JPS6348257A - Alkoxyminoalkylamide - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel substituted alkoximinoalkylamides, several methods of their preparation, and their pest control agents (pe
stic ide).

It is already a known fact that certain substituted amides, such as 2-(4-chlorobenzamide)-2-ethoxyacetonitrile, have bactericidal and fungicidal properties (for example,
(see European Patent Specification No. 59,536).

However, the action of these previously known compounds is not completely satisfactory in all fields of application, especially when applied in small amounts and in low concentrations.

General formula (I) in which R1 represents alkyl, alkenyl, aralkyl, heteroarylalkyl, aryl or heteroaryl, which may in each case be substituted, and I R2 is cyano, the group -C-NH2 or represents the group -C-NH2, R3 and R4 independently of each other represent hydrogen or optionally substituted alkyl, alkenyl or alkynyl, or the carbon atoms to which they are attached; A new alkoximinoalkylamide representing a saturated carbocyclic ring was discovered.

The compounds of formula (I) can exist both as geometric isomers and as isomeric combinations of various compositions. Both the pure isomers and the isomeric combinations are claimed according to the invention.

Furthermore, the general formula (, I') 0 0-NmoC R=C-NH7qH, R' (I) In the formula, RI is substituted or substituted alkyl, alkenyl, aralkyl, represents heteroarylalkyl, aryl or heteroaryl, R2 is cyano, group -C-Nl-1□ or group -C-NH
□, and R3 and R4 each independently represent hydrogen or optionally substituted alkyl, alkenyl, or alkynyl, or together with the carbon atom to which they are bonded, A novel alkoximinoalkylamide representing a carbocyclic ring is represented by (a) general formula (II), where R1 has the above meaning and R2-1 represents a cyano or carbamoyl group. III) react with an oxime of HO-N-C(lII) in which R3 and R4 have the above meanings, optionally in the presence of a diluent and optionally in the presence of an acid binder, and , optionally, (b) Subsequently, an alkoximinoalkyla, mido of general formula (Ia) obtained by method (a), where Rl , R3 and R4 have the above meanings, is optionally added to a diluent. dehydrated using a de-16= aqueous solution in the presence of an acid binder and optionally in the presence of an acid binder, and further optionally (,C) subsequently obtained by method (a) or (b) An alkoximinoalkylamide of general formula (Ib) CN , (Ib) where 1:j I , R3 and R4 have the above meanings is treated in the presence of an appropriate diluent and in the presence of an appropriate basic catalyst. It was discovered that the seeds obtained by reacting with hydrogen sulfide in the presence of

Finally, it has been found that the novel alkoximinoalkylamides of general formula (I) have bactericidal and fungicidal properties.

Surprisingly, the alkoximinoalkylamides of general formula (I) according to the invention are substituted amides known from the state of the art, such as compounds which are similar both chemically and in terms of their action. N-(cyanoethoxymethyl)-
It has better bactericidal and fungicidal properties than 4-chlorobenzamide.

Formula (I) provides a general definition of the alkoximinoalkylamides according to the invention. Preferred compounds of formula (I) are those in which R1 is a straight-chain or branched alkyl having 1 to 8 carbon atoms, 1 to 5 in the alkyl moiety;
straight-chain or branched cyanoalkyl having 1 to 5 carbon atoms and 1 to 9 carbon atoms;
straight-chain or branched halogenoalkyl having halogen atoms, in each case 1 to 5 carbon atoms in each alkyl moiety, in either case straight-chain or branched alkoxyalkyl or alkylthioalkyl, straight-chain or branched alkenyl having 3 to 8 carbon atoms, or having 3 to 8 carbon atoms and 1 to 5 halogen atoms; represents a straight-chain or branched halogenoalkyl, in addition 1 to 4 carbon atoms in the alkyl part and 6 to 1 carbon atoms in the aryl part;
Aralkyl having 0 carbon atoms and which may be mono- or polysubstituted in the aryl moiety, the substituents may be the same or different, 1 to 4 in the alkyl moiety 2 to 9 carbon atoms and 1 to 3 heteroatoms (especially nitrogen, oxygen and sulfur) in the heteroaryl moiety, mono- or polysubstituted in the heteroaryl moiety heteroarylalkyl, the substituents of which may be the same or different; aryl having 6 to 10 carbon atoms, which may be mono- or polysubstituted; and the substituents may be the same or different, or contain 2 to 9 carbon atoms and 1 to 3 heteroatoms (in particular nitrogen, oxygen and sulfur). represents a heteroaryl which may be -substituted or polysubstituted, and whose substituents may be the same or different, and where the appropriate substituent of the above aryl or heteroaryl is In each case: halogen, cyano, nitro, alkyl having in each case 1 to 4 carbon atoms and in each case linear or branched;
alkoxy or alkylthio, in each case having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in each case linear or branched; Good halogenoalkyl, halogenoalkoxy or halogenoalkylthio, alkylenedioxy having 1 to 3 carbon atoms, phenyl, phenoxy, formyl, alkanoyl having 1 to 5 carbon atoms, having 1 to 5 carbon atoms or alkoximinoalkyl having 1 to 5 carbon atoms in each alkyl moiety, and R2 is cyano, a group -C-N H2 or a group -C-N R
2 and R3 and R4 independently of each other are in each case hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkyl having 1 to 5 carbon atoms or branched cyanoalkyl, 1
straight-chain or branched halogenoalkyl having from 1 to 5 carbon atoms and from 1 to 9 halogen atoms, in each case from 1 to 5 carbon atoms in each alkyl moiety; alkoxyalkyl or alkylthioalkyl, which may be straight-chain or branched, or in any case from 3 to 7;
represents an alkenyl or alkynyl having in each case straight or branched carbon atoms, or R3 and R4, together with the carbon atom to which they are bonded, are saturated It represents a 5- to 7-membered carbon ring.

