Title of Invention

2-[(DIHYDRO) PYRAZOL-3'-YLOXYMETHYLEN] ANILIDES, AND THE PROCESS FOR PREPARING THE SAME

Abstract This invention concerns 2-[(dihydro)pyrazol-3'-yloxymethylene]anilides, of formula (I) in which this a single or double bond and the subscripts and substituents are as follows : n 0, 1, 2, 3 or 4; m 0, 1 or 2; X a direct bond or CH2 oxygen or NRa , Ra being hydrogen, alkyl, alkenyl, alkinyl, cycloalkyl or cycloalkeny; R1 nitro, cyano, halogen or optionally substituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy or alkinyloxy; R2 nitro, cyano, halogen, alkyl, haloalkyl, alkoxy, alkylthio or alkoxycarbonyl, R3 optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, heterocyclyl, aryl or heteroaryl; R4 hydrogen or optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, alkylcarbonyl or alkoxycarbonyl; R5 hydrogen, alkyl, alkenyl, alkinyl, cycloalkyl or cycloalkenyl. This invention also concerns methods of preparing such compounds, intermediates used in their preparation.
Full Text


where ... is a single or double bond and the indices and the sub-stituents have the following meanings:
n is 0, 1, 2, 3 or 4, it being possible for the substituents R^ to be different if n is greater than 1;
m , is 0, 1 or 2, it being possible for the substituents R^ to be different if m is greater than 1;
X is a direct bond, 0 or NRa;
Ra is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl;
R1 is nitro, cyano, halogen,
unsubstituted or substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy or
in the case where n is 2, additionally is an unsubstituted or substituted bridge bonded to two adjacent ring atoms and containing three to four members from the group consisting of 3 or 4 carbon atoms, 1 to 3 carbon atoms and 1 or 2 nitrogen, oxygen and/or sulfur atoms, this bridge together with the ring to which it is bonded being able to form a partly unsaturated or aromatic radical;
R2 is nitro, cyano, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1--C4—alkoxy, C1-C4—alkylthio or C1-C4—alkoxycarbonyl;
R3 is unsubstituted or substituted alkyl, alkenyl or alkynyl;







It may be advantageous for the reaction to add a catalytic amount of a crown ether (eg. 18—crown-6 or 15—crown-5).
The reaction can also be carried out in two-phase systems consisting of a solution of alkali metal or alkaline earth metal hydroxides or carbonates in water and an organic phase (eg. aromatic and/or halogenated hydrocarbons). Suitable phase transfer catalysts in this case are, for example, ammonium halides and tetrafluoroborates (eg. benzyltriethylsmunonixom chloride, benzyltributylaimmonium bromide, tetrabutylaromoniiom chloride, hexadecyltrimethylsutimonium bromide or tetrabutyl-ammonium tetrafluoroborate) and phosphonium halides (eg. tetra-butylphosphonium chloride and tetraphenylphosphonivim bromide).
It may be advantageous for the reaction first to convert the
3—hydroxy(dihydro)pyrazole to the corresponding hydroxylate using
the base and then to react it with the benzyl derivative.
The starting substances II required for preparing the compounds I are disclosed in EP—A 513 580 or can be prepared by the methods described there [Synthesis 1991,. 181; Anal. Chim. Acta 185 (1986), 295; EP-A 336 567].
3—Hydroxypyrazoles Ilia and 3—hydroxydihydropyrazoles IIlb are likewise disclosed in the literature or can be prepared by the methods described there [Ilia: J. Heterocycl. Chem. IQ. (1993), 49, Chem. Ber. UH (1974), 1318, Chem. Pharm. Bull. H (1971), 1389, Tetrahedron Lett, l1 (1970), 875, Chem. Herterocycl. Comp. (1969), 527, Chem. Ber. 102 (1969), 3260, Chem. Ber. Ml (1976), 261, J. Org. Chem. 21 (1966), 1538, Tetrahedron Lett, il (1987), 607; Illb: J. Med. Chem. H (1976), 715].
The 3—hydroxypyrazoles Ilia are obtained particularly advantageously by the process described in the earlier German Appl. No. 4 15 484.4.
The nitro compounds IV are reduced to the corresponding N—hydroxyanilines Va in a similar manner to methods known from the literature, for example using metals such as zinc [cf. Ann. 'Chem. 316 (1901), 278] or with hydrogen (cf. EP-A 085 890).
The N—hydroxyanilines Va are reacted with the carbonyl compounds VI under alkaline conditions, according to the conditions described above for the reaction of the compounds II with the I 3—hydroxy(dihydro)pyrazoles III. The reaction is in particular carried out at from —10*C to 30*C. The preferred solvents are methylene chloride, toluene, tert-butyl methyl ether or ethyl

acetate. Tne prererrea oases are sodium nyarogen caroonate, potassium carbonate or aqueous sodium hydroxide solution.
The compounds of the formula I where X is a direct bond or oxygen are additionally obtained, for example, by first reducing a benzyl derivative of the formula Ila to the corresponding hydroxyaniline of the formula Vb, converting Vb using a carbonyl compound of the formula VI to the corresponding anilide of the formula VII, then converting VII using a compound VIII to the amide of the formula IX, then converting IX to the corresponding benzyl halide X and converting X to I in the presence of a base using a 3—hydroxy(dihydro)pyrazole of the formula III.



