Substituted oxime ethers and fungicides which contain these compounds

Abstract

Substituted oxime ethers of the general formula ##STR1## where R.sup.1 is alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, alkoxyalkyl, cycloalkyl, cycloalkylalkyl, cyanoalkyl, alkoxycarbonylalkyl, arylalkyl, heteroarylalkyl, arylalkenyl or aryloxyalkyl, the aromatic or heteroaromatic ring being substituted or unsubstituted,R.sup.2 and R.sup.3 are hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, halogen, cyano or nitro,R.sup.4 is hydrogen, alkyl or aryl, the aromatic ring being substituted or unsubstituted, andX is CH or N, and fungicides containing these compounds.

Description

The present invention relates to novel substituted oxime ethers and fungicides which contain these compounds.

The use of oxime ethers such as, for example, methyl 2-phenoxymethylphenylglyoxylate O-methyloxime as fungicides has been disclosed (EP 253,213). However, their fungicidal action is often inadequate.

We have now found that substituted oxime ethers of the general formula I ##STR2## where R.sup.1 is C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.4 -alkynyl, C.sub.1 -C.sub.6 -haloalkyl, C.sub.3 -C.sub.6 -haloalkenyl, C.sub.1 -C.sub.4 -alkoxy-C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.6 -cycloalkyl, C.sub.3 -C.sub.6 -cycloalkyl-C.sub.1 -C.sub.4 -alkyl, cyano-C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -alkoxycarbonyl-C.sub.1 -C.sub.6 -alkyl, aryl-C.sub.1 -C.sub.6 -alkyl, heteroaryl-C.sub.1 -C.sub.6 -alkyl, aryl-C.sub.3 -C.sub.6 -alkenyl or aryloxy-C.sub.1 -C.sub.6 -alkyl, it being possible for the aromatic or heteroaromatic ring to be substituted by one or more of the following: C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.2 -haloalkyl, C.sub.3 -C.sub.6 -cycloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.2 -haloalkoxy, halogen, aryl or aryloxy, R.sup.2 and R.sup.3 are identical or different and are hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.2 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.2 -haloalkoxy, halogen, cyano or nitro, R.sup.4 is hydrogen, C.sub.1 -C.sub.6 -alkyl or aryl, it being possible for the aromatic ring to be substituted by one or more of the following: C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.2 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.2 -haloalkoxy, halogen, cyano or nitro, and X is CH or N, have an excellent fungicidal action which is better than that of the known oxime ethers.

Examples of possible meanings of the radicals in the general formula are:

R.sup.1 : C.sub.1 -C.sub.6 -alkyl (C.sub.1 -C.sub.4 -alkyl) (eg. methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, n-, iso-, sec-, tert- or neo-pentyl, hexyl), C.sub.3 -C.sub.6 -alkenyl (eg. allyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl), C.sub.3 -C.sub.4 -alkynyl (eg. propargyl, 2-butynyl), C.sub.1 -C.sub.6 -haloalkyl (eg. 2-fluoroethyl), C.sub.3 -C.sub.6 -haloalkenyl (eg. 3-chloroallyl), C.sub.1 -C.sub.4 -alkoxy-C.sub.1 -C.sub.6 -alkyl (eg. 2-methoxyethyl, 3-ethoxypropyl), C.sub.3 -C.sub.6 -cycloalkyl (eg. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl), C.sub.3 -C.sub.6 -cycloalkyl-C.sub.1 -C.sub.4 -alkyl (eg. cyclopropylmethyl, cyclohexylmethyl), cyano-C.sub.1 -C.sub.6 -alkyl (eg. cyanomethyl, 3-cyanopropyl), C.sub.1 -C.sub.6 -alkoxy-carbonyl-C.sub.1 -C.sub.6 -alkyl (eg. ethoxycarbonylmethyl, tert-butoxycarbonylmethyl, tert-butoxycarbonylpropyl), aryl-(phenyl)-C.sub.1 -C.sub.6 -alkyl (eg. benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl), heteroaryl-(pyridyl, thienyl)-C.sub.1 -C.sub.6 -alkyl (eg. 3-pyridylmethyl, 2-thienylmethyl), aryl-(phenyl)-C.sub.3 -C.sub.6 -alkenyl (eg. 4-phenyl- 2-butenyl, 4-phenyl-3-butenyl), aryloxy-(phenoxy)-C.sub.1 -C.sub.6 -alkyl (eg. phenoxymethyl, phenoxyethyl, phenoxypropyl, phenoxybutyl, naphthoxymethyl, naphthoxyethyl), it being possible for the aromatic (phenyl) or heteroaromatic (pyridyl, thienyl) ring to be substituted by one or more, eg. 1 to 5, in particular 1 to 3, of the following: C.sub.1 -C.sub.4 -alkyl (eg. methyl, ethyl, propyl, butyl), C.sub.1 -C.sub.2 -haloalkyl (eg. trifluoromethyl, trichloromethyl), C.sub.3 -C.sub.6 -cycloalkyl (eg. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl), C.sub.1 -C.sub.4 -alkoxy (eg. methoxy, ethoxy, propoxy, butoxy), C.sub.1 -C.sub.2 -haloalkoxy (eg. trifluoromethoxy), halogen (eg. fluorine, chlorine, bromine), aryl (eg. phenyl), aryloxy (eg. phenoxy),

R.sup.2 and R.sup.3, which can be identical or different, hydrogen, C.sub.1 -C.sub.4 -alkyl (eg. methyl, ethyl, n- or iso-propyl, butyl), C.sub.1 -C.sub.2 -haloalkyl (eg. trifluoromethyl, trichloromethyl), C.sub.1 -C.sub.4 -alkoxy (eg. methoxy, ethoxy, n- or iso-propoxy, butoxy), C.sub.1 -C.sub.2 -haloalkoxy (eg. trifluoromethoxy), halogen (eg. fluorine, chlorine, bromine, iodine), cyano or nitro,

R.sup.4 : C.sub.1 -C.sub.6 -alkyl (C.sub.1 -C.sub.4 -alkyl) (eg. methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-, iso-, sec-, tert- or neo-pentyl, hexyl) or aryl (eg. phenyl), it being possible for the aromatic ring to be substituted by one or more, eg. 1 to 5, in particular 1 to 3, of the following: C.sub.1 -C.sub.4 -alkyl (eg. methyl, ethyl, propyl, butyl), C.sub.1 -C.sub.2 -haloalkyl (eg. trifluoromethyl, trichloromethyl), C.sub.1 -C.sub.4 -alkoxy (eg. methoxy, ethoxy, propoxy, butoxy), C.sub.1 -C.sub.2 -haloalkoxy (eg. difluoromethoxy, trifluoromethoxy), halogen (eg. fluorine, chlorine, bromine, iodine), cyano or nitro,

X: CH or N.

The radical --C(R.sup.4).dbd.N--O--R.sup.1 on the phenyl can be in the 2 or, preferably, in the 3 or 4 position with respect to the --O--CH.sub.2 -- radical.

Because of the C.dbd.C and C.dbd.N double bonds, preparation of the novel compounds of the general formula I may result in mixtures of E and Z isomers. These can be separated in a conventional manner, eg. by crystallization or chromatography. The present invention relates both to the individual isomeric compounds and to mixtures thereof, and all of them can be used as fungicides. With regard to the --C(COOCH.sub.3).dbd.X--OCH.sub.3 group, preferred compounds have the E configuration of the COOCH.sub.3 and OCH.sub.3 on the C.dbd.X double bond. With regard to the --C(R.sup.4).dbd.N--OR.sup.1 group, preferred compounds have the Z configuration of R.sup.4 and OR.sup.1 on the C.dbd.N double bond.

The novel compounds of the general formula I as claimed in claim 1 are prepared, for example, in such a way that a substituted oxime ether of the general formula II is reacted with a substituted benzyl compound of the general formula III where Y is a leaving group (eg. chloride, bromide, p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate). ##STR3## R.sup.1, R.sup.2, R.sup.3, R.sup.4 and X have the abovementioned meanings.

These reactions can be carried out, for example, in an inert solvent or diluent (eg. acetone, acetonitrile, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, N,N'-dimethylpropyleneurea or pyridine), using a base (eg. sodium carbonate, potassium carbonate). It may also be advantageous to add a catalyst such as tris(3,6-dioxoheptyl)amine to the reaction mixture.

An alternative procedure is such that the compounds of the general formula II are initially converted with a base (eg. sodium hydroxide, potassium hydroxide, sodium methanolate) into the corresponding sodium or potassium phenolates, and the latter are then reacted in an inert solvent or diluent (eg. dimethylformamide) with the substituted benzyl compounds of the general formula III to give the compounds of the formula I according to the invention.

These reactions can also be carried out in a two-phase system (eg. carbon tetrachloride/water). Examples of suitable phase-transfer catalysts are trioctylpropylammonium chloride or cetyltrimethylammonium chloride.

The substituted oxime ethers of the formula II required to prepare the novel compounds of the general formula I are either known or can be prepared by conventional processes.

