Table 1.
Table CDI provides 345 compounds of formula la wherein Tl is N T2 is CR4e T3 is N T4
is CR4f and the values ofR8 R4c and R4rare given in Table 2.
























Table CDII provides 345 compounds of formula lb wherein Tl is N T2 is CR4e T3 is N T4
is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDIII provides 345 compounds of formula Ic wherein Tl is N T2 is CR4e T3 is N T4
is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDIV provides 345 compounds of formula Id wherein Tl is N T2 is CR4e T3 is N T4
is CR4f and the values of R8 R4* and R4f are given in Table 2.
Table CDV provides 345 compounds of formula Ie wherein Tl is N T2 is CR4e T3 is N T4
is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDVI provides 345 compounds of formula If wherein Tl is N T2 is CR4c T3 is N T4
is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDVTI provides 345 compounds of formula Ig wherein Tl is N T2 is CR4e T3 is N
T4 is CR4f and the values of R8 R4* and R4f are given in Table 2.

Table CDVIII provides 345 compounds of formula Di wherein Tl is N T2 is CR4e T3 is N
T4 is CR4f and the values of R8 R4c and R4f are given in Table 2.
Table CDIX provides 345 compounds of formula Ii wherein Tl is N T2 is CR4c T3 is N T4
is CR4f and the values of R8; R4c and R4f are given in Table 2. =
Table CDX provides 345 compounds of formula Ij wherein Tl is N T2 is CR4e T3 is N T4
is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXI provides 345 compounds of formula Ik wherein Tl is N T2 is CR4e T3 is N T4
is CR4r and the values of R8 R4c and R4f are given in Table 2.
Table CDXII provides 345 compounds of formula II wherein Tl is N T2 is CR4e T3 is N
T4 is CR4f and the values of R8 R4* and R4f are given in Table 2.
Table CDXI1I provides 345 compounds of formula Im wherein Tl is N T2 is CR4e T3 is N
T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXIV provides 345 compounds of formula In wherein Tl is N T2 is CR4e T3 is N
T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXV provides 345 compounds of formula Io wherein Tl is N T2 is CR4* T3 is N
T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXVI provides 345 compounds of formula Ip wherein Tl is N T2 is CR4e T3 is N
T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXVII provides 345 compounds of formula Iq wherein Tl is N T2 is CR4a T3 is N
T4 is CR4r and the values of R8 R4c and R4f are given in Table 2.
Table CDXVIII provides 345 compounds of formula Ir wherein Tl is N T2 is CR4e T3 is N
T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXIX provides 345 compounds of formula Is wherein Tl is N T2 is CR4e T3 is N
T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXX provides 345 compounds of formula It wherein Tl is N T2 is CR4e T3 is N
T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXI provides 345 compounds of formula Iu wherein Tl is N T2 is CR4e T3 is N
T4 is CR4r and the values of R8 R4e and R4f are given in Table 2.
Table CDXXII provides 345 compounds of formula Iv wherein Tl is N T2 is CR4e T3 is N
T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXIII provides 345 compounds of formula Iw wherein Tl is N T2 is CR4e T3 is
N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.

Table CDXXIV provides 345 compounds of formula Ix wherein Tl is N T2 is CR4c T3 is
N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXV provides 345 compounds of formula Iy wherein Tl is N T2 is CR46 T3 is N
T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXVI provides 345 compounds of formula Iz wherein Tl is N T2 is CR4e T3 is N
T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXVD provides 345 compounds of formula Iaa wherein Tl is N T2 is CR46 T3 is
N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXV11I provides 345 compounds of formula lab wherein Tl is N T2 is CR4e T3 is
N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXIX provides 345 compounds of formula lac wherein Tl is N T2 is CR4e T3 is
N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXX provides 345 compounds of formula lad wherein Tl is N T2 is CR4e T3 is
N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXXI provides 345 compounds of formula Iae wherein Tl is N T2 is CR4e T3 is
N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXXII provides 345 compounds of formula Iaf wherein Tl is N T2 is CR4e T3 is
N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXXITI provides 345 compounds of formula lag wherein Tl is N T2 is CR4e T3 is
N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXXIV provides 345 compounds of formula Iah wherein Tl is N T2 is CR4c T3 is
N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXXV provides 345 compounds of formula Iai wherein Tl is N T2 is CR4e T3 is
N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXXVI provides 345 compounds of formula Iaj wherein Tl is N T2 is CR4e T3 is
N T4 is CR4f and the values of R8 R4c and R4f are given in Table 2.
Table CDXXXVII provides 345 compounds of formula Iak wherein Tl is N T2 is CR4e T3
is N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXXVIII provides 345 compounds of formula lal wherein Tl is N T2 is CR4* T3
is N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXXXIX provides 345 compounds of formula lam wherein Tl is N T2 is CR4c T3
is N T4 is CR4f and the values of R8 R4c and R4f are given in Table 2.

Table CDXL provides 345 compounds of formula Ian wherein Tl is N T2 is CR4c T3 is N T4 is CR4r and the values of R8 R4e and R4f are given in Table 2.
Table CDXLI provides 345 compounds of formula Iao wherein Tl is N T2 is CR4e T3 is N
*" T4 is CR4f arid the values of R8 R4e and R4f are given in Table 2. ;
Table CDXLII provides 345 compounds of formula lap wherein Tl is N T2 is CR4e T3 is N T4 is CR4f and the values of R8 R4c and R4f are given in Table 2.
Table CDXLIII provides 345 compounds of formula Iaq wherein Tl is N T2 is CR4e T3 is N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2. Table CDXLIV provides 345 compounds of formula lar wherein Tl is N T2 is CR4* T3 is N T4 is CR4f and the values 6f R8 R4c and R4f are given in Table 2.
Table CDXLV provides 345 compounds of formula las wherein Tl is N T2 is CR4c T3 is N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXL VI provides 345 compounds of formula Iat wherein Tl is N T2 is CR4e T3 is N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2. Table CDXLVII provides 345 compounds of formula Iau wherein Tl is N T2 is CR4* T3 is N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDXLVIII provides 345 compounds of formula lav wherein Tl is N T2 is CR4e T3 is N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2. Table CDIL provides 345 compounds of formula law wherein Tl is N T2 is CR4c T3 is N T4 is CR4rand the values of R8 R4c and R4f are given in Table 2.
Table CDL provides 345 compounds of formula lax wherein Tl is N T2 is CR4c T3 is N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDLI provides 345 compounds of formula wherein Tl is N T2 is CR4e T3 is N T4 is CR4f and the values of R8 R46 and R4f are given in Table 2.
Table CDLII provides 345 compounds of formula Iaz wherein Tl is N T2 is CR4e T3 is N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDLUI provides 345 compounds of formula Iba wherein Tl is N T2 is CR4c T3 is N T4 is CR4f and the values of R8 R4e and R4r are given in Table 2.
Table CDLIV provides 345 compounds of formula Ibb wherein Tl is N T2 is CR4e T3 is N T4 is CR4f and the values of R8 R4c and R4f are given in Table 2.
Table CDLV provides 345 compounds of formula Ibc wherein Tl is N T2 is CR4c T3 is N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.

Table CDLVI provides 345 compounds of formula Ibd wherein Tl is N T2 is CR4e T3 is N
T4 is CR4f and the values of R8 R4c and R4r are given in Table 2.
Table CDLV1I provides 345 compounds of formula Ibe wherein Tl is N T2 is CR4e T3 is N
-T4- is CR4f and the values of R8 R4? and R4f are given in Table 2. _. _..
Table CDLVHI provides 345 compounds of formula Ibf wherein Tl is N T2 is CR4c T3 is
N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDLIX provides 345 compounds of formula Ibg wherein Tl is N T2 is CR4c T3 is N
T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDLX provides 345 compounds of formula Ibh wherein Tl is N T2 is CR4e T3 is N
T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDLXI provides 345 compounds of formula Ibi wherein Tl is N T2 is CR4e T3 is N
T4 is CR4f and the values of R8 R4c and R4f are given in Table 2.
Table CDLXI1 provides 345 compounds of formula Ibj wherein Tl is N T2 is CR4e T3 is N
T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDLXIII provides 345 compounds of formula Ibk wherein Tl is N T2 is CR4e T3 is
N T4 is CR4f and the values of R8 R4c and R4f are given in Table 2.
Table CDLXIV provides 345 compounds of formula Ibl wherein Tl is N T2 is CR4c T3 is
N. T4 is CR4r and the values of R8. R4e and R4f are eiven in Table 2.
Table CDLXV provides 345 compounds of formula Ibm wherein Tl is N T2 is CR4e T3 is
N T4 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table CDLXVI provides 345 compounds of formula Ibn wherein Tl is N T2 is CR4e T3 is
N T4 is CR4r and the values of R8 R4e and R4f are given in Table 2.
Table CDLXVII provides 345 compounds of formula Ibo wherein Tl is N T2 is CR4e T3 is
N T4 is CR4f and the values of R8 R4* and R4f are given in Table 2.
Table DI provides 345 compounds of formula la wherein Tl is CR4e T2 is N T3 is CR4f T4
is N and the values of R8 R4* and R4f are given in Table 2.
Table DII provides 345 compounds of formula lb wherein Tl is CR4e T2 is N T3 is CR4f
T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table Dili provides 345 compounds of formula Ic wherein Tl is CR4e T2 is N T3 is CR4f
T4 is N and the values of R8 R4* and R4f are given in Table 2.
Table DIV provides 345 compounds of formula Id wherein Tl is CR4* T2 is N T3 is CR4f
T4 is N and the values of R8 R4e and R4f are given in Table 2.

Table DV provides 345 compounds of formula Ie wherein Tl is CR4c T2 is N T3 is CR4f
T4 is N and the values of R8 R4c and R4f are given in Table 2.
Table DVI provides 345 compounds of formula If wherein Tl is CR4e T2 is N T3 is CR4f
T4 is N and the values of R8 R and R are given in Table 2.
Table DVII provides 345 compounds of formula Ig wherein Tl is CR4e T2 is N T3 is CR4a
T4 is N and the values of R8 R4a and R4f are given in Table 2.
Table DVm provides 345 compounds of formula Di wherein Tl is CR4c T2 is N T3 is CR4f
T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DIX provides 345 compounds of formula li wherein Tl is CR4c T2 is N T3 is CR4f
T4 is N and the values of R8 R4c and R4f are given in Table 2.
Table DX provides 345 compounds of formula Ij wherein Tl is CR4c T2 is N T3 is CR4f T4
is N and the values of R8 R4c and R4f are given in Table 2.
Table DXI provides 345 compounds of formula Ik wherein Tl is CR4e T2 is N T3 is CR4f
T4 is N and the values of R8 R4c and R4f are given in Table 2.
Table DXII provides 345 compounds of formula II wherein Tl is CR4c> T2 is N T3 is CR4f
A At*
T4 is N and the values of R8 R e and R arc given in Table 2.
Table DXIII provides 345 compounds of formula Im wherein Tl is CR4e T2 is N T3 is
CR4r T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DXIV provides 345 compounds of formula In wherein Tl is CR4e T2 is N T3 is CR4r
T4 is N and the values of R8 R4e and R4r are given in Table 2.
Table DXV provides 345 compounds of formula Io wherein Tl is CR4c T2 is N T3 is CR4f
T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DXVI provides 345 compounds of formula Ip wherein Tl is CR4c T2 is N T3 is CR4f
T4 is N and the values of R8 R4e and R4r are given in Table 2.
Table DXVII provides 345 compounds of formula Iq wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4c and R4f are given in Table 2.
Table DXVTII provides 345 compounds of formula Ir wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DXIX provides 345 compounds of formula Is wherein Tl is CR4e T2 is N T3 is CR4f
T4 is N and the values of R8 R4e and R4r are given in Table 2.
Table DXX provides 345 compounds of formula It wherein Tl is CR4e T2 is N T3 is CR4f
T4 is N and the values of R8 R4c and R4f are given in Table 2.

Table DXXI provides 345 compounds of formula Iu wherein Tl is CR4e T2 is N T3 is CR4f
T4 is N and the values of R8 R4c and R4f are given in Table 2.
Table DXXII provides 345 compounds of formula Iv wherein Tl is CR4e T2 is N T3 is
CR4f T4 is K and the values of R8 R4c and R4f a^e given in Table 2. ~ - -
Table DXXIII provides 345 compounds of formula Iw wherein Tl is CR4c T2 is N T3 is
CR4f T4 is N and the values of R8 R4* and R4f are given in Table 2.
Table DXXIV provides 345 compounds of formula Ix wherein Tl is CR4c T2 is N T3 is
CR4f T4 is N and the values of R8 R4c and R4r are given in Table 2.
Table DXXV provides 345 compounds of formula Iy wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4c and R4f are given in Table 2.
Table DXXVI provides 345 compounds of formula Iz wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4c and R4f are given in Table 2.
Table DXXVII provides 345 compounds of formula Iaa wherein Tl is CR4c T2 is N T3 is
CR4f T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DXXVm provides 345 compounds of formula lab wherein Tl is CR4c T2 is N T3 is
CR4f T4 is N and the values of R8 R4c and R4f are given in Table 2
Table DXXIX provides 345 compounds of formula lac wherein Tl is CR4e T2 is N T3 is
CR4* T4 is N and the vaiues of R8 R e and R are given in Table 2.
Table DXXX provides 345 compounds of formula lad wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4c and R4f are given in Table 2.
Table DXXXI provides 345 compounds of formula Iae wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4c and R4f are given in Table 2.
Table DXXXII provides 345 compounds of formula Iaf wherein Tl is CR4e T2 is N T3 is
CR4r T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DXXXIII provides 345 compounds of formula lag wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DXXXIV provides 345 compounds of formula Iah wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4c and R4f are given in Table 2.
Table DXXXV provides 345 compounds of formula Iai wherein Tl is CR4c T2 is N T3 is
CR4f T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DXXXVI provides 345 compounds of formula Iaj wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4e and R4f are given in Table 2.

Table DXXXVI1 provides 345 compounds of formula lak wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DXXXVUI provides 345 compounds of formula Ial wherein Tl is CR4e T2 is N T3 is
CR4f T4 is tfand the values of R8 R4c and R4f are givenin Table 2.
Table DXXXIX provides 345 compounds of formula lam wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4c and R4f are given in Table 2.
Table DXL provides 345 compounds of formula Ian wherein Tl is CR4e T2 is N T3 is CR4r
T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DXLI provides 345 compounds of formula lao wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4c and R4f are given in Table 2.
Table DXL1I provides 345 compounds of formula lap wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DXLI1I provides 345 compounds of formula Iaq wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4e and R4rare given in Table 2.
Table DXLFV provides 345 compounds of formula Iar wherein Tl is CR4e T2 is N T3 is
CR4r T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DXLV provides 345 compounds of formula las wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DXLV1 provides 345 compounds of formula lat wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DXLVII provides 345 compounds of formula lau wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DXLV1I1 provides 345 compounds of formula lav wherein Tl is CR40 T2 is N T3 is
CR4f T4 is N and the values of R8 R4c and R4r are given in Table 2.
Table DDL provides 345 compounds of formula law wherein Tl is CR4e T2 is N T3 is CR4f
T4 is N and the values of R8 R4c and R4f are given in Table 2.
Table DL provides 345 compounds of formula lax wherein Tl is CR4e T2 is N T3 is CR4f
T4 is N and the values of R8 R4e and R4r are given in Table 2.
Table DLI provides 345 compounds of formula wherein Tl is CR4e T2 is N T3 is CR4f T4
is N and the values of R8 R4e and R4f are given in Table 2.
Table DLII provides 345 compounds of formula Iaz wherein Tl is CR4e T2 is N T3 is CR4f
T4 is N and the values of R8 R4c and R4f are given in Table 2.

