AU663214B2

AU663214B2 - N-methylamides, their preparation and intermediates therefor and control of pests therewith

Info

Publication number: AU663214B2
Application number: AU44918/93A
Authority: AU
Inventors: Eberhard Ammermann; Herbert Bayer; Remy Benoit; Gisela Lorenz; Klaus Oberdorf; Franz Roehl; Hubert Sauter; Horst Wingert
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1992-08-29
Filing date: 1993-08-27
Publication date: 1995-09-28
Anticipated expiration: 2013-08-27
Also published as: HUT66127A; PL174670B1; DK0585751T3; JPH06199765A; SK92693A3; HU9302444D0; JP3490741B2; ES2094432T3; DE59304268D1; SK281650B6; ATE144494T1; PL300213A1; IL106765A0; CA2104806A1; ZA936299B; CZ293802B6; GR3021735T3; EP0585751A1; IL106765A; NZ248522A

Abstract

N-methylamides of the formula I <IMAGE> in which R denotes alkyl or cyclopropyl, the radicals A denote hydrogen, halogen, cyano, nitro, alkyl, cycloalkyl, OR<1>, cycloalkyloxy, haloalkyl, haloalkyloxy, alkenyl, alkenyloxy, alkynyl, alkoxyalkyl, cyanoalkyl, nitroalkyl, phenyl, phenoxy, C(O)R<1>, CO2R<1>, C(O)NR<1>R<2>, C(S)NR<1>R<2>, NR<1>R <2>, NR<1>C(O)R<2>, NR<1>CO2R<2>, OC(O)R<1>, SR<1>, S(O)R<1>, S(O)2R<1>, the groups -C(R<1>)=NR<2>, -N=CR <1>R<2>, <IMAGE> where the radicals R<1>, R<2> and R<3> denote hydrogen or C1-C6-alkyl or X denotes S, O and NR<3> and n denotes the numbers 0 or 1, or two of the groups Am in adjacent positions together denote the group -CH=CH-CH=CH and m represents the numbers 1, 2 or 3, and fungicides containing these compounds.

Description

M-'UMu I 2&V91~ PRogulalon 3,2(2)

AUSTRALIA

Patents Act 1990 663214

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT

S.

55.5*4 S. S

S

C S *5 S

S.

S

*SSS**

S S 4 App',cation Number: Lodged: Invention Title: N-METHYLAMIDES, THEIR PREPARATION AND INTERMEDIATES THEREFOR AND CONTROL OF PESTS THEREWITH The following statement is a full description of this Invention, Including the best method of performing it known to us SBASF Aktiengesellsehaft O.Z. 0050/43498 N-Methylamides, their preparation and intermediates therefor and control of pests therewith The present invention relates to novel N-methylamides, processes and intermediates for their preparation and processes for controlling pests, in particular fungi, insects, nematodes and spider mites, using these compounds.

It is known to use substituted N-methylamides as pesticides (cf.

EP 463 488, EP 398 692). However, their action is unsatisfactory.

It has surprisingly been found that N-methylamides of the general formula I nN Am NmW OCH 3

N-

CH

3

H

have an excellent fungicidal, insecticidal, nematicidal and aca- 25 ricidal action which is better than that of the known N-methylamides.

The fungicidal action is preferred.

The radicals mentioned under the general formula I can have, for example, the following meanings:

R

can be C1-C3-alkyl (eg. methyl, ethyl, n- or isopropyl) or cyclo- 35 propyl,

A

can be i-entical or different and is hydrogen, halogen (eg. fluorine, chlorine, bromine or iodine), cyano, nitro, Ci-C 6 -alkyl (eg.

methyl, ethyl, n- or isopropyl, iso-, sec- or tert-butyl, npentyl, neopentyl, tert-pentyl or hexyl), or C3-C6-cycloalkyl (eg. cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), EBASY Aktiengesellschaft O.Z. 0050/43498 2

OR

1 (eg. hydroxyl, methoxy, ethoxy, n-propoxy, isopropoxy, iso-, sec- or tert-butoxy, n-pentoxy, tert-pentoxy, neopentoxy or nhexoKy),

C

3

-C

6 -cycloalkoxy (eg. cyclopropoxy, cyclobutoxy, cyclopentoxy or cyclohexoxy), Cl-C 6 -haloalkyl (eg. trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, fluorodichioromethyl, difluorochlorornethyl, chioromethyl, dichioromethyl, trichioroinethyl, 2 chioroethyl, 2,2,2-trichioroethyl, pentachioroethyl or 3-chloro-2-methylprop-2-yl), Cl-C 6 -haloalkoxy (eg. difluoromethoxy, trifluoromethoxy, pentafluoroethoxy, 1,1, 2,2-tetrafluoroethoxy or 2, 2,2-trifluoroethoxy),

C

2

-C

6 -alkeny. (vinyl, l-propen-1-yl, 2-propenyl, 2-butenyl, 1-rethyl-2-propenyl, ally., but-2-en-2-yl),

C

2

-C

6 -alkenyloxy (eg. vinyloxy or allyloxy),

C

2 -Cs--alkynyl (ethynyl, 1-propynyl or 3-propj~nyl),

CI-C

6 -alkoxy-C 1

-C

6 -alkyl (eg. methoxymethyl, etihoxymethyl, dimethoxymethyl, l,1-dimethoxyeth-1-yl), n- or isopropoxynethyl, n-, o iso-, sec- or tert-butoxymethyl, 1-niethoxy-2-methylprop-2-yl, 2-methoxyprop-2-yl, 2-ethoxyprop-2-yl, 2-n- or isopropoxyprop-2-yl, iso-, sec- or tert-butoxyprop-2-yl), 0 *0* o o cyano-Cl-C 6 -alkyl (eg. cyanomethyl, l-cyano-2-methylprop-2-yl or 2-cyanoethyl), nitro-C 1

-C

6 -alkyl (eg. nitromethyl) phenyl or phenoxy, C(O)RI (eg. formyl, acetyl, propionyl, butyryl, isobutyryl or pivaloyl), C0 2

R

1 (eg. hydroxycarbonyl, methoxycarbonyl, ethoxycarbonyl, or isopropoxycarbonyl, iso-, sec- and tert-butoxycarbonyl),

C(O)NR

1

R

2 (eg. aminocarbonyl, N-methylaminocarbonyl, dimethylaminocarbonyl or diethylaminocarbonyl), BASF Aktiengaesellchaft O.Z. 0050/43498 3 C NR 1

R

2 (eg. amino thiocarbonyl, N-methylaxninothiocarbonyl or N, N-cimethylaminothiocarbonyl),

NR'R

2 (eg. amino, N-methylamino, N-ethylamino, N-isopropylamino, N-n-propylamino, N-n-butylamTino, N-sec-butylanino, N-tert-butylamino, N-isobutylamino or N,N-dimethylamino),

NR

1 C (O)R 2 (eg. N-acylamino, N-methyl-N-acylamino or N-athyl-N-acylamino),

NR

1

CO

2

R

2 (eq. N-carboxymethylarnine or N-methyl-N-carboxymethylamine), OCCO)R' teg. OC(O)methyl, OC(O)Gthyl, OC(O)n-propyl, OCO)i-propyl, OCt')n-butyl or OC(O)tert-butyl),

SR

1 (eg. S-H, S-methyl, S-ethyl, S-n-propyl, S-i-propyl, S-:d-butyl, S-sec-butyl, S-isobutyl, S-tert-butyl, S-n-penty1 or S-n-

S(O)R

1 (eq. 5(O)-methyl, S(O)-ethyl or. S(O)n-propyl, S0 2

R

1 (eg. S0 2 -methyl Or S0 2 -ethyl), -C(Rl)-NR 2 (eg. -CH=NH, -CH=N-methyl, -CH=N-ethyl, -C(CH3 =NH, -C (CH3) =NCH' 3

-N=CR

1

R

2 (eg. -N=C (CH3) 2 -N=C (CH 3 (ethyl)) C NOR I .2 3(eg. methoxyiminomethyl, ethoxyiminomethyl, n-propoxyiminomethyl, n-butoxyiminomethyl, methoxyimino-l-ethyl, ethoxyimino-l-ethyl, n-propoxyimino-l-ethyl, n-butoxyimino-1-ethyl, i-propoxyimino-l-ethyl, sec-, iso- or tert-butoxyimino-l-ethyl, n-pentoxyimino-l-ethyl, n-hexoxyimino--1-ethyl,-C (OMe) =NOMe, -C(SMe)=NOMe, 0-C (NH 2 =NOMe, -c (NMe 2 =NQMe, -C (NHMe) =NOMe, -C (QEt) ,.-NOEt, C(5.:e)=NOEt), with the exception of compounds of the formula I in which R is methyl and Am is 2-chioro, 3-chioro, 4-chioro, 2,3,4-trichloro, 2-methyl, 4-methyl, 3-bromo, 4-nitro or hydrogen and with the exception of compounds of the for- 4mula I in which R is cyclopropyl and Am is hydrogen, 4-chioro, 4-tert-butyl or 4-methoxy.

The invention also relates to compounds of the formrula Ia ,RASP AktiengesellschaftOZ.00/38 O.Z. 0050/43498 R A 1

CH

3

CH

3 where p 0* p.

R is methyl, ethyl, n-propyl or isopropyl, Al, A 2

A

3

A

4 and As are 4,dentical or different and are hydrogen, halogen, cyano, nitro, CI-C 6 -alkyl, 0 3

-C

6 -cycloalkyl, OR 1 C3-C 6 -cycloalkoxy, Cl-C6-haloalkcyl, Cl-C6-haloalkoxy, C 2

-C

6 -alkenyl, C2-C 6 -alkenyloxy, C2-C6-alkynyl, Cl-C 6 -alkoxy-Cl-C-alkyl, cyano-CI-C 6 -a'.kyl, nitro-C 1

C

6 -alkyl, phenyl, phenoxy, C R 1

CO

2

R

1

C(O)NR

1

R

2

C(S)NR'R

2

NR

1

R

2

NR

1

C(O)R

2

NR

1

CO

2

R

2

OC(O)R

1

SR

1

S(O)

2 the groups -C =NR 2

-N=CR

1

R

2 -CN OR' the radicals RI, R 2 and R.