Particularly preferred compounds of the general formula (I) are those in which R1 is straight-chain or branched alkyl having 1 to 5 carbon atoms, methoxymethyl, methylthiomethyl, allyl or butenyl; benzyl, phenylethyl, phenyl or naphthyl, which may be mono- or trisubstituted in the aryl moiety, and the substituents may be the same or different; or in any case hetero Represents a heteroarylmethyl or heteroaryl which may be mono- or tri-substituted in the aryl moiety, and the substituents may be the same or different, and a suitable heteroaromatic compound is , in each case: (wherein X in each case represents oxygen or sulfur) and the appropriate substituents of the aryl or heteroaryl are in each case: fluorine, chlorine, bromine, Iodine, cyano,
Nitro, methyl, ethyl, n- or i-propyl, n-1i-1S- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methylenedioxy, ethylenedioxy, phenyl, phenoxy, pormyl, acetyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, methoximinoethyl and ethoximinomethyl, R2 represents a cyano or thiocarbamoyl group, and R3 and R4 independently of each other, in each case Also hydrogen, methyl, ethyl, n- or i-propyl, n-
1i-5S- or t-butyl, allyl, propargyl, n- or i-butenyl or propargyl, or such that, together with the carbon atom to which it is attached, represents a cyclopentyl or cyclohexyl group.

Very particularly preferred compounds of formula (I) are phenyl, pyridyl, in which R1 is in each case optionally -substituted to trisubstituted in the aryl moiety;
benzoxacylyl, benzthiazolyl, furyl or chenyl, the substituents of which may be the same or different, in each case with suitable substituents: methyl, ethyl, methoxy, fluorine, chlorine, Bromine, methylenedioxy or ethylenedioxy, such that R2 represents cyano and R3 and R4, independently of one another, represent hydrogen, methyl or ethyl in each case.

In addition to the compounds mentioned in the production examples, the following general formula (
The alkoximinoalkylamides of I) may be mentioned individually.

=CH-CH3 CH3 =C CH.

=CH2 =CH' CH3 l CH3 CN =CCH3 CN =CH2CN
, =CH-CH3Ha CN =CCH3 CN 2CH2 ry =CI-
T-CT4. .

CH3CN=CCH3CN=CH2CN
=CH-CH.

CHl CN =CHs CN =CH2CN
=CH-CH.

CH3 CN = CHz =CH2 =CHCHs CH.

twenty CH.

=CH2 =CHCHHz CH.

CH3 =C CH.

=CH2 “CHCH3 CH3 =C CH.

=CH2 =CH-CH.

(CHshCHCH2- CH3 CN =CHs CNHa =CHCH*CNH2=C
HCH3CN=CH-CH3CN
=CH-CH.

CN = CH-CH.

CN=CH-CH3CN
=CN-CH.

If CN=CH-CH3, for example N-(bromocyanomethyl)-4-chlorobenzamide and acetaldehyde oxime are used as starting materials, the course of the reaction of process (a) according to the invention can be represented by the following equation.

For example, if the compound 2-(4-chlorobenzamide)-2-ethylideneiminooxyacetamide disclosed by the present invention is used as starting material and p-)luenesulponyl chloride is used as the dehydrating agent, the method according to the present invention b
) reaction process can be expressed by the following equation.