Table DLIII provides 345 compounds of formula Iba wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DLIV provides 345 compounds of formula Ibb wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4c and R4f are given in Table 2.
Table DLV provides 345 compounds of formula Ibc wherein Tl is CR4e T2 is N T3 is CR4f
T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DLVI provides 345 compounds of formula Ibd wherein Tl is CR4c T2 is N T3 is
CR*f T4 is N and the values of R8 R4* and R4r are given in Table 2.
Table DLVII provides 345 compounds of formula Ibe wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DLVII1 provides 345 compounds of formula Ibf wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 .R4e and R4f are given in Table 2.
Table DLIX provides 345 compounds of formula Ibg wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DLX provides 345 compounds of formula Ibh wherein Tl is CR4e T2 is N T3 is CR4f
T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DLXI provides 345 compounds of formula Ibi wherein Tl is CR4e T2 is N T3 is CR4r
T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DLXII provides 345 compounds of formula Ibj wherein Tl is CR4e T2 is N T3 is
CR4f T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DLXIII provides 345 compounds of formula Ibk wherein Tl is CR4 CR4f T4 is N and the values of R8 R4* and R4f are given in Table 2.
Table DLXTV provides 345 compounds of formula Ibl wherein Tl is CR4* T2 is N T3 is
CR4f T4 is N and the values of R8 R46 and R4f are given in Table 2.
Table DLXV provides 345 compounds of formula Ibm wherein Tl is CR4e T2 is N T3 is
CR4r T4 is N and the values of R8 R4c and R4f are given in Table 2.
Table DLXVI provides 345 compounds of formula Ibn wherein Tl is CR4c T2 is N T3 is
:R4f T4 is N and the values of R8 R4e and R4f are given in Table 2.
Table DLXVTJ provides 345 compounds of formula Ibo wherein Tl is CR4e T2 is N T3 is
^R4f T4 is N and the values of R8 R4* and R4f are given in Table 2.
Table DCI provides 345 compounds of formula lea


wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4e and R4f are given in Table 2. Table DCII provides 345 compounds of formula Icb

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4c and R4f are given in Table 2. Table DCIH provides 345 compounds of formula Ice

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4c and R4fare given in Table 2. Table DCIV provides 345 compounds of formula led

wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4c and R4fare given in Table 2. Table DCV provides 345 compounds of formula Ice


wherein T1 is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCVI provides 345 compounds of formula Icf

wherein Tl is S? T2 is CR4 wherein Tl is S T2 is CR4e T3 is CR4fand the values of R8 R4e and R4rare given in Table 2. Table DCVIII provides 345 compounds of formula Ich


wherein Tl is S T2 is CR4e T3 is CR4fand the values of R8 R4e and R4fare given in Table 2. Table DCIX provides 345 compounds of formula Ici

i wherein Tl is S T2 is CR4a T3 is CR4f and the values of R8 R4e and R4f are given in Table 2. Table DCLX provides 345 compounds of formula IC1-

wherein Tl is S T2 is CR4* T3 is CR4f and the values of R8 R4c and R4f are given in Table 2.

Table DCXI provides 345 compounds of formula Ick

wherein Tl is S T2 is CR4* T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.

Table DCXII provides 345 compounds of formula Icl

wherein Tl is S T2 is CR4* T3 is CR4f and the values of R8 R4c and R4fare given in Table 2. Table DCXIII provides 345 compounds of formula Icm

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4f are given in Table 2. Table DCXIV provides 345 compounds of formula Icn

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCXV provides 345 compounds of formula Ico

wherein Tl is S T2 is CR4* T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.

Table DCXVI provides 345 compounds of formula Icp

wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4e and R4f are given in Table 2. Table DCXVII provides 345 compounds of formula Icq

wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4c and R4f are given in Table 2. Table DCXVIB provides 345 compounds of formula Icr
wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4c and R4fare given in Table 2. Table DCXDC provides 345 compounds of formula Ics


wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4* and R4f are given in Table 2. Table DCXX provides 345 compounds of formula let

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4fare given in Table 2. Table DCXXI provides 345 compounds of formula Icu

wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4c and R4f are given in Table 2. Table DCXXD provides 345 compounds of formula lev


wherein Tl is S T2 is CR4e T3 is CR4rand the values of R8 R4e and R4f are given in Table 2.
Table DCXXITJ provides 345 compounds of formula Jew

wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4* and R4f are given in Table 2.
Table DCXXIV provides 345 compounds of formula lex

wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4e and R4f are given in Table
2.
Table DCXXV provides 345 compounds of formula Icy


wherein Tl is S T2 is CR4* T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCXXVI provides 345 compounds of formula Icz

wherein Tl is S T2 is CP.4e T3 is CP.4f and the values of R.8 R4c and R.4f are CTiven in Table 2.
Table DCXXVII provides 345 compounds of formula Ida

wherein Tl is S T2 is CR40 T3 is CR4f and the values of R8 R4e and R4r are given in Table 2.
Table DCXXVIII provides 345 compounds of formula Idb


wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCXX1X provides 345 compounds of formula Idc

wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4e and R4r are given in Table 2.
Table DCXXX provides 345 compounds of formula Idd

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4c and R4f are given in Table 2.
Table DCXXXI provides 345 compounds of formula Ide


wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4f are given in Table Table DCXXXII provides 345 compounds of formula Idf

wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4e and R4f are given in Table Table DCXXXIII provides 345 compounds of formula Idg

wherein Tl is S T2 is CR46 T3 is CR4f and the values of R8 R4e and R4f are given in Table

Table DCXXXIV provides 345 compounds of formula Idh

wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R46 and R4f are given in Table Table DCXXXV provides 345 compounds of formula Idi

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4c and R4f are given in Table Table DCXXXVI provides 345 compounds of formula Idj


wherein Tl is S T2 is CR4e T3 is CR4rand the values of R8 R4e and R4f are given in Table 2.
Table DCXXXVII provides 345 compounds of formula Idk

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCXXXVTfl provides 345 compounds of formula Idl

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCXXX1X provides 345 compounds of formula Idm


wherein Tl is S T2 is CR4e T3 is CR4r and the values of R8 R4e and R4f are given in Table 2.
Table DCXLX provides 345 compounds of formula Idn

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCXLI provides 345 compounds of formula Ido

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.

Table DCXL11 provides 345 compounds of formula Idp

wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4e and R4f are given in. Table 2.
Table DCXLUI provides 345 compounds of formula Idq

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4c and R4f are given in Table 2.
Table DCXLIV provides 345 compounds of formula Idr

wherein Tl is S T2 is CR40 T3 is CR4f and the values of R8 R4e and R4r are given in Table 2.
Table DCXLV provides 345 compounds of formula Ids


wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4c and R4f are given in Table 2.
Table DCXLV provides 345 compounds of formula Idl

wherein Tl is S T2 is CR4e T3 is CR4r and the values of R8 R4e and R4rare given in Table 2.
Table DCXLVII provides 345 compounds of formula Idu

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCXLVIO provides 345 compounds of formula Idv


wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCIL provides 345 compounds of formula Idw

wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCL provides 345 compounds of formula Idx

wherein Tl is S T2 is CR4* T3 is CR4r and the values of R8 R4c and R4f are given in Table 2.
Table DCLI provides 345 compounds of formula Idy


wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCLII provides 345 compounds of formula Idz

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCLD1 provides 345 compounds of formula lea

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4c and R4r are given in Table 2.
Table DCLIV provides 345 compounds of formula Ieb


wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCLV provides 345 compounds of formula Iec

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCLVI provides 345 compounds of formula led

wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4c and R4f are given in Table 2.
Table DCLVfi provides 345 compounds of formula lee


wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCLVJII provides 345 compounds of formula Ief

wherein Tl is S T2 is CR4e T3 is CR4fand the values of R8 R4e and R4f are given in Table 2.
Table DCLIX provides 345 compounds of formula leg

wherein Tl is S T2 is CR4* T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCLX provides 345 compounds of formula Ieh


wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4c and R4f are given in Table 2.
Table DCLXI provides 345 compounds of formula lei

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCLXII provides 345 compounds of formula Iej

wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4c and R4f are given in Table 2.
Table DCLXIII provides 345 compounds of formula Iek


wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCLXFV provides 345 compounds of formula Iel

wherein Tl is S T2 is CR4e T3 is CR4r and the values of R8 R4c and R4f are given in Table 2.
Table DCLXV provides 345 compounds of formula Iem


wherein Tl is S T2 is CR4c T3 is CR4f and the values of R8 R4e and R4f are given in Table 2.
Table DCLXVI provides 345 compounds of formula Ien

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4c and R4f are given in Table 2.
Table DCLXVI1 provides 345 compounds of formula Ieo

wherein Tl is S T2 is CR4e T3 is CR4f and the values of R8 R4e and R4r are given in Table 2.
Table DCCI provides 207 compounds of formula lea wherein Tl is S T2 is CR4e T3 is N and the values of R8 and R4c are given in Table 3.
Table 3















Table DCCE provides 207 compounds of formula Icb wherein Tl is S T2 is CR4e T3 is N
and the values of R8 and R4e are given in Table 3.
Table DCCm provides 207 compounds of formula Ice wherein Tl is S T2 is CR4e T3 is N
and the values of R and R are given in Table 3.
Table DCdV provides 207 compounds of formula led wherein T1 is S T2 is CR4c T3 is N
and the values of R8 and R4e are given in Table 3.
Table DCCV provides 207 compounds of formula Ice wherein Tl is S T2 is CR4e T3 is N
and the values of R8 and R4c are given in Table 3.
Table DCCVI provides 207 compounds of formula Icf wherein Tl is S T2 is CR4c T3 is N
and the values of R8 and R4* are given in Table 3.
Table DCCVII provides 207 compounds of formula leg wherein Tl is S T2 is CR4c T3 is N
and the values of R8 and R4e are given in Table 3.

Table DCCVIII provides 207 compounds of formula Ich wherein Tl is S T2 is CR4c T3 is N
and the values of R8 and R4c are given in Table 3.
Table DCCIX provides 207 compounds of formula Ici wherein Tl is S T2 is CR4e T3 is N
and the values of R8 and R4e are given in -Table 3.
Table DCCX provides 207 compounds of formula IC1- wherein Tl is S T2 is CR4e T3 is N
and the values of R and R are given in Table 3.
Table DCCXI provides 207 compounds of formula Ick wherein Tl is S T2 is CR4e T3 is N
and the values of R8 and R4c are given in Table 3.
Table DCCXU provides 207 compounds of formula Icl wherein Tl is S T2 is CR4c T3 is N
and the values of R8 and R4* are given in Table 3.
Table DCCXIH provides 207 compounds of formula km wherein Tl is S T2 is CR4c T3 is
N and the values of R8 and R4* are given in Table 3.
Table DCCXIV provides 207 compounds of formula Icn wherein Tl is S T2 is CR4* T3 is
N and the values of R and R are given in Table 3.
Table DCCXV provides 207 compounds of formula Ico wherein Tl is S T2 is CR4e T3 is N
and the values of R8 and R4e are given in Table 3.
Table DCCXVI provides 207 compounds of formula Icp wherein Tl is S T2 is CR4c T3 is
N and th* values of R and R are eiven in Table 3.
Table DCCXVII provides 207 compounds of formula Icq wherein T1 is S T2 is CR4c T3 is
N and the values of R8 and R4c are given in Table 3.
Table DCCXVUI provides 207 compounds of formula Ir wherein Tl is S T2 is CR4e T3 is
N and the values of R8 and R4c are given in Table 3.
Table DCCXIX provides 207 compounds of formula Ics wherein Tl is S T2 is CR4c T3 is N
and the values of R8 and R4e are given in Table 3.
Table DCCXX provides 207 compounds of formula let wherein Tl is S T2 is CR4c T3 is N
and the values of R8 and R4e are given in Table 3.
Table DCCXXI provides 207 compounds of formula Icu wherein Tl is S T2 is CR4e T3 is
N and the values of R8 and R4* are given in Table 3.
Table DCCXXII provides 207 compounds of formula lev wherein Tl is S T2 is CR4* T3 is
N and the values of R8 and R4c are given in Table 3.
Table DCCXXHI provides 207 compounds of formula lew wherein Tl is S T2 is CR4e T3 is
N and the values of R8 and R4c are given in Table 3.

Table DCCXXIV provides 207 compounds of formula lex wherein Tl is S T2 is CR4e T3 is
N and the values of R8 and R4e are given in Table 3.
Table DCCXXV provides 207 compounds of formula Icy wherein Tl is S T2 is CR4c T3 is
N and thfe values of R8 and R4e are given in Table-3.
Table DCCXXVI provides 207 compounds of formula Icz wherein Tl is S T2 is CR4e T3 is
N and the values of R8 and R4c are given in Table 3.
Table DCCXXVD provides 207 compounds of formula Ida wherein Tl is S T2 is CR4c T3
is N and the values of R8 and R4c are given in Table 3.
Table DCCXXVIII provides 207 compounds of formula Idb wherein Tl is S T2 is CR4e T3
is N and the values of R8 and R4e are given in Table 3.
Table DCCXXIX provides 207 compounds of formula Idc wherein Tl is S T2 is CR4e T3 is
N and the values of R8 and R4e are given in Table 3.
Table DCCXXX provides 207 compounds of formula Idd wherein Tl is S T2 is CR4c T3 is
N and the values of R and R are given in Table 3.
Table DCCXXXI provides 207 compounds of formula Ide wherein Tl is S T2 is CR4e T3 is
N and the values of R8 and R4c are given in Table 3.
Table DCCXXXII provides 207 compounds of formula Idf wherein Tl is S T2 is CR4c T3 is
N and the values of R8 and R4c are given in Table 3.
Table DCCXXXHI provides 207 compounds of formula ldg wherein Tl is S T2 is CR4e T3
is N and the values of R8 and R4c are given in Table 3.
Table DCCXXXIV provides 207 compounds of formula Idh wherein Tl is S T2 is CR4e T3
is N and the values of R8 and R4e are given in Table 3.
Table DCCXXXV provides 207 compounds of formula Idi wherein Tl is S T2 is CR4c T3
ft A*
is N and the values of R and R are given in Table 3.
Table DCCXXXVI provides 207 compounds of formula Idj wherein Tl is S T2 is CR4c T3
is N and the values of R8 and R4c are given in Table 3.
Table DCCXXXVII provides 207 compounds of formula Idk wherein Tl is S T2 is CR4e T3
is N and the values of R8 and R4c are given in Table 3.
Table DCCXXXVITI provides 207 compounds of formula Idl wherein Tl is S T2 is CR4e
T3 is N and the values of R8 and R4^ are given in Table 3.
Table DCCXXXIX provides 207 compounds of formula Idm wherein Tl is S T2 is CR4e T3
is N and the values of R8 and R4c are given in Table 3.

