HU188690B - Insecticide, miticide and nematocide compositions and process for producing carbamate derivatives active agents - Google Patents

Abstract

A carbamate derivative having the formula (I): <IMAGE> wherein each of R<1> and R<2>, which are the same or different, is (1)-X-COOR<3>, in which X is C1 to C6 (preferably C1 or C2) alkylene and R<3> is C1 to C8 (preferably C1 to C4) alkyl or C3 to C6 cycloalkyl; or (2)-Y-CN, in which Y is C1 to C6 (preferably C1 or C2) alkylene; and R<2> further represents C1 to C8 (preferably C1 to C6) alkyl; C3 to C6 cycloalkyl a benzyl group which may be substituted with a halogen atom or C1 to C3 alkyl or alkoxyl; a phenyl group which may be substituted with a halogen atom or C1 to C3 alkyl or alkoxyl; or -Z-R, in which Z is a carbonyl sulfonyl, and R is C1 to C6 alkyl, phenyl, benzyl, C1 to C6 alkoxy or a phenoxy.

Description

The present invention relates to a process for the preparation of insecticidal, miticidal and nematicidal compounds and to the preparation of carbamate derivatives as active ingredients in the compositions. í applies.

The term insecticide preparation in idiocy includes both acaricide and nematocide preparations unless otherwise indicated.

Many carbamate derivatives are known to be potent insecticides and are used in practice. However, the disadvantage of carbamate (most derivatives) is that they are poisonous to warm-blooded people.

2,3-Dihydro-2,2-dimethyl-fenzofuran-7? 41-N-methylcarbamate (hereinafter referred to as "carbofuran") is known as an effective insecticide, but its practical use causes problems because very toxic to warm-blooded animals. If carbamate derivatives are obtained which have insecticidal activity similar to carbofuran but are less toxic to warm-blooded animals, very useful compounds will be obtained. In view of these considerations, the relationships between their insecticidal activity and their toxicity to warm-blooded animals have been synthesized and investigated. For example, in Belgian Patent 817 517 a

2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N, N-dibutylaminosulfenyl) -N-methylcarbamate, disclosed in German Patent Publication No. 2,254,359. and the preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-methyl-N-benzenesulfonylamino) sulfenyl] -N-methylcarbamate. unsatisfactory, poisonous to warm-blooded animals, fish and difficult to produce.

Extensive research has been carried out to develop carbamate derivatives which are non-toxic and easy to prepare.

It has been found that the compounds of formula I are suitable. In the formula (I):

R ^{1 and} R ² independently of one another may be -X-COOR ³ , wherein

--- X is C 1-5 alkylene and - R ³ is C 1-8 alkyl or C 3-6 cycloalkyl; flaunt '

Y-CN represents a group of the formula wherein

Y is C 1 -C 4 alkylene;

- R ² can also be C 1-10 alkyl, C 3-6 cycloalkyl, benzyl optionally substituted with halo or C 1-3 alkoxy, or phenyl optionally substituted with halo, C 1-3 alkyl or C 1-3 alkoxy; obsession

-ZR ₄ wherein

- Z represents a carbonyl or sulfonyl group, and

----- IV is C 1 -C 4 alkyl or phenyl optionally substituted by halogen, and benzyl, C 1 -C 4 alkoxy or phenoxy.

In the formula (I), the alkyl moiety in the alkyl, alkylene and alkoxy groups may be straight or branched

Compounds of formula (Γ), anw 'yek, are preferred

-R ¹ 'and R ² ' can be independently of one another

-X'COOR ³ 'in which

--X 'is a C 1-2 alkylene group.

and

R ³ 'is C 1 -C 4 alkyl, or

-Y'-CN represents a group in which

- Y 'is C 1-2 alkylene;

R ² 'may also be C 1-6 alkyl or C 3-6 cycloalkyl.

The compounds of formula (I) are new and have not yet been described in the literature; Compositions containing these novel compounds have been found to have significant insecticidal activity and are therefore well suited for use in controlling insecticides in agriculture and household, and to achieve the activity of carbofuran, which is the highest activity known to date. The compounds of the formula I are active against a variety of harmful insects, mites and nematodes, which damage plants, trees, fruits and humans, which are insects of the following families: Hemiptera, Lepidoptera, Coleoptera, Diptera, Thysanoptera, Orthoptera, Isopoda, Acarina, Tylenchida and others. Examples of insects, mites and nematodes include:

Hemiptera '

1. Deltocephalidae: Nephotettix cincticeps,

2. Delphacidae: Laodelphax striatellus,

Nilaparvan lugens,

3. Aphididae: Myzus Persicae, Aphis gossypii,

4. Pentatomidae: Nezara antennata, Nezara viridula, Lepidoptera

1. Noctuidae: Spodoptera Iitura, Agrotis fucosa,

Laphygma exigua,

2. Tortricidae: Adoxophyes orana,

3. Pyralidae: Chilo suppressalis, Ostrinia fumacalis,

Cnaphalocrocis medinalis,

4. Plutellidae.-Plutellaxylostella,

Coleoptera

(a) Curculionidae: Echinocnemus squaméus,

Lissorhoptrus oryzophilus,

2. Scarabaeidae.-Popilliajaponica,

3. Coccinellidae: Henosepilachna vigintioctopunctata, Diptera

1. Muscidae: Musca domestica,

2. Cecidonyiidae: Aspondylia sp.

3. Agromyzidae: Phytobia cepae,

Thysanoptera

Thripidae: Thrips tabaci, Scirtothrips dorsalis, Orthoptera

Gryllotalpidae: Gryllotalpa africana,

Isopoda

Armandillidae: Armadillidium vulgare,

Acaridea

Tetranychidae: Tetranychus teiarius, Tetranychus. urticae, Panonychus citri,

Tylenchida

Heteroderidae: Meoidoidne incognita.

Toxicity of the carbamate derivatives of formula I to carbofuran in warm-blooded animals 1 / 5-1 / 100

Part of -2188,690. The formulations containing the active compounds of formula (I) have insecticidal, miticidal and nematocidal activity against any of the above listed pests at any stage of their growth and are thus effective in agriculture, forestry and health.

Compounds of general formula (I) can be prepared very easily in an impure and high yield, economically, as described in more detail below.

Representative examples of the compounds of formula (I) and their preparation are described in Examples 1-54. are illustrated by Examples. Of these compounds, the following are particularly useful:

2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- [N, N-bis' - [ethoxycarbonylmethyl] sulfonyl] -N-methylcarbamate,

2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- / N-methyl-N-ethoxycarbonylaminosulfonyl-N-methylcarbamate,

2,3-dihydro-2,2-dimethyl-benzofuran-7-yl-N- / N-isopropyl-N-ethoxycarbonyl-ethylamine-sulfonyl-N-inethylcarbamate,

2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-butyl) -N-ethoxycarbonyl-ethylamino-sulfenyl-N-methylcarbamate .

2,3-Dihydro-2,2-dimethyl-benzofuran-7-yl-N- / N-cyclohexyl-N-ethoxycarbonyl-methyl-sulfonyl-N-methylcarbamate, 2,3'-dihydro 2,2-dimethyl-benzofuran-7-yl-N- / N- (n-butyl) -N-cyano-ethylamino-szulfeniV-N-methyl carbamate.

