CS227026B2 - Insecticide,acaricide and nematocide compositions and method of preparing active components thereof - Google Patents

Abstract

NEW MATERIAL:A 2, 3-dihydro-2, 2-dimethylbenzofuran-7-yl N-( N, N-disubstituted aminosulfenyl) N-methylcarbamate derivative expressed by formulaI[R<1> is -X-COOR<3> or -X-CN; R<2> is -Y-COOR<3> or -Y-CN (R<3> is 1-6C alkyl or 3-6C cycloalkyl; X and Y are 1-6C alkylene, except when X and Y are methylene groups)]. EXAMPLE:2,3- Dihydro 2,3-dimethylbenzofuran-7-yl N-[N,N-bis( methoxycarbonylethyl)aminosulfenyl]N-methylcarbamate. USE:An insecticide having very low toxicity to warm-blooded animals. PROCESS:A compound expressed by formula II is reacted with sulfur dichloride to give a compound expressed by formula III, which is then reacted with a compound expressed by formula IV to afford the compound expressed by formula I.

Description

(54) An insecticidal, acaricidal and nematicidal composition and a process for the manufacture of an active ingredient

The present invention relates to an insecticidal, acaricidal or non-natococidal composition comprising the novel carbamates as an active ingredient. The invention further relates to a process for the preparation of these novel insecticidally, acaricidally and nematocidally active novel carbamates. In this specification, the term "insecticidal" also includes the term nematocidal and acaricidal as well as the term "insect" includes mites and nematodes unless otherwise indicated.

It is known that some carbamates have high insecticidal activity and are actually used. However, many of these carbamates have the disadvantage of being toxic to warm-blooded animals. In particular, 2,3-dihydro-2,2-dimethylbenzofuran-7H-yl-N-methylcarbamate (hereinafter referred to as "carbofuran", as it is commonly called) is known to have a high insecticidal activity, but in practice it causes a high insecticidal activity. toxicity to warm-blooded problems. Therefore, it would be highly desirable to provide carbamates that are comparable in insecticidal effect to &quot; carbofuran &quot; and have reduced toxicity to warm-blooded animals. Such compounds would be highly useful in practice. In view of this, various carbofuran sulphenyl derivatives have already been synthesized and the relationship between their insecticidal activity and toxicity to warm-blooded animals has been investigated and the results of this study have been published. Thus, for example, Belgian Patent Specification No. 817,517 describes 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N, N-dibutylaminosulfenyl) -N-methylcarbamate and U.S. Pat. discloses 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-methyl-N-benzenesulfonylaminosulfenyl) -N-methylcarbamate.

However, these compounds do not fully meet the requirements with respect to insecticidal activity, toxicity to warm-blooded animals and fish, and to the complicated process for their preparation.

After intensive efforts to prepare carbamates that meet all of these requirements, compounds of Formula I have now been found

(I) in which:

R ¹ and R ² , which may be the same or different from each other, represent

1) a group -X-COOR 3 wherein X represents an alkylene group having 1 to 6 carbon atoms and R ³ represents an alkyl group having 1-8 carbon atoms or cycloalkyl having 3 to 6 carbon atoms, or

2] a -Y-CN group wherein Y is a C 1 -C 6 alkylene group, and a

R2 is furthermore an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a benzyl group optionally substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; phenyl optionally substituted by halogen, C1-C3 alkyl or C1-C3 alkoxy; or is -Z-R 4 in which Z is carbonyl or sulfonyl and R ⁴ is C 1 -C 6 alkyl, phenyl, benzyl, C 1 -C 6 alkoxy or phenoxy.

In the above definition of the meanings of the formulas I, the alkyl moiety in the alkyl group, the alkylene group and the alkoxy group is an alkyl moiety which may be straight or branched.

Preferred compounds of the present invention are those of the formula ΓΓCHa, у.

S-N.

in which

R4 ‘and R2‘, which may be the same or different from each other, mean

1] a group - X'-COOR ³ in which X represents an alkylene group having 1 to 2 carbon atoms and R 3 represents an alkyl group having 1 to 4 carbon atoms which may have a straight or branched chain, or

2] a group —Y‘ — CN wherein Y ‘represents an alkylene group having 1 to 2 carbon atoms; and

R 2 dále is furthermore an alkyl group having 1 to 6 carbon atoms which may have a straight or branched chain, or a cycloalkyl group having 3 to 6 carbon atoms.

The compounds of formula (I) are novel compounds which have not been previously described in any literature and have been discovered for the first time by us. These novel compounds have been found to have excellent insecticidal activity or the ability to maintain pests and household insects at an acceptable level in agriculture and forestry and are comparable to carbofuran, which has been known to date as the highest insecticidal activity. These compounds are active against. many insects, mites and nematodes harmful to vegetables, trees, other plants and humans, such as Hemiptera, butterflies (Lepidoptera), beetles (Coleoptera), diptera, Thysanoptera, Orthopter, Isopoda, Acarina, Tylenchida, etc.

Examples of these insects, mites and nematodes include:

Hymenoptera [Hemiptera]

1] Beetles (Deltocephalidae):

Nephotettix cincticeps

2] Delphacidae:

Laodelphax striatellus Nilaparvata lugens

3] Aphids. (Aphididae):

Peach Aphid (Myzus persicae) Aphis gossypii]

4] Shield bugs (Pentatomidae):

Nezara antennata

Nezara viridula butterflies (Lepidoptera)

1] Noctuidae:

Spodoptera Litura Agrotis fucosa Laphygma exigua

2] Tortricidae:

Adoxophyes orana

(3) Pyralidae:

Chilo suppressalis - Ostrinia furnacalis Cnaphalocrocis medinalis

4] Babies (Pluttellidae):

lizard (Plutela xylostella] beetles (C <^] ^ i ^ (^] ^ te: ra)

1] weevils (Curculionidae):

Echinocnemus squameus Lissorhoptrus oryzophhus

(2) Scarabaeidae:

Popilia japonica

(3) ladybugs (Coccinellidae):

Henosepilachna vigintioctopunctata Diptera

(1) flies (Muscidae):

house fly [Musea domestica)

2) Cecldomyiidae: fruitfly (Aspondylia sp.)

(3) fruit flies (Agromyzidae):

Phytobia cepae thrips (Thysanoptera) thrips [Thripidae]: thrips [Thrips tabaci] Scirtothrips dorsalis grasshoppers (Orthoptera) mole crickets (Gryllotalpidae):

Mole Cricket (Gryllotalpa africana) Pillbugs (Isopoda) Pigs (Armadlllidae):

Common Muck (Armadillidium vulgare) Mites (Acarina) Spiders (Tetranychidae):

Weaving Spider (Tetranychus telarius) Weaving Spider [Tetranychus urticae]

Panonychus citri Tylenchidae (Heteroderieae):

nematode (Meloidogyne ineognita).

The toxicity of the carbamates of the formula I according to the invention to warm-blooded animals is about 1/5 to about 1/100 of the toxicity of carbofuran. The compounds according to the invention have excellent insecticidal activity or the ability to control insects mentioned above, at any stage or at a specific stage of their life, and can therefore be effectively used for controlling insects in agriculture, forestry and hygiene.