Table DCCXL provides 207 compounds of formula Idn wherein Tl is S T2 is CR4e T3 is N
and the values of R8 and R4c are given in Table 3.
Table DCCXLI provides 207 compounds of formula Ido wherein Tl is S T2 is CR4c T3 is N
and the valuesj>£R8 and R4c are given in Table 3 _._
Table DCCXLI1 provides 207 compounds of formula Idp wherein Tl is S T2 is CR4e T3 is
N and the values of R8 and R4c are given in Table 3.
Table DCCXLIII provides 207 compounds of formula Idq wherein Tl is S T2 is CR4e T3 is
N and the values of R8 and R4c are given in Table 3.
Table DCCXLIV provides 207 compounds of formula Idr wherein Tl is S T2 is CR4e T3 is
N and the values of R and R are given in Table 3.
Table DCCXLV provides 207 compounds of formula Ids wherein Tl is S T2 is CR4c T3 is
N and the values of R and R are given in Table 3.
Table DCCXLVI provides 207 compounds of formula Idt wherein Tl is S T2 is CR4e T3 is
N and the values of R8 and R4c are given in Table 3.
Table DCCXLVII provides 207 compounds of formula Idu wherein Tl is S T2 is CR4c T3
is N and the values of R8 and R4c are given in Table 3
Table DCCXLVm provides 207 compounds of formula Idv wherein Tl is S T2 is CR4c T3
is N and the values of R and R are given in Table 3.
Table DCCIL provides 207 compounds of formula Idw wherein Tl is S T2 is CR4c T3 is N
and the values of R8 and R4c are given in Table 3.
Table DCCL provides 207 compounds of formula Idx wherein Tl is S T2 is CR4e T3 is N
and the values of R8 and R4c are given in Table 3.
Table DCCLI provides 207 compounds of formula wherein Tl is S T2 is CR4c T3 is N and
the values of R8 and R4c are given in Table 3.
Table DCCLII provides 207 compounds of formula Idz wherein Tl is S T2 is CR4c T3 is N
and the values of R8 and R4c are given in Table 3.
Table DCCLm provides 207 compounds of formula lea wherein Tl is S T2 is CR4e T3 is N
and the values of R8 and R4c are given in Table 3.
Table DCCLIV provides 207 compounds of formula Ieb wherein Tl is S T2 is CR4e T3 is N
and the values of R8 and R4* are given in Table 3.
Table DCCLV provides 207 compounds of formula Iec wherein Tl is S T2 is CR4* T3 is N
and the values of R8 and R4e are given in Table 3.

Table DCCLVI provides 207 compounds of formula led wherein Tl is S T2 is CR4c T3 is N
md the values of R8 and R4e are given in Table 3.
Table DCCLVI1 provides 207 compounds of formula lee wherein Tl is S T2 is CR4c T3 i
l and the values o?R8 and R4e are given in Table 3.
Table DCCLVUl provides 207 compounds of formula lef wherein Tl is S T2 is CR4e T3 is
and the values of R8 and R4c are given in Table 3.
Table DCCLIX provides 207 compounds of formula leg wherein Tl is S T2 is CR4c T3 is N
ind the values of R8 and R4e are given in Table 3.
Table DCCLX provides 207 compounds of formula Ieh wherein Tl is S T2 is CR4e T3 is N
md the values of R8 and R4* are given in Table 3.
Table DCCLXI provides 207 compounds of formula lei wherein Tl is S T2 is CR4e T3 is N
and the values of R8 and R4e are given in Table 3.
Table DCCLXII provides 207 compounds of formula Iej wherein Tl is S T2 is CR4e T3 is N
and the values of R8 and R4c are given in Table 3.
Table DCCLXHI provides 207 compounds of formula Iek wherein Tl is S; T2 is CR4c T3 is
N and the values of R and R are given in Table 3.
Table DCCLXIV provides 207 compounds of formula Iel wherein Tl is S T2 is CR4e T3 is
N and the values of R8 and R4c are given in Table 3.
Table DCCLXV provides 207 compounds of formula Iem wherein Tl is S T2 is CR4e T3 is
N and the values of R8 and R4e are given in Table 3.
Table DCCLXVI provides 207 compounds of formula Ien wherein Tl is S T2 is CR4e> T3 is
N and the values of R8 and R4e are given in Table 3.
Table DCCLXVH provides 207 compounds of formula Ieo wherein Tl is S T2 is CR4e T3 is
N and the values of R8 and R4e are given in Table 3.
Mass spectra data were obtained for selected compounds of Tables I to DCCLXVH using LCMS: LC5 (or LCMS:LC3; retention times with * in the table 4): 254nm - gradient 10% A to 100% B A=H2O+0.01%HCOOH B=CH3CN/CH3OH+0.01%HCOOH positive electrospray 150-1000 m/z.
The data are shown in Table 4.
Table 4






The compounds of the invention may be made in a variety of ways. For example as shown in Scheme I.
SCHEME I

Thus a compound of formula 1 may be synthesised from compounds of formula 2 by reaction with an alkylating agent of the formula R8-L where L is chloride bromide iodide or a sulfonate (e.g. mesylate or tosylate) or similar leaving group at a temperature of between ambient temperature and 100°C typically 65°C in an organic solvent such as dichloromethane chloroform or 1 2-dichloroethane in the presence of a tertiary amine base

such as triethylamine or diisopropylethylamine and optionally catalysed by halide salts such as sodium iodide potassium iodide or tetrabutylammonium iodide.
Alternatively a compound of formula 2 may be reacted with an aldehyde of the formula RCHO at a temperature between ambient temperature and 100°C in an organic solvent such as tetrahydrofuran or ethanol or mixtures of solvents in the presence of a reducing agent such as borane-pyridine complex sodium borohydride sodium (triacetoxy)borohydride sodium cyanoborohydride or such like to produce a compound of formula 1 where R8 is CH2-R.
Alternatively a compound of formula 2 maybe reacted with paraformaldehyde and a boronic acid of the formula R-B(OH)2 at a temperature between ambient temperature and 100°C in an organic solvent such as ethanol 1 4-rdioxane or water to produce a compound of formula 1 where R8 is CH2-R.
A compound of formula 2 may be obtained from a compound of formula 3 by reaction with an acid such as trifluoroacetic acid at ambient temperature in an organic solvent such as dichloromethane chloroform or 1 2-dichloroethane followed by neutralisation of the reaction mixture with an aqueous solution of an inorganic base such as sodium carbonate sodium bicarbonate or similar compound.
Compounds of formula 3 may be obtained from compounds of formula 4 by reaction with a suitable electrophilic species. Compounds of formula 3 where Y is a carbonyl group may be formed by the reaction of compounds of formula 4 with a carboxylic acid derivative of formula R1-C(0)-Z where Z is chloride hydroxy alkoxy or acyloxy at a temperature between 0°C and 150°C optionally in an organic solvent such as dichloromethane chloroform or 1 2-dichloroethane optionally in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine and optionally in the presence of a coupling agent such as dicyclohexylcarbodiimide. Compounds of formula 3 where Y is a carbonyl group and Rl is an amino substituent of formula R'-NH- may be formed by the reaction of compounds of formula 4 with an isocyanate of formula R'-N=C=0 under similar conditions. Compounds of formula 3 where Y is a group of formula S(0)q maybe formed from compounds of formula 4 by treatment with compounds of formula of Rl-S(0)q-Cl under similar conditions. Compounds of formula 3 where Y is a thiocarbonyl group and Rl is an amino substituent of formula R'-NH- may be formed by the reaction of compounds of formula 3 with an isothiocyanate of formula R*-N=C=S under similar conditions. Alternatively compounds of

formula 3 where Y is a thiocarbonyl group and Rl is a carbon substituent may be formed by treatment of compounds of formula 3 where Y is a carbonyl group and Rl is a carbon substituent with a suitable thionating agent such as Lawesson's reagent.
In the above procedures acid derivatives of the formula Rl -C(0)-Z -isocyanates of formula R'-N=C=0 isothiocyanates of formula R'-N=C=S and sulfur electrophiles of formula Rl -S(0)q-Cl are either known compounds or may be formed from known compounds by known methods by a person skilled in the art.
Compounds of formula 4 maybe obtained from compounds of formula 5 by reaction with a suitable reducing agent such as lithium-tri-tert-butoxyaluminohydride or similar hydrides or alkoxyhydrides in an organic solvent such as in dioxane or at temperature of between 100°C and 125°C following the procedure described in WO-0027845.
Compounds of formula 5 may be obtained from compounds of formula 6 following the procedure described in WO00/27845.
Compounds of formula 6 maybe obtained following the procedure described by Bremner etal. in Synthesis 1991 528.
Compounds of formula 5 and 6 are either known compounds or may be formed from known compounds by known methods by a person skilled in the art.
Certain compounds of formula 2 3 and 4 are novel compounds and as such form a further aspect of the invention.
Alternatively compounds of formula 1 may be made by the reactions summarised in Scheme II
SCHEME II


Thus a compound of formula 1A may be synthesised from compounds of formula 7 by reaction with an alkylating agent of the formula R8-L where L is chloride bromide iodide or a sulfonate (e.g. mesylate or tosylate) or similar leaving group at a temperature of between ambient temperature and 100°C typically 65°C in an organic solvent such as dichloromethane chloroform or 1 2-dichloroethane in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine and optionally catalysed by halide salts such as sodium iodide potassium iodide or tetrabutylammonium iodide.
Alternatively a compound of formula 7 may be reacted with an aldehyde of the formula RCHO at a temperature between ambient temperature and 100°C in an organic solvent such as tetrahydrofuran or ethanol or mixtures of solvents in the presence of a reducing agent such as borane-pyridine complex sodium borohydride sodium (triacetoxy)borohydride sodium cyanoborohydride or such like to produce a compound of formula 1A where R8 is CH2-R.
Alternatively a compound of formula 7 may be reacted with paraformaldehyde and a boronic acid of the formula R-B(OH)2 at a temperature between ambient temperature and 100°C in an organic solvent such as ethanol 1 4-dioxane or water to produce a compound of formula 1A where R8 is CH2-R.
A compound of formula 7 may be obtained from a compound of formula 8 by reaction with an acid such as trifluoroacetic acid at ambient temperature in an organic solvent

such as dichloromethane chloroform or 1 2-dichloroethane followed by neutralisation of the reaction mixture with an aqueous solution of an inorganic base such as sodium carbonate sodium bicarbonate or similar compound.
Compounds of formula 8 may be obtained from compounds of formula 9 by reaction with a suitable electrophilic species. Compounds of formula 8 where Y is a carbonyl group maybe formed by the reaction of compounds of formula 9 with a carboxylic acid derivative of formula R1-C(0)-Z where Z is chloride hydroxy alkoxy or acyloxy at a temperature between 0°C and 150°C optionally in an organic solvent such as dichloromethane chloroform or 1 2-dichloroethane optionally in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine and optionally in the presence of a coupling agent such as dicyclohexylcarbodiimide. Compounds of formula 8 where Y is a carbonyl group and Rl is an amino substituent of formula R'-NH- may be formed by the reaction of compounds of formula 9 with an isocyanate of formula R^-N^C^ under similar conditions. Compounds of formula 8 where Y is a group of formula S(0)q may be formed from compounds of formula 9 by treatment with compounds of formula of Rl-S(0)q-Cl under similar conditions. Compounds of formula 8 where Y is a thiocarbonyl group and Rl is an amino substituent of formula R'-NH- may be formed by the reaction of compounds of formula 8 with an isothiocyanate of formula R5-N=C=S under similar conditions. Alternatively compounds of formula 8 where Y is a thiocarbonyl group and Rl is a carbon substituent may be formed by treatment of compounds of formula 8 where Y is a carbonyl group and Rl is a carbon substituent with a suitable thionating agent such as Lawesson's reagent.
In the above procedures acid derivatives of the formula R1-C(0)-Z isocyanates of formula R'-N=C=0 isothiocyanates of formula R^N-C^S and sulfur electrophiles of formula Rl-S(0)q-Cl are either known compounds or may be formed from known compounds by known methods by a person skilled in the art.
Compounds of formula 9 maybe obtained from compounds of formula 10 by reaction with a suitable reducing agent such as lithium-tri-tert-butoxyaluminohydride or similar hydrides or alkoxyhydrides in an organic solvent such as in dioxane or at temperature of between 100°C and 125°C following the procedure described in WOOO/27845.
Compounds of formula 10 may be obtained from compounds of formula 11 and 12 following known procedures.

Compounds of formula 10 11 and 12 are either known compounds or may be formed from known compounds by kiiown methods by a person skilled in the art.
Certain compounds of formula 7 8 and 9 are novel compounds and as such form a further aspect of the invention.
Compounds of formula 1 may also be made by the routes described in scheme III:


Compounds of formula 16 and 17 are either known compounds or may be formed from known compounds by known methods by a person skilled in the art.
Certain compounds of formula 13 14 and 15 are novel compounds and as such form
a further aspect of the invention.
Further compounds of formula I may be made by the route of Scheme IV.


A compound of formula 1C may be synthesised from compounds of formula 22 by reaction with an alkylating agent of the formula R8-L where L is chloride bromide iodide or a sulfonate (e.g. mesylate or tosylate) or similar leaving group at a temperature of between ambient temperature and 100°C typically ambient temperature in an organic solvent such as acetonitrile dimethylformamide dichloromethane chloroform or 1 2-dichloroethane in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine and optionally catalysed by halide salts such as sodium iodide potassium iodide or tetrabutylammonium iodide.
A compound of formula 22 may be obtained from a compound of formula 23 by reaction with an acid such as trifluoroacetic acid and a reducing agent such as tri ethyl si lane at ambient temperature in an organic solvent such as dichloromethane chloroform or 1 2-dichloroethane followed by neutralisation of the reaction mixture with an aqueous solution of an inorganic base such as sodium carbonate sodium bicarbonate or similar compound.
A compound of formula 23 maybe obtained by cyclising a compound of formula 24 under Heck conditions in the presence of a catalyst such as palladium acetate optionally a

ligand such as triphenylphosphine or/and an additive such as tetrabutylammonium bromide and a base such as triethylamine in an organic solvent such as tetrahydrofuran acetonitrile or dimethylformamide at a temperature of between 50°C to 140°C.
Compounds of formula 24 may be obtained from compounds of formula 25 by reaction with a suitable electrophilic species. Compounds of formula 24 where Y is a carbonyl group may be formed by the reaction of compounds of formula 25 with a carboxylic acid derivative of formula R1-C(0)-Z where Z is chloride hydroxy alkoxy or acyloxy at a temperature between 0°C and 150°C optionally in an organic solvent such as dichloromethane chloroform or 1 2-dichloroethane optionally in the presence of a tertiary amine base such as triethylamine or diisopropylethylamine and optionally in the presence of a coupling agent such as dicyclohexylcarbodiimide. Compounds of formula 24 where Y is a carbonyl group and Rl is an amino substituent of formula R'-NH- maybe formed by the reaction of compounds of formula 25 with an isocyanate of formula R*-N=C~0 under similar conditions. Compounds of formula 1C where Y is a group of formula S(0)q maybe formed from compounds of formula 22 by treatment with compounds of formula of Rl-S(0)q-Cl under similar conditions. Compounds of formula 24 where Y is a thiocarbonyl group and Rl is an amino substituent of formula R'-NH- may be formed by the reaction of compounds of formula 25 with an isothiocyanate of formula R'-N'OS under similar conditions. Alternatively compounds of formula 24 where Y is a thiocarbonyl group and Rl is a carbon substituent may be formed by treatment of compounds of formula 24 where Y is a carbonyl group andRl is a carbon substituent with a suitable thionating agent such as Lawesson's reagent.
In the above procedures acid derivatives of the formula R1-C(0)-Z isocyanates of formula R*-N=C=0 isothiocyanates of formula R*-N=C=S and sulfur electrophiles of formula Rl-S(0)q-Cl are either known compounds or may be formed from known compounds by known methods by a person skilled in the art.
Compounds of formula 25 may be synthesised by alkylating a compound of formula 27 (in which the amino group may if necessary be protected e.g. by an acyl group which can be removed after the reaction) with a compound of formula 26 in the presence of a base such as sodium hydride lithium aluminium hydride or potassium tertbutoxide at a temperature of between -78°C to 100°C in an organic solvent such as tetrahydrofuran or dimethyformamide.