The compounds of formula (I) are prepared by reacting a compound of formula (II) with sulfur dichloride to form the 2,3-dihydro-2,2-dimethyl-benzo-furan-7-yl-N-formula (III). - reacting the (chlorosulfenyl) -N-methylcarbamate with an amine of the formula R ¹ and R ² as defined above.

Optionally, the compound of formula (II) is reacted with dichloromethane in a solvent. Suitable solvents are, for example, dichloromethane ^J , chloroform, tetrachloromelane, diethyl ether, dibutyl ether, tetrahydrofuran and other ethers. The proportion of sulfur dichloride in the compound of formula (II) is undetermined and can be varied accordingly. . Usually 1 to 2 moles, preferably 1 to 1.2 moles, of sulfuric dichloride ^U are used for 1 mole of compound (II), preferably in the presence of a base.

Suitable basic compounds such as triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine and the like, tertiary amines, pyridine, ⁴ Ο, β, γ-picoline, lutidine and others. The base must be present in an amount sufficient to bind the hydrogen chloride formed as a by-product of the reaction. Usually 1-2 moles of base are used per mole of compound θ (II). The reaction, which takes place under cooling at ⁰ ° C, at room temperature and under heating, is usually carried out at a temperature of -70 ° C to 50 ° C, preferably -10 ° C to 30 ° C.

The reaction time is about 2-7 hours, preferably 3-5 hours. The compound of formula (III) is then reacted with the amine of formula (IV).

The secondary amines of formulas (V) to (IX) may be used as amurals of formula (IV):

<X COOR ³

R

Y-CN

HN <5 *

R> 0 (V) (VI)

HN

NH <5

X-COOR ³ (VII)

X "-COOR"

X-COOR ³ (VIII)

Y-CN

Y ~ CN

In the formulas (V) to (IX), X, Y and R ³ are as defined above, - R is C 1 -C 10 alkyl,

C 3-6 cycloalkyl, optionally substituted benzyl by halogen or C 1-3 alkoxy, phenyl optionally substituted by halogen, C 1-3 alkyl or C 1-3 alkoxy; obsession

Zab powder of formula Z-R ^{4 in} which

- Z 'represents a carbonyl group, a sulfonyl group, and - the presence of R ⁴ ' represents a C 1 -C 4 alkyl group optionally substituted by a halogen atom, or a phenyl group, a benzyl group, a C 4 -C 4 alkoxy group or a phenoxy group;

- R ³ 'has the same meaning as R ³ ;

- X 'has the same meaning as X and

- Y 'has the same meaning as Y].

Representative of the antins of formula (V) are the following compounds: N-methylglycine methyl ester, N-methylglycine ethyl ester, N-methylglycine butyl ester, N-ylylglycine ethyl ester, N-propylglycine ethyl ester, N-isopropylglycine ethyl ester, Nn-butylglycine ethyl ester, N-isobutylglycine ethyl ester, N-scc butylglycine ethyl ester, Nn-octylglycine ethyl ester, N-cyclohexylglycine ethyl ester, N-benzylglycine ethyl ester, N- (4-methylbenzyl) glycine ethyl ester, N- (4-chlorobenzyl) glycine ethyl ester, N-methyl-glycine ethyl ester, N- (3-methylphenyl) glycine ethyl ester, N- ( 4-methoxyphenyl) glycyl ethyl ester, ethyl N-methylaninopropionate, ethyl N-propylaminopropionate, methyl N-isopropylaminopropionate, ethyl N-isopropyl- aminopropionate, butyl N-isopropylaminopropionate, 2-ethyl-β-xyl-N-isopropyl-aminopropionate, methyl-Nn-bulyl-amyl-propionate, ethyl-Nn-butyl-anrin-propionate, ethyl- N-isobutyl allo-propionate, e. butylaminopropionate, ethyl-N-tert-butylaminopropionate, ethyl-Nn-amylaminopropionate, ethyl-N-isoamylaminopropionate, ethyl-Nn-butylaminopropionate, ethyl- N-cyclohexylaminopropionate, N-acetylglycine ethyl ester, N-chloroacetylaminoglycine ethyl and / or, N-propionoylglycine ethyl and tert, N-benzoyl ethyl glyceryl, N- (4-chlorobenzoyl) glycine ethyl ester, N-tosylglycine ethyl ester.

Representative of the amine compounds of formula (VI) are the following compounds: N-roethylaminoacetonitrile, N-ethylaminoacetonitrile, Nn-propylimino-acetonitrile, N-isopropopropylaminoacetonitrile, Nn-butyl- aminoacetonitrile, N-isobutylaminoacetonitrile, N-benzylaminoacetonitrile, N-phenylaminoacetonitrile, N- (4-n-butylphenyl) -aminoacetoylitrile, N-methylamino-pro3

-3188,690 pionitrile, Ν-n-propylaminopropionitrile, N-isopropylaminopropionitrile, Nn-butylaminopropionitrile, N-isobutylamine-propionitrile, N-sec-butylaminopropionitrile, N -octylaminopropionitrile, N-cyclohexaminopropionitrile.

Representative amines of formula (VII) include the following compounds: methyliminodiacetate, ethyliminodiacetate, isopropyliminodiacetate, cyclohexyliminodiacetate, methyliminodipropionate, ethyliminodipropionate, N-. methoxycarbonylglycine ethyl ester, N-ethoxycarbonylglycine ethyl ester, N-phenoxycarbonylglycine ethyl ester, e-Nethoxycarbonylmethylaminopropionate , ethyl 4- (ethoxycarbonylmethylamino) butyrate, ethyl 2-ethoxycarbonylmethylamino) butyrate, ethyl N-ethoxycarbonylaminopropionate.

Representative amines of formula (VIII) include the following compounds: methyl N-cyanomethyl carbamate, ethyl N-cyanomethyl carbamate, ethyl N-cyanoethyl carbamate, N-cyanomethyl glycine. ethyl ester, N-cyanoethylglycine ethyl ester, ethyl N-cyanomethylaminopropionate, ethyl N-cyanoethylaminopropionate.

Representative amines of formula IX include the following compounds: iminodiacetonitrile, iminodiopropionitrile, iminodibutyronitrile.

The compound of formula (III) is reacted with an amine of formula (IV) optionally in the presence of a solvent. Any solvent suitable for the reaction of the compound of formula II with sulfur dichloride may be used. The ratio of the compound of formula (III) to the amine is undetermined and can vary widely. Usually 1 to 2 moles, preferably 1 to 1.2 moles, of amine are used per 1 mole of compound (III). The reagents are preferably conjugated in the presence of a base, which may be any of the bases mentioned above. The base is used in an amount sufficient to absorb the hydrogen chloride formed as a by-product of the reaction. The amount of base used is 1 to 2 mol, preferably 1 to 1.5 mol, based on 1 mol of compound (III). The reagents may be reacted with cooling, at room temperature or with heating, typically at -20 ° C to 50 ° C, preferably 0 ° C to 30 ° C. The reaction time is about 10 to 15 hours,

The compounds of formula (I) which are useful as active ingredients in the compositions of the present invention are isolated and purified by conventional means such as solvent extraction, recrystallization or chromatography.