Tosyl chloride H20 For example, if the compound disclosed by the present invention 2-(4-chlorobenzamido)-2-ethylideneiminooxyacetonitrile and hydrogen sulfide are used as starting materials,
The reaction process of method (C) according to the present invention can be represented by the following formula.

=31- 〇+ H2S -〉 Formula (II) provides a general definition of the brominated amides required as starting materials in carrying out invention (a) as described herein. In this formula (II), RI is preferably
In the context of the description of the substances of formula (I) according to the invention, R2-1 represents groups such as those already mentioned for these substituents.
preferably represents a cyano or carbamoyl group.

Brominated amides of formula (II) are known substances (see European Patent Specification Box 59,538 and European Patent Specification Box 135,304).

Formula (III) also provides a general definition of the oximes required as starting materials when carrying out process (a) according to the invention. In this formula (III), R3 and R4
represents the groups already mentioned for these substituents in connection with the description of the substances of formula (I) according to the invention.

Oximes of formula (III) are well-known compounds in organic chemistry.

Formula (Ia) provides a general definition of the alkoximinoalkylamides required as starting materials when carrying out the process (b) according to the invention. In this formula (Ia), R1,
R3 and R4 represent groups as already mentioned for these substituents in connection with the description of the substances of formula (I) according to the invention.

Alkoximinoalkylamides of formula (Ia) are compounds disclosed by the present invention and are used in process (a) according to the present invention.
can be obtained using

Formula (Ib) provides a general definition of the alkoximinoalkylamides required as starting materials when carrying out process (c) according to the invention. In this formula (, L b ) R1, R3 and R4 represent groups such as those already mentioned for these substituents in connection with the description of the substances of formula (I) according to the invention.

Alkoximinoalkylamides of formula (Ib) are compounds disclosed by the present invention and can be used in process (a) according to the present invention.
Alternatively, it can be obtained using (b).

Suitable diluents when carrying out process (a) according to the invention are inert organic solvents.

This includes, in particular, aliphatic, cycloaliphatic or aromatic, sometimes halogen-substituted hydrocarbons, such as benzine, benzene, toluene, xylene, chlorobenzene, petroleum needles, hexane, cyclohexane, dichloromethane, chloroform, tetrachloride. carbon; ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; ketones, such as acetone or butanone;
Dimethylacetamide, N-methylborumanilide, N-
Included are methylpyrrolidone or hexamethylphosphoric triamide; esters such as ethyl acetate; or sulfoxides such as dimethylsulfoxide.

, process (a) according to the invention is preferably carried out in the presence of a suitable acid binder Q. Preference is given here to tertiary amines such as triethylamine, N,N-dimethylaniline, pyridine, N.

N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabidichrono, nene (DBN)
or diazabicycloundecene (DBU).

When carrying out process (a) according to the invention, the reaction temperatures can be varied within a relatively wide range. - Generally, the process is carried out at a temperature of -50°C to +100°C, preferably -30°C to +50°C. - To carry out the method (a>) according to the invention, generally the formula (
1.0 to 3 per mole of brominated amide of II)
．． 0 mol, in particular 1.0 to 1.2 mol of the formula (III
) and 1,0 to 3.0 mol, in particular 1.0 to 2.0 mol, of the acid binder.

In a preferred embodiment of carrying out this reaction, the bromine-substituted amide used as starting material is reacted with a suitable "cyanomethylamide" of the formula (Iv)', where R1 has the meaning given above, in a reaction flask. using a suitable brominating agent, such as elementary bromine, in a suitable diluent, such as acetic acid or ethyl acetate, optionally in the presence of a suitable acidic catalyst, such as hydrobromic acid, at a temperature of -20°C to +20°C. Produced directly in the first step reaction by bromination with
Immediately thereafter, this product is processed according to the method according to the invention (
I), the reaction is carried out in the "-tank method".

Depending on the choice of diluent and depending on the acid concentration, a corresponding amide of the formula (IIa) in which R1 has the abovementioned meaning or a corresponding amide of the formula (IIb) r 0 ON in which R+ has the meaning given above for amides in which the nitrile group is retained (see European Patent Specification Box 59,536, European Patent Specification Box 135.304 and Preparation Examples) )but,
It is obtained through this first stage bromination reaction.

Then, the method (a) according to the present invention is carried out to obtain the formula (■a)
or ('Ib>) is worked up and isolated analogously to known methods (see European Patent Specification Box 59,536).

Dehydrating agents suitable for carrying out process (b) according to the invention are all customary dehydrating agents. Particular preference is given to using acyl chlorides or acyl anhydrides, such as trifluoroacetic anhydride, p-)luenesulfonyl chloride, trichloroacetyl chloride, methanesulfonyl chloride, titanium tetrachloride or phosphorous acid chloride.