Also required for the preparation of the compounds of the general formula I according to the invention are the substituted benzyl compounds of the general formula III. Compounds of the general formula IIIa (X=N, Y=chloride, bromide) are obtained by halogenation of methyl 2-methylphenylglyoxylate O-methyloxime IV by literature methods. This is achieved, for example, with bromine or chlorine in an inert solvent (eg. tetrachloromethane), with or without irradiation from a light source (eg. Hg vapor lamp, 300 W) or by reaction with N-chloro- or N-bromosuccinimide (cf. Horner, Winkelmann, Angew. Chem. 71 (1959) 349). ##STR4##

Methyl 2-methylphenylglyoxylate O-methyloxime IV can be prepared by reacting methyl 2-methylphenylglyoxylate V for example a) with O-methylhydroxylamine hydrochloride or b) with hydroxylamine hydrochloride to give the corresponding oxime and reacting the latter with a methylating agent of the formula CH.sub.3 --L where L is a leaving group (eg. chloride, bromide, iodide, methylsulfate) (cf. DE 3,623,921). ##STR5##

Benzyl halides of the general formula IIIa (X=N, Y=chloride, bromide) are also obtained when methyl 2-halomethylphenylglyoxylates of the formula VI (Y=chloride, bromide) are reacted a) with O-methylhydroxylamine hydrochloride or b) with hydroxylamine hydrochloride to give the corresponding oxime and reacting the latter with a methylating agent of the formula CH.sub.3 --L where L is a leaving group (eg. chloride, bromide, iodide, methylsulfate) (cf. DE 3,623,921). ##STR6##

Methyl 2-halomethylphenylglyoxylates of the formula VI (Y=chloride, bromide) can be prepared by halogenating methyl 2-methylphenylglyoxylate V by literature methods. The reaction is carried out, for example, with bromine or chlorine in an inert solvent (eg. tetrachloromethane) with or without irradiation from a light source (eg. Hg vapor lamp, 300 W) or with N-chloro- or N-bromosuccinimide (cf. Horner, Winkelmann, Angew. Chem. 71 (1959) 349). ##STR7##

Substituted benzyl compounds of the general formula IIIb (X.dbd.CH, Y=chloride, bromide) are either known or can be prepared by conventional processes. Appropriate methods of preparation are described, for example, in DE 3,519,280, DE 3,545,318 and DE 3,545,319.

Substituted benzyl compounds of the general formula IIIc (X.dbd.CH or N, Y=p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate) can be prepared from the corresponding compounds of the general formula IIIa (X=N, Y=chloride, bromide) or IIIb (X=CH, Y=chloride, bromide) by reaction with p-toluenesulfonic acid (Y=p-toluenesulfonate), methanesulfonic acid (Y=methanesulfonate) or trifluoromethanesulfonic acid (Y=trifluoromethanesulfonate). The reactions can be carried out, for example, in an inert solvent or diluent (e.g. dimethylformamide) in the presence of a base (e.g. potassium carbonate). An alternative procedure is such that the appropriate sulfonic acid is initially converted into a sodium or potassium salt and the latter is then reacted in an inert solvent or diluent (e.g. dimethylformamide) with a compound of the general formula IIIa or IIIb to give the substituted benzyl compounds of the general formula IIIc.

The novel compounds of the general formula I can also be prepared by reacting the novel substituted carbonyl compounds of the general formula VII with a substituted hydroxylamine of the general formula VIII or with an acid addition salt (e.g. hydrochloride, hydrobromide) of VIII. ##STR8## R.sup.1, R.sup.2, R.sup.3, R.sup.4 and X have the abovementioned meanings.

The reaction can be carried out in an inert solvent or diluent (e.g. methanol, ethanol, toluene) or in a two-phase system (e.g. toluene/water). It may also be advantageous to add a base (e.g. triethylamine, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide) to the reaction mixture.

The novel carbonyl compounds of the general formula VII are required as starting compounds. These are obtained by reacting the substituted benzyl compounds of the general formula III where Y is a leaving group (e.g. chloride, bromide, p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate) with substituted carbonyl compounds of the general formula IX. The compounds of the general formula IX are known. They can be prepared by conventional processes. ##STR9## R.sup.1, R.sup.2, R.sup.3, R.sup.4 and X have the abovementioned meanings.

The examples and procedures which follow are intended to illustrate the preparation of the novel active ingredients and their precursors.

PROCEDURE 1

Methyl 2-bromomethylphenylglyoxylate O-methyloxime

21.4 g (0.133 mol) of bromine are added to a stirred solution of 27.5 g (0.133 mol) of methyl 2-methylphenylglyoxylate O-methyloxime in 400 ml of tetrachloromethane. The mixture is then refluxed while irradiating with a 300 W Hg vapor lamp for four hours. It is then concentrated, the residue is taken up in ethyl acetate/water, and the organic phase is washed with H.sub.2 O, dried with sodium sulfate and evaporated. The crude product is purified by chromatography on silica gel with cyclohexane/ethyl acetate (9/1). 17.4 g (46%) of the abovementioned compound are obtained as an oil.

EXAMPLE 1

Methyl 2-(2-methoxyiminomethylphenoxymethyl)phenylglyoxylate O-methyloxime

3.0 g (20 mmol) of 2-hydroxybenzaldehyde O-methyloxime are dissolved in 20 ml of methanol, and 3.6 g (20 mmol) of sodium methanolate (30% strength in methanol) are added. The mixture is refluxed for four hours and then concentrated. The residue is taken up in 100 ml of dimethylformamide, and 6.5 g (23 mmol) of methyl 2-bromomethylphenylglyoxylate O-methyloxime in 50 ml of dimethylformamide are added. The mixture is stirred at 100.degree. C. for 5 hours, the solvent is stripped off, and the residue is taken up in ethyl acetate. The organic phase is washed with water, dried and concentrated. The residue is triturated with pentane to induce crystallization. 4.8 g (67% of theory) of the title compound are obtained in the form of colorless crystals (melting point 73.degree.-76.degree. C., compound no. 2).

EXAMPLE 2

Methyl .alpha.-[2-(2-ethoxyiminomethylphenoxymethyl)phenyl]-.beta.-methoxyacrylate

6.9 g (42 mmol) of 2-hydroxybenzaldehyde O-ethyloxime and 10.0 g (35 mmol) of methyl .alpha.-(2-bromomethylphenyl)-.beta.-methoxyacrylate are dissolved in 100 ml of dimethylformamide, and 7.3 g (53 mmol) of potassium carbonate are added. The mixture is stirred at room temperature for 48 hours and then concentrated, and the residue is taken up in methylene chloride. The organic phase is washed with water, dried over MgSO.sub.4 and concentrated. The resulting oil is purified by chromatography on silica gel (cyclohexane/ethyl acetate). 8.4 g (65% of theory) of the title compound are obtained in the form of colorless crystals (melting point 86.degree.-88.degree. C., compound no. 23).

EXAMPLE 3

Methyl .alpha.-[2-(3-(1-ethoxyiminoethyl)phenoxymethyl)phenyl]-.beta.-methoxyacrylate

7.5 g (0.042 mol) of 3-(1-ethoxyiminoethyl)phenol and 10.0 g (0.035 mol) methyl .alpha.-(2-bromomethylphenyl)-.beta.-methoxyacrylate are dissolved in 100 ml of dimethylformamide, and 7.3 g (0.053 mol) of potassium carbonate are added. The mixture is stirred at room temperature (20.degree. C.) for 48 hours, hydrolyzed with water and extracted with diethyl ether. The organic phase is washed with water, dried over magnesium sulfate and concentrated. The resulting oil is purified by chromatography on alumina (cyclohexane). 7.3 g (54%) of the title compound are obtained as a colorless oil (compound no. 447).

EXAMPLE 4

Methyl 2-[3-(1-n-butoxyiminoethyl)phenoxymethyl]phenylglyoxylate O-methyloxime

a) 3.0 g (0.022 mol) of 3-hydroxyacetophenone and 6.0 g (0.021 mol) of methyl 2-bromomethylphenylglyoxylate O-methyloxime are dissolved in 30 ml of dimethylformamide, and 5.5 g (0.040 yol) of potassium carbonate are added. The mixture is stirred at room temperature for 24 hours, hydrolyzed with water and extracted with methyl tert-butyl ether. The organic phase is washed with water, dried and concentrated. 5.8 g (85%) of methyl 2-(3-acetylphenoxymethyl)phenylglyoxylate O-methyloxime are obtained as a colorless oil.

b) 5.8 g (0.017 mol) of methyl 2-(3-acetylphenoxymethyl)phenylglyoxylate O-methyloxime and 2.5 g (0.020 mol) of n-butoxyamine hydrochloride in 60 ml of methanol are stirred at room temperature for 24 hours. The mixture is then hydrolyzed with water and extracted with methyl tert-butyl ether. The organic phase is washed with water, dried and concentrated. 5.0 g (71%) of the title compound are obtained as a colorless oil (compound no. 470).

EXAMPLE 5

Methyl 2-[4-(1-benzyloxyiminoethyl)phenoxymethyl]phenylglyoxylate O-methyloxime

a) 3.0 g (0.022 mol) of 4-hydroxyacetophenone and 6.0 g (0.021 mol) of methyl 2-bromomethylphenylglyoxylate O-methyloxime are dissolved in 30 ml of dimethylformamide, and 5.5 g (0.040 mol) of potassium carbonate are added. The mixture is stirred at room temperature for 24 hours, hydrolyzed with water and extracted with methyl tert-butyl ether. The organic phase is washed with water, dried and concentrated. 5.3 g (78%) of methyl 2-(4-acetylphenoxymethyl)phenylglyoxylate O-methyloxime are obtained as a colorless oil.

b) 5.3 g (0.016 mol) of methyl 2-(4-acetylphenoxymethyl)phenylglyoxylate O-methyloxime and 3.0 g (0.019 mol) of benzyloxyamine hydrochloride in 60 ml of methanol are stirred at room temperature for 24 hours. The mixture is then hydrolyzed with water and extracted with methyl tert-butyl ether. The organic phase is washed with water, dried and concentrated. 5.9 g (83%) of the title compound are obtained in the form of colorless crystals (melting point 104.degree.-106.degree. C., compound no. 590).

The compounds listed in Tables 1 to 3 can be prepared in a corresponding manner.

