SK92693A3 - Process for production of n-methyl amides and their intermediates and process for production of pesticides - Google Patents

Abstract

N-methylamides of the formula (I) in which R denotes methyl and R1 denotes C1-C4-alkyl and method for their preparation. The invention also discloses intermediates used for preparation of N-methylamides of formula (I), fungicides containing these compounds and their use as pesticides.

Description

Technical field

The present invention relates to novel N-methylamides, a process and intermediates for their production, as well as a method for combating pests, in particular fungi, various insects, nematodes and mites, with these compounds.

BACKGROUND OF THE INVENTION

It is known that substituted N-methylamides are used as pests for controlling pests (cf. European Pat.

463,488 and 398,692). However, their effect is unsatisfactory.

SUMMARY OF THE INVENTION

It has now surprisingly been found that the N-methylamides of the formula I

they have an excellent fungicidal, insecticidal, nematicidal and acaricidal effect which is superior to the known N-methylamides.

A fungicidal effect is preferred.

For example, the radicals of formula I may have the following meanings:

R can be C 1 -C 3 alkyl (e.g., methyl, ethyl, n-propyl or isopropyl) or cyclopropyl,

A may be the same or different and represents a hydrogen atom, a halogen atom (for example fluorine, chlorine, bromine or iodine), a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms (for example methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, tert-pentyl or hexyl) cycloalkyl having 3 to 6 carbon atoms (e.g. cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl),

OR ¹ (e.g., hydroxy, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, n-pentyloxy, t-pentyloxy, or nentyloxy).

C 3 -C 6 cycloalkoxy (e.g., cyclopropyloxy, cyclobutyloxy, cyclopentyloxy or cyclohexyloxy), (C 1 -C 6) haloalkyl (e.g., trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, pentafluoroethyl, pentafluoroethyl, pentafluoroethyl, pentafluoroethyl, pentafluoroethyl, pentafluoroethyl, pentafluoroethyl, pentafluoroethyl, pentafluoroethyl) chloromethyl, dichloromethyl, trichloromethyl, _{2-chloroethyl,} 2,2,2-trichloroethyl, pentachloroethyl, or ... 3-cblór.-2-methyl-prop-2-yl 1), halogenoalkoxy of 1 to 6 carbon atoms ( e.g., difluoromethoxy, trifluoromethoxy, pentafluoroethoxy, 1,1,2,2-tetrafluoroethoxy or 2,2,2-trifluoroethoxy), (C 2 -C 6) alkenyl (vinyl, 1-propen-1-yl, 2-propenyl, 2 -butenyl, 1-methyl-2-propenyl, allyl or but-2-en-2-yl), alkenyloxy of 2 to 6 carbon atoms (e.g. vinyloxy or allyloxy), alkynyl of 2 to 6 carbon atoms (ethynyl, 1-methyl-2-enyl) propynyl or 3-propynyl) alkoxy (C až-C) alkyl group in both the alkyl and alkoxy moieties (e.g., methoxymethyl, ethoxymethyl, dimethoxymethyl, 1,1-dimethoxyethyl-1-yl, n- or isopropoxymethyl, n-, iso-, sec- or tert- butoxymethyl, 1-methoxy-2-methylprop-2-yl, 2-methoxyprop-2-yl, 2-ethoxyprop-2-yl, 2-n- or isopropoxyprop-2-yl, 2-n-, -iso-, (sec-or-tert-butoxyprop-2-yl), a cyanoalkyl group having 1 to 6 carbon atoms (e.g., cyanomethyl, 1-cyano-2-methylprop-2-yl or 2-cyanethyl).

(C 1 -C 6) nitroalkyl (e.g., nitromethyl), phenyl or phenoxy;

C (O) r 1 (e.g. formyl, acetyl, propionyl, butyryl, isobutyryl or pivaloyl),

CO2R ¹ (for example, hydroxycarbonyl, methoxycarbonyl, ethoxycarbonyl, n- or isopropoxycarbonyl, n-, iso-, sec- or tert-butoxycarbonyl),

Ί 9

C (O) RRR. (e.g., aminocarbonyl, N-methylaminocarbonyl, dimethylaminocarbonyl or diethylaminocarbonyl);

C (S) NR R (e.g., aminocarbonyl, N-methylaminothiocarbonyl, or. N _r N-dimetylamino.ti.okarbon.yl.}.

Ί P

NRR (e.g., amino, N-methylamino, N-ethylamino, N-isopropylamino, N-n-propylamino, N-n-butylamino, N-sec-butylamino, N-tert-butylamino, N-isobutylamino or N, N-dimethy,

Nr1c (O) r2 (e.g. N-acetylamino, N-methyl-N-acetylamino or N-ethyl-N-acetylamino),

NR ¹ CO ₂ R ² (e.g., N-carboxymethylamino or N-methyl-N-carboxymethylamino),

OC (O) R ¹ (e.g., OC (O) methyl, OC (O) ethyl, OC (O) n-propyl, OC (O) isopropyl, OC (O) n-butyl or OC (O) tert-butyl )

SR ¹ (e.g. SH, S-methyl, S-ethyl, Sn-propyl, S-isopropyl, Sn-butyl, S-sec-butyl, S-isobutyl, S-tert-butyl, Sn-pentyl or Sn- hexyl)

SiO ¹ R ¹ (e.g., S (O) -methyl, S (O) -ethyl or S (O) n -propyl),

SO ₂ R ¹ (e.g. SO ₂ -ethyl or SO ₂ -ethyl)

-C 1 R 4 -N-NR ² (e.g., -CH = NH, -CH = N-methyl, -CH = N-ethyl, -C (CH ₃ ) = NH or -C (CH ₃ ) = NCH ₃ ),

-N = CR ¹ R ² (e.g. -N = C (CH ₃ ) ₂ or -N = C (CH ₃ ) (ethyl)),

-C = NOR ¹

(e.g., methoxyiminomethyl, ethoxyiminomethyl, n-propoxyiminomethyl, n-butoxyiminomethyl, methoxyimino-1-ethyl, ethoxyimino-1-ethyl, n-propoxyimino-1-ethyl, n-butoxyimino-1-ethyl, isopropoxyimino-1-ethyl, sec. -, iso- or tert-butoxyimino-1-ethyl, n-pentyloxy imino-1-ethyl,

C (SCH ₃₎ = NOCH _3, n-hexyloxyimino-l-ethyl,

-c (nh ₂ ) = noch ₃

-c (och ₃ ) = noch ₃ , -C [N (CH ₃ ) 2> NOCH ₃ ,

-C (NHCH ₃ ) = NQCH ₃ nC (OC ₂ H ₅ ) = NOC ₂ H ₅ or -C (SCH ₃ ) = NOC ₂ H ₅ ), with the exception of compounds of formula I wherein R is methyl and A _m is 2-chloro, 3-chloro, 4-chloro, 3,5-dichloro,

2,3,4-trichloro, 2-methyl, 4-methyl, 3-bromo, 4-nitro or a hydrogen atom and with the exception of compounds of formula I in which R is cyclopropyl and A _m is hydrogen , 4-chloro, 4-tert-butyl or 4-methoxy.

The invention further relates to compounds of general formula Ia

(Ia)

CH ₃ in which

R is methyl, ethyl, n-propyl or isopropyl,

A ¹ , A ² , A ³ , A ⁴ and A ⁵ are the same or different and represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, OR ¹ , (C 3 -C 6) cycloalkyloxy, (C 1 -C 6) haloalkyl, (C 1 -C 6) haloalkoxy, (C 2 -C 6) alkenyl, (C 2 -C 6) -alkyloxy group; (C1-C6) -alkyloxy, C1-C6-alkoxy-C1-C6-alkoxyalkyl, C1-C6alkoxyalkyl, both in the alkyl and alkoxy moieties; C 1 -C 6 nitroalkyl, C 1 -C 6 nitroalkyl, phenyl, phenoxy, C (O) R, CO 2 R, C ¹ H ⁴ NR 2 -R ² , C (S) NR ¹ R ² , NR ¹ R ² , NR ¹ C (O) R ^2, CO 2 R ² N'R ^1, OCÍOjR ^1, SR ^1, S (O) R ^1, S02R ¹ moiety -CÍR ^ NR ^2, -N = CR ¹ R ^2,

-C = NOR ¹ ,

I

X _n R ²

Wherein R, R and R are each independently hydrogen or C 1 -C 6 -alkyl,

X is S, O and NR and n is 0 or 1 or

5, two groups A and A at adjacent positions represent the group -CH = CH-CH = CH with the exception that

a.) .. .two., to. four ... of the substituents A ¹ to A ⁵ are hydrogen,

(b) two or three of A ¹ to A ⁵ are hydrogen if one of A ¹ to is chlorine, bromine, nitro or methyl;

(c) one of the halogen atoms is a fluorine or bromine atom if A ² + A ⁴ or A ¹ + A ² + A ³ simultaneously represent a halogen atom.

Preferred substituents for R are methyl or ethyl, especially methyl, for A or A to A, a hydrogen, fluorine, chlorine or bromine atom, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, cyano, methoxy , ethoxy, isopropoxy, tert-butoxy, tert-pentyloxy, methoxymethyl, 2-methoxyprop2-yl, trifluoromethyl, 1,1,2,2-tetrafluoroethyl, 1-chloro-2-methylprop2-yl and -or-trifluoromethoxy .

Preferred are compounds having A substituents other than hydrogen at the A ² , A ³ or A ^{4 positions} .

Preferred are the compounds which occur when they represent the substitution model below with substituents other than a hydrogen atom.

(a) A ² (or A ⁴ ) is not hydrogen and all other substituents are hydrogen;

b) A ^{3 is} not a hydrogen atom and all remaining substituents are a hydrogen atom,

(c) A ² and A ³ (or A ³ and A ⁴ ) are not hydrogen and all remaining substituents are hydrogen,

d) A ² and A ⁴ do not represent a hydrogen atom, and all remaining substituents are a hydrogen atom, by 3 4 · · *

e) A and A and A are not hydrogen and all remaining substituents are hydrogen.

Particular preference is given to substituents with substituents A ² , A ³ and A ⁴ , which are mentioned above as preferred.

The novel compounds of the formula I can be formed on the basis of C = N double bonds as E / Z isomer mixtures. These mixtures can be separated into the individual components in the usual manner, for example by crystallization or chromatography. As individual isomeric compounds, also mixtures thereof are included in the invention and are useful as a pest control agent. However, as a rule, the compounds of the invention are formed in a broadly predominant (E, E) -configuration. These isomers are also preferred due to their activity.

0, hrch _3, general formula I, E, E-configuration

The novel compounds of the formula I can be prepared as shown, for example as follows:

ABOUT

X

Starting from compounds of formula 2 ⁱⁿ which X represents a hydroxyl group, a chlorine atom or an O - ((C 1-4) alkyl) group (the compounds are known from European Patent Nos. 453 488, 472 300 and 426 460) and left to react. reacted with monomethylamide, the compound of the formula I according to the invention is obtained in a manner analogous to that known from the literature for the reaction with methylamine (po-z-i-Organi-cum-, 16, eds., p. 408 et seq.) /).