In the formula X, Hal is a halogen atom, in particular chlorine or bromine.
L3 in the formula VIII is a nucleophilically replaceable group, for example halogen (eg, chlorine, bromine or iodine), or an alkyl— or arylsulfonate (eg. methylsulfonate, trifluoromethyl-sulfonate, phenylsulfonate or 4-methylphenylsulfonate) and R* is not hydrogen.
The reactions are carried out in a similar manner to the processes mentioned above.
The compounds IX are halogenated using free radicals, it being possible to employ as halogenating agents, for example, N—chloro— or N—bromosuccinimide, elemental halogens (eg. chlorine or bromine) or thionyl chloride, sulfuryl chloride, phosphorus trichloride or phosphorus pentachloride and similar compounds. A radical initiator is customarily additionally used (eg. azobis-isobutyronitrile) or the reaction is carried out with irradiation (by UV light). The halogenation is carried out in a manner known per se in a customary organic diluent.
The compounds I where R4 is not hydrogen are additionally obtained by reacting a corresponding compound of the formula I where R* is hydrogen with a compound of the formula VIII.



The reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base at from 0*C to 50*C.
The bases used are, in particular, sodium hydrogen carbonate, potassium carbonate, sodium hydroxide and aqueous sodium hydroxide solutions.
The solvents used are, in particular, acetone, dimethylformamide, toluene, tert-butyl methyl ether, ethyl acetate and methanol.
The compounds of the formula I where X is NRa are advantageously obtained by converting a benzylanilide of the formula IXa to the corresponding benzyl halide of the formula Xa, converting Xa in the presence of a base using a 3—hydroxy(dihydro)pyrazole of the formula III to a compound of the formula I.A and then reacting I.A with a primary or secondary amine of the formula XI to give I.



A in the formula Vila is alkyl (in particular C1-C6—alkyl) or phenyl; Hal in the formula Villa is halogen (in particular chlorine or bromine)•
The reactions of IXa to Xa and of Xa to I.A are carried out in general and in particular under the conditions described above.
The compounds I.A are reacted with the primary or secondary cunines of the formula XIa or Xlb at from 0*C to 100C in an inert solvent or in a solvent mixture.
Suitable solvents are, in particular, water, tert-butyl methyl ether and toluene, or their mixtures. To improve the solubility of the starting materials, it may be advantageous additionally to add one of the following solvents (as solubilizers): tetrahydro-furan, methanol, dimethylformamide and ethylene glycol ether.
The amines XIa and Xlb are customarily employed in an excess of up to 100% based on the compounds X or can be used as solvents. With respect to the yield, it may be advantageous to carry out the reaction under pressure.

where the substituents and the index have the following meanings:
n is 0, 1, 2, 3 or 4, it being possible for the substituents R1 to be different if n is greater than 1;
Ri is nitro, cyano, halogen,
unsubstituted or substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy or

r
in the case where n is 2, additionally is an unsubstituted or substituted bridge bonded to two adjacent ring atoms and containing three to four members from the group consisting of 3 or 4 carbon atoms, 1 to 3 carbon atoms and 1 or 2 nitrogen, oxygen and/or sulfur atoms, this bridge together with the ring to which it is bonded being able to form a partly unsaturated or aromatic radical;

an unsubstituted or substituted, saturated or mono— or diunsaturated ring which, in addition to carbon atoms, can contain one to three of the following heteroatoms as ring members; oxygen, sulfur and nitrogen, or
an unsubstituted or substituted, mono— or binuclear aromatic radical which, in addition to carbon atoms, can contain one to four nitrogen atoms or one or two nitrogen atoms and one oxygen or sulfur atom or one oxygen or sulfur atom as ring members.

f
In particular, intermediates of the formula XII are preferred in the preparation where Y is NHOH and Z is the group Za.
Additionally, intermediates of the formula IX are preferred in the preparation where Y is NO2 and Z is the group Z*.
With respect to the preparation of the compounds I where X is NR*, intermediates of the general formula XIII

are preferred where the substituents R1 and R4 and also the index n have the meanings given at the outset and the substituents W . and A have the following meanings:
W is hydrogen, halogen or Za, and A is alkyl or phenyl.
In particular, compounds XIII are preferred in this case where the substituent W is hydrogen, chlorine, bromine or Z*.
Additionally, those compounds XIII are preferred where the substituent A is C1—C6—alkyl.
In particular, those compounds XIII are also particularly preferred where the substituent A is phenyl.
Equally preferred are those compounds XIII where R^ is hydrogen, methyl or ethyl.
In addition, compounds XIII are preferred where n is 0 or 1.
Particularly preferred compounds XIII are those where the substituents and the index have the following meanings:
n is 0,
W is hydrogen, chlorine, bromine or Za,
R4 is hydrogen, methyl or ethyl and
A is phenyl.





