The compounds of the formula I according to the invention can be prepared in a very simple manner. of high purity and high yield, and have considerable commercial use as will be described hereinafter.

Typical compounds of Formula I are those described in Examples 1 through 56 below. Of these, the following are particularly preferred:

2,3-dihydro-2,2-dimethylbenzofuran, n-7-yl-N- [Ν, Ν-bis [ethoxycarbonylmethyl) aminosulfenyl] -N-methylcarbamate

2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-methyl-N-ethoxycarbonylmethylaminosulfenyl) -Nmethylcarbamate

2,3-dib.ydro-2,2-dimethylbenzofuran-7-yl-N- [N-isopropyl-N-ethoxycarbonylethylaminosulfenyl] -N-methylcarbamate

2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-n-butyl-N-ethoxycarbonylethylaminosulphenyl) -N-methylcarbamate

2,3-d ⁵ Hydro-2,2-dimethylbenzofuran-7-yl-N- (N-cyclohexyl-N-ethoxycarbonylethylaminosulfenyl) -N-methylcarbamate

2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- [N-n-butyl-N-cyanethylaminosulfenyl) -N-methylcarbamate.

According to the invention, the compounds of formula (I) are prepared by treating the compound of formula (II)

(II) is treated with 1 to 2 moles of sulfur trichloride per mole of a compound of formula II in the presence of a solvent selected from methylene chloride, chloroform, carbon tetrachloride, diethyl ether, dibutyl ether, tetrahydrofuran and dioxane and optionally a basic compound selected from the group; which consists of triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine, pyridine, ζζ, β, χ-picoline and lutidine, to give 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (chlorosulfenyl) - N-methylcarbamate of formula III

(III)

-Г г _С ^ г _Х т-, - -Τ '..........-....... ..........;

which is then reacted with a compound of formula IV

R ¹

OF

HN (IV), \

R ² in which

R ¹ and R 2 are as defined above, in an amount of 1 to 2 moles per mole of the compound of formula III, optionally in the presence of a solvent selected from the group consisting of methylene chloride, chloroform, carbon tetrachloride, diethyl ether, dibutyl ether, tetrahydrofuran and dioxane; the presence of a basic compound selected from the group consisting of triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine, pyridine, and β-picolm and lutidine.

The reaction of the compound of formula II with sulfur trichloride can be carried out in the presence or absence of solvents. Examples of useful solvents include methylene chloride, chloroform, carbon tetrachloride and the like halogenated hydrocarbons, diethyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like ethers. The ratio of the compound of formula (II) to sulfur trichloride is not particularly limited, and a wide range of both are suitable. Generally, 1 to 2 moles, preferably about 1 to about 1.2 moles of sulfur trichloride per mole of the compound of formula II is used. Preferably, the reaction is carried out in the presence of a basic compound. Examples of useful basic compounds include triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine and the like tertiary amines, pyridine, N, N-picoline, lutidine, arth. The basic compound is used in an amount sufficient to bind the hydrogen chloride formed as a side reaction in the reaction. product. Typically, 1 to 2 moles of the basic compound is used per mole of the compound of formula (II). The reaction, which takes place with cooling, at room temperature or with heating, is carried out usually at temperatures from -70 to 50 ° C, preferably at temperatures from about -10 to about 30 ° C. The reaction time is about 2 (V) (VI) (VII) (VIII) (IX) hours to about 7 hours, preferably about 3 to 5 hours. The compound of formula III is then reacted with an amine of formula IV.

Examples of useful amines of formula IV include secondary amines of formulas V to IV

X — COOR ³

OF

HN \

R

Y — CN

OF

HN \

R

X — COOR ³

OF

HN \

X “—COOR ³ “

X — COOR3

OF

HN \

Y — CN

Y — CN

OF

HN \

Y “—CN

In formulas V to IX, X, Y and R 3 are as defined above;

R is C 1 -C 8 alkyl, C 3 -C 6 cycloalkyl, benzyl optionally substituted by halogen, C 1 -C 3 alkyl or C 1 -C 3 alkoxy, furthermore phenyl optionally substituted by halogen, C 1 -C 3 alkyl or C 1 -C 3 alkoxy, Z'-R ⁴ 'further wherein Z' is carbonyl or sulfonyl and R ⁴ ' is C1-C6alkyl, phenyl, benzyl, C1-C6alkoxy or phenoxy (in which the alkyl and alkoxy groups may be straight or branched);

R ³ 'has the same meaning as R ^3;

X "has the same meaning as X and Y" has the same meaning as Y.

Examples of amines of formula V include:

N-methylglycine methyl ester, N-methylglycine ethyl ester, N-methylglycine butyl ester, N-ethylglycine ethyl ester, Nn-propylglycine ethyl ester, N-isopropylglycine ethyl ester, N-butylglycine ethyl ester, N-isobutylglycine ethyl ester, N-sec.butyl ester N-octylglycine, ethyl ester of N-cyclohexylglycine, ethyl ester of N-benzylglycine, ethyl ester of N- (4-methylbenzyl) glycine, ethyl ester of N- (4-chlorobenzyl) glycine, ethyl ester of N-phenylglycine, ethyl ester of N- (3-methylphenyl) glycine, N- (4-methoxyphenyl) glycine ethyl ester, ethyl-N-methylaminopropionate, ethyl-N-propylaminopropionate, methyl-N-isopropylaminopropionate, ethyl-N-isopropylaminopropionate, butyl-N-isopropylanilopropionate, methyl-n-isopropylhexyl, N, N-butylaminopropionate, ethyl-N-butylaminopropionate, ethyl-N-isobutylaminopropionate, ethyl-n-sec-butylaminopropionate, ethyl-N-tert-butylaminopropionate, ethyl-N-niamylaminopropionate, ethyl-N-isoamylaminopropionate, hexy laminopropionate, ethyl N-cyclohexylaminopropionate, N-acetylglycine ethyl ester, N-chloroacetylanoglycyl ethyl ester, N-propionylglycine ethyl ester, N-benzoylglycine ethyl ester, N- (4- (4-chloro-benzo-4)) glycine ethyl ester, etc. N-ethyl ester.

Examples of amines of formula VI include:

^N4m: e ^ ^ ic ^ Ihy'b3mii acetonitrile, N-ethyl amino acetonitrile, N, N-propylammoacetomtril, N'iscpropylammoacetonitrИ ₅ Nn-butylammoacetonitril, Nnsobutylammoacetonitril, N-benzyl amino, Nf enylaminoacetonitri l

N- [4-methylphenyl] aminoacetonitrile, N-methylaminopropyl piperidine, N, n-propylaminopropyl nitrile. N-isopropylaminopropionitrile, N-n-butylaminopropionitrile, N-isobutylaminopropionitrile, N-sec-butylaminopropionitrile, N-octylaminepropionitrile, N-cyclohexylaminopropionitrile, etc.