Compounds of formula 25 26 and 27 are either known compounds or maybe formed from known compounds by known methods by a person skilled in the art.
Certain compounds of formula 22 23 and 24 are novel compounds and as such form a further aspect of the invention.
Compounds of formula I where R and R are other than hydrogen may be made by routes described in WO03/106457. Thus for example a compound of formula 26a or 36a which are compounds of formula 26 or 36 respectively wherein the carbon atom adjacent to the leaving group X carries groups R2 and R3 may be converted to compounds of formula I using the methods described for converting compounds of 26 or 36 respectively into compounds of formula 1.
Compounds where the ring T is a heteroaromatic ring (such as pyrimidine or thiophene) may be prepared according to the synthetic routes described for instance in Organic Reactions (New York) (2002) 60 157 either by route shown in scheme V or scheme VI (both based on intramolecular Heck reactions):



The above methods particularly scheme V may be varied according to the knowledge of the skilled person. Thus for example compounds of formula 1 where the ring T is a thiophene ring may be synthesised by the method outlined in Scheme VII.
Thus a compound of formula ID may be synthesised by alkylating a compound of formula 42 with a reagent of formula R8-L by methods known per se.
A compound of formula 42 may be obtained by reacting a compound of formula 43 with a reducing agent such as triethylsilane sodium borohydride sodium cyanoborohydride or borane in the presence of an acid such as tnfluoroacetic acid in an organic solvent such as dichloromethane at a temperature of between -10°C to 80 °C.
A compound of formula 43 may be synthesised from a compound of formula 44 by reacting with a suitable electrophilic species by methods known per se.
A compound of formula 44 may be prepared from a compound of formula 45 by treatment with a suitable base such as potassium carbonate at a temperature of between 0°C to 80°C in an organic solvent such as methanol or ethanol in combination with water.
A compound of formula 45 may be synthesised by cyclising a compound of formula 46 under Heck conditions typically in the presence of a catalyst such as palladium(II) acetate optionally a ligand such as triphenylphosphine or/and an additive such as tetrabutylammonium bromide and a base such as triethylamine in an organic solvent such as

tetrahydrofuran acetonitrile dimethylformamide N-methyl-pyrrolidinone or dimethylacetamide at a temperature of between 20°C to 140°C.
Compounds of formula 46 may be synthesised by coupling compounds of formula 47 with the known alcohol 8 (J. Org. Chem. 2001 66 5545-5551) under Mitsunobu conditions typically using a phosphine such as triphenylphosphine and an azo compound such as diethylazodicarboxylate or diisopropylazodicarboxylate in an organic solvent such as tetrahydrofuran or toluene at a temperature of between 0°C to 80°C.
Compounds of formula 46 and 47 are either known compounds or may be formed from known compounds by known methods by a person skilled in the art.
Certain compounds of formula 42 43 and 44 are novel compounds and as such form a further aspect of the invention.


The skilled person will readily recognize that other compounds of formula 1 may be prepared using the methods described in Scheme VII.
The compounds of formula (I) can be used to combat and control infestations of . insect pests such as Lepidoptera Diptera Hemiptera Thysanoptera Orthoptera Dictyoptera Coleoptera Siphonaptera Hymenoptera and Isoptera and also other invertebrate pests for example acarine nematode and mollusc pests. Insects acarines nematodes and molluscs are. hereinafter collectively referred to as pests. The pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products) horticulture and animal husbandry companion animals forestry and the storage of products

of vegetable origin (such as fruit grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies).
Examples of pest species which may be controlled by the compounds of formula (I) include: Myzus persicae (aphid) Aphis gossypii (aphid) Aphis fabae (aphid) Lygus spp. (capsids) Dysdercus spp. (capsids) Nilaparvata lugens (planthopper) Nephotettixc incticeps (leafhopper) Nezara spp. (stinkbugs) Euschistus spp. (stinkbugs) Leptocorisa spp. (stinkbugs) Frankliniella occidentalis (thrip) Thrips spp. (thrips) Leptinotarsa decemlineata (Colorado potato beetle) Anthonomus grandis (boll weevil) Aonidiella spp. (scale insects) Trialeurodes spp. (white flies) Bemisia iabaci (white fly) Ostrinia nubilalis (European corn borer) Spodoptera littoralis (cotton leafworm) Heliothis virescens (tobacco budworm) Helicoverpa armigera (cotton bollworm) Helicoverpa zea (cotton bollworm) Sylepta derogata (cotton leaf roller) Pieris brassicae (white butterfly) Plutella xylostella (diamond back moth) Agrotis spp. (cutworms) Chilo suppressalis (rice stem borer) Locusta. migratoria (locust) Chortiocetes terminifera (locust) Diabrotica spp. (rootworms) Panonychus ulrni (European red mite) Panonychus citri (citrus red mite) Tetranychus urticae (two-spotted spider mite) Tetranychus cinnabarinus (carmine spider mite) Phyllocoptruta oleivora (citrus rust mite) Polyphagotarsonemus latus (broad mite) Brevipalpus spp. (flat mites) Boophilus microplus (cattle tick) Dermacentor variabilis (American dog tick) Ctenocephalides felis (cat flea) Liriomyza spp. (leafminer) Musca domestica (housefly) Aedes aegypti (mosquito) Anopheles spp. (mosquitoes) Culex spp. (mosquitoes) Lucillia spp. (blowflies) Blattella germanica (cockroach) Periplaneta americana (cockroach) Blatta orientalis (cockroach) termites of the Mastotermitidae (for example Mastotermes spp.) the Kalotermitidae (for example Neotermes spp.) the Rhinotermitidae (for example Coptotermesformosanus Reticulitermesflavipes R. speratu R. virginicus R. Hesperus and R. santonensis) and the Termitidae (for example Globitermes sulphureus) Solenopsis geminata (fire ant) Monomorium pharaonis (pharaoh's ant) Damalinia spp. and Linognaihus spp. (biting and sucking lice) Meloidogyne spp. (root knot nematodes) Globodera spp. and Heterodera spp. (cyst nematodes) Pratylenchus spp. (lesion nematodes) Rhodopholus spp. (banana burrowing nematodes) Tylenchulus spp.(citrus nematodes) Haemonchus contortus (barber pole worm) Caenorhabditis elegansSyintgzr

eelworm) Trichostrongylus spp. (gastro intestinal nematodes) and Deroceras reticulatum (slug).
The invention therefore provides a method of combating and controlling insects acarines nematodes or molluscs which comprises applying an insecticidally acaricidally nematicidally or molluscicidally effective amount of a compound of formula (I) or a composition containing a compound of formula (I) to a pest a locus of pest or to a plant susceptible to attack by a pest The compounds of formula (I) are preferably used against insects acarines or nematodes.
The term "plant" as used herein includes seedlings bushes and trees.
In order to apply a compound of formula (I) as an insecticide acaricide nematicide or molluscicide to a pest a locus of pest or to a plant susceptible to attack by a pest a compound of formula (I) is usually formulated into a composition which includes in addition to the compound of formula (I) a suitable inert diluent or carrier and optionally a surface active agent (SFA). SFAs are chemicals which are able to modify the properties of an interface (for example liquid/solid liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise by weight 0.0001 to 95% more preferably I to 85% for example 5 to 60% of a compound of formula (I). The composition is generally used for the control of pests such that a compound of formula (I) is applied at a rate of from 0.1 g to 10kg per hectare preferably from 1 g to 6kg per hectare more preferably from 1 g to 1kg per hectare.
When used in a seed dressing a compound of formula (I) is used at a rate of 0.0001 g to lOg (for example O.OOlg or 0.05g) preferably O.OOSg to 10g more preferably 0.005g to 4g per kilogram of seed.
In another aspect the present invention provides an insecticidal acaricidal nematicidal or molluscicidal composition comprising an insecticidally acaricidally nematicidally or molluscicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor. The composition is preferably an insecticidal acaricidal nematicidal or molluscicidal composition.
In a still further aspect the invention provides a method of combating and controlling pests at a locus which comprises treating the pests or the locus of the pests with an insecticidally acaricidally nematicidally or molluscicidally effective amount of a

composition comprising a compound of formula (I). The compounds of formula (I) are preferably used against insects acarines or nematodes.
The compositions can be chosen from a number of formulation types including dustable powders (DP) soluble powders (SP) water soluble granules (SG) water dispersible granules (WG) wettable powders (WP) granules (GR) (slow or fast release) soluble concentrates (SL) oil miscible liquids (OL) ultra low volume liquids (UL) emulsifiable concentrates (EC) dispersible concentrates (DC) emulsions (both oil in water (EW) and water in oil (EO)) micro-emulsions (ME) suspension concentrates (SC) aerosols fogging/smoke formulations capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical chemical and biological properties of the compound of formula (I).
Dustable powders (DP) may be prepared by mixing' a compound of formula (I) with one or more solid diluents (for example natural clays kaolin pyrophyllite bentonite alumina montmorillohite kieselguhr chalk diatomaceous earths calcium phosphates calcium and magnesium carbonates sulphur lime flours talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
Soluble powders (SP) may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and optionally one or more wetting agents one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
Wettable powders (WP) may be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers one or more wetting agents and preferably one or more dispersing agents and optionally one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).
Granules (GR) may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof in a suitable agent) in a porous granular material (such as pumice attapulgite clays fuller's earth kieselguhr diatomaceous earths or ground com cobs) or by adsorbing a compound of formula (I) (or a

solution thereof in a suitable agent) on to a hard core material (such as sands silicates mineral carbonates sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents alcohols ethers ketones and esters) and sticking agents (such as polyvinyl acetates polyvinyl alcohols dextrins sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent wetting agent or dispersing agent).
Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula (I) in water or an organic solvent such as a ketone alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).
Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes exemplified by SOLVESSO 100 SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark) ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol furfiiryl alcohol or butanol) N-alkylpyrrolidones (such as N-methylpyrrplidone or N-octylpyrrolidone) dimethyl amides of fatty acids (such as Cs-Cio fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature it may be melted at a reasonable temperature typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs under high shear to produce an emulsion. Suitable solvents for use in EWs include vegetable oils chlorinated hydrocarbons (such as chlorobenzenes) aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of formula (I) is present initially in either the

water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium optionally with one or more dispersing agents to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively a compound of formula (I) may be dry milled and added to water containing agents hereinbefore described to produce the desired end product.
Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example n-butane). A compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid such as w-propanol) to provide compositions for use in non-pressurised hanC1-actuated spray pumps.
A compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating in an enclosed space a smoke containing the compound.
Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and optionally a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment. A compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow controlled release of the compound.
A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting retention or distribution

on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)). Such additives include surface active agents spray additives based on oils for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil) and blends of these with other bio-enhancing adjuvants (ingredients which may aid or-modify the action of a compound of formula (I)).
A compound of formula (I) may also be formulated for use as a seed treatment for example as a powder composition including a powder for dry seed treatment (DS) a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS) or as a liquid composition including a flowable concentrate (FS) a solution (LS) or a capsule suspension (CS). The preparations of DS SS WS FS and LS compositions are very similar to those of respectively DP SP WP SC and DC compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
Wetting agents dispersing agents and emulsifying agents may be surface SFAs of the cationic anionic amphoteric or non-ionic type.
Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide) imidazolines and amine salts.
Suitable anionic SFAs include alkali metals salts of fatty acids salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate) salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate calcium dodecylbenzenesulphonate butylnaphthalene sulphonate and mixtures of sodium di-/sopropyl- and tri-fsopropyl-naphthalene sulphonates) ether sulphates alcohol ether sulphates (for example sodium laureth-3-sulphate) ether carboxylates (for example sodium laureth-3-carboxylate) phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters) for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated) sulphosuccinamates paraffin or define sulphonates taurates and lignosulphonates.
Suitable SFAs of the amphoteric type include betaines propionates and glycinates.
Suitable SFAs of the non-ionic type include condensation products of alkylene oxides such as ethylene oxide propylene oxide butylene oxide or mixtures thereof with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol

nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); ammFSxides (for example lauryl dimethyl amine oxide); and lecithins.
Suitable suspending agents include hydrophilic colloids (such as polysaccharides polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
A compound of formula (I) may be applied by any of the known means of applying pesticidal compounds. For example it may be applied formulated or unformulated to the pests or to a locus of the pests (such as a habitat of the pests or a growing plant liable to infestation by the pests) or to any part of the plant including the foliage stems branches or roots to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots the soil generally paddy water or hydroponic culture systems) directly or it may be sprayed on dusted on applied by dipping applied as a cream or paste formulation applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.
A compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods or applied by land or aerial irrigation systems.
Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient the concentrate being added to water before use. These concentrates which may include DCs SCs ECs EWs MEs SGs SPs WPs WGs and CSs are often required to withstand storage for prolonged periods and after such storage to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10% by weight) depending upon the purpose for which they are to be used.
A compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen potassium- or phosphorus-containing fertilisers). Suitable formulation types