Table 2
Compounds of the general formula I.l where R4 is methyl, R^x is ethyl and Rxp is a substituent of one line of Table A
Table 3
Compounds of the general formula 1.2 where R4 is methyl, R^x is methyl and Rxp is a substituent of one line of Table A

Table 4
Compounds of the general formula 1.2 where R4 is methyl, R^x is ethyl and Rxp is a substituent of one line of Table A
Table 5
Compounds of the general formula I.l where R4 is methyl, R^X is methoxy and Rxp is a substituent of one line of Table A
Table 6
Compounds of the general formula 1.2 where R4 is methyl, R^X is methoxy, R2 is methoxy and Rxp is a substituent of one line of Table A
Table 7
Compounds of the general formula I.l where R4 is methyl, R5X is methylamino and Rxp is a substituent of one line of Table A

Table 8
Compounds of the general formula 1.2 where R4 is methyl, R^x is methylamino and Rxp is a substituent of one line of Table A
Table 9
Compounds of the general formula 1.3 where R4 is methyl, R^x is methyl, RY is hydrogen, R2 is chlorine and Rxp is a substituent of one line of Table A

Table 10
Compounds of the general formula 1.3 where R4 is methyl, R^x is ethyl, Ry is hydrogen, R2 is chlorine and Rxp is a substituent of one line of Table A
Table 11
Compounds of the general formula 1.3 where R4 is methyl, R^x is methoxy, Ry is hydrogen, R2 is chlorine and Rxp is a substituent of one line of Table A
Table 12
Compounds of the general formula 1.3 where R4 is methyl, R5X is methylamino, Ry is hydrogen, R2 is chlorine and Rxp is a substituent of one line of Table A
Table 13
Compounds of the general formula 1.3 where R4 is methyl, R5x is methyl, Ry is methyl, R2 is hydrogen and Rxp is a substituent of one line of Table A

Table 14
Compounds of the general formula 1.3 where R^ is methyl, R^x is ethyl, Ry is methyl, Rz is hydrogen and R^^p is a substituent of one line of Table A
Table 15
Compounds of the general formula 1.3 where R4 is methyl, R^x is methoxy, Ry is methyl, R4 is hydrogen and Rxp is a substituent of one line of Table A
Table 16
Compounds of the general formula 1.3 where R4 is methyl, R^x is methylamino, Ry is methyl, R1 is hydrogen and Rxp is a substituent of one line of Table A
Table 17
Compounds of the general formula 1.3 where R4 is methyl, R^x is methyl, Ry is trifluoromethyl, R2 is hydrogen and Rxp is a substituent of one line of Table A
Table 18
Compounds of the general formula 1.3 where R4 is methyl, R^X is ethyl, Ry is trifluoromethyl, R2 is hydrogen and Rxp is a substituent of one line of Table A
Table 19
Compounds of the general formula 1.3 where R4 is methyl, R^x is methoxy, Ry is trifluoromethyl, Rzis hydrogen and Rxp is a substituent of one line of Table A
Table 20
Compounds of the general formula 1.3 where R^ is methyl, R^x is methylamino, Ry is trifluoromethyl, R^ is hydrogen and R^^p is a substituent of one line of Table A

Table 21
Compounds of the general formula 1.4 where R5x is methyl and the combination of the substituents R1, Ry, Rz, R3 and R4 is a compound, in each case of one line of Table B

Table 22
Compounds of the general formula 1.4 where R5X is ethyl and the combination of the substituents R1, Ry, R4, R3 and R4 is a compound, in each case of one line of Table B
Table 23
Compounds of the general formula 1.4 where R5X is methoxy and the combination of the substituents Ri, Ry, Rz, R3 and R4 is a compound, in each case of one line of Table B
Table 24
Compounds of the general formula 1.4 where R5x is methylamino and the combination of the substituents R1, Ry, R4, R3 and R^ is a compound, in each case of one line of Table B
Table 25
Compounds of the general formula I.l where R4 is hydrogen, R^X is methyl and Rxp is a substituent of one line of Table A
Table 26
Compounds of the general formula I.l where R^ is hydrogen, R^X is ethyl and Rxp is a substituent of one line of Table A
Table 27
Compounds of the general formula 1.2 where R4 is hydrogen, R^x is methyl and Rxp is a substituent of one line of Table A

Table 28
Compounds of the general formula 1.2 where R4 is hydrogen, R^x is ethyl and Rxp is a substituent of one line of Table A
Table 29
Compounds of the general formula I.l where R4 is hydrogen, R^x is methoxy and Rxp is a substituent of one line of Table A
Table 30
Compounds of the general formula 1.2 where R4 is hydrogen, R^x is methoxy and Rxp is a substituent of one line of Table A
Table 31
Compounds of the general formula I.l where R4 is hydrogen, R^X is methylaunino and Rxp is a substituent of one line of Table A
Table 32
Compounds of the general formula 1.2 where R4 is hydrogen, R^x is methylamino and Rxp is a substituent of one line of Table A
Table 33
Compounds of the general formula 1.3 where R4 is hydrogen, R^x is methyl, RV is hydrogen, Rz is chlorine and Rxp is a substituent of one line of Table A
Table 34
Compounds of the general formula 1.3 where R4 is hydrogen, R^x is ethyl, Ry is hydrogen, Rz is chlorine and Rxp is a substituent of one line of Table A
Table 35
Compounds of the general formula 1.3 where R4 is hydrogen, R^X is methoxy, Ry is hydrogen, R4 is chlorine and Rxp is a substituent of one line of Table A