Typical examples of amines of formula VII include:

methyl iminiacetate, ethylminodiacetate, isopropylpropyliminodiacetate, cyclohexyliminodiacetate, methyliminodipropionate, ethyliminodipropionate, N-methoxycarbonylglycine ethyl ester, N-ethoxycarbonylglycine ethyl ester, N-phenoxycarbonylmethoxymethyl ester, ethyl ester, N-phenoxycarbonylmethoxymethyl ester ) butyrate, N-ethoxycarbonylaminopropionate, etc.

Typical examples of amines of formula VIII include:

methyl N-cyanomethylcarbamate, ethyl N-cyanomethylcarbamate, ethyl N-cyanethylcarbamate, N-cyanomethylglycine ethyl ester, N-cyanomethylglycine ethyl ester, ethyl N-cyanomethylaminopropionate, ethyl N-cyanomethyl-aminopropionate and the like.

Typical examples of amines of formula IX include:

immcdmcttomt.ril, im ^, incdipropionitrile, immcdlbutyromtril etc.

The reaction of the compound of formula (III) with an amine of formula (II) may be carried out in the presence or absence of a solvent. Some of the solvents that are useful for the reaction of the compound of Formula II with sulfur dichloride are useful for this reaction. The ratio of the compound of formula (III) to the amines is not particularly limited, and a wide range of ratios are appropriate. In general, about 1 to about 2 moles of preferably about 1 to about 1.2 moles of amine per 1 mol of compound of formula III are used. It is preferred to carry out this reaction also in the presence of a basic compound, which may be any of the aforementioned basic compounds. The basic compound can be used in such an amount as is necessary to bind the hydrogen chloride formed in the reaction as a by-product. Usually 1 to 2 mol, preferably 1 to 1.5 mol, of the basic compound per 1 mol of the compound of formula III is used. The reaction, which takes place with cooling, at room temperature or with heating, is carried out usually at temperatures from -20 to 50 ° C, preferably from 0 to 30 ° C. The reaction time is usually about 10 to about 15 hours.

The compounds of formula (I) produced by the process of the present invention can be isolated and purified by conventional methods of separation, such as solvent extraction, recrystallization, or chromatography.

The compounds of the formula I according to the invention can be formulated as emulsions, wettable powders, suspensions, suspension concentrates, granulates, fine particles, spheres, dusts, powder trays, foam sprays, aerosols, encapsulated formulations, impregnated formulations containing as carrier of natural or synthetic substances, fumigants and concentrates to be applied in small quantities, etc.

Various surfactants are useful for preparing such emulsions, dispersions, suspensions, and foams. Examples of useful nonionic surfactants include polyoxyethylene-alkyl ethers, polyoxyethylene-alkyl esters, polyoxyethylene sorbitan alkyl esters, sorbitan alkyl esters, etc. Examples of useful anionic surfactants include alkylbenzene sulfonates, alkylsulfosuccinates, alkylsulfates, alkylsulfonyl-alkyl ether ethers, ligninsulfonates etc.

Suitable solvents, diluents and carriers for the compounds of the invention are various organic solvents, aerosol propellants, natural minerals, plant materials, synthetic materials, etc. Examples of preferred organic solvents include benzene, toluene, xylene, ethylbenzene, chlorobenzene, alkylnaphthalene , dichloromethane, chlorethylene, cyclohexane, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohols, dimethylformamide, dimethylsulfoxide, acetonitrile, mineral oil fractions, etc. Examples of useful aerosol propellants include propane, butane, halogenated hydrocarbons, nitrogen, carbon dioxide, etc. Examples of usable natural minerals include kaolin, talc, bentonite, diatomaceous earth, clay, montmorillonite, chalk, calcium carbonate, pumice, dolomite, etc. Examples of useful organic substances include coconut shells, tobacco stems Examples of useful synthetic compounds include alumina, silicates, sugar polymers, etc. In addition, adhesives such as carboxymethylcellulose, acacia, polyvinyl alcohol, polyvinyl acetate, etc. are useful. The compositions may also be colored with organic or inorganic colorants.

The compounds of formula (I) according to the invention are formulated into various compositions as described above so that the compositions contain as an active ingredient an insecticidally, acaricidally or nematocidally effective amount (e.g., about 0.1 to 95% by weight, preferably about 0.5 to about 90% (w / w) of the compound. Depending on the intended application, the compositions are used as such or diluted with a carrier or water.

The following examples illustrate the invention but do not limit it in any way.

Example 1

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- [Ν, Ν-bis12 (cyanomethyl) aminosulfenyl] -N-methylcarbamate g (0.05 mol) 2,3-dihydro-2 Dissolve 2-dimethylbenzofuran-7-yl-N-methylcarbamate in 70 ml of methylene chloride, add 5.2 g (0.05 mol) of sulfur dichloride (with cooling) and dropwise to the solution at 0 ° C add 5 g (0.05 mol) of triethylamine. The reaction mixture is stirred at the same temperature for 2 hours, then a solution of 4.8 g (0.05 mol) of iminodiacetonitrile in 40 ml of tetrahydrofuran is added dropwise at the same temperature, and 5 g (0.05 mol) of triehylamine are added dropwise thereto. . The resulting mixture was stirred at 0 ° C for 4 hours and then allowed to stand overnight at room temperature. After addition of 100 ml of methylene chloride, the reaction mixture is washed three times with 100 ml of water. The methylene chloride layer was dried and then concentrated in vacuo to give an oily product which consisted almost entirely of the desired product containing a small amount of starting materials. Yield; 13.8 g (79.8%).

To identify the product, a portion was purified by silica gel column chromatography eluting with benzene / ethyl acetate (4: 1) to give crystals of m.p. 94-95 ° C.

NMR spectrum (in deuterated chloroform):

1.48 ppm (s, 6H);

3.02 ppm. [s, 3H]

3.50 ppm (s, 3H);

4.32 ppm (s, 4H);

6.6 to 7.2 ppm (s, 3H)

Elementary analysis:

for C16H18N4O3S (molecular weight

346,418) found:

% H, 5.31;% N, 16.05;

calculated:

H, 5.24; N, 16.17.

The product corresponds to the following formula:

Example 2

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- [Ν, Ν-bis- (ethoxycarbonylmethyl) aminosulfenyl] -N-methylcarbamate g (0.05 mol) 2,3- dihydro-2,2-dimethylbenzofuran-7-yl-4-ethylcarbamate is dissolved in 50 ml of chloroform, 5.2 g (0.05 mol) of sulfur dichloride are added to the solution while cooling, and 5 g (0 g) are added dropwise at 0 ° C. (05 mol) of thiethylamine. After stirring at the same temperature for 2 hours, a solution of 9.5 g (0.05 mol) of ethyliminodiacetate in 20 ml of chloroform was added dropwise at the same temperature, and 5 g (0.05 mol) were added dropwise. triethylamine. The resulting mixture was stirred at 0 ° C for 2 hours and then allowed to stand overnight at room temperature. Then, 100 ml of chloroform was added to the mixture, and the reaction mixture was washed three times with 100 ml of water. The chloroform layer is dried and then concentrated in vacuo to give an oily product which almost entirely consists of the desired product containing a small amount of starting materials.

Yield: '

15.9 g (72.3%).

A portion was purified by column chromatography on silica gel using benzene / ethyl acetate (4: 1) as eluent to give the product as an oil.