3 independently of one another are 3hydrogen or Ci-C 6 -alkyl and X is S, 0 or NR 3 and n is 0 or 1o or two of the g~joups Al to A 5 in adjacent positions are the group

CH=CH-CH=CH-

the proviso that tot oro hesbttet ltoA r yrga a) two to fore of the substituents Al to A 5 are hydrogeni n of the substituents A 1 to A 5 is Cl, Br, NO 2 or CH 3 c) one of the halogen atoms is F or Br if A 2

+A

4 or Al+A 2

+A

3 are simultaneously halogen.

4Preferred substituents for R are methyl anxd ethyl, in particular methyl, and for A or Al to As are hydrogen, fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, cyano, methoxy, ethoxy, isopropoxy, tert-butoxy, tert-pentoxy, me- ,BASF Aktiengesellschaft O.Z. 0050/43498 thoxymethyl, 2-methoxyprop-2-yl, trifluoromethyl, 1,1,2,2tetrafluoroethyl, 1-chloro-2-methylprop-2-yl and trifluoromethoxy.

Preferred compounds are those whose substituents A other than hydrogen are in the positions A 2

A

3 or A 4 Preferred compounds in this case are those which result if the subs,tituents other than hydrogen represent the following substition pattern.

a) A 2 (or A 4 t H; other substituents H b) A 3 0 H; all other substituents H c) A 2 and A 3 (or A 3 and A 4 H; all other substituents H d) A 2 and A 4 H; all other substituents H e) A 2 and A 3 and A 4 H; all other substituents H (e means: other than) Particularly preferred substitution patterns are those with the substituents A 2

A

3 and A 4 which are given above as preferred.

On account of the C=N double bonds, the novel compounds of the general formula I can be obtained as E/Z isomer mixtures. These can be separated into the individual components in conventional manner, for example by crystallization or chromatography. Both S 25 the individual isomeric compounds and their mixtures are covered by the invention and can be used as pesticides. As a rule, however, the compounds according to the invention are mainly obtained in the E) configuration. These isomers are also preferred with respect to their action.

.BASF Aktiengesellochaft O.Z. 0050/43498

R

'N Am Formula I, E)-configuration

HNCH

3 The novel compounds of the formula I can be pie, as follows: prepared, for exam-

NH

2

CH

3 .r 5555

S*

S

Starting from the compounds of the formula Z, where X OH, Cl or 25 0(Cl-C4-alkyl) [disclosed in EP 463 488, 472 300 and 426 460], the monomethylamides I according to the invention can be obtained analogously to methods known from the literature by reaction with methylamina (cf. Organikum; 16th edition (1985) p. 408 et seq).

30 A particularly advantageous method of preparing the compounds I is to react 0-benzylhydroxylamine 3 with the phenylketones A (cf.

D. Otzanak, J. Chem. Soc., Chem. Commun. 1986, 903). The intermediate 3 required for this can surprisingly be prepared particularly smoothly and advantageously in a simple reaction by triple aminolysis of 3l (with methylamine).

This one-step reaction procedure 3a avoids the conventional more involved and more elaborate two-step procedure, eg. setting free the O-benzylhydroxylamine group from the phthalimide protective group with the aid of hydrazinolysis and beforehand or subsequently converting the methyl ester group to the methylamide.

The high yields of this reaction are surprising, although normally the optimum conditions are very different on the one hand for the aminolysis o. a methyl ester to the methylamide and on the other hand for setting free an 0-benzylhydroxylamine from the corresponding 0-benzylhydroxyphthalimide.

,BASP' AktiengesellschaftO..05/3 8 O.Z. 0050/43498

NNH

2

T

N

CH

3

H

NII

2 CH3 S. S S S

S.

S

245 The phenylketones I are known or can be prepared analogously to known processes (Houben-Weyl, Vol. 7/2a and 7/3a).

The novel Compounds of the formula I are also obtained by reacting a monomethylamide benzyl compound in which L is a leaving group (eg. bromine, chlorine, iodine, mesylate, tosylate or triflate) eg. EPS 398 692 and 463 488), with an oxime of the formula k~ eg. Houben-Weyl, Vol. 10/1, p. 1186 et seq).

0.

go* I 010N 1% H

CH

3 The oximes k~ are known or can be prepared by known processes (cf.

Houben-Weyl, Vol. 10/4; J. Med. Chem. a5, (1983) 1360).

,BASF Aktiengesellschaft

V

O.Z. 0050/43498 **to 00 t o.

to The novel compounds of the formula I can furthermore be prepared by reacting the benzyl alcohol 2 with oximes in conventional manner (cf. J. Jurczak, Synthesis, 1976, 682).

OH

O 6 I O N OCH3

N

CH3 2.

Alternatively, for this purpose the ketoamides can be reacted in conventional manner with methoxylamine (hydrochloride) to give the novel compounds I eg. DE 3623921).

A^ R N

H

2 NOMe HC1 Am I ,N H 8 30 CH 3 The ketoamides 8 themselves can be obtained, for example, from the ketoesters 9 by aminolysis, the ketoesters 9 themselves being accessible either by Pinner reaction from benzoyl cyanides 1i or by reaction of oximes with benzyl compounds 11.

BAST' Aktiengesellschaft O.Z. 0050/43498 9 0 Zm z P 0/ z 0/0 0 0 veto 406#6.

BASF Aktiengesellocbaft O.Z. 0050/43498 Suitable further starting materials for the preparation of the ketoamides or of the ketoesters 9 are aryl halides 12. (Hal chlorine, bromine or iodine). These can be converted into the corresponding organometal by metallization (eg. with magnesium, methylma:nesium bromide, sodium or n-butyllithium), which can then be reacted with oxalic acid derivatives oxalic acid diester, oxalic acid ester N-methylamide) to give the products a or 9 eg. L.M. Weinstock, Synth. Commun. 11, (1981) 943).

The cyanooxime ethers 12 can also be converted with methylamine in conventional manner into the novel compounds of the formula I (cf. EP 468 775).

H

2 NMe

P

A

S.

I 9* 4, 5 C

S

SIC

S

S..

I S S

S.

*I

The cyanooxime ethers 12 are obtained, for example, known processes by reaction of oximes with benzyl according to bromide 13.

The ketoamides of the formula 8 can additionally be obtained in a simple manner from nitrilium salts 1J by hydrolysis either in acidic or in alkaline solution (cf. Houben-Weyl, Vol. E5/part 2, p. 1580 et seq).

I I I SBASF Aktiengesellschaft O.Z. 0050/43498 c

H

20 /N

CH

3

R

'000%

N

EDC:

CH

3

I

P

The nitrilium salts of the formula 12 are easily accessible, for example, from compounds of the formula 1l by reaction with trimethyloxonium salts such as, for example, trimethyloxonium tetrafluoborate or by reaction of 1. with, for example, methyl trifluoromethanesulfonate (cf. Houben-Weyl, V61. E5/part 2, pp.

1573-6).

In a corresponding manner, the compounds of the general formula I can also be obtained easily from nitrilium salts of the formula l by hydrolysis in acidic or alkaline solution (cf. Houben-Weyl, Vol. E5/part 2, p. 1580 et seq).

BASF Aktiengesellschaft0 O.Z. 0050/43498 EDl 3

C

N/~

CH3 4) *u

.N

CH3 0

CH

3 The nitrilium salts of the formula Ia in turn are easily accessible, for example, from compounds of the formula .12 by reaction with trimethyloxonium salts such as, for example, trimethyloxonium tetrafluoborate or by reaction of 12 with, for example, methyl trifluoromethanesulfonate (cf. Houben-Weyl, Vol. 2, pp. 1573-6).

The novel compounds of the formula I can also be prepared by methylation of suitable intermediates such as, for example, 14 16.

I- BASF Aktiengesellschaft O.Z. 0050/43498 MeX 2 Me.

I

MeX

A

m

S

Alkylation expediently takes place in the presence of a base such as, for example, KOH, K 2

CO

3 or triethylamine. Suitable alkylating agents are methyl halides or dimethylsulfate (cf. for example Houben-Weyl, vol. X/1 pp. 1186 ff; or G. L. Isele, Synthesis, 266 (1971)).

The substituents R and Am shown in the formulae 2 J1 have the meanings given in claim 1. The substituent L is a leaving group such as, for example, halogen (chlorine, bromine or iodine), tosylate, mesylate or triflate.

The following examples are intended to illustrate the preparation of the novel active compounds and of the novel intermediates: BASE Aktiengesellschaft O.Z. 0050/43498 14 EXAMPLE 1 Preparation of methyl E-2-methoxyimino-2-(2'-phthalimidooxymethyl)phenylacetate 59 g (0.58 mol) of triethylamine is added dropwise to a solution of 150 g (0.52 mol) of methyl 2-methoxyimino-2-(2'-bromomethyl)phenylacetate and 85 g (0.52 mol) of N-hydroxyphthalimide in 350 ml of N-methylpyrrolidone. The reaction mixture is stirred at 70C for 2 h and poured into 2 1 of ice-water, and the precipitated crystals are filtered off with suction and taken up in methylene chloride. After the organic phase has been washed with water and dried over sodium sulfate, and the solvent has been removed on a rotary evaporator, 168 g (88% yield) of methyl E-2-methoxyimino-2-(2'-phthalimidooxymethyl)phenylacetate is obtained as a pale gray powder of melting point 152 1530C.

IH-NMR (CDC13) 6 3.81 3H); 3.95 3H); 5.05 2H); 7.12 7.81 8H) ppm.

EXAMPLE 2 0 Preparation of N-methyl-E-2-methoxyimino-2-(2'-aminooxymethyl)phenylacetamide S 168 g (0.46 mol) of methyl E-2-methoxyimino-2-(2'-phthalimidooxymethyl)phenylacetate is treated with 1 1 of 40% strength aqueous monomethylamine solution and the mixture is stirred at 40 0 C for 4 hours. After cooling, it is extracted with methylene chloride, and the organic phase is washed with water, dried over sodium sulfate and concentrated. After crystallization of the residue from methyl tert-butyl ether/n-hexane, 92 g (84% yield) of N-methyl-E-2-methoxyimino-2-(2'-aminooxymethyl )phenylacetamide is obtained as pale yellow crystals of melting point 78 810C. The 35 mother liquor contains further final product.