Table 36
Compounds of the general formula 1.3 where R4 is hydrogen, R^x is methylautiino, Ry is hydrogen, Rz is chlorine and Rxp is a substitu-ent of one line of Table A
Table 37
Compounds of the general formula 1.3 where R4 is hydrogen, R5x is methyl, RV is methyl, R4 is hydrogen and Rxp is a substituent of one line of Table A
Table 38
Compounds of the general formula 1.3 where R4 is hydrogen, R^x is ethyl, Ry is methyl, R4 is hydrogen and Rxp is a substituent of one line of Table A
Table 39
Compounds of the general formula 1.3 where R4 is hydrogen, R5X is methoxy, Ry is methyl, Rz is hydrogen and Rxp is a substituent of one line of Table A
Table 40
Compounds of the general formula 1.3 where R4 is hydrogen, R5X is methylamino, Ry is methyl, Rz is hydrogen and Rxp is a substituent of one line of Table A
Table 41
Compounds of the general formula 1.3 where R4 is hydrogen, R^X is methyl, Ry is trifluoromethyl, R1 is hydrogen and Rxp is a substituent of one line of Table A
Table 42
Compounds of the general formula 1.3 where R4 is hydrogen, R^x is ethyl, Ry is trifluoromethyl, R4 is hydrogen and Rxp is a substituent of one line of Table A

Table 43
Compounds of the general formula 1,3 where R4 is hydrogen, R^x is methoxy, RV is trifluoromethyl, R2 is hydrogen and R^^p is a sub-stituent of one line of Table A
Table 44
Compounds of the general formula 1.3 where R4 is hydrogen, R^X is methylamino, Ry is trifluoromethyl, Rz is hydrogen and R^^p is a substituent of one line of Table A
Table A







































particular from the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes classes.
They are of particular importance for the control of a multiplicity of fungi on various crop plants such as wheat, rye, barley, oats, rice, corn, grass, cotton, soybeans, coffee, sugar cane, grapes, fruit and decorative plants and vegetable plants ' such as cucumbers, beans and cucurbits, and on the seeds of these plants.
The compounds I are specifically suitable for the control of the following plant diseases:
* Erysiphe graminis (powdery mildew) in cereals,
* Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
* Podosphaera leucotricha on apples,
* Uncinula necator on vines,
* Puccinia species on cereals,
* Rhizoctonia species on cotton and grass,
* Ustilago species on cereals and sugar cane,
* Venturia inaegualis (scab) on apples,
* Helminthosporium species on cereals,
* Septoria nodorum on wheat,
* Botrytis cinerea (gray mold) on strawberries, vines,
* Cercospora arachidicola on groundnuts,
* Pseudocercosporella herpotrichoides on wheat, barley,
* Pyricularia oryzae on rice,
* Phytophthora infestans on potatoes and tomatoes,
* Fusarium and Verticillium species on various plants,
* Plasmopara viticola on vines,
* Alternaria species on vegetables and fruit.
The novel compounds can also be employed in the protection of materials, eg. for the protection of wood, paper and textiles, eg. against Paecilomyces variotii.
They can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes or granules. The use forms here depend on the particular intended use; in each case they should if possible guarantee the finest dispersion of the active compounds.
The formulations are prepared in a known manner, eg. by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants, where if water is used as a

particular from the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes classes.
They are of particular importance for the control of a multi-plicity of fungi on various crop plants such as wheat, rye, barley, oats, rice, corn, grass, cotton, soybeans, coffee, sugar cane, grapes, fruit and decorative plants and vegetable plants such as cucumbers, beans and cucurbits, and on the seeds of these plants.
The compounds I are specifically suitable for the control of the following plant diseases:
* Erysiphe graminis (powdery mildew) in cereals,
* Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
* Podosphaera leucotricha on apples,
* Uncinula necator on vines,
* Puccinia species on cereals,
* Rhizoctonia species on cotton and grass,
* Ustilago species on cereals and sugar cane,
* Venturia inaegualis (scab) on apples,
* Helminthosporium species on cereals,
* Septoria nodorum on wheat,
* Botrytis cinerea (gray mold) on strawberries, vines,
* Cercospora arachidicola on groundnuts,
* Pseudocercosporella herpotrichoides on wheat, barley,
* Pyricularia oryzae on rice,
* Phytophthora infestans on potatoes and tomatoes,
* Fusarium and Verticillium species on various plants,
* Plasmopara viticola on vines,
* Alternaria species on vegetables and fruit.
The novel compounds can also be employed in the protection of materials, eg. for the protection of wood, paper and textiles, eg. against Paecilomyces variotii.
They can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes or granules. The use forms here depend on the particular intended use; in each case they should if possible guarantee the finest dispersion of the active compounds.
The formulations are prepared in a known manner, eg. by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants, where if water is used as a