include granules of fertiliser. The mixtures suitably contain up to 25% by weight of the compound of formula (I).
The invention therefore also provides a fertiliser composition comprising a fertiliser
andjyjompound of formula (I). ___ - .=. .--.
The compositions of this invention may contain other compounds having biological activity for example micronutrients or compounds having fungicidal activity or which possess plant growth regulating herbicidal insecticidal nematicidal or acaricidal activity.
The compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide fungicide synergist herbicide or plant growth regulator where appropriate. An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition. Examples of suitable pesticides include the following:
a) Pyrethroids such as permethrin cypermethrin fenvalerate esfenvalerate deltamethrin cyhalothrin (in particular lambda-cyhalothrin) bifenthrin fenpropathrin cyfluthrin tefluthrin fish safe pyrethroids (for example ethofenprox) natural pyrethrin tetramethrin s-bioallethrin fenfluthrin prallethrin or 5-benzyl-3-furylmethyl-(E)-(lR 3S)-2 2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate;
b) Organophosphates such as profenofos sulprofos acephate methyl parathion azinphos-methyl demeton-s-methyl heptenophos thiometon fenamiphos monocrotophos profenofos triazophos methamidophos dimethoate phosphamidon malathion chlorpyrifos phosalone terbufos fensulfothion fonofos phorate phoxim pirimiphos-methyl pirimiphos-ethyl fenitrothion fosthiazate or diazinon;
c) Carbamates (including aryl carbamates) such as pirimicarb triazamate cloethocarb carbofuran furathiocarb ethiofencarb aldicarb thiofurox carbosulfan bendiocarb fenobucarb propoxur methomyl or oxamyl;
d) Benzoyl ureas such as diflubenzuron triflumuron hexaflumuron flufenoxuron or chlorfluazuron;
e) Organic tin compounds such as cyhexatin fenbutatin oxide or azocyclotin;

f) Pyrazoles such as tebufenpyrad and fenpyroximate;
g) Macrolides such as avermectins or milbemycins for example abamectin emamectin benzoate ivermectin milbemycin spinosad or azadirachtin;
h) Hormones oVpheromones;
i) Organochlorine compounds such as endosulfan benzene hexachloride DDT chlordane or
dieldrin;
j) Amidines such as chlordimeform or amitraz;
k) Fumigant agents such as chloropicrin dichloropropane methyl bromide or metam;
1) Chloronicotinyl compounds such as imidacloprid thiacloprid acetamiprid nitenpyram or
thiamethoxam;
m) Diacylhydrazines such as tebufenozide chromafenozide or methoxyfenozide;
n) Diphenyl ethers such as diofenolan orpyriproxifen;
o) Indoxacarb;
p) Chlorfenapyr; or
q) Pymetrozine.
In addition to the major chemical classes of pesticide listed above other pesticides having particular targets may be employed in the composition if appropriate for the intended utility of the composition. For instance selective insecticides for particular crops for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed. Alternatively insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides such as clofentezine flubenzimine hexythiazox or tetradifon; acaricidal motilicides such as dicofol or propargite; acaricides such as bromopropylate or chlorobenzilate; or growth regulators such as hydramethylnon cyromazine methoprene chlorfluazuron or diflubenzuron).
*
Examples of fungicidal compounds which may be included in the composition of the invention are (£)-^V-methyl-2-[2-(2 5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoacetamide (SSF-129) 4-bromo-2-cyano-Ar^V-dimethyl-6-trifluoromethylbenzimidazole-1-sulphonamide a-[A^3-chloro-2 6-xylyl)-2-methoxyacetam
2-cyano-A^^V-dimethyl-5-/?-tolylimidazole-l-sulfonamide(IKF-916 cyamidazosulfamid) 3-5-dichloro-AH3-chloro-1 -ethyl-1 -methyl-2-oxopropyl)-4-methylbenzamide (RH-7281 zoxamide) 7/-allyl-4 5 -dimethyl-2-trimethylsilylthiophene-3-carboxamide (MON65500) N-

(l-cyano-l 2-dimethylpropyI)-2-(2 4-dichlorophenoxy)propionam!de(AC382042) W-(2-methoxy-5-pyridyI)-cyclopropane carboxamide acibenzolar (CGA245704) alanycarb aldimorph anilazine azaconazole azoxystrobin benalaxyl benomyl biloxazol bitertanol blasticidin S bromuconazole bupirimate captafol captan xarbendazim carbendazim chlorhydrate carboxin caipropamid carvone CGA41396 CGA41397 chinomethionate chlorothalonil chlorozolinate clozylacon copper containing compounds such as copper oxychloride copper oxyquinolate copper sulphate copper tallate and Bordeaux mixture cymoxanil cyproconazole cyprodinil debacarb di-2-pyridyl disulphide l T-dioxide dichlofluanid diclomezine dicloran diethofencarb difenoconazole difenzoquat diflumetorim
triazoxide tricyclazole tridemorph trifloxystrobin (CGA279202) triforine triflumizole triticonazole validamycin A vapam vinclozolin zineb and ziram.
The compounds of formula (I) may be mixed with soil peat or other rooting media for the protection of plantsTagainst seeC1-borne soil-borne or foliar fungal diseases.
Examples of suitable synergists for use in the compositions include piperonyl butoxide sesamex safroxan and dodecyl imidazole.
Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
An example of a rice selective herbicide which may be included is propanil. An example of a plant growth regulator for use in cotton is PIX™.
Some mixtures may comprise active ingredients which have significantly different physical chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example where one active ingredient is a water insoluble solid and the other a water insoluble liquid it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.

The invention is illustrated by the following Examples:
EXAMPLE 1
This example illustrate the preparation of compound CCCIII-3 7-aza-\'(2' cWoropyridin-4-yl-)carbonyl-r-[tra^ Step A:
NaH (4.25 g) was slowly added to a solution of 3-chloro-2-pyridylacetonitrile (10 g) in DMSO (140 ml) under nitrogen. The mixture was stirred at room temperature for lh. A solution of bis-(2-chloro-ethyl)-carbamic acid tert-butyl ester (15.87 g) in DMSO (140 ml) was added and the resulting mixture was stirred at 70°C for 2 hrs. After cooling the reaction mixture was partitioned between ethyl acetate and water the combined organic layers were washed with saturated sodium bicarbonate and brine dried (sodium sulfate) filtered and concentrated in vacuo. The crude product was purified by chromatography [S1O2; ethyl acetate-hexane (3:7)] to give 12.96 g (61%) of 2-chloro-4 -cyano-3 4' 5 6 -tetrahydro-2'H-[3 4']bipyridinyl-r-carboxylic acid tert-butyl ester as a white solide; MS (ES+) 322/324 (M+H+). Step B:
A mixture of 2-chloro-4 -cyano-3t 4! 5 6!-tetrahydro-2 H-[3 4!]bipyridinyl-r-carboxylic acid tert-butyl ester (6 g) and lithium tri-tert-butoxyaluminohydride (72.34 ml). 1M solution in THF) in 1-4-dioxane (90 ml) was refluxed overnight. After cooling 1 N NaOH (100 ml) and H2O (100 ml) were added slowly at 0°C. Dichloromethane was added to the mixture. The aqueous phase was extracted twice with dichloromethane and the combined organic layers were washed with saturated sodium bicarbonate dried (magnesium sulfate) filtered and concentrated in vacuo. The crude product was purified by chromatography [S1O2; dichloromethane-methanol (95:5)] to give 5.5 g (46%) of 7-Aza- spiro[indoline-3 4'-piperidine]-l '-carboxylic acid tert-butylester; MS (ES+) 290 (M+H+). Step C:
A mixture of 2-chloro-isonicotinic acid (441 mg) thionyl chloride (0.6 ml) DMF (trace) in toluene (9 ml) was heated to reflux for 2 hrs. After concentration in vacuo the residue was dissolved in 12 ml dichloromethane and added dropwise at 0°C under nitrogen to a mixture of 7-aza- spirofindolineO^'-piperidineJ-r-carboxylic acid tert-butylester (405 mg) triethylamine (0.86 ml) and dichloromethane ((12 ml). The mixture was stirred at room temperature for 2 hrs. The mixture was diluted in a saturated sodium carbonate solution. The

organic layer was separated and the aqueous phase was extracted twice with dichloromethane and the combined organic layers were washed with saturated sodium bicarbonate dried (magnesium sulfate) filtered and concentrated in vacuo 630 mg of 7-Aza-l-(2-chloropyridin-4-y]-)carbonyl-l '-carboxylic acid tert-butylester spiro[indoline-3 4'-prperidine; MS (ES+) 429 (M+H+). Step D:
Trifluoroacetic acid (1.92 ml) was added to a stirred solution of 7-Aza-l -(2-chloropyridin-4-yl-)carbonyl-l'-carboxylic acid tert-butylester spiro[indoline-3 4'-piperidine] (0.62 g) in anhydrous dichloromethane (20 ml) under an atmosphere of nitrogen. The reaction was left as such for 2 h. The reaction was washed with saturated bicarbonate solution and dried over sodium sulphate and concentrated in vacuo to yield 427 mg (90%) of 7-aza-l-(2-chloropyridin-4-yl0carbonyl-spiro[indoline-3 4'-piperidine]; MS (ES+) 329 (M+H+).
Step E:
A solution of 4-chlorocinnamyl chloride (68 mg) in acetonitrile (4 ml) was added slowly to a
stirred mixture of 7-Aza-l-(2-chloropyridin-4-yl-)carbonyl«spiro[indoline-3 4 -piperidine];
(100 mg) and potassium carbonate (0.42 g) in acetonitrile (16 ml) under an atmosphere of
nitrogen at room. The reaction was heated to 70 C for 2 hrs. The reaction was diluted in
diethylether washed with H2O and dried over sodium sulphate and concentrated in vacuo.
The crude product was purified by chromatography [SiCh; hexane-ethyl acetate-triethylamine
(2:8:0.1)] to give 84 mg (58%) of 7-aza-l-(2-chloropyridin-4-yl-)carbonyl-r-[trans-3-(4-
chlorophenylallyl]spiro[indoline-3 4'-piperidine]; MS (ES+) 479 (M+H4).
Compound Nos CCC1-3 CCCV-3 and CCCVI-3 were prepared by analogous methods to
those of Example 1.
EXAMPLE 2
This Example illustrates the preparation of compound CCHI-3 6-Aza-l-(2-
chloropyridin-4-yl-)carbonyl-r-[trans-3--(4-chlorophenylallyl]spiro[indoline-3 4'-
piperidine].
Step A:
Potassium hexamethyldisilazane (1.2 ml 0.5 M solution in toluene) was slowly added to a
solution of 4-chloro-3-fluoro-pyridin (0.5 g) and N-Boc-4-Cyano-Piperidine (0.312 g) in
1.5ml toluene at room temperature under nitrogen. The mixture was stirred at 80°C for 2

hrs. After cooling the reaction mixture was quenched in IN HC1. The aqueous phase was
extracted twice with toluene and the combined organic were dried over anhydrous
magnesium sulfate and concentrated in vacuo. The crude product was purified by
chromatography [S1O2; ethyl acetate-hexane (1:1)] to give 104 mg(90%) of4-cyano-3l-
fluoro-3 4 5 6-tetrahydro-2H-[4 4 ]bipyridinyl-l-carboxylic acid tert-butyl ester; MS (ES+)
306 (M+H+).
Step B:
A mixture of 4-cyano-3'-fluoro-3 4 5 6-tetrahydro-2H-[4 4']bipyridinyM-carboxylic acid
tert-butyl ester (1 g) and lithium tri-tert-butoxyaluminohydride (12.7 ml) 1M solution in
THF) in 1-4-dioxane (15 ml) was stirred at 130°C (sealed tube) for 1 hr. After cooling 1 N
NaOH (100 ml) and H20 (100 ml) were added slowly at 0°C. Ethyl acetate was added to the
mixture. The aqueous phase was extracted twice with ethyl acetate and the combined organic
layers were washed with saturated sodium bicarbonate dried (magnesium sulfate) filtered
and concentrated in vacuo. The crude product was purified by chromatography [Si02;
hexane-ethyl acetate (7:3)] to give 230 mg g (24%) of 6-aza- spiro[indoline-3 4'-piperidine]-
T-carboxylic acid tert-butylester; MS (ES+) 290 (M+H*).
Step C:
A mixture of 2-chloro-isonicotinic acid (239 mg)? thionyl chloride (0.33 ml). DMF (trace) in
toluene (5 ml) was heated to reflux for 2 hrs. After concentration in vacuo the residue was
dissolved in 2 ml dichloromethane and added dropwise at 0°C under nitrogen to a mixture of
6-aza- spirofindoline-S^-piperidineJ-r-carboxylic acid tert-butylester (220 mg)
triethylamine (0.47 ml) and dichloromethane ((13 ml). The mixture was stirred at room
temperature for 1 hr. The mixture was diluted in a saturated sodium carbonate solution. The
organic layer was separated and the aqueous phase was extracted twice with dichloromethane
and the combined organic layers were washed with saturated sodium bicarbonate dried
(magnesium sulfate) filtered and concentrated in vacuo 340 mg of 6-aza-l-(2-chloropyridin-
4-yl-)carbonyl-r-carboxylic acid tert-butylester spirofindoline-S^'-piperidine]; MS (ES+)
429 (M+H+).
StepD:
Trifluoroacetic acid (1 ml) was added to a stirred solution 6-aza-l-(2-chloropyridin-4-yl-
)carbonyl-r-carboxylic acid tert-butylester spirofindoline-S^'-piperidine] (0.33 g) in
anhydrous dichloromethane (10 ml) under an atmosphere of nitrogen. The reaction was left

as such for 2 h. The reaction was washed with saturated bicarbonate solution and dried over
sodium sulphate and concentrated in vacuo to yield 210 mg (83%) of 4-aza-l-(2-
chloropyridin^-yl^carbonyl-spirofindoline-S^'-piperidine]; MS (ES+) 329 (M+H+).
Step E:
A solution of 4-chlorocinnamyl chloride (40 mg) in acetonitrile (3 ml) was added slowly to a
stirred mixture of 4-aza-l-(2-chloropyridin-4-yl-)carbonyl-spiro[indoline-3 4'-piperidine]
(100 mg) and N N-diisopropyl-ethylamine (0.66 ml) in acetonitrile (13 ml) under an
atmosphere of nitrogen at room. The reaction was stirred at room temperature for 2 hrs
heated to reflux for 2 hrs and then stirred overnight at room temperature. The reaction was
diluted in diethylether washed with H2O then with brine and dried over sodium sulphate
and concentrated in vacuo. The crude product was purified by chromatography [Si02i ethyl
acetate-methanol-triethylamine (9:10:0.1)] to give 72 mg (76% over 3 steps) of 6-aza-l-(2-
chloropyridin^-yl^carbonyl-r-ftTans-S^^hlorophenylallyljspirofindoIine-S^'-piperidine];
MS (ES+) 479 (M+H+).
Compound Nos CCIII-6 and CCIII-7 were prepared by analogous methods to those of
Example 2.
EXAMPLE 3
This Example illustrates the preparation of compound III-210 6-chloro-4»aza-l-(2-
chloropyridin-4-yl-)carbonyl-r-[trans-3-(4-chlorophenylallyl]spiro [indoline-3 4*-
piperidine]
Step A:
Potassium hexamethyldisilazane (1.34 ml 0.5 M solution in toluene) was slowly added to a
solution of 5-Chloro-2 3-difluoro-pyridine (0.1 g) and N-Boc-4-Cyano-Piperidine (0.14 g) in
3 ml toluene at 0°C under nitrogen. The mixture was stirred at 0°C for lhr. After cooling
the reaction mixture was quenched in IN HC1. The aqueous phase was extracted twice with
ethyl acetate and the combined organic were washed with water dried over anhydrous
sodium sulfate and concentrated in vacuo. The crude product was purified by
chromatography [Si02i hexane-ethyl acetate-hexane (4:1)] to give 111 mg (49%) of 5-
chloro-4 -cyano-3-fluoro-3! 4 5 6 -tetrahydro-2fH-[2 4 ]bipyridinyl-1 '-carboxylic acid tert-
butyl ester; MS (ES+) 240 (M-Boc+ H^.
Step B:
A mixture of 5-chloro-4 -cyano-3-fluoro-3\4 5 6 -tetrahydro-2 H-[2 4 ]bipyridinyl-r-
carboxylic acid tert-butyl ester (0.05 g) and lithium tri-tert-butoxyaluminohydride (0.57 ml)