A particularly advantageous possibility of preparing the compounds of formula I is to react the O-benzylhydroxylamine of formula 2 with a phenylketone of formula 4 (cf. D. Otzanak, J. Chem. Soc., Chem. Commun. 903 (1986)). Surprisingly, the intermediate of formula (2X) can be prepared relatively smoothly and preferably by a simple reaction, by triple aminolysis of the compound of formula (3a) (with methylamine).

This one-step reaction of 3a ---------> 3 avoids the usual more lengthy and costly two-step process where, for example, hydrazinolysis releases an O-benzylhydroxylamine group from a phthalimine protecting group, and before or immediately thereafter the methyl ester group is converted to the methyl ester group. . Surprising as high yields of this reaction, although generally "is calculated's team ~ · that ^- they are not optimal conditions both for different methyl aminolysis of the methyl amide and also to release the O-benzyl from the corresponding O-benzylhydroxy- phthalimide.

The phenyl ketones of formula (4) are known compounds or can be purged using a method analogous to the known method (Houben-Weyl, Vol. 7 / 2a and 7 / 3a).

The novel compounds of formula (I) are also obtained when the monomethylamide of a benzyl compound of formula (5) in which L represents a leaving group (e.g., bromine, chlorine or iodine, the mesylate, tosylate or triflate residue) (cf. e.g. European Patent Nos. 398,692). and 463,488) is reacted with an oxime of formula 6 (cf., for example, Houben-Weyl, Vol. 10/1, pp. 1186 et seq.).

5th

The oximes of formula 6 are known compounds or can be prepared by known methods (cf. Houben-Weyl, Vol. 10/4, J. Med. Chem. 26, 1360 (1983)).

The novel compounds of the formula I can further be prepared by reacting the benzyl alcohol of the formula 7 in a known manner with oximes of the general formula 6 (cf. J. Jurczak, Synthesis, 682 (1976)).

Alternatively, the ketonamides of the formula 8 can be reacted in a known manner with methoxyamine (methoxyamine hydrochloride) to give novel compounds of the formula I (cf. DE 36 23 921).

For example, ketonamides 8 can be obtained from keto esters 9 by aminolysis, keto esters 9 alone, either by Pinner reaction from benzoyl cyanides 10 or oximes 6 with benzyl compounds 11.

ABOUT

Still further precursors for the production of keto amides of formula 8 or keto esters of formula 9 are suitable aryl halides of formula 19 (wherein Hal represents a chlorine, bromine or iodine atom). These compounds can be converted by metallization (for example with magnesium, methylmagnesium bromide, sodium or n-butyllithium) to the corresponding organometallic compounds, which can then be converted in a known manner by treatment with oxalic acid derivatives (such as oxalic acid ester or N'-methylamidic acid ester). oxal) to compounds of formula 8 or 9 (cf., for example, LM Weiristock, Synth. Commun. 11, 943 (1981)).

can also be converted in a known manner, by reaction with methylamine, into the novel compounds of the formula I (cf.

Cyanoximether 12

468,775).

H ₂ NMe

------------> _NC 3 _N / ° ^{CH 3}

The cyano oxime of formula 12 is obtained, for example, by a known method by reacting oximes of formula 6 with benzyl bromide 13.

The ketonamides of formula (8) can also be obtained in a simple manner from the nitrile salts of formula (17) by hydrolysis, both in acid and in alkaline solution (cf. Houben-Weyl, Vol. E5, Part 2, pp. 1580 et seq.).

For example, the nitrile salts of formula 17 are readily available from the compound of formula I by reaction with a terimethyloxonium salt, such as trimethyloxonium tetrafluoroborate, or by reaction of a compound of formula 10 with, for example, trifluoromethanesulfonic acid methyl ester. (cf. Houben-Weyl, Vol. E5, Volume 2, pp. 1573-1576).

Correspondingly, the compounds of the formula I can also be easily obtained from the nitrile salts of the formula 18 by hydrolysis in an acid or alkaline solution (cf. Houben-Weyl, vol. E5, vol. 2, p. 1580 et seq.).

Nitrile salts of formula 18 are again readily available, for example, from compounds of formula 12 by reaction with trimethyloxonium salts, such as tetrafluoroboronate, trimethyloxonium, or by reaction of a compound of formula 12, for example, with methyl trifluoromethanesulfonic acid (cf. Houben-Weyl vol. 1573 - 1576).

Furthermore, the novel compounds of the formula I can also be prepared by methylation of suitable intermediates, such as those of the formulas 14 to 16.

MeX

MeX

-β> · I

ΝΗ ₂

MeX

The alkylation is conveniently carried out in the presence of a base such as potassium hydroxide, potassium carbonate or triethylamine. Methyl halide or also dimethyl sulfate can be used as the alkylating agent (cf., for example, Houben-Weyl, Vol. X / 1, p. 1186 et seq., Or G. L. Isele, Synthesis, 266 (1971)).

The substituents R and A ^ shown in formulas 2 to 19 have the meanings contained in claim 1. Substituent L denotes a leaving group, such as a halogen atom (chlorine, bromine or iodine atom), the tosylate, mesylate or triflate residue.

DETAILED DESCRIPTION OF THE INVENTION

The following examples are intended to illustrate the preparation of novel compounds and novel intermediates.

Example 1

Process for the preparation of E-2-methoxyimino-2- (2'-phthalimidooxymethyl) phenylacetic acid nretylester

To a solution of 150 g (0.52 mol) of 2-methoxyimino-2- (2'-bromomethyl) phenylacetic acid methyl ester and 85 g (0.52 mol) of N-hydroxyphthalimide in 350 ml of N-methylpyrrolidone is added dropwise 59 g (0.58 mol) of triethylamine and stirred at 70 ° C for 2 hours. The reaction mixture was poured onto 2 L of ice water, the precipitated crystals were filtered off with suction and taken up with methyl chloride. The organic phase is washed with water, dried over sodium sulphate and the solvent is removed by rotary evaporation. 168 g of E-2-methoxyimino-2- (2'-phthalimidooxymethyl) phenylacetic acid methyl ester are obtained as a pale-gray powder, m.p. 152-153 ° C. Yield 88%.

¹ H-NMR (CDC1 _3): δ = 3.81 (s, 3H), 3.95 (s, 3H), 5.05 (s, 2H), 7.12 to 7.81 (m, 8 H Example 2

Process for preparing E-2-methoxyimino-2- (2'-aminooxymethyl) phenylacetic acid monomethylamide

168 g (0.46 mol) of E-2-methoxyimino-2- (2'-phthaliminooxymethyl) -phenylacetic acid methyl ester are added to 1 L of a 40% aqueous monomethylamine solution and stirred at 40 ° C for 4 hours. After cooling, the reaction mixture is extracted with methylene chloride, the organic phase is washed with water, dried over sodium sulphate and evaporated. After crystallization of the residue from a mixture of methyl-tert-butyl ether and n-hexane, 92 g of E-2-methoxyimino-2- (2'-amino-oxymethyl) -phenylacetic acid monomethylamide is obtained in the form of pale yellow crystals, m.p. C. From the mother liquors, another final product is obtained.

¹ H-NMR (CDC1 _3): δ = 2.91 (d, 3H), 3.94 (s, 3H), 4.58 (s, 2H), 5.28 (br s, 2H), 6 88 (broad singlet, 1H), 7.14-7.43 (m, 4H) ppm.

Example 3

Method for the preparation of 2-methoxyimino-2- [2 '- / 1' '- (4' '' - tert-butylphenyl) -L '' -methyl / aminooxylmethyl-phenylacetic acid monomethylamide ((E, E) - isomer, Table 1, number 118)

A mixture of 4.3 g (18 mmol) of ε-2-methoxyimino-2- (2'-aminooxymethyl) -phenylacetic acid monomethylamide, 3.2 g (18 mmol) of 4-tert. -butylacetophenone and 1.0 g of molecular sieve (3.10 ^-10 m) in 10 ml of methanol are added to 100 mg of p-toluenesulfonic acid monohydrate and stirred at room temperature (20 ° C) for 16 hours.

After filtering off the molecular sieves, the reaction mixture is evaporated and the residue is crystallized from a mixture of methyl tert-butyl ether and n-hexane. This gives 4.8 g of the (E, E) -isomer of the title compound consisting of colorless crystals, m.p. 107-110 ° C. Yield: 68%.

x - Ί

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

¹ H-NMR (CDC1 _3): δ = 1.31 (s, 9 H), 2.18 (s, 3H), 2.83 (d, 3H), 3.95 (s, 3H), 5, 11 (s, 2H), 6.70 (broad singlet, 1H), 7.19-7.55 (m, 8H) ppm.

In the mother liquors after recrystallization, in addition to the (E, E) -isomer, the ¹ H-NMR spectroscopy is also capable of 20% [Z (C = NO-benzyl)].

E (C = NOCH ₃ )] - isomer (shift of the benzylic proton signal by 0.18 ppm towards the higher pole).

Example 4

(E, E) -2-methoxyimino-2- [2 '- / 1' '- (2' '- naphthyl) -1' '- methyl / iminooxymethyl] phenylacetic acid monomethylamide (Table 1, Number 1) )

3.0 g (7.7 mmol). acid monomethyl ester (E, E) -2-methoxyimino-2- [2 '- / 1''- (2 ^{rr'-naphthyl)} -L '' methyl / iminooxymethy] -phenyl-j (known from European patent no. 463 488) was contacted with 50 ml of a 40% aqueous monomethylamine solution and stirred at 40 ° C for 6 hours. After cooling, the reaction mixture is extracted three times with methyl tert-butyl ether, the organic phase is washed with water, dried over sodium sulphate and evaporated. Trituration with diisopropyl ether gave 1.9 g of the title compound as pale yellow crystals, m.p. 92-95 ° C. Yield: 64%.

¹ H-NMR (CDC1 _3): δ = 2.30 (s, 3H), 2.83 (d, 3H), 3.94 (s, 3H), 5.15. (S, 2H), 6 69 (broad singlet, 1H), 7.14-7.93 (m, 11H) ppm.

Example 5

(E, E) -2-: Methoxyimino-2- [2- (1 '- (4' '- chlorophenyl) -1'-n-propyl) iminooxymethyl] phenylacetic acid monomethylamide (Table 2, Number 44)

0.6 g (1.5 mmol) of (E, E) -2-methoxyimino-2 [2 '- / 1' '- (4' '' - chlorophenyl) -1 '' - n-propyl / iminooxymethyl methyl ester Phenylacetic acid (a compound known from European Patent No. 463 488) is dissolved in 15 ml of tetrahydrofuran, treated with 0.5 g of a 40% aqueous monomethylamine solution and stirred at 40-45 ° C for 6 hours. The reaction mixture is then evaporated, the residue is taken up with methyl tert-butyl ether, the organic phase is extracted with water, dried over sodium sulphate and evaporated again. Chromatography of the residue on a silica gel column (1: 1 cyclohexane / methyl tert-butyl ether) gave 0.5 g of the title compound as a colorless resin. yield: 83% of theory.

