Title of Invention

5,6-DIALKYL-7- AMINOTRIAZOLOPYRIMIDINES, THEIR PREPARATION AND COMPOSITIONS COMPRISING THESE COMPOUNDS

Abstract The invention discloses a triazolopyrimidine of the formula I in which the substituents are as defined below: R1 is C2-C12-alkenyl or C2-C12-alkynyl, where the carbon chains are unsubstituted or carry one to three identical or different groups Ra and/or Rb: Ra is halogen, cyano, nitro, hydroxyl, C1-C6-alkylthio, C3-C12-alkenyloxy, C3- C12-alkynyloxy, Rb is C1-C4-alkyl, cyano, nitro, hydroxyl, C1-C6-alkoxy, C1-C6-alkylthio, C3- C6-alkenyloxy and C3-C6-alkynyloxy; where the carbon chains of the groups Ra for their part may be halogenated; R2 is C1-C12-alkyl, C2-C12-alkenyl or C2-C12-alkynyl, where the carbon chains may be substituted by one to three groups Rc: Rc is cyano, nitro, hydroxyl; or C3-C6-cycloalkyl which may carry one to four identical or different groups C1-C4-alkyl, halogen, cyano, nitro, hydroxyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-C6-alkenyloxy or C3-C6- alkynyloxy. The invention is also for a process for preparing the said compound and a fungicidal composition comprising it.
Full Text compositions comprising them and methods for controlling harmful fungi using the
compounds I.
The compounds of the formula I differ from those in the abovementioned publications
by the specific embodiment of the substituent in the 6-position of the triazolopyrimidine
skeleton, which is a haloalkyl group or an unsaturated aliphatic group.
Compared to the known compounds, the compounds of the formula I are more
effective against harmful fungi.
The compounds according to the invention can be obtained by different routes.
Advantageously, the compounds according to the invention are obtained by converting
substituted (3-ketoesters of the formula II with 3-amino-1,2,4-triazole of the formula III to
give 7-hydroxytriazolopyrimidines of the formula IV. The groups R1 and R2 in formulae
II and IV are as defined for formula I and the group R in formula II is C1-C4-alkyl; for
practical reasons, preference is given here to methyl, ethyl or propyl.

The reaction of the substituted p-ketoesters of the formula II with the aminoazoles of
the formula III can be carried out in the presence or absence of solvents. It is
advantageous to use solvents to which the starting materials are substantially inert and
in which they are completely or partially soluble. Suitable solvents are in particular
alcohols, such as ethanol, propanols, butanols, glycols or glycol monoethers,
diethylene glycols or their monoethers, aromatic hydrocarbons, such as toluene,
benzene or mesitylene, amides, such as dimethylformamide, diethylformamide,
dibutylformamide, N,N-dimethylacetamide, lower alkanoic acids, such as formic acid,
acetic acid, propionic acid, or bases, such as alkali metal and alkaline earth metal
hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth
metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates
and also alkali metal bicarbonates, organometallic compounds, in particular alkali metal
alkyls, alkylmagnesium halides and also alkali metal and alkaline earth metal alkoxides
and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such
as trimethylamine, triethylamine, triisopropylethylamine, tributylamine and N-
methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines, such as
collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines and mixtures
of these solvents with water. Suitable catalysts are bases, such as those mentioned
above, or acids, such as sulfonic acids or mineral acids. With particular preference, the
reaction is carried out in the absence of a solvent or in chlorobenzene, xylene, dimethyl
sulfoxide or N-methylpyrrolidone. Particularly preferred bases are tertiary amines, such

as triisopropylamine, tributylamine, N-methylmorpho!ine or N-methylpiperidine. The
temperatures are from 50 to 300°C, preferably from 50 to 180°C, if the reaction is
carried out in solution [cf. EP-A 770 615; Adv. Het. Chem. 57 (1993), 81ffj.
The bases are generally employed in catalytic amounts; however, they can also be
employed in equimolar amounts, in excess or, if appropriate, as solvent.

In most cases, the resulting condensates of the formula IV precipitate from the reaction
solutions in pure form and, after washing with the same solvent or with water and
subsequent drying they are reacted with halogenating agents, in particular chlorinating
or brominating agents, to give the compounds of the formula V in which Hal is chlorine
or bromine, in particular chlorine. The reaction is preferably carried out using
chlorinating agents such as phosphorus oxychloride, thionyl chloride or sulfuvyl
chloride at from 50*0 to 150°C, preferably in excess phosphorus oxytrichloride at reflux
temperature. After evaporation of excess phosphorus oxytrichloride, the residue is
treated with ice-water, if appropriate with addition of a water-immiscible solvent. In
most cases, the chlorinated product isolated from the dried organic phase, if
appropriate after evaporation of the inert solvent, is very pure and is subsequently
reacted with ammonia in inert solvents at from 100°C to 200°C to give the 7-amino-
triazolo[1,5-a]pyrimidines. This reaction is preferably carried out using a 1- to 10-molar
excess of ammonia, under a pressure of from 1 to 100 bar.
The novel 7-aminoazolo[1,5-a]pyrimidines are, if appropriate after evaporation of the
solvent, isolated as crystalline compounds, by digestion in water.
The β-ketoesters of the formula II can be prepared as described in Organic Synthesis
Coll. Vol. 1, p. 248, and/or they are commercially available.
Alternatively, the novel compounds of the formula I can be obtained by reacting
substituted acyl cyanides of the formula VI in which R1 and R2 are as defined above
with 3-amino-1,2,4-triazole of the formula III.