Solvents suitable for carrying out the method (b) according to the invention are likewise:
It is an inert organic solvent.

This includes, in particular, aliphatic or aromatic halogen-substituted hydrocarbons, such as benzine, benzene, toluene, xylene, chlorobenzene, pyridine,
petroleum ethers, hexane, cyclohexane, dichloromethane, chloroform and carbon tetrachloride; ethers such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; nitriles such as acetonitrile or propionitrile; or amides such as dimethyl Contains formamide.

Process (b) according to the invention is optionally carried out in the presence of a suitable acid binder. Suitable for this are in particular tertiary amines such as N-methylmorpholine, triethylamine,
N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, diazabicyclooctane (DABC
O), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When carrying out process (b) according to the invention, the reaction temperature can be varied within a relatively wide range. - Generally, the process is carried out at temperatures of -20°C to +80°C, preferably at temperatures of 0°C to +40°C.

To carry out the method (b) according to the invention, the formula (
1 per mole of alkoximinoalkylamide of Ia)
．． 0 to 5.0 moles, preferably 1.0 to 3.0 moles.
Use 0 moles of dehydrating agent. After carrying out the reaction, the formula (
The reaction product of Ib) is worked up and isolated analogously to known methods (see European Patent Specification Box 59,536).

-39-1 Suitable diluents when carrying out the method (C) according to the invention are likewise inert organic solvents. This includes in particular the organic solvents mentioned in the case of process (a). Particular preference is given to using toluene or pyridine as diluent.

Process (C) according to the invention is preferably carried out in the presence of a basic catalyst. Particularly suitable for this are method (a)
These are the tertiary amines listed in the case of Particular preference is given to using triethylamine.

When carrying out process (C) according to the invention, the reaction temperatures can be varied within a relatively wide range. - Generally, the process is carried out at a temperature of -20°C to +30°C, preferably at a temperature of 0°C to +20°C.

When carrying out process (C) according to the invention, - generally from 1.0 to 5.0 mol, preferably from 1.0 to 2.0 mol, per mole of alkoximinoalkylamide of formula Hb). A basic catalyst is used and gaseous hydrogen sulfide is passed through the reaction solution. separating the precipitated solid product or removing volatile substances from the reaction mixture by evaporation;
The reaction product of formula (I) is worked up and isolated (see also European Patent Specification Box 59,536).

The active compounds according to the invention have a strong microbicidal action;
It can be put to practical use for controlling undesirable microorganisms. The active compounds are suitable, for example, for use as plant protection agents.

In the field of plant protection, fungicides and fungicides are commonly used in the field of plant protection.
, Oomycetes , chytrid fungi (
ChitridiomyceteS), Zygomycetes (Zy
gomyetes), Ascomyc
etes), Basidiomycetes
s ) and Deuteromycete
It is used for the control of s).

Examples include some fungal and fungal disease-causing microorganisms belonging to the above classification names, but this is by no means intended to be limiting.

Pythium species, such as 1'ythium ultimum
; Phytophthora species,
For example, Phytophthora infestans (Phytophthora infestans)
phthora 1nfestans); Pseudoperonospora
species, such as the shoot Veronosvora humuli (1'5e
ud.

peronospora humuli) or Pseudoperomesbora 0 cubensis
ospora cubensis); Plasmopara species, e.g.
Viticola (Plasmopara viticola)
; Peronospora species, such as Peronospora pis;
'+ ) or Veronosvora brassicani (P, br
assicae) ; powdery mildew (Erysiphe
) species, such as Erysiphue graminis (Erysip
he graminis) ; Sphaerotheca (5pha
erotheca ) species, such as Sphaerotheca fuliginea
a); Podosphaera species, such as Podosphaera leucotricha;
phaera 1eucotrict+a); Venturia species, such as Venturia 1naequali
s); Pyrenophora species, for example and Pyrenophora teres;
ra teres ) or Pyrenophora graminea (P, graminea) (conidial type: Drechslera, synonym: Ilelminthosporium)
; Cochliobolus species, such as Cochliobolus
lus sat, 1vus) (conidial type: Dreehslera, synonym: Helmintbosporium; Uromyces species, such as Uromyces ape
ndiculatus); sabikin (Puccinia
) species, such as Brassinia recondita (Pucein
ia recondita); Namagusakuropokin (
Tilletia species, such as Tilletia caries;
Ustilago) species, such as Ustilago knoop (
Ustilago nuda or Ustilago avenae; Pellicularia species, such as Pellieularia 5
asakii); Pyrieular
ia) species, such as Pyri
eula=43- ria oryzae; Fusarium
un) species, such as Fusarium curmorum (Fusa
Botrytis species, such as Botrytis einerea; Septoria species, such as Septoria nodorum; Leptosphaeria; haeria) species, such as Leptosphaeria nodorum (Leptosphae
ria nodorum) ; Cercospora (Cerc
ospora ) species, such as Cereospora canescens
;Alternaria species, such as Alternaria brassicas;
brassicae); and Pseulocercosporel
a) Species, such as Pseulocereosporel
1aherpotrichoides).