Formulations of the invention containing the compounds of formula I as active ingredients are emulsions, wettable powders, suspensions, concentrated suspensions, granules, fines, pellets, powders, coated compositions, sprays, aerosols, microcapsules, natural or synthetic impregnating agents. Suitable products include, for example, incense agents, concentrated preparations for use in small amounts.

Various surfactants are used to form emulsions, dispersions, suspensions, and foams. Nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, sorbitan alkyl esters and the like. Anionic surfactants include, for example, alkyl benzene sulfonates, alkyl ether sulfonates, alkyl naphthalene sulfonates, lignin sulfonates.

Solvents, diluents and carriers useful in the preparation of the compositions of the present invention include various organic solvents, aerosol propellants, natural minerals, plant materials, synthetic compounds, and the like. Preferred organic solvents include benzene, toluene, xylene, ethylbenzene, chlorobenzene, alkylnaphthalenes, dichloromethane, chloroethylene, cyclohexane, cyclohexanone, acetone, methylethylketone, iethylisobutyl ketone, alcohols, dimethyl- formamide, dimethyl sulfoxide, acetonitrile, petroleum fractions. Preferred aerosol propellants include propane, butane, halogenated hydrocarbons, nitrogen, and carbon dioxide. Examples of natural minerals include kaolin, talc, bentonite, diatomaceous earth, clay, montmorillonite, limestone, chelate, pumice and dolomite, and others. Useful plant materials include powdered coconut shells, tobacco stalks, and sawdust. Suitable synthetic compounds are alumina, silicates, sugar polymers. Adhesives may also be used, such as carboxymethyl cellulose, arabic gums, polyvinyl alcohol, polyvinyl acetate and the like. The compositions may be colored with organic or inorganic dyes.

The compounds of formula (I) are present in the various formulations of the present invention in an amount sufficient to control insect, acarid and nematode activity. The amount of active ingredient in the compositions of the invention is from about 0.1% to about 95% by weight, preferably from about 0.5% to about 90% by weight. Depending on the mode of administration, formulations may be used or formulations diluted with water or vehicle.

The agents of the present invention and the preparation of the active ingredient are illustrated in detail in the following examples.

Example 1

Preparation of 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-N- [N, N-bis (cyanomethyl) aminosulfonyl] -N-methylcarbamate g (0.05) mole) 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N-methylcarbamate was dissolved in 70 ml of methylene chloride and 5.2 g (0.05 mole) of sulfur was added under cooling. dichloride and then 5 g (0.05 mol) of triethylamine was added dropwise at 0 ° C. After stirring at this temperature for 2 hours, a solution of 4.8 g (0.05 mol) of iminodiacetonitrile in 40 ml of tetrahydrofuran is added dropwise at the same temperature, and triethylamine (5 g, 0.05 mol) is added dropwise. The resulting mixture was stirred at 0 ° C for 4 hours and then allowed to stand overnight at room temperature. Dichloromethane (100 mL) was added and the reaction mixture was stirred three times with 100 mL of CH2Cl2. The dichloromethane layer is dried and then concentrated in vacuo to give an oil which is the title product, although it contains small amounts of starting materials.

Yield: 13.8 g (79, 8% of theory).

Part of the product was purified by silica gel column chromatography using a 4: 1 by volume mixture of benzene and ethyl acetate to give a crystalline product having a melting point of 94-95 ° C.

NMR in chloroform: d:

δ! , 48 ppm (s, 611) δ 3.02 ppm (s, 2H) δ 3.50 ppm (s, 3H) δ 4.32 ppm (s, 4H) δ 6.6 7.2 ppm (m, 311 )

188,690

Elemental Analysis for C ₁₆ H ₁₈ N ₄ O ₃ S [t%] (MW 346.418) found% C 55.36; H5,31; N, 16.05;

Found:% C, 55.48; H5,24; N, 16.17.

The product obtained is of formula (1).

Example 2

Preparation of 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-N- [N, N-bis (ethoxycarbonylmethyl) amino sulfonyl] -N-methylcarbamate g (0 (05 mol) 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N-methylcarbamate was dissolved in chloroform (50 ml) and sulfur dichloride (5.2 g, 0.05 mol) was added. with cooling at 0 ^u C, 5 g (0.05 mol) of triethylamine are added dropwise. The mixture was stirred at this temperature for 2 hours and a solution of ethyl iminoacetate (9.5 g, 0.05 mol) in chloroform (20 ml) and triethylamine (5 g, 0.05 mol) was added dropwise at the same temperature. The resulting mixture was stirred at 0 ° C for 2 hours and then allowed to stand overnight at room temperature. Chloroform (100 mL) was added and washed with water (3 x 100 mL). The chloroform layer was dried and concentrated in vacuo to give an oil which was almost entirely the title compound but also contained small amounts of starting material. Yield 15.9 g (72.3% of theory).

A portion of the product was identified by silica gel column chromatography using a 4: 1 by volume benzene / ethyl acetate mixture as an oil.

NMR in chloroform-dj δ.1.24 ppm (t, 6H) δ 1.48 ppm (s, 6H) δ 3.02 ppm (s, 2H) δ 3.42 ppm (s, 3H) δ 4.20 ppm (q, 4H) δ 4.28 ppm (s, 4H) δ 6.6-7.2 ppm (m, 3H)

Analysis for C α H _{2 O 2} g of the N ₂ O ₇ S Calcd Found [% by weight] (molecular weight 440.526) value% C 54.68; H6,46; N, 6.38.

Found:% C, 54.53; H6,41; N, 6.36.

The product corresponds to formula (2).

Examples 3-5

The compounds listed in Table 1 were prepared as described in Examples 1 or 2. In the table, besides the exemplary number, the starting amine and the R ¹ and R ² substituents of the product are given in the formula (Ϊ), their physical characteristics and their NMR data (chloroform-d).

188,690

Example A Amine R ¹ R ² H-NMR [S, (ppm) in CDCl ₃ ] Elemental analysis number Experimental formula

Found value

Sz cn ch vo r * <Γ \ o

Ch oo ví <n r-4 Π τ-H rí rí £

.cn cn t

while c «z

<M

SS ts

ΌΟ0 üOp in * r · * O \ σ \ οο <Ö> O m O cn ^ t <0 'kO

X \ C> X rí £ cn ^ .. ~ rn X X c Χ Μ · χ £, £ stone £ stone ~ s \ ►lH PM CN 5Z) GFL w? 'SSF's IRI ^ T3 Vi r. sw / r- rí F < cn stone , cn p. r ^ cn CN p 1 "H cn cn ' cn Tt Vol t-M v-t cn lake lake lake tototo lake lake lake

m <Ch in cn ro

C4 z

She

T ·

X e »