1H-NMR (CDCl 3 6 2.91 3H); 3.94 3H); 4.58 2H); 5.28 br, 2H); 6.88 br, 1H); 7.14 7.43 4H) ppm.

.BASF Aktiengesellschaft O.Z. 0050/43498 EXAMPLE 3 Preparation of N-methyl-2-methoxyimino-2-[2'-(l''-(4' tert-butylphenyl)-1''-methyl)iminooxymethyl]phenylacetamide ((E,E)isomer: Tab. 1, No. 118) A mixture of 4.3 g (18 mmol) of N-methyl-E-2- methoxyimino-2-(2'-aminooxymethyl)phenylacetamide, 3.2 g (18 mmol) of 4-tert-butylacetophenone and 1.0 g of molecular sieve (3 A) in 10 ml of methanol is treated with 100 mg of p-toluenesulfonic acid monohydrate and stirred at room temperature (20 0 C) for 16 hours.

After filtering off the molecular sieve, the mixture is concentrated and the residue is crystallized from methyl tert-butyl ether/n-hexane. 4.8 g (68% yield) "of the isomer of the title compound is thus obtained as colorless crystals of melting point 107 110 0

C.

The stereochemistry of the compound is confirmed by 13 C-NMR spectroscopy (C(CH 3 )=N-methyl group: 13 ppm].

1H-NMR (CDCl3): 6 1.31 9H); 2.18 3H); 2.83 3H); 3.95 3H); 5.11 2H); 6.70 br, 1H); 7.19 7.55 8H) ppm.

i 20% of [Z(C=NObenzyl), E(C=NOCH 3 isomer was also detected in the mother liquor after recrystallization by 1H-NMR spectroscopy besides the isomer (shift of the signal from the benzyl protons by 0.18 ppm to higher field).

EXAMPLE 4 Preparation of (E,E)-N-methyl-2-methoxyimino-2-[2'-(l''- '-naphthyl)-''-methyl) iminooxymethyl]pheylacetamide 35 (Tab. 1, No. 1) g (7.7 mmol) of methyl (E,E)-2-methoxyimino-2-[2'-(1"- (2'''-naphthyl)-l' '-methyl)iminooxymethyl]phenylacetate (disclosed in EP 463 488) is treated with 50 ml of 40% strength aqueous monomethylamine solution. The mixture is stirred at 40 0

C

for 6 h and, after cooling, extracted three times with methyl tert-butyl ether, and the organic phase is washed with water, dried over sodium sulfate and concentrated. After triturating the residue with diisopropyl ether, 1.9 g (64% yield) of the title compound is obtained as pale yellow crystals of melting point 92 950C.

~I

SBASF, Aktiengesellschaft 0050/43498 16 1H-NMR (CDC13):6 2.30 3H); 2.83 3H); 3.94 3H); 5.15 2H); 6.69 br, 1H); 7.14 7.93 11H) ppm.

EXAMPLE Preparation of (E,E)-N-methyl-2-methoxyimino-2-[2'-(1''- '-chlorophenyl-1-n-propyl)imiooxyethylnphenylacetamide (Tab. 2, No. 44).

0.6 g (1.5 mmol) of methyl (EE)-2-methoxyimino-2-[2'-(1''- '-chlorophenyl)-' '-n-propyl)iminooxymethyl]phenylacetate (disclosed in EP 463 488) is dissolved in 15 ml of tetrahydrofuran, and the solution is treated with 0.5 g of 40% strength aqueous monomethylamine solution. The mixture is stirred at 40 450C for 6 hours and then concentrated, the residue is taken up in methyl tert-butyl ether, and the organic phase is extracted with water, dried over sodium sulfate and concentrated again. After 'chromatography of the residue on a silica Qel column (cyclohexane/methyl tert-butyl ether 0.5 g (83% yield) of the title compound is obtained as a colorless resin.

1H-NMR (CDC 3 0.94 3H); 1.54 2H); 2.70 2H); 2.89 3H); 3.97 3H); 5.11 2H); 6.74 br, 1H); 7.19 7.58 8H) ppm.

o EXAMPLE 6 9 Preparation of E-2-methoxyimino-2-(2'-methylphenyl)acetonitrile.

188 g (1.68 mol) of dry potassium tert-butoxide is introduced into 2 1 of dry toluene and treat:d rapidly with 200 g (1.53 mol) of ortho-methylbenzyl cyanide and 173 g (1.68 mol) of tert-butyl nitrite in- 200 ml of toluene. The mixture warms up to about 700C and is stirred for 2 hours and treated with 1 1 of methyl tert-bu tyl ether. The yellow potassium salt is filtered off with suction, washed with methyl tert-butyl ether and dried under reduced pressure at 290 g (1.46 mol) of this salt is then introduced into 2.5 1 of dry acetone with 20 g (0,15 mol) of potassium carbonate. While 234 g (1.65 mol) of iodomethane are added dropwise, the temperature rises to about 35C. The mixture is stirred overnight and then partitioned between water and methyl tert-butyl ether. The organic phase is washed with water, dried over Na 2

SO

4 concentrated and distilled under reduced pressure 95 100 0

C/

,BASF Aktiengesellschaft O.Z. 0050/43498 17 0.3 0.1 mm). 229 g (78% total yield) of the title compound are thus obtained as a poorly mobile liquid.

1H-NMR (CDC13):6 2.53 3H); 4.22 3H); 7.2 7.4 (m, 3H); 7.54 (dd, 1H) ppm.

EXAMPLE 7 Preparation of E-2-methoxyimino-2-(2'-bromomethylphenyl)acetonitrile.

48 g (0.28 mol) of E-2-methoxyimino-2-(2'-methylphenyl)acetonitrile and 54 g (0.30 mol) of N-bromosuccinimide are introduced into 250 ml of carbon tetrachloride. The mixture is illuminated from outside with a mercury vapor'lamp (300 W) for 40 min. The succinimide is filtered off with suction and the solution is evaporated under reduced pressure. 62 g (88% yield) of the title compound remain, which is about 80% strength according to the result of the 1H-NMR spectrum.

1H-NMR (CDCl 3 4.27 3H); 4.80 2H); 7.4 7.5 (m, 3H); 7.69 (dd, 1H) ppm.

EXAMPLE 8 Preparation of 2-methoximino-2-(2'-bromomethylphenyl)acetic acid- N-methylamide 10 g of 2-methoximino-2- [(2-methylphenyloxymethyl)-phenyl]acetic acid-N-methylamide is added to 50 ml of dichloromethane. At 100C, 9 g of HBr is gassed into this solution. It is then allowed to thaw and is stirred for 3 days at room temperature. 50 ml of dichloromethane is added, and the mixture is washed with strength NaOH and with water, dried and evaporated down. There is 35 obtained 7 g of the title compound as a pale brown solid.

a 128 129 0

C

1 H-NMR (CDC13 TMS): S. 2.95 3H); 3.95 3H); 4.35 2H); 6.85 7.1-7.5 ppm 4H).

,BASF Aktiengesellchaft o,z. 0050/43498 18 EXAMPLE 9 Preparation of 2 -minethoximino-2-(2 -chloromethylphenyl)acetic acid-N-methylamid At 10 0 C, 18.8 g of a boron trichloride solution (1 molar in n-hexane) is dripped into a solution of 2 g (6.4 mmol) of 2-methoximino-2 [2 -methylphenyloxymethyl)-phenyl lacet iC acid-N-methylamide in 30 ml of dichloromethane, and the mixture is refluxed for hours. Subsequently, 8.2 g of methanol is added and the mixture is stirred overnight at room temperature. After washing with strength NaGH and with water, drying and evaportinf down, there is obtained 1.2 g of the title compound as a solid.

1 H-NMR (CDC1 3 TMS): 6 2.96 3H); 3.96 3H); 4.46 2H); 6.86 7.3,3-7.49 ppm 4H).

EXAMPLE Preparation of 2-methoximino-2-(2'-1'"-(4" '-methylphenyl)1"'-methyl)iminoxymethyl]phenylacetic acid-N-methylamide A spatula tip of tetra-n-butlyammonium iodide is added to a solution of 2 g (7 mmol) of oxime ether amide bromide (from Example ~25 8) in 20 ml of dichloromethane, and then a solution of 1.2 g (7 mmol) of p-methylacetophenone oxime in 10 ml of dichlormethane. 20 ml of 10% strength NaOH is dripped in and the mixture is refluxed for 6 hours. After phase separation, extraction with dichloromethane, drying and evaporting down, the residue is chro- 30 matographed on silica gel with hexane/methyl tert.-butyl ether.

1.1 g of the title compound remaii.

1 H-NMR (CDC13/TMS): 8 2.18; 2.34 31i); 2.85 3H); 3.95 3H); 5.09 6.67 (NH); 7.12-7.50 ppm 8H).

EXAMPLE 11 Preparation of 4-methoxyacetophenone oxime-O-[2-bromo]benzyl ether Under a nitrogen blanket, a solution of 14 g (85 mmol) of p-methoxyacetophenone oxime is dripped into a suspension of 2.8 g (94 mml) of NaH (80% strength) in 250 ml of DMF, and the solution is stirred for 2 hours at room temperatuire. A solution of 21.3 g mmol) of o-bromobenzyl chloride in 10 ml of DMF is then dripped in and the mixture is stirred for 1.5 hours. After hydro- 3 ,BASF Aktiengesellschaft O.Z. 0050/43498 19 lysis with 10% strength HC1, extraction with methyl tert-butyl ether, drying and evaporating down, 27.7 g of the title compound remain as a yellowish-brown oil.