The good tolerance of plants to the concentrations of active compounds required for controlling plant diseases makes it possible to treat the above-ground parts of the plants, the asexually propagated rootstocks and seeds, and the soil.

The active compounds according to the invention can be used in particular for the control of vegetable diseases.
For example, the pathogen of tomato brown rot (Phytophthora 1nfestan)
For example, rice disease pathogens (Pyrieularia oriza) can be used to control cereal diseases.
e) or against Pythium spp., especially seed dressing.
g) can be used successfully during

The active compounds according to the invention are microbicidal, acalizide (
It is also useful as acaricide.

Depending on their individual physical and/or chemical properties, the active compounds can be prepared in customary formulations, e.g. solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active compounds. natural and synthetic materials impregnated with microcapsules in polymeric substances and in seed coating compositions, as well as combustion devices such as fumigation cartridges,
It can be converted into formulations for use with fumigation cans, fumigation coils, etc., as well as ULV cold mist and warm mist formulations.

These formulations are prepared in a known manner, for example by combining the active compounds with fillers, liquid solvents, pressurized liquefied gases and/or solid carriers and, optionally, surfactants, ie emulsifiers and/or dispersants and/or additives. is prepared by combining with a foaming agent.

If water is used as extender, organic solvents can also be used as auxiliary solvents, for example. Principal suitable liquid solvents include: aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes; chlorine-substituted aromatic hydrocarbons or chlorine-substituted aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride; cyclohexane. or paraffins, such as aliphatic hydrocarbons such as mineral oil fractions; alcohols, such as butanol or glycols and their ethers and esters; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; highly polar solvents, Examples include dimethylpolamide and dimethylsulfoxide and water. By liquefied gas bulking agent or carrier is meant a liquid that is a gas at normal temperature and pressure, such as aerosol propellants such as halogen-substituted hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers include: milled natural minerals such as kaolin, clay, talc, chalk, quartz, atabalujite, montmorillonite or diatomaceous earth, as well as synthetic materials such as highly dispersed silicic acid, alumina and silicates. There are crushed minerals. Suitable solid carriers for the granules include: crushed and fractionated natural rocks such as calcite, marble, pumice, seviolite and dolomite; and synthetic granules of inorganic and organic coarse powders; organic H materials such as sawdust. , coconut shell, I. Umo □
There are granules of cobs and tobacco stalks. Suitable emulsifiers and/or foaming agents include, for example, polyoxyethylene-fatty acid nysdels, polyoxyethylene-fatty alcohol ethers, such as alkylaryl polyglycol ethers, alkyl sulfonates,
There are nonionic and anionic emulsifiers such as alkyl sulfates, arylsulfonates, and albumin hydrolysis products. Suitable dispersants include:
Examples include lithium sulfite effluent and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate in the form of powders, granules or latexes, as well as natural phospholipids such as cephalin and thiophyltin, and synthetic phospholipids are also included. Can be used in drugs.

Other possible additives are mineral and vegetable oils.

Inorganic pigments such as iron oxide, titanium oxide and Prussian blue, and organic dyes such as alizarin dyes, azo dyes and metal cyclocyanine dyes, also contain trace amounts of nutrients. budea and zinc. It is also possible to use salt.

The formulations generally contain from 0.1 to 95% by weight of active compound=48-, preferably from 0.5 to 90% by weight.

The active compounds according to the invention may be used in combination with other known active compounds, such as fungicides, insecticides ('1
nsecticide), acaricide (acariai)
de ) and herbicides, and also in combination with fertilizers and growth regulators. 'The active compounds can be used alone or in the form of their combinations or in the form of use forms prepared from them, for example in the form of prepared solutions, suspensions, pastes, soluble powders, dusts and granules.

These are conventional techniques, such as liquid wipes, sprays,
Use by spraying, spreading granules, spreading powder, foaming, brushing, etc. Furthermore, it is possible to apply the active compounds by ultra-low volume methods and also to inject the active compound formulation or the active compound itself into the soil. Plant seeds can also be "treated".