CJ σ> <n cn cn n

cn ch

CN

££ 33 She £ ι-h CG CJ CN £££ s £ XX ££ J. cn Ό CN cn Tt wT cs CA tA r. r. T "4 tA water * · r- Cl CNkO i 1 1 00 <N cn oo 1 Ttríjnp She. * fr o. Tt ^ r ^ tn ^ cn Tt Tt d '-Γ cn cn Tt Tt * to tototo lake to <o to <O to

cn in

188,690

Example 6

Preparation of 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl] -4NN'-bis (ethoxymethylcarbonylethyl) aminosulfenyl] -N-methylcarbamate g (0.05 mol) 2,3-dihydro -2,2-Dimethylbenzofuran-5-7-yl-N-methylcarbamate is dissolved in 70 ml of dichloromethane and 5.2 g (0.05 mol) of sulfur dichloride are added under cooling, followed by -10 ° C. 5 g of triethylamine are added dropwise between -5 ° C and -5 ° C. The mixture was stirred for 1 hour at 0 ° C and for 2 hours at room temperature. The mixture was then cooled to -10 ° C to -5 ° C and diethyliminodipropionate (10.9 g, 0.05 mol) was added dropwise followed by triethylamine (5 g, 0.05 mol). The resulting mixture was stirred at 0 ° C for 2 hours and then allowed to stand overnight at room temperature. Dichloromethane (100 mL) was added and the reaction mixture was washed with water (3 x 100 mL). The dichloromethane layer is dried and concentrated in vacuo to give an oil which is the title compound but also contains small amounts of impurities. 20

Yield: 16.9 g (72.2% of theory).

A portion of the product was identified by silica gel column chromatography (5: 1 v / v benzene / ethyl acetate) to give an oil. 25

NMR. (chlorolormane-d)) δ 1.21 ppm (t, 611) δ 2.67 ppm (t, 4II) δ 3.37 ppm (s, 3H) δ 4.04 ppm (q, 4H) δ 1.44 ppm (s, 6H) δ 2.97 ppm (s, 211) δ 3.42 ppm (t, 4H) δ 6.5-7.2 ppm (ni, 3H)

Elemental Analysis for C ₂₂ H ₃₂ N ₂ O ₇ S [t%] (molecular weight 468.58) found% C 56.26; H6,91; N, 5.52;

Found:% C, 56.39; H6,88; N, 5.98.

The product corresponds to formula (3).

Example 7

Preparation of 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-N- [N, N-bis (cyanoethyl) aminosulfenyl] -N-methylcarbamate. (05 mol) 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N-methylcarbamate was dissolved in 50 ml of chloroform and 5.2 g (0.05 mol) of dichloride, at a temperature between-10 and ^U-5 ° C and triethylamine (5 g, 0.05 mol) was added dropwise. The mixture was stirred at 0 ° C for one hour and then at room temperature for another hour. The reaction mixture was cooled to -10 ° C to -5 ° C and 6.2 g (0.05 mol) of iminodipropiononitrile and 5 g (0.05 mol) of triethylamine were added dropwise. The resulting mixture was stirred at 0 ° C for 2 hours and then allowed to stand overnight at room temperature. Chloroform (100 mL) was added to the reaction mixture, followed by washing with water (3 x 100 mL). The chloroform layer was dried and concentrated in vacuo to give an oil which was almost entirely the title product but also contains minor impurities Yield 12.2 g (65.2% of theory).

A portion of the product was identified by silica gel column chromatography (4: 1 v / v benzene / ethyl acetate) to give an oil.

Nuclear Magnetic Resonance Spectrum (CHCl3) δ 1.43 ppm (s, 6H) δ 2.97 ppm (s, 211) δ 3.43 ppm (t, 4H)

Elemental analysis δ 2.73 ppm (t, 4H) δ 3.37 ppm (s, 3H) δ 6.5-7 ppm (m, 3H) for Cj _k 11 _{2 2} N ₄ O ₃ S (molecular weight 374.47) a) low value% C 57.91;

Found:% C, 57.73;

The product corresponds to formula (4).

H5,79; NI5,04; H5,92; N, 14.96.

-11. example

The compounds listed in Table 2 were prepared as described in Example 6 or Example 7. In the table, exemplified by, exemplified by, the number of substituents R ¹ and R ^{2 in place of the} compound of formula (I) and in addition to the amine are given. NMR data (chlorophyll-d |) and elemental analysis from empirical formula.

188,690 cu

The example is Amin R ¹ . R ² H-NMR [δ value, (ppm) in CDCl ₃ ] Elemental analysis _____ 'Τ ο «« m4 η ΐ ot <

• <U '' C

G3

N «Λ

O <Z5 <N <© r ~,

Ο m cfo in Ό O. ~ kO 'χΟ

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o <n z

m n

K o \ cn

C \ »- <00 C5

C-Q 'O in

X m

oo 3? <T> m m tt- I rr ο I oo ο i

Tf M3 O Tf ~ ογ rr <O - <rr rrT co rn Tf Tf \ o <©> © <© 4 © 4 © CO 4 © 4 ©

UO

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SHE

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you

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188,690

Example A Amine R ¹ R ² H-NMR [δ, (ppm) in CDCl ₃ ] Elemental analysis number Experimental formula

Value found e

S z x

uo $$ rq oc o \

UO 00 <Λ ro

Ct% {»1 G \ m x Z ct ct u

xt o O \ rf

IZ> c- SHE cl z Z * s ct 00 She\ C- 00 ^ X ct cl u dif QI ·

co © ιζγ xt

M3 \ O V0 ^ 0 x

co x Β E

Cl C4 £ Λ CFÍN

Γ · xt in | t-h «ζγ ιζγ xt xt χΟ 60 to

X xt

X co

X cs

X X

C- ro + -J ΕΛ Ά cfl '+ - Ο],'--'—' _{r |} -_- - '-. '-''-' f ».

cs in I o vi rs co v-ι c- I CS rf c ^ C3 Γ0 tT T-J,

-ί ή - m rr, <r, rí -t ú e COCOíOí-OCOtOí-OtOCCs ^ O

Oh o

o u

n

X

Q

I «η

X ci <_>

o o

u ct

X u

-root

Q et

X

X ct

Q o

o u

cl

X <y

ct

X o

ct

X υ

UO

o <u>

ct

X d

'sX o

ci c

SHE

Oh o

cl

X c

X ct «& x S

X «uX X Ξ x'x 'E E

CO Ό Cl ro ♦ J {Λ yj uo ^ c {rq tí- cco co I rq oo I 1 rq ^ xt ^ νγ o co mo »ζγ

Τ-Γ 1-s 1-I co CT) fCi ”kO to 6Q« 0 60 to 60 60

J1 X X η c. n Q She X She She She She CJ ct υ n X X X <_> - • υ (_>

188,690

Example 12

Preparation of 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-4 - [[N-butyl-N-butoxycarbonylaminosulfenyl] -N-methylcarbamate g (0.05) mole) 2,3-Dihydro-2,2-dimethylbenzofuran-5-7-yl-N-methylcarbamate was dissolved in 70 ml of methylene chloride and 5.2 g (0.05 mole) was added thereto under cooling. sulfur dichloride was added and 5 g (0.05 mol) of triethylamine was added dropwise at -10 ° C to -5 ° C.