NMR spectrum (in deuterated chloroform):

δ 1.24 ppm (t, 6 H),

1.48 ppm (s, 6H);

3.02 ppm (s, 2H);

3.42 ppm (s, 3H);

4.20 ppm (q, 4H);

4.28 ppm (s, 4H); 7.6-7.2 ppm (m, 3H).

For C20H2SN2O7S (molecular weight 440.526) found:

% C, 54.68;% H, 6.46;% N, 6.38;

calculated:

H, 6.41; N, 6.36.

The product corresponds to the following formula:

CHX CHCQOOHr ^{of 2S} ^ CH ^COOCC

Examples 3 to 5

The compounds listed in Table 1 were prepared in the same manner as described in Example 1 or 2. Physical properties and NMR data (in deuterated chloroform). These compounds are also listed in Table 1.

cd N 2?

honor д honor> ч М О Д тз о

Table 1

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1 £) гЧ СТ) *!

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ь. О <м

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О со ьО см% ю ж § гЧ со СТ со со со ω О

СО z

о я

СО см

О

СТ ио СО оо К t <

rH (Μ ιό ο 04 CD rH 0Q ’-'Φ what 04 / CN 04 co 00 rH rH Ю ΙΌ Ιό Ιό 00 00

О я л гЧ ОО

04 о 04

X К

СО

To identify the product, a portion is chromatographed on a silica gel column using benzene / ethyl acetate (5: 1) as eluent to give an oily product.

NMR spectrum (in deuterated chloroform):

Example 6

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N [Ν, Ν-bis (ethoxycarbonylethyl) aminosulfonyl] -N-methylcarbamate g (0.05 mol) 2,3-dihydro -2,2-dimethylbenzofuran-7-yl-N-methylcarbamate is dissolved in 70 ml of methylene chloride, then 5.2 g (0.05 mol) of sulfur dichloride are added to the solution while cooling, and then added dropwise to the solution at - 10 ° C to -5 ° C 5 g (0.05 mol) of triethylamine. The mixture was stirred at 0 ° C for one hour and further stirred at room temperature for 2 hours. After cooling to -10 to -5 ° C, 10.9 g (0.05 mol) of diethyl iminodipropionate was added dropwise to the reaction mixture, followed by the dropwise addition of 5 g (0.05 mol) of triethylamine. The resulting mixture was stirred at 0 ° C for 2 hours and then allowed to stand overnight at room temperature. To the mixture was added 100 mL of methylene chloride and the reaction mixture was washed three times with 100 mL of water. The methylene chloride layer was dried and then concentrated in vacuo to give an oily product which almost consisted of the desired product containing a small amount of impurities.

Yield:

16.9 g (72.2%).

δ 1,21 ppm (t, 6 H),

1.44 ppm (s, 6H);

2.67 ppm (t, 4H);

2.97 ppm. (s, 2H)

3.37 ppm [s, 3H]

3.42 ppm (t, 4H);

4.04 ppm (q, 4H);

6.5-7.2 ppm (m, 3H).

Elementary analysis:

for C22H32N2O7S:

(molecular weight: 468.58) found:

% C, 56.26;% H, 6.91;% N / 5.52;

calculated:

% H, 6.88;% N, 5.98.

The product obtained corresponds to the following formula:

CH-CH-COOCl ₂ ch ₂ cooc ₂ w ₅

Example 7

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- [N, N-bis (cyanethyl) aminosulfenyl] -N-methylcarbamate g (0.05 mol) 2,3-dihydro-2,2 -dimethylbenzofuran-7-yl-N-methylcarbamate is dissolved in 50 ml of chloroform, and 5.2 g (0.05 mol) of sulfur dichloride are added thereto while cooling, and the solution is added dropwise thereto at a temperature of -10 ° to -5 °. C, 5 g (0.05 mol) of triethylamine. The reaction mixture was stirred at 0 ° C for 1 hour and further stirred at room temperature for 1 hour. After cooling to -10 ° C to -5 ° C, 6.2 g (0.05 mol) of iminodipropionitrile was added dropwise and 5 g (0.05 mol) of triethylamine was added dropwise. The resulting mixture was stirred at 0 ° C for 2 hours and then allowed to stand overnight at room temperature. 100 ml of chloroform are now added to the mixture, and the reaction mixture is washed three times with 100 ml of water. The chloroform layer was dried and then concentrated in vacuo. An oily product is obtained which consists almost entirely of the desired product containing small amounts of impurities.

Yield: 12.2 g (65.2%).

A portion was purified by column chromatography on silica gel using benzene / ethyl acetate (4: 1) as eluent to give the product.

NMR spectrum (in deuterated chloroform):

δ 1.43 ppm (s, 6H)

2.73 ppm (t, 4H);

2.97 ppm (s, 2H).

3.37 ppm (s, 3H);

3.43 ppm (t, 4H);

6.5-7.2 ppm (m, 3H).

Elementary analysis:

for C18H22N4O5S (molecular weight: 374.47) found:

% H, 5.79;% N, 15.04;

U calculated:

% H, 5.92;% N, 14.96.

The product obtained corresponds to the following formula:

^ CH ^ CH ^ CN

Examples8 to 11

The compounds listed in Table 2 were prepared in the same manner as in Examples 6 or 7. The physical properties and NMR spectra (in deuterated chloro form) of these compounds are also shown in Table 2.

Table 2

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(Λ cd Q and c> Ό

O Λ if co CD ri

O CD σι in cd cd

Ti O CD Ю irT in lf in

Ό cd

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2 7 0 2-6 example amine R1 R2 H-NMR spectrum elemental analysis number [δ value (ppm) empirical formula in CDCls] found values

ID O0 CM OT cd in rH 00 oo by in UD

OO CD tx 00

FROM WHAT ABOUT LO Týl ω oo ”LO LO

a portion was purified by silica gel column chromatography using a 4: 1 mixture of benzene and ethyl acetate as eluent to give an oily product.

NMR spectrum (in deuterated chloroform):

Example 12

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-butyl-N-ethoxycarbonylaminosulfenyl) -N-methylcarbamate g (0.05 mol) 2,3-dihydro-2,2-dimethylbenzofuran Of 7-yl-N-methylcarbamate is dissolved in 70 ml of methylene chloride, 5.2 g (0.05 mol) of sulfur dichloride are added thereto while cooling, and the solution is then added dropwise to the solution at a temperature of -10 to -5 ° C, 5 g (0.05 mol) of triethylamine. The mixture was stirred at 0 ° C for 1 hour and further at room temperature for 2 hours. After cooling to -10 to -5 ° C, 8.0 g (0.05 mol) of N-butylglycine ethyl ester was added dropwise and triethylamine (5 g, 0.05 mol) was added dropwise. The resulting mixture was stirred at 0 ° C for 2 hours and then left at room temperature overnight. To the mixture was then added 100 mL of methylene chloride, and the reaction mixture was washed three times with 100 mL of water. The methylene chloride layer was dried and then concentrated in vacuo to give an oily product which almost consisted of the desired product containing a small amount of impurities. Yield 15.7 g (76.6%).

In order to identify the product, its δ 0,6-1,9 ppm (m, 7H),

1.22 ppm (t, 3H);

1.44 ppm (s, 6H);

3.03 ppm (s, 2H).

3.30 ppm (t, 2 H),

3.42 ppm (s, 3H);

4.14 ppm (s, 2H).

4.13 ppm (q, 2H).

6.5-7.2 ppm (m, 3H).

For C20H30N2O5S (molecular weight 410.54) found:

58.39% (, (, 44% H, (, 77% N. calculated):

% C, 58.52;% H, 7.37;% 6.83.

The product obtained corresponds to the following formula:

^ _CH2 C00CzH _s' = CH ₂ CH ₂ C ^HjCHj

Example 13

Preparation of 2,3-dihydro-2- (2-dimethylbenzofuran-7-yl-N- (N-phenyl-N-ethoxycarbonylmethylaminosulfenyl) -N-methylcarbamate g (0.05 mol) 2,3-dihydro-2,2- dimethylbenzofuran-6-yl-N-methylcarbamate is dissolved in 70 ml of methylene chloride, 5.2 g (0.05 mol) of sulfur dichloride are added to the obtained solution with cooling, and the solution is then added at -10 to -5 ° C. triethylamine (5 g, 0.05 mol) was added dropwise, the mixture was stirred at 0 ° C for 1 hour and then at room temperature for 2 hours, and after cooling to -10 to -5 ° C, 9 g (0.05 mol) was added dropwise. 5 g (0.05 mol) of triethylamine are added dropwise, the mixture is stirred at 0 DEG C. for 2 hours and then left to stand overnight at room temperature. The reaction mixture was washed with 100 mL of water, the methylene chloride layer was dried and concentrated in vacuo to give an oily product. Xan (1: 1) to precipitate crystals, which are then filtered off and the mother liquor is concentrated to give an oily product which, upon cooling, yields additional crystals. The crystals thus obtained are recrystallized from diethyl ether (13.4 g, yield: 62.3%) of white crystals having a melting point of 92 DEG-93 DEG C. is obtained.

NMR spectrum (in deuterated chloroform):

δ 1.15 ppm (t, 3 H),

1.46 ppm (s, 6H);

3.00 ppm (s, 2H).

3.32 ppm (s, 3H);

4.12 ppm (q, 2 H),

4.76 ppm (s, 2H).

6.5-7.5 ppm (m, 8H).

For C22H2GN2O5S (molecular weight 430.53) found:

% C, 61.11;% H, 6.15;% N, 6.49.

% C, 61.38;% H, 6.09;

The product obtained corresponds to the following formula:

Examples 14 to 32

The compounds listed in Table 3 were prepared in the same manner as described in Example 12 or 13. The physical properties and NMR spectra (in deuterated chloroform) of these compounds are also shown in Table 3.

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Example 33

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-butyl-N-cyanomethylaminosulfenyl) -N-methylcarbamate g (0.05 mol) 2,3-dihydro -2,2-dimethylbenzofuran-7-yl-N-methylcarbamate is dissolved in 70 ml of methylene chloride, 5.2 g (0.05 mol) of sulphurdichloride are added to the solution while cooling, and then added to the solution at - 5 g (0.05 mol) of triethylamine are added dropwise at 10 DEG to -5 DEG C. The mixture is stirred at 0 DEG C. for 1 hour and further stirred at room temperature for 2 hours. 5.6 g (0.05 mol) of N-butylaminoacetonitrile was added dropwise to the mixture, followed by the dropwise addition of 5 g (0.05 mol) of triethylamine, and the resulting mixture was stirred at 0 [deg.] C. for 2 hours and then allowed to stand over 100 ml of methylene chloride are added to the mixture, and the reaction mixture is washed three times with 100 ml of water, and the methylene chloride layer is dried and then concentrated in vacuo to give an oily product. kt, which almost completely consists of the desired product containing a small amount of impurities. Yield 13.0 g (71.4%).

To identify the product, a portion is purified by silica gel column chromatography using a 5: 1 mixture of benzene and ethyl acetate as eluent to give an oily product.

NMR spectrum (in deuterated chloroform):

δ

0.7-2.0 ppm (m, 7H),

1.42 ppm (s, 6H);

2.92 ppm (s, 2H).

2.9-3.5 ppm (m, 2H),

3.33 ppm (s, 3H);

4.01 ppm (s, 2H).

6.5-7.1 ppm (m, 3H).

For C18H25N3O3S (molecular weight 363.488) found:

% C, 59.19;% H, 7.02;% N, 11.69.

% H, 6.93;% N, 11.56.

The product obtained corresponds to the following formula:

Examples 34 to 42 ........

The compounds listed in Table 4 were prepared in the same manner as described in Example 33. Physical properties and NMR spectra (in deuterated-chloro form) of these compounds. are also shown in Table 4.

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NMR spectrum (in deuterated chloroform):

Example 43

Preparation of 2,3-diliydro-2,2-dimethylbenzofuran-y-yl-N- (N-propionyl-N-ethoxycarbonylamino-ethylaminosulfenyl) -N-methylcarbamate g (0.05 mol) 2,3-dihydro-2,2 Dimethylbenzofuran-7-yl-N-methylcarbamate is dissolved in 70 ml of methylene chloride, 5.2 g (0.05 mol) of sulfur dichloride are added to the solution while cooling, and then the solution is stirred at -50 ° C. 10 to -5 ° C is added dropwise 5 g (0.05 mol) of triethylamine. The reaction mixture was stirred at 0 ° C for 1 hour and further at room temperature for 2 hours. After cooling to -10 to -5 ° C, a solution of 8 g (0.05 mol) of N-propionylglycine ethyl ester in 10 ml of tetrahydrofuran was added dropwise, followed by dropwise addition of 5 g (0.05 mol) of triethylamine. The resulting mixture was stirred at 0 ° C for 2 hours and then left to stand overnight at room temperature. To the mixture was then added 100 mL of methylene chloride and the reaction mixture was washed three times with 100 mL of water. The methylene chloride layer is dried and then concentrated in vacuo to give an oily product which almost entirely consists of the desired product containing a small amount of starting materials and impurities. Yield 14.3 g (69.8%).

To identify the product, a portion thereof is purified by chromatography on a sill8 column at 1.14 ppm (t, 3H),

1.23 ppm (t, 3H);

1.49 ppm (s, 6 H),

3.3-1.3 ppm- (m, 2H);

3.02 ppm (s, -2H),

3.48 ppm (s, 3H);

4.15 ppm (q, 2H).

4.50 ppm (s, 2H).

7.6-7.1 ppm (m, 3H).

Elemental analysis: Found:

% C, 55.35;% H, 6.44;% N, 6.77.

H, 6.38; N, 6.82.