¹ H-NMR (CDC1 _3): δ = 0.94 (t, 3H), 1.54 (m, 2H), 2.70 (t, 2H), 2.89 (d, 3H), 3, 97 (s, 3H), 5.11 (s, 2H), 6.74 (broad singlet, 1H), 7.19-7.58 (m, 8H) ppm.

Example 6

A process for the preparation of E-2-methoxyimino-2- (2'-methylphenyl) acetonotril

188 g (1.68 mol) of dry potassium tert-butoxide are added to 2 liters of dry toluene and treated with 200 g (1.53 mol) of o-methylbenzyl cyanide and 173 g (1.68 mol) of tert. butylnitrile in 200 ml toluene. The mixture is heated to about 70 ° C, further stirred for 2 hours and treated with 1 liter of methyl tert-butyl ether. The yellow-colored potassium salt is filtered off with suction, then washed with methyl tert-butyl ether and dried at 50 [deg.] C. under reduced pressure.

200 g (1.46 mol) of this salt are then added to 2.5 dry acetone containing 20 g (0.15 mol) of potassium carbonate. During the dropwise addition of 243 g (1.65 mol) of iodomethane, the temperature rises to approximately 35 ° C. The reaction mixture was allowed to stir overnight and then partitioned between water and methyl tert-butyl ether. The organic phase is washed with water, dried over sodium sulphate, evaporated and distilled under reduced pressure (boiling point 95-100 [deg.] C / 1 mmHg). This gives 229 g of the title compound as a viscous liquid. The total yield corresponds to 78% of theory.

(CDCl3): δ = 2.53 (s, 3H), 4.22 (s, 3H), 7.2-

7.4 (dd, 1 H) ppm.

Example 7

Method for the preparation of E-2-methoxyimino-2- (2'-bromomethylphenyl) acetonitrile g (0.28 mol) E-2-methoxyimino-2- (2'-methylphenyl) acetonitrile and 54 g ~ (~, '3Ό) The N-bromosuccinimide is pre-loaded into 250 ml of carbon tetrachloride and irradiated from the outside for 40 minutes with a 300 W mercury pressure lamp. The succinimide is filtered off with suction and the solution is evaporated under reduced pressure. 62 g of the title compound (20) remain, which, according to the result of the @ ³ H-NMR spectrum, is approximately 80%. Yield: 88%.

• H-NMR spectrum (CDC1 _3): δ = 4.27 (s, 3H), 4.80 (s, 2H), 7.4 -

7.5 (m, 3H), 7.69 (dd, 1H) ppm.

Example 8

2-Methoxyimino-2- (2'-bromomethylphenyl) acetic acid N-methylamide g 2-Methoxyimino-2 - [(2'-methylphenoxymethyl) phenyl] acetic acid N-methylamide was added to 50 ml of dichloromethane. 9 g of hydrogen bromide are introduced into this solution at 10 ° C. Finally, all is dissolved and the reaction mixture is stirred for 3 days at room temperature. To the reaction mixture is added 50 ml of dichloromethane, washed with 5% sodium hydroxide solution and water, dried and evaporated. This gives 7 g of the title compound as a light brown solid.

Melting point: 128 to 129 C.

¹ H-NMR (CDC1 ₃ / TMS): δ = 2.95 s (d, 3H), 3.95 (s, 3H), 4.35 (s, 2H), 6, 85 .. (NH 7.1-7.5- (m, 4H-). p.pm ...

Example 9

Process for the preparation of 2-methoxyimino-2- (2'-chloromethylphenyl) acetic acid N-methylamide

To a solution of 2 g (6.4 mmol) of 2-methoxyimino-2 - [(2'-methylphenoxymethyl) phenyl] acetic acid N-methylamide in 30 mL of dichloromethane at 10 ° C was added dropwise 18.8 g of 1- of normal solution of boron trichloride in n-hexane and refluxing for 90 minutes. . is coming .. 8.2. g of methanol and the reaction mixture is stirred at room temperature overnight. The reaction mixture was washed with 5% sodium hydroxide solution and water, evaporated and dried. This gives 1.2 g of the title compound as a solid. Yield: 78%.

1 H-NMR spectrum (CDCl 3 / TMS): δ = s 2.96 (s, 3H), 3.96 (s, 3H), 4.46 (s, 2H), 6.86 (NH), 7 13-7.49 (m, 4H) ppm.

Example TD

2-Methoxyimino-2- [2 '- 1' - (4 '' - methylphenyl) -1''-methyl / iminooxymethyl] phenylacetic acid N-methylamide

To the solution. 2. g. (7 mmol) of oxime etheramide bromide (from example) in 20 ml of dichloromethane is added to the tip of a spatula with tetra-n-butylammonium iodide followed by a solution of 1.2 g (7 mmol) of p-methylacetophenone oxime in 10 ml of dichloromethane. 20 ml of 10% sodium hydroxide solution are then added dropwise to the reaction mixture and the mixture is refluxed for 6 hours. After separation of the phases, extraction with dichloromethane is carried out, the phases are dried, evaporated and the residue is chromatographed on silica gel with a mixture of hexane and methyl tert-butyl ether. This gives 1.1 g of the title compound. Yield: 45%.

¹ H-NMR spectrum (CDCl ₃ / TMS): δ = s 2.18, 2.34 (s, 3H), 2.85 (d, 3H), 3.95 (s, 3H), 5.09 ( s, 2H), 6.67 (NH), 7.12-7.50 (m,

8H) ppm.

Example 11

Process for preparing 4-methoxyacetophenoxime-O- (2-bromo) benzyl ether

To a suspension of 2.8 g (94 mmol) (80% sodium hydride in 250 mL of DMF) was added dropwise a solution of 14 g (85 mmol) of p-methoxycyanoacetophenoxime under a nitrogen atmosphere and stirred for 2 hours at room temperature. 3 g (85 mmol) of o-bromobenzyl chloride in 10 ml of dimethylformamide were stirred for 90 minutes, the reaction mixture was hydrolyzed with 10% hydrochloric acid and extracted with methyl tert-butyl ether, after drying and evaporation, 27.7 g of the title compound remained. The title compound was a yellow-brown oil with a yield of 98% of theory.

¹ H-NMR spectrum (CDCl ₃ / TMS): δ = s 2.21, 3.85 (s, 3H), 5.34 (s, 2H), 6.91-7.66 (m, 8H) ppm .

Example 12

Process for the preparation of 2-methoxyimino-2- [2 '- 1' '(4' '' - methoxyphenyl) -1 '' - methyl / iminooxymethyl] phenylacetic acid N-methylamide

To a solution of 5 g (15 mmol) of bromide (from Example 11) in 40 mL of tetrahydrofuran was added at room temperature. -78 ’C under a nitrogen atmosphere

6.6 g (15 mmol) of a solution of n-butyllithium in hexane and immediately thereafter 4.4 g (30 mmol) of diethyl oxalic acid ester are added. The reaction mixture is allowed to dissolve, water is added, extraction is carried out with methyl tert-butyl ether, dried and evaporated. The residue is chromatographed on silica gel using hexane / methyl tert-butyl ether. 2.7 g of the corresponding α-ketoester are obtained in the form of an oil. Yield: 51%.

To a solution of 400 mg of this ketoester in 10 mL of tetrahydrofuran was added 50 mL of a 40% N-methylamine solution and heated to 50 ° C for one hour. Finally, 2 g of methoxyamine hydrochloride was added and the whole was heated again at 50 ° C. The reaction mixture was allowed to cool, extracted with dichloromethane, dried and evaporated. 300 mg of the title compound are obtained (Table 1, No. 219).

¹ H-NMR spectrum (CDCl 3 / TMS): δ = 2.15, 3.13, 3.77 (s, 3H),

2.86 (d, 3H), 5.06 (s, 2H), 6.84-7.56 (m, 8H) ppm.

Other compounds of formula I according to the invention are listed in Tables 1 and 2.

Table 1

NHCH ₃

Number am Physical data * 1 2+ 3 2F t. t. : 43 - 4 7 'C 4 3F oil, IR (film):

3350,2945,1671,1526

1037.979

5 4F 1.1. : 60 - 63 ° C 6 2,3-F ₂ 1.1. : 73 - 75 'C 7 ² ' ⁴ - ^F 2 ... 8 2,5-F ₂ t. t. : 78 - 80 'C 9 2,6-F ₂ 1.1. : 123 - 125 'C 10 3,4-F ₂ 1.1. : 103 - 104 • c 11 3,5-F ₂ t. t. : 98 - 100 'C 12 2,3,4-F ₃

Number % physical data • 13 ' 2, 3,5-F ₃ 14 2,4,5-F ₃ t. t. : 67 - 70 ° C 15 ' 3,4,5-F ₃ 16 2,3-Cl ₂ t. t ..: 92 - 94 C 17 2,4-Cl ₂ t. t ..: 97 - 99 C 18 2,5-Cl ₂ 1.1. : 118 - 120 C 19 3,4-Cl ₂ mp : 98 - 101 C 20 3-F, 4-OCH ₃ 21 2,3,5-Cl ₃ 22 2,4,5-Cl ₃ 23 3.4 _f 5-C1 ₃ t. t. : 84 - 88 C 24 2-Br t. t. : 83 - 86 'C 25 4-Br t. t. : 94 - 96 C 26 2,3-Br ₂ 27 2,4-Br ₂ ²⁸ . 2,5-Br ₂ - 29 ..... 3rd - 4th -Br 2 ..... 30 3,5-Br ₂ 1.1. : 120 - 122 C

Number am Physical data 31 ’ 2,3,4-Br ₃ 32 2 _t 3 _t 5-Brβ 3 3 2 ', 4,5-Br ₃ 34 3,4,5-Br ₃ 35 2-1 36 3-1 37 4-1 38 2,3-I ₂ 39 2,4-I ₂ 40 2.5-I ₂ 41 3,4-I ₂ 42 3,5-I ₂ 43 2-F, 3-C1 44 2-F, 4-C1 45 2-F, 5-C1 46 2-F, 3-Br 47 ...... . 2.-E. _r .. 4.-Br ......... 48 2-F, 5-Br

Number physical data 4 9 - 2-C1, 3-Br 50 2-C1, 4-Br 51 '' 2-Cl, 5- Br 52 3-F, 4-C1 53 3-F, 5-C1 54 3-F, 6-C1 55 3-F, 4-Br 56 3-F, 5-Br 57 3-F, 6-Br 58 3-C1, 4-Br 59 3-C1, 5-Br 60 3-C1, 6-Br 61 4-F, 5-C1 m.p .: 150 - 154 C 62 4-F, 6-C1 63 4-F, 5-Br 1.1. :: 80 - 82 ° C 64 4-F, 6-Br 65th 4-C1 ,. 5-Br 66 4-C1, 6-Br

Number ^ ιη Physical data • 67 5-F, 6-C1 68 5-F, 6-Br 69 ' 5-C1, 6-Br 70 3-C1, 4-F, 5-C1 71 ' '3-Br, 4-Cl, 5-Br 72 3-C1, 4-Br, 5-Cl 7 3 ' 2-CN 74 3-CN tt: 121-125 ⁰ C 75 4-CN 76 2-NO ₂ 1.1. :: 97-99 ⁰ C 77 3-NQ ₂ 1.1. 101-103 ⁰ C 78 3-CH ₃ oil, IR (film):