The mixture was stirred at 0 ° C for 1 hour and at room temperature for 2 hours, then cooled to 40 ° C to -5 ° C, dropwise with 8.0 g (0.05 mol) of N-butylglycine. ethyl ester was added 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 allowed to stand overnight at room temperature. Dichloromethane (100 mL) was added to the reaction mixture and washed with water (3 x 100 mL). The dichloromethane layer was dried and evaporated in vacuo to give an oil which was the title compound, albeit with a small amount of impurities.

Yield: 15.7 g (76.6% of theory).

Part of the product was purified by chromatography on a silica gel column using a 4: 1 by volume mixture of benzene and ethyl acetate to give an oil.

NMR (in chloroform-d ₍ )

S0.6-1.9 ppm (m, 7H) δ 1.44 ppm (s, 611) δ 3.30 ppm (t, 2H) δ 4.14 ppm (s, 2H) δ 6.5-7, 2 ppm (m, 3H) δ 1.22 ppm (t, 3H) δ 3.03 ppm (s, 211) δ 3.42 ppm (s, 3H) 30 δ 4.13 ppm (q, 2H)

Elemental analysis value is C ₂₀ H _{3 (N 2} O ₅ S Calcd (molecular weight 410.54) found [wt%] C 58.39%; H7,41; N, 6.75;

Found:% C, 58.52; H7,37; N6,83.

The product corresponds to formula (5).

Example 13

2,3-Dihydro-2,2-dimethyl-benzofuran-7-yl-N- [N-phenyl ·

Preparation of -N-ethoxy-4-arbonylmethylaminosulfenyl] -N-methyl-arbamate 2,3-dihydro-2,2-dimethylbenzofuran-7-yl49-methylcarbamate (~ 11 g, 0.05 mol) Dissolve in 70 ml of dichloromethane and add 5.2 g (0.05 mole) of sulfur dichloride while cooling and add 5 g (0.05 mole) of triethylamine at -10 ° C to -5 ° C. . The mixture was stirred at 0 ° C for 1 hour and at room temperature for 2 hours and then cooled to -10 ° C to -5 ° C. N-Phenylglycine ethyl ester (9 g, 0.05 mol) and triethylamine (5 g, 0.05 mol) were then added dropwise. The resulting mixture was stirred at 0 ° C for 2 hours and then allowed to stand overnight at room temperature. Thereafter, 100 ml of dichloroethane are added and the mixture is washed three times with 100 ml of water each. The dichloromethane layer was dried and concentrated in vacuo to give an oil. To the oil was added a 1: 1 mixture of benzene-hexane to give a crystalline product which was isolated by filtration and concentrated to the mother ligof. At this time, an oil was again obtained which was cooled to give crystals again. These crystals were combined and recrystallized from diethyl ether to give white crystals.

Yield: 13.4 g (62.3% of theory).

M.p. 92-93 ° C.

NMR (in chloroform-d,) δ 1.15 ppm (t, 3H) δ 3.00 ppm (s, 2H) δ 4.12 ppm (q, 211) δ 6.5-7.5 ppm (ni, 811 )

Elemental Analysis for: γ C-2 21 h <, hk O ₅ .3 (molecular weight 430.53) found% C 61.11;

Found:% C, 61.38;

δ 1.46 ppm (s, 6H) δ 3.32 ppm (s, 3H) δ 4.76 ppm (s, 2H) | t%]

H6,15; N, 6.49.

H6,09; N6.51.

The compound thus obtained corresponds to the key (6).

14-32. example

The compounds shown in the table are prepared as described in Table 12 or

The method described in Example 13 was prepared. Apart from the example compound, the amine used, the R ¹ and R ² substituents of the compound of formula I, the NMR values (chloroform-dj) and other physical constants are given.

-101

188,690

X

The Example Amine ^A R R ² H-NMR [S value (ppm) in _CDCl3] Analysis Empirical Formula ID

Value found (Calculated value)

CM u

o o

CM

X o

0Ί r-Η

NO Tf in «n ~ in irt c- pt« o i i Ch CO NO NO r ~ xr

CO

X

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E

Q

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in ri »- <» - «r-í 'M' Ό m in cZ and in o

CM z

ir> »rí cn γ-Λ ^ in n oo'oo in m t-M cn £ Γχχ xlx 6 η π s R

Z «<'ΖΛ

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\ z

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Z Z T * rr> / O ~. & w.

co ^^ roo r *> xr Ch! ο Γ4 I »-r χζ Ch CN <O O / n

V — 1 r-M o cn <Λ xt xt NO {O <C to <O co <O

X XX Es m no γι'— + - »Z σι 'CO σι

CO CC ¢ / 3

EC Z

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Δ 4.03 (s, 2H) δ 4.08 (q, 2H1 δ 6.7-7.1 (m, 31

-111

188,690

Example A Amine R ¹ R ² H-NMR [δ, (ppm) in CDCl 3] Elemental analysis number Experimental formula

Found value (Calculated value) Kö nO

CM Pp NO \ O cn O NO cn NO no o \ <n NO cc <X3

V »o

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3.0-3.5 (m, 3F) 5 3.31 (s, 3H)

3.51 (s, 3H)

6.5-7.1 (m. 3H)

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-131

188,690

Table 3 (continued)

Example A Amine R ¹ R ² H-NMR Good value (p_pm) in CDCl ₃ J Elemental analysis number Experimental formula

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-161

188,690

Example 33

Preparation of 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl4M-N-biphenyl-N-cyanomethylamide sulfenyl] -N-methylcarbamate g (0.05) mole) 2,3-dihydro-2,2-dimethylbenzofuran-5-7-yl-N-methylcarbamate was dissolved in 70 nd methylene chloride and 5.2 g (0.05 mole) was added while cooling. sulfur dichloride was added followed by dropwise addition of 5 g (0.05 mol) of triethylamine at -10 ° C to -5 ° C. After stirring at 0 ° C for 1 hour and at room temperature for 2 hours, the mixture was cooled to 10 ° C to -5 ° C and 5.6 g (0.05 mol) of N-butylaminoactonitrile were added dropwise, then 5 g (0.05 mol) of triethylamine was added dropwise. The resulting mixture was stirred at 0 ° C for 2 hours and left to stand at room temperature overnight. Dichloromethane (100 mL) was added to the reaction mixture and washed with water (3 x 100 mL). The dichloromethane layers were dried and concentrated in vacuo to give an oil which is the title product but also contains small amounts of impurities.

Yield 13.0 g, 71.4% of theory)

To identify the products, it was purified by column chromatography on a -y · '· silica gel column. sulfur 5; A mixture of benzene and ethyl acetate (1 volume) was stirred at room temperature to give an oil. NMR (chloroform-d _') fi 0.7-2.0 ppm (m, 7H) δ ppm 2.92 (s, 2H) δ 3.33 ppm (s, 3H), δ 6.5-7.1 ppm (ni, 3H)

Δ 1.42 ppm (s, oil) δ 2.9-3.5 ppm (in, 211) δ 4.01 ppni (s, 211)

Elemental analysis for C, gfl ₂ sNjOjS ft% | j (after weight 3x3.488) found% C 59.19; H, 7.02;

Found:% C, 59.48; H, 6.93;

Compound el corresponds to formula (7).