TABLE 1__________________________________________________________________________Compounds of the general formula Ia (2-position of the oxime ether).The configuration statement (E) relates to the methyl.beta.-methoxyacrylate group or the methyl glyoxylate O-methyloximegroup. ##STR10## IaComp. no. R.sup.1 R.sup.2 R.sup.3 R.sup.4 X mp. (.degree.C.)__________________________________________________________________________ 1 CH.sub.3 H H H CH 82-84 (E) 2 CH.sub.3 H H H N 73-76 (E) 3 CH.sub.3 4-Cl H H CH 4 CH.sub.3 4-Cl H H N 5 CH.sub.3 4-CH.sub.3 H H CH 6 CH.sub.3 4-CH.sub.3 H H N 7 CH.sub.3 4-OCH.sub.3 H H CH 8 CH.sub.3 4-OCH.sub.3 H H N 9 CH.sub.3 5-F H H CH 10 CH.sub.3 5-F H H N 11 CH.sub.3 5-Cl H H CH 12 CH.sub.3 5-Cl H H N 13 CH.sub.3 5-Br H H CH 14 CH.sub.3 5-Br H H N 15 CH.sub.3 5-CH.sub.3 H H CH 16 CH.sub.3 5-CH.sub.3 H H N 17 CH.sub.3 5-OCH.sub.3 H H CH 18 CH.sub.3 5-OCH.sub.3 H H N 19 CH.sub.3 6-OCH.sub.3 H H CH 20 CH.sub.3 6-OCH.sub.3 H H N 21 CH.sub.3 4-Cl 6-Cl H CH 22 CH.sub.3 4-Cl 6-Cl H N 23 CH.sub.3CH.sub.2 H H H CH 86-88 (E) 24 CH.sub.3CH.sub.2 H H H N 89-90 (E) 25 CH.sub.3CH.sub.2 4-Cl H H CH 95-97 (E) 26 CH.sub.3CH.sub.2 4-Cl H H N 27 CH.sub.3CH.sub.2 4-CH.sub.3 H H CH 28 CH.sub.3CH.sub.2 4-CH.sub.3 H H N 29 CH.sub.3CH.sub.2 4-OCH.sub.3 H H CH 30 CH.sub.3CH.sub.2 4-OCH.sub.3 H H N 31 CH.sub.3CH.sub.2 5-F H H CH 32 CH.sub.3CH.sub.2 5-F H H N 33 CH.sub.3CH.sub.2 5-Cl H H CH 34 CH.sub.3CH.sub.2 5-Cl H H N 35 CH.sub.3CH.sub.2 5-Br H H CH 36 CH.sub.3CH.sub.2 5-Br H H N 37 CH.sub.3CH.sub.2 5-CH.sub.3 H H CH 38 CH.sub.3CH.sub.2 5-CH.sub.3 H H N 39 CH.sub.3CH.sub.2 5-OCH.sub.3 H H CH 40 CH.sub.3CH.sub.2 5-OCH.sub.3 H H N 41 CH.sub.3CH.sub.2 6-OCH.sub.3 H H CH 42 CH.sub.3CH.sub.2 6-OCH.sub.3 H H N 43 CH.sub.3CH.sub.2 4-Cl 6-Cl H CH 44 CH.sub.3CH.sub.2 4-Cl 6-Cl H N 45 CH.sub.3CH.sub. 2CH.sub.2 H H H CH 46 CH.sub.3CH.sub.2CH.sub.2 H H H N 47 CH.sub.2CHCH.sub.2 H H H CH 48 CH.sub.2CHCH.sub.2 H H H N 49 CH.sub.3CH(CH.sub.3) H H H CH 50 CH.sub.3CH(CH.sub.3) H H H N 51 HCCCH.sub.2 H H H CH 52 HCCCH.sub.2 H H H N 53 cyclo-C.sub.3 H.sub.5CH.sub.2 H H H CH 54 cyclo-C.sub.3 H.sub.5CH.sub.2 H H H N 55 CH.sub.3CH.sub.2CH.sub.2CH.sub.2 H H H CH 56 CH.sub.3CH.sub.2CH.sub.2CH.sub.2 H H H N 57 CH.sub.3CHCHCH.sub.2 H H H CH 58 CH.sub.3CHCHCH.sub.2 H H H N 59 CH.sub.3(CH.sub.2).sub.5 H H H CH 60 CH.sub.3(CH.sub.2).sub.5 H H H N 61 cyclo-C.sub.6 H.sub.11 H H H CH 62 cyclo-C.sub.6 H.sub.11 H H H N 63 C.sub.6 H.sub.5CH.sub.2 H H H CH 64 C.sub.6 H.sub.5CH.sub.2 H H H N 65 4-ClC.sub.6 H.sub.4CH.sub.2 H H H CH 66 4-ClC.sub.6 H.sub.4CH.sub.2 H H H N 67 3-CF.sub.3C.sub.6 H.sub.4CH.sub.2 H H H CH 68 3-CF.sub.3C.sub.6 H.sub.4CH.sub.2 H H H N 69 4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2 H H H CH 70 4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2 H H H N 71 C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2 H H H CH 72 C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2 H H H N 73 C.sub.6 H.sub.5(CH.sub.2).sub.4 H H H CH 74 C.sub.6 H.sub.5(CH.sub.2).sub.4 H H H N 75 C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2 H H H CH 76 C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2 H H H N 77 4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2 H H H CH 78 4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2 H H H N 79 t-C.sub.4 H.sub.9 OCOCH.sub.2 H H H CH 80 t-C.sub.4 H.sub.9 OCOCH.sub.2 H H H N 81 t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3 H H H CH 82 t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3 H H H N 83 ClCHCHCH.sub.2 H H H CH 84 ClCHCHCH.sub.2 H H H N221 C.sub.2 H.sub.5 6-OC.sub.2 H.sub.5 H H CH222 C.sub.2 H.sub.5 6-OC.sub.2 H.sub.5 H H N223 CH.sub.3C(CH.sub.3).sub.2 H H H CH224 CH.sub.3C(CH.sub.3).sub.2 H H H N225 CH.sub.3CH(CH.sub.3)CH.sub.2 H H H CH226 CH.sub.3CH(CH.sub.3)CH.sub.2 H H H N227 CH.sub.2C(CH.sub.3)CH.sub.2 H H H CH228 CH.sub.2C(CH.sub.3)CH.sub.2 H H H N229 CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2 H H H CH230 CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2 H H H N231 CH.sub.3(CH.sub.2).sub.4 H H H CH232 CH.sub.3(CH.sub.2).sub.4 H H H N233 2-FC.sub.6 H.sub.4CH.sub.2 H H H CH234 2-FC.sub.6 H.sub.4CH.sub.2 H H H N235 3-FC.sub.6 H.sub.4CH.sub.2 H H H CH236 3-FC.sub.6 H.sub.4CH.sub.2 H H H N237 2-ClC.sub.6 H.sub.4CH.sub.2 H H H CH238 2-ClC.sub.6 H.sub.4CH.sub. 2 H H H N239 3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 H H H CH240 3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 H H H N241 2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 H H H CH242 2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 H H H N243 C.sub.6 H.sub.5CH.sub.2CH.sub.2 H H H CH244 C.sub.6 H.sub.5CH.sub.2CH.sub.2 H H H N245 C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2 H H H CH246 C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2 H H H N247 4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H H CH248 4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H H N249 4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H H CH250 4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H H N311 CH.sub.3 H H CH.sub.3 CH312 CH.sub.3 H H CH.sub.3 N313 CH.sub.3 4-Cl H CH.sub.3 CH314 CH.sub.3 4-Cl H CH.sub.3 N315 CH.sub.3 4-CH.sub.3 H CH.sub.3 CH316 CH.sub.3 4-CH.sub.3 H CH.sub.3 N317 CH.sub.3 4-OCH.sub.3 H CH.sub.3 CH318 CH.sub.3 4-OCH.sub.3 H CH.sub.3 N319 CH.sub.3 5-F H CH.sub.3 CH320 CH.sub.3 5-F H CH.sub.3 N321 CH.sub.3 5-Cl H CH.sub.3 CH322 CH.sub.3 5-Cl H CH.sub.3 N323 CH.sub.3 5-Br H CH.sub.3 CH324 CH.sub.3 5-Br H CH.sub.3 N325 CH.sub.3 5-CH.sub.3 H CH.sub.3 CH326 CH.sub.3 5-CH.sub.3 H CH.sub.3 N327 CH.sub.3 5-OCH.sub.3 H CH.sub.3 CH328 CH.sub.3 5-OCH.sub.3 H CH.sub.3 N329 CH.sub.3 6-OCH.sub.3 H CH.sub.3 CH330 CH.sub.3 6-OCH.sub.3 H CH.sub.3 N331 CH.sub.3 4-Cl 6-Cl CH.sub.3 CH332 CH.sub.3 4-Cl 6-Cl CH.sub.3 N333 CH.sub.3CH.sub.2 H H CH.sub.3 CH334 CH.sub.3CH.sub.2 H H CH.sub.3 N335 CH.sub. 3CH.sub.2 4-Cl H CH.sub.3 CH336 CH.sub.3CH.sub.2 4-Cl H CH.sub.3 N337 CH.sub.3CH.sub.2 4-CH.sub.3 H CH.sub.3 CH338 CH.sub.3CH.sub.2 4-CH.sub.3 H CH.sub.3 N339 CH.sub.3CH.sub.2 4-OCH.sub.3 H CH.sub.3 CH340 CH.sub.3CH.sub.2 4-OCH.sub.3 H CH.sub.3 N341 CH.sub.3CH.sub.2 5-F H CH.sub.3 CH342 CH.sub.3CH.sub.2 5-F H CH.sub.3 N343 CH.sub.3CH.sub.2 5-Cl H CH.sub.3 CH344 CH.sub.3CH.sub.2 5-Cl H CH.sub.3 N345 CH.sub.3CH.sub.2 5-Br H CH.sub.3 CH346 CH.sub.3CH.sub.2 5-Br H CH.sub.3 N347 CH.sub.3CH.sub.2 5-CH.sub.3 H CH.sub.3 CH348 CH.sub.3CH.sub.2 5-CH.sub.3 H CH.sub.3 N349 CH.sub.3CH.sub.2 5-OCH.sub.3 H CH.sub.3 CH350 CH.sub.3CH.sub.2 5-OCH.sub.3 H CH.sub.3 N351 CH.sub.3CH.sub.2 6-OCH.sub.3 H CH.sub.3 CH352 CH.sub.3CH.sub.2 6-OCH.sub.3 H CH.sub.3 N353 CH.sub.3CH.sub.2 4-Cl 6-Cl CH.sub.3 CH354 CH.sub. 3CH.sub.2 4-Cl 6-Cl CH.sub.3 N355 CH.sub.3CH.sub.2CH.sub.2 H H CH.sub.3 CH356 CH.sub.3CH.sub.2CH.sub.2 H H CH.sub.3 N357 CH.sub.2CHCH.sub.2 H H CH.sub.3 CH358 CH.sub.2CHCH.sub.2 H H CH.sub.3 N359 CH.sub.3CH(CH.sub.3) H H CH.sub.3 CH360 CH.sub.3CH(CH.sub.3) H H CH.sub.3 N361 HCCCH.sub.2 H H CH.sub.3 CH362 HCCCH.sub.2 H H CH.sub.3 N363 cyclo-C.sub.3 H.sub.5CH.sub.2 H H CH.sub.3 CH364 cyclo-C.sub.3 H.sub.5CH.sub.2 H H CH.sub.3 N365 CH.sub.3CH.sub.2CH.sub.2CH.sub.2 H H CH.sub.3 CH366 CH.sub.3CH.sub.2CH.sub.2CH.sub.2 H H CH.sub.3 N367 CH.sub.3CHCHCH.sub.2 H H CH.sub.3 CH368 CH.sub.3CHCHCH.sub.2 H H CH.sub.3 N369 CH.sub.3(CH.sub.2).sub.5 H H CH.sub. 3 CH370 CH.sub.3(CH.sub.2).sub.5 H H CH.sub.3 N371 cyclo-C.sub.6 H.sub.11 H H CH.sub.3 CH372 cyclo-C.sub.6 H.sub.11 H H CH.sub.3 N373 C.sub.6 H.sub.5CH.sub.2 H H CH.sub.3 CH374 C.sub.6 H.sub.5CH.sub.2 H H CH.sub.3 N375 4-Cl-C.