The reaction can be carried out in the presence or absence of solvents. It is
advantageous to use solvents to which the starting materials are substantially inert and
in which they are completely or partially soluble. Suitable solvents are in particular
alcohols, such as ethanol, propanols, butanols, glycols or glycol monoethers,
diethylene glycols or their monoethers, aromatic hydrocarbons, such as toluene,

benzene or mesitylene, amides, such as dimethylformamide, diethylformamide,
dibutylformamide, N,N-dimethylacetamide, lower alkanoic acids, such as formic acid,
acetic acid, propionic acid, or bases, such as those mentioned above, and mixtures of
these solvents with water. The reaction temperatures are from 50 to 300°C, preferably
from 50 to 150°C, if the reaction is carried out in solution.
Some of the substituted alky! cyanides of the formula VI required for preparing the
7-aminoazolo[1,5-a]pyrimidines are known, or they can be prepared by known methods
from alkyl cyanides and carboxylic acid esters using strong bases, for example alkali
metal hydrides, alkali metal alcoholates, alkali metal amides or metal alkyls (cf.: J.
Amer. Chem. Soc. 73, (1951), p. 3766).
Compounds of the formula I in which R1 is C2-C12-haloalkenyl or C2-C12-haloalkynyl can
be obtained advantageously by halogenating corresponding triazolopyrimidines of the
formula VII:

In the formula VII, R is C2-C12-alkenyl, C2-C12-alkynyl. where the carbon chains may
carry one to three groups R3.
The halogenation is usually carried out at temperatures of from 0°C to 200°C,
preferably from 20°C to 110°C, in an inert organic solvent in the presence of a free-
radical initiator (for example dibenzoyl peroxide or azobisisobutyronitrile or under UV
irradiation, for example with an Hg vapor lamp) or an acid [cf. Synthetic Reagents,
volume 2, pp. 1-63, Wiley, New York (1974)].
The reaction partners are generally reacted with one another in equimolar amounts. In
terms of yield, it may be advantageous to employ an excess of halogenating agent,
based on VII.
Suitable halogenating agents are, for example, elemental halogens (for example Cl2,
Br2, b), N-bromosuccinimide, N-chlorosuccinimide or dibromodimethylhydrantoin. The
halogenating agents are generally employed in equimolar amounts, in excess or, if
appropriate, as solvent.
Alternatively, compounds of the formula I, in which R1 is C2-C12-haloalkenyl or C2-C12-
haloalkynyl can be obtained by ether cleavage of corresponding triazoiopyrimidines of
the formula VIla:

The present invention relates to 5,6-dialkyl-7-aminotriazolopyrimidines of the formula I

in which the substituents are as defined below:
R1 is C2-C12-alkenyl or C2-C12-alkynyl, where the carbon chains are unsubstituted or
carry one to three identical or different groups Ra and/or Rb;
Ra is halogen, cyano, nitro, hydroxyl, C1-C6-alkyithio, C3-C12-alkenyloxy and
C3-C12-alkynyloxy,
Rb is C1-C4-alkyl, cyano, nitro, hydroxyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-
C6-alkenyloxy and C3-C6-alkynyloxy
where the carbon chains of the groups Ra for their part may be
halogenated;
R2 is C1-C12-alkyl, C2-C12-alkenyl or C2-C12-alkynyl, where the carbon chains may be
substituted by one to three groups Rc:
Rc is cyano, nitro, hydroxyl, NR11R12; or C3-C6-cycIoalkyl which may carry one
to four identical or different groups C1-C4-alkyl, halogen, cyano, nitro,
hydroxyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-Cs-alkenyloxy or C3-C5-
alkynyloxy
Moreover, the invention relates to processes for preparing these compounds, to
compositions comprising them and to their use for controlling phytopathogenic harmful
fungi.
5,6-Dialkyl-7-aminotriazolopyrimidines are proposed in a general manner in
GB 1 148 629. Individual fungicidally active 5,6-dialkyl-7-aminotriazolopyrimidines are
known from EP-A 141 317. However, in many cases their activity is unsatisfactory.
Based on this, it is an object of the present invention to provide compounds having
improved activity and/or a wider activity spectrum.
We have found that this object is achieved by the definitions defined at the outset.
Furthermore, we have found processes and intermediates for their preparation,