N, 11.69; N, 11.56

34-42. example

The compounds shown in the table were prepared as described in Example 33. In the table with my example, something like that. R ¹ and R ^{2 are} compounds of formula (1). in addition to the rackets, physical data and NMR (chloroform-di) values are given.

-171

188,690

Example A Amine R ¹ R ² H-NMR [S, (ppm) in CDCl 3] Elemental analysis number Experimental formula

Value found (Calculated value) ____'_ C (%) H (%) N (% 'π

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-191

188,690

Example 43

Preparation of 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-N- [N-propionyl-N-ethoxycarbonylmethyl-aminosulfenyl] -N-methylcarbamate A solution of 2,3-dihydro-2,2-dimethylbenzofuran-5-7-yl-N-methylcarbamate (05 mol) in dichloromethane (70 ml) was cooled to 5.2 g (0.05 mol). sulfur dichloride was added and 5 g (0.05 mol) of triethylamine was added dropwise at -10 ° C to -5 ° C. The mixture was stirred at 0 ° C for one hour at room temperature for 2 hours and then cooled to -10 ° C to -5 ° C and 8 g (0.05 mol) of N-propionylglycine ethyl ester were added. of tetrahydrofuran (5 ml.) and triethylamine (5 g, 0.05 mol) was added dropwise. The resulting mixture was stirred for 2 hours at 0 ° C and allowed to stand at room temperature overnight. Dichloromethane (100 mL) was then added to the reaction mixture, which was washed with water (3 x 100 mL). The dichloromethane layer was dried and concentrated in vacuo to give an oil, which is the title product but also contains small amounts of starting materials and impurities. Yield: 14.3 g (69.8% of theory).

Part of the product was purified by column chromatography on silica gel using a 9: 1 mixture of benzene and ethyl acetate as the solvent. A crystalline material is obtained, m.p. 108-10 ° C.

NMR (in chloroform-di)

1.14 ppm (t, 3H) δ 1.49 ppm (s. 6H) δ 3.02 ppm (s, 211) δ 4.15 ppm (q, 2H) δ 6.6 - 7.1 ppm (in, 311)

Analysis for the C ₁₉ H ₂₆ N ₂ O _b S calcd found (molecular weight 410.499) value% C 55.35;

Found:% C, 55.59;

The product corresponds to formula (8).

δ 1.23 ppm (t, 3H) 30 δ 2.7 3.3 pp.m (m, 2H) δ 3.48 ppm (s, 3H) δ 4.50 ppm (s, 2H)

11% 1

H6.41; N, 6.77. H, 6.38; N, 6.82.

Example 44

Preparation of 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-N- [N-ethoxycarbonyl-N-ethoxycarbonylmethyl-aminosulfenyl] -N-methylcarbamate g. 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-N-methylcarbamate (0.05 mol) was dissolved in dichloromethane (70 ml) and cooled to 5.2 g (0.05 mol). dichloromethane and 5 g (0.05 mol) of triethylamine is added dropwise at -10 ° C to -5 ° C. The mixture was stirred at 0 ° C for 1 hour and at room temperature for 2 hours and 8.8 g (0.05 mol) of N-ethoxycarbonylglycine ethyl ester followed by 5 g (0.05 mol) of triethyl -what we drop at it. The resulting mixture was stirred at 0 ° C for 2 hours and allowed to stand overnight at room temperature. Dichloromethane (100 mL) was added and the reaction mixture was washed with water (3 x 100 mL). The dichloromethane layer is dried and concentrated in vacuo to give an oil which is the title product but also contains small amounts of starting materials and impurities.

Yield: 18.2 g (84.7% of theory).

A portion of the product was identified by silica gel column chromatography using a 4: 1 by volume mixture of benzene and ethyl acetate as an oil. NMR (in chloroform-d,) δ 1.17 ppm (t, 611) δ 2.94 ppm (s, 211) δ 4.05 ppm (q, 211) δ 4.41 ppm (s, 211) δ 1.44 ppm (s, 6H) δ 3.4] ppm (s, 3H) δ 4.15 ppm (q, 2H)

Δ 6.5-7.0 ppm (m, 3II)

Elemental Analysis for C ₉ H ₂₆ N ₂ O ₇ S found% C 53.82; H6,19; N, 6.44;

calculated% C 53.51; H, 6.14; N, 6.57. The product corresponds to formula (9).

45-54. example

The compounds listed in Table 5 were prepared as described in Examples 43 or 44. In my example. in addition to the starting amine, the physical constants and NMR values (chloroform-d,) in addition to the R ¹ and R ² substituents of the compound of formula (I).

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188,690

The following are some examples of formulations that are valid for the active ingredients described above and are adapted to each application. These specifications are, of course, for information only and the proportions of the active compounds, organic solvents, surfactants and carriers may be varied as desired. In some cases, organic solvents, surfactants, carriers, and other ingredients may also vary. Percentages are by weight / percent.

Formulation Example 1: 60% emulsion in beaker. The mixture is then gently punctured, simply slugged or ball milled to obtain a powder of the appropriate particle size.

The compound of Example 25 is either 60.097 the compound of Example 23 nonylphenol-poly (ethylene glycol) - 15 -ether (EO: 4 15) 10.097 xylene 30.0% 2. Preparation Example 509f emulsion 20 The compound of Example 12 is either 50.097 the compound of Example 14 poly (oxy-etilcn) sorbitol; tendon monooleáf 6.5% · (Tween 81, fILB: 10) 25 sorbitan monooleate 3,597 xylene 30.0% cyclohexanone 10.0% 3. Preparation Example Example 2097 emulsion 30 The compound of Example 22 is either 20.097 Example 27 poly (oxy-e-ethylene) lauryl ester 5.0% 9.5) xylene 45.0. 35 petrolélci 30.0% 1-3. for each of their preparation examples the ingredients are evenly mixed. 4. Preparation Example 4Π 90% wettable powder HU The compound of Example 1 is either 90.0% Compound according to Example 2 sodium lignin / sulfonate 3.0% clay 7.0% 45 5. Preparation Example 5097 wettable powder 2l. or a compound of Example 50.0% · the compound of Example 32 C2-C18 alcohol sulfate 30.0% · · 50 naphthalenesulfonic acid / formaldehyde kondenzátuni 10.097 di (2-ethylhexyl) phosphate 5.5% kaolin 3.5%. · t-dkum 1.0% 55 6. Preparation Example 3097 wettable powder Example 30 30.097 alkyl into, i zol s ζι 11 background 3.097 80 twice with sodium ligninsulfonate 2.0%. it is soot 35.0%. clay 50.097 4 -6. each of the preparation examples the soul of the creator

parts are evenly distributed over a Shinagawa type 24

Formulation Example 5% powder

Vegyület Example 46 5.0% diatomaceous earth 10.0% talc 85.0% 8. Preparation Example 2% powder Preparation Example 5 wettable powder 4.0% clay 95.8%. isopropyl phosphate 0.297 Preparation Example 0.5% powder Example 6 of Preparation Preparation wettable powder 1.7% clay 100.397 7-9. preparation examples For each of the ingredients are evenly mixed with a Shina- 'Awí · type mixer. ! 0th Preparation Example 20%. os granules In the preparation of Preparation Example 5, rint wettable powder · 40.0% dolomite 60.0%. These ingredients are thoroughly mixed together and 15 parts by weight of 297 per 100 parts by weight of the mixture carboxymethylcellulose solution was added and the san mix. It is then granulated and chop it. then dried. 11. Preparation Example 10% granulate Compound according to Example 40 10.097 sodiun dodecyl sulfonate beuzol 0,597 Sodium ligninsulfonate 2.0% diatomaceous earth 27.5% bentonite 60.0%.