diluent other organic solvents can also be used as auxiliary solvents •
Suitable auxiliaries for this purpose are mainly:
solvents such as aromatics (eg. xylene), chlorinated aromatics (eg. chlorobenzenes), paraffins (eg. petroleum fractions), alcohols (eg• methanol, butanol), ketones (eg. cyclohexanone), amines (eg. ethanolamine, dimethylformamide) and water;
carriers such as ground natural minerals (eg. kaolins, aluminas, talc, chalk) and ground synthetic minerals (eg. highly disperse silica, silicates),
emulsifiers such as nonionic and anionic emulsifiers (eg. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and - dispersants such as lignin-sulfite waste liquors and methyl-cellulose.
Suitable surface-active substances are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, eg. lignosulfonic, phenolsulfonic, naphthalenesulfonic and dibutyl-naphthalenesulfonic acid, and also of fatty acids, alkyl— and alkylarylsulfonates, alkyl—, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa->, hepta— and octadeca-nols, and also of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl—, octyl— or nonylphenol, alkylphenol or tributylphenylpolyglycol ethers, alkylaryl poly-ether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene or polyoxy-propylenealkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.
Aqueous use forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by addition of water. To prepare emulsions, pastes or oil dispersions, the substrates can be homogenized in water as such or dissolved in an oil or solvent, by means of wetting agents, adhesives, dispersants or emulsifiers. However, concentrates consisting of active substance, wetting agent, adhesive, dispersant or emulsifier and possibly solvent or oil can also be prepared which are suitable for dilution with water.

Powder, scattering and dusting compositions can be prepared by mixing or joint grinding of the active substances with a solid carrier.
Granules, eg. coated, impregnated and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
Solid carriers are mineral earths such as silica gel, silicic acids, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesiiim oxide, ground synthetic materials, fertilizers, such as aunmonium sulfate, euximonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flour, tree bark meal, wood meal and nutshell meal, cellulose powder or other solid carriers. The active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges.
Very generally, the compositions contain from 0.0001 to 95% by weight of active compound.
Formulations containing more than 95% by weight of active compound can be applied highly successfully in the ultra-low volume process (ULV), it even being possible to use the active compound without additives.
For use as fungicides, concentrations of from 0.01 to 95% by weight, preferably of from 0.5 to 90% by weight, of active compound are recommended. For use as insecticides, formulations containing from 0.0001 to 10% by weight, preferably from 0.01 to 1% by weight, are suitable.
The active compounds are normally employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum) .
Exeunples of such preparations are:
I. a solution of 90 parts by weight of a compound I according to the invention and 10 parts by weight of N—methyl— a—pyrrolidone, which is suitable for application in the form of very small drops;
II. a solution of 20 parts by weight of a compound I according to the invention in a mixture of 80 parts by weight of alkylated benzene, 10 parts by weight of the addition product of from 8 to 10 mol of ethylene oxide to 1 mol of

oleic acid N—monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 5 parts by weight of the addition product of 40 mol of ethylene oxide to 1 mol of castor oil; a dispersion is obtained by finely dispersing the formulation in water.
III. a solution of 20 parts by weight of a compound I according to the invention in a mixture of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 7 mol of ethylene oxide to 1 mol of isooctylphenol and 10 parts by weight of the addition product of 40 mol of ethylene oxide to 1 mol of castor oil; a dispersion is obtained by finely dispersing the formulation in water.
IV. an aqueous dispersion of 20 parts by weight of a compound I according to the invention in a mixture of 25 parts by weight of cyclohexanone, 65 parts by weight of a petroleum fraction of boiling point from 210 to 280*C and 10 parts by weight of the addition product of 40 mol of ethylene oxide to 1 mol of castor oil; a dispersion is obtained by finely dispersing the formulation in water.
V. a mixture, ground in a haunmer mill, of 20 parts by weight of a compound I according to the invention, 3 parts by weight of the sodium salt of diisobutylnaphthalene—
a—sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel; a spray mixture is obtained by finely dispersing the mixture in water;
VI. an intimate mixture of 3 parts by weight of a compound I according to the invention and 97 parts by weight of finely divided kaolin; this dusting composition contains 3% by weight of active compound;
VII. an intimate mixture of 30 parts by weight of a compound I according to the invention, 92 parts by weight of powdered silica gel and 8 parts by weight of liquid paraffin which has been sprayed onto the surface of this silica gel; this preparation gives the active compound a good adhesion;
VIII. a stable aqueous dispersion of 40 parts by weight of a compound I according to the invention, 10 parts by weight of the sodium salt of a phenolsulfonic acid/urea/ formaldehyde condensate, 2 parts by weight of silica gel

and 48 parts by weight of water, which can be further diluted;
IX. a stable oily dispersion of 20 parts by weight of a compound I according to the invention, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid/urea/ formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil;
X. a mixture, ground in a hammer mill, of 10 parts by weight of a compound I according to the invention, 4 parts by weight of the sodium salt of diisobutylnaphthalene-
a—sulfonic acid, 20 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor, 38 parts by weight of silica gel and 38 parts by weight of kaolin. By finely dispersing the mixture in 10,000 parts by weight of water, a spray mixture is obtained which contains 0.1% by weight of the active compound.
The compounds I are applied by treating the fungi or the seeds, plants, materials or the soil to be protected from fungal attack with a fungicidally active amount of the active compounds.
They are applied before or after the infection of the materials, plants or seeds by the fungi.
Depending on the type of effect desired, the application rates are from 0.02 to 3 kg of active compound per ha, preferably from 0.1 to 1 kg/ha.
In seed treatment, amounts of active compound of from 0.001 to 50 g, preferably from 0.01 to 10 g, per kilogram of seed are in general needed.
The application rate of active compound for controlling pests under outdoor conditions is from 0.02 to 10, preferably from 0.1 to 2.0 kg/ha.
The compounds I, on their own or in combination with herbicides or fungicides, can also be applied jointly mixed with further crop protection agents, for example with growth regulators or with agents for controlling pests or bacteria. Of interest is also the miscibility with fertilizers or with mineral salt