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 CH376 4-Cl-C.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 N377 3-CF.sub.3C.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 CH378 3-CF.sub.3C.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 N379 4-Cl-C.sub.6 H.sub.4CH.sub.2CH.sub.2 H H CH.sub.3 CH380 4-Cl-C.sub.6 H.sub.4CH.sub.2CH.sub.2 H H CH.sub.3 N381 C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2 H H CH.sub.3 CH382 C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2 H H CH.sub.3 N383 C.sub.6 H.sub.5(CH.sub.2).sub.4 H H CH.sub.3 CH384 C.sub.6 H.sub.5(CH.sub.2).sub.4 H H CH.sub.3 N385 C.sub. 6 H.sub.5CH.sub.2CHCHCH.sub.2 H H CH.sub.3 CH386 C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2 H H CH.sub.3 N387 4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2 H H CH.sub.3 CH388 4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2 H H CH.sub.3 N389 t-C.sub.4 H.sub.9 OCOCH.sub.2 H H CH.sub.3 CH390 t-C.sub.4 H.sub.9 OCOCH.sub.2 H H CH.sub.3 N391 t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3 H H CH.sub.3 CH392 t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3 H H CH.sub.3 N393 ClCHCHCH.sub.2 H H CH.sub.3 CH394 ClCHCHCH.sub.2 H H CH.sub.3 N395 C.sub.2 H.sub.5 6-OC.sub.2 H.sub.5 H CH.sub.3 CH396 C.sub.2 H.sub.5 6-OC.sub.2 H.sub.5 H CH.sub.3 N397 CH.sub.3C(CH.sub.3).sub.2 H H CH.sub.3 CH398 CH.sub.3C(CH.sub.3).sub.2 H H CH.sub.3 N399 CH.sub.3CH(CH.sub.3 )CH.sub.2 H H CH.sub.3 CH400 CH.sub.3CH(CH.sub.3)CH.sub.2 H H CH.sub.3 N401 CH.sub.2C(CH.sub.3)CH.sub.2 H H CH.sub.3 CH402 CH.sub.2C(CH.sub.3)CH.sub.2 H H CH.sub.3 N403 CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2 H H CH.sub.3 CH404 CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2 H H CH.sub.3 N405 CH.sub.3(CH.sub.2).sub.4 H H CH.sub.3 CH406 CH.sub.3(CH.sub.2).sub.4 H H CH.sub.3 N407 2-FC.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 CH408 2-FC.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 N409 3-FC.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 CH410 3-FC.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 N411 2-ClC.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 CH412 2-ClC.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 N413 3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 H H CH.sub.3 CH414 3,4-Cl.sub.2C.sub.6 H.sub.3 CH.sub.2 H H CH.sub.3 N415 2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 H H CH.sub.3 CH416 2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 H H CH.sub.3 N417 C.sub.6 H.sub.5CH.sub.2CH.sub.2 H H CH.sub.3 CH418 C.sub.6 H.sub.5CH.sub.2CH.sub.2 H H CH.sub.3 N419 C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2 H H CH.sub.3 CH420 C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2 H H CH.sub.3 N421 4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H CH.sub.3 CH422 4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H CH.sub.3 N423 4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H CH.sub.3 CH424 4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H CH.sub.3 N425 CH.sub.3 H H C.sub.6 H.sub.5 CH426 CH.sub.3 H H C.sub.6 H.sub.5 N427 C.sub.2 H.sub.5 H H C.sub.6 H.sub.5 CH428 C.sub.2 H.sub.5 H H C.sub.6 H.sub.5 N429 CH.sub.3CH.sub.2CH.sub.2 H H C.sub.6 H.sub.5 CH430 CH.sub.3CH.sub.2CH.sub.2 H H C.sub.6 H.sub.5 N431 CH.sub.3(CH.sub.2).sub.5 H H C.sub.6 H.sub.5 CH432 CH.sub.3(CH.sub.2).sub.5 H H C.sub.6 H.sub.5 N433 C.sub.6 H.sub.5CH.sub.2 H H C.sub.6 H.sub.5 CH434 C.sub.6 H.sub.6CH.sub.2 H H C.sub.6 H.sub.5 N__________________________________________________________________________ TABLE 2__________________________________________________________________________Compounds of the general formula Ib (3-position of the oxime ether). Theconfigurationstatement relates to the methyl .beta.-methoxyacrylate group or themethylglyoxylate O-methyloxime group. ##STR11## IbComp. no. R.sup.1 R.sup.2 R.sup.3 R.sup.4 X mp. (.degree.C.)__________________________________________________________________________ 85 CH.sub.3 H H H CH 75-77 (E) 86 CH.sub.3 H H H N oil (E) 87 CH.sub.3 2-Cl 5-Cl H CH 88 CH.sub.3 2-Cl 5-Cl H N 89 CH.sub.3 4-Cl H H CH 90 CH.sub.3 4-Cl H H N 91 CH.sub.3 4-CH.sub.3 H H CH 92 CH.sub.3 4-CH.sub.3 H H N 93 CH.sub.3 5-OCH.sub.3 H H CH 94 CH.sub.3 5-OCH.sub.3 H H N 95 CH.sub.3 6-OCH.sub.3 H H CH 96 CH.sub.3 6-OCH.sub.3 H H N 97 CH.sub.3CH.sub.2 H H H CH oil (E) 98 CH.sub.3CH.sub.2 H H H N oil (E) 99 CH.sub.3CH.sub.2 2-Cl 5-Cl H CH100 CH.sub.3CH.sub.2 2-Cl 5-Cl H N101 CH.sub.3CH.sub.2 4-Cl H H CH102 CH.sub.3CH.sub.2 4-Cl H H N103 CH.sub.3CH.sub.2 4-CH.sub.3 H H CH104 CH.sub.3CH.sub.2 4-CH.sub.3 H H N105 CH.sub.3CH.sub.2 5-OCH.sub.3 H H CH106 CH.sub.3CH.sub.2 5-OCH.sub.3 H H N107 CH.sub.3CH.sub.2 6-OCH.sub.3 H H CH 96-98 (E)108 CH.sub.3CH.sub.2 6-OCH.sub.3 H H N 124-126 (E)109 CH.sub.3CH.sub.2CH.sub.2 H H H CH110 CH.sub.3CH.sub.2CH.sub.2 H H H N111 CH.sub.2CHCH.sub. 2 H H H CH oil (E)112 CH.sub.2CHCH.sub.2 H H H N oil (E)113 CH.sub.3CH(CH.sub.3) H H H CH oil (E)114 CH.sub.3CH(CH.sub.3) H H H N oil (E)115 HCCCH.sub.2 H H H CH116 HCCCH.sub.2 H H H N117 cyclo-C.sub.3 H.sub.5CH.sub.2 H H H CH118 cyclo-C.sub.3 H.sub.5CH.sub.2 H H H N119 CH.sub.3CH.sub.2CH.sub.2CH.sub.2 H H H CH oil (E)120 CH.sub.3CH.sub.2CH.sub.2CH.sub.2 H H H N oil (E)121 CH.sub.3CHCHCH.sub.2 H H H CH122 CH.sub.3CHCHCH.sub.2 H H H N123 CH.sub.3(CH.sub.2).sub.5 H H H CH oil (E)124 CH.sub.3(CH.sub.2).sub.5 H H H N oil (E)125 cyclo-C.sub.6 H.sub.11 H H H CH126 cyclo-C.sub. 6 H.sub.11 H H H N127 C.sub.6 H.sub.5CH.sub.2 H H H CH oil (E)128 C.sub.6 H.sub.5CH.sub.2 H H H N oil (E)129 4-ClC.sub.6 H.sub.4CH.sub.2 H H H CH130 4-ClC.sub.6 H.sub.4CH.sub.2 H H H N131 3-CF.sub.3C.sub.6 H.sub.4CH.sub.2 H H H CH132 3-CF.sub.3C.sub.6 H.sub.4CH.sub.2 H H H N133 4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2 H H H CH134 4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2 H H H N135 C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2 H H H CH136 C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2 H H H N137 C.sub.6 H.sub.5(CH.sub.2).sub.4 H H H CH138 C.sub.6 H.sub.5(CH.sub.2).sub.4 H H H N139 C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2 