The concentration of chemical compounds can be varied over a considerable range.

Generally it is 1 to O', O'OO' 1% by weight, preferably 0.5 to O, oot% by weight.

In seed treatment, generally 1 kg of seeds or
, oot to 508, preferably 0.01 to 1
0 g of active compound violet is required.

For the treatment of soil, 0.00001 to 0.1% by weight, preferably 0.0001 to 0.00% by weight at the site of application.
An active compound concentration of 0.02% by weight is required.

Maru 1 Katsu-Y: (Method a) 4-chlorobenzoylaminoacetonitrile 5.07
g (0,0261 mol) in 250 ml of absolute ethyl acetate, to which a few drops of bromine are added at 0 °C and the reaction is started by adding a few drops of a 33% strength glacial acetic acid solution of hydrogen bromide. . The reaction mixture is decolorized. Subsequently, the remaining bromine [total amount 4.2 g (0,0262 mol)] was gradually added at 0°C, and when the addition was completed, the combination was cooled to -25°C and 1 ml of acetaldehyde oxime was added. .55
g (0,0262 mol) and triethylamine 5.3
g (0.0523 mol) in 50 ml of absolute ethyl acetate are added in total at -. The reaction mixture is heated to -10°C and triethylamine hydrochloride precipitates. The combination is stirred for 15 minutes at 0° C., filtered, the lachrymal fluid concentrated and the oily residue purified by chromatography on silica gel (eluent dichloromethane).

1.3 g of 2-(4-chlorobenzoylamino)-2-ethylideneiminooxyacetonitrile (20% of the theoretical amount)
) is obtained as a F,/Z combination with a melting point of 100°C.

The following alkoximinoalkylamides of general formula (I) are obtained in a corresponding manner according to the general instructions for their preparation.

=CH2127 =CH-CH31H-NMR book): 1,95CN
=CH2'H-NNR*):6.7=C)l-C
H=CH21H-N88):6.7=C)l-CH=
CH2106 =C=CH-C2H51H-N*):6.7=CH-C
H368 = CH-C2H5-82 = CH-CH, IH-NMR vehicle): 1.95 = C to CH
=CH21H-NMR*):2.45=CH-C2H5
'H-NNR*): 6.7=CI-C11,134 =CH-C)13141-143 =CH-C)13155 (decomposition) =CH-CH,106-108 =CHC2H5'H-NMR*): 6.65"Cl-C
2H5'H-NMR): 6.65 CI.

= C200 CH.

CH.

=C144-146 CH.

=CH-CI (, IH-NMR book): 1.9L: 2H.

=CH-C(CH3), 'H-NMR*):
1.12-64-=CH-C(CH3)3'H-NMR book): 1.12"
CH2Fp, 142°-144°C = CH-C (CH, ), 'H-NMR book): 8.711888 book): 6,75 = CI-CH, IH-NMR*): 1,9 envoy 1J mouth number The compounds shown below were used as comparative substances in the following usage examples.

2-(4-chlorobenzoylamino)-2-ethoxyacetoniFlyl (known from European Patent Specification No. 59,536).

Fruit mA Yukine B Ukin test (tomato) / Protective active solvent: 4.7
Parts by weight of a7tone emulsifier = 0.3 parts by weight of alkylaryl polyglycol ether To make a suitable formulation of the active compound, 1 part by weight of the active compound is combined with the above amounts of solvent and emulsifier, and this concentrated Dilute the solution with water to the desired concentration.

To test the protective activity, young seedlings are sprayed with the active compound formulation until dripping wet. After the spray coating has dried, the seedlings are treated with Phytophthora.
inoculate with an aqueous suspension of spores of Infestans.

The seedlings are placed in an incubator at approximately 20° C. and 100% relative humidity.

Evaluation is performed 3 days after inoculation.

In this test, a clearly superior activity compared to the prior art is shown by the compounds described in the Preparation Examples below.

Production examples: 1.2.4.5.6 and 22° batter-9 (Ekibyokin test (tomato)/protective activity (known) (^
) Hu11L-W Pyricularia test (rice)/protective active solvent: 12.5 parts by weight of A7Tone emulsifier 20.3
To make a suitable formulation of parts by weight of alkyl aglycol ether active compound, one part by weight of active compound is combined with the above amount of solvent and this concentrate is diluted with water and the above amount of emulsifier to the desired concentration. do.

To test the protective activity, young rice seedlings are sprayed with the active compound formulation until dripping wet. After the spray coating has dried, the seedlings are inoculated with an aqueous suspension of Pyricularia oryzae spores. The seedlings are then placed in a greenhouse at 25° C. and 100% relative humidity.