(1.67 mol) of dimethyl sulfate. The reaction mixture warms to about 40*C during the course of this. The reaction mixture is stirred overnight at room temperature and then filtered through kieselguhr. The filtrate is washed with NH3 soln. and water, dried over MgS04 and concentrated. The residue crystallizes and is stirred with hexane. 324 g (75%) of the title compound are obtained as colorless solid.
iH-NMR(CDCl3 ; 5 in ppm): 7.1 - 7.6 (m, 9H, phenyl); 3.8 (s,3H,OCH3); 2.4 (s, 3H, CH3)
c) Phenyl N-Methoxy-N—(2—bromomethylphenyl)carbamate
A mixture of 324 g (1.3 mol) of phenyl N-methoxy-N—(2—me-thylphenyl)carbamate (Example 2b), 258 g (1.45 mol) of N—bromosuccinimide and 1 g of azoisobutyronitrile in 1 1 of CCI4 is irradiated using a 300 W UV lamp for about 6 hours, whereby the reaction mixture is heated to boiling. 13 g of N—bromosuccinimide are then added and the mixture is irradiated for a further 8 hours. It is then cooled to room temperature and the precipitated succinimide is filtered off. The organic phase is then extracted with water, dried over MgS04 and concentrated. The residue crystallizes and is stirred with cyclohexane. 300 g (68%) of the title compound are obtained as a beige solid.
iH-NMR(CDCl3 ; 8 in ppm): 7.0 - 7.6 (m, 9H, phenyl) ;4.65 (s,2H,CH2-Br); 3.9 (s, 3H, OCH3)
d) Phenyl N-Methoxy-N-(2—((N'—pyrazinyl)pyrazolyl-
3 '—oxymethyl)phenyl)carbamate
A mixture of 3.1 g (9.2 mmol) of phenyl
N—methoxy-N—(2-bromomethylphenyl) carbamate (Example 2c), 1.5 g (9.2 mmol) of N-pyrazinyl-3—hydroxypyrazole and 2 g (14.5 mmol) of K2CO3 in 10 ml of DMF is stirred at room temperature overnight. The reaction mixture is then diluted with water and extracted three times with methyl t—butyl ether. The combined organic phases are extracted with water, dried over MgS04 and concentrated. The residue is purified by column chromatography using cyclohexane/ethyl acetate mixtures. 2.4 g (63%) of the title compound are obtained as a yellow oil.

iH-NMR(CDCl3; 8 in ppm): 9.15 (d, IH, pyrazolyl); 8.3 (m,
3H, pyrazinyl); 7.7 (m, IH, phenyl); 7.1-7.6 (m, 8H,
phenyl); 6.0 (d, IH, pyrazolyl); 5.5 (s, 2H, OCH2); 3.85
(s, 3H, OCH3)
e) N-Methyl-N'-methoxy-N'-{2-((N^-pyrazinyl)pyrazolyl-3"-oxymethyl)phenyl)urea
A mixture of 1.9 g (4.6 mmol) of phenyl N-methoxy-N—(2—((N'—pyrazinyl)pyrazolyl-3'—oxyInet:hyl)-phenyl)carb^UQate (Example 2d) and 15 ml of aqueous methylamine solution (40% strength) is stirred overnight at room temperature. Water is then added and the aqueous phase is extracted twice with methylene chloride. The combined organic phases are washed with water, dried over MgS04 and concentrated. The residue crystallizes and is stirred with cyclohexane. 0.9 g (55%) of the title compound are obtained as a beige solid.
iH-NMR(CDCl3; 5 in ppm): 9.15 (d, IH, pyrazolyl); 8.3 (m, 3H, pyrazinyl); 7.6 (m, IH, phenyl); 7.35 (m, 3H, phenyl); 6.0 (m, 2H, NH, pyrazinyl); 5.45 (s, 2H, OCH2); 3.7 (s, 3H, OCH3); 2.9 (d, 3H, NCH3)