(molecular weight 410,499)

The product obtained corresponds to the following formula:

cw ₂ cooq / Ý сосн ₂ сн ₃

Example 44

Preparation of 3,3-dihydro-3,3-dimethylbenzofuran-7-yl-N- (N-ethoxycarbonyl-N-ethoxycarbonylmethylaminosulfenylene) -N-methylcarbamate g (0.05 mol) 3, 3-d-ihydro-3,2-dimethylbenzofuran-7-yl-N-methylcarbamate is dissolved in 70-ml-methyl-enc-chloride, and 5.2 g (0.05 mol) of sulfur dichloride are added thereto under cooling. and then 5 g (0.05 mol) of triethylamine are added dropwise to the solution at -10 to -5 ° C. The mixture was stirred at 0 ° C for 1 hour and then at room temperature for 2 hours. After cooling to -10 to -5 ° C, 8.8 g (0.05 m) of N-ethoxycarbonylglycine ethyl ester was added dropwise and triethylamine (5 g, 0.05 mole) was added dropwise. The resulting mixture was stirred at 0 ° C for 2 hours and then allowed to stand overnight at room temperature. To the mixture was then added 100 mL of methylene chloride, and the reaction mixture was washed three times with 100 mL of water. The methylene chloride layer is dried and then concentrated in vacuo to give an oily product which almost completely consists of the desired product containing a small amount of starting materials and impurities. Yield 18.2 g (84.7%).

To identify the product, a portion of it was purified by chromatography on a silica gel column using a 4: 1 mixture of benzene and ethyl acetate to give an oily product.

NMR spectrum (in deuterated chloroform):

δ 1.17 ppm (it, 6H)

1.44 ppm (s, 6H);

2.94 ppm (s, 2H).

3.41 ppm (s, 3 H),

4.05 ppm (q, 2H), _ч

4.15 ppm (q, 2H).

4.41 ppm (s, 2H).

6.5-7.0 ppm (m, 3H).

For C19H23N2O7S (molecular weight 426.499) found:

53.82% C, 6.11% CH 6.44 ·%. 61, calculated:

H, 6.14; N, 6.57.

The product obtained corresponds to the following formula:

^ CH 2 COOC 3 H 5 O 3 OocH

Examples 45 to 52

The compounds listed in Table 5 were prepared in the same manner as described in Examples 43 or 44. Table 5 also lists the physical properties and NMR spectra (in deuterated chloroform) of these compounds.

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Examples of compositions of the present invention are set forth below. These regulations are applicable to all compounds of the invention. The regulations are given for illustration only and the proportions of the active ingredient, the organic solvent, the surfactant and the carrier are interchangeable as desired. Thus, in some cases, the type of organic solvent, surfactant, carrier, etc. may be varied.

Example I

60% emulsion: Example 25 60.0% polyoxyethylene nonylphenyl ether 10.0% xylene 30.0%

Example II

50% emulsion:

Example 12 50.0% polyoxyethylene sorbitan monooleate 6.5% sorbitan monooleate 3.5% xylene 30.0% cyclohexanone 10.0%

Example III

20% emulsion:

Example compound 20 20% polyoxyethylene alkyl ether 5.0% xylene 45.0% petroleum ether 30.0%

In each of Examples I to III, the individual components are mixed homogeneously and the resulting mixture is dissolved to the desired emulsion.

Example IV

90% wettable powder:

Example 1 compound 90.0% ligninsulfonic acid sodium 3.0% clay 7.0%

Example V

50% wettable powder:

Example 21 50.0% alkylsulfate 30.0% naphthalenesulfonic acid-formaldehyde condensation product 10.0% alkyl phosphate 5.5% kaolin 3.5% talc 1.0%

Example VI

30% wettable powder:

Example 30 30.0% alkylbenzenesulfonate 3.0% ligninsulfonic acid sodium 2.0% silica 15.0% clay 50.0%

In each of Examples IV to VI, the individual components are homogeneously mixed using a stirrer. The mixture is then milled to a powder using a suitable mill, for example a ball mill, to obtain the desired wettable powder.

Example VII

5% dust:

Example 46 5.0% diatomaceous earth 10.0% talc 85.0%

Example VIII

2% dust:

wettable powder of Example V 4.0% clay 95.8% isopropyl phosphate 0.2%

Example IX

0.5% dust:

wettable powder of Example VI 1.7% clay 100.3%

In each of Examples VII to IX, the individual components are mixed to a homogeneous mixture using a suitable mixer type to obtain the desired dust.

Example X

20% granulate:

wettable powder of Example V 40.0% dolomite 60.0%

The ingredients are mixed to a homogeneous mixture and a 2% aqueous solution of carboxymethylcellulose is added to the mixture in an amount of 15 parts by weight per 100 parts by weight of the mixture, and the resulting mixture is bent thoroughly. The mixture is then granulated using a suitable fine granulated granulator, which is then dried. In this way the desired granulate is obtained.

Example XI

10% granulate:

compound of Example 40 10.0% sodium dodecylbenzenesulfonic acid 0.5% ligninsulfonic acid sodium 2.0% diatomaceous earth 27.5% bentonite 60.0%

These components are mixed to a homogeneous mixture and water is added to the mixture. The resulting mixture is thoroughly bent and then granulated using a granulator. The product obtained is a fine pulp which is dried to give the desired granulate.

Example XII

3% granulate:

the compound of Example 8 polyvinyl alcohol clay

3.0%

3.0% 94.0%

The procedure was as described in Example XI to obtain the desired granulate.

Biological activity tests are listed below.

Test 1

Brassica plants grown in a pot (1 month old seedlings) are populated with larvae of Spodoptera litura (third instar). 50% of the test compound emulsion is diluted to a certain concentration and applied to the leaves of the plants until completely wetted. Each test compound concentration was tested on plants in two pots. After three days, larval mortality was determined. The results obtained are shown in Table 6 below, which also shows the results obtained for control and untreated groups of plants.

Table 6

test compound (example #) mortality in% at active substance concentration (ppm) 2 000 1000 500 1 100 ALIGN! 80 65 2 100 ALIGN! 70 60 3 100 ALIGN! 80 65 4 100 ALIGN! 70 60 5 100 ALIGN! 80 65 6 100 ALIGN! 75 60 7 100 ALIGN! 75 60 8 100 ALIGN! 80 75 9 100 ALIGN! 90 80 10 100 ALIGN! 85 75 11 100 ALIGN! 80 70 12 100 ALIGN! 90 75 13 100 ALIGN! 90 75 14 100 ALIGN! 90 75 15 Dec 100 ALIGN! 90 75 16 100 ALIGN! 85 65 17 100 ALIGN! 80 60 18 100 ALIGN! 90 75 19 Dec 100 ALIGN! 85 65 20 May 100 ALIGN! 85 65 21 100 ALIGN! 90 75 22nd 100 ALIGN! 85 65 23 100 ALIGN! 85 70 24 100 ALIGN! 85 75 25 100 ALIGN! 90 75 26 100 ALIGN! 80 60 27 Mar: 100 ALIGN! 90 75 28 100 ALIGN! 90 75 29 100 ALIGN! 80 60 30 100 ALIGN! 85 65 31 100 ALIGN! 80 60 32 100 ALIGN! 80 65 33 100 ALIGN! 90 75 34 100 ALIGN! 90 75

34

test compound (example #) 2 000 mortality in% at active substance concentration (ppm) 1000 500 35 100 ALIGN! 80 65 36 100 ALIGN! 80 65 37 100 ALIGN! 85 70 38 100 ALIGN! 90 75 39 100 ALIGN! 90 75 40 100 ALIGN! 85 75 41 100 ALIGN! 80 65 42 100 ALIGN! 85 70 43 100 ALIGN! 85 70 44 100 ALIGN! 90 75 45 100 ALIGN! 90 75 46 100 ALIGN! 85 70 47 100 ALIGN! 80 65 48 100 ALIGN! 80 65 49 100 ALIGN! 90 75 50 100 ALIGN! 80 65 51 100 ALIGN! 85 70 52 100 ALIGN! 85 70 control*' 80 60 35 untreated 0

* ’1-naphthyl-N-methylcarbamate was used as a control.