H H H CH140 C.sub.6 H.sub.5 CH.sub.2CHCHCH.sub.2 H H H N141 4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2 H H H CH142 4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2 H H H N143 t-C.sub.4 H.sub.9 OCOCH.sub.2 H H H CH144 t-C.sub.4 H.sub.9 OCOCH.sub.2 H H H N145 t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3 H H H CH146 t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3 H H H N147 ClCHCHCH.sub.2 H H H CH148 ClCHCHCH.sub.2 H H H N251 C.sub.2 H.sub.5 6-OC.sub.2 H.sub.5 H H CH 83-85 (E)252 C.sub.2 H.sub.5 6-OC.sub.2 H.sub.5 H H N 104-106 (E)253 CH.sub.3C(CH.sub.3).sub.2 H H H CH254 CH.sub.3C(CH.sub.3).sub.2 H H H N255 CH.sub.3CH(CH.sub.3)CH.sub.2 H H H CH256 CH.sub.3CH(CH.sub.3 )CH.sub.2 H H H N257 CH.sub.2C(CH.sub.3)CH.sub.2 H H H CH258 CH.sub.2C(CH.sub.3)CH.sub.2 H H H N259 CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2 H H H CH260 CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2 H H H N261 CH.sub.3(CH.sub.2).sub.4 H H H CH262 CH.sub.3(CH.sub.2).sub.4 H H H N oil (E)263 2-FC.sub.6 H.sub.4CH.sub.2 H H H CH oil (E)264 2-FC.sub.6 H.sub.4CH.sub.2 H H H N oil (E)265 3-FC.sub.6 H.sub.4CH.sub.2 H H H CH oil (E)266 3-FC.sub.6 H.sub.4CH.sub.2 H H H N oil (E)267 2-ClC.sub.6 H.sub.4CH.sub.2 H H H CH oil (E)268 2-ClC.sub.6 H.sub.4CH.sub.2 H H H N269 3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 H H H CH oil (E)270 3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 H H H N oil (E)271 2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 H H H CH oil (E)272 2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 H H H N oil (E)273 C.sub.6 H.sub.5CH.sub.2CH.sub.2 H H H CH oil (E)274 C.sub.6 H.sub.5CH.sub.2CH.sub.2 H H H N oil (E)275 C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2 H H H CH oil (E)276 C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2 H H H N oil (E)277 4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H H CH oil (E)278 4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H H N oil (E)279 4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H H CH oil (E)280 4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H H N oil (E)435 CH.sub.3 H H CH.sub.3 CH oil (E)436 CH.sub.3 H H CH.sub. 3 N oil (E)437 CH.sub.3 2-Cl 5-Cl CH.sub.3 CH438 CH.sub.3 2-Cl 5-Cl CH.sub.3 N439 CH.sub.3 4-Cl H CH.sub.3 CH440 CH.sub.3 4-Cl H CH.sub.3 N441 CH.sub.3 4-CH.sub.3 H CH.sub.3 CH442 CH.sub.3 4-CH.sub.3 H CH.sub.3 N443 CH.sub.3 5-OCH.sub.3 H CH.sub.3 CH444 CH.sub.3 5-OCH.sub.3 H CH.sub.3 N445 CH.sub.3 6-OCH.sub.3 H CH.sub.3 CH446 CH.sub.3 6-OCH.sub.3 H CH.sub.3 N447 CH.sub.3CH.sub.2 H H CH.sub.3 CH oil (E)448 CH.sub.3CH.sub.2 H H CH.sub.3 N oil (E)449 CH.sub.3CH.sub.2 2-Cl 5-Cl CH.sub.3 CH450 CH.sub.3CH.sub.2 2-Cl 5-Cl CH.sub.3 N451 CH.sub.3CH.sub.2 4-Cl H CH.sub.3 CH452 CH.sub.3CH.sub.2 4-Cl H CH.sub.3 N453 CH.sub.3CH.sub.2 4-CH.sub.3 H CH.sub.3 CH454 CH.sub.3CH.sub.2 4-CH.sub.3 H CH.sub.3 N455 CH.sub.3CH.sub.2 5-OCH.sub.3 H CH.sub.3 CH456 CH.sub.3CH.sub.2 5-OCH.sub.3 H CH.sub.3 N457 CH.sub.3CH.sub. 2 6-OCH.sub.3 H CH.sub.3 CH458 CH.sub.3CH.sub.2 6-OCH.sub.3 H CH.sub.3 N459 CH.sub.3CH.sub.2CH.sub.2 H H CH.sub.3 CH oil (E)460 CH.sub.3CH.sub.2CH.sub.2 H H CH.sub.3 N 73-74 (E)461 CH.sub.2CHCH.sub.2 H H CH.sub.3 CH oil (E)462 CH.sub.2CHCH.sub.2 H H CH.sub.3 N 51-53 (E)463 CH.sub.3CH(CH.sub.3) H H CH.sub.3 CH oil (E)464 CH.sub.3CH(CH.sub.3) H H CH.sub.3 N 58-60 (E)465 HCCCH.sub.2 H H CH.sub.3 CH466 HCCCH.sub.2 H H CH.sub.3 N467 cyclo-C.sub.3 H.sub.5CH.sub.2 H H CH.sub.3 CH468 cyclo-C.sub.3 H.sub.5CH.sub.2 H H CH.sub.3 N469 CH.sub.3CH.sub.2CH.sub.2CH.sub.2 H H CH.sub.3 CH oil (E)470 CH.sub.3CH.sub.2CH.sub.2CH.sub.2 H H CH.sub.3 N oil (E)471 CH.sub. 3CHCHCH.sub.2 H H CH.sub.3 CH oil (E)472 CH.sub.3CHCHCH.sub.2 H H CH.sub.3 N 76-78 (E)473 CH.sub.3(CH.sub.2).sub.5 H H CH.sub.3 CH oil (E)474 CH.sub.3(CH.sub.2).sub.5 H H CH.sub.3 N oil (E)475 cyclo-C.sub.6 H.sub.11 H H CH.sub.3 CH476 cyclo-C.sub.6 H.sub.11 H H CH.sub.3 N477 C.sub.6 H.sub.5CH.sub.2 H H CH.sub.3 CH478 C.sub.6 H.sub.5CH.sub.2 H H CH.sub.3 N oil (E)479 4-ClC.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 CH480 4-ClC.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 N481 3-CF.sub.3C.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 CH482 3-CF.sub.3C.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 N483 4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2 H H CH.sub.3 CH484 4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2 H H CH.sub.3 N485 C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2 H H CH.sub.3 CH486 C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2 H H CH.sub.3 N487 C.sub.6 H.sub.5(CH.sub.2).sub.4 H H CH.sub.3 CH488 C.sub.6 H.sub.5(CH.sub.2).sub.4 H H CH.sub.3 N489 C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2 H H CH.sub.3 CH490 C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2 H H CH.sub.3 N491 4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2 H H CH.sub.3 CH492 4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2 H H CH.sub.3 N493 t-C.sub.4 H.sub.9 OCOCH.sub.2 H H CH.sub.3 CH494 t-C.sub.4 H.sub.9 OCOCH.sub.2 H H CH.sub.3 N495 t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3 H H CH.sub.3 CH496 t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3 H H CH.sub.3 N497 ClCHCHCH.sub.2 H H CH.sub.3 CH oil (E)498 ClCHCHCH.sub.2 H H CH.sub.3 N oil (E)499 C.sub.2 H.sub.5 6-OC.sub.2 H.sub.5 H CH.sub.3 CH500 C.sub.2 H.sub.5 6-OC.sub.2 H.sub.5 H CH.sub.3 N501 CH.sub.3C(CH.sub.3).sub.2 H H CH.sub.3 CH oil (E)502 CH.sub.3C(CH.sub.3).sub.2 H H CH.sub.3 N 83-85 (E)503 CH.sub.3CH(CH.sub.3)CH.sub.2 H H CH.sub.3 CH oil (E)504 CH.sub.3CH(CH.sub.3)CH.sub.2 H H CH.sub.3 N 70-72 (E)505 CH.sub.2C(CH.sub.3)CH.sub.2 H H CH.sub.3 CH oil (E)506 CH.sub.2C(CH.sub.3)CH.sub.2 H H CH.sub.3 N 64-65 (E)507 CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2 H H CH.sub.3 CH oil (E)508 CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2 H H CH.sub.3 N oil (E)509 CH.sub.3(CH.sub.2).sub.4 H H CH.sub.3 CH510 CH.sub.3(CH.sub.2).sub.4 H H CH.sub.3 N511 2-FC.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 CH512 2-FC.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 N513 3-FC.sub. 6 H.sub.4CH.sub.2 H H CH.sub.3 CH514 3-FC.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 N515 2-ClC.