3350,2938,1671,1526,

1093,1037,979,787,697

79 2,3- _{(CH3) 2} 80 2,4- _{(CH3) 2} 1.1. : 107 - Mp 110 ° C 81 2,5- _{(CH3) 2} mp .: 85 - 86 ° C 82 2,6- (CH _{3) second} 83 3,4- _{(CH3) 2}

Number % physical data 8 · 4 · · • 3,5- _{(CH3) 2} mp: 88 - 90 ' 'C 85 2,3,4- _{(CH3) 3} 86 2,3,5- _{(CH3) 3} 87 2,3,6- _{(CH3) 3} 88 ...... 2,4,5- _{(CH3) 3} 89 2,4,6- _{(CH3) 3} 90 "3,4,5- (CH _{3) 3} 91 2-C ₂ ^H p 92 ³ ' ^C 2 ^H 5 93 4- ^c ₂ ^H 5 m.p .: 87 - 89 ⁰ C 94 2,3- (C ₂ H _{5) 2} 95 2,4- (C ₂ H _{5) 2} 96 2,5- (C ₂ H _{5) 2} 97 3,4- (C ₂ H _{5) 2} 98 3,5- (C ₂ H _{5) 2} m.p .: 61 - 64 ° C 99 3,4,5- (C ₂ H ₅ ) ₃ 100 3-nC ₃ H _? 101 4 mp : 78 - 80 ⁰ C

Number % Physical data 101A 3,4- (n-C1 H-y) 2 102 3,5- (n-CjH ·?) 2 103 3 ~ iso-C 104 4-cis-C ₃ H ₇ mp: 93-95 ° C 105 3 _t 4 - (ISO-C3H7) 2 106 3,5- (iso-C ₃ H ₇₎ 2 107 3-cyclopropyl 108 4-cyclopropyl 109 3-C ₄ H _g 110 4 ~ nC ₄ Hg 111 3,4- (n-C ₄ H ₉ ) ₂ 112 3,5- (nC ₄ H ₉ ) 2 113 3 sec-C ₄ H ₉ 114 4 sec-C ₄ H _g 115 3-iso-C ₄ H _g 116 4-iso-C ₄ H _g 117 ... 3-tert-C ₄ Hg ...

118 4-tert-C ₄ Hg

mp: 107

Mp 110 ° C

Number ^A m Physical data 119 3,4- (t-C ₄ H _g ) ₂ 120 3,5- (t-C ₄ H _g ) ₂ 121 ^3-n_c 5 ^H 11 122 4-n- ^c ₅ Hn 123 3 ^- n-C ₈ H 13 124 4-n- ^c ₆ ^H 13 125 3-cyclohexyl 126 4-cyclohexyl tt: 110-112 ⁰ C 127 3-phenyl tt: 70-72 ⁰ C 128 4-phenyl tt: 138-140 ⁰ C 129 3-viny 1 130 4-vinyl 131 3-allyl 132 4-allyl 133 3-propargyl 134 4-propargyl 135 ..... 3. propylene-2-yl. .. - 136 4- (propen-2-yl)

Number ^A m Physical data 13 7 ' Of 3- (but-2-en-2-yl) 138 4- (but-2-en-2-yl) 13 9 ’ 3-t. C ^ H ^ · 140 4-t-C ^ hij 141 2-CH ₃ , 3 -C ₂ H ₅ 142 2-CH ₃ , 4-C ₂ H ₅ 143 2-CH ₃ , 5-C ₂ H ₅ 144 _2-CH3, 3-n-C ₃ H ₇ 145 2-CH ₃ , 4-nC ₃ H _? 146 2-CH ₃ , 5-nC ₃ H _? 147 2 ~ ΟΗ.β f 3 “Ϊ3θ“ ΟβΗ- ^ 148 2-CH ₃ , 4-iso-C ₃ H ₇ 149 2-CH ₃ , 5-iso-C ₃ H ₇ 150 2-CH ₃ , 3-nC ₄ H _g 151 _2-CH3, 4-n-C ₄ H _g 152 2-CH ₃ , 5-nC ₄ H _g 153 2-CH. _3. , ..... 3-sec.-C ₄ H ₉ .... 154 2-CH ₃ , 4-sec-C ₄ H _g

Number am Physical data “155 ..... 2-CH _3, 5-sec.-C ₄ H ₉ 156 2-CH _3, 3-iso-C ₄ H _g 1'57 ' 2-CH _3, 4-iso-C _"4 Hg 158 2-CH _3, 5-iso-C ₄ H _g 159 2-CH _3, 3-t-C ₄ Hg 160 2-CH _3, 4-t. ^- C ₄ Hg 161 2-CH _3, 5-tert-C ₄ H _g 162 2-CH _3, 3-cyclohexyl 163 2-CH _3, 4-cyclohexyl 164 2-CH _3, 5-cyclohexyl 165 2-CH. ₃ , 3-phenyl 166 2-CH _3, 4-phenyl 167 2-CH _3, 5-phenyl 168 2-CH _3, 4-vinyl 169 2-CH _3, 4-allyl 170 2-CH _3, 4-propargyl 171 2-CH _3, 4- (propen-2-yl) 172 2-CH _3, 4- (but-2-en-2-yl)

Number ^A m Physical data 17'3 ~ ··· 3-CH ₃ , 4-C ₂ H ₅ 174 3-CH ₃ , 5-C ₂ H ₅ 175 ~ 3-eH-3,4-nC ₃ H-7 176 3-CH3, 5-n-C ₃ H ₇ 177 3-CH 3, 4-iso-C 3 H ₇ 178 f 5-isoC 1 H-y 179 3-CH 3, 4-cyclopropyl 180 3-CH ₃ , 4-nC ₄ H ₉ 181 3-CH ₃ , 5-nC ₄ H ₉ 182 _3-CH3, 4-sec-C ₄ H _g 183 3-CH ₃ , 5-sec-C ₄ H ₉ 184 3-CH ₃ , 4-iso-C ₄ H _g 185 3-CH ₃ , 5-iso-C ₄ H ₉ 186 3-CH ₃ , 4-tert-C ₄ H ₉ 187 3-CH ₃ , 5-tert-C ₄ H _g 188 3-CH ₃ , 4-cyclohexyl 189 3-CH 3, 5-cyclohexyl 190 3-CH ₃ , 4-phenyl

Number Physical data 191 3-CH ₃ 5-phenyl 192 3-CH _3, 4-vinyl 193 3-¾. 4-allyl ' 194 3-CH _3, 4-propargyl 195 3-CH _3, 4- (propen-2-yl) 196 3-CH _3, 4- (but-2-en-2-yl) 197 4-CH _3, 5-C ₂ ^H s 198 4-CH _3, 5-nC ₃ H _? 199 4 — CH ₃ , 5-iso-C ₃ H ₇ 200 4-CH _3, 5-cyclopropyl 201 4-CH _3, 5-nC ₄ H ₉ 202 4-CH _3, 5 sec-C ₄ H _g 203 4-CH _3, 5-iso-C ₄ H _g 204 4-CH _3, 5-tert-C ₄ H _g 205 4-CH _3, 5-cyclohexyl 206 4-CH _3, 5-phenyl 20.7 ... 4-CH ₃ '. 5-vinyl 208 4-CH _3, 5-allyl

Number % physical data '209 4-CH ₃ , 5-propargyl 210 _4-CH3, 5- (propen-2-yl) 211 " 4-CH ₃ 5- (But-2-eth-yl) 212 _3-CH3, 4-t-C ₄ H _{g, 5-CH3} 213 3-tert-C 4 H 8, 4-CH ₃ , 5-tert. - ^C 4 ^H 9 214 2-OH m.p .: 108 - Mp 110 ° C 215 3-OH m.p .: 123 - 125 “C 216 4-OH m.p .: 170 - 171 ° C 217 2-OCH ₃ m.p .: 79 - 81 ° C 218 3-OCH ₃ 1.1. :: 93 - 95 ’C 219 4-OCH ₃ mp: 65 - 68 ° C 220 2,3- _{(OCH3) 2} 221 2,4- _{(OCH3) 2} m.p .: 113 - 114 ’C 222 2,5- _{(OCH3) 2} m.p .: 98 - 101 ’C 223 3,4- _{(OCH3) 2} m.p .: 132 - 135 ’C 224 3,5- _{(OCH3) 2} m.p .: 97 - 99 “C 225. 3 .. .4, 5 - (. QCH. _{3.) 3} m.p .: 118 - 120 ° C

Number ^A m Physical data 226 ..... 2,3,4- (OCH ₃ ) ₃ oil, IR (film): 3370,2945,1675,1496, 1463,1412,1094,1037 227 ‘ 3-OC ₂ H · ^ · oil, IR (film):

3350,2936,1671,1526,

1223,1038,980

228 4-OC ₂ H ₅ t. t. : 106 - 108 ° C 229 3,4- (OC ₂ H ₅ ) ₂ 230 3,5 (OC ₂ H _{5) 2} 231 3-OnC ₃ H _? t. t. : 106 - 109 ° C 232 4-OnC ₃ H ₇₂ mp : 99 - 102 C 233 3,4 _{(3H onc?) 2} 234 3,5-CO-nC ₃ H ₇ ) ₂ 235 3-O-iso-C ₃ H ₇ oil, Company ID (a movie):

3350,2975,1672,152.

1223,1037,979 236 4-0-ISO-C ₃ H ₇ oil ID (film): 3396 ,, 2980,1659,1513, 1252, 1047 237 3,4- (0-iso-C ₃ H _{7) 2} 238 3,5- (0-iso-C ₃ H ₇₎ 2 239 3-O-cyclopropyl

Number % Physical data '240 ..... 4-O-cyclopropyl 241 3,4- (O-cyclopropyl) ₂ 23 2 · · ' 3,5- (O-Cyclopropyl) ₂ 243 3-O-n-C ^ Hg oil, IR (film):

3360,2958,2935,1671,

1526,1224,1037,979

244 4-OnC ₄ H ₉ t. t. : 112-115 • c 245 3,4- (O-nC ₄ H _g ) ₂ 246 3,5- (OnC ₄ H ₉ ) ₂ 247 3-O-sec-C ₄ H ₉ 248 4-0-sec.-C ₄ H ₉ 1.1. : 95-97 C 249 3,4- (O-sec-C ₄ H ₉ ) ₂ 250 3,5- (O-sec-C ₄ H ₉ ) ₂ 251 3-O-iso-C ₄ H ₉ oil, ID (film):

3350,2958,2936,1672,

1225,1038,979 252 4-O-iso-C ₄ H ₉ oil, IR (film): 3350,2959,2936,1672, 1514,1248,1036 253 3 _ζ 4 ~ (0 “· θ5θ · Ό ^ Ηθ) 2 254 3,5- (O-iso-C ₄ H _g ) ₂