1M solution in THF) in 1-4-dioxane (0.75 ml) was refluxed under nitrogen for 4 hrs. After
cooling 1 N NaOH and H2O and ethyl acetate were added slowly to the mixture at 0°C. The
aqueous phase was extracted twice with ethyl acetate and the combined organic layers were
washed with saturated sodium bicarbonate^dried (sodium sulfate) filtered and concentrated
in vacuo. The crude product was purified by chromatography [S1O2; hexane-ethyl acetate-
triethylamine (75:25:1)] to give 18 mg g (38%) of 6-chloro-4-aza-spiro[indoline-3 4'-
piperidine]-F-carboxylic acid tert-butylester; MS (ES+) 324 (M+H+).
StepC:
A mixture of 2-chloro-isonicotinic acid (324 mg) thionyl chloride (0.43 ml) DMF (trace) in
toluene (6.4 ml) was heated to reflux for 2 hrs. After concentration in vacuo the residue was
dissolved in 2 ml dichloromethane and added dropwise at 0°C under nitrogen to a mixture of
6-chloro-4-aza-spiro[indoline-3 4*-piperidine]-r-carboxylic acid tert-butylester (220 mg)
triethylamine (0.6 ml) and dichloromethane ((20 ml). The mixture was stirred at room
temperature for 1 hr. The mixture was diluted in a saturated sodium carbonate solution. The
organic layer was separated and the aqueous phase was extracted twice with dichloromethane
and the combined organic layers were washed with saturated sodium bicarbonate dried
(magnesium sulfate) filtered and concentrated in vacuo 473 mg (102%) of 6-chloro-4-aza-l-
(2-chloropyridin-4-yl-)carbonyl-r-carboxylic acid tert-butylester spiro[indoline-3 4'-
piperidine];
MS (ES+) 407 (M - Me2C=CH2+H+).
Step D:
Trifluoroacetic acid (1.47 ml) was added to a stirred solution 6-chloro-4-aza-l-(2-
chloropyridin-4-yl-)carbonyl-l'-carboxylic acid tert-butylester spiro[indoline-3 4'-piperidine]
(0.47 g) in anhydrous dichloromethane (15 ml) under an atmosphere of nitrogen. The
reaction was left as such for 1 hr. The reaction was washed with saturated bicarbonate
solution and dried over sodium sulphate and concentrated in vacuo to yield 363 mg (98%) of
6-chloro-4-aza-l-(2-chloropyridin-4-yl-)carbonyl-spiro[indoline-3 4*-piperidine];MS(ES+)
363 (M+H+).
Step E:
A solution of 4-chlorocinnamyl chloride (165 mg) in acetonitrile (20 ml) was added slowly to
a stirred mixture of 6-chlo^o-4-aza-l-(2-chloropyridin-4-yl-)carbonyl-spiro[indoline-3 4 -
piperidine] (300 mg) and N N-diisopropyl-ethylamine (0.66 ml) in acetonitrile (40 ml) under
an atmosphere of nitrogen at room. The reaction was stirred at room temperature for 4 hrs

and heated to reflux overnight. The reaction was diluted in diethylether washed with H2O then with brine and dried over sodium sulphate and concentrated in vacuo. The crude product was purified by chromatography [S1O2; hexane-ethyl acetate-triethylamine (8:2:0.1)] to give-310 mg (73%) of 6-chloro-4-aza-l-(2-chloropyridin-4-yl-)carbonyl-r-[trans-3-(4- -— chlorophenylallylJspirofindoline-S^'-piperidine]; MS (ES+) 513 (M+H*). Compound Nos 1-26 1-29 1-30 1-210 1-213 1-214 1-233 1-237 11-26 11-29 11-30 11-210 11-213 11-214 ni-3 m-6 m-7 m-26 m-29 ffl-30 ffl-210 Hl-210N-oxide m-213 m -214 in-233 HI-236 m-237 m-302 IH -325 m -328 ffl -329 V-26 V-29 V-30 V-209 V-210 V-213 V-214 V-233 V-236 V-237 V-509 VHI-26 Vni-29 Vni-30 Vm-210 Vm-213 Vffl-214 XX-26 XX-29 XX-30 XX-210 XX-213 XX-214 XX-233 XX-236 XX-237 Cni-49 CHI-52 Cni-53 Cni-210 Cm-214 Cffl-555 CCC1-3 CCCm-26 CCCUI-29 CCCIH-30 CCCV-26 CCCV-29 and CCCV-30 were prepared by analogous methods to those of Example 3.
EXAMPLE 4
This Example illustrates the preparation of compound DCIH-3 4-(2-chloropyridin-4-
yI)carbonyl-r-[/ra/z5-3-(4-chlorophenyl)allyl]spiro[5 6-dihydro-4H-thieno[3 2-&]pyrrole-
6 4'-piperidine)]
Step A: Triphenylphosphine (2.29 g) was dissolved in tetrahydrofiiran (50 ml) and the
solution was cooled to -10°C under argon. Diisopropylazodicarboxylate (1.70 ml) was added
dropwise over 10 min and the resulting mixture was stirred at -10°C for 20 min (formation of
a white precipitate). 2 2 2-Trifluoro-N-(2-iodo-thiophen-3-yl)-acetamide (2.25 g) dissolved
in a minimum volume of tetrahydrofiiran was added followed by 4-Hydroxymethyl-3 6-
dihydro-2H-pyridine-l-carboxylic acid tert-butyl ester (J. Org. Chem. 2001 66 5545-5551
1.49 g) dissolved in a minimum volume of tetrahydrofiiran. The reaction mixture was
allowed to waim to room temperature and stirred for 12 hours. The solution was then
concentrated in vacuo and the residue subjected to silica gel chromatography
(cyclohexane:ethyl acetate 93:7) to afford 4-{[(2-Iodo-thiophen-3-yl)-(2 2 2-trifluoro-acetyl)-
amino]-methyl}-3 6-dihydro-2H-pyridine-l-carboxylic acid tert-butyl ester as a colourless oil
(2.27 g). *H NMR (400 MHz CDC13) 1.5 (s 9H) 2.15 (m 2H) 3.43 (m IH) 3.52 (m IH)
3.75 (d J = 19 Hz IH) 3.77 (m 2H) 4.76 (d J = 17 Hz IH) 5.41 (s IH) 6.68 (br d J =

5.5 Hz 1H) 7.42 (d J = 5.5 Hz 1H); MS (ES+) 417 (M+H+-C02-isobutene) 458 (M+H+-isobutene).
Step B: In a dried argon purged flask -{[(2-Iodo-thiophen-3-yl)-(2 2 2-trifluoro-acetyl)-amino]-meUiyl}-356-dihydro-2H-pyridine-l-xacboxylic acid tert-butyl ester obtained in Step A (1.57 g) was dissolved in dimethylacetamide (25 ml); triethylamine (1.05 ml) tetrabutylammonium bromide (1.08 g) and palladium(II) acetate (103 mg) were successively added and the solution was heated at 80°C for 4 hours. Palladium(II) acetate (20 mg) was added again and the mixture stirred at 80°C for 3 more hours. After cooling to room temperature the reaction mixture was diluted with ethyl acetate washed with brine dried over sodium sulphate and concentrated in vacuo. Silica gel chromatography of the residue (cyclohexane:ethyl acetate 8:2) afforded 4-trifluoroacetyl-spiro[5 6-dihydro-4H-thieno[3 2-&]pyirole-6 4Xl\2S3\4^tetrahydropyridine)]-r carboxylic acid tert-butyl ester (0.9 g). ]H NMR (40 MHz CDC13) 2 rotamers 1.54 (s 9H) 2.05 (m 2H) 3.65-3.80 (m 2H) 4.20-4.30 (m 2H) 4.70 and 4.80 (m 1H) 6.82 and 6.96 (m 1H) 7.23 (d J = 5.5 Hz 1H) 7.42 (d J = 5.5 Hz 1H); MS (ES+) 288 (M+H+-isobutene).
Step C: 4-trifluoroacetyl-spiro[5 6-d^ tetrahydropyridine)]-l' carboxylic acid tert-butyl ester obtained in Step B (0.9 g) was dissolved in methanol (30 ml) and water (5 ml) placed under argon and potassium carbonate (28 g) was added. The reaction mixture was stirred for 10 min at room temperature the mixture was filtered and the filtrate concentrated in vacuo. The residue was diluted with ethyl acetate washed with brine dried (sodium sulphate) and concentrated in vacuo. The residue was immediately dissolved in dichloromethane (40 ml) and acylated with 2-chloroisonicotinoyl chloride (800 mg) in the presence of triethylamine (1 ml) at 0°C for 1 hour. Standard aqueous work-up and silica gel chromatography (cyclohexane:ethyl acetate 8:2) afforded 4-(2-chloropyridin-4-yI)carbonyl-spiro[5 6-dihydro-4H-thieno[3 2-6]pyrrole-6 4X1 \2\3\4Metrahydropyridine)]-l' carboxylic acid tert-butyl ester (0.83 g). M.p. 63-65°C; MS (ES+) 332/334 (M+H^COa-isobutene) 376/378 (M+H+-isobutene) 432/434 (M+H*).
StepD:4-(2-chloropyridin-4-yl)carbonyl-spiro[5 6-dihydro-4H-thieno[3 2-t]pyrrole-6 4 -(r 2' 3 4 -tetrahydropyridine)]-r carboxylic acid tert-butyl ester obtained in Step C (216 mg) was dissolved in dichloromethane (15 ml) and treated successively with

triethylsilane (0.4 ml) and trifluoroacetic acid (0.75 ml); the solution was stirred under argon for 6 hours diluted with dichloromethane neutralised with aqueous sodium bicarbonate dried (sodium sulphate) and concentrated in vacuo. The residue was dissolved in acetonitrile (15 ml) and treated with diisopropylethylamine (0.14 ml) and 4-chlorocinnamy! chloride (96 mg) for 24 hours at room temperature. Standard aqueous work-up afforded a residue which was purified by flash chromatography (silica gel cyclohexane:ethyl acetate 8:2+ 0.5 % triethylamine) to give the title product (J 70 mg) as a colourless solid. M.p. 81-82°C; ]H NMR (600 MHz CDC13) 2 rotamers: 1.81-1.94 (m 4H) 2.60-2.71 (m 4H) 3.21 and 3.23 (d J = 7 Hz 2H) 4.03 and 4.35 (s 2H) 5.63 and 7.55 (d J = 5.9 Hz 1H) 6.26 and 6.29 (dt J = 12.9 Hz 7 Hz 1H) 6.51 and 6.53 (d J = 12.9 Hz 1H) 6.96 and 7.23 (d J = 5.9 Hz 1H) 7.26-7.49 (m 6H) 8.53 and 8.54 (d J = 5.9 Hz 1H); 13C NMR (125 MHz CDC12CDC12 80°C) selected data 37.3 51.0 61.1 67.1 and 77.2 114.4and 117.5 120.3 122.3 127.1 127.5 127.9 128.8 132.0 150.6; MS (ES+) 484/486/487/489 (M+H+). Compound Nos DCIII-3 DCII1-6 DCIII-7 DCHI-52 DCm-53 and DCV-53. were prepared by analogous methods to those of Example 4.
EXAMPLE 5
This Example illustrates the preparation of compound CIII-210 4-chloro-5-aza-l-(2-chloropyridin-4-yI)carbonyl-r-[/raws-^
Step A: 2-Chloro-4-amino-pyridine was brominated according to the method described in Synthesis 2001 14> 2175-2179: a solution of 4-chloro-4-amino-pyridine (12.3 g) in acetonitrile (500 ml) was treated with N-bromosuccinimide (17.8 g) and the resulting solution was stirred at room temperature for 24 hours. The solution was then concentrated in vacuo and the residue subjected to silica gel chromatography (cyclohexane:ethyl acetate 8:2) to afford 3-bromo-2-chloro-4-aminopyridine (12.2 g m.p. 146°C (hexane/ether)) and 5-bromo-2-chIoro-4-aminopyridine (2.9 g m. p. 117-119°C).
Step B: Lithium bis(trimethylsilyl)amide (1M solution in THF 5.1 ml) was added dropwise to a stirred solution of 3-bromo-2-chloro-4-aminopyridine (1.04 g) in tetrahydrofuran (15 ml) at -78°C under N2. The resulting solution was then stirred at room temperature for 30 min. warmed to 0°C then cooled again at -78°C. 4-Chloromethyl-3 6- . dihydro-2H-pyridine-l-carboxy!ic acid tert-butyl ester (1.16 g prepared according to WO 98/25605) dissolved in a minimum volume of THF was added dropwise then the solution

was refluxed for 14 hours. The reaction mixture was cooled to room temperature poured into diluted aqueous ammonium chloride extracted with EtOAc. The organic layer was washed with brine dried over sodium sulfate and concentrated in vacuo. The residue was purified by silica gel chromatography (CH2CI2 then CH2Cl2/EtOAc 8:2 cyclohexane:ethyl acetate 8:2) to afford 4-[(3-bromo-2-chloro-pyridin-4-ylamino)-methyl]-3 6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester (1.42 g) which was identified by its mass and 1H NMR spectra. MS (ES+) 346/348/350 (MH+-isoprene) 402/404/406 (MH+). .
Step C: Lithium bis(trimethylsilyl)amide (1M solution in THF 3 ml) was added dropwise to a stirred solution of 4-[(3-Bromo-2-chloro-pyridin-4-ylamino)-methyl]-3 6-dihydro-2H-pyridine-l-carboxylic acid tert-butyl ester (0.53 g) in tetrahydrofuran (20ml) at -78°C under N2. The yellow solution was warmed to 0°C and then 2-chloroisonicotinoyl chloride (50% solution in toluene 0.95 g) was added. The solution was stirred at 0°C for 10
*
min. quenched by addition of aqueous ammonium chloride extracted with EtOAc dried (Na2S04) and concentrated in vacuo. The residue was purified by silica gel chromatography (CH2C12 then CH2Cl2/EtOAc 8:2 cyclohexane:ethyl acetate 8:2) to afford 4-{[(3-bromo-2-chloro-pyridin-4-yl)-(2-chloro-pyridine-4-carbonyl)-amino]-methyl}-3 6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester (0.63 g) which was identified by its mass and 1H NMR spectra. MS (ES+) 443/445 (MH+-BOC) 484/486 (MH+-isoprene).
Step D: In a dried argon purged flask 4-{[(3-bromo-2-chloro-pyridin-4-yl)-(2-chloro-pyridine-4-carbonyl)-amino]-methyl}-3 6-dihydro-2H-pyridine-l-carboxylic acid tert-butyl ester obtained in Step C (0.63 g) was dissolved in dimethylacetamide (10 ml); triethylamine (0.41 ml) tetrabutylammonium bromide (0.40 g) and palladium(II) acetate (40 mg) were successively added and the solution was heated at 90°C for 18 hours. After cooling to room temperature the reaction mixture was diluted with diethyl ether washed with brine dried over sodium sulphate and concentrated in vacuo. Silica gel chromatography of the residue (cyclohexane:ethyl acetate 8:2) afforded l-(2-chloro-pyridine-4-carbonyl)-spiro[[(4-chloro-2 3-dihydro-lH-pym>lo[3 2^
carboxylic acid tert-butyl ester (0.21 g) which was identified by its mass and 1H NMR spectra. MS (ES+) 461/463 (MH+).
Step E: l-(2»chloro-pyridine-4-carbonyl)-spiro[[(4-chloro-2 3-dihydro-lH-pyrrolo[3 2-c]pyridine)-3 4 -(r 2%3\4 -tetrahydropyridine)]-r carboxylic acid tert-butyl ester obtained in Step D (0.19 g) was dissolved in dichloromethane (13 ml) and treated