Evaluation of disease infection is performed 4 days after inoculation.

In this test, a clearly superior activity compared to the prior art is shown, for example, by the compounds described in the Preparation Examples below.

Examples: 4, 5, 6, 7, 10, 40 and 47.

Ju-J- Pyricularia test (rice)/Protective activity (known) Pyricularia test (rice)/Rhizome self-storing solvent: 1
To make a suitable formulation of 2.5 parts by weight of a7tone emulsifier: 0.3 parts by weight of furkylaryl polyglycol ether active compound, 1 part by weight of active compound is combined with the above amount of solvent; This concentrate is diluted to the desired concentration with water and the above amount of emulsifier.

□ To test intrarhizoactivity, 40 xl of the active compound formulation is sprayed onto a standard soil in which young rice seedlings have been grown. Seven days after this treatment, the above-mentioned plants are inoculated with an aqueous suspension of Pyricularia oryzae spores. The seedlings are then kept in a greenhouse at a temperature of 25° C. and a relative humidity of 100% until evaluation.

Evaluation of disease infection is performed 4 days after inoculation.

In this test, a clearly superior activity compared to the prior art is shown by the compounds described in the Preparation Examples below.

Examples: 4.5.6.7.8.22.40 and 54゜u Pyricularia test (rice)/Rhizome autoactivity (known) Tetranychus test (resistance) Solvent: 3 parts by weight dimethyl Formamide emulsifier:
To make a suitable formulation of 1 part by weight of furkylaryl polyglycol ether active compound, 1 part by weight of the active compound is combined with the solvents and emulsifiers described above and this concentrate is diluted with water to the desired concentration. .

common spidermite or two-spotted spidermite) (T etranychus) in various stages of growth
urticae) with many standing plants (P hase
olusvulBaris) were treated by immersing them in the active compound formulation at a predetermined concentration.

Mortality rate % was measured after a predetermined period of time. 100% means all spidermites are dead; 0% means no spidermites are dead.