Number

Physical data

- 255- ' 3 '0-t-C ₄ Hg mp: 66-67 ° C 256 4-0-t-C ^ Hg Mp: 51-55 ° C 257 - '· 3,4- (O-tert-G ₄ H ₉ ) ₂ 258 3,5- (O-t-C ₄ H _{g) 2} 259 β-Ο-η-Ω ^ ^ Η oil, IR (film): 3360,2955,2935,1672, 1526,1226,1037,980 260 4-OnC ₅ H _xl mp .: 60 - 65 CC 261 3,4- (O-D-C 8 H _xx ) ₂ 262 3,5- (OnC ₅ H _{1 L} ) ₂ 263 3-O ^- n-ΟθΗ _χ 3 oil, IR (film): 3350,2933,1670,1524, 1223,1037,979 264 4-OnC ₆ H ₁₃ mp: 74-76 ° C 265 3,4 (onc ₆ H _{13) 2} 266 3,5 (onc ₆ H _{13) 2} 267 3-O-cyclohexyl 268 4-O-cyclohexyl 269 3,4- (O-Cyclohexyl) ₂ 270 3,5- (O-Cyclohexyl) ₂

Number Physical data * 2 71 ' 3-OC ₆ H ₅ 272 4-OC ₆ H ₅ 1.1. Mp 118-120 ° C 2'73 '' 3,4 - ('OC2H5) 2 274 3,5- (OC ₆ H ₅ ) ₂ 275 3-O-allyl oil, IR (film): 3340,2942,1669,1523, 1225,1037,980 276 4-O-allyl mp: 94-97 ° C 277 3,4- (O-allyl) ₂ 278 3,5- (O-allyl) ₂ 279 3-O-tert. 280 4-O-tert "CGH-L! 281 2-CF ₃ 282 3-CF ₃ oil, IR (film): 3345,2940,1672,1341, 1276,1167,1126,1038 283 4-CF ₃ mp: 83-85 ° C 284 2,3- (CF ₃ ) ₂ 285 2,4- (CF ₃ ) ₂ 286 2,5- (CF ₃ ) ₂

Number % Physical data • - 2'87 ’ 3 ', 4- (CF ₃ ) ₂ 288 3,5- (CF ₃ ) ₂ mp: 138-140 ° C 2'89 ..... 3 ', 4-, 5- (CF ₃ ) ₃ 290 2-CF ₂ Cl 291 3-CF ₂ Cl 292 4-CF ₂ Cl 293 3-CFCl ₂ 294 4-CFCl ₂ 295 3-CCl ₃ 296 4-CCl ₃ 297 3 _of 4- (CC1 ₃ ) ₂ '298 3,5- (CCl 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 ^F 5

304 4-C ₂ F ₅

Number % Physical data  305 · 3-CHCl 2 306 4-CHCl ₂ 307 " 3-CH ₂ Cl ..... 308 _4-CH2 Cl 309 ' 3,4- (CH ₂ Cl) ₂ 310 3,5- (CH ₂ Cl) ₂ 311 3 - CF ₂ CHF ₂ 312 4-CF ₂ CHF ₂ 313 3-CH ₂ CCl ₃ 314 4-CH ₂ CCl ₃ 315 3-C ₂ ^c5 316 4-C ₂ ^c5 317 3-C (CH ₃ ) ₂ CH ₂ Cl 318 4-C (CH ₃ ) 2 ^CH 2 ^Cl 319 3-CH ₂ CH ₂ Cl 320 4-CH ₂ CH ₂ Cl .321 2-OCF ₃ 322 3-OCF ₃

Number ^A m Physical data '3 23' 4-OCF ₃ m.p .: 72 -  74 C 324 2,3- _{(OCF3) 2} 3 25 2,4- (0CF _a ) ₂ 326 2,5- _{(OCF3) 2} 327 3,4- _{(OCF3) 2} 328 3,5- _{(OCF3) 2} 329 3-OCHF ₂ 330 4-OCHF ₂ m.p .: 78 - 80 ° C 331 3-OCCl ₃ 332 4-OCCl 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-OC ₂ F ₅ 338 4-OC ₂ F ₅ 3 3 .9. . 4 - (_OC ₂ F ₅ ) ₂ . 340 3.5— (OC ₂ F5) 2

Number ^A m physical data ..... 3 4 ¾ ' 3-OCF ₂ CHF ₂ mp: 67 - 68 ° C 342 4-OCF ₂ CHF ₃ mp: 75 - 77 ° C 343 3,4- (OCF CHF ^ ^) 344 3,5- (OCF ₂ CHF _{2) 2} 345 3-CF ₃ , 4-OCF ₃ 346 _{3-CF3, 5-OCF3} 347 _{4-CF3, 5-OCF3} 348 3-CH ₂ OCH ₃ 349 4-CH ₂ OCH ₃ 350 3-CH ₂ O (tert-C 1 H 6) 351 4-CH ₂ O (tert-C ₄ H _g ) 352 3-C (CH ₃ ) ₂ CH ₂ OCH ₃ 353 4-C (CH ₃ ) ₂ CH ₂ OCH ₃ 354 3-C (CH ₃ ) ₂ OCH ₃ 355 4-C (CH ₃ ) ₂ OCH ₃ 356 3-C (CH ₃ ) (OCH ₃ ) ₂ 357 4-C ₍₃ .CH). _{(OCH3) 2} 358 3-CH (OCH ₃ ) ₂

Number WITH physical data 359 · 4 -CH (QCH'3) ₂ 360 _3-CH2 (CN) 361 - _4-CH2 (CN) ..... 362 3-C (CH ₃ ) ₂ CH ₂ CN 363 ' 4-C (CH ₃ ) ₂ CH ₂ CN 364 3-CH ₂ (NO ₂ ) 365 ..... 4-CH ₂ (NO ₂ ) 366 3-CH0 367 4-CHO 368 3-CO-CH ₃ 369 4-CO-CH ₃ 370 3-CO-C ₂ H ₅ 371 4-CO-C ₂ H ₅ 372 2-CO ₂ H 373 3-CO ₂ H 374 4-CO ₂ H mp: 188 - 190 ’C 375 3-CO ₂ CH ₃ 376 4-CO ₂ CH ₃

Number Physical data 377 3-CO ₂ C ₂ H ₅ 378 4-CO2C2H5 mp: 69-72 ° C 37 9 ' 3 _C0-2-n-C3H7 380 381 3-CO 2 -SO 2 -C 1 H 2 382 4 · "002 ** * Ϊ2θ ΌβΗ · ^ 383 5-CO ₂ -nC ₄ H _g 384 4-CO2n-C ^ Hg 385 3-CO2 ~ s. * C ^ Hg 386 4-CO ₂ -sec-C ₄ Hg 387 3 "CO2" iso-C ^ Hg 388 4-CO ₂ -iso-C ₄ H _g 389 3-CO ₂ -t-C ₄ H _g 390 4-CO ₂ -t-C ₄ H _g 391 ^3-CO 2 ^-nC 5 ^H 11 392 ^4-CO 2 ~ ^n_C 5 ^H 11 393 ^3-c0 2 ~ ^nC 6 ^H 13 394 ^4-Co 2 ~ ^nC 6 ^H 13

Number physical data • 395 ..... 2-C (= O) -NH ₂ 396 3-C (= O) -NH ₂ 397 ~ · 4-C (= O) -NH ₂ 398 3-C (= O) -NHCH ₃ 3 99 ' 4-C (= O) NHCH ₃ 400 3-C (= O) -N (CH ₃ ) ₂ • 4 0¾ “ 4-C (= O) -N (CH ₃ ) ₂ 402 3-C (= O) -N (C ₂ H ₅ ) ₂ 403 4-c (= o) -ncc ₂ h ₅ ) ₂ 404 2-C (= S) -NH ₂ 405 3-C (= S) -NH ₂ 1.1. :: 174 - 175 ° C 406 4-C (= S) -NH ₂ 407 2-NH ₂ 408 _3-NH2 mp .: 92 - 94 ° C 409 _4-NH2 m.p .: 131 - 133 C 410 3-NCH ₃ 411 4-NCH ₃ 412 3-N (CH ₃ ) ₂

Number ^A m Physical data 413 - 4-N _{(CH3) 2} mp: 98-100 ° C 414 3-NHC (= O) _CH3 415 ...... 4-NHC ('= O3CH3 ₎ mp: 165-167 ° C 416 3-N (CH ₃ ) C (= O) CH ₃ 417 '' 4-N (CH ₃ ) C (= O) CH ₃ 418 3-NHCO ₂ CH ₃ 419 · - 4-NHCCT ₂ CH ₃ 420 2-CH ₃ , 4-cyclopropyl 421 ........ 3-N (CH ₃ ) CO ₂ CH ₃ ' 422 4-N (CH ₃ ) CO ₂ CH ₃ 423 3-O-CH (= O) CH ₃ 1.1. :: 108-110 ° C 424 4-OC (= O) _CH3 oil, IR (film):

3360,2942,1754,1671,

1199.1036

425 3,4- [OC (= 0) CH _{3] 2} 426 3,5- [OC (= O) CH _{3] 2} 427 3-O-C (= O) C ₂ H ₅ 428 4-OC (= O) C ₂ H ₅ 429 3-OC (= O) (iso-C _{3 H?)}

Number % physical data  430 ..... 4-0-0 (= 0) (ISO-C ₃ H ₇ ) 431 3-0-0 (= 0) (t-C ₄ H ₉ ) 432 4-0-0 (= 0 ^-) fterc. -¾) 433 3-SH 434 4-SH 435 3-SCH ₃ 436 4-SCH ^- ^ m.p .: 97 - 100 ° c 437 3-SC ₂ ^h 5 438 4-SC ₂ H ₅ 439 3-S-iso-C ₃ H ₇ 440 4-S-cis-C ₃ H ₇ 441 3-S-t-C ₄ Hg 442 4-S-t-C ₄ Hg - 443 3-S (= O) _CH3 444 4-S (= O) _CH3 445 3-SO ₂ CH ₃ 446. 4-SO ₂ CH ₃ . 447 3-CH = NH

Number % Physical data  448 · 4-CH-NH 449 3-CH = NCH ₃ 4 50 4-CH = NCH ₃ 451 3-C (CH ₃ ) = NH 452 4-C (CH ₃ ) = NH 453 3-C (CH ₃ ) = NCH ₃ 454 4-C (CH ₃ ) = NCH ₃ 455 3-N = C (CH ₃ ) ₂ 456 4-N = C (CH ₃ ) ₂ 457 3-C (SCH ₃₎ = NOCH ₃ 458 4-C (SCH ₃₎ = NOCH ₃ 459 3-C _(OCH3) = NOCH ₃ 460 4-C _(OCH3) = NOCH ₃ 461 3-C (NH ₂ ) = NOCH ₃ 462 4-C (NH ₂₎ = NOCH ₃ 463 3-C _(NCH3) = NOCH ₃ 464 4-C _(NCH3) = NOCH ₃ - 465 3-CH = NOCH ₃