In the formula VIla, RA is C1-C14-alkyl, C2-C12-alkenyl or C2-C12-alkynyl, where the
groups RA are substituted by hydroxyl or alkoxycarbonyl groups. By heating the
compounds VIla in the presence of mineral acids [HX], such as hydrochloric acid or
hydrobromic acid, or nitric acid, the compounds I are obtained [cf. Organikum, 15th
edition, p. 237 ff., VEB Deutscher Verlag der Wissenschaften, Berlin 1981].
Some of the triazolopyrimidines of the formulae VII and Vila required for preparing the
compounds I described above are known, or they can be prepared by known methods
[cf. EP-A 141 317].
If individual compounds I can not be obtained by the routes described above, they can
be prepared by derivatization of other compounds I.
If the synthesis yields mixtures of isomers, a separation is generally not necessarily
required since in some cases the individual isomers can be interconverted during work-
up for use or during application (for example under the action of light, acids or bases).
Such conversions may also take place after use, for example during the treatment of
plants within the treated plants, or in the harmful fungus to be controlled.
In the definitions of symbols given above, collective terms were used which are
generally representative of the following substituents:
halogen: fluorine, chlorine, bromine and iodine in particular fluorine or chlorine;
alkyl: saturated straight-chain or branched hydrocarbon radicals having 1 to 4, 6, 8 or
10 carbon atoms, for example C1-C6-alkyI such as methyl, ethyl, propyl, 1-methylethyl,
butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-
methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl,
1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,
1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-
dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-
trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;
haloalkyl: straight-chain or branched alkyl groups having 1 to 2, 4 or 6 carbon atoms
(as mentioned above), where some or all of the hydrogen atoms in these groups may
be replaced by halogen atoms as mentioned above: in particular C1-C2-haloalkyl such
as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl,
difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl,

chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-
difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-
dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1,1,1 -trifluoroprop-2-yl;
alkenyl: unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4, 6, 8
or 10 carbon atoms and one or two double bonds in any position, for example C2-C6-
alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl,
3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-
propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-
1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-
butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-
propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-
2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-
1-pentenyl, 2-methyl-l-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-
2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-
3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyi-
4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,
1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-
2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl,
1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl. 2,3-dimethyl-
2-butenyl. 2,3-dimethyl-3-butenyl. 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl.
1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-
2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl,
1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;
alkoxyalkyl: a saturated straight-chain or mono-, di- or tribranched hydrocarbon chain
which is interrupted by an oxygen atom, for example C5-C12-alkoxyalkyl: a hydrocarbon
chain as described above having 5 to 12 carbon atoms which may be interrupted by an
oxygen in any position, such as propoxyethyl, butoxyethyl, pentoxyethyl, hexyloxyethyl,
heptyloxyethyl, octyloxyethyl, nonyloxyethyl, 3-(3-ethylhexyloxy)ethyl, 3-(2,4,4-tri-
methylpentyloxy)ethyl, 3-(1-ethyl-3-methylbutoxy)ethyl, ethoxypropyl, propoxypropyl,
butoxypropyl, pentoxypropyl, hexyloxypropyl, heptyloxypropyl, octyloxypropyl,
nonyloxypropyl, 3-(3-ethylhexyloxy)propyl, 3-(2,4,4-trimethylpentyloxy)propyl,
3-(1-ethyl-3-methylbutoxy)propyl, ethoxybutyl, propoxybutyl, butoxybutyl, pentoxybutyl,
hexyloxybutyl, heptyloxybutyl, octyloxybutyl, nonyloxybutyl, 3-(3-ethylhexyloxy)butyl,
3-(2,4,4-trimethylpentyloxy)butyl, 3-(1-ethyl-3-methylbutoxy)butyl, methoxypentyl,
ethoxypentyl, propoxypentyl, butoxypentyl, pentoxypentyl, hexyloxypentyl, heptyloxy-
pentyl, 3-(3-methylhexyloxy)pentyl, 3-(2,4-dimethylpentyloxy)pentyl, 3-(1-ethyl-3-
methylbutoxy)pentyl;
haloalkenyl: unsaturated straight-chain or branched hydrocarbon radicals having 2 to
10 carbon atoms and one or two double bonds in any position (as mentioned above),


where some or all of the hydrogen atoms in these groups may be replaced by halogen
atoms as mentioned above, in particular by fluorine, chlorine and bromine;
alkynyl: straight-chain or branched hydrocarbon groups having 2 to 4, 6, 8 or 10 carbon
atoms and one or two triple bonds in any position, for example C2-C6-alkynyl such as
ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-
pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-
methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-
hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-
pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-
pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-
2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-
dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-
methyl-2-propynyl;
cycloalkyl: mono- or bicyclic saturated hydrocarbon groups having 3 to 6 carbon ring
members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
The scope of the present invention includes the (R)- and (S)-isomers and the
racemates of compounds of the formula I having chiral centers.
With a view to the intended use of the triazolopyrimidines of the formula I, particular
preference is given to the following meanings of the substituents, in each case on their
own or in combination:
Preference is given to compounds I in which the group R1 has at most 9 carbon atoms.
Likewise, preference is given to compounds of the formula I in which R1 is a straight-
chain or mono-, di-, tri- or polybranched haloalkyl group.
If R1 is haloalkyl, the halogenation is preferably at the terminal carbon. Preference is
given to monohaloalky! groups.
In one embodiment of the compounds I according to the invention, R1 is C2-C12-
haloalkenyl or C2-C12-haloalkynyl, the groups having one or two halogen atoms.
In another embodiment of the compounds I, R1 is a group C2-C12-haloalkenyl or C2-C12-
haloalkynyl, which groups contain a halogen atom at the α carbon atom.
In a further embodiment of the compounds I, R1 is C2-C12-alkenyl or C2-C12-Alkynyl,
where the hydrocarbon chains are unsubstituted or carry one to three identical or
different groups Ra and/or Rb.