These are the ones. the ingredients are evenly mixed and water added, and again thoroughly mixed, granulated in a granulating machine. The granulated products are flattened and dried.

Example 12 of prestressing

3% granulate

Example 8 Compound 3.097 Polyvinyl Alcohol 3.0%.

. clay 94.0% ·

All granules. in a formulation preparation example.

The compositions of the invention will now be further illustrated by means of experimental examples.

Experimental Example J.

The larval forms of tobacco-damaging bagolypille (Spodoptera iitura) were placed on a pot planted cabbage plant (a one-month-old plant) and the leaves of the plant were incubated with aqueous emulsions of the test composition diluted in 50% emulsion of the young material. The leaves were sprayed with emulsions until they dropped off. Three days after treatment, we examined how many larvae died. The results are given in Table 6, where a

-24 with untreated and control groups.

Table 6

Destruction 7 / a *

The serial concentration of the viral concentration in ppm is' ............

2000 1000 500 uh, 100 80 65 Second 100 70 60 Third 100 80 65 4th 100 70 60 5 .. 100 80 65 6th 100 75 60 7th 100 75 60 8th 100 80 75 9th 100 90 80 10th 100 85 75 11th 100 80 70 12th 100 90 75 13th 100 90 75 14th 100 90 75 15th 100 90 75 16th 100 85 65 17th 100 80 60 18th 100 90 75 19th 100 85 65 20th 100 85 65 21st 100 90 75 22nd 100 85 65 23rd 100 85 70 24th 100 85 75 25th 100 90 75 26th 100 80 60 27th 100 90 75 28th 100 90 75 29th 100 80 60 30th 100 85 65 31st 100 80 60 32nd 100 85 65 33rd 100 90 75 34th 100 90 75 35th 100 80 65 36th 100 80 65 37th 100 85 70 38th 100 90 75 39th 100 90 75 40th 100 85 75 41st 100 80 65 42 100 85 70 43rd 100 85 70 44th 100 90 75 45th 100 90 75 46th 100 85 70 47th 100 80 65 48th 100 80 65 49th 100 90 75 50th 100 80 65 51st 100 85 70 52nd 100 85 70 Take control ^! 80. 60 35 untreated 0

Control used: 1-naphthalene-N-methylcarbamate.

experimental example

50% wettable powder containing the test compound was formulated into emulsions of various concentrations and sprayed on the leaves of rice plants (one-month-old seedlings) grown in bowls. After drying of the periwinkle, the plates were covered with mesh and 10 adult female green rice leaf grasses (Nepholettix cincticcps) were placed in each. Each concentration was assayed using a light dish. Three days after treatment, dead insects were counted and the results are shown in Table 7, which is shown as control groups. and the results obtained with untreated groups for comparison '.

Table 7% of deaths

gonad Substance Concentration in ppm soo 400 200 i. 100 85 50 ··> 100 85 45 Third 100 85 45 4th 100 70 40 5th 100 80 45 6th 95 75 55 7th 90 70 50 8th 95 85 60 9th 100 90 60 10th 100 90 60 11th 95 80 55 12th 100 90 65 13th 100 90 65 14th 100 90 65 15th 100 90 65 16th 100 90 65 17th 95 75 55 18th 100 90 65 19th 100 • 80 60 20th 100 80 60 21st 100 90 65 22nd 100 80 60 23rd 100 85 55 24th 100 90 60 25th 100 90 65 26th 100 75 55 27th 100 90 65 28th 100 90 65 29th 100 75 45 ' 30th 100 80 60 31st 100 75 55 32nd 100 75 55 33rd 100 90 70 34th 100 90 65 35th 95 75 60 36th 95 75 60 37th 100 85 65 38th 100 90 70 39th 100 90 70 40th 100 85 70

-251

690

Table 7 (continued)

% Of death

serial number of joint tested Concentration of active substance in ppm 5 800 400 200 41st 95 75 60 ~ 42nd 100 85 65 43rd 100 85 60 10 44th 100 90 70 45th 100 90 65 46th 100 90 65 47th 95 75 60 48th 95 75 60 15 49th 100 90 70 50th 95 75 60 51st 100 85 65 . 52nd 100 85 65 Kontroif 75 '50 25 20 untreated 0 0 0

⁺ Control compound: 2-isopropoxy-phenyl-N-methylcarbamate. 25

She. experimental example

Granules containing 10% of the test compound were mixed with a predetermined amount of the soil infested with the larvae of the rootworm (Meloidogyne incognita) and tomato seedlings were planted in the soil. One month later, the roots of the plants were examined and the number of nodules formed on them was determined. Two 2 x ² m ² areas were used for each test compound. The degree of knot formation was determined according to the criteria described below and the results obtained are shown in Table 8. For comparison, the values obtained for the control and untreated areas are also given. 40

Table 8 (continued)

The investigated compound number The knots rate of formation ) pellets / kg / 4.1 hectares / Alkal nrazc 100 50 20 9th 0 t Ί 10th 0 1 2 11th 1 2 3 12th 0 1 2 13th 0 1 2 14th 0 1 2 15th 0 1 2 16th '0 1 3 17th 0 1 3 18th 0 1 2 19th 0 1 2 20th 0 I 3 21st 0 1 2 22nd 0 1 3 23rd 0 1 2 24th 0 0 1 25th 0 1 2 26th 0 ] 2 27th 0 1 2 28th 0 0 1 29th 0 1 2 30th 0 1 2 31st 0 2 3 32nd 0 2 3 33rd 0 0 1 34th 0 0 1 35th 0 1 3 36th 0 1 3 37th 0 1 2 38th 0 0 1 39th 0 0 1 40th 0 1 1

Degree of lump formation: 41st 0 1 3 0: 0% 42nd 0 1 2 1: to 25% 43rd 0 1 2 2: 50% 45 44th 0 0 I 3: to 75% 45th 0 I 2 4: 100% 46th 0 1 2 47th 0 1 3 Table 8 48th 0 1 3 50 49th 0 0 1 Degree of lump formation 50th 0 1 3 51st 0 1 2 The investigated Applied granules (kg / 4.1 ha) 52nd 0 1 · -) compound control * 2 4 4 number 55 untreated 4 100 50 20 • The coni alkali alkaline that compound: bis /. (2-clone-1 - I 0 1 -1-ethyl-ethyl) 'ICR. 2 0 2 3 Third 0 0 3 60 4th 0 2 3 Experimental Example 4 5th 0 2 3 The test compound is administered in a predetermined amount. 6th 1 2 3 of acetone. The solution was mixed with various concentrates. 7th 1 3 3 diluted to concentrations and we applied them locally « 1 1 2 65 house fly (Musca doinestiea). A .9. in table I P, "

-26 values are those determined by the Probif method from the 24 hours observed mortality.