Number % Physical data 466 4-CH = NOCH ₃ 467 3-C _(CH3) = NOCH ₃ 468 4-C (CH ₃₎ = NOCH ₃ mp: 105-107 ° C 469 3-C (CH ₃ ) = NOC ₂ H ₅ 470 4-C (CH ₃ ) = NOC ₂ H ₅ oil, IR (film): 3350,2935,1671,1525, 1947.979 471 3-C _(CH3) = NO-n-C ₃ H ₇ 472 4-C _(CH3) = NO-n-C ₃ H ₇ oil, IR (film): 3350,2963,2935,1672, 1525,1037,979,927 473 3-C (CH ₃ ) = NO-cis-C ₃ H ₇ 474 4-C (CH ₃ ) = NO-ISO-C ₃ H ₇ 475 3-C (CH ₃ ) = NO-nC ₄ H ₉ 476 4-C _(CH3) = NO-n-C ₄ H ₉ oil, IR (film): 3350,2957,2935,1673, 1525,1038,979 477 3-C (CH ₃ ) = NO-sec-C ₄ H ₉ 478 4-C (CH ₃ ) = NO-sec-C ₄ H _g 479 3-C (CH ₃ ) = NO-iso-C ₄ H _g

Number % Physical data 480 ' 4-c (ch ₃ ) = no-iso-c ₄ h ₉ oil, IR (film): 3350,2958,2935,1673, 1525,1039,979,927 481- 3-C (CH ₃ -) = NQ-tert-C ₄ H _g 482 4-C (CH ₃ ) = NO-t-C ₄ H ₉ 483 ..... ... 3-C (CH ₃ ) = NO-n C ₅ H _{1: L} 484 4-C (CH ₃ ) = NO-n C ₅ H ₁₁ 485- - - 3-C (CH ₃ ) - = NO-nC ₆ H ₁₃ - 486 4-C (CH ₃ ) = NO-nC ₆ H ₁₃ 487 2-C1, _3-CH3 488 2-C1, _4-CH3 489 - 2-ei, 5-ch ₃ 490 3-C1, _4-CH3 mp: 88-90 ° C 491 - 3-C1, _5-CH3 mp .: 86-88 ° C 492 2-C1, 2-CH ₃ 493 2-CH3 4-C1 494 2-CH ₃ 5-Cl 495 3-CH ₃ 4-Cl mp: 88-90 ° C 496 3-Cl, 5-t-C ₄ H _g

Number % physical data 497 2-Cl, 4-t-C ₄ H ₉ 498 3-Cl, 4-t-C ₄ H _g 499 3-Cl, 4-cyclohexyl 500 2-F, _4-CH3 501 3-F, _4-CH3 t. t. :: 42 - 44 ° C 502 3-F, _5-CH3 503 _2-CH3, 4-F 504 _3-CH3, 4-F t. t. : 75 - 78 ⁰ C 505 2-F, 3-t-C ₄ H _g 506 2-F, 4-t-C ₄ H _g 507 3-F, 4-t-C ₄ H _g 508 2-F, _4-OCH3 1.1. : 65 - 6 ° C 509 2-Br, _4-CH3 510 3-Br, _4-CH3 t. t. : 54 - 56 ° C 511 3-Br, _5-CH3 512 _2-CH3, 4-Br 513 _3-CH3, 4-Br t. t. : 97 - 99 ° C 514 2-Br, 3-t-C ₄ H _g

Number % Physical data 515 ' 2-Br, 4-t-C ₄ H ₉ 516 3-Br, 4-t-C ₄ H ₉ 517- 2-Cl, 4-NO2 518 3-Cl, _4-NO2 519 ..... 3-Cl, 5-N0 ₂ 520 _3-NO2, 4-C1 mp: 108-110 ° C 5'21 .....  3-Cl, 4- (but-2-en-2-yl) 522 3-Cl, _4-OCH3 oil, IR (film): 3340,2940,1672,1507, 1271,1063,1037 523 _3-OCH3, 4-C1 524 3-Cl 4 _f - OC2H5 oil, IR (film): 3345,2940,1671,1505, 1270,1060,1038 525 ' 3-Cl, 4-O-iso-C ₃ H ₇ oil, IR (film): 3345,1280,2940,1671, 1525,1502,1269,1037, 979 526 3-Cl, 4-O-t-C ₄ H ₉ 527 2-C1, _5-CF3 528 3-Cl, 4-CF ₃

Number WITH physical data 529 - 3-Cl ·, 5-CF ₃ 530 _3-CF3, 4-C1 t. t. : 68 - 70 ° C 531 3-Cl, _4-CH2 Cl 532 3-Cl, 4-OCF ₃ 533 ...... .. .3-Cl, _5-OCF3 534 _3-OCF3, 4-C1 535 ... - . . 3-Cl. ... 4-OCH ₂ CF ₃ .. .... 536 3-Cl, 4-OC ₂ F ₅ 5 3-8 - · 3-Cl, 4-OCF ₂ CHF ₂ · 538 _3-NH2, 4-C1 539 ' • - 3-σΐ-, 4 * -σ-σ (= σ) -σΗ · ₃ 540 3-Cl, 4-S-t-C ₄ Hg 541- • 3-Cl, 5-S-tert-C ₄ Hg 542 4-C1, 3-S-t-C ₄ Hg 543 · 3-F, 5-CF ₃ t. t. : 76 - 78 ° C 544 2-CH ₃ , 4-CN 545 3-NO ₂ , 4-CH ₃

546 2-CH ₃ , 4-OCH ₃

Number am Physical data 547 · - 3-CH _3, - 4-OCH 3 mp: 85-89 ° C 548 3-CH 3, 5-OCH 3 549 3-OCH 3, 4-CH 3 - 550 3-t-C ₄ H _g , 4-OCH 3 551 ... 3-t-C ₄ H 8, 5-OCH 3 552 3-OCH 3, 4-tert-C ₄ H _g 553 2.-CH 3,. 4.-O-iZQ-C ₃ H ₇ 554 3-CH 3, 4-O-iso-C ₃ H ₇ 555 ...... . . . 3rrQ-iso-C ₃ H _{7 A 4} .4-CH 3. 556 3-tert-C ₄ H 8, 4-O-iso-C ₃ H ₇ 557 3-tert-C ₄ H 8, 5-O-iso-C ₃ H ₇ 558 3-O-iso-C ₃ H ₇ , 4-tert-C ₄ Hg 559 - 3-tert. -G ₄ Hg, 4-O-tert-C ₄ H _g 560 2-CH ₃ , 4-CF ₃ 561 - 2-CH 3, 5-GF ₃ 562 3-CH ₃ , 4-CF ₃ 563 3-CH ₃ , 5-CF ₃ 564 3-CF ₃ , 4-CH ₃

Number physical data 565- 2-CH ₃ , 4-OCF ₃ 566 3-CH ₃ , 4-OCF ₃ Number. physical data 567 3-CH ₃ , 5-OCF ₃ 568 _{3-OCF3, 4-CH3} 569 3-CH ₃ , 4-OCH ₂ CF ₃ 570 3-CH ₃ , 4-OC ₂ H ₅ 571 _3-CH3, 4-OCF ₂ CHF ₂ 572 3-CH ₃ , 4-S-tert-C ₄ H _g 573 3-CF ₃ , 4-OCH ₃ 574 3-CF ₃ , 4-O-tert-C ₄ H ₉ 575 _{3-OCH3, 4-CF3} 576 2-CH ₃ , 4-C (CH ₃ ) = NOCH ₃ 577 3-CH ₃ , 4-C (CH ₃ ) = NOCH ₃ 578 3-Cl, 4-CH ₃ , 5-Cl 579 CT-3, 4-tert-C ₄ Hg; 5-C1 580 3-C1, _4-OCH3, 5-C1

Number ^A m Physical data 581 3-Cl-, 4-O-t-C ₄ H _g , 5-Cl 582 3-C1, _4-NH2, 5-C1 583 3-CO ₂ CH ₃ , 4-0¾ 584 _3-NH2, 4-0¾ 585 .. 2-OH, _5-CH3 mp: 128-131 ° C 586 2-0¾, 3-C1, 5-C1 mp: 65-67 ° C 587 - - 3-Br, 4-OCH, 5-Br 588 3-iso-C ₃ H _7, 4-OCH _3, 5-iso-C ₃ Hy 589 3-NO ₂ , 4-OCH ₃ mp: 118-120 ° C 590 3- (tert-C ₄ H 8), 4-OCH ₃ , 5- (tert .-C ₄ Hg) 591 3-C1 ,. 4-sec.-C ₄ H ₉ mp .: 58-60 ° C 592 3-Cl, 4-iso-C ₃ H ₇ mp: 91-92 C 593 3-C1, 4-C ₂ H ₅ 594 3-C1, 4-OC ₆ H ₅ 595 3-Cl, 4-OCHF ₂ mp: 60-62 ° C 596 3-CF ₃ , 4-OC ₆ H ₅ oil, IR (film): 3340,2940,1675,1498, 1279,1249,1133,1053, 1037

Number am Physical data 597 3 ”iZO“ Ci4 ~ ΟΟΗβ 598 3-CHF ₂ oil, IR (film): 3340,2940,1670,1528, i2Qa., iQ36, AAQ 599 4-CHF ₂ 600 3-Br, _4-OCH3, 5-C1 mp: IOS 111 C 601 3-Br, 4-OC ₆ H ₅ , 5-Br 602 3,5- (CO ₂ CH ₃ ) ₂ 603 3-OC ₂ H ₅ , 4-Cl 60 4 3-O-iso-C ₃ H ₇ , 4-Cl 605 3-O-t-C ₄ H _g , 4-Cl 606 3-CH ₃ , 4-OC ₂ H ₅ oil, IR (film): 3340,2940,1671,1507, 1247.1939 607 3-CH ₃ , 4-O-tert-C ₄ H ₉ 608 3-OC ₂ H ₅ , 4-CH ₃ 609 3-O-t-C ₄ H _g , 4-CH ₃ 610 3-C1, _{4-OCH3, 5-CH3}

Number

Physical data

611

mp: 92-95 ° C

ch ₃

612

oil, IR (film):

3350,2932,1671,1525,

1037,979,777

613 '3-Cl, 4-nC ₃ H ₇ oil, IR (film): 3349,2937,1671,1506, 1271,1037,978 61'4 · 3-cl · 4-O-4-alkyl -... oil, IR (film): 3340,2930,1672,1504, 1270,1037,980 615 '·' 3-Cl, 4-OnC ₄ H ₉ oil, IR (film): 3350,2936,1672,1506 1271,1037,979 616 3-C1, 4-O-iso-C ₄ H ₉ oil, IR (film): 3345,2960,1670,1506, 1271,1059,1037 617 3-Cl, 4-O-CH ₂ -CH = CHCH ₃ oil, IR (film): 3345,2937,1673,1504, 1269,1.037,980 618 3-C1, 4-O-CH ₂ CH ₂ CH ₂ CH ₂ Cl oil, IR (film): 3340,2938,1675,1506, 1270.1037

Number % Physical data 619 3-Cl, 4-0-3-) - 05 ^ 2 oil, IR (film): 3345, .2936,1673,1506. 1270,1058,1037,980 620 3-01-, 4-Qisis-C ₅ K ₁₁ oil, IR (film) 3340,2955,1672,1506, 1269,1060,1037,979 621 3-Cl, 4-O-CH ₂ -CH = C (CH ₃ ) ₂ oil, IR (film): 3345,2940,1674,1504, 1269,1037,980 622 3-C1, 4-O-neo-C1-4H- oil, IR (film): 3345,2956,1673,1507, 1259,1061,1038,1014 623 3-Cl, 4-OnC ₆ H ₁₃ oil, IR (film): 3417,1681,1267,1034, 1026.937 624 3-CH ₃ , 4-OnC ₃ H _? oil, IR (film): 3340,2937,1671,1506, 1038.979 625 3-CH ₃ , 4-O-alkyl oil, IR (film): 3350,2940,1669,1505, 1036.980 626 3-CH ₃ , 4-OHC ₄ H ₉ oil, IR (film): 3340,2935,1671,1507, 1248,1038,979 627 _3-chloro-3, 4-0 -CH ₂ -CH = CHCH ₃ oil, IR (film): 3350,2940,1672,1525, 1505,1247,1037,979

Number Physical data 628 ·· 3-CH ₃ , 4-OnC ₅ H _; oil, IR (film): 3340,2935,1668,1526, 1507,1250,1037,980 629 3-CHg _from 4-Q-XSQ-CgEj j oil, IR (film): 3340,2954,1671,1507, 1248,1038,980 630 3-CH ₃ , 4-O-CH ₂ -CH = C (CH ₃ ) ₂ oil, IR (film): 3350,2935,1672,1505, 1037.979 631 - 3 ' CH3 (4-O-neo-C1-4H4) oil, IR (film): 3340,2954,1670,1507, 1247.1038 63 2 3-CIT ₃ 7 4-onc ₆ fr ₁₄ oil, IR (film): 3345,2934,1672,1506, 1247.1038 633 4-O-GH ₂ -CH ₂ -CH ₂ -CH ₂ Nr mp: 74-77 ° C 634 3,5- _{(OCH3) 2,} 4-OH mp: 80-83 ° C 635 2,3,4,5,6-F ₅ mp: 83-84 ° C 636 3,5- (OH) ₂ 1.1 .: 68-70 ^° C 637 4-O-iso-C ₅ H ₁₁ mp: 91-93 ° C 638 4-0-neo-C 5 H ^ - ^ oil, IR (film): 3350,2956,1675,1514, 1248,1038,1017 639 4- [O-CH ₂ -CH = C (CH ₃ ) ₂ ] mp: 113-116 C

Number ^A m Physical data 640 4-O-CH ₂ CH ₂ CH ₂ CH ₂ Cl mp 77 - 80 'C 641 4-O-CH ₂ -CH ₂ -CH ₂ CN oil, IR (film): 3375,2940,2245,1674, 1514, 1249, LQ37. 642 2-0-iso-CtjHjTL oil, IR (film):

3350,2955,2935,1672,

1525,1222,980

643 3- [O-CH ₂ -CH = C (CH ₃ ) _2] oil, IR (film): 3355,2935,1673, 1219,1037,980 1525 644 3-O-CH ₂ -CH ₂ -CH ₂ -CH ₂ Cl oil, IR (film) 3355,2938,1675, 1225,1037,979 1525 645 4-NHC (= O) H mp: 140-142 'C 6'4 5 3-CH ₃ '-, 4-OH mp: 159-161 ^Q C 647 3-CN mp: 200-202 C 648 3-CH ₃ , 4-O-iso-C ₃ H ₇ mp : 85-87 'C 649 3-Cl, 4-OH mp: 160-163 C 650 4-C (CH ₃ ) ₂ CN mp: 83-85 'C 651 _3-CF3, 4-F mp: 60-62 'C

Table 2

NHCH3

Number % R Physical data 1 H ^C 2 ^H 5 oil, IR (film): 3350,2938,1671,1525, 1463,1091,1037,979. 912,770,696 2 2-C1 ^C 2 ^H 5 1.1 .: 71-72 ⁰ C 3 3-C1 ^C 2 ^H 5 mp: 106-107 ° C 4 4-C1 ^C 2 ^H 5 5 3,4-Cl ₂ ^C 2 ^H 5 mp: 120-122 ° C 6 3,5-Cl ₂ ^C 2 ^H 5 7 2,3,4-Cl ₃ ^C 2 ^H 5 8 3,4,5-Cl ₃ ^C 2 ^H 5 9 2-Br ^C 2 ^H 5 10 3-Br ^C 2 ^H 5

Number % R Physical data 11 4-Br ^C 2 ^H 5 mp: 107-108 ° C 12 2-NO ₂ ^C 2 ^H 5 13 3-NO ₂ ^C 2 ^H 5 14 4-NO ₂ ^C 2 ^H 5 15 _2-CH3 ^C 2 ^H 5 16 3-CH3 ^C 2 ^H 5 17 4-CH3 ^C 2 ^H 5 oil, IR (film): 3350,2937,1670,1525, 1514,1463,1037,979. 911.822 18 2,4- _{(CH3) 2} ^C 2 ^H 5 19 3,4- (CH _{3). 2nd} ^C 2 ^H 5 20 3,5- _{(CH3) 2} ^c 2 ^H 5 21 3-cis-C ₃ H ₇ ^C 2 ^H 5 22 4-cis-C ₃ H ₇ ^C 2 ^H 5 23 3-tert-C ₄ H _g ^C 2 ^H 5 24 4-tert-C ₄ H _g ^C 2 ^H 5 mp: 94-95 ° C 25 3-CH ₃ , 4-tert-C ₄ H _g ^C 2 ^H 5 26 3-t-C ₄ H _g , 4-CH ₃ ^C 2 ^H 5

Number am R Physical data 27 3-OCH ₃ ^C 2 ^H 5 28 4-OCH ₃ ^C 2 ^H 5 mp: 96-97 ° C 29 3-0-IsO-C ₃ H ₇ ^C 2 ^H 5 30 4-0-ISO-C ₃ H ₇ ^C 2 ^H 5 31 3-0-t-C ^ Hg ^C 2 ^H 5 32 4-O-t-C ₄ H _g ^C 2 ^H 5 33 3-CF ₃ ^C 2 ^H 5 34 4-CF ₃ ^C 2 ^H 5 35 3-OCF ₃ ^C 2 ^H 5 36. 4-OCF ₃ ^C 2 ^H 5 37 3-S-tert-C ₄ H _g ^C 2 ^H 5 38 4-S-t-C ₄ H ₉ ^C 2 ^H 5 39 3-C _(CH3) = NOCH ₃ ^C 2 ^H 5 40 4-C (CH ₃₎ = NOCH ₃ ^C 2 ^H 5 41 H ^n_C 3 ^H 7 · 42 .. 2 - C1 nC ₃ H ₇ 43 3-C1 ^nC 3 ^H 7

4-Cl n-C ₃ H ₇ see Example 5

Number R Physical data 45 3,5-Cl ₂ nC ₃ H _? 46 2,3,4-Cl ₃ nC ₃ H ₇ 47 2-Br ^p n_C ₃ H 4 L. 48 3-Br nC ₃ Hy 49 4-Br nC ₃ H ₇ 50 _2-CH3 nC ₃ H ₇ 51 3-CH ₃ nC ₃ H ₇ 52 _4-CH3 nC ₃ H ₇ 53 4-tert-C ₄ H ₉ nC ₃ H ₇ 54 4-CF ₃ n- ^c 3 ^H ₇ 55 4-0-t-C ₄ Hg Π “0βΗ ₇ 56 4-OCF ₃ n ~ ^c 3 ^H 7 57 H iso-C ₃ H ₇ 58 2-C1 cis-C ₃ H ₇ 59 3-C1 cis-C ₃ H ₇ 6.0 ..... 4-CX .. cis-C ₃ H ₇ ..... 61 3,5-Cl ₂ cis-C ₃ H ₇

2,3,4-Cl ₃

ISO-C ₃ H ₇

Number R Physical data 63 2-Br iso-C ₃ H ₇ 64 3-Br cis-C ₃ H ₇ 65 4-Br · cis-C ₃ H ^ ^ä '· 66 _2-CH3 Iso-C ₃ H ₇ 67 3-CH ₃ Iso-C ₃ H ₇ 68 _4-CH3 ISO-C ₃ H ₇ 69 4-tert-C ₄ H _g cis-C ₃ H ₇ 70 4-CF ₃ Iso-C ₃ H ₇ 71 4-O-t-C ₄ H _g cis-C ₃ H ₇ 72 4-OCF ₃ cis-C ₃ H ₇ 73 2-C1 cyclopropyl 74 3-C1 cyclopropyl 75 3,4-Cl ₂ cyclopropyl 76 3,5-Cl ₂ cyclopropyl 77 2,3,4-Cl ₃ cyclopropyl 78 ... 2-Br ... cyclopropyl 79 3-Br cyclopropyl 80 4-Br cyclopropyl

Number A _m

R

Physical data

81 _2-CH3 cyclopropyl 82 3-CH ₃ cyclopropyl 83 _4-CH3 cyclopropyl 84 4-CF ₃ cyclopropyl 85 4-O-t-C ₄ H ₉ cyclopropyl 86 4-OCF ₃ cyclopropyl 87 4F C ₂ H ₅ tt: 94-95 ° C

Applicability

The novel compounds are useful as fungicidal and insecticidal compositions.

For example, the fungicidally active compounds of the present invention or compositions comprising such compounds may be used in the form of directly sprayable solutions, powders, suspensions, as well as high percentage aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusting and spreading agents. compositions or granules by spraying, misting, dusting, sprinkling or sprinkling. The dosage forms depend on the intended use, and in any case are intended to ensure the finest possible distribution of the active compounds according to the invention;

Generally, the plants are sprayed or dusted with the active substances or treated with the seeds of the plants.

The compositions are prepared in a manner known per se, for example by extending the active ingredient with solvents and / or carriers, optionally using an emulsifying agent and a dispersing agent, and in the case of using water as a diluent other organic solvents such as auxiliary solvents may also be used. Basically suitable excipients for this purpose are: solvents, such as aromatic compounds (e.g. xylene), chlorinated aromatics - (e.g., Ti-d-chloroenzene), paraffinic compounds (e.g. fractions from petroleum distillation), alcohols (e.g. methanol or butanol) ), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine), amides (e.g. dimethylformamide) and water, carriers such as natural stone meal (e.g. kaolins, clays, talc or chalk) and synthetic stone meal (e.g. highly disperse silicic acid or silicates) emulsifying agents such as nonionic or anionic emulsifiers (e.g. polyoxyethylene ethers of aliphatic alcohols, alkylsulfonates or arylsulfonates) and dispersing agents such as lignin from sulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal salts, alkali metal salts and ammonium salts of aromatic sulfonic acids, such as salts of ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, and dibutylnaphthalenesulfonic acid, as well as fatty acids, alkylsulfonate, and the like. . alkyl, aryl sulfonates, alkyl sulfates, lauryl ether sulfates and sulfates of aliphatic alcohols, as well as salts of sulfated hexadecanols, heptadecanols, as well as salts of glycol ethers of aliphatic alcohols, condensation products of sulfonated naphthalene and its formaldehyde condensation derivatives, Products of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde. polyoxyethyleneoctylphenol ether, ethoxylated isooctylphenol, octylphenol or nonylenol. alkylphenol polyglycol ether, tributylphenyl glycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, condensation products of ethylene oxide with aliphatic alcohols, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene, acetate of polyglycol ether of lauryl alcohol, sorbate.

Powder, grit and dusting compositions can be made by mixing or grinding the active ingredients with a solid carrier.

Granules, for example coated, impregnated and homogeneous granules, can be prepared by applying the active ingredient to a solid carrier. Solid carriers are mineral clays such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, sowing earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground -first materials, fertilizers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, urea and plant products such as cereal flour, tree bark flour, wood and nutshell flour, cellulose powder and other solid carriers.

Examples of such compositions and methods of manufacture include:

I. 90 parts by weight of Compound No. 5 of Table 1 (5/1) is mixed with 10 parts by weight of N-methylpyrrolidone to form a solution suitable for use as minimal drops.

II. 20 parts by weight of compound 6/1 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of an adduct of 8 to 10 moles of ethylene oxide and 1 mol of N-monoethanolamide oleic acid, 5 parts by weight of calcium dodecylsulfonic acid and 5 parts. % by weight of the addition product of 40 moles of ethylene oxide and 1 mol of castor oil. Pouring this solution into water and finely distributing it gives an aqueous dispersion.

III. 20 parts by weight of compound No. 8/1 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight, isobutariol and 20 parts by weight of an adduct of 40 moles of ethylene oxide and 1 mol of castor oil. Pouring this solution into water and finely distributing it gives an aqueous dispersion.

IV. 20 parts by weight of compound 9/1 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction boiling at 210 to 280 ° C and 10 parts by weight of an adduct of 40 moles of ethylene oxide and 1 mol of castor. oil. Pouring this solution into water and finely distributing it gives an aqueous dispersion.

V. Mix 80 parts by weight of Compound No. 10/1 with 3 parts by weight of diisobutyl-naphthalenesulfonic acid sodium salt, 10 parts by weight of sodium lignosulphonic acid from sulphite waste liquors and 7 parts by weight of powdered silica gel, and grind to a hammer mill. Gently dispersing this mixture in water gives a spray suspension.

VI. 3 parts by weight of compound No. 11/1 are mixed thoroughly with 97 parts by weight of finely dispersed kaolin. In this way, a dusting composition is obtained which contains 3% by weight of active ingredient.

VII. 30 parts by weight of compound No. 16/1 is mixed intimately with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this way, an effective composition with good adhesion is obtained.

VIII. 40 parts by weight of compound No. 18/1 are mixed intimately with 10 parts by weight of sodium of the condensation product, acid, phenolsulfonic acid, urea and formaldehyde, 2 parts by weight of silica gel and 48 parts by weight of water. A stable aqueous dispersion is obtained which can be further diluted with water to form an aqueous dispersion.

IX. 20 parts by weight of compound No. 19/1 are mixed intimately with 2 parts by weight of calcium dodecylbenzenesulfonic acid, 8 parts by weight of polyglycol ether of aliphatic alcohol, 20 parts by weight of sodium salt of the condensation product of phenolsulfonic acid, urea and formaldehyde and 68 parts by weight of paraffinic mineral oil. A stable oil dispersion is obtained.

The novel compounds exhibit excellent activity against a broad spectrum of plant pathogenic fungi, in particular from the Ascomyceten and Basidiomyceten classes. These compounds are partially systemically active and can be used as foliar and soil fungicidal agents.

The compounds are of particular importance for controlling a variety of fungi on various crop plants, such as wheat, rye, barley oats, rice, corn, grasses, cotton, soybeans, coffee, sugar cane, vines, fruit trees and ornamental plants, as well as vegetables, such as cucumbers, beans and pumpkin plants, as well as on the seeds of these plants.

The compounds are useful when the seed, plants, materials or soil to be protected from fungi or fungal infestations are treated with a fungicidally effective amount of a mixture of these compounds.

The use takes place before or after infection of the materials, plants or seeds by the fungi.

The compounds are particularly suitable for controlling the following plant diseases:

Erysiphe graminis for grain,

Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants,

Podosphaera leucotricha on apple trees,

Unicinula necator on vines, Pucinia species for grain, Rhizoctonia species for cotton and turf grass, Ustilago species for grain and sugar cane,

Venturia inaegualis on apple trees, Helminthosporia species on grain, Septoria nodorum on wheat,

Botrytis cinerea on strawberry. and vines,

Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice,

Phytophthora infestans. on., potatoes and tomatoes, Fusaria and Verticillia species on various plants, Plasmopara viticola on vines and Alternaria species on vegetables and fruits.

The novel compounds can also be used to protect materials (wood protection), for example against Paecilomyces variotii.

The fungicidal composition generally comprises from 0.1 to 95% by weight of active ingredient, preferably from 0.5 to 90% by weight of active ingredient.

Depending on the type of effect desired, the amount used is from 0.02 to 3 kg of active substance per hectare.

In the treatment of seed, it is generally necessary to use an amount of active compound of from 0.001 to 50 g, preferably from 0.01 to 10 g, for each kilogram of seed.

The composition according to the invention may also be in a form intended for use as a fungicidal composition together with other active substances, for example with herbicidal compositions, insecticidal compositions, plant growth regulators, other fungicidal compositions or also with fertilizers.

When mixing such substances with fungicides. in this case, the spectrum of fungicidal action is broadened by means of the compositions.

Examples of use

In the examples below, the following substances are used as comparative compounds:

Comparative compound A - 2-methoxyimino-2- [2 '- / 1' '- (1' '' - naphthyl) -1 '' - methyl / iminooxymethyl] phenylacetic acid methyl ester, Comparative compound B - 2-methoxyimino- methyl ester 2- [2 '- / 1' '- (2' '' - naphthyl) -1'-methyl / iminooxymethyl] phenylacetic acid, reference compound C - 2-methoxyimino-2- [2 '- / 1' '- - methyl ester (1''-phenyl) -1''-methyl / iminooxymethyl] phenylacetic acid, all of which are known from European patent no. 463 488.

Example of use 1

Action against Fusarium culmorum on wheat

Kanzler wheat, in the first leaf stage, which is grown in pots, is sprayed until completely moistened with a spraying aqueous suspension which contains 80% active ingredient and 20% emulsifier in the dry matter. The next day, the plants are inoculated with a spore suspension of Fusarium culmorum and then the test plants are kept in a climate chamber at 20-24 ° C at high air humidity (greater than 90%). After six days, the extent of disease symptoms is assessed visually.

Active ingredient% leaf infestation after application of an aqueous preparation containing 500 ppm of active ingredient

Table 1, number 1 0 Table 1, Number 2 5 Reference Compound 70 Reference Compound B 25 untreated 70

Application example 2

Effect against Plasmopara viticola

The vine leaves of the Muller Thurgau variety grown in pots are sprayed with an aqueous spray suspension which contains 80% by weight of active ingredient and 20% by weight of emulsifier in the dry matter. In order to assess the duration of action of the active substances, the plants are placed in a greenhouse for 8 days after the spray coating has dried. Only then are the leaves infected with a zoospore suspension of vine perenospore (Plasmopara viticola). The plants were first placed in a water-saturated chamber at 24 ° C for 48 hours and then placed in a greenhouse for 5 days at 20 to 30 ° C. Spores are placed in a humid chamber for 16 hours. The degree of fungal infestation on the undersides of the leaves is then assessed.

Effective i substance % leaf infestation after application of an aqueous preparation containing 16 ppm of active ingredient table 1, number 5 5 table 1, number 19 0 table 1 ,. Number 63 5 table 1, number 74 15 table 1, number 118 5 table 1, Issue 228 5 table 1, number 282 0 table 1, number 283 5 Reference Compound C 25 untreated 70

- 76 Application example 3

Effect against Pucinia recondita

The leaves of Kanzler wheat seedlings grown in pots are dusted with spores of Puccinia recondita. The condensers were then placed for 2-4 hours at 20-22 ° C in a high humidity chamber (90-95%). During this time, the spores germinate and the germinated portion penetrates the leaf tissue. The infected plants are then sprayed until completely wetted with an aqueous spray suspension which contains 80% active ingredient and 20% emulsifier in the dry matter. After the spray layer has dried, the test plants are placed in a greenhouse at a temperature of 20 to 22 ° C at a high relative humidity of 65 to 70%. After eight days, the extent of fungal infestation of the leaves is determined on the leaves.

Effective. substance % leaf infestation after application of an aqueous preparation containing 16 ppm of active ingredient table 1, number 1 0 table 1, number 2 5 table 1, number 19 15 table 1, number 63 0 table 1, number 118 5 table 1, number 282 0 table 1, number 283 0 Reference Compound 35

Active substance % leaf infestation after application of an aqueous preparation containing 16 ppm of active ingredient Reference Compound B 25 Reference Compound C 65 untreated 65

The results of the application examples show that the active substances number 1, 2, 5, 19, 63, 74, 118, 228, 282 and 283 of Table 1, when used as spray suspensions, have a better fungicidal effect at each given concentration than the known comparative compounds A , B and C '.

Claims (3)

PATENT CLAIMS N-Methylamides of general formula I (I) in which R is C 1 -C 3 alkyl or cyclopropyl, radicals A may be the same or different and is hydrogen, halogen, cyano, nitro, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, OR ¹ , C 3 -C 6 cycloalkyloxy (C 1 -C 6) haloalkyl, (C 1 -C 6) haloalkoxy, (C 2 -C 6) alkenyl, (C 2 -C 6) alkenyloxy, (C 2 -C 6) alkynyl (C 1 -C 6) alkyloxy to 6 carbon atoms, such alkyl and alkoxy, cyanoalkyl having 1 to 6 carbon atoms, nitroalkyl having 1 to 6 carbon CÍOJR ^1, CO 2 R ^1, C (O) NR ¹ R ^2, NR ¹ CO ₂ R ^2, OC (O) R ¹ , SR ¹ , —C (R ¹ ) = NR ² , —N = CR ¹ R ² , carbon, phenyl, phenoxy, C (S) NR ¹ R ^2, LS ^R R ¹ R ^2, NR ¹ C (O) R ^2, S (O) R ¹ , S (O) ₂ R ¹ , grouping -C = NOR ¹ , with residues R ^1, R ² and R ¹ are independently H, or alkyl of 1 to 6 carbon atoms, X represents a sulfur atom, an oxygen atom or a group NR ³ and n represents the number 0 or 1 or two groups A ^ at adjacent positions together represent the group -CH = CHrCH_ = CH-. and ... m is 1, 2 or 3, with the exception of the compounds of formula I in which R is methyl and A _m represents 2-chloro, 3-chloro, 4-chloro, 3,5-dichloro, 2 ', 3', 4-trichloro, 2-methyl, 4-methyl, 3-bromo, 4-nitro or an atom hydrogen and with the exception of compounds of formula I in which: R Am represents cyclopropyl and represents a hydrogen atom, 4-chloro, 4-tert-butyl or 4-methoxy. A process for the preparation of the N-methylamides of the formula I according to claim 1 1, characterized in that the benzyl derivative of the general formula (II) in which: L represents a leaving group, reacted with an oxime of formula III OH (III) in which R, A and m are as defined in claim 1. A fungicidal composition comprising an inert carrier and a fungicidally effective amount of an N-methylamide of the formula I according to claim 1.