successively with triethylsilane (0.33 ml) and trifluoroacetic acid (0.63 ml); the solution was stirred under argon for 8 hours diluted with dichloromethane neutralised with aqueous sodium bicarbonate dried (sodium sulphate) and concentrated in vacuo. The residue was dissolved in acetonitrile (13 ml) and treated with diisopropylethylamine (0.12 ml) and 4-chlorocinnamyl chloride (84 mg) for 48 hours at room temperature. Standard aqueous workup afforded a residue which was purified by flash chromatography (silica gel cyclohexanerethyl acetate 8:2+ 0.5 % triethylamine) to give the title product (43 mg) as a colourless solid. M.p. 95-96°C; MS (ES+) 513/515 (M+H+).
Compound Nos CDIIM9 CDIH-52 CDHI-53 CDV-49 CDV-52 DIH-3 DIII-210 DV-3 DV-213 and DV-214 were prepared by analogous methods to those of Example 5.
EXAMPLE 6
This Example illustrates the pesticidal/insecticidal properties of compounds of formula (I).
Test against were performed as follows:
Spodoptera littoralis (Egyptian cotton leafworm)
Cotton leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test
solutions at an application rate of 200 ppm. After drying the leaf discs were infested with 5
Li larvae. The samples were checked for mortality repellent effect feeding behaviour and
growth regulation 3 days after treatment (DAT). The following compounds gave at least 80%
control of Spodoptera littoralis:
1-26 1-30 1-237 H-26 11-29 11-30 11-210 11-213 11-214 IC1-3 IU-6 III-7 IH-26 IH-29 III-30 ID -210 IE -210 N-oxide IH-233 ffl-236 HI-237 111-302 m -325 III -328 in-329 V-26 V-29 V-30 V-209 V-210 V-213 V-214 V-233 V-236 V-237 V-509 VIII-26 Vm-29 Vm-30 Vffl-210 Vm-213 XX-26 XX-29 XX-30 XX-210 XX-214 XX-233 XX-236 XX-237 Cm-210 CIII-214 CCCDI-3 CCCIII-26 CCCV-3 CCCV-26 CCCVI-3 CDIH-49 CDIII-52 CDHI-53 CDV-49 CDV-52 and DV-3.
Heliothis virescens ( Tobacco budworm):
Eggs (0-24 h old) were placed in 24-well microtiter plate on artificial diet and treated with
test solutions at an application rate of 200 ppm by pipetting. After an incubation period of 4
days samples were checked for egg mortality larval mortality and growth regulation. The
following compounds gave at least 80% control of Heliothis virescens:
1-26 1-29 1-30 1-210 1-213 1-214 1-233 1-237 11-26 11-29 11-30 11-210 11-213 11-214 EI-3 HI-6 IH-7 m-26 m-29 m-30 IE -210 in -210 N-oxide IH -213 in -214 UI-233 III-236 IH-237 10-302 ffl -325 III -328 m -329 V-26 V-29 V-30 V-209

V-210 V-213 V-214 V-233 V-236 V-237 V-509 VIU-26 VIE-29 VIII-30 VIII-210 Vffl-213 Vffl-214 XX-26 XX-29 XX-30 XX-210 XX-213 XX-214 XX-233 XX-236 XX-237 CUI-49 CIII-52 CHI-53 CIII-210 CHI-214 CHI-555 CCIH-3 CCIII-6 CCII1-7 CCC1-3 CCCHI-3 CCCUI-26 CCCm-29 CCCm-30 CCCV-3 CCCV-26 CCCV-29 CCCV-30 CCCVI-3 CDIII-49 CDIU-52 CDIH-53 CDV-49 CDV-52 DI1I-3 Din-210 DV-3 DCIU-3 DCm-7 DCm-52 andt>CV-53.
Plutella xylostella (Diamond back moth):
24-well microtiter plate (MTP) with artificial diet was treated with test solutions at an application rate of 18.2 ppm by pipetting. After drying the MTP's were infested with larvae (L2)(10-15 per well). After an incubation period of 5 days samples were checked for larval mortality antifeedant and growth regulation. The following compounds gave at least 80% control of Plutella xylostella:
n-26 n-29 n-30 .n-210 n-214 ni-3 m-6 in-7 m-26 m-29 m-30 m -210 m -210 N-
oxide ffl -213 HI -214 ffl-233 ffl-236 10-237 111-302 HI -325 m -328 m -329 V-26 V-29 V-30 V-209 V-210 V-213 V-214 V-233 V-236 V-237 V-509 VHI-26 Vm-29 Vm-30 VIH-210 Vm-213 Vin-214 XX-26 XX-29 XX-30 XX-210 XX-213 XX-214 XX-233 XX-236 XX-237 CIII-49 CIII-52 CIH-53 CHI-210 Cffl-214 Cni-555 CCffl-3 CCCin-3 CCCin-26 CCCm-29 CCCV-3 CCCV-26 CCCV-29 CCCV-30 CCCVI-3 CDHI-49 CDIU-52 CDffl-53 CDV-52 DV-3 DV-213 DV-214 DCIQ-53 and DCV-53.
Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions at an application rate of 200 ppm. After drying the leaf discs were infested with an aphid population of mixed ages. After an incubation period of 6 DAT samples were checked for mortality. The following compounds gave at least 80% control of Myzus persicae: HI-3 m-7 V-213 Vm-29 CCCm-3 CCCV-3 and DCHI-3.
Aedes aegypti (Yellow fever mosquito):
10-15 Aedes larvae (L2) together with a nutrition mixture are placed in 96-well microtiter
plates. Test solutions at an application rate of 2ppm are pipetted into the wells. 2 days later
insects were checked for mortality and growth inhibition. The following compounds gave at
least 80% control of Aedes aegypti
1-26 1-210 1-213 1-214 1-233 1-236 1-237 11-26 11-29 11-30 11-210 0-213 11-214 HI-3
ni-6 ni-7 m-26 m-29 m-30 m -210 m -210 N-oxide m -213 in -214 m-233 m-236 ni-237 in-302 m -325 m-328 m-329 v-26 v-29 v-30 v-210 v-213
V-214 V-236 V-237 V-509 VHI-26 VEI-29 VIII-30 VHI-210 VHI-213 VHI-214

KX-26 XX-29 XX-30 XX-210 XX-213 XX-214 XX-233 XX-236 XX-237 CIU-52/
:rn-53 cm-21 o cni-214 ccm-3 ccm-6 cciu-7 ccC1-3 cccm-3 cccm-26
XCV-3 CCCHI-26 CCCVI-3 CDIII-49 CDII1-52 CDIII-53 CDV-49 CDV-52 DCm-3 DCIII-6 DCffl-52 DCIII-53 and DCV-53.
Diabrotica balteaia (Corn root worm ):
A 24-well microtiter plate (MTP) with artificial diet was treated with test solutions at an
application rate of 200 ppm (concentration in well 18 ppm) by pipetting. After drying the
MTP's were infested with larvae (L2) (6-10 per well). After an incubation period of 5 days
samples were checked for larval mortality and growth regulation.
The following compounds gave at least 80% control of Diabrotica balteaia :
11-29 11-30 m-29 111-30 HI-213 ffl-236 ffl-237 V-26 V-29 V-30 V-210 V-213 V-214 V-236 V-237 VII1-29 Vffl-30 XX-30 XX-237 CIH-52 CIH-210 CHJ-214 CCCUI-29 CCCm-30 CCCV-3 CCCV-26 CCCV-29 CCCV-30 CD1H-49 CDffl-52 CDIH-53 CDV-49 CDV-52 DV-3 DV-210 DV-213 DCIfI-6 DCIH-7 and DCV-53.

CLAIMS 1
A method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula I.

wherein Y is a single bond, C=0, C=S or S(0)m where m is 0, 1 or 2; R1 is hydrogen, optionally substituted alkyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl. aminocarbonyl. optionally substituted alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted heterocyclyloxy, cyano, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, formyl, optionally substituted heterocyclyl, optionally substituted alkylthio, NO or NRI3RU where R13 and R14 are independently hydrogen, COR15, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl or R13 and R14 together with the N atom to which they are attached form a group -N=C(R,6)-NR17R18; R15 is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy optionally substituted heteroaryl, optionally substituted heteroaryloxy or NR19R20; R16, R17 and R18 are each independently H or lower alkyl;

R19 and R20 are independently optionally substituted alkyl, optionally substituted aryl
or optionally substituted heteroaryl;
R2 and R3 are independently hydrogen, halogen, cyano, optionally substituted alkyl,
optionally substituted alkoxy or optionally-substituted aryl;
the ring

is a 5 or 6 membered heteroaromatic ring;
each R4 is independently halogen, nitro, cyano, optionally substituted Ci_8 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl, optionally substituted alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl, optionally substituted C3.7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted alkylthio or R2IR22N where R21 and R22 are, independently, hydrogen, Ci-g alkyl, C3.7 cycloalkyl, C3-6 alkenyl, C3.6 alkynyl, C3.7 cycloalkyl(Ci. 4)alkyl, C2-6 haloalkyl, Ci-6 alkoxyalkylt Cue alkoxycarbonyl or R21 and R22 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two C1.6 alkyl groups, or 2 adjacent groups R4 together with the carbon atoms to which they are attached form a 4, 5, 6,or 7 membered carbocyclic or heterocyclic ring which may be optionally substituted by halogen; n is 0,1, 2 or 3;
each Ra is independently hydrogen, halogen, hydroxy, cyano, optionally substituted C1-8 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl, optionally substituted alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl, optionally substituted C3.7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted

alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted alkylthio, optionally substituted arylthio or R23R24N where R23 and R are, independently, hydrogen, Ci-g alkyl, C3.7 cycloalkyl, C3.6 alkenyl, C3-6 alkynyl^JC^? cycloalkyl(CM)alkyl, C2-6 haloalkyl, alkoxy(Ci_6)alkyl, Cue alkoxycarbonyl or R23 and R24 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two C1-6 alkyl groups, or two Ra groups attached to the same carbon atom are =0 or two Ra groups attached to adjacent carbon atoms form a bond, or two Ra groups together with the carbon atom to which they are attached form a three- to seven-membered ring, that may be saturated or unsaturated, and that may contain one or two hetero atoms selected from the group consisting of N, O and S, and which may be optionally substituted by one or two C\-& alkyl groups; or two Ra groups together form a group -CH2-, -CH=CH- or -CH2CH2;
p is 0,1, 2, 3,4, 5 or 6; q is 0,1,2, 3,4, 5 or 6 provided that p+q is 1,2, 3,4, 5 or 6; R8 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl or optionally substituted alkenylcarbonyl; or salts or N-oxides thereof.
A method according to claim 1 wherein the ring

is a 5 or 6 membered heteroaromatic ring wherein the ring members are each independently CH, S, N, NR4,0, or CR4 provided that at least one ring member is other than CH or CR4 and that there are no more than one O or S atoms present in the
ring.

A method according to claim 1 or claim 2 wherein Y is a single bond or C=0.
A method according to any preceeding claim wherein R and R are each independently-hydrogen, Ci_6 alkyl, Ci_6 haloalkyl, Ci-6 alkoxy or cyano.
A method according to any preceeding claim wherein Rl is hydrogen, Q-6 alkyl, Cue cyanoalkyl,C1-4 haloalkyl, C3-7 cycloalkyl(Ci-4)alkyl,C1-4 alkoxy(Ci.6)alkyl, heteroaryl(Cj-6)alkyl (wherein the heteroaryl group maybe optionally substituted by halo, nitro, cyano,C1-4 alkyl,C1-4 haloalkyl, C1-6 alkoxy,C1-4 haloalkoxy,C1-4 alkylsulfonyl,C1-4 alkylsulfinyl,C1-4 alkylthio,C1-4 alkoxycarbonyl,C1-4 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), aryl(Ci^)alkyl (wherein the aryl group may be optionally substituted by halo, nitro, cyano,C1-4 alkyl,C1-4 haloalkyl,C1-4 alkoxy, Ci. 6 haloalkoxy,C1-4 alkylsulfonyl, C1.6 alkylsulfinyl, C1.6 alkylthio,C1-4 alkoxycarbonyl,C1-4 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the aryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen),C1-4 alkylcarbonylamino(Ci-6)alkyl, aryl (which maybe optionally substituted by halo, nitro, cyano,C1-4 alkyl,C1-4 haloalkyl, Ci-6 alkoxy,C1-4 haloalkoxy,C1-4 alkylsulfonyl,C1-4 alkylsulfinyl, Ci-6 alkylthio,C1-4 alkoxycarbonyl,C1-4 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the aryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), heteroaryl (which may be optionally substituted by halo, nitro, cyano,C1-4 alkyl,C1-4 haloalkyl, Ci-e alkoxy,C1-4 haloalkoxy,C1-4 alkylsulfonyl,C1-4 alkylsulfinyl,C1-4 alkylthio,C1-4 alkoxycarbonyl,C1-4 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5,6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen),C1-4 alkoxy,C1-4 haloalkoxy, phenoxy (wherein the phenyl group is optionally substituted by halogen,C1-4 alkyl,C1-4 alkoxy,C1-4 haloalkyl,C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryloxy (optionally substituted by halo, nitro, cyano,C1-4 alkyl, Ci-6 haloalkyl,