1 H-NMR (CDC13 TMS): 6 2.21; 3.85 3H); 5.34 2H); 6.91-7.66 ppm 8H), EXAMPLE 12 Preparation of 2-methoximino-2-[2-((1''-(4''-methoxyphenyl) 1''-methyl)iminooxymethyl]phenylacetic acid-N-methylamide At -780C and under a nitrogen blanket, 6.6 g (15 mmol) of n-butyllithium (15% strength solution in hexame) is added to a solution of 5 g (15 mmol) of bromide (from'Example 11) in 40 ml of THF, and 4.4 g (30 mmol) of diethyl oxalate is run in immediately afterwards. After thawing, water is added, followed by extraction with methyl tert-butyl ether, drying and evaporating down. The residue is chromatographed on silica gel using hexane/methyl tert.-butyl ether. There is obtained 2.7 g of the corresponding a-keto ester as an oil.

m) of a 40% strength n-methylamine solution is added to a solution of 400 mg of this keto ester in 10 ml of THF, and the 25 mixture is heated for 1 hour at 500C. 2 g of methoxyamine hydrochloride is added and the mixture is again heated for 1 hour at 5000C. After cooling, extraction with dichloromethane, drying and evaporating down, 300 mg of the title compound remains (Table 1, No. 219).

1 H-NMR (CDC13 TMS): 6 2.15; 3.13; 3.77 3H); 2.85 3H); 5.06 2H); 6.84-7.56 ppm 8H).

Further compounds of the formula I according to the invention are 35 shown in Tables 1 and 2.

Table 1

CH

3 Am 1 ,BASF AktiengesellschiaftO..00/38 O.Z. 0050/43498 99** ~No, Am Data 2+ 3 2 F m. 43- 470C 4 3F oil; IR (film): 3350, 2945, 1671, 1526, 1037, 979 4F 60 63 0

C

6 2,3-F 2 73 0

C

7 '2,4-F 2 8 2,5-F 2 78 0

C

9 2,6-F 2 123 12 3,4-F 2 103 104C 11 3 05-F 2 Mn.P.: 98- 100C 12 13 2,3,5-F3 14 2,4,5-F 3 67- 3,4,5-F 3 16 2,3-Cl 2 92 9 4 0

C

17 2,t4-Cl 2 97 9 18 215-Cl 2 m.p. 118 120C 19 3,4-Cl 2 rnip.: 98 101 0

C

3-F,4-OCH3 21 2, 3, 5-Cl 3 22 2,4,5-013 23 3,4,5-Cl 3 m~p 84 8 8 0

C

i24 2-Br mp:83- I t 860C ,BASF~ AktienlgesellschaftOZ.05/39 O.Z. 0050/43498 0 *0 0* 0*0* *000 00 0 0* 00 0 *0*0 0 *000 No. Am Data 4-Br m. 94- 9 6 0

C

26 2,3-Br 2 27 2,4-Br 2 28 2,5-Br 2 29 3, 4-Br 2 3, 5-Br 2 120- 122 0

C

31. 2, 3, 4-Br 3 32 2,3, 5-Br 3 33 2, 4, 5-Br 3 34 3, 4, 5-Br 3 2-I 36 3-1 37 4-1 38 2,3-12 39 204-12 40 2,5-12 41 13,4-12 42 3,5-12 43 2-F, 3-C1 44 2 4-C1 2-F, 46 2 3-Br 47 2-F, 4-Br 48 2-F, 49 2-C1, 3 -,Br 50 2-Cl, 4-Br 51 2-C1, 52 3-F, 4-Cl 53 3-F, 54 3-F, 6-Cl 3-F, 4-Br )56 3-F, 57 3-F, 6-Br 58 3-Cl, 4-Br 59 3-Cl, 60 3-C1, 6-Br 61 4-F, 5-Cl 150- I 7 15 4 0 c ,BASF Aktiengesellschafto..05/39 o.z. 0050/43498 9 .9 9 9 .9 9 *9.9 99 9. 9 99..

9.9.

99 .9 9 9 9999 99 99 9 .9 9 9 99 9*9* 9 No. Am Data 62 4-F, 6-Cl 63 4-F, 5-Bt Mn.P.: 820C~ 64 4-F, 6-Br 4-Cl, 66 4-Cl, 6-Br 67 5-F, 6-Cl 68 5-F, 6-Br 69 5-Cl, 6-Br 3-Cl, 4-F, 71 3-Br, 4-Cl, 72 3-Cl, 4-Br, 73 2-CN 74 3-CN 121- 125 0

C

4-CN 76 2-N02 97- 990~C 77 3-NO 2 101- 103 0

C

78 3-CH 3 oil; IR (film)3 3350, 2938, 1671, 1526, 1093, 1037, 979, 787, 697 1 79 2, 3- (CH 3 80 2, 4 -(CH 3 2 107 110 0

C

81 2, 5- (CH 3 2 35 8 6 0

C

82 2, 6- (CH 3 2 83 314- (CH 3 2 84 3 15- (CH 3 2 88 9 0 0

C

2, 3, 4 -(CH3) 3 86 2,,5 C)3 S87 12, 3o6- (CH 3 3 88 2, 4,5- (CH 3 3 89 2 j416- (CH 3 3, 4, 5-(CH3 91 2 -C 2 Hs 92) 13-C 2 Hs BASF Aktiengesellschaft o.z. 0050/43498 0 .e a a @9*9 *1.*S ebb.

I.

S. a No. Am Data 93 4-C2Hs 87 89 0

C

94 2,3-(C 2

HS)

2 2,4-(C 2 Hs) 2 96 2,5-(C 2 Hs) 2 97 3,4-(C 2 Hs) 2 98 3,5-(C 2

H

5 2 61 64C 99 3,4,5-(C 2

H

5 3 100 3-n-C 3

H

7 101 4-n-C 3

H

7 78 101 3,4-(n-C 3

H

7 2 102 3,5-(n-C 3

H

7 2 103 3-i-C 3

H

7 104 4-i-CIH 7 m.p. 93 0

C

105 3,4 -(i-C 3 Hy) 2 106 3,5-(i-C 3 1 )2 107 3-cyclopropyl 108 4-cyclopropyl 109 3-n-C 4

H_

110 4-n-C4Hg 111 3,4-(fl-C 4 Hg) 2 112 3,5-(n-C 4 Hg) 2 113 3-S-C 4 Hg 114 4-S-C4H 9 115 3-i-C4Hg 116 4-i-C 4 Hg 117 3-tC4H9 118 4-t-C 4

H

9 mp: 107 110 0

C

119 3,4-(t-C 4 Hg)2 120 3,5-(t-C 4 Hg) 2 0 121 3-n-CSHii 122 4-n-C 5

H

11 123 3-n-C 6

H

1 3 124 4-n-C 6

H

1 3 125 3-Cyclohexyl 126 4-Cyclohexyl 110 1120C iBASFAktiengesellachaft OZ 05/39 O.Z. 0050/43498 No. Am Data 127 3-Phenyl 70 72 0

C

128 4-Phenyl 138 140C 129 3-Vinyl 130 4-Vinyl 1u31 3-Allyl 132 4-Allyl 133 3-Propargyl 134 4-Propargyl 135 3-(Propen-2-yl) 136 4-(Propen-2-yl) 137 3- (But-2--en-2-yl) 138 4- (But-2-en-2-yl) 139 3-t-CsHll 140 4-t-CSHll 141 2-CH- 3 3-C 2

HS

142 2 -CH 3 4-C 2

HS

143 2-CU 3 5-C 2

H

144 2-CU 3 3-n-C 3

H

7 145 2-CU 3 4-n-C 3

H

7 146 2-CU 3 5-n-C 3

H

7 147 2 -CU 3 3-i-C 3

H

7 148 2-CU 3 4-i-C 3

H

7 149 2-CH 3 5-i-C 3

H

7 150 2 -CH 3 3-n-C 4

H

9 151 2-CU 3 4-n-C 4 H9 152 2-CU 3 5-n-C 4 H9 153 2-CU 3 3-S-C 4

H

9 154 2-CU 3 4-S-C 4 H9 155 2 -CU 3 5-s-C 4

U

9 156 2-CU 3 3-i-C 4 Ug 157 2-CU 3 4-i-C4HO 158 2-CU 3 5-i-C 4

H

9 159 2-CH 3 0 3-t-C 4

U

9 160 2-CU 3 4-t-C 4 H9 161 2-CH 3 5-t-C 4

H

9 162 2-CU 3 3-Cyclohexyl 163 12-CHI, 4-Cyclohexyl 164 12-C-U 3

S.

*5

S

0S S S 00 55.5

S

I BASF BFAktiengeaellachaftOZ.00/38 O.Z. 0050/43498 No. fAm 0 Data 165 f2-CH 3 ,_3-Phenyl 166 f2-CH3, 4-Phenyl 167 2-OH 3 168 2-CH 3 4-Vinyl 169 2-OH 3 4-Allyl 170 2-OH 3 4-Propargyl 171 2-OH 3 4-(Propen-2,-y1) 172 2-OH 3 4-(But-2-en-2-yl) 173 3-OH 3 4--C 2

H

174 3-CH 3 5-C 2

H

175 3-OH 3 4-n-C 3

H

7 176 3-CH 3 5-n- 3

H

7 177 3-OH 3 4-i- 3

H

7 178 3 -CH:3, 5-i-C 3

H

7 179 3-CH 3 4-Cyclopropyl 180 3 -CH 3 4-n-C 4

HO

181 3-OH 3 5-n-C 4

H

9 182 3-OH 3 4-S-C 4

H

9 183 3-OH 3 5-S-C 4

H

9 184 3-CH 3 4-i-C 4 H9 185 3-OH 3 5-i-0 4

H

9 186 3-CH 3 4-t-C 4 H9 187 3-CH 3 5-cr-C 4

H

9 188 3-OH 3 4-Cyclohexyl 189 3-CH 3 190 3-OH 3 4-Phenyl 191 3-CH 3 192 3 -OH 3 4-Vinyl 193 3-OH 3 4-Allyl 194 13-CH 3 4-Propargy], 195 .3-CH 3 4-(Propen-2-yl) 196 3-OH 3 4-(But-2-en-2-yl) 197 4-OH 3 5- 2

H

198 4-OH 3 5-n- 3

H

7 199 4-OH 3 5-i- 3

H

7 200 4-OH 3 201 14-OH 3 5-,n-0 4

H

9 202 4-OH 3 5-S- 4

H

9 203_ 4-OH 3 5-i- 4

H

9 3 ,BASF Aktiengeellscbaft 0050/43498 No. Am Data 204 4-CH 3 5-t-C 4

H

9 205 4-CH 3 206 4-CH 3 207 4-CH 3 208 4-CH 3 209 4-CH 210 4-CH 3 5-(Propen-2-yl) 211 4-CH 3 5-(But-2-en-2-yl) 212 3-CU 3 4 -t-C4H9, 5-CH 3 213 3-t-C 4

H

9 4-CU 3 5-t-C 4 H9 214 2-OH 108 1100C 215 3-OH 123 1250C 216 4-OH 170 1710C 217 2-OCH3 79 810C 218 3-OCH 3 93 0

C

219 4-OCH 3 65 68 0

C

220 2,3-(OCH 3 2 221 2,4-(OCH 3 2 113 114 0

C

222 2, 5- (OCH 3 2l.p.: 9 1010C 223 3,4-(OCH 3 2 132 1350C 224 3,5-(OCH 3 2 97 99 0

C

225 3,4,5-(0CH 3 3 118 120 0

C

226 2,3,4- (OCH 3 3 oil; IR (film): 3370, 2945, 1675, 1496, 1463, 1412, 1094, 1037 227 3-OC 2

H

5 oil; IR (film): 3350, 2936, 1671, 1526, 1223, 1038, 980 228 4-OC2Hs 106 108 0

C

229 3,4-(c 2

H

5 2

S

*5*S

S

230 ___3,5-(oc2HS)7

'I

BnASF A±ktiengeell chaft O.Z. 0050/43498 No. A, Data 231 3 -O-n-C3H7 106 1090C 232 4-O-n-C 3

H

7 99 102 0

C

233 3 4 (O--CH7) 2 234 3,5-(0-n-C 3

H

7 )2 235 3-o-i-C 3

H

7 oil; IR (film): 3350, 2975, 1672, 152, 1223, 1037, 979 236 4-O-i-C 3

H

7 oil; IR (film): 3396, 2980, 1659, 1513, 1252, 1047 237 3 4- (0-i-C 3

H

7 2 238 3, i-CH 7 2 239 240 241 3,4-(O-Cyclopropyl)2 242 3,5-(O-Cyclopropyl)2 243 3--n-C 4 iH oil; IR (film): 3360, 2958, 2935, 1671, 1526, 1224, 103', 979 244 4-O-n-C 4 Hg m.p: 112 115 0

C

245 3, 4- (O-n-C 4 H9)2 2 246, 3,5- (-n-C 4 Hg) 2 247 3-O-S-C 4 H9 248 4-O-s-C4H 9 m.p: 95 97 0

C

249 3,4-(0-s-C 4 Hg) 2 250 3,5-(O-S-C 4 H9)2 251 3-Ori-C 4 HQ oil; IR (film): :3350, 2958, 2936, 1672, 1225, 1038, 919 252 4-O-i-C4Hg oil; IR (film): 3350, 2959, 2936, 1672, 1514, 1248, 1036 253 3,4-(0-i-C 4 H9) 2 254 3 5-(O(-i-C 4

H

9 2 255 3-O-t-C4H 9 m.p: 66 670C 256 4-O-t-C 4 H9 m.p: 51 550C 257 3,4-(0-t-C 4

H

9 2 258 3,5-(0-t-C4Hg) 2_ 0I p.

pp p. p p..

p. pp p p p

BASF

I

Aktiengesellschaft0 0050/43498 No. Am Data 259 3-O-n-CsHii oil; IR (film): 3360, 2955, 2935.

1672, 1526, 1226, 1037, 980 260 4-O-n-C 5

H

11 m.p: 60 65 0

C

261 3,4-(O-n-CsHl) 2 262 3,5-(0-n-CH 1 1 2 263 3-O-n-C 6

H

13 oil; IR (film)'.

3350, 2933, 1670, 1524, 1223, 1037, 979 264 4-O-n-C 6

H

13 74 76 0

C

265 3,4-(O-n-CGH 13 2 266 3,5-(O-n-C 6

H

13 2 267 268 269 3,4-(O-Cyclohexyl) 2 270 3,5-(O-Cyclohexyl) 2 271 3-0C 6

H

272 4-OC 6 HS 118 120 0

C

273 3,4-(OC 6 Hs) 2 274 3,5-(OC 6 Hs) 2 275 3-0-Allyl oil; IR (film): 3340, 2942, 1669, 1523, 1225, 1037, 980 276 4-0-Allyl 94 97 0

C

277 3,4-(O-Ally1) 2 278 3,5-(O-A1ly1) 2 279 3-O-t-C 5

H

1 280 4-0-t-CH 1 1 281 2-CF 3 282 3-CF 3 oil; IR (film) 3345, 2940, 1672, 1341, 1276, 1167, 1126, 1038 283 4-CF 3 83 0

C

284 2,3-(CF 3 )2 285 2,4-(CF 3 2 B BASF, Aktiengesellchaft0 o.Z. 0050/43498 No. A, Data 286 2,5-(CF 3 2 287 3,4-(CF 3 2 288 3,5- (CF 3 2 138 140 0

C

289 3,4,5-(CF 3 3 290 2-CF 2 C1 291 3-CF 2 C1 292 4-CF 2 C1 293 3-CFC1 2 294 4-CFC1 2 295 3 -CC1 3 296 4-CC13 297 3,4-(CC1 3 2 298 3,5-(CC1 3 2 299 3-CH 2

CH

2

F

300 4-CH 2

CH

2

F

301 3-CH 2

CF

3 302 4-CH 2

CF

3 303 3-C 2 Fs 304 4-C 2

F_

305 3-CHC1 2 306 4-CHC1 2 307 3-CH 2 C1 308 4-CH 2 C1 309 3, 4-(CH 2 C1) 2 310 3,5-(CH C1)2 311 3-CF 2

CHF

2 312 4-CF 2

CHF

2 313 3-CH 2 CC1 3 314 4-CH 2 CC1 3 315 3-C 2 C1s 316 4-C 2 C1s 317 3 -e .(CH 3 2

CH

2 C1 318 4-C(CH 3 2

CH

2 C1 319 3-CH 2

CH

2 C1 320 4-CH 2

CH

2 C1 321 2-OCF 3 322 3-OCF 3 323 4-OCF 3 msp.: 72 74 0

C

5, *r *5 ~.BASi" AktiengesellschaftO..05/38 O.Z. 0050/43498 No. A, Data 324 2, 3- (QCF 3 2 325 2, 4- (OCF 3 326 2,5- (OCF3) 2 327 3, 4 -(OCF 3 2 328 3, 5- (OCF 3 2 329 3 -QCHF 2 330 4-QCHF 2 m. 1. 78- 8000 331. 3-OCC 1 3 332 4-OCC1.

3 333 3-OCH 2

CF

3 334 4-OCH 2

CF

3 335 3,4- (OCH 2

CF

3 2 336 3, 5- (OCH 2

CF

3 2 337 3-0C 2

F

338 4-OC 2

FS

339 3, 4- (0C 2

F

5 2 340 3,5- (0C2FS) 2 341 3 -OCF 2

CHF

2 67- 6 8 0

C

342 4-OCF 2

CHF

2 170C 343 3 14- (OCF2CHF 2 2 344 3, 5- (OCF 2

CRF

2 2 345 3-CF 3 i 4-OCF 3 346 3-CF 3 5-OCF 3 347 4-CF3, 5-OCF 3 348 3-CH 2 00H 3 349 4-CH 2 0CH3 350 3-CH 2 O(t-C4Hg) 351 4-CH 2 O(t-C 4

R

9 352 3 -C (CR3) 2

CH

2

OCH

3 353 4-c(CH 3 2

CHZOCR

3 )354 3-C (CH3) 2 0CHZ 355 4-C (CH 3 2 0CH 3 356 3 -C (CR 3

(OCHO)

2 357 4 -C (CR 3

(OCR

3 2 358 3-CH (OCH 3 359 4-CH (OCR 3 2 0 13-CR 2 I S

BASF,

AktiengesellschaftO..05/39 O.Z. 0050/43498 No. Am Data 361 4-CH 2

(CN)

362 3-C (CH 3 2

CH

2

CN

363 4-C (CE 3 2

CH

2

CN

364 3-C- 2 (N02) 365 4-CH- 2

(NO

2 366 13-CHO 367 4-CHO 368 3 -CO-CH 3 369 4-CO-CH3 370 3-CO-C 2

H

371 4-CO-C 2

H

372 2 -C0 2

H

373 3 -CO 2

H

374 4-CO 2 H 188- 190 0

C

375 3 -CO 2

CH

3 376 4-CO 2

CH

3 377 3-C0 2

C

2

H

378 4-CO 2

C

2 Hs 69 72 0

C

379 3-C0 2 -n-C 3

H

7 380 4-C0 2 -n-C 3

H

7 381 3-C0 2 -i-C 3

H

7 382 4-C0 2 -i- 3

H

7 383 3-C0 2 -n-C 4 H9 384 4-C0 2 -n-C 4

H

9 385 3-C0 2

-S-C

4

H

9 386 4-C0 2

-S-C

4

H

9 387 3-C0 2 -i-C 4 Hg 388 4-00 2 -i-C 4 H9 389 3-C0 2 -t-C 4 H9 390 4-C0 2 -t-C 4 H9 391 3-C0 2 D 392 4-CO 2 -n-CSH 1 393 3-CO2-n-C 6

-I

3 394 4-C02-fl-C6Hu3 395 2-C(=O)-NH 2 S396 3-C(=O)-NH 2 397 4,-C -NH 2 398 .3-C(=O)-NHCH 3 G d~

I~

ai i Aktiengesellschaft 0.Z. 0050/43498 No. A, Data 399 4-C(=O)-NHCH3 400 3-C(=0)-N(CH3)2 401 4-C -N (CH3)2 402 3-C(=0)-N(C 2 H5) 2 403 4-C(=0)-N(C 2 HS)2 404 -NH 2 5 3-C(=S)-NH 2 174 175 0

C

406 4-C(=S)-NH 2 407 2-NH 2 408 3-NH 2 92 94 0

C

409 4-NH 2 131 133 0

C

410 3-NCH 3 411 4-NCH 3 412 3-N(CH3) 2 413 4-N (CH 3 )2 98 100 OC 414 3-NHC(=0)CH 3 415 4 -NHC CH 3 165 1670C 416 3 -N (CH 3 C CH3 417 4-N(CH 3 )C(=O)CH3 418 3-NHCO 2

CH

3 419 4-NHCO 2

CH

3 420 2-CH 3 4-Cyclopropyl 421 3 -N (CH3) C02CH 3 422 4-N(CH3)C0 2

CH

3 423 3-0-C(=O)CH 3 10a 110 0

C

424 4 -O-C CH, oil; IR (film): 3360, 2942, 1754, 1671, 1199, 1036 425 CHO)2 426 3,5-[0-C(=0)CH 3 2 427 3-0-C(=)C 2

H_

428 4-0-C(-0)C 2 Hs 429 3 -0-C (i-C 3 H7) j 430 4-0-C i-C 3 H7) 431 (t-C 4 Hg) 432 (t-C 4

H

9 .4 5* S S S. I.

S.

*r S

S.

S

1BASF AtiengesellschaftO. 0 0/ 48 O.Z. 0050/43498 No. Am Data 433 3 -SH 43 4 4-SH 435 3 -SCH 3 436 4 -SCH 3 97- 1000C 437 3-SC 2

HS

438 4-SC 2

H

439 3-S-i-C 3

H

7 440 4-S-i-C 3

H

7 441 3-S-t-C 4 H9 442 4-S-t-C 4 H9 443 3-S(=O)CH 3 444 4-S(=O)CH 3 445 S0 2

CH

3 446 4-SO 2

CH

3 447 3-CH=NH 448 14-CH=NH 449 3-CH=NCH 3 450 4-CH=NCH 3 451. 3-C(CH 3

)=NH

452 4-C(CH 3

)=NH

453 3-C (CH 3 454 4-C (CH 3 =NCH3 455 3-N=C (CH 3 2 456 4-N=C (CH3) 2 457 3-C (SCH 3

NOCH

3 458 4-C (SCH 3

=NONH

3 458 3-C(OCH 3

)=NOCH

3 460 4-C(OCH 3 =NOCh 3 461 3-C (NH 2 =NOCH3 462 4-C (NH 2 =NOCH3 463 3-C (NCH3) =NOCH 3 464 4-C (NCH 3

=NOCH

3 465 3-CH=NOCH3- 466 4-CH=NOCH3 467 3-C (CH 3

=NOCHI

468 4-C (CH 3 =NOCH3 mr:105- 107 0

C

49 13-C (CH 3 NOC2HS V 9

V*

a ~@5t a a.

S

.059 6**e a.

S S S aes.

a.

S. S.

I .I Aktiengesellslchaft 0 O.Z. 0050/43498 No. Am Data 470 4-C (CH 3

=NOC

2 HS oil; IR (film): 3350, 2935, 1671, 1525, 1947, 979 471 3-C (CR 3 =NO-n-C 3

H

7 472 4-C (CH 3 )=NO-n-C 3 H7 oil; IR (film): 3350, 2963, 2935, 1672, 1525, 1037, 979, 927 473 3-C (CH 3 =NO-i-C 3

H

7 474 4-C (CH 3 =NO-i-C 3

H

7 475 3-C (CH 3 NO-n-C 4 H9 476 4-C (CH 3 )=NO-n-C 4 H9 oil; IR (film): 3350, 2957, 2935, 1673, 1525, 1038, 979 477 3-C (CR 3 =NO-S-C4H9 478 4-C (CH 3 =NO-s-C 4 H9 479 3-C (CH1):41O-i-C 4

H

9 480 4-C (CH 3 )=NO-i-C 4 H9 oil; IR (film): 3350, 2958, 2935, 1673, 1525, 1039, 979, 927 481 3-C (CH 3 =NO-t-C 4

H_

482 4-C (CH 3 =NO-t-C 4

H

9 483 3-C (CH 3 =NO-n-CsHii 484 4-C(CH 3 )=NO-n-CSHii 485 3-C (CH 3 =NO-n-C 6 HI3 486 4-C (CR 3 =NO-n-C 6

H

1 3 487 2-Cl, 3-CH3 488 2-Cl, 4-CH3 489 2-Cl, 5-CH 3 490 3-Cl, 4-CR 3 88 0

C

491 3-Cl, 5-CR 3 mP.: 86 1880C 492 3-Cl, 2-CR 3 493 2-CR 3 4-Cl 494 2-CH 3 5\95 3-CR 3 4-C1 88- 4=6 3-Cl, 5-t-C 4

R

9 900_ BASF AItiengeellschaft o.z. 0050/43498 9* No. Am Data 497 2-Cl, 4-t-C 4 H9 498 3-Cl, 4-t-C4H9 499 3-Cl, 4-Cyclohexyl 500 2-F,4-CH 3 501 3-F,4-CH 3 42 44 0

C

502 3-F,5-CH 3 503 2-CH 3 4-F 504 3-CH 3 4-F 75 78 0

C

505 2-F, 3-t-C 4 Hg 506 2-F, 4-t-C 4 Hg 507 3-F, 4-t-C 4 Hg 508 2-F, 4-OCR 3 65 509 2-Br, 4-CH 3 510 3-Br, 4-CH 3 54 56 0

C

511 3-Br, 5-CH 3 512 2-CR 3 4-Br 513 3-CH3, 4-Br 97 990C 514 2-Br, 3-t-C 4 H9 515 2-Br, 4-t-C 4 H9 516 3-Br, 4-t- 4 H9 517 2-Cl, 4-NO 2 518 3-Cl, 4-NO2 519 3-Cl, 5--W02 520 3-NO2, 4-C1 108 1100C 521 3-C-1, 4-(But-2-en-2-yl) 522 3-C1, 4-OCR 3 oilt IR (film): 3340, 2940, 1672 1507, 1271, 1063, 1037 523 3-OCR 3 4-C1 524 3-Cl, 4-OC2H oil; Ift (film)% 3345, 2940, 1671, 1505, 1270, 1060, 1038 525 3-Cl, 4-O-i-C 3

H

7 oil; IR (film): 3345, 1280, 2940, 1671, 1525, 1502, 1269 1037, 979 1'326 13-Cl, 4-0-t-C4H9 BASF, Aktiengesellschaft O.Z. 0050/43498

S

S*

9**O No. Am Data 527 2-Cl, 5-CF 3 528 3-Cl, 4-CF 3 529 3-Cl 1 5-CF 3 530 3-CF 3 4-C1 68- 0 0

C

531 3-Cl 1 4-CH 2 C1 532 3-C1, 4-OCF 3 533 3-C1, 5-OCF 3 534 3-OCF 3 4- Cl 535 3-Cl, 4-OCH 2

CF

3 536 3-Cl, 4-0C 2

FS

537 3-Cl, 4-OCF 2

CHF

2 538 3 -NH 2 4-Cl 539 3-Cl, 4-0-C(=O)CH 3 540 3-Cl, 4-S-t-C 4

H

9 541 3-Cl, 5-S-t-C 4

H

9 542 4-C1, 3-S-t-C 4

H

9 543 3-F, 5-CF 3 76- 7 8 0

C

544 2-CH 3 4-CN 545 3-NO 2 4-CA 3 546 2 -CA 3 4-OCH 3 547 3-CH- 3 4-OCH3 8 9 0

C

548 3-CA 3 5-OCH 3 549 3-OCH 3 4-CA 3 550 3-t-C 4 H9, 4-W.H 3 551 3-t-C 4

H

9 5-OCH 3 552 3-0CH 3 4-t-C 4 H9 553 2-CA 3 4-O-i-C 3

H

7 554 3-CA 3 4-O--C3H7 555 3-O-i-C 3

H

7 4-CA 3 556 3-t-C 4

H

9 4-O-i-C 3

H

7 1,7 3-t-C 4

H

9 5-O-i-C 3

H

7 -0iCH7 49 559 3-t-C4H 9 4-O-t-C 4

H

9 56 12C3 *F 560 2-CA 3 4-CF 3 562. 2-CH 3 5-CF 3 562 3-CA 3 4-CF 3 1BASF Aktiengesellschaft O.Z. 0050/43498 9. *0 *99* 9.

9@ 9 *999 *99* 9~S* *099 9. .9 9 0 0 0*90 99 99 99 9 *9 900* 0 9*00 No. Am Data 564 3-CF 3 4-CH- 3 565 2 -CH 3 4-OCF 3 566 3 -CH 3 4-OCF 3 567 3 -CH 3 5-OCF 3 568 3-OCF 3 4-CH 3 569 13-CH 3 4-008 2

CFI

570 3-CH 3 4-0C 2 Fs 571 3-CH 3 4-OCF 2

CHF

2 572 3-CH 3 4-S-t-C 4

H

9 573 13-CF 3 4-OCH 3 574 3-CF 3 4-O-t-C 4

H

9 575 3-OCH 3 4-CF 3 576 2-CH 3 4-C (CH 3

=NOCH

3 577 3-OH 3 4-C (CH 3

=NOCH

3 578 3-Cl, 4-C- 3 579 3-Cl, 4-t-C 4

H

9 1580 13-Cl, 4-OCH 3 581 3-Cl, 4-O-t-C 4 H9, 582 3-C1, 4-NH 2 583 3-CO 2

CH

3 4-OCH 3 584 3-NH 2 4-OCHI 585 2-OH, 5-CH 3 128- 131 0

C

586 2-OCH 3 3-Cl, 5-Cl in#p,: 670C 587 3-Br, 4-OCH, 588 3-i-C 3

H

7 4-01.H3, 5-i-C3H7 589 3-NO 2 4-OCH 3 118- 12000 590 3- (t-C 4

H

9 4-0C8 3 5- (t-C 4 591 3-Cl, 4-S-C 4 HO 58- 0

C

592 3-Cl, 4-i-C 3

H

7 91- 92 (0C 593 3-Cl, 4-C 2 HSl 594 3-Cl, 5195 3-C1, 4-001W 2 jm.p.: 60 1620C It Aktiengesellschaft 0 O.Z. 0050/43498

S

No. Am Data 596 3-CF 3 4-OCSH5 oil, IR (film): 3340, 2940, 1675, 1498, 1279, 1249, 1133, 1053, 1037 597 3-i-C 3 7 4-OCH3 598 3-CHF 2 oil, IR (film): 3340, 2940, 1670, 1528, 1208, 1036, 980 599 4-CHF 2 600 3-Br, 4-'CH 3 5-Cl 108 111 0

C

601 3-Br, 4-0C 6

H

5 602 3,5-(CO 2

CH

3 2 603 3-0C 2

H

5 4-Cl 604 3-0-i-C3H7, 4-Cl 605 3--t-C 4

H

9 4-Cl 606 3-EH3, 4-OC25 oil, IR (film): 3340, 2940, 1671, 1507, 1247, 1939 607 3-CH 3 4-0-t-C 4

H

9 608 3-0C 2

H

5 4-CH 3 609 3-0-t-C 4 8 9 4-CH3 610 3-Cl, 4-OCH 3 5-CH3

H

3 92 95 0

C

611 H "1 I N N0I

CH

3 0 CH 3 H oil, IR (film): 3350, 2932, 0 1671, 1525, 612 H 1037, 979, 777 ;N *.0 CH CH3 613 3-cl, 4-n-C3H 7 oil; IR (film): 3349, 2937, 1571, 1506, 1271, 1037, 978 BASF AktiengeaeljlschaftO.,00/38 O.Z. 0050/43498 9 9* 9 No. Am Data 614 3-Cl, 4-0-Alkyl oil; IR (film); 3340, 2930, 1672, 1504, 1270, 1037, 980 615 3-Cl, 4-0-n-C 4 N9i oil; IR (film): 3350, 2936, 1672, 1506, 1037, 979 616 3-Cl, 4-0-i-C 4 H9 oil; IR (film): 3345, 2960, 1670, 1506, 1271, 1059, 1037 617 3-Cl, 4-0-CH 2

-CH=CHCH

3 oil; IR 3345, 2937, 1673, 1504, 1269, 1037, 980 618 3-Cl, 4-0-CH 2

-CH

2

-CH

2

-CH

2 Cl oil; IR (film): 3340, 2938, 1675, 1506, 1270, 1037 619 3-Cl, 4-0-n-C5H 11 oil; IR (film): 3345, 2936, 1673, 1506, 1270, 1058, 1037, 980 620 3-Cl, 4-0-i-C 5

H

11 oil; IR (film): 3340, 2955, 1672, 1506, 1269, 1060, 1037, 979 621 3-Cl, 4-0-CH 2

-CH=C(CH

3 2 oil; IR (film): 3345, 2940, 1674, 1504, 1269, 1037, 980 622 3-Cl, 4-0-neo-." 5

H

1 1 oil; IR (film): 3345, 2956, 1673, 1507, 1259, 1061, 1038, 1014 623 3-cls 4-0-n-CH 13 oil; IR (film): 3417, 1681, 1267, 1034, 1026, 937 624 3-CH 3 4-0-n-C 3

H

7 oil; IR (film): 3340, 2937, 1671, 1506, 11038, 979 I I BASF, B~AktiengesellschaftOZ.05/39 O.Z. 0050/43498 t.

*S

C

4,

S

Se*9 549s *4 .5 5 V

S

ec *5

C

SS

p *9tI No. Am Data 625 3-CH 3 4-0-Alkyl oil; IR (film): 3350, 2940, 1669, 1505, 1036, 980 626 j3-CH 3 4-0-n-C 4 'Hg oil; IR (film): 3340, 2935, 1671, 1507, 12, 4 48, 1038, 979 627 13..CH 3 4-0-CH 2

-CH=CHCH

3 oil; IR (film): 3350, 2940,~ 1672. 1I525, 1505, 1247, 1037, 979 628 3-CH 3 4-0-n-C 5

H

11 oil; IR (film): 3340, 2935, 1668, 1526, 1507, 1250, 1037, 980 629 3-CH 3 4-0-i-C 5

H

11 oil; IR (film): 3340, 2954, 1671, 1507, 1038, 980 630 3-CH 3 4-0-CH2-CH=C(CH 3 2 oil; IR (film): 3350, 2935, 1672, 1505, 1037, 979 631 3-CH 3 4-0-neo-C5Hit oil; IR (film): 3340, 2954, 1670, 1507, 1247, 1038 632 3-CH 3 4-0-n-C 6

H

13 oil; IR (film): 3345, 2934, 1672, 1506, 1247, 1038 633 4-0-CH 2

-CH

2

-CH

2

-CH

2 Nr 74 77 0

C

634 3,5-(OCH 3 2 4 OH 80 83 0

C

635 2,3,4,5,6-F 5 83 840C~ 636 3,5-(OH) 2 68 7 0 0

C

637 4-0-i-CSHii 91 9311C 638 4-0-neo-C 5

H

11 oi3; IR (film): 3350, 2956, 1675, 1514, 1248, 1038, 11017 I 1 ,fBASIT AktiengesjellschaftO..05/39 O.Z. 0050/43498 No. Am Data 639 4 [O-CH 2 -CH=C (CH 3 2 1 m.p. 113 11 6 0

C

640 4 0-CH 2

-CH

2

-CH

2

-CH

2 C1 77 800C 641 4-0-CH 2

.CH

2

-CH

2 rN oil; IR (film): 3375, 2940, 2245, 1674, 1514, 1249, 1037 642 2-0-i-C 5

H

11 oil; IR (film): 3350, 2955, 2935, 1672, 1525, 1222, 1038, 980 643 3- tO-CH2-CH=C (CH 3 2 oil; IR (film): 3355, 2935, 1673, 1525, 1219, 1037, 980 ~54 3-0O-CH 2

-CH

2

-CH

2

-CH

2 Cl oil; IR (film): 3355, 2938, 1675, 1525, 1225, 1037, 979 645 4-NHC(=0)H 140 1420C 646 3-CH3, 4 OH 159 1610C 647 3 CN 200 202 0

C

648 3-CH3, 4-0-iC 3

H

7 85 870C 649 3-Cl, 4-OH 160 1630C~ 650 4-C (CH 3 2 CNq m.p. 83 I 651 13-OF 3 4 F 60 620oC 0 *0 0*00 IBAS,Ationgesellach~aftO..00/39 O.Z. 0050/43498 Table 2 NO00

CH

3 NHCH 3 No. Am R Data 1 H C 2

H

5 oil; IR (film): 3350, 2938, 1671, 1525, 1463, 1091, 1037, 979, 912, 696 2 2-Cl C 2 HS m.p. 71 720C~ 3 3-Cl C 2 HS m.p. 106 107 0

C

4 4-Cl C 2 HS 3,4-Cl 2

C

2 HS m.p. 120 122 0

C

6 31,5-Cl 2 C 2 7 2,3,4-C1 3 C 2 8 3,4,5-Cl 3

C

2

H

5 9 2-Br C2HS 3-Br C 2

HS

11 4-Br C 2 HS 'ia.p. 107- 8 0

C

12 2-NO 2

C

2

H

13 3-NO 2

C

2 14 4-NO 2

C

2 2-CM 3

C

2

H

5 16 3-CM 3 C 2

H-

5 17 4-CM 3 C2HS oil; IR (film): 3350, 2937, 1670, 1525, 1514, 1463, 1037t 979t 959, 911, 822 18 2-4- (CHO) 2

C

2

HS

19 3,4-(CH 3 2

C

2 HS BAS1r Aktiengesellsch~aft O.Z. 0050/43498

Q

S.

S

S S

S.

*5 5* *5*5*5 *5 5

S

3, 5- (CH 3 2

C

2 Hs 21 3 -i-C 3

H

7

C

2

HS

2 4-i-C 3

H

7 C2HS 23 3-t-C 4

H

9

C

2 24 4-t-C 4 H9

C

2 H5 m.p. 94 9 3-CH 3 4-t-C 4 H9

C

2 26 3-t-C 4 H9, 4-CH- 3

C

2 27 3 -OCH 3

C

2 HS 28 4 -OCH 3

C

2 HS m. p. 96- 9 7 0

C

29 3-O-i -C 3

H

7

C

2 4-o-i-C 3

H

7 *jC 2 HS 31 3-O-t-C 4 H9

C

2 Hs 32 4-O-t-C 4 H9

C

2

HS

33 3 -CF 3

C

2 Hs 34 4-CF 3

C

2

HS

35 3 -OC~i

C

2 H5 36 4-OCF 3

C

2 37 3-S-t-C 4 H9

C

2

HS

38 4-S-t-C4H9

C

2

HS

539 3-C (CH 3 =NOCH3

C

2 40 4-C (CH 3 =NOCH3

C

2 HS 41 H n-C3H7 42 2-Cl n-C 3 H7 0 43 3-Cl n-C 3 H7 44 4-Cl n-C3H7~ cf. Example 45 3 ,5-Cl 2 n-C 3 H7 46 2,3,4-C1 3 n-C3H7 547 2 -sr n--C 3 48 3 -Br n-C 3 49 4-Br fl-C 3 H7 2-CH 3 n-C 3 H7 51 3-CH 3 n-C 3 H7 52 4-CH 3 ri-C3H7 53 4-t-C 4 H9 n-C 3 H7 54 4-CF 3 n-C 3 H7 4-O-t-C 4 H9 n-C 3 H7 S56 4-OCF 3 n-C 2

H

7 57 H i-C 3

H

7 58 1 Cl i-C 3 H7L I ,,BASK~ Aktiengesellschaft O.Z. 0050/43498 to..

6 to 59 3-C2 i-C 3

H

7 4 -Cl i-C 3

H

7 61 3, 5-Cl 2 i-C 3

H

7 562 2, 3 ,4-Cl 3 i-C 3

H

7 63 2-Br i-C 3

H

7 64 3 -Br i-C 3

H

7 4-Br i-C 3

H

7 66 2 -CH 3 i-C 3

H

7 L067 3-CH 3 i-C 3

H

7 68 4-CH 3 i-C 3 H7 69 4-t-C 4 H9 i-C 3

H

7 4-CF 3 i-C 3

H

7 1 4-O-t-C 4

H

9 i-C 3

H

7 72 4 -OCF 3 i C 3

H

7 73 2-Cl Cyc lopropyl 74 3-Cl Cyclopropyl 75 3,r4-Cl 2 Cyclopropyl 76 3,05-Cl 2 Cyclopropyl 77 2,3,4-Cl 3 fCyclopropyl 78 2-Br Cyclopropyl 3-Br Cyclopropyl 4-Br Cyc lopropyl 81 2-CH 3 Cyclopropyl 82 3-CH 3 Cyclopropyl 83 4-CH 3 Cyclopropyl 30 84 4-CF 3 cyclopropyl 4-O-t-C 4 Hg Cyclopropyl 86 4-OCF 3 Cyclopropyl 87 4F~ C 2 H5 m~p. 94- 1 1_ 9 The novel compounds are suitable as fungicides and insecticides.

The fungicidal compounds according to the invention, or agents containing them, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine -BASF Aktiengesellschaft O.Z. 0050/43498 a distribution of the active ingredients according to the invention as possible.

Normally, the plants are sprayed or dusted with the active ingredients or the seeds of the plants are treated with the active ingredients.

The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics xylene), chlorinated aromatics chlorobenzenes), paraffins crude oil fractions), alcohols methanol, butanol), ketones cyclohexanone), amines (e.g.,.ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals kaolins, aluminas, talc and chalk) and ground synthetic minerals highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin-sulfite waste liquors and methylcellulose.

to 0 25 Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethy- 35 lene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

.BASF Aktiengesellschaft O.Z. 0050/43498 46 Granules, coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers.

Examples of solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

Examples of formulations are given below.

I. A solution of 90 parts by weight of compound no. 5 from Table 1 and 10 parts by weight of'N-methyl-a-pyrrolidone, which is suitable for application in the form of very fine drops.

II. A mixture of 20 parts by weight of compound no. 6/1, parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of moles of ethylene oxide and 1 mole of castor oil. By finely dispersing the mixture in water, an aqueous dispersion is ob- 25 tained.

III. An aqueous dispersion of 20 parts by weight of compound no.

8/1, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.

IV. An aqueous dispersion of 20 parts by weight of compound no.

9/1, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 2800C, S 35 and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.

V. A hammer-milled mixture of 80 parts by weight of compound no.

10/1, 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel. By finely dispersing the mixture in water, a spray liquor is obtained.

S'BASE Aktiengesellschaft O.Z. 0050/43498 47 VI. An intimate mixture of 3 parts by weight of compound no.

11/1 and 97 parts by weight of particulate kaolin. The dust contains 3wt% of the active ingredient.

VII. An intimate mixture of 30 parts by weight of compound no.

16/1, 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of this silica gel. This formulation of the active ingredient exhibits good adherence.

VIII. A stable aqueous dispersion of 40 parts by weight of compound no. 18/1, 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water, which dispersion can be further diluted.

IX. A stable oily dispersion of 20 parts by weight of compound no. 19/1, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a 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.

The compounds are extremely effective on a broad spectrum of ,phytopathogenic fungi, in particular those from the class consisting of the Ascomycetes and Basidiomycetes. Some of them have a systemic action and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.

35 The compounds are applied by treating the fungi or the seeds, plants or materials to be protected against fungus attack, or the soil with a fungicidally effective amount of the active ingredients.

The active ingredients may be applied before or after infection of the materials, plants or seeds by the fungi.

Specifically, the compounds I are suitable for controlling the following plant diseases: BASF Aktiengesellschaft O.Z. 0050/43498 48 Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, Rhizoctonia solani in cotton, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries and grapes, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Fusarium and Verticillium species in-various plants, Plasmopara viticola in grapes, Alternaria species in fruit and vegetables.

The novel compounds may also be used for protecting materials (timber), for example against Paecilomyces variotii.

a The fungicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt% of active ingredient.

0. The application rates depend on the type of effect desired, and vary from 0.02 to 3 kg/ha.

S

When the active ingredients are used for treating seed, rates of from 0.001 to 50, and preferably from 0.01 to 10, g per kg of seed are generally required.

>p t When the agents according to the invention are used as fungicides, they may be applied together with other active ingredi- 35 ents, for example herbicides, insecticides, growth regulators, other fungicides and fertilizers.

When mixed with other fungicides, the spectrum of fungicidal action is frequently increased.

Use examples For the following use examples the comparative substances employed were methyl 2-methoximino-2- 2 '-naphthyl)-1' '-methyl)-iminooxymethyl-phenylacetate methyl 2-methoximino-2-[2 -naphthyl)-1''-methyl)-iminooxymethyl phenylacetate and methyl 2-methoximino-2-[2'-(1" I I I BASF Aktiengeellschaft O.Z. 0050/43498 t 49 phenyl)-l"'-methyl)iinooethyl)-iminooxymethyl]-phenylacetate all known from EP 463 488.

Use Example 1 Action on Fusarium culmorum in wheat Leaves of pot-grown wheat seedlings of the "Kanzler" variety were sprayed to runoff with aqueous liquors containing (dry basis) of active ingredient and 20% of emulsifier. The following day they were inoculated with a spore suspension of Fusarium culmorum and then placed in a climatic cabinet of high humidity 90%) at 22-240C. The extent of fungus spread was assessed visually after 6 days.

Leaf attack in after ap- Active ingredient plication of aqueous formulations containing 500 ppm of active ingredient Table 1, No. 1 0 Table 1, No. 2 Comparative product A 25 Comparative product B Untreated @9 9 .9 6 9S 9 0 9.9.

BASF Aktiengesellschaft Use Example 2 Action on Plasmopara viticola 0050/43498 Leaves of potted vines of the MQller-Thurgau variety were sprayed with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsifier. To assess the duration of action, the plants were set up, after the sprayed-on layer had dried, for 8 days in the greenhouse. Then the leaves were infected with a zoospore suspension of Plasmopara viticola. The plants were first placed for 48 hours in a water vapor-saturated chamber at 240C and then in a greenhouse for 5 days at from 20 to 30oC. To accelerate and intensify the sporangiophore discharge, the plants were then again placed in the moist chamber for 16 hours. The extent of fungus attack was then assessed on the undersides of the leaves.

Leaf attack in after ap- Active ingredient plication of aqueous formulations containing 16 ppm of active ingredient Table 1, No. 5 Table 1, No. 19 0 Table 1, No. 63 Table 1, No. 74 Table 1, No. 118 Table 1, No. 228 Table 1, No. 282 0 Table 1, No. 283 30 Comparative product C Untreated *r S. S *505 00

SSSS

S

I- I oBASg: AItiengeaeJ.schaft O.U. 0050/43498 Use example 3 Action on wheat brown rust Leaves of pot-grown wheat seedlings of the "FrO;hgold" variety were dusted with spores of brown rust (Puccinia recondita). The pots were then placed for 24 hours at 20 to 220C in a high-humidity (90 95%) chamber. During this period the spores germinated and the germ tubes penetrated the leaf tissue. The infected plants were then sprayed to runoff with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier.

After the sprayed-on layer had dried, the plants were set up in the greenhouse at 20 to 22 0 C and a relative humidity of 65 to The extent of rust fungus spread on the leaves was assessed after 8 days.

Leaf attack in after ap- Active ingredient plication of aqueous formulations containing 63 ppm of active ingredient Table 1, No. 1 0 Table 1, No. 2 Table 1, No. 19 25 Table 1, No. 63 0 Table 1, No. 118 Table 1, No. 282 0 Table 1, No. 283 0 Comparative product A 30 Comparative product B Comparative product C Untreated 35 The results obtained in these comparative experiments show that the active ingredients from Table 1, Nos. 1, 2, 5, 19, 63, 74, 118, 228, 282 and 283, when applied in the stated concentrations in spray liquors, have a better fungicidal action than the prior art comparative active ingredients A, B and C.

9.* 9 9. o9o.

99 0 9 09@9

.S

9.* 9999 or 0 *i

Claims

1. An N-methylamide of the formula I, R NN <'N-OCH 3 N A where R Is methyl, A is -C(CH 3 )=NOR1, and RI IS Ci -04-alkyl.

2. A compound of the formula V 0O*1 0 WOCH3V CH-" N, H A compound of the formula IX Br 0 Ix NO N OH 3

4. A fungicide containing an inert carrier and a fungicidally effective amount of an N-methylamide of the formula I as set forth In claim 1. 1 ~1 A process for combating fungi, wherein the fungi or the materials, plants, seed or the soil threatened by fungus attack are treated with a fungicidally effective amount of a compound I as set forth in claim 1. DATED this 17th day of May, 1995. BASF AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA LCG:JGC:JZ: (Doc.3)AU4491893.WPC S 0 P -k i n e e l c a 920527 O.Z4 0050/43498 N-Methylanides, their preparation and intermediates theref or and control of pests therewith ABSTRACT OF THE DISCLOSURE: N-Methylamides of the formula I0 NMOCH 3 -N CH 3 H S where R is Cl-C 3 alkyl or cyclopropyl, A is hydrogen, halogen, cyano, nitro, alkyl, cycloalkyl, OR', cycloalkyloxy, haloalkyl, haloalkyloxy, alkenyl, al- kenyloxy, alkynyl, alkoxyalkyl, cyanoalkyl, nitroalkyl, phenyl, phenoxy, CO 2 Rl, C(O)NR1R 2 C(S)NRlR2, NR 1 R 2 NR 1 C(O)R 2 NR1C0 2 R 2 OC(O)R', SR1, S(O) 2 R1, -C (R1) =NR 2 -N=CRlR 2 C =NOR R where R 1 R 2 and R 3 are hydrogen or CI-C 6 -alkyl and X is 35 S; 0 or NR 3 and n is 0 or 1 or two or' the groups Am in adjacent positions may together be -CH=CH-CH=CH- and m isi1, 2 or 3, S 5555 *5 55*5*O S 55 5 S S S 5 5* and fungicides containing these compounds.