In a preferred embodiment of the compounds of the formula I the group Ra is absent.
Particular preference is given to compounds I in which the carbon chains of R1 and R2
together do not have more than 14 carbon atoms.
In one embodiment of the compounds I according to the invention, R2 is methyl, ethyl,
isopropyl, n-propyl or n-butyl, preferably methyl, ethyl, isopropyl or n-propyl, in
particular methyl or ethyl.
Halogen atoms in the groups R1 are preferably located at the α or Ω carbon atom.
Cyano groups in R1 and/or R2 are preferably located at the terminal carbon atom.
In a further preferred embodiment of the compounds of the formula I the group Rb is
absent.
In particular with a view to their use, preference is given to the compounds I compiled
in the tables below. Moreover, the groups mentioned for a substituent in the tables are
per se, independently of the combination in which they are mentioned, a particularly
preferred embodiment of the substituent in question.
Table 1
Compounds of the formula I in which R1 for each compound corresponds to one row of
Table A and R2 is methyl
Table 2
Compounds of the formula I in which R1 for each compound corresponds to one row of
Table A and R2 is ethyl
Table 3
Compounds of the formula I in which R' for each compound corresponds to one row of
Table A and R2 is n-propyl
Table 4
Compounds of the formula I in which R1 for each compound corresponds to one row of
Table A and R2 is isopropyl
Table 5
Compounds of the formula I in which R1 for each compound corresponds to one row of
Table A and R2 is n-butyl








The compounds I are suitable as fungicides. They are distinguished by an outstanding
effectiveness against a broad spectrum of phytopathogenic fungi, especially from the
classes of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes, in
particular from the class of the Oomycetes. Some are systemically effective and they
can be used in plant protection as foliar fungicides, as fungicides for seed dressing and
soil fungicides.
They are particularly important in the control of a multitude of fungi on various
cultivated plants, such as wheat, rye. barley, oats, rice, corn, grass, bananas, cotton,
soya, coffee, sugar cane, vines, fruits and ornamental plants, and vegetables, such as
cucumbers, beans, tomatoes, potatoes and cucurbits, and on the seeds of these
plants.
They are especially suitable for controlling the following plant diseases:
• Alternaria species on fruit and vegetables,
• Bipolaris and Drechslera species on cereals, rice and lawns,
• Blumeria graminis (powdery mildew) on cereals,
• Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and
grapevines,
• Bremia lactucae on lettuce,
• Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
• Fusarium and Verticillium species on various plants,
• Mycosphaerella species on cereals, bananas and peanuts,
• Peronospora species on cabbage and bulbous plants,
• Phakopsora pachyrhizi and P. meibomiae on soybeans
• Phytophthora infestans on potatoes and tomatoes,
• Phytophthora capsici on peppers,
• Plasmopara viticola on grapevines,

• Podosphaera leucotricha on apples,
• Pseudocercosporella herpotrichoides on wheat and barley,
• Pseudoperonospora species on hops and cucumbers,
• Puccinia species on cereals,
• Pyricularia oryzae on rice,
• Pythium aphanidermatum on lawns,
• Rhizoctonia species on cotton, rice and lawns,
• Septoria tritici and Stagonospora nodorum on wheat,
• Uncinula necator on grapevines,
• Ustilago species on cereals and sugar cane, and
• Venturia species (scab) on apples and pears.
They are particularly suitable for controlling harmful fungi from the class of the
Oomycetes, such as Peronospora species, Phytophthora species, Plasmopara viticola
and Pseudoperonospora species.
The compounds I are also suitable for controlling harmful fungi, such as Paecilomyces
variotii, in the protection of materials (e.g. wood, paper, paint dispersions, fibers or
fabrics) and in the protection of stored products.
The compounds I are employed by treating the fungi or the plants, seeds, materials or
soil to be protected from fungal attack with a fungicidally effective amount of the active
compounds. The application can be carried out both before and after the infection of
the materials, plants or seeds by the fungi.
The fungicidal compositions generally comprise between 0.1 and 95%, preferably
between 0.5 and 90%, by weight of active compound.
When employed in plant protection, the amounts applied are, depending on the kind of
effect desired, between 0.01 and 2.0 kg of active compound per ha.
In seed treatment, amounts of active compound of 1 to 1000 g/100 kg, preferably 5 to
100 g/100 kg of seed are generally required.
When used in the protection of materials or stored products, the amount of active
compound applied depends on the kind of application area and on the desired effect.
Amounts customarily applied in the protection of materials are, for example, 0.001 g to
2 kg, preferably 0.005 g to 1 kg, of active compound per cubic meter of treated
material.
The compounds I can be converted into the customary formulations, for example
solutions, emulsions, suspensions, dusts, powders, pastes and granules. The

application form depends on the particular purpose; in each case, it should ensure a
fine and uniform distribution of the compound according to the invention.
The formulations are prepared in a known manner, for example by extending the active
compound with solvents and/or carriers, if desired using emulsifiers and dispersants.
Solvents/auxiliaries which are suitable are essentially:
- water, aromatic solvents (for example Solvesso products, xylene), paraffins (for
example mineral oil fractions), alcohols (for example methanol, butanol, pentanol,
benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone),
pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid
dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may
also be used,
carriers such as ground natural minerals (for example kaolins, clays, talc, chalk)
and ground synthetic minerals (for example highly disperse silica, silicates);
emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene
fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as
lignosulfite waste liquors and methylcellulose.
Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of
lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid,
dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty
alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore
condensates of sulfonated naphthalene and naphthalene derivatives with
formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol
and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol,
octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether,
tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty
alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl
ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol
esters, lignosulfite waste liquors and methylcellulose.
Suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil
dispersions are mineral oil fractions of medium to high boiling point, such as kerosene
or diesel oil. furthermore coal tar oils and oils of vegetable or animal origin, aliphatic,
cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin,
tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol,
propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents,
for example dimethyl sulfoxide, N-methylpyrrolidone and water.
Powders, materials for spreading and dustable products can be prepared by mixing or
concomitantly grinding the active substances with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous
granules, can be prepared by binding the active compounds to solid carriers. Examples
of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay,
limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,
magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as,
for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and
products of vegetable origin, such as cereal meal, tree bark meal, wood meal and
nutshell meal, cellulose powders and other solid carriers.
In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1
to 90% by weight, of the active compound. The active compounds are employed in a
purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
The following are examples of formulations: 1. Products for dilution with water
A Water-soluble concentrates (SL)
10 parts by weight of a compound according to the invention are dissolved in water or
in a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The
active compound dissolves upon dilution with water.
B Dispersible concentrates (DC)
20 parts by weight of a compound according to the invention are dissolved in
cyclohexanone with addition of a dispersant, for example polyvinylpyrrolidone. Dilution
with water gives a dispersion.
C Emulsifiable concentrates (EC)
15 parts by weight of a compound according to the invention are dissolved in xylene
with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each
case 5%). Dilution with water gives an emulsion.
D Emulsions (EW, EO)
40 parts by weight of a compound according to the invention are dissolved in xylene
with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each
case 5%). This mixture is introduced into water by means of an emulsifying machine
(Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an
emulsion.
E Suspensions (SC, OD)
In an agitated ball mill, 20 parts by weight of a compound according to the invention are
comminuted with addition of dispersants, wetters and water or an organic solvent to
give a fine active compound suspension. Dilution with water gives a stable suspension
of the active compound.

F Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of a compound according to the invention are ground finely with
addition of dispersants and wetters and made into water-dispersible or water-soluble
granules by means of technical appliances (for example extrusion, spray tower,
fluidized bed). Dilution with water gives a stable dispersion or solution of the active
compound.
G Water-dispersible powders and water-soluble powders (WP, SP)
75 parts by weight of a compound according to the invention are ground in a rotor-
stator mill with addition of dispersants, wetters and silica gel. Dilution with water gives a
stable dispersion or solution of the active compound.
2. Products to be applied undiluted
H Dustable powders (DP)
5 parts by weight of a compound according to the invention are ground finely and
mixed intimately with 95% of finely divided kaolin. This gives a dustable product.
I Granules (GR, FG, GG, MG)
0.5 part by weight of a compound according to the invention is ground finely and
associated with 95.5% carriers. Current methods are extrusion, spray-drying or the
fluidized bed. This gives granules to be applied undiluted.
J ULV solutions (UL)
10 parts by weight of a compound according to the invention are dissolved in an
organic solvent, for example xylene. This gives a product to be applied undiluted.
The active compounds can be used as such, in the form of their formulations or the use
forms prepared therefrom, for example in the form of directly sprayable solutions,
powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable
products, materials for spreading, or granules, by means of spraying, atomizing,
dusting, spreading or pouring. The use forms depend entirely on the intended
purposes; the intention is to ensure in each case the finest possible distribution of the
active compounds according to the invention.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable
powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions,
pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can
be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier.
Alternatively, it is possible to prepare concentrates composed of active substance,
wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such

concentrates are suitable for dilution with water.
The active compound concentrations in the ready-to-use preparations can be varied
within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from
0.01 to 1%.
The active compounds may also be used successfully in the ultra-low-volume process
(ULV), by which it is possible to apply formulations comprising over 95% by weight of
active compound, or even to apply the active compound without additives.
Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or
bactericides may be added to the active compounds, if appropriate not until
immediately prior to use (tank mix). These agents can be admixed with the agents
according to the invention in a weight ratio of 1:10 to 10:1.
The compositions according to the invention can, in the use form as fungicides, also be
present together with other active compounds, e.g. with herbicides, insecticides, growth
regulators, fungicides or else with fertilizers. Mixing the compounds I or the
compositions comprising them in the application form as fungicides with other
fungicides results in many cases in an expansion of the fungicidal spectrum of activity
being obtained.
The following list of fungicides, in conjunction with which the compounds according to
the invention can be used, is intended to illustrate the possible combinations but does
not limit them:
• acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl,
• amine derivatives, such as aldimorph, dodine, dodemorph, fenpropimorph,
fenpropidin, guazatine, iminoctadine, spiroxamine ortridemorph,
• anilinopyhmidines, such as pyrimethanil, mepanipyrim or cyprodinyl,
• antibiotics, such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin
or streptomycin,
• azoles, such as bitertanol, bromoconazole, cyproconazole, difenoconazole,
dinitroconazole, enilconazole, epoxiconazole, fenbuconazole, fluquinconazole,
flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole,
myclobutanil, penconazole, propiconazole, prochloraz, prothioconazole,
simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole or
triticonazole,
• dicarboximides, such as iprodione, myclozolin, procymidone or vinclozolin,
• dithiocarbamates, such as ferbam, nabam, maneb, mancozeb, metam, metiram,
propineb, polycarbamate, thiram, ziram or zineb,
• heterocyclic compounds, such as anilazine, benomyl, boscalid, carbendazim,

carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone, fenamidone,
fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol,
picobenzamid, probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen,
silthiofam, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole or
triforine,
• copper fungicides, such as Bordeaux mixture, copper acetate, copper oxychloride
or basic copper sulfate,
• nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton or nitrophthal-
isopropyl,
• phenylpyrroles, such as fenpiclonil or fludioxonil,
• sulfur,
• other fungicides, such as acibenzolar-S-methyl, benthiavalicarb, carpropamid,
chlorothalonil, cyflufenamid, cymoxanil, diclomezine, diclocymet, diethofencarb,
edifenphos, ethaboxam, fenhexamid, fentin acetate, fenoxanil, ferimzone,
fluazinam, fosetyl, phosphorous acid, fosetyl-aluminum, iprovalicarb,
hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide, tolclofos-
methyl, quintozene orzoxamide,
• strobilurins, such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin,
kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or
trifloxystrobin,
• sulfenic acid derivatives, such as captafol. captan, dichlofluanid, folpet or
tolylfluanid,
• cinnamides and analogous compounds, such as dimethomorph, flumetover or
flumorph.
Synthesis examples
The procedures given in the synthesis examples below were, with appropriate
modification of the starting materials, used to obtain further compounds I. The
compounds obtained in this manner are listed in the table that follows, together with
physical data.
Example 1: Preparation of
7-Amino-6-(5-cyanopentyl)-5-ethyl-[1,2,4]triazolo-[1,5-a]pyrimidine
1.a) 4,9-Dicyanononan-3-one
5.6 g of ethyl propionate were added dropwise to a solution of 6.8 g of 1,6-dicyano-
hexane and 11.2 g of 95% pure potassium tert-butoxide in 100 ml of anhydrous
dimethylformamide (DMF). After the addition had ended, the reaction mixture was
stirred at 20 to 25°C for 17 hours and then diluted with water and washed with tert-butyl
methyl ether (MTBE). After acidification with concentrated HCI, the aqueous phase was

extracted with MTBE. This ether phase was washed with water and, after drying, freed
from the solvent. What remained were 7.1 g of the title compound as an oil which was
reacted without further purification.
1 .b) 7-Amino-6-(5-cyanopentyl)-5-ethyltriazolo-(1,5-a)-pyrimidine [I-3]
4.76 g of 4,9-dicyanononan-3-one, 2.5 g of 3-amino-1H-1,2,4-triazole and 0.94 g of
p-toluenesulfonic acid in 25 ml of mesitylene were stirred at 170°C for four hours,
during which time small amounts of mesitylene were distilled off continuously. The
solvent was then distilled off, and the residue was taken up in dichloromethane and
water. After removal of insoluble components, the organic phase was washed with
water, saturated NaHC03 solution and saturated NaCI solution and then dried, and
volatile components were removed. The residue was digested with MTBE. After
removal of the solvent. 2.0 g of the title compound remained as colorless crystals of
m.p. 158-160°C.
Example 2: Preparation of
5-Ethyl-6-(5,6,6-trifluorohex-5-enyl)-[1,2,4]-triazolo[1,5-a]pyrimidin-7-ylamine [I-5]
2a) Methyl 7,8;8-trifluoro-2-propionyloct-7-enoate
At 20 to 25°C, 5.40 g of methanolic potassium methoxide solution (30% strength,
23 mmol) were added dropwise to a solution of 3.30g (23 mmol) of ethylpropionyl
acetate in 2.5ml of methanol.. After 1 hour of stirring at this temperature and then
30 min of stirring at 40°C, 5.00 g (23 mmol) of 6-bromo-1,1,2-trifluoro-1-hexene were
added dropwise at 40°C over a period of 5 min. The reaction mixture was then stirred
at this temperature for 15 hours. The suspension formed was taken up in methyl tert-
butyl ether (MTBE) and then filtered through silica gel. The eluate was washed with
water and then with saturated NaCI solution and then dried, and the solvent was
removed. What remained were 2.34 g of the title compound as a colorless oil.
2b) 5-Ethyl-6-(5,6.6-trifluorohex-5-enyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ol
A mixture of 5.28 mmol of methyl 7,8,8-trifluoro-2-propionyloct-7-enoate, 0.86 g
(10.2 mmol) of 3-amino-1,2,4-triazole and 10 ml of propionic acid was heated under re-
flux for about 15 hours. The propionic acid was then distilled off, and the residue was
chromatographed on silica gel (cyclohexane/ethyl acetate mixture). What remained
was 0.6 g of the title compound in the form of yellow crystals.
2c) 7-Chloro-5-ethyl-6-(5,6,6-trifluorohex-5-enyl)-[1,2,4]triazolo[1,5-a]pyrimidine

0.60 g (2 mmol) of the compound from Ex. 3b) in 20 ml of phosphoryl chloride was
heated under reflux for 15 hours. The volatile components were then distilled off, the
residue was taken up in CH2CI2, the solution was washed with NaHC03 solution until
neutral and dried and the solvent was removed. The residue gave, after chroma-
tography on silica gel (ethyl acetate/methanol mixture), 0.38 g of the title compound as
a yellow oil.
2d) 5-Ethyl-6-(5,6,6-trifluorohex-5-enyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine
A solution of 0.35g (1.1 mmol) of the compound from Ex. 3c) in 2 ml of methanol and
10 ml of a 7M methanolic NH3 solution were stirred at 20 to 25°C for 48 hours. The
solution was freed from the volatile components and the residue was suspended in wa-
ter in an ultrasonic bath, filtered off and then dried. What remained was 0.21 g of the
title compound in the form of white crystals of m.p. 199°C.

Examples of the action against harmful fungi
The fungicidal action of the compounds of the formula I was demonstrated by the
following experiments:
The active compounds were prepared as a stock solution with 25 mg of active
compound which was made up to 10 ml with a mixture of acetone and/or DMSO and
the emulsifier Uniperol® EL (wetting agent having emulsifying and dispersing action
based on ethoxylated alkylphenols) in a ratio by volume of solvent/emulsifier of 99/1.
The mixture was then made up to 100 ml with water. This stock solution was, using the
solvent/emulsifier/water mixture described, diluted to the active compound
concentration stated below.
Use Example 1 -Activity against peronospora of grapevines caused by Plasmopara
viticola
Leaves of potted vines were sprayed to runoff point with an aqueous suspension
having the concentration of active compounds stated below. The next day, the
undersides of the leaves were inoculated with an aqueous sporangia suspension of
Plasmopara viticola. The vines were then initially placed in a water-vapor-saturated

chamber at 24°C for 48 hours and then in a greenhouse at temperatures between 20
and 30°C for 5 days. After this time, the plants were once more placed in a humid
chamber for 16 hours to promote the eruption of sporangiophores. The extent of the
development of the infection on the undersides of the leaves was then determined
visually.
In this test, the plants which had been treated with 250 ppm of the compound I-7
showed no infection, whereas the untreated plants were 90% infected.
Use Example 2: Activity against late blight of tomatoes caused by Phytophthora
infestans, protective treatment
Leaves of potted tomato plants were sprayed to runoff point with an aqueous suspension
of the active compounds. Four days after the application, the leaves were infected with an
aqueous sporangia suspension of Phytophthora infestans. The plants were then placed
on a water-vapor-saturated chamber at temperatures between 18 and 20°C. After 6 days
the infection was determined visually in %.
In this test, the plants which had been treated with 250 ppm of the compound I-7 showed
no infection, whereas the untreated plants were 100% infected.

We claim:
1. A triazolopyrimidine of the formula I

in which the substituents are as defined below:
Rt is C2-C12-alkenyl or C2-C12-alkynyl, where the carbon chains are
unsubstituted or carry one to three identical or different groups Ra and/or
Rb:
Ra is halogen, cyano, nitro, hydroxyl, C1-C6-alkylthio, C3-C12-alkenyloxy. C3-
C12-alkynyloxy,
Rb is C1-C4-alkyl, cyano, nitro, hydroxyl, C1-C6-alkoxy, C1-C4-alkylthio, C3-
C6-alkenyloxy and C3-C6-alkynyloxy:
where the carbon chains of the groups Ra for their part may be
halogenated:
R2 is C1-C12-alkyl, C1-C12-alkenyl or C1-C12-alkynyl, where the carbon chains
may be substituted by one to three groups Rc:
Rc is cyano, nitro, hydroxyl; or C3-C6-cycloalkyl which may carry one to four
identical or different groups C1-C4-alkyl, halogen, cyano, nitro,
hydroxyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-C5-alkenyloxy or C3-C6-
alkynyloxy.
2. The compound of the formula I according to claim 1, in which R1 and R2
together do not have more than 14 carbon atoms.
3. The compound of the formula I according to any of claims 1 or 2, in
which R2 is methyl, ethyl, isopropyl, n-propyl or n-butyl.
4. The compound of the formula I according to claim 1:
5-ethyl-6-hex-5-enyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine;
6-hex-5-enyl-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine;
5-methyl-6-(5,6,6-trifluorohex-5-enyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine.

5. A process for preparing compounds of the formula I according to any of
claims 1 to 4 wherein β-ketoesters of the formula II,

in which R is C1-C4-aIkyl are reacted with 3-amino-1,2,4-triazole of the formula III

to give 7-hydroxytriazolopyrimidines of the formula IV

which are halogenated to give compounds of the formula V

in which Hal is chlorine or bromine and V is reacted with ammonia.
6. A process for preparing compounds of the formula I according to any of
claims 1 to 4 wherein acylcyanides of the formula VI,

are reacted with 3-amino-1,2,4-triazole of the formula III according to claim 10.
7. A compound of the formula IV or V as defined in claim 5.
8. A fungicidal composition comprising a solid or liquid carrier and a
compound of the formula I according to any of claims 1 to 4.


The invention discloses a triazolopyrimidine of the formula I

in which the substituents are as defined below:
R1 is C2-C12-alkenyl or C2-C12-alkynyl, where the carbon chains are
unsubstituted or carry one to three identical or different groups Ra and/or
Rb:
Ra is halogen, cyano, nitro, hydroxyl, C1-C6-alkylthio, C3-C12-alkenyloxy, C3-
C12-alkynyloxy,
Rb is C1-C4-alkyl, cyano, nitro, hydroxyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-
C6-alkenyloxy and C3-C6-alkynyloxy;
where the carbon chains of the groups Ra for their part may be
halogenated;
R2 is C1-C12-alkyl, C2-C12-alkenyl or C2-C12-alkynyl, where the carbon chains
may be substituted by one to three groups Rc:
Rc is cyano, nitro, hydroxyl; or C3-C6-cycloalkyl which may carry one to
four identical or different groups C1-C4-alkyl, halogen, cyano, nitro,
hydroxyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-C6-alkenyloxy or C3-C6-
alkynyloxy.
The invention is also for a process for preparing the said compound and a fungicidal
composition comprising it.

Documents:

02287-kolnp-2006-abstract.pdf

02287-kolnp-2006-claims.pdf

02287-kolnp-2006-correspondence others.pdf

02287-kolnp-2006-correspondence-1.1.pdf

02287-kolnp-2006-description(complete).pdf

02287-kolnp-2006-form-1.pdf

02287-kolnp-2006-form-3.pdf

02287-kolnp-2006-form-5-1.1.pdf

02287-kolnp-2006-form-5.pdf

02287-kolnp-2006-international publication.pdf

02287-kolnp-2006-others.pdf

02287-kolnp-2006-pct other document.pdf

02287-kolnp-2006-priority document.pdf

2287-kolnp-2006-correspondence.pdf

2287-kolnp-2006-examination report.pdf

2287-kolnp-2006-form 18.pdf

2287-kolnp-2006-form 3.pdf

2287-kolnp-2006-form 5.pdf

2287-kolnp-2006-gpa.pdf

2287-kolnp-2006-granted-abstract.pdf

2287-kolnp-2006-granted-claims.pdf

2287-kolnp-2006-granted-description (complete).pdf

2287-kolnp-2006-granted-form 1.pdf

2287-kolnp-2006-granted-form 2.pdf

2287-kolnp-2006-granted-specification.pdf

2287-kolnp-2006-others.pdf

2287-kolnp-2006-reply to examination report.pdf

2287-kolnp-2006-translated copy of priority document.pdf

abstract-02287-kolnp-2006.jpg


Patent Number 253771
Indian Patent Application Number 2287/KOLNP/2006
PG Journal Number 34/2012
Publication Date 24-Aug-2012
Grant Date 23-Aug-2012
Date of Filing 10-Aug-2006
Name of Patentee BASF AKTIENGESELSCHAFT
Applicant Address 67056 LUDWIGSHAFEN
Inventors:
# Inventor's Name Inventor's Address
1 GRAMMENOS WASSILIOS ALEXANDER-FLEMING-STR.13,67071 LUDWIGSHAFEN.
2 TORMO I BLASCO JORDI CARL-BENZ-STR.10-3,69514 LAUDENBACH
3 GROTE THOMAS IM HOHNHAUSEN 18,67157 WACHENHEIM.
4 RHEINHEIMER JOACHIM MERZIGER STR.24,67063 LUO63 LUDWIGSHAFEN.
5 SCHAFER PETER ROMERSTR.1,67308 OTTERSHEIM.
6 SCHIEWECK FRANK LINDENWEG 4,67258 HESSHEIM.
7 SCHWOGLER ANJA HEINRICH-LANZ-STR.3,68165 MANNHEIM.
8 WAGNER OLIVER IM MEISENTAL 50,67433 NEUSTADT.
9 NIEDENBRUCK MATTHIAS ALBERT-EINSTEIN-ALLEE 3,67117 LIMBURGERHOF,
10 SCHERER MARIA HERMANN-JURGENS-STR.30,76829.
11 STRATHMANN SIEGFRIED DONNERSBERGSTR.9,67117 LIMBURGERHOF.
12 SCHOFL ULRICH ERLENSTR.8,68782 BRUHL.
13 STIERL REINHARD JAHNSTR.8,67251 FREINSHEIIM.
14 MULLER BERND STOCKINGER STR.7,67227 FRANKENTHAL.
15 GEWEHR MARKUS GOETHESTR.21,56288 KASTELLAUN,
16 BLETTNER CARSTEN RICHARD-WAGNER-STR.48,68165 MANNHEIM
17 HUNGER UDO KURT-SCHUMACHER-STR. 43, 55124 MAINZ
PCT International Classification Number C07D 487/04
PCT International Application Number PCT/EP2005/002424
PCT International Filing date 2005-03-08
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 102004012021.8 2004-03-10 Germany
2 102004012019.6 2004-03-10 Germany