Chang H2 I H2 H2 Cl-C11゜ Cl-Cl+, H2 Patent applicant: Bayer Akchendeselschat

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I) In the formula, R^1 is alkyl, alkenyl, aralkyl, which may be substituted in any case. , represents heteroarylalkyl, aryl or heteroaryl, R^2 is cyano, group ▲ Numerical formula, chemical formula, table, etc. ▼
or the group ▲ has a mathematical formula, chemical formula, table, etc. ▼, and R^3 and R^4 each independently represent hydrogen or an optionally substituted alkyl, alkenyl, or alkynyl. or an alkoximinoalkylamide which represents a saturated carbocyclic ring together with the carbon atom to which it is attached. 2. In the general formula (I), R^1 is a straight chain or branched alkyl having 1 to 8 carbon atoms, a straight chain or branched alkyl having 1 to 5 carbon atoms in the alkyl moiety; cyanoalkyl, straight-chain or branched halogenoalkyl having 1 to 5 carbon atoms and 1 to 9 halogen atoms, in each case 1 to 5 carbon atoms in each alkyl moiety; and in each case straight-chain or branched alkoxyalkyl or alkylthioalkyl, straight-chain or branched alkenyl having 3 to 8 carbon atoms, or 3 to 8 carbon atoms; carbon atoms and 1 to 5
represents a straight-chain or branched halogenoalkyl having halogen atoms and, in addition, 1 to 4 carbon atoms in the alkyl part and 6 to 10 carbon atoms in the aryl part; Aralkyl, which may be mono- or polysubstituted in moieties, the substituents may be the same or different; aralkyl having 1 to 4 carbon atoms in the alkyl moiety; Heteroarylalkyl having 2 to 9 carbon atoms and 1 to 3 heteroatoms (in particular nitrogen, oxygen and sulfur), which may be mono- or polysubstituted in the heteroaryl moiety; Aryl having 6 to 10 carbon atoms, which may be mono- or polysubstituted, even if the substituents are the same or different; heteroaryl having 2 to 9 carbon atoms and 1 to 3 heteroatoms, which may be mono- or polysubstituted, which substituents may be the same or different, and the appropriate substituent of the above aryl or heteroaryl is in each case: halogen, cyano, nitro, in each case 1 to 4
alkyl, alkoxy or alkylthio, in each case straight-chain or branched, having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, halogenoalkyl, halogenoalkoxy or halogenoalkylthio, in each case linear or branched, alkylenedioxy having 1 to 3 carbon atoms, phenyl, phenoxy, formyl, alkanoyl having 1 to 5 carbon atoms, alkoxycarbonyl having 1 to 5 carbon atoms, or alkoximinoalkyl having 1 to 5 carbon atoms in each alkyl moiety; ^2 is cyano, group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
or represents a group ▲a mathematical formula, a chemical formula, a table, etc.▼, in which R^3 and R^4 are, independently of each other, in each case hydrogen, a linear or branched chain having 1 to 8 carbon atoms; alkyl, straight-chain or branched cyanoalkyl having 1 to 5 carbon atoms, straight-chain or branched cyanoalkyl having 1 to 5 carbon atoms and 1 to 9 carbon atoms; halogenoalkyl, alkoxyalkyl or alkylthioalkyl, in each case having 1 to 5 carbon atoms in each alkyl moiety, which may be straight-chain or branched, or in any case Also 3 to 7
represents an alkenyl or alkynyl having, in each case, a straight-chain or branched carbon atom, or together with the carbon atom to which it is attached, a saturated 5- to 7-membered The alkoximinoalkylamide according to claim 1, characterized in that it represents a carbocyclic ring. 3. In the general formula (I), R^1 is a straight-chain or branched alkyl having 1 to 5 carbon atoms, methoxymethyl, methylthiomethyl, allyl or butenyl; in each case in the aryl moiety benzyl, phenylethyl, phenyl or naphthyl, which may be mono- or pentasubstituted, and the substituents may be the same or different; or in each case in the heteroaryl moiety; Heteroarylmethyl or heteroaryl, which may be mono- or trisubstituted, and whose substituents may be the same or different; Also in the case of: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲Mathematical formulas, chemical formulas,
There are tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼
▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. But in each case: fluorine, chlorine, bromine, iodine, cyano,
nitro, methyl, ethyl, n- or i-propyl,
n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methylenedioxy, ethylenedioxy, phenyl, phenoxy, formyl, acetyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, methoximinoethyl and ethoximinomethyl, R^2 represents a cyano or thiocarbamoyl group, and R^3 and R^4 each independently represent hydrogen, methyl; , ethyl, n- or i-propyl, n
-, i-, s- or t-butyl, allyl, propenyl, n- or i-butenyl, or propargyl, or together with the carbon atom to which it is attached, represents a cyclopentyl or cyclohexyl group The alkoximinoalkylamide according to claim 1. 4. In the general formula (I), R^1 is phenyl, pyridyl, benzoxazolyl, benzthiazolyl, furyl or chenyl, which may be mono- or tri-substituted in each case,
the substituents may be the same or different and the appropriate substituents are in each case: methyl, ethyl, fluorine, chlorine, bromine, methylenedioxy or ethylenedioxy; Alkoximinoalkyl according to claim 1, characterized in that R^2 represents cyano, and R^3 and R^4 each independently represent hydrogen, methyl or ethyl. Amide. 5. (a) General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) In the formula, R^1 is alkyl, alkenyl, aralkyl, heteroaryl, which may be substituted in any case. A bromine-substituted amide that represents alkyl, aryl or heteroaryl and R^2^-^1 represents cyano or carbamoyl is represented by the general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) In the formula, R^ 3 and R^4 independently of each other represent hydrogen or optionally substituted alkyl, alkenyl or alkynyl, or together with the carbon atom to which they are attached represent a saturated carbocyclic ring; (b) followed by the reaction with an oxime of the general formula ( I
a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I a) In the formula, R^1, R^3 and R^4 have the above meanings. , and optionally dehydrated using a dehydrating agent in the presence of an acid binder, and further, optionally, (c) Subsequently, general formula (I b) obtained by method (a) or (b) ▲ Formula , chemical formulas, tables, etc. ▼ (I b) In the formula, R^1, R^3 and R^4 have the above meanings. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In the formula, R^1, R^3 and R^ 4 has the above meaning, R^2 is cyano, group ▲ includes mathematical formula, chemical formula, table, etc. ▼
Or a method for producing alkoximinoalkylamides representing the group ▲ has a mathematical formula, chemical formula, table, etc. ▼. 6. Pest control agent characterized by containing at least one compound of general formula (I) as set forth in claim 1; 7. At least one compound of formula (I) as set forth in claim 1 A method for controlling harmful bacteria and molds, which comprises causing one type of compound to act on harmful bacteria and molds and/or their habitat. 8. Use of the compound of general formula (I) according to claim 1 for controlling harmful bacteria and molds. 9. A method for producing a pest control agent, which comprises combining the compound of general formula (I) according to claim 1 with a filler and/or a surfactant.