Table 9

Test compound LD ₅₀ sequence numbers tn (ágig)

1. -21.3

-7 '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. 33.0

16. 44.4

17. 42.3

18. 32.5

19. 22.2

20. 61.9

21. 10.4

22. 45.2

23. 44.3

24. 38.6

25. 50.1

26. 64.7

27. 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 * Compound used as control: 2-isopropoxytenyl-N-methylcarbamate. »

5, Experimental Example

The acute toxicity of the compounds of formula (I) used as active ingredients in the compositions of the present invention was determined after oral administration in male mice. Table 10 shows the resulting SD _S0 values determined by the Litchfield Wilcoxon method seven days after treatment.

Table 10

t compound LD number (Ug / g) First 58 7 140 Third 145 4th 122 s. 90 5th 135 7th 75 s. 105 9th 158 10th 115 1!. 93 1? .. 125 13th 115 14th 120 15th 110 16th 110 17th 69 13 135 19th 108 20th 75 21st 105 22nd 88 23rd 113 24th 77 25th 123 26th 150 27th 105 23rd 89 29th 120 30th 133 31st 135 32nd 107 33rd 103 34th 95 35th 95 36th 70 37th 65 38th 125 39th 110 40th 103 41st 105 42nd 88 43rd 43 44th 128 45th 80 46th 105 47th 95 48th 80 49th 105 50th 95 51st 88 52nd 125

· control

-27188 690 * 2,3-dihydro-2,2-dimethyl-7-benzofuran-7-yl-N-methylcarbamate is the control compound used.

Claims (17)

Claims Insecticidal, miticidal and nematocidal compositions which are preferably active ingredients, solid carriers, preferably talc, clay, diatomaceous earth, liquid carriers, preferably organic solvents, optionally surfactants, preferably n-ionic or anionic surfactants, alcohol), characterized in that they contain from 0.5 to 90% by weight of the active ingredient a carbamate derivative having the formula - R ¹ and R ² independently of one another can be -X-COOR ³ , wherein - is C 1 -C 5 alkylene and - R ³ is C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl, or -Ύ- is a group of the formula CN, wherein Y is C 1-4 alkylene; -R ² may also be C 1 -C 10 alkyl, C 3 -C 6 cycloalkyl, benzyl optionally substituted by halogen or C 1 -C 3 alkoxy, phenyl optionally substituted by C 1 -C 3 alkyl or C 1 -C 3 alkoxy, or - Z - R ⁴ group, wherein Z represents a group - or a sulfonyl group, and R ⁴ represents optionally halogen-substituted C 1-4 alkyl or phenyl, and benzyl, C 1-4 alkoxy or phenoxy. (Priority: August 28, 1981) 2. A composition according to claim 1 wherein the active ingredient is a carbamate derivative represented by the general formula (I) which is a narrow group of compounds of formula (I): -R ¹ 'and R ² ' are independently of the formula -X '-COOR-, wherein -X' is C 1 -C 2 alkylene and -R ³ 'is C 1 -C 4 alkyl, or -Y'-CN, wherein -Y 'is C 1 -C 2 alkylene and -R ² ' may also be C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl. (Priority: August 28, 1981) Composition according to claim 1 or 2, characterized in that the active ingredient is 2,3-dihydro-2,2-dimethyl-1-benzofuran-7-yl-N- [N, N-bis (ethoxycarbonylmethyl) ) -aminosulfonyl-N-methylcarbamate. (Priority: 9/9/1980) 4. A composition according to claim 1 or 2 wherein the active ingredient is 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-methyl-N-ethoxycarbonyl). -methylaminosulfenyl) -N-methylcarbamate. (Priority 02.06.1981) Composition according to claim 1 or 2, characterized in that the active ingredient is 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-isopropyl-N-ethoxycarbonyl). ethylamine sulfonyl) -N-methylcarbamate. (Priority: 06.02.1981) 6. The composition according to claim 1 or 2, wherein the active ingredient is 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- [N- (n-butyl) -N- (ethoxycarbonyl-ethyl-aminosulfenyl) -N-methylcarbamate. (Priority 02.06.1981) 7. A composition according to claim 1 or claim 2 wherein the active ingredient is 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-cyclohexyl-N-ethoxycarbonyl). ethyl aninosulfenyl) -N-methylcarbamate. (Priority 02.06.1981) 8. A composition according to claim 1 or 2 wherein the active ingredient is 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- [N- (n-butyl) -N-. (cyanoethylaminosilylphenyl)) - N-methylcarbamate. (Priority 02.06.1981) 9. A process for the preparation of carbamate derivatives having the formula -R ¹ and R ² independently of one another -X-COOR ³ where - X is C 1 -C 5 alkylene and -R ³ is C 1 -C 8 alkyl, or C 3 -C 6 cycloalkyl, or -Y-CN wherein Y is C 1 -C 4 alkylene; R ² may also be C 1 -C 10 alkyl, C 3 -C 6 cycloalkyl, benzyl optionally substituted with halo or C 1-3 alkoxy, phenyl optionally substituted with halo, C 1-3 alkyl or C 1-3 alkoxy; obsession -ZR ⁴ wherein -Z is carbonyl or sulfonyl; and -R ⁴ is an optionally halogen substituted C1-4alkyl or phenyl, and benzyl, C 1-4 alkoxy or phenoxy, characterized in that 1 mole of compound (II) is reacted with two moles of sulfur dichloride, preferably solvent and a base in the presence of 1 mol of the resulting 2,3-dihydro-2,2-dimethylbenzofuran-7'-N-chlorosulfenyl-N-methylcarbamate of formula (III), preferably a solvent and a base. in the presence of - rsagáltatunk - (IV) 1-2 mole amount of amine - R ^l and R ² are the same as defined above. (Priority: August 28, 1981) The process of claim 9, wherein the compound of formula (III) is reacted with dichloromethane in the presence of a solvent. . '! Later: 08.08.1981. 28) 11. The process of claim 10 wherein the solvent is dichloroethane, chloroform, carbon tetrachloride, diethyl ether, dibutyl ether, tetrahydrofuran or dioxane (Priority 28 Aug 1981). The process of claim 9, wherein the compound of formula (II) is reacted with dichloromethane in the presence of a g of basic compound. (Priority: August 28, 1981) 13. A process according to claim 12 wherein the basic compound is triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine, pyridine, α, β, γ-plolin or lutidine. (Priority: August 28, 1981) 14. The process of claim 9, wherein the compound of formula (III) is reacted with the amine compound of formula (IV) in the presence of a solvent. (Priority: August 28, 1981) 15. A process according to claim 14 wherein the solvent is methylene chloride, chloroform, carbon tetrachloride, diethyl ether, dibutyl ether, tetrahydrofuran or dioxane. (Priority: 08/28/1981) 16. The process of claim 9, wherein the compound of formula (III) is reacted with the amine compound of formula (IV) in the presence of a basic compound. (Priority: August 28, 1981) 17. The process of claim 16 wherein the basic compound is triethylamine, tributylaniline, diethylaniline, ethylmorpholine, pyridine, α, β, γ-picoline or lutidine.