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 CH516 2-ClC.sub.6 H.sub.4CH.sub.2 H H CH.sub.3 N517 3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 H H CH.sub.3 CH518 3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 H H CH.sub.3 N519 2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 H H CH.sub.3 CH520 2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2 H H CH.sub.3 N521 C.sub.6 H.sub.5CH.sub.2CH.sub.2 H H CH.sub.3 CH522 C.sub.6 H.sub.5CH.sub.2CH.sub.2 H H CH.sub.3 N523 C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2 H H CH.sub.3 CH524 C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2 H H CH.sub.3 N525 4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H CH.sub.3 CH526 4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H CH.sub.3 N527 4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H CH.sub.3 CH528 4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2 H H CH.sub.3 N529 CH.sub.3 H H C.sub.6 H.sub.5 CH530 CH.sub.3 H H C.sub.6 H.sub.5 N531 C.sub.2 H.sub.5 H H C.sub.6 H.sub.5 CH532 C.sub.2 H.sub.5 H H C.sub.6 H.sub.5 N533 CH.sub.3CH.sub.2CH.sub.2 H H C.sub.6 H.sub.5 CH534 CH.sub.3CH.sub.2CH.sub.2 H H C.sub.6 H.sub.5 N535 CH.sub.3(CH.sub.2).sub.5 H H C.sub.6 H.sub.5 CH536 CH.sub.3(CH.sub.2).sub.5 H H C.sub.6 H.sub.5 N537 C.sub.6 H.sub.5CH.sub.2 H H C.sub.6 H.sub.5 CH538 C.sub.6 H.sub.5CH.sub.2 H H C.sub.6 H.sub.5 N__________________________________________________________________________ TABLE 3__________________________________________________________________________Compounds of the formula Ic (4-position of the oxime ether).The configuration statement relates to the methyl.beta.-methoxyacrylate group or the methyl glyoxylate O-methyloximegroup. ##STR12## IcComp. no. R.sup.1 R.sup.2 R.sup.3 R.sup.4 X mp. (.degree.C.)__________________________________________________________________________149 CH.sub.3 H H H CH 84-86 (E)150 CH.sub.3 H H H N 88-91 (E)151 CH.sub.3 2-Cl H H CH152 CH.sub.3 2-Cl H H N153 CH.sub.3 2-CH.sub.3 H H CH154 CH.sub.3 2-CH.sub.3 H H N155 CH.sub.3 2-OCH.sub.3 H H CH oil (E)156 CH.sub.3 2-OCH.sub.3 H H N 105-107 (E)157 CH.sub.3 3-Cl H H CH158 CH.sub.3 3-Cl H H N159 CH.sub.3 3-CH.sub.3 H H CH160 CH.sub.3 3-CH.sub.3 H H N161 CH.sub.3 3-OCH.sub.3 H H CH162 CH.sub.3 3-OCH.sub.3 H H N163 CH.sub.3 2-Cl 6-Cl H CH164 CH.sub.3 2-Cl 6-Cl H N165 CH.sub.3 CH.sub.2 H H H CH 108-110 (E)166 CH.sub.3 CH.sub.2 H H H N 106-108 (E)167 CH.sub.3 CH.sub.2 2-Cl H H CH168 CH.sub.3 CH.sub.2 2-Cl H H N169 CH.sub.3 CH.sub.2 2-CH.sub.3 H H CH170 CH.sub.3 CH.sub.2 2-CH.sub.3 H H N171 CH.sub.3 CH.sub.2 2-OCH.sub.3 H H CH172 CH.sub.3 CH.sub.2 2-OCH.sub.3 H H N173 CH.sub.3 CH.sub.2 3-Cl H H CH174 CH.sub.3 CH.sub.2 3-Cl H H N175 CH.sub.3 CH.sub.2 3-CH.sub.3 H H CH176 CH.sub.3 CH.sub.2 3-CH.sub.3 H H N177 CH.sub.3 CH.sub.2 3-OCH.sub.3 H H CH178 CH.sub.3 CH.sub.2 3-OCH.sub.3 H H N179 CH.sub.3 CH.sub.2 2-Cl 6-Cl H CH180 CH.sub.3 CH.sub.2 2-Cl 6-Cl H N181 CH.sub.3 CH.sub.2 CH.sub.2 H H H CH182 CH.sub.3 CH.sub.2 CH.sub.2 H H H N183 CH.sub.2 CHCH.sub.2 H H H CH 103-105 (E)184 CH.sub.2 CHCH.sub.2 H H H N 82-84 (E)185 CH.sub.3 CH(CH.sub.3) H H H CH186 CH.sub.3 CH(CH.sub.3) H H H N187 HCCCH.sub.2 H H H CH188 HCCCH.sub. 2 H H H N189 cyclo-C.sub. 3 H.sub.5 CH.sub.2 H H H CH190 cyclo-C.sub. 3 H.sub.5 CH.sub.2 H H H N191 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 H H H CH192 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 H H H N193 CH.sub.3 CHCHCH.sub.2 H H H CH194 CH.sub.3 CHCHCH.sub.2 H H H N195 CH.sub.3 (CH.sub.2).sub.5 H H H CH 62-63 (E)196 CH.sub.3 (CH.sub.2).sub.5 H H H N 72-73 (E)197 cyclo-C.sub.6 H.sub.11 H H H CH198 cyclo-C.sub.6 H.sub.11 H H H N199 C.sub.6 H.sub.5 CH.sub.2 H H H CH 103-105 (E)200 C.sub.6 H.sub.5 CH.sub.2 H H H N 151-153 (E)201 4-ClC.sub.6 H.sub.4 CH.sub.2 H H H CH202 4-ClC.sub.6 H.sub.4 CH.sub.2 H H H N203 3-CF.sub.3 C.sub.6 H.sub.4 CH.sub.2 H H H CH204 3-CF.sub.3 C.sub.6 H.sub.4 CH.sub.2 H H H N205 4-ClC.sub.6 H.sub.4 CH.sub.2 CH.sub.2 H H H CH206 4-ClC.sub.6 H.sub.4 CH.sub.2 CH.sub.2 H H H N207 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2 H H H CH208 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2 H H H N209 C.sub.6 H.sub.5 (CH.sub.2).sub.4 H H H CH210 C.sub.6 H.sub.5 (CH.sub.2).sub.4 H H H N211 C.sub.6 H.sub.5 CH.sub.2 CHCHCH.sub.2 H H H CH212 C.sub.6 H.sub.5 CH.sub.2 CHCHCH.sub.2 H H H N213 4-FC.sub. 6 H.sub.4 CHCHCH.sub.2 CH.sub.2 H H H CH214 4-FC.sub.6 H.sub.4 CHCHCH.sub.2 CH.sub.2 H H H N215 t-C.sub.4 H.sub.9 OCOCH.sub.2 H H H CH216 t-C.sub.4 H.sub.9 OCOCH.sub.2 H H H N217 t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3 H H H CH218 t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3 H H H N219 ClCHCHCH.sub.2 H H H CH oil (E)220 ClCHCHCH.sub.2 H H H N 95-97 (E)281 C.sub.2 H.sub.5 6-OC.sub.2 H.sub.5 H H CH282 C.sub.2 H.sub.5 6-OC.sub.2 H.sub.5 H H N283 CH.sub.3 C(CH.sub.3).sub.2 H H H CH284 CH.sub.3 C(CH.sub.3).sub.2 H H H N285 CH.sub.3 CH(CH.sub.3)CH.sub.2 H H H CH286 CH.sub.3 CH(CH.sub.3)CH.sub.2 H H H N287 CH.sub.2 C(CH.sub.3)CH.sub.2 H H H CH 100-102 (E)288 CH.sub.2 C(CH.sub.3)CH.sub.2 H H H N 95-96 (E)289 CH.sub.3 CH(CH.sub.3)CH.sub.2 CH.sub.2 H H H CH290 CH.sub.3 CH(CH.sub.3)CH.sub.2 CH.sub.2 H H H N291 CH.sub.3 (CH.sub.2).sub.4 H H H CH292 CH.sub.3 (CH.sub.2).sub.4 H H H N oil (E)293 2-FC.sub.6 H.sub.4 CH.sub.2 H H H CH294 2-FC.sub.6 H.sub.4 CH.sub.2 H H H N295 3-FC.sub.6 H.sub.4 CH.sub.2 H H H CH296 3-FC.sub.6 H.sub.4 CH.sub.2 H H H N297 2-ClC.sub.6 H.sub.4 CH.sub.2 H H H CH298 2-ClC.sub.6 H.sub.4 CH.sub.2 H H H N299 3,4-Cl.sub.2 C.sub.6 H.sub.3 CH.sub.2 H H H CH300 3,4-Cl.sub.2 C.sub.6 H.sub.3 CH.sub.2 H H H N301 2,6-Cl.sub.2 C.sub.6 H.sub.3 CH.sub.2 H H H CH302 2,6-Cl.sub.2 C.sub.6 H.sub.3 CH.sub.2 H H H N303 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 H H H CH304 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 H H H N305 C.sub.6 H.sub.5 CHCHCH.sub.2 CH.sub.2 H H H CH306 C.sub.6 H.sub.5 CHCHCH.sub.2 CH.sub.2 H H H N307 4-ClC.sub.6 H.sub.4 CH.sub.2 CHCHCH.sub.2 H H H CH308 4-ClC.sub.6 H.sub.4 CH.sub.2 CHCHCH.sub.2 H H H N309 4-CF.sub.3 C.sub.6 H.sub.4 CH.sub.2 CHCHCH.sub.2 H H H CH310 4-CF.sub.3 C.sub.6 H.sub.4 CH.sub.2 CHCHCH.sub.2 H H H N539 CH.sub.3 H H CH.sub.3 CH oil (E)540 CH.sub.3 H H CH.sub.3 N 99-100 (E)541 CH.sub.3 2-Cl H CH.sub.3 CH542 CH.sub.3 2-Cl H CH.sub.3 N543 CH.sub.3 2-CH.sub.3 H CH.sub.3 CH544 CH.sub.3 2-CH.sub.3 H CH.sub.3 N545 CH.sub.3 2-OCH.sub.3 H CH.sub.3 CH546 CH.sub.3 2-OCH.sub.3 H CH.sub.3 N547 CH.sub.3 3-Cl H CH.sub.3 CH548 CH.sub.3 3-Cl H CH.sub.3 N549 CH.sub.3 3-CH.sub.3 H CH.sub.3 CH550 CH.sub.3 3-CH.sub.3 H CH.sub.3 N551 CH.sub.3 3-OCH.sub.3 H CH.sub.3 CH552 CH.sub.3 3-OCH.sub.3 H CH.sub.3 N553 CH.sub.3 2-Cl 6-Cl CH.sub.3 CH554 CH.sub.3 2-Cl 6-Cl CH.sub.3 N555 CH.sub.3 CH.sub.2 H H CH.sub.3 CH 71-73 (E)556 CH.sub.3 CH.sub.2 H H CH.sub.3 N 79-80 (E)557 CH.sub.3 CH.sub.2 2-Cl H CH.sub.3 CH558 CH.sub.3 CH.sub.2 2-Cl H CH.sub.3 N559 CH.sub.3 CH.sub.2 2-CH.sub.3 H CH.sub.3 CH560 CH.sub.3 CH.sub.2 2-CH.sub.3 H CH.sub.3 N561 CH.sub.3 CH.sub.2 2-OCH.sub.3 H CH.sub.3 CH562 CH.sub.3 CH.sub.2 2-OCH.sub.3 H CH.sub.3 N563 CH.sub.3 CH.sub.2 3-Cl H CH.sub.3 CH564 CH.sub.3 CH.sub.2 3-Cl H CH.sub.3 N565 CH.sub.3 CH.sub.2 3-CH.sub.3 H CH.sub.3 CH566 CH.sub.3 CH.sub.2 3-CH.sub.3 H CH.sub.3 N567 CH.sub.3 CH.sub.2 3-OCH.sub.3 H CH.sub.3 CH568 CH.sub.3 CH.sub.2 3-OCH.sub.3 H CH.sub.3 N569 CH.sub.3 CH.sub.2 2-Cl 6-Cl CH.sub.3 CH570 CH.sub.3 CH.sub.2 2-Cl 6-Cl CH.sub.3 N571 CH.sub.3 CH.sub.2 CH.sub.2 H H CH.sub.3 CH 97-99 (E)572 CH.sub.3 CH.sub.2 CH.sub.2 H H CH.sub.3 N 100-101 (E)573 CH.sub.2 CHCH.sub.2 H H CH.sub.3 CH 90-92 (E)574 CH.sub.2 CHCH.sub.2 H H CH.sub.3 N 107-108 (E)575 CH.sub.3 CH(CH.sub.3) H H CH.sub.3 CH 120-123 (E)576 CH.sub.3 CH(CH.sub.3) H H CH.sub.3 N 109-110 (E)577 HCCCH.sub.2 H H CH.sub.3 CH578 HCCCH.sub.2 H H CH.sub.3 N579 cyclo-C.sub.3 H.sub.5 CH.sub.2 H H CH.sub.3 CH580 cyclo-C.sub.3 H.sub.5 CH.sub.2 H H CH.sub.3 N581 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 H H CH.sub.3 CH 64-66 (E)582 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 H H CH.sub.3 N oil (E)583 CH.sub.3 CHCHCH.sub.2 H H CH.sub.3 CH oil (E)584 CH.sub.3 CHCHCH.sub.2 H H CH.sub.3 N 100-103 (E)585 CH.sub.3 (CH.sub.2).sub.5 H H CH.sub.3 CH 64-67 (E)586 CH.sub.3 (CH.sub.2).sub.5 H H CH.sub.3 N 60-63 (E)587 cyclo-C.sub.6 H.sub.11 H H CH.sub.3 CH588 cyclo-C.sub.6 H.sub.11 H H CH.sub.3 N589 C.sub.6 H.sub.5 CH.sub.2 H H CH.sub.3 CH 110-112 (E)590 C.sub.6 H.sub.5 CH.sub.2 H H CH.sub.3 N 104-106 (E)591 4-ClC.sub.6 H.sub.4 CH.sub.2 H H CH.sub.3 CH592 4-ClC.sub.6 H.sub.4 CH.sub.2 H H CH.sub.3 N593 3-CF.sub.3 C.sub.6 H.sub.4 CH.sub.2 H H CH.sub.3 CH594 3-CF.sub.3 C.sub.6 H.sub.4 CH.sub.2 H H CH.sub.3 N595 4-ClC.sub.6 H.sub.4 CH.sub.2 CH.sub.2 H H CH.sub.3 CH596 4-ClC.sub.6 H.sub.4 CH.sub.2 CH.sub.2 H H CH.sub.3 N597 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2 H H CH.sub.3 CH598 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2 H H CH.sub.3 N599 C.sub.6 H.sub.5 (CH.sub.2).sub.4 H H CH.sub.3 CH600 C.sub.6 H.sub.5 (CH.sub.2).sub.4 H H CH.sub.3 N601 C.sub.6 H.sub.5 CH.sub.2 CHCHCH.sub.2 H H CH.sub.3 CH602 C.sub.6 H.sub.5 CH.sub.2 CHCHCH.sub.2 H H CH.sub.3 N603 4-FC.sub.6 H.sub.4 CHCHCH.sub.2 CH.sub.2 H H CH.sub.3 CH604 4-FC.sub.6 H.sub.4 CHCHCH.sub.2 CH.sub.2 H H CH.sub.3 N605 t-C.sub.4 H.sub.9 OCOCH.sub.2 H H CH.sub.3 CH606 t-C.sub.4 H.sub.9 OCOCH.sub.2 H H CH.sub.3 N607 t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3 H H CH.sub.3 CH608 t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3 H H CH.sub.3 N609 ClCHCHCH.sub.2 H H CH.sub.3 CH 98-100 (E)610 ClCHCHCH.sub.2 H H CH.sub.3 N 105-107 (E)611 C.sub.2 H.sub.5 6-OC.sub.2 H.sub.5 H CH.sub.3 CH612 C.sub.2 H.sub.5 6-OC.sub.2 H.sub.5 H CH.sub.3 N613 CH.sub.3 C(CH.sub.3).sub.2 H H CH.sub.3 CH 88-90 (E)614 CH.sub.3 C(CH.sub.3).sub.2 H H CH.sub.3 N 75-78 (E)615 CH.sub.3 CH(CH.sub.3)CH.sub.2 H H CH.sub.3 CH 85-87 (E)616 CH.sub.3 CH(CH.sub.3)CH.sub.2 H H CH.sub.3 N 79-81 (E)617 CH.sub.2 C(CH.sub.3)CH.sub.2 H H CH.sub.3 CH 94-96 (E)618 CH.sub.2 C(CH.sub.3)CH.sub.2 H H CH.sub.3 N 88-89 (E)619 CH.sub.3 CH(CH.sub.3)CH.sub.2 CH.sub.2 H H CH.sub.3 CH 46-48 (E)620 CH.sub.3 CH(CH.sub.3)CH.sub.2 CH.sub.2 H H CH.sub.3 N oil (E)621 CH.sub.3 (CH.sub.2).sub.4 H H CH.sub.3 CH622 CH.sub.3 (CH.sub.2).sub.4 H H CH.sub.3 N623 2-FC.sub.6 H.sub.4 CH.sub.2 H H CH.sub.3 CH624 2-FC.sub.6 H.sub.4 CH.sub.2 H H CH.sub.3 N625 3-FC.sub.6 H.sub.4 CH.sub.2 H H CH.sub.3 CH626 3-FC.sub.6 H.sub.4 CH.sub.2 H H CH.sub.3 N627 2-ClC.sub.6 H.sub.4 CH.sub.2 H H CH.sub.3 CH628 2-ClC.sub.6 H.sub.4 CH.sub.2 H H CH.sub.3 N629 3,4-Cl.sub.2 C.sub.6 H.sub.3 CH.sub.2 H H CH.sub.3 CH630 3,4-Cl.sub.2 C.sub.6 H.sub.3 CH.sub.2 H H CH.sub.3 N631 2,6-Cl.sub.2 C.sub.6 H.sub.3 CH.sub.2 H H CH.sub.3 CH632 2,6-Cl.sub.2 C.sub.6 H.sub.3 CH.sub.2 H H CH.sub.3 N633 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 H H CH.sub.3 CH634 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 H H CH.sub.3 N635 C.sub.6 H.sub.5 CHCHCH.sub.2 CH.sub.2 H H CH.sub.3 CH636 C.sub.6 H.sub.5 CHCHCH.sub.2 CH.sub.2 H H CH.sub.3 N637 4-ClC.sub.6 H.sub.4 CH.sub. 2 CHCHCH.sub.2 H H CH.sub.3 CH638 4-ClC.sub.6 H.sub.4 CH.sub.2 CHCHCH.sub.2 H H CH.sub.3 N639 4-CF.sub.3 C.sub.6 H.sub.4 CH.sub.2 CHCHCH.sub.2 H H CH.sub.3 CH640 4-CF.sub.3 C.sub.6 H.sub.4 CH.sub.2 CHCHCH.sub.2 H H CH.sub.3 N641 CH.sub.3 H H C.sub.6 H.sub.5 CH642 CH.sub.3 H H C.sub.6 H.sub.5 N643 C.sub.2 H.sub.5 H H C.sub.6 H.sub.5 CH644 C.sub.2 H.sub.5 H H C.sub.6 H.sub.5 N645 CH.sub.3 CH.sub.2 CH.sub.2 H H C.sub.6 H.sub.5 CH646 CH.sub.3 CH.sub.2 CH.sub.2 H H C.sub.6 H.sub.5 N647 CH.sub.3 (CH.sub.2).sub.5 H H C.sub.6 H.sub.5 CH648 CH.sub.3 (CH.sub.2).sub.5 H H C.sub.6 H.sub.5 N649 C.sub.6 H.sub.5 CH.sub.2 H H C.sub.6 H.sub.5 CH650 C.sub.6 H.sub.5 CH.sub. 2 H H C.sub.6 H.sub.5 N__________________________________________________________________________ TABLE 4______________________________________.sup.1 H--NMR data of selected compounds from Tables 1, 2 and 3.The chemical shift (.delta.) is given in ppm relative totetramethylsilane. The solvent employed is CDCl.sub.3.______________________________________Compound no. 13.67 (s, 3H); 3.77 (s, 3H); 3.93 (s, 3H); 4.98 (s, 2H); 6.81-7.81 (m,8H); 7.57 (s, 1H); 8.49 (s, 1H).Compound no. 23.40 (s, 3H); 3.95 (s, 3H); 4.05 (s, 3H); 4.95 (s, 2H); 6.80-7.85 (m,8H); 8.45 (s, 1H).Compound no. 231.31 (t, 3H); 3.67 (s, 3H); 3.79 (s, 3H); 4.20 (q, 2H); 4.97 (s, 2H);6.83-7.83 (m, 8H); 7.59 (s, 1H); 8.51 (s, 1H).Compound no. 241.30 (t, 3H); 3.80 (s, 3H); 4.05 (s, 3H); 4.20 (q, 2H); 4.95 (s, 2H);6.80-7.85 (m, 8H); 8.45 (s, 1H).Compound no. 853.65 (s, 3H); 3.68 (s, 3H); 3.92 (s, 3H); 4.95 (s, 2H); 6.85-7.52 (m,8H); 7.55 (s, 1H); 7.98 (s, 1H).Compound no. 971.28 (t, 3H); 3.68 (s, 3H); 3.73 (s, 3H); 4.20 (q, 2H); 4.97 (s, 2H);6.85-7.53 (m, 8H); 7.57 (s, 1H); 8.00 (s, 1H).Compound no. 1493.68 (s, 3H); 3.77 (s, 3H); 3.92 (s, 3H); 4.98 (s, 2H); 6.87-7.53 (m,8H); 7.59 (s, 1H); 7.98 (s, 1H).Compound no. 1651.31 (t, 3H); 3.69 (s, 3H); 3.80 (s, 3H); 4.20 (q, 2H); 5.00 (s, 2H);6.87-7.53 (m, 8H); 7.60 (s, 1H); 8.00 (s, 1H).Compound no. 4471.32 (t, 3H); 2.18 (s, 3H); 3.68 (s, 3H); 3.77 (s, 3H); 4.22 (q, 2H);4.97 (s, 2H); 6.83-7.53 (m, 8H); 7.55 (s, 1H).Compound no. 4881.32 (t, 3H); 2.17 (s, 3H); 3.82 (s, 3H); 4.00 (s, 3H); 4.23 (q, 4H);4.97 (s, 2H); 6.83-7.57 (m, 8H).Compound no. 4700.95 (t, 3H); 1.43 (m, 2H); 1.70 (m, 2H); 2.18 (s, 3H); 3.83 (s, 3H);4.00 (s, 3H); 4.17 (t, 2H); 4.97 (s, 2H); 6.82-7.55 (m, 8H).Compound no. 4740.87 (t, 3H); 1.32 (m, 6H); 1.70 (m, 2H); 2.18 (s, 3H); 3.83 (s, 3H);4.02 (s, 3H); 4.17 (t, 2H); 4.95 (s, 2H); 6.83-7.57 (m, 8H).Compound no. 4782.22 (s, 3H); 3.78 (s, 3H); 4.00 (s, 3H); 4.97 (s, 2H); 5.23 (s, 2H);6.82-7.53 (m, 8H).Compound no. 5561.33 (t, 3H); 2.20 (s, 3H); 3.83 (s, 3H); 4.02 (s, 3H); 4.22 (q, 2H);4.97 (s, 2H); 6.85-7.60 (m, 8H).Compound no. 5820.97 (t, 3H); 1.40 (m, 2H); 1.68 (m, 2H); 2.17 (s, 3H); 3.83 (s, 3H);4.00 (s, 3H); 4.15 (t, 2H); 4.95 (s, 2H); 6.82-7.57 (m, 8H).Compound no. 5860.88 (t, 3H); 1.32 (m, 6H); 1.70 (m, 2H); 2.18 (s, 3H); 3.83 (s, 3H);4.01 (s, 3H); 4.15 (t, 2H); 4.95 (s, 2H); 6.83-7.57 (m, 8H).Compound no. 5902.22 (s, 3H); 3.83 (s, 3H); 4.02 (s, 3H), 4.95 (s, 2H); 5.22 (s, 2H);6.82-7.57 (m, 8H).______________________________________

Generally speaking, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the Ascomycetes and Basidiomycetes classes. 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.

The novel compounds are particularly useful for controlling the following plant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia species in cotton and lawns,

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 compounds are applied by spraying or dusting the plants with the active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi.

The novel substances can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. 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 (e.g., xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin, sulfite waste liquors and methylcellulose.

The fungicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt % of active ingredient. The application rates are from 0.02 to 3 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials, for example against Paecilomyces variotii.

The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 85 is mixed with 10 parts by weight of N-methyl-.alpha.-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 97 is dissolved in a mixture consisting of 80 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 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

III. 20 parts by weight of compound no. 447 is dissolved in a mixture consisting of 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. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.

IV 20 parts by weight of compound no. 470 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210.degree. and 280.degree. C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

V. 80 parts by weight of compound no. 149 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-.alpha.-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, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.

VI. 3 parts by weight of compound no. 165 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

VII. 30 parts by weight of compound no. 590 is intimately mixed with a mixture consisting 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. A formulation of the active ingredient is obtained having good adherence.

VIII. 40 parts by weight of compound no. 448 is intimately mixed with 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in water gives an aqueous dispersion.

IX. 20 parts by weight of compound no. 85 is intimately mixed with 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. A stable oily dispersion is obtained.

In these application forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fungicides frequently results in an increase in the fungicidal spectrum.

USE EXAMPLES

The comparative agent which was employed was methyl 2-(phenoxymethyl)phenylglyoxylate O-methyloxime (A) disclosed in EP 253,213.

USE EXAMPLE 1

Action on wheat brown rust

Leaves of pot-grown wheat seedlings of the "Kanzler" variety were dusted with spores of brown rust (Puccinia recondita). The pots were then placed for 24 hours at 20.degree. to 22.degree. C. 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.degree. to 22.degree. C. and a relative humidity of 65 to 70%. The extent of rust fungus spread on the leaves was assessed after 8 days.

The results show that active ingredients 85 and 97, applied as 0.025 wt % spray liquors, have a better fungicidal action (100%) than prior art comparative agent A (35%).

In another experiment, it was found that active ingredients 111, 112, 113, 119, 123, 195, 220, 262, 265, 266, 273, 275, 447 and 470, applied as 0.025 wt % spray liquors, have a better fungicidal action (95%) than prior art comparative agent A (35%).

USE EXAMPLE 2

Action on Plasmopara viticola

Leaves of potted vines of the Muller-Thurgau variety were sprayed with aqueous liquors 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 24.degree. C. and then in a greenhouse for 5 days at from 20.degree. to 30.degree. C. 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.

The results show that active ingredients 85, 97, 149 and 165, applied as 0.0125% spray liquors, have a better fungicidal action (100%) than prior art comparative agent A (50%).

In a further experiment, it was found that active ingredients 86, 88, 111, 113, 114, 119, 120, 123, 124, 127, 150, 155, 183, 184, 199, 219, 220, 263, 265, 267, 273, 275, 277, 287, 288, 447 and 448, applied as 0.0125% spray liquors, have a better fungicidal action (95%) than prior art comparative agent A (50%).

Claims

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 substituted oxime ether of the general formula I ##STR13## where R.sup.1 is C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.4 -alkynyl, C.sub.1 -C.sub.6 -haloalkyl, C.sub.3 -C.sub.6 -haloalkenyl, C.sub.1 -C.sub.4 -alkoxy-C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.6 -cycloalkyl, C.sub.3 -C.sub.6 -cycloalkyl-C.sub.1 -C.sub.4 -alkyl, cyano-C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -alkoxycarbonyl-C.sub.1 -C.sub.6 -alkyl, aryl-C.sub.1 -C.sub.6 -alkyl, pyridyl-C.sub.1 -C.sub.6 -alkyl, thienyl-C.sub.1 -C.sub.6 -alkyl aryl-C.sub.3 -C.sub.6 -alkenyl or aryloxy-C.sub.1 -C.sub.6 -alkyl, it being possible for the aromatic, pyridyl on thienyl ring to be substituted by one or more of the following: C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.2 -haloalkyl, C.sub.3 -C.sub.6 -cycloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.2 -haloalkoxy, halogen, aryl or aryloxy,

R.sup.2 and R.sup.3 are identical or different and are hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.2 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.2 -haloalkoxy, halogen, cyano or nitro,

R.sup.4 is hydrogen, C.sub.1 -C.sub.6 -alkyl or aryl, it being possible for the aromatic ring to be substituted by one or more of the following: C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.2 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.2 -haloalkoxy, halogen, cyano or nitro, and

X is CH or N.