CM alkoxy or Ci-6 haloalkoxy), heterocyclyloxy (optionally substituted by halo, Ci-6 alkyl, C]_6 haloalkyl,C1-4 alkoxy orC1-4 haloalkoxy), cyano, C2-6 alkenyl, C2-e alkynyl, C3-6 cycloalkyl, C5.7 cycloalkenyl, heterocyclyl (optionally substituted by halo, nitro, cyano,C1-4 alkyl,C1-4 haloalkyl,C1-4 alkoxy or Ci_6 haloalkoxy),C1-4 alkylthio, C].6 haloalkylthio or NR!3R14 where R13 and R14 are independently hydrogen, Ci-6 alkyl,C1-4 haloalkyl,C1-4 alkoxy(Ci^)alkyl, phenyl (which may be optionally substituted by halogen,C1-4 alkyl,C1-4 alkoxy,C1-4 haloalkyl,C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino, dialkylamino orC1-4 alkoxycarbonyl), phenyl (Ci.6)alkyl (wherein the phenyl group may be optionally substituted by halogen,C1-4 alkyl,C1-4 alkoxy,C1-4 haloalkyl,C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino, dialkylamino, Ci-6 alkylsulfonyl,C1-4 alkoxycarbonyl, or two adjacent positions on the phenyl ring may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with'halogen), heteroaryl (Ci-6)alkyl (wherein the heteroaryl group may be optionally substituted by halo, nitro, cyano,C1-4 alkyl, Ci-6 haloalkyl,C1-4 alkoxy,C1-4 haloalkoxy, d-6 alkylsulfonyl,C1-4 alkylsulfinyl,C1-4 alkylthio,C1-4 alkoxycarbonyl,C1-4 alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5,6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen) or heteroaryl (which may be optionally substituted by halo, nitro, cyano,C1-4 alkyl,C1-4 haloalkyl,C1-4 alkoxy orC1-4 haloalkoxy,C1-4 alkoxycarbonyl Cue alkylcarbonylamino, phenyloxycarbonylamino (wherein the phenyl group is optionally substituted by halogen, C\^ alkyl,C1-4 alkoxy,C1-4 haloalkyl,C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), amino, Ci-6 alkylamino or phenylamino (wherein the phenyl group is optionally substituted halogen,C1-4 alkyl,C1-4 alkoxy,C1-4 haloalkyl,C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino)).
A method according to any preceeding claim wherein each R4 is independently halogen, cyano,C1-4 alkyl,C1-4 haloalkyl,C1-4 cyanoalkyl,C1-4 alkoxy(Ci-6)aIkyl, C3-7 cycloalkyl(Ci-6)alkyl, C5-6 cycloalkenyl(Ci-6)alkyl, C3-6 aIkenyloxy(Ci-6)alkyl, C3-6 alkynyloxy(Ci-6)alkyl, aryloxy(CM)alkyl,C1-4 carboxyalkyl, C).6 alkylcarbonyl(Ci-6)alkyl, C2-6 alkenylcarbonyl(CM)alkyl, C2-6 alkynylcarbonyl(CM)-alkyl,C1-4

alkoxycarbonyl(Ci-6)alkyl, Cj.6 alkenyloxycarbonyl(Ci-6)alkyl, C3-6 alkynyloxycarbonyl(Ci-6)alkyI, aryloxycarbonyl(Ci-6)alkyl, C1-6 alkyl thio(CM)alkyl,C1-4 alkylsulfinyl(Ci-6)alkyl,C1-4 alkylsulfonyl(CM)alkyl, aminocarbonyl(C]^)alkyl, ^i.6alkylaminocarbonyl(Gr-6)alkyl, di(Ci-6)alkylaminocarbonyl(Ci_6)alkyl, phenyl(C]-4)alkyl (wherein the phenyl group is optionally substituted by halogen,C1-4 alkyl,C1-4 alkoxy,C1-4 haloalkyl,C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl(CM)aIkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano,C1-4 alkyl,C1-4 haloalkyl,C1-4 alkoxy orC1-4 haloalkoxy), heterocyclyl(Ci^)alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C1-6 alkyl,C1-4 haloalkyl,C1-4 alkoxy or C1-6 haloalkoxy), C2-6 alkenyl, aminocarbonyl(C2-6)aIkenyl, Ci_6alkylaminocarbonyl(C2. 6)alkenyl, di(Ci.6)aIkylaminocairbonyl(C2-6)alkenyl, phenyl(C2-4)-alkenyl, (wherein the phenyl group is optionally substituted by halogen,C1-4 alkyl,C1-4 alkoxy,C1-4 haloalkyl,C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), C2-6 alkynyl, trimethylsilyl(C2-6)a!kynyl, aminocarbonyl(C2-6)alkynyl, C1-6 alkylaminocarbonyl(C2-6)alkynyl, di(Cj-6)alkylaminocarbonyl(C2-6)alkynyl, C1-6 alkoxycarbonyl, C3-7 cycloalkyl, C3.7 halocycloalkyl, C3.7 cyanocycloalkyl, C1.3 alkyl(C3-7)-cycloalkyl, C1-3 alkyl(C3-7)halocycloalkyl,phenyl (optionally substituted by halogen,C1-4 alkyl,C1-4 alkoxy,C1-4 haloalkyl,C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halo, nitro, cyano,C1-4 alkyl,C1-4 haloalkyl,C1-4 alkoxy orC1-4 haloalkoxy), heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano,C1-4 alkyl, C1-6 haloalkyl,C1-4 alkoxy orC1-4 haloalkoxy), or 2 adjacent groups R4 together with the carbon atoms to which they are attached form a 4, 5,6 or 7 membered carbocylic or heterocyclic ring which may be optionally substituted by halogen, Ci-g alkoxy,C1-4 haloalkoxy, phenoxy (optionally substituted by halo, nitro, cyano,C1-4 alkyl,C1-4 haloalkyl,C1-4 alkoxy orC1-4 haloalkoxy), heteroaryloxy (optionally substituted by halo, nitro, cyano,C1-4 alkyl,C1-4 haloalkyl,C1-4 alkoxy orC1-4 haloalkoxy),C1-4 alkylthio or R19R20N where R19 and R20 are, independently, hydrogen, Q.g alkyl, C3.7 cycloalkyl, C3-6 alkenyl, C3-6 alkynyl, C2-6 haloalkyl,C1-4 alkoxycarbonyl or R19 and R20 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two

further heteroatoms selected from O, N or S and which may be optionally substituted by one or two Cj-6 alkyl groups; and n is 0, 1, 2 or 3.
A method according to any preceeding claim wherein R8 isC1-4o alkyl,C1-4O haloalkyl, aryl(Ci-6)alkyl (wherein the aryl group is optionally substituted by halogen,C1-4 alkyl,C1-4 alkoxy,C1-4 haloalkyl,C1-4 haloalkoxy, CN, NO2, aryl, heteroaxyl, amino or dialkylamino), heteroaryl(Ci-6)alkyl (wherein the heteroaryl group is optionally substituted by halogen,C1-4 alkyl,C1-4 alkoxy,C1-4 haloalkyl,C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), arylcarbonyKCj. 6)alkyl (wherein the aryl group may be optionally substituted by halogen,C1-4 alkyl,C1-4 alkoxy,C1-4 haloalkyl,C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino and the alkyl group may be optionally substituted by aryl), C2-8 alkenyl, C2.8 haloalkenyl, aryl(C2-6)-alkenyl (wherein the aryl group is optionally substituted halogen,C1-4 alkyl,C1-4 alkoxy,C1-4 haloalkyl,C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino,C1-4 alkoxycarbonyl, or two adjacent substituents can cyclise to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring), heteroaryl(C2-6)-alkenyi (wherein the heteroaryl group is optionally substituted halogen,C1-4 alkyl,C1-4 alkoxy,C1-4 haloalkyl,C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino,C1-4 alkoxycarbonyl, or two adjacent substituents can cyclise to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring), C2-6 alkynyl, phenyl(C2-$)alkynyl (wherein the phenyl group is optionally substituted by halogen,C1-4 alkyl, C\^ alkoxy,C1-4 haloalkyl,C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), C3.7 cycloalkyl,C1-4 alkoxycarbonyl,C1-4 alkylcarbonyl,C1-4 haloalkylcarbonyl or aryl(C2^)alkenylcarbonyl (wherein the aryl group may be optionally substituted halogen, C\^ alkyl,C1-4 alkoxy,C1-4 haloalkyl,C1-4 haloalkoxy, CN, NO2, aryl, heteroaryl, amino or dialkylamino), or -C(R5,)(R52)-[CR53=CR ^jz-R55 where z is 1 or 2, R51 and R52 are each independently H, halo orC1-4 alkyl, R53 and R54 are each independently H, halogen,C1-4 alkyl or C\^ haloalkyl and R55 is optionally substituted aryl or optionally substituted heteroaryl.
A method according to any preceeding claim wherein each Ra is hydrogen.

9. A method according to any preceeding claim wherein p is 1 or 2 and q is 2 or 3.
10. A compound of formula V

wherein Y is C=0, C=S;
R1 is hydrogen, optionally substituted alkyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl, aminocarbonyl, optionally substituted alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heleroaryloxy, optionally substituted heterocyclyloxy, cyano, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, formyl, optionally substituted heterocyclyl, optionally'substituted alkylthio, NO or NRt3Ru where R13 and Ru are independently hydrogen, COR15, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl or R13 and R14 together with the N atom to which they are attached fomt a group-N=C0(Rl6)-NR17; R18; R15 is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy optionally substituted heteroaryl, optionally substituted heteroaryloxyorNR19, R20; Rl6,R17 andR18 are each independently H or lower alkyl; R19 and R20 are independently optionally substituted alkyl, optionally substituted aryl or optionally substituted heteroaryl;
R2 and R3 are independently hydrogen, halogen, cyano, optionally substituted alkyl, optionally substituted alkoxy or optionally substituted aryl;

the ring

is a 5 or 6 membered heteroaromatic ring;
each R4 is independently halogen, nitro, cyano, optionally substituted Ci-8 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl, optionally substituted alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl, optionally substituted €3-7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted alkylthio or R2)R22N where R21 and R22 are, independently, hydrogen, C1-8 alkyl, C3.7 cycloalkyl, C3-6 alkenyl, C3-6 alkynyl, C3.7 cycloalkyl(Ci-4)alkyl, C2-6 haloalkyl, C1-6 alkoxy(Ci^)alkyl, C1-6 alkoxycarbonyl or R21 and R22 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two C1-6 alkyl groups, or 2 adjacent groups R4 together with the carbon atoms to which they are attached form a 4, 5, 6,or 7 membered carbocyclic or heterocyclic ring which may be optionally substituted by halogen; n is 0,1,2 or 3;
each Ra is independently hydrogen, halogen, hydroxy, cyano, optionally substituted C1-8 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl, optionally substituted alkylaminocarbonyl, optionally substituted dialkylamirtocarbonyl, optionally substituted C3.7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted alkylthio, optionally substituted arylthio or R R N where R and R24 are, independently, hydrogen, Ci-g alkyl, C3.7 cycloalkyl, C3.6 alkenyl, C3-6 alkynyl, C3-7 cycloalkyl(Ci-4)alkyl, C2-6 haloalkyl, C1-6 alkoxy(Ci-6)alkyl, Q-6

alkoxycarbonyl or R23 and R24 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two Ci-e alky] groups, or two Ra groups attached to the same carbon atom are =0 or two Ra groups attached to adjacent carbon atoms form a bond, or two Ra groups together with the carbon atom to which they are attached form a three- to seven-membered ring, that may be saturated or unsaturated, and that may contain one or two hetero atoms selected from the group consisting of N, O and S, and which may be optionally substituted by one or two C1-6 alkyl groups; or two Ra groups together form a group -CH2-, -CH=CH- or -CH2CH2;
pis 0, 1,2, 3,4, 5 or 6; q is 0, 1, 2, 3,4, 5 or 6 provided that p+q is 1,2, 3,4,5 or 6; R8 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl or optionally substituted alkenylcarbonyl; or salts or N-oxides thereof.
11. A compound of formula II

wherein R8 is H or tert-butoxycarbonyl and n, p, q, R1 , R2, R3, R4 and Ra are as
*
defined in claim 10.
12. An insecticidal acaricidal and nematicidal composition comprising an insecticidally,
acaricidally or nematicidally effective amount of a compound of formula I as defined


Documents:

2073-chenp-2006 form-3 02-06-2011.pdf

2073-CHENP-2006 AMENDED PAGES OF SPECIFICATION 30-05-2011.pdf

2073-CHENP-2006 AMENDED CLAIMS 30-05-2011.pdf

2073-CHENP-2006 AMENDED CLAIMS 13-03-2013.pdf

2073-CHENP-2006 AMENDED PAGES OF SPECIFICATION 13-03-2013.pdf

2073-chenp-2006 correspondence others 02-06-2011.pdf

2073-CHENP-2006 CORRESPONDENCE OTHERS 05-03-2013.pdf

2073-CHENP-2006 CORRESPONDENCE OTHERS 22-02-2013.pdf

2073-CHENP-2006 CORRESPONDENCE OTHERS 13-03-2013.pdf

2073-CHENP-2006 FORM-1 13-03-2013.pdf

2073-chenp-2006 form-3 30-05-2011.pdf

2073-CHENP-2006 OTHER PATENT DOCUMENT 30-05-2011.pdf

2073-CHENP-2006 POWER OF ATTORNEY 30-05-2011.pdf

2073-chenp-2006 amended claims 16-08-2011.pdf

2073-chenp-2006 amended pages of specification 16-08-2011.pdf

2073-CHENP-2006 CORRESPONDENCE OTHERS 08-10-2010.pdf

2073-CHENP-2006 CORRESPONDENCE OTHERS 16-08-2011.pdf

2073-CHENP-2006 EXAMINATION REPORT REPLY RECEIVED 30-05-2011.pdf

2073-chenp-2006-abstract.pdf

2073-chenp-2006-claims.pdf

2073-chenp-2006-correspondnece-others.pdf

2073-chenp-2006-description(complete).pdf

2073-chenp-2006-form 1.pdf

2073-chenp-2006-form 26.pdf

2073-chenp-2006-form 3.pdf

2073-chenp-2006-form 5.pdf

2073-chenp-2006-pct.pdf


Patent Number 255988
Indian Patent Application Number 2073/CHENP/2006
PG Journal Number 16/2013
Publication Date 19-Apr-2013
Grant Date 15-Apr-2013
Date of Filing 12-Jun-2006
Name of Patentee SYNGENTA PARTICIPATIONS AG
Applicant Address Schwarzwaldallee 215, CH-4058 Basel
Inventors:
# Inventor's Name Inventor's Address
1 MOLLEYRES, Louis-Pierre Syngenta Crop Protection AG, Werk Rosental, Schwarzwaldallee 215, CH-4058 Basel
2 CASSAYRE, Jerome Syngenta Crop Protection AG, Werk Rosental, Schwarzwaldallee 215, CH-4058 Basel
3 CEDERBAUM, Fredrik Syngenta Crop Protection AG, Werk Rosental, Schwarzwaldallee 215, CH-4058 Basel
4 MAIENFISCH, Peter Syngenta Crop Protection AG, Werk Rosental, Schwarzwaldallee 215, CH-4058 Basel
PCT International Classification Number C07D471/20,A01N43/40
PCT International Application Number PCT/IB2004/004083
PCT International Filing date 2004-12-09
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 0328905.5 2003-12-12 U.K.