Test 2

An emulsion of a certain concentration is prepared from 50% wettable powder containing the test compound and applied to irrigated rice leaves (1 month old seedlings) until the leaves of the plants are completely wet. After the emulsion spray has dried, the pots are covered with a net cage in which 10 adult Nephotettix cincticeps females are placed. The compound at each concentration was tested in 2 pots. Insect mortality was determined after 3 days. The results obtained are shown in Table 7 below, which also compares the results obtained for control and untreated groups of plants.

Table 7

test compound (example #) mortality in% at active substance concentration (ppm) 800 400 200 1 100 ALIGN! 85 50 2 100 ALIGN! 85 45 3 100 ALIGN! 85 45 4 100 ALIGN! 70 40 5 100 ALIGN! 80 45 6 95 75 55 7 90 70 50 8 95 85 60 9 100 ALIGN! 90 60 10 100 ALIGN! 90 60 11 95 80 55 12 100 ALIGN! 90 65 13 100 ALIGN! 90 65 14 100 ALIGN! 90 65 15 Dec 100 ALIGN! 90 65 16 100 ALIGN! 90 65 17 95 75 55 18 100 ALIGN! 90 65 19 Dec 100 ALIGN! 80 60 20 May 100 ALIGN! 80 60 21 100 ALIGN! 90 65 22nd 100 ALIGN! 80 60 23 100 ALIGN! 85 55 24 100 ALIGN! 90 60 25 100 ALIGN! 90 65

35 227026 36 test compound (example #) mortality in% at active substance concentration (ppm) 800 400 200

26 100 ALIGN! 75 55 27 Mar: 100 ALIGN! 90 65 28 100 ALIGN! 90 65 29 100 ALIGN! 75 45 30 100 ALIGN! 80 60 31 100 ALIGN! 75 55 32 100 ALIGN! 75 55 33 100 ALIGN! 90 70 34 100 ALIGN! 90 65 35 95 75 60 36 95 75 60 37 100 ALIGN! 85 65 38 100 ALIGN! 90 70 39 100 ALIGN! 90 70 40 100 ALIGN! 85 70 41 95 75 60 42 100 ALIGN! 85 65 43 100 ALIGN! 85 60 44 100 ALIGN! 90 70 45 100 ALIGN! 90 65 46 100 ALIGN! 90 65 47 95 75 60 48 95 75 60 49 100 ALIGN! 90 70 50 95 75 60 51 100 ALIGN! 85 65 52 100 ALIGN! 85 65 check * ¹ 75 50 25 0 0 0 untreated 0

^} 2-isopropoxyphenyl N-methylcarbamate was used as control.

Test 3 Stage Creation:

The soil infested with Meloidogyne incognita nematode larvae is mixed with a certain amount of granulate containing 10% of the test compound, and tomato seedlings are immediately transplanted into the soil. After 1 month, the roots of the plants are examined to detect the formation of the hooks. Each amount of test substance is tested on two test plots, each measuring 2 X 2 m.

0 ° / o up to 25% up to 50% up to 75% up to 100%.

The results obtained are shown in Table 8 below, which also includes the results obtained on control and untreated plots for comparison.

22702В

Table 8 Tested degree of pitch formation when applying granulate in an amount (kg / ha) of compound 1000 500 200 (Example.)

1 0 1 2 2 0 2 3 3 0 2 3 4 0 2 3 5 0 2 3 6 1 2 3 7 1 3 3 8 1 1 2 9 0 1 2 10 0 1 2 11 1 2 3 12 0 1 2 13 0 1 2 14 0 1 2 15 Dec 0 1 2 16 0 1 3 17 0 1 3 18 0 1 2 19 Dec 0 1 2 20 May 0 1 3 21 0 1 2 22nd 0 1 3 23 0 1 2 24 0 0 1 25 0 1 2 26 0 1 2 27 Mar: 0 1 2 28 0 0 1 29 0 1 2 30 0 1 2 31 0 2 3 32 0 2 3 33 0 0 1 34 0 0 1 35 0 1 3 36 0 1 3 37 0 1 2 38 0 0 1 39 0 0 1 40 0 1 1 41 0 1 3 42 0 1 2 43 0 1 2 44 0 0 1 45 0 1 2 46 0 1 2 47 0 1 3 48 0 1 3 49 0 0 1 50 0 1 3 51 0 1 2 52 0 1 2 control*' 2 4 4 untreated 4

* 'Bis- (2-chloro-1-methylethyl) ether was used as a control.

Test 4

The test compound is dissolved in a predetermined amount of acetone. This solution is diluted to various concentrations and used for topical application to housefly (Musea domestica). The following Table 9 shows the LD 50 values determined by the 24-hour mortality provenance method.

Tested ^{Table 9} Compound (from Example #) LD 50 (^^ / ^) 1 21.3 2 58.8 3 40.0 4 28.9 5 75.6 6 38.3 7 54.0 8 24.6 9 31.7 10 46.0 11 93.9 12 16.7 13 12.5 14 9.9 15 Dec 33.0 16 44.4 17 42.3 18 32.5 19 Dec 22.2 20 May 61.9 21 10.4 22nd 45.2 23 44.3 24 38.6 25 50.1 - 26 64.7 27 Mar: 13.8 28 17.7 29 22.5 30 23.8 31 33.1 32 32.7 33 9.1 34 16.7 35 65.6 36 59.3 37 ’ 11.8 38 17.5 39 13.7 40 37.9 41 54.6 42 46.0 43 14.4 44 16.2 45 29.2 46 33.2 47 57.8 48 58.6 49 15.7 50 34.7 51 45.3 52 54.3 control* 22.5

2-Isopropoxyphenyl-N-methylcarbamate is used as a control

T e s t 5

The compounds of the invention were tested in male mice for acute toxicity by oral administration. Table 10 shows the LD 50 values determined by the Lichfield-Wilcoxon method from day 7 mortality.

Table 10

test compound (example #) LD 50 (mg / kg) 1 58 2 140 3 145 4 122 5 90 6 135 7 75 8 105 9 158 10 115 11 93 12 125 13 115 14 120 15 Dec 110 16 110 17 69 18 135 19 Dec 108 20 May 75 21 105 22nd 88 23 113 24 77 25 123 26 150 27 Mar: 105 28 89 29 120 30 133 31 135 32 107 33 103 34 95 35 95 36 70 37 65 38 125 39 110 40 103 41 105 42 88 43 43 44 128 45 80 46 105 47 95 48 80 49 105 50 95 . 51 88 52 125 kontroaa * ¹ 5.6

2,3-dihydro-2,2-dimethyl-7-banzofuran-7-yl-N-methylcarbamate was used as a control

Claims (13)

pRedmet vynalezu An insecticidal, acaricidal and nematicidal composition comprising, as active ingredient, an insecticidal, acaricidal or nematicidal effective amount of a carbamate of the formula I wherein: R 1 and R 2, which may be the same or different from each other, represent 1. A group —X — COOR3 in which X represents an alkylene group having 1 to 6 carbon atoms, and R 3 is C 1 -C 8 alkyl or C 3 -C 6 cycloalkyl; or 2. a —Y — CN group in which Y is a (C1-C6) alkylene group; and R 2 is furthermore a C 1 -C 8 alkyl group, a C 3 -C 6 cycloalkyl group, a benzyl group optionally substituted by a halogen atom, a C 1 -C 3 alkyl group or a C 1 -C 3 alkoxy group; phenyl optionally substituted with (halogen, C 1 -C 3 alkyl or C 1 -C 3 alkoxy) or -Z-R 4 in which Z is carbonyl or sulfonyl and R 4 is C1-C6alkyl, phenyl, benzyl, C1-C6alkoxy or phenoxy. 2. A composition according to claim 1, wherein the active ingredient is an insecticidally, acaricidally or nematocidally effective amount of a carbamate of the formula: 1. a group 'X'-COOR ³ ' in which X 'is a C 1 -C 2 alkylene group and R 3' is a C 1 -C 4 alkyl group which may be straight or branched; .or 2. represents a group —Y‘ — CN in which Y * represents an alkylene group having 1 to 2 carbon atoms; and R 2 dále is furthermore an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. 3. A composition according to claim 1, wherein the active ingredient is an insecticidally, acaricidally or nematocidally effective amount of a carbamate of the formula (I). (a) in which: R1 'represents a group -X' COOR3 "ebo _n -X ', -CN, and R 2 "represents a group" Y "" COOR '3 "or" Y "—CN, wherein R3 'represents an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms and X "and Y" denote a straight or branched alkylene group having 1 to 6 carbon atoms, with the proviso that X "and Y" do not simultaneously denote a methylene group. 4. A composition according to claim 1, wherein the active ingredient comprises an insecticidally, acaricidally or nematocidally effective amount of a carbamate of the formula (I) in which: R ¹ and R 2, which are the same or different from each other, represent R 1 '"means the group" X "" - COOR ³ * ", where X ‘'means a straight or branched alkylene group having 1 to 6 carbon atoms, and R ³ '' represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms; and R ² "'is alkyl having 1-8 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, benzyl or phenyl wherein benzyl or phenyl are optionally subtitucvána least one substituent selected from the group which is formed by a halogen atom , C 1 -C 3 alkyl and C 1 -C 3 alkoxy. 5. A composition according to claim 1 or 2, wherein the active ingredient is 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- [N, N-bis- (ethoxycarbonylmethyl) aminosulfenyl] - N-methylcarbamate. 6. A composition according to claim 4, wherein the active ingredient is 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-methyl-N-ethoxycarbonylmethylaminosulfenyl) -N- methylcarbamate. 7. A composition according to claim 4, wherein the active ingredient is 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-isopropyl-N-ethoxycarbonylethylaminosulfenyl) -N-methylcarbamate. 8. A composition according to claim 4, wherein the active ingredient is 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-n-butyl-N-ethoxycarbonylethylaminosulfenyl) -N-methylcarbamate. 9. A composition according to claim 4, wherein the active ingredient is 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-cyclohexyl-N-ethoxycarbonylethylaminosulfenyl) -N-methylcarbamate. . 10. A composition according to claim 1 or 2, wherein the active ingredient is 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-butyl-N-cyanethylaminosulfenyl) -N-methylcarbamate. . 11. A process according to claim 1, wherein the compound of formula (II) is treated with sulfur trichloride in an amount of 1 to 2 moles per mole of compound of formula (II) in the presence of a solvent selected from the group consisting of: methylene chloride, chloroform, carbon tetrachloride, diethyl ether, dibutyl ether, tetrahydrofuran and dioxane, and optionally in the presence of a basic compound selected from the group consisting of triethylamine, tributylamine, dimehylaniline, diethylaniline, ethylmorpholine, pyridine, and N, N-picidine, and to form 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (chlorosulfenyl) -N-methylcarbamate of formula III (III) which is then reacted with a compound of formula IV R ¹ / I-IN (IV) \ R ² in which R ¹ and R ² are as defined in Item 1 in an amount of 1-2 moles per 1 mole of the compound of formula III, optionally in the presence of a solvent selected from the group that is formed by methylene chloride, chloroform, carbon tetrachloride, diethyl ether, dibutyl ether, tetrahydrofuran and dioxane; and optionally in the presence of a basic compound selected from the group consisting of triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine, pyridine, and, [beta], - picoline and lutidine. 12. The method of item 11, к manufacture of the active ingredient according to claim 3 of formula I ^й, characterized in that the compound of formula II, stated in paragraph 11, acts sulfur dichloride in an amount of 1-2 mol per 1 mol of compound II, optionally in the presence of a solvent selected from the group consisting of methylene chloride, chloroform, carbon tetrachloride, diethyl ether, dibutyl ether, tetrahydrofuran and dioxane, and optionally in the presence of a basic compound selected from the group consisting of triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine to give 2,3 <2,2-dihydro-dimethylbenzof uran-7-yl-N- (chlorosulphenyl) -N-methylcarbamate of the formula III mentioned in paragraph 11, which is then reacted with a compound of formula IV ^й Rl ' HN ^ (IV ') \ R2 "wherein r 1" _and r 2 "are as defined in point 3, in an amount of 1 to 2 moles per mole of the compound of formula III, optionally in the presence of a solvent selected from methylene chloride, chloroform, carbon tetrachloride, diethyl ether, dibutyl ether, tetrahydrofuran and dioxane and optionally in the presence of a basic compound selected from the group consisting of triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine and pyridine. 13. The process of claim 11, wherein the compound of formula II is treated with sulfur trichloride in an amount of 1 to 2 moles per mole of the compound of formula (II). II, optionally in the presence of a solvent selected from the group consisting of methylene chloride, chloroform, carbon tetrachloride, diethyl ether, dibutyl ether, tetrahydrofuran and dioxane, and optionally in the presence of a basic compound selected from the group consisting of triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine pyridine, to give 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (chlorosulfenyl) -N-methylcarbamate of formula III, as described in point 11, which is then reacted with an amine of formula IV ' R1 ‘" HN ⁷ (IV "j, ^ R ² "'in which R ¹ '* and R ² ''have the meanings given in point 4, in an amount of 1 to 2 mol per 1 mol of the compound of formula III in the presence of a solvent selected from methylene chloride, chloroform, carbon tetrachloride, diethyl ether, dibutyl ether, tetrahydrofuran and dioxane and optionally in the presence of a basic compound selected from the group consisting of triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine and pyridine.