Examples of the action against harmful fungi
It was possible to show the fungicidal action of the compounds of the formula I by the following tests:
The active compounds were prepared as a 20% strength emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil® LN (Lutensol® AP6, wetting agent having emulsifier and dispersant action based on ethoxylated alkylphenols) and 10% by weight Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols) and diluted with water according to the concentration desired.
Activity against Puccinia recondita
Leaves of wheat seedlings (Kanzler variety) were dusted with spores of brown rust (Puccinia recondita). The plants treated in this way were incubated for 24 h at 20—22*C and a relative atmospheric humidity of 90—95% and then treated with the aqueous active compound preparation (63 ppm of active compound). After a further 8 days at 20—22*C and 65—70% relative atmospheric humidity, the extent of fungal development was determined. Assessment was carried out visually.
In this test, the plants treated with the compounds 2—6, 8, 11—15, 18-20, 22, 23 and 26-29 according to the invention showed 5% or less attack, while the plants treated with a compound (Table 7, Example No. 8) disclosed in WO-A 93/15,046 were attacked to 25%. The untreated plants were attacked to 70%.
In a corresponding experiment, the plants treated with 250 ppm of compound No. 1 according to the invention showed an attack of 3% while plants which were treated with 250 ppm of a compound (Table 7, No. 21) disclosed in WO-A 93/15,046 were attacked to 70%, like the untreated plants.
In a corresponding experiment, the plants treated with 250 ppm of compound Nos. 1-8, 10-16, 18-20, 22, 23, 27-30, 34, 36-38, 41, 47 and 51-56 according to the invention showed an attack of 15% and less while plants which were treated with 250 ppm of a compound (Table 7, No. 21) disclosed in WO-A 93/15,046 were attacked to 70%, like the untreated plants.

Activity against Plasmopara viticola
Potted vines (variety: Muller Thurgau) were sprayed with the active compound preparation until dripping wet. After 8 days, the plants were sprayed with a zoospore suspension of the fungus Plasmopara viticola and kept at high atmospheric humidity for 5 days at 20—30*C. Before assessment, the plants were then kept at high atmospheric humidity for 16 h. Assessment was carried out visually.
In this test, the plants treated with the compounds 1—3, 5, 6, 13, 15 and 29 according to the invention showed an attack of 10% or less, while the plants treated with a compound (Table 7, Example No. 8) disclosed in WO-A 39/15,046 were attacked to 25%. The untreated plants were attacked to 70%.
Activity against Botrytis cinerea (gray mould)
Paprika seedlings (variety: Neusiedler Ideal Elite) having 4—5 leaves were sprayed until dripping wet with the active compound preparation (application rate: 500 ppm). After drying off, the plants were sprayed with a conidia suspension of the fungus Botrytis cinerea and kept for 5 days at 22—24*C at high atmospheric humidity. Assessment was carried out visually.
In this test, the plants treated with compound No. 1 according to the invention showed no attack, while the plants treated with a compound (Table 7, No. 21) disclosed in WO—A 93/15,046 were attacked to 70%. The untreated plants were attacked to 80%.
Activity against Erysiphe grsminis var. tritici
Leaves of wheat seedlings (Friihgold variety) were first treated with the aqueous preparation (application rate 250 ppm) of the active compounds. After about 24 h, the plants were dusted with spores of wheat mildew {Erysiphe graminis var. tritici). The plants treated in this way were then incubated for 7 days at 20—22*C and a relative atmospheric humidity of 75—80%. The extent of fungal development was then determined.
In this test, the plants treated with compound No. 1 according to the invention showed no attack, while the plants treated with a compound (Table 7, No. 21) disclosed in WO—A 93/15,046 were attacked to 25%. The untreated plants were attacked to 70%.

In a corresponding experiment/ the plants trearea wi-cn ZDU ppm uj. compound Nos. 1-7, 10, 13, 14, 18-20, 27-29, 34, 36, 41, 50 and 56 according to the invention showed an attack of 15% or less, while plants which were treated with 250 ppm of a compound (Table 7, No. 21) disclosed in WO-A 93/15,046 were attacked to 25%. The untreated plants were attacked to 70%.
In a corresponding experiment, the plants treated with 63 ppm of compound Nos. 1-7, 10, 13, 14, 18-20, 27-29, 34, 36, 41, 50 and 56 according to the invention showed an attack of 15% or less, while plants which were treated with 250 ppm of a compound (Table 7, No. 21) disclosed in WO-A 93/15,046 were attacked to 40%. The untreated plants were attacked to 70%.
In a corresponding experiment, the plants treated with 16 ppm of compound Nos. 1-7, 10, 13, 14, 18-20, 27-29, 34, 36, 41, 50 and 56 according to the invention showed an attack of 25% or less, while plants which were treated with 250 ppm of a compound (Table 7, No. 21) disclosed in WO-A 93/15,046 were attacked to 65%. The untreated plants were attacked to 70%.
Exeunples of the action against animal pests
It was possible to show the action of the compounds of the general formula I against animal pests by the following tests: The active compounds were prepared
and diluted with acetone in the case of a) or with water in the case of b) according to the desired concentration.
After conclusion of the tests, the lowest concentration at which the compounds still caused an 80—100% inhibition or mortality in comparison with untreated control tests was determined in each case (activity threshold or minimum concentration).





X is a direct bond, 0 or NRa;
RA is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl;
R1 is ni'Cro, cyano, halogen,
unsubstitutad or substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy or
in the case where n is 2, additionally is an unsubsti-tuted or substituted bridge bonded to two adjacent ring atoms and containing three to four mezobers from the group consisting of 3 or 4 carbon atc»s, 1 to 3 carbon atoms and 1 or 2 nitrogen, oxygen and/or sulfur atoms, this bridge together with the ring to which it is bonded being able to form a partly unsaturated or aromatic radical;
R2 is nitro, cyano, halogen, C1—C4—alkyl, C1—C4—haloalkyl, C1—C4—alkoxy, 01-C4—alkylthio or 01—04—alkoxycarbonyl;
R3 is unsubstituted or substituted alkyl, alkenyl or alkynyl;

an unsubstltuted or substituted, saturated or mono— or diunsaturated ring which, in addition to carbon atoms, can contain one to three of the following heteroatoms as ring members: oxygen, sulfur and nitrogen, or an unsubstltuted or substituted, mono-- or binuclear aromatic radical which, in addition to carbon atoms, can contain one to four nitrogen atoms or one or two nitrogen atoms and one oxygen or sulfur atom or one oxygen or sulfur atom as ring members;
R4 is hydrogen,
unsxibstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkylcarbonyl or alkoxy-carbonyl;
R5 is alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl, or
in the case where X is MR9, additionally is hydrogen.






then converting IX t;o the corresponding benzyl halide of -the formula X

where Hal is a halogen atom, and converting X to I in the presence of a base using a 3-4iydroxy(dihydro)pyrazole of the formula III as claimed in claim 2.
4. The process for preparing 2-[(dihydro)pyrazol-3'-yloxymethylene]anilides of the formula I

as claimed in claim 1, where R4 is unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkylcarbonyl or alkoxycarbonyl and X is a direct bond or oxygen, which comprises reacting a corresponding compound of the formula I where R4 is hydrogen
with a compound of the formula VIII as claimed in claim 3.
5. The process for preparing 2-[(dihydro)pyrazol-3'-yloxymethylene]anilides of the formula I

as claimed in claim 1, where X is NRa which comprises converting a benzylanilida of the formula IXa


whore A Is alkyl or phanyl to the corresponding benzyl hallde of the formula Xa

where Hal Is a halogen atom, converting Xa in the presence of a base using a 3—hydroxy(dihydro)pyrazole of the formula III as in claim 2 to a compound of the formula I.A

and then reacting I.A with an amine of the formula XI
H2NRa HNRaR5
(XIa) (Xlb)
to give I. 6. An intermediate of the formula XII

where the substituents and the index have the following meanings:



heteroatoms as ring members: oxygen, sulfur and nitrogen, or
an unsubstituted or substituted, mono- or binuclear aromatic radical which, in addition to carbon atoms., can contain one to four nitrogen atoms or one or two nitrogen atoms and one oxygen or sulfur atom or one oxygen or sulfur atom as ring members.
7. A composition suitable for controlling animal pests or harmful fungi, containing a solid or liquid carrier and a compound of the general formula I as claimed in claim !•
8 . An intermediate of the general formula XIII

where the substituents R^ and R^ and also the index n have the meanings given in claim 1 and the substituents W and A have the following meanings:
W is hydrogen or halogen, and A is alkyl or phenyl.
9. The compounds I as claimed in claim 1. for preparing
a composition suitable for controlling animal pests or harmful fungi.
10. A composition for controlling animal pests or harmful fungi comprising a
compound I as claimed in claim 1.


Documents:

1679-MAS-1995 OTHER PATENT DOCUMENT 19-05-2011.pdf

1679-mas-1995 form-19.pdf

1679-mas-1995 form-4.pdf

1679-MAS-1995 OTHER DOCUMENT 01-09-2009.pdf

1679-mas-1995 others.pdf

1679-mas-1995 petition.pdf

1679-mas-1995- abstract.pdf

1679-mas-1995- claims.pdf

1679-mas-1995- correspondence others.pdf

1679-mas-1995- correspondence po.pdf

1679-mas-1995- descripition complete.pdf

1679-mas-1995- form 1.pdf

1679-mas-1995- form 26.pdf

1679-mas-1995- form 3.pdf

1679-mas-1995- other documents.pdf


Patent Number 242743
Indian Patent Application Number 1679/MAS/1995
PG Journal Number 37/2010
Publication Date 10-Sep-2010
Grant Date 08-Sep-2010
Date of Filing 19-Dec-1995
Name of Patentee BASF SE
Applicant Address D-67056 LUDWIGSHAFEN, GERMANY
Inventors:
# Inventor's Name Inventor's Address
1 DR. HUBERT SAUTER, NECKARPROMENADE 20, 68167 MANNHEIM
2 DR.REINHARD KIRSTGE ERKENBRECHSTR.23, 67434 NEUSTADT
3 DR. KLAUS OBERDOR, BIENENSTR 3, 69117 HEIDEBERG
4 DR. FRANZ ROHL, SEBASTIAN-KNEIPP-STR 17, 67105 SCHIFFERSTADT
5 DR. NORBEGOTZ, SCHOFERSTR 25, 67547 WORMS,
6 DR. GISEL LORENZ ERLENWEG 13, 67434 HAMBACH
7 DR. EHERHARD AMMERMANN, VON-GAGERN-STR. 2, 64646 HEPPENHEIM
8 DR.BERND MULLER JEAN-GANSS-STRASSE 21, 67227 FRANKENTHAL
9 DR.HARTMANN KONIG BLUMENSTRASSE 16, 69115 HEIDELBERT
PCT International Classification Number A01N043/56
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA