CH649765A5 - CARBAMATE DERIVATIVES, INSECTICIDE, MITICIDE OR NEMATOCIDE COMPOSITIONS CONTAINING THESE DERIVATIVES AND PROCESS FOR THE PREPARATION THEREOF. - Google Patents

Description

The present invention relates to carbamate derivatives, to insecticide, miticide or nematocidal compositions containing these derivatives as active ingredient, as well as to a process for the preparation of these derivatives and to a method for the destruction of insects, mites or harmful nematodes. In the description, the term insecticide also means miticide and nematocide, and the term insect also means mite and nematode, respectively, unless otherwise indicated.

It is known that some carbamate compounds have a high insecticidal activity, certain elements being currently used. However, several of these carbamate compounds have the disadvantage of being toxic towards warm-blooded animals. Among these, 2,3-dihydro-2,2-dimethylbenzofuran N-methylcarbamate (hereinafter referred to as carbofuran, as it is generally called) is known to have high insecticidal activity, but it causes problems in its practical use because of high toxicity towards warm-blooded animals. Therefore, if it is possible to prepare carbamate compounds which are comparable to carbofuran with regard to insecticidal activity and having reduced toxicity towards warm-blooded animals, such compounds would be very useful. From this point of view, different carbofuransulfenyl compounds have been synthesized, and the relationship between their insecticidal activity and the toxicity vis-à-vis warm-blooded animals has been studied, the results of these studies having been published. For example, Belgian patent No. 817517 discloses N- (N, N-dibutyl-aminosulfenyl) -N-2,3-dihydro-2,2-dimethyl-benzofuran-7-yl-methylcarbamate and the German patent DT- OS No. 2254359 discloses 2,3- dihydro-2,2-dimethylbenzofuran-7-yl N- (N-methyl-N-benzenesulfonylaminosulfenyl) -N-methyl-carbamate. These compounds do not, however, fully meet the requirements with regard to insecticidal activity, toxicity towards warm-blooded animals and the manufacturing process.

The present inventors carried out in-depth research in an attempt to develop carbamate compounds which completely fulfill all of the above requirements and found that this objective was achieved by the compounds represented by the general formula (I):

o-c-n;

, ch3

^ S-N

\ R2

in which R1 and R2, identical or different, each represent: 1) a group - X —COOR3 in which X represents an alkylene group having from 1 to 6 carbon atoms, and R3 represents an alkyl group having from 1 to 8 atoms carbon or a cycloalkyl group having from 3 to 6 carbon atoms, or 2) a —Y — CN group, in which Y represents an alkylene group having from 1 to 6 carbon atoms, and R2 further represents an alkyl group having 1 to 8 carbon atoms; a cycloalkyl group having 3 to 6 carbon atoms; a benzyl group, which may be substituted with a halogen atom, an alkyl group having from 1 to 3 carbon atoms or an alkoxy group having from 1 to 3 carbon atoms; a phenyl group, which may be substituted with a halogen atom, an alkyl group having from 1 to 3 carbon atoms or an alkoxy group having from 1 to 3 carbon atoms, or a group - Z — R4, in which Z represents a carbonyl group or a sulfonyl group, and R4 represents an alkyl group having from 1 to 6 carbon atoms; a phenyl group, a benzyl group, an alkoxy group having 1 to 6 carbon atoms or a phenoxy group.

In the above definition of formula (I), the alkyl nucleus in the alkyl, alkylene and alkoxy group may be in a linear or branched chain.

The preferred compounds are represented by the formula (! '):

35

(I)

(the i in which R1 'and R2', identical or different, each represent: 1) a group - X '—COOR3', in which X 'represents an alkylene group having 1 or 2 carbon atoms and R3' represents a alkyl group having from 1 to 4 carbon atoms in straight or branched chain, or 2) a group - Y '—CN in which Y' represents an alkylene group having 1 or 2 carbon atoms, and R2 'represents in addition a group alkyl having from 1 to 6 carbon atoms in a straight or branched chain, or a cycloalkyl group having from 3 to 6 carbon atoms.

The compounds of formula (I) are new compounds which have hitherto never been disclosed and which have been discovered by the present inventors for the first time. They have found that these new compounds have a significant insecticidal activity or a destructive effect on agricultural and forestry pests as well as on household pests, and are comparable as regards their effect to carbofuran which has the highest insecticidal activity known to date. The compounds are effective on a wide variety of harmful insects, mites and nematodes, which are harmful to plants, trees, other plants as well as humans, such as He-miptera, Lepidoptera, Coleoptera, Diptera, Tysanoptera, Orthoptera, Isopoda, Acarina, Tylenchida, etc. Examples of these insects, mites and nematodes include the following:

Hemiptera

Nephotettix cincticeps Laodelphax striatellus, Nilaparvata lugens

Myzus persicae, Aphis grossypii Nezara antennata, Nezara viridula

1) Deltocephalidae:

2) Delphacidae:

3) Aphididae:

4) Pentatomidae:

Lepidoptera

1) Noctuidae:

2) Tortricidae:

3) Pyralidae:

4) Plutellidae: 45 Coleoptera

1) Curculionidae:

2) Scarabaeidae:

3) Coccinellidae:

50

Diptera

1) Muscidae:

2) Cecidomyiidae:

3) Agromyzidae:

55 Thysanoptera Thripidae: Orthoptera

Gryllotalpidae:

60

Isopoda

Armandillidae: Acarina

Tetranychidae:

Spodoptera litura, Agrotis fucosa, Laphygma exigua Adoxophyes orana

Chilo suppressalis, Ostriniafurnacalis, Cnaphalocrocis medinalis Plutella xylostella

Echinocnemus squameus, Lissorhoptrus oryzophilus

Popillia japonica

Henosepilachna vigintioctopunctata

Musca domestica Aspondylia sp.

Phytobia cepae

Thrips tabaci, Scirtothrips dorsalis Gryllotalpa africana

65

Tylenchida

Heteroderidae:

Armadillidium vulgare

Tetranychus telarius, Tetranychusurticae, Panonychus citri

Meloidogyne incognita

649765

4

The toxicity of the carbamate derivatives of formula (I) vis-à-vis warm-blooded animals is as low as about Vs to about Vioo of the toxicity of carbofuran. These compounds (I) exhibit an insecticidal activity or a destructive effect on the organisms mentioned above at any stage of their growth, and are therefore usable effectively for the destruction of these in the field of agriculture, forestry and health.

The compounds of formula (I) are very easy to prepare with high purities and high yields, and have significant commercial advantages as will be described in more detail below.

As typical examples of the compounds of formula (I), mention may be made of those described in examples 1 to 56 below. Among these compounds, the following compounds are more particularly preferred in this invention: 1

N- [N, N-bis (ethoxycarbonylmethyl) aminosulfenyl] -N-methyl-2,3-dihydro-2,2-dimethylbenzofuran-7-yl methyl carbamate,

N- (N-methyl-N-ethoxycarbonylmethylaminosulfenyl) -N-methyl-2,3-dihydro-2,2-dimethylbenzofuran-methyl carbamate,

N- (N-isopropyl-N-ethoxycarbonylethylaminosulfenyl) -N-: 2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate, N- (Nn-butyl-N-ethoxycarbonylethylaminosulfenyl) -N-methyl-carbamate 2,3-dihydro-2,2-dimethylbenzofuran-7-yl,

N- (N-cyclohexyl-N-ethoxycarbonylethylaminosulfenyl) -N-2,3-dihydro-2,2-dimethylbenzofuran-7-yl 2,3-dihydro-methyl-carbamate,

N- (N-n-butyl-N-cyanoethylaminosulfenyl) -N-methylcarbamate of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl.

The compounds of formula (I) can be prepared, for example, by reaction of a compound of formula (II):

similar tertiary, pyridine, a, ß, y-picoline, lutidine, etc. The basic compound can be used in an amount sufficient to capture the hydrogen chloride formed as a by-product of the reaction. Generally 1 to 2 mol of the basic compound are used per mole of the compound of formula (II). The reaction, which takes place with cooling, at room temperature or with heating, is generally carried out at -70 to + 50 ° C, preferably between -10 and + 30 ° C. The reaction time is from about 2 to about 7 hours, preferably from about 3 to 5 hours. The compound of formula (III) is reacted with an amine of formula (IV). Examples of usable amines of formula (IV) are secondary amines represented by formulas (V) to (IX):

0

o-c-n

-ch,

(II)

with sulfur dichloride to form the 2,3- dihydro-2,2-dimethylbenzofuran-7-yl N- (chlorosulfenyl) -N-methylcarbamate represented by formula (III):

0

o-c-n;

, ch,

"SCI

(III)

which is then reacted with an amine of formula (IV):

R1

y

50

HN

\

(iv)

R2

in which R1 and R2 are as defined above.

The reaction of the compound of formula (II) with sulfur dichloride can be carried out in the presence or in the absence of a solvent. Examples of solvents which can be used are methylene chloride, chloroform, carbon tetrachloride and similar hydro-carbon halides, as well as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like. The proportions of the compound of formula (II) and of SC12 are not particularly limited, but can vary very appropriately. Generally 1 to 2 mol, preferably about 1 to 1.2 mol of the latter is used per mole of the former. Preferably, the reaction is carried out in the presence of a basic compound. Examples of such basic compounds which can be used are triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine and amines

60

HN

/ \

X — COOR3

HN

./ \

R

Y-CN

HN

HN

HN

\

/ \

/ \

R

X — COOR3

X "—COOR3 X — COOR3

Y-CN Y-CN

-CN

(V)

(VI)

(VII)

(VIII)

(IX)

In the above formulas (V) to (IX), X, Y and R3 are as defined above 40; R represents an alkyl group having from 1 to 8 carbon atoms; a cycloalkyl group having 3 to 6 carbon atoms; a benzyl group which may be substituted with a halogen atom, an alkyl group having from 1 to 3 carbon atoms or an alkoxy group having from 1 to 3 carbon atoms; a phenyl group which may be substituted with a halogen atom, an alkyl group having from 1 to 3 carbon atoms or an alkoxy group having from 1 to 3 carbon atoms; or Z'— R4 ', wherein Z' represents a carbonyl group or a sulfonyl group, and R4 represents an alkyl group having from 1 to 6 carbon atoms, a phenyl group, a benzyl group, an alkoxy group having from 1 to 6 carbon atoms or a phenoxy group (in which the alkyl group and the alkoxy group may be in a straight or branched chain); R3 "has the same meaning as R3; X" has the same meaning as X, and Y "has the same meaning as Y.

Representative examples of the amine of formula (V) are as follows:

N-methylglycinemethylester, N-methylglycinethylester, N-meth-ylglycinebutylester, N-ethylglycinethylester, Nn-propylglycinethyl-ester, N-isopropylglycinethylester, Nn-butylglycinethylester, N-iso-butylglycinethylester, N-ethyl-glycol-ester. , N-cyclohexylglycinethylester, N-benzylglycinethylester, N- (4-methylbenzyl) glycinethylester, N- (4-chlorobenzyl) glycinethyl-ester, N-phenylglycinethylester, N- (3-methylphenyl) glycinethylester, N- (4-methoxyphenyl) , Ethyl N-methylaminopropionate 65, ethyl Nn-propylaminopropionate, methyl N-isopropylamino-propionate, ethyl N-isopropylaminopropionate, butyl N-isopropylaminopropionate, 2-ethylhexyl N-isopropylaminopropionate, methyl Nn-butylaminopropionate , Nn-butyl-

5

649,765

ethyl aminopropionate, ethyl N-isobutylaminopropionate, ethyl N-sec.-butylaminopropionate, ethyl Nt-butylaminopropionate, ethyl Nn-amylaminopropionate, ethyl N-isoamylamino-propionate, Nn-hexylaminopropionate ethyl, ethyl N-cyclo-hexylaminopropionate, N-acetylglycinethylester, N-chloro-acetylaminoglycinethylester, N-propionylglycinethylester, N-benzo-ylglycinethylester, N- (4-chlorobenzoyl) glycinethylester, N-tosylglycinethylester, etc.

Representative examples of the amine of formula (VI) are as follows:

N-methylaminoacetonitrile, N-ethylaminoacetonitrile, Nn-propylaminoacetonitrile, N-isopropylaminoacetonitrile, Nn-butyl-aminoacetonitrile, N-isobutylaminoacetonitrile, N-benzylamino-acetonitrile, N-phenylamino-acetonitrile, N-phenylamino-acetonitrile , Nn-propylaminopropio-nitrile, N-isopropylaminopropionitrile, Nn-butylaminopropio-nitrile, N-isobutylaminopropionitrile, N-sec.-butylaminopropio-nitrile, N-octylaminopropionitrile, N-cyclohexylaminopropionitrile, etc.

Representative examples of the amine of formula (VII) are as follows:

Methyl iminodiacetate, ethyl iminodiacetate, isopropyl iminodiaceae, cyclohexyl iminodiacetate, methyl iminodipropionate, ethyl iminodipropionate, N-methoxycarbonylglycin-ethylester, N-ethoxycarbonylglycinethylester, N-phenoxycarbonyl ester ethyl, ethyl 4- (ethoxycarbonylmethylamino) butyrate, ethyl 2- (ethoxycarbon-ylmethylamino) butyrate, ethyl N-ethoxycarbonylaminopropionate, etc.

Representative examples of the amine of formula (VIII) are as follows:

Methyl N-cyanomethylcarbamate, Ethyl N-cyanomethylcarbamate, Ethyl N-cyanoethylcarbamate, N-cyanomethylglycineth-ylester, N-cyanoethylglycinethylester, N-cyanomethylaminopropio-nate of ethyl, N-cyanoethylaminopropionate, etc.

Representative examples of the amine of formula (IX) are as follows:

Iminodiacetonitrile, iminodipropionitrile, imiiiodibutyronitrile,

etc.

The reaction of the compound of formula (III) with the amine of formula (IV) can be carried out in the presence or in the absence of a solvent. Any of the solvents useful for the reaction of the compound of formula (II) with sulfur dichloride can be used for this reaction. The proportions of the compound of formula (III) and of the amine are not particularly limited, but are to a large extent suitably variable. Generally about 1 to about 2 mol, preferably 1 to 1.2 mol of the latter is used per mole of the former. It is preferable to carry out this reaction also in the presence of a basic compound, which may be one of those already mentioned. The basic compound can be used in an amount such that it is sufficient to fix the hydrogen chloride formed by the reaction as a by-product. Generally 1 to 2 mol, preferably 1 to 1.5 mol, of the basic compound is used per mole of the compound of formula (III). The reaction, which takes place with cooling, at room temperature or with heating, is generally carried out between —20 and + 50 ° C., preferably between 0 and 30 ° C. The reaction time is generally between approximately 10 and approximately 15 h.

The compounds of formula (I) according to the invention as obtained as mentioned above can be easily isolated and purified by a usual separation technique, such as solvent extraction, recrystallization or chromatography.

The compounds of formula (I) according to the invention can be in the form of emulsions, wettable powders, suspensions, concentrated suspensions, granules, fine particles, pills, dust, coating compositions, foaming spray, aerosols, microcapsule compositions, products to be impregnated in natural or synthetic materials, products to be vaporized, concentrated preparations to be applied in small quantities, etc.

Different surfactants can be used for the preparation of such emulsions, dispersions, suspensions and foams. Examples of nonionic surfactants which can be used are the polyoxyethylene alkyl ethers, the polyethylene alkyl esters, the poly oxyethylenesorbitan alkyl esters, the alkyl estersorbitans, etc.

Examples of usable anionic surfactants are the alkyl benzenesulfonates, alkyl sulfosuccinates, polyoxyethylenealkyl ether sulfates, alkylnaphthalene sulfonates, ligninsulfonates, alkyl sulfates, etc.

Solvents, diluents and carriers for the compounds of formula (I) include various organic solvents, aerosol propellants, natural minerals, plants, synthetic compounds, etc. Examples of preferred organic solvents are benzene, toluene, xylene, ethylbenzene, chlorobenzene, alk-ylnaphthalene, dichloromethane, chloroethylene, cyclohexane, cyclohexanone, acetone, methyl ethyl ketone, methyl -isobutylketone, alcohols, dimethylformamide, dimethylsulfoxide, acetonitrile, fractions of mineral oils, etc. Examples of suitable aerosol propellants are propane, butane, hydrocarbon halides, nitrogen, carbon dioxide, etc. Examples of usable natural mineral products are kaolin, talc, bentonite, diatomaceous earth, clay, montmorillonite, chalk, calcite, pumice, dolomite, etc. Examples of usable plant products are coconut shells, tobacco stems, sawdust, etc. Examples of usable synthetic compounds are alumina, silicanes, sugar polymers, etc. Also suitable are adhesives such as carboxymethylcellulose, gum arabic, polyvinyl alcohol, polyvinyl acetate, etc. The preparations can be colored with organic or inorganic dyes.

The compounds of formula (I) according to the invention are formulated in various preparations, such as those given as an example above, so that these preparations contain, as active ingredient, an amount effective from the insecticide, miticide or nematocidal point of view. of the compound (for example about 0.1 to about 95% by weight; preferably between about 0.5 and about 90% by weight). Depending on the desired application, such preparations are used as such, or in diluted form with a support or with water.

The present invention will now be described in detail with reference to the following examples:

Example 1:

Preparation of 2,3- dihydro-2,2-dimethylbenzofuran-7-yl N- [N, N-bis (cyanomethyl) aminosulfenyl] -N-methyl-carbamate

11 g (0.05 mol) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate was dissolved in 70 ml of methylene chloride, 5.2 g (0.05 mol) of sulfur dichloride were added to the solution while cooling, and 5 g (0.05 mol) of triethylamine were added dropwise to the solution at 0 ° C. The mixture was stirred at the same temperature for 2 h, then a solution of 4.8 g (0.05 mol) of iminodiacetonitrile in 40 ml of tetrahydrofuran was added dropwise to the mixture at the same temperature, and 5 g (0.05 mol) of triethylamine were then added dropwise to the mixture. The mixture obtained was stirred at 0 ° C for 4 h, then left to stand overnight at room temperature. With the addition of 100 ml of methylene chloride, the reaction mixture was washed with 100 ml of water three times. The methylene chloride layer was dried, then concentrated in vacuo to give an oily product, which was almost entirely of the desired product although containing small amounts of the starting materials. Yield: 13.8 g (79.8%).

For the identification of the product, a portion of it was purified by column chromatography on Silicagel, using a mixture of benzene / ethyl acetate (4: 1) as solvent, so as to obtain crystals having a melting point of 94 to 95 ° C.

5

10

15

20

25

30

35

40

45

50

55

60

65

649765

6

NMR in chloroform-d,:

5 1.48 ppm (s, 6H) 5 3.02 ppm (s, 2H)

8 3.50 ppm (s, 3H) 8 4.32 ppm (s, 4H)

8 6.6-7.2 ppm (m, 3H)

Analysis for C16H18N403S:

Calculated: C 55.48 H 5.24 N 16.17%

Found: C 55.36 H 5.31 N 16.05%

(Molecular Weight 346,418)

Thus, it was confirmed that the product obtained had the following formula:

0

He / CH3 o-c-n, ch2cn

CH3. 1 S-N ^

ch, "" • 'ck2cn

Example 2:

Preparation of N- [N, N-bis (ethoxycarbonylmethyl) aminosulfenylJ-N-2,3-dihydro-2,2-dimethylbenzofuran-7-yl 2,3-dihydro-methylcarbamate An amount of 11 g (0.05 mol) of N-methylcarbamate 2,3-dihydro-2,2-dimethylbenzofuran-7-yl was dissolved in 50 ml of chloroform, then 5.2 g (0.05 mol) of sulfur dichloride was added to the solution while cooling, and 5 g (0.05 mol) of triethylamine was added dropwise to the solution at 0 ° C. The mixture was stirred at the same temperature for 2 h, then a solution of 9.5 g (0.05 mol) of ethyl iminodiacetate in 20 ml of chloroform was added dropwise to the mixture at the same temperature , and 5 g (0.05 mol) of triethylamine were then added dropwise to the mixture. This was stirred at 0 ° C for 2 h, then left to stand overnight at room temperature. With the addition of 100 ml of chloroform, the reaction mixture was washed with 100 ml of water three times. The chloroform phase was dried, then concentrated in vacuo to give an oily product, which was almost entirely composed of the desired product although containing small amounts of the starting materials. Yield: 15.9 g (72.3%).

In order to identify the product, a portion of it was purified by column chromatography on Silicagel using a benzene / ethyl acetate mixture (4: 1) as solvent, so as to obtain an oily product.

NMR in chloroform-dj:

5 1.24 ppm (t, 6H) 5 1.48 ppm (s, 6H)

8 3.02 ppm (s, 2H) 8 3.42 ppm (s, 3H)

6 4.20 ppm (q, 4H) 5 4.28 ppm (s, 4H)

8 6.6-7.2 ppm (m, 3H)

Analysis for C2oH28N207S:

Calculated: C 54.53 H 6.41 N 6.36%

Found: C 54.68 H 6.46 N 6.38%

(Molecular Weight 440,526)

It was thus confirmed that the product obtained had the following formula:

Example 6:

Preparation of N- [N, N-bis (ethoxycarbonylethyl) aminosulfenyl] -N-2,3-dihydro-2,2-dimethylbenzofuran-7-yl-methylcarbamate

5 11 g (0.05 mol) of 2,3-dihydro-2,2-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate was dissolved in 70 ml of methylene chloride, then 5.2 g (0.05 mol) of sulfur dichloride was added to the solution with cooling, and 5 g (0.05 mol) of triethylamine were then added dropwise to the solution between -10 and - 5 ° C. The mixture was stirred at 0 ° C for 1 h, then at room temperature for 2 h. After cooling to -10 to -5 ° C, 10.9 g (0.05 mol) of diethyl iminodi-propionate were added dropwise to the mixture, and 5 g (0.05 mol) of triethylamine were added dropwise to the mixture. This was stirred at 0 ° C for 2 h, and then left to stand overnight at room temperature. After adding 100 ml of methylene chloride, the reaction mixture was washed with 100 ml of water three times. The methylene chloride phase was dried and then concentrated in vacuo to give an oily product, which was almost entirely composed of the desired product, although containing small amounts of impurities. Yield: 16.9 g (72.2%).

For identification of the product, a portion thereof was purified by column chromatography on Silicagel, using a benzene / ethyl acetate mixture (5: 1) as solvent, so as to obtain a product oily. NMR in chloroform-di:

8 1.21 ppm (t, 6H) 8 1.44 ppm (s, 6H)

8 2.67 ppm (t, 4H) 8 2.97 ppm (s, 2H)

30 8 3.37 ppm (s, 3H) 8 3.42 ppm (t, 4H)

8 4.04 ppm (q, 4H) 8 6.5-7.2 ppm (m, 3H)

Analysis for C22H32N2O7S:

Calculated: C 56.39 H 6.88 N5.98%

Found: C 56.26 H 6.91 N5.52%

35 (Molecular Weight 468.58)

It was thus confirmed that the product obtained had the following formula:

ch ch

0

o-c-n '

.ch3 • s-n:

.ch2ch2cooc2h5

-ch2ch2cooc2h5

ch3 ch3

0

He ,

0-c-nv

-ch:

"s-n:

, ch2c00c2h5

■ ch2cooc2h5

Examples 3 to 5:

The compounds represented in table 1 were prepared in the same way as that described in examples 1 and 2. The physical properties and the NMR data (in chloroform-dj) of these compounds are also mentioned in this table 1.

(Table at the top of the next page)

Example 7:

Preparation of 2,3- dihydro-2,2-dimethylbenzofuran-7-yl N- [N, N-bis (cyanoethyl) aminosulfenyl] -N-methyl-carbamate

11 g (0.05 mol) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate was dissolved in 50 ml of chloroform, then 5.2 g (0.05 mol) of sulfur dichloride was added to the solution while cooling and 5 g (0.05 mol) of triethylamine were then added dropwise to the solution at -10 to -5 ° C. The mixture was stirred at 0 ° C for 1 h, then at room temperature for 1 h. After cooling between -10 and 55-5 ° C, 6.2 g (0.05 mol) of iminodipropionitrile was added dropwise to the mixture, and 5 g (0.05 mol) of triethylamine were added dropwise. drop into the mixture. This was stirred at 0 ° C for 2 h, and then left to stand overnight at room temperature. After adding 100 ml of chloroform, the reaction mixture was washed with 100 ml of water three times. The chloroform phase was dried, then concentrated in vacuo to give an oily product, which was almost entirely composed of the desired product although containing small amounts of impurities. Yield: 12.2 g (65.2%).

65 In order to identify the product, a portion of it was purified by column chromatography on Silicagel using a benzene / ethyl acetate mixture (4: 1) as solvent, so as to obtain an oily product .

649,765

ch3 ch3

Table 1 0

il ^ ch3 o-c-n r *

^ S-N

XR2

Ex. No.

Amine r1

r2

h-nmr (8ppm value in cdc13)

Elementary analysis Empirical formula Value found (Calculated value)

c (%) h (%) n (%)

3

ch2c00ch3

hn ch2c00ch3

-ch2cooch3

-ch2cooch3

81.47 (s, 6h) 83.02 (s, 2h) 83.41 (s, 3h) 83.73 (s, 6h) 84.30 (s, 4h) 86.7-7.2 (m, 3h)

cigh24n207s

52.11 5.91 6.63 (52.42) (5.87) (6.79)

4

.ch2coo- /

hn ch2coo- (

-ch2coo- {

-ch2coo- (

81.23 (d, 6h) 81.46 (s, 6h) 83.03 (s, 2h) 83.42 (s, 3h) 84.26 (s, 4h)

84.5-5.3 (m, 1h)

86.6-7.2 (m, 3h)

c22h32n207s

56.35 6.91 5.86 (56.40) (6.89) (5.98)

5

ch2coo- / h \

hn ^

ch2c00 - ^ "h ~ ^

-ch2coo - ^ "h" ^

-ch2coo- ^ ~ h "^

81.0-2.2 (m, 20h) 81.48 (s, 6h) 53.02 (s, 2h) 83.43 (s, 3h) 84.28 (s, 4h) 54.5-5, 1 (m, 2h) 56.7-7.2 (m, 3h)

c28h40n2o7s

61.32 7.39 4.95 (61.29) (7.35) (5.11)

NMR in chloroform-dj:

8 1.43 ppm (s, 6H) 5 2.73 ppm (t, 4H)

8 2.97 ppm (s, 2H) 8 3.37 ppm (s, 3H)

8 3.43 ppm (t, 4H) 8 6.5-7.2 ppm (m, 3H)

Analysis for C18H22N403S:

Calculated: C 57.73 H 5.92 N 14.96%

Found: C 57.91 H 5.79 N 15.04%

(Molecular Weight 374.47)

It was thus confirmed that the product obtained had the following form:

o-c-n;

-ch3

-S-N '

.ch2ch2cn • ch2ch2cn

50

Examples 8 to 11:

The compounds shown in Table 2 were prepared in the same manner as that described in Examples 6 and 7. The physical properties and the NMR data (in chloroform-dj) of these compounds are also mentioned in Table 2.

(Table at the top of the next page)

Example 12:

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N- (N-butyl-N-ethoxycarbonylaminosulfenyl) -N-meth-ylcarbamate

45 An amount of 11 g (0.05 mol) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate was dissolved in 70 ml of methylene chloride, then 5.2 g (0 0.05 mol) of sulfur dichloride was added to the solution while cooling, and 5 g (0.05 mol) of triethylamine were then added dropwise to the solution at -10 to -5 ° C. The mixture was stirred at 0 ° C for 1 h, then at room temperature for 2 h. After cooling to -10 to -5 ° C, 8.0 g (0.05 mol) of N-butylglycinethylester was added dropwise to the mixture and 5 g (0.05 mol) of triethylamine were also added dropwise. drop this mixture. The 5J mixture obtained was stirred at 0 ° C for 2 h, then left to stand overnight at room temperature. After adding 100 ml of methylene chloride, the reaction mixture was washed three times with 100 ml of water. The methylene chloride phase was dried and concentrated in vacuo to give an oily product which was almost entirely composed of the desired product although containing small amounts of impurities. Yield: 15.7 g (76.6%).

For the identification of the product, a portion of it was purified by column chromatography on Silicagel, using a benzene / ethyl acetate mixture (4: 1) as solvent, so as to obtain a product oily.

NMR in chloroform-dj:

8 0.6-1.9 ppm (m, 7H) 8 1.22 ppm (t, 3H)

8 1.44 ppm (s, 6H) 8 3.03 ppm (s, 2H)

649765

8

Table 2

li / CH3 O-C-N. ^ Rj

^ S-N ^

R2

Ex.

No.

Amine

R1

R2

H-NMR (Value 5ppm in CDCI3)

Elementary analysis Empirical formula Value found (Calculated value)

C (%) H (%) N (%)

8

• xCH2CH2CN HN

CH2C00C2H5

-ch2ch2cn

-ch2cooc2h5

51.26 (t, 3H) 51.47 (s, 6H) 52.6-3.1 (m, 2H) 53.02 (s, 2H) 53.40 (s, 3H) 53.3-3, 8 (m, 2H) 54.18 (s, 2H) 54.20 (q, 2H) 56.6-7.2 (m, 3H)

C19H2SN3O5S

55.89 6.31 10.64 (56.01) (6.19) (10.31)

9

-.CH2CH2C00C2H5

King

CH2C00C2H5

-ch2ch2cooc2h5

-ch2cooc2h5

51.23 (t, 6H) 51.45 (s, 6H) 52.70 (t, 2H) 53.00 (s, 2H)

53.39 (s, 2H)

53.40 (t, 2H) 54.09 (q, 2H) 54.14 (s, 2H) 54.55 (q, 2H) 86.5-7.2 (m, 3H)

C21H3oN207S

55.94 6.79 6.05 (55.50) (6.65) (6.16)

10

/ CH2CH2CH2C00C2H5

HN

^ CH ^ OOC ^ s

-ch2ch2ch2cooc2h5

-ch2cooc2h5

51.22 (t, 6H) 81.45 (s, 6H) 81.7-2.6 (m, 4H) 83.00 (s, 2H) 83.35 (t, 2H) 83.42 (s, 3H) 84.13 (q, 2H) 54.15 (s, 2H) 54.17 (q, 2H) 86.5-7.2 (m, 3H)

C22ÌH32N2O7S

55.94 6.93 6.25 (56.40) (6.89) (5.98)

11

ch2ch3 .chcooc2h5

HN

CH2C00C2H5

ch2ch3 -chcooc2h5

-ch2cooc2h5

80.99 (t, 3H) 81.20 (t, 3H) 81.23 (t, 3H) 81.43 (s, 6H) 51.5-2.5 (m, 2H) 53.02 (s, 2H) 53.38 (s, 3H) 83.5-4.5 (m, 7H) 86.5-7.2 (m, 3H)

C22H32N2O7S

56.53 6.78 5.81 (56.40) (6.89) (5.98)

S 3.30 ppm (t, 2H) 5 4.14 ppm (s, 2H) 8 6.5-7.2 ppm (m, 3H)

Analysis for C20H30N2O5S: Calculated: C 58.52 H 7.37 Found: C 58.39 H 7.41 (Molecular Weight 410.54)

ô 3.42 ppm (s, 3H) 5 4.13 ppm (q, 2H)

N 6.83% N 6.75%

It was thus confirmed that the product obtained had the following formula:

0

He ^ CH,

65

0-c-nv

VS-NC

, ch2cooc2h5 -ch2ch2ch2ch3

649,765

Example 13:

Preparation of N- (N-jhenyl-N-ethoxycarbonylmethylaminosulfenyl) -N-methylcarbamr., -, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl

11 g (0.05 mol) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate was dissolved in 70 ml of methylene chloride, then 5.2 g (0, 05 mol) of sulfur dichloride were added to the solution while cooling, and 5 g (0.05 mol) of triethylamine were then added dropwise to the solution between -10 and -5 ° C. The mixture was stirred at 0 ° C for 1 h, then at room temperature for 2 h. After cooling to -10 to -5 ° C, 9 g (0.05 mol) of N-phenylglycinethylester were then added dropwise to the mixture, and 5 g (0.05 mol) of triethylamine were added dropwise drop by drop to the mixture. This was stirred at 0 ° C for 2 h, then left to stand overnight at room temperature. After adding 100 ml of methylene chloride, the reaction mixture was washed three times with 100 ml of water. The methylene chloride phase was dried, then concentrated in vacuo to give an oily product. A benzene / hexane mixture (1: 1) was added to the oily product, so as to obtain the precipitation of crystals. These were filtered, and the mother liquor was concentrated to give an oily product which was then cooled to obtain crystals. The crystals thus obtained were recrystallized from diethyl ether to obtain 13.4 g (yield: 62.3%) of white crystals having a melting point of 92 to 93 ° C.

NMR in chloroform-d,:

8 1.15 ppm (t, 3H)

8 3.00 ppm (s, 2H)

5 4.12 ppm (q, 2H) 8 6.5-7.5 ppm (m, 8H)

Analysis for C22H26N2O5S: Calculated: C 61.38 H 6.09 Found: C 61.11 H 6.15 (Molecular Weight 430.53)

8 1.46 ppm (s, 6H) 8 3.32 ppm (s, 3H) 8 4.76 ppm (s, 2H)

N 6.51% N 6.49%

It was thus confirmed that the product obtained had the following formula:

I / CH3

o-c-n // ch2c00c2h5 s-n

20

Examples 14 to 32:

The compounds presented in Table 3 were prepared in the same manner as that described in Examples 12 and 13. The physical properties and the NMR data (in chloroform-d ^ of these compounds are also mentioned in Table 3.

Table 3 0

He / CH3

0-c-NC / R1

S-N

XR2

Ex.

No.

Amine

R1

R2

H-NMR (8ppm value in CDCI3)

Elementary analysis Empirical formula Value found (Calculated value)

c (%) H (%) N (%)

14

CH2COOC2H5

hn ch3

-ch2c00c2H5

-ch3

81.24 (t, 3H)

81.47 (s, 6H) 83.02 (s, 2H) 83.17 (s, 3H)

83.48 (s, 3H) 84.10 (s, 2H) 84.17 (q, 2H) 86.6-7.2 (m, 3H)

cnh24n205s

55.61 6.45 7.83 (55.43) (6.56) (7.61)

15

^ ✓ch2cooc2h5

hn ^ ch3 ch.

ch3

-ch2cooc2h5

/ ch3

-cl}

ch3

81.16 (d, 6H) 81.18 (t, 3H) 81.43 (s, 6H) 82.94 (s, 2H) 83.29 (s, 3H) 83.1-3.7 (m, 1H) 84.00 (q, 2H) 84.02 (s, 2H) 86.5-7.0 (m, 3H)

c, 9h28n2o5s

57.34 7.15 7.17 (57.56) (7.12) (7.07)

16

/ CH2COOC2H5

hn vvaec-cith9

-ch2cooc2h5

-sec-Ct, Hg

80.8-1.8 (m, 8H) 81.22 (t, 3H) 81.45 (s, 6H) 82.97 (s, 2H)

82.9-3.3 (m, 1H) 83.30 (s, 3H) 84.03 (s, 2H) 84.08 (q, 2H) 86.7-7.1 (m, 3H)

C20H30N2O5S

58.55 7.25 6.91 (58.52) (7.37) (6.83)

649,765 10

Table 3 (continued)

Ex. No.

Amine

R1

R2

H-NMR (Value 5ppm in CDCI3)

Elementary analysis Empirical formula Value found (Calculated value)

C (%) H (%) N (%)

17

/

J ^ COOCjiHs

HIk n-C6H17

-ch2cooc2h5

-n-CgHi7

80.7-1.8 (m, 18H) 51.45 (s, 6H) 82.97 (s, 2H) 53.1-3.5 (m, 2H) 53.36 (s, 3H) 54, 01 (s, 2H) 54.07 (q, 2H) 86.6-7.2 (m, 3H)

c24.h38n2oss

61.53 8.11 6.24 (61.78) (8.21) (6.00)

18

^ ci ^ coocahs

HN

\ D

-ch2cooc2h5

<D

80.7-2.4 (m, 14H) 81.43 (s, 6H) 82.93 (s, 2H) 83.32 (s, 3H) 84.06 (q, 2H) 54.08 (s, 2H) 56.6-7.2 (m, 3H)

C22H32N2O5S

60.95 7.42 6.51 (60.53) (7.39) (6.42)

19

x.CH2C00C2H5

A

\ h2 ^ 3

-ch2cooc2h5

-CH2- <2>

51.22 (t, 3H) 51.40 (s, 6H) 52.97 (s, 2H) 53.24 (s, 3H) 53.82 (s, 2H) 54.11 (q, 2H) 54, 15 (s, 2H) 56.5-7.6 (m, 8H)

C23H28N2O5S

62.04 6.39 6.63 (62.15) (6.35) (6.30)

20

xch2COOC2h5

HN

-ch2cooc2h5

-ch ^ c

51.25 (t, 3H) 51.42 (s, 6H) 53.04 (s, 2H) 53.42 (s, 3H) 53.92 (s, 2H) 84.21 (q, 2H) 84, 23 (s, 2H) 86.7-7.2 (m, 3H) 87.2-7.5 (m, 4H)

C23H27N205C1S

58.01 5.54 5.69 (57.67) (5.68) (5.85)

21

/ CH2C00G2H5

HN

ch3

-ch2cooc2h5

■ Q

ch3

81.17 (t, 3H) 81.48 (s, 6H) 82.35 (s, 3H) 83.05 (s, 2H) 83.40 (s, 3H)

84.18 (q, 2H) 84.80 (s, 2H) 86.7-7.5 (m, 7H)

C23H28N2O5S

61.84 6.42 6.19 (62.15) (6.35) (6.30)

22

yCH2COOC2H5

HN

\ r ^ OCH3

-ch2cooc2h5

- ^ CH3

81.15 (t, 3H) 81.48 (s, 6H) 83.02 (s, 2H) 83.31 (s, 3H) 83.76 (s, 3H) 84.17 (q, 2H) 83, 70 (s, 2H) 86.7-7.4 (m, 7H)

C23H28N206S

60.31 6.22 6.11 (59.99) (6.13) (6.08)

23

^ ch2ch2cooc2h5

HNV CH,

\ / CH3

CH

ch3

-ch2ch2cooc2h5

^ CH3

-CH

^ CH3

81.21 (t, 3H) 81.23 (d, 6H) 81.47 (s, 6H) ■ 82.78 (t, 2H) 83.04 (s, 2H) 83.40 (s, 3H) 83 , 2-3.8 (m, 3H) 84.12 (q, 2H) 56.6-7.2 (m, 3H)

C20H30N2OsS

58.43 7.29 6.65 (58.52) (7.37) (6.83)

1

Board

1

3 (continued)

649765

Ex. No.

Amine

R1

R2

H-NMR (8ppm value in CDCI3)

Elementary analysis Empirical formula Value found (Calculated value)

C (%) H (%) N (%)

24

/ ch2ch2c00ch3

H \

nch ch3

-ch2ch2c00ch3

/ ch3

-ch ch3

SI, 18 (d, 6H) 81.43 (s, 6H) §2.68 (t, 2H) 82.99 (s, 2H) 83.0-3.5 (m, 3H) 83.31 (s , 3H) 83.51 (s, 3H) 86.5-7.1 (m, 3H)

C19H28N2O5S

58.01 7.32 7.11 (57.56) (7.12) (7.07)

25

CH2CH2COOC4H9

H \

C <

ch3

-ch2ch2c0004h9

^ ch3

-ch

^ cha

80.6-1.8 (m, 7H) 81.17 (d, 6H) '81.42 (s, 6H) 82.65 (t, 2H) 82.94 (s, 2H) 83.31 (s, 3H ) 83.0-3.6 (m, 3H)

83.7-4.1 (m, 2H) 86.5-7.0 (m, 3H)

C22H34N2O5S

60.48 7.69 6.13 (60.25) (7.82) (6.39)

26

^, cnzcnzcoo - \\ /

h \ / ch3

ch xch3

-CH2CH2C00-XA /

^ ch3 -ch ^

ch3

80.6-1.8 (m, 15H) 81.16 (d, 6H) 81.42 (s, 6H) 82.68 (t, 2H) 82.98 (s, 2H) 83.0-3, 6 (m, 3H) 83.33 (s, 3H) 83.6-4.1 (m, 2H) 86.5-7.0 (m, 3H)

C26H42N2O5S

63.45 8.62 5.49 (63.13) (8.56) (5.66)

27

ch2ch2cooc2h5

hnv n-c ^ hg

-CH2CH2C00C2HS

-n-ct, hg

80.7-1.8 (m, 10H) 81.41 (s, 6H) 82.4-2.8 (m, 2H) 82.95 (s, 2H) 83.33 (s, 3H) 83, 1-3.4 (m, 4H) 83.97 (q, 2H) 56.6-7.2 (m, 3H)

C2lH32N2OsS

59.01 7.38 6.79 (59.42) (7.60) (6.60)

28

^, ch2ch2cooch3

hn

^ n-c ^ hg

-ch2ch2cooch3

-n this, hg

80.6-2.0 (m, 7H) 51.45 (s, 6H) 52.66 (t, 2H) 82.97 (s, 2H) 82.9-3.7 (m, 4H) 83, 35 (s, 3H) 83.54 (s, 3H) 86.5-7.0 (m, 3H)

C20H30N2O5S

58.79 7.14 6.66 (58.52) (7.37) (6.83)

29

ch2ch2cooc2h5

hn

^ sec-c ^ hg

-ch2ch2cooc2h5

-a ec-Ci, Hg

80.6-1.8 (m, 11H) 81.42 (s, 6H) 82.66 (t, 2H) 82.96 (s, 2H) 83.0-3.7 (m, 3H) 53, 31 (s, 3H) 53.95 (q, 2H) 86.6-7.0 (m, 3H)

c21h32n2o5s

59.62 7.71 6.53 (59.42) (7.60) (6.60)

649,765

12

Table 3 (continued)

Ex. No.

Amine

R1

R2

H-NMR (8ppm value in CDCI3)

Elementary analysis Empirical formula Value found (Calculated value)

C (%) H (%) N (%)

30

^, ch2ch2c00c2h5 HN ^

ÌBO-c4h9

-ch2ch2c00c2h5

-iso-CijHg

80.84 (d, 6H) 81.18 (t, 3H) 81.42 (s, 6H) 81.6-2.2 (m, 1H) 82.70 (t, 2H) 82.97 (s, 2H) 83.1-3.6 (m, 4H) 83.37 (s, 3H) 84.04 (q, 2H) 86.5-7.1 (m, 3H)

C2iH32N205S

59.71 7.54 6.63 (59.42) (7.60) (6.60)

31

xh2ch2cooc2h5

will go n-C6H13

-ch2CHzc00c2h5

-n-cghi3

80.7-2.0 (m, 14H) 81.46 (s, 6H) 82.63 (t, 2H) 82.98 (s, 2H) 82.9-3.6 (m, 4H) 83, 35 (s, 3H) 83.97 (q, 2H) 86.5-7.0 (m, 3H)

C23H36N2O5S

60.85 8.11 6.32 (61.04) (8.02) (6.19)

32

, »Ch2ch2c00c2H5

hn

\ z>

-CH2ch2c00c2hS

80.9-2.0 (m, 10H) 81.17 (t, 3H) 81.43 (s, 6H) 82.64 (t, 2H)

82.94 (s, 2H) 83.0-3.6 (m, 3H) 82.97 (s, 3H)

83.95 (q, 2H) 86.5-7.1 (m, 3H)

C23H34N2O5S

61.59 7.49 6.09 (61.31) (7.61) (6.22)

Example 33:

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N- (N-butyl-N-cyanomethylaminosulfenyl) -N-methyl-carbamate

11 g (0.05 mol) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate was dissolved in 70 ml of methylene chloride, then 5.2 g (0, 05 mol) of sulfur dichloride were added to the solution with cooling, and 5 g (0.05 mol) of triethylamine were added dropwise to the solution at -10 to -5 ° C. The mixture was stirred at 0 ° C for 1 h, then at room temperature for 2 h. After cooling, between -10 and -5 ° C, 5.6 g (0.05 mol) of N-butylaminoacetonitrile was added dropwise to the mixture, and 5 g (0.05 mol) of triethylamine were added dropwise drop by drop to the mixture. This was stirred at 0 ° C for 2 h, then left to stand overnight at room temperature. After adding 100 ml of methylene chloride, the reaction mixture was washed with 100 ml of water three times. The methylene chloride phase was dried, then concentrated in vacuo to give an oily product, which was almost entirely composed of the desired product although containing small amounts of impurities. Yield: 13.0 g (71.4%).

For the identification of the product, a portion of it was purified by column chromatography on Silicagel using a benzene / ethyl acetate mixture (5: 1) as solvent, so as to obtain an oily product.

NMR in chloroform-d! :

8 0.7-2.0 ppm (m, 7H) 8 1.42 ppm (s, 6H)

5 2.92 ppm (s, 2H) 8 2.9-3.5 ppm (m, 2H)

8 3.33 ppm (s, 3H) 8 4.01 ppm (s, 2H)

8 6.5-7.1 ppm (m, 2H)

Analysis for C18H2sN303S:

Calculated: C 59.48 H 6.93 N 11.56%

Found: C 59.19 H 7.02 NI 1.69%

(Molecular Weight 363,488)

It was thus confirmed that the product obtained had the following formula:

o-c-nc

, ch,

"s-n;

-ch-cn

* ch2ch2ch2ch3

Examples 34 to 42:

The compounds presented in Table 4 were prepared in the same manner as that described in Example 33. The physical properties and the NMR data (in chloroform-d,) of these compounds are also presented in Table 4.

(Table on following pages)

Example 43:

60

Preparation of N- (N-propionyl-N-ethoxycarbonylmethylamino-sulfenyl) -N-2,3-dihydro-2,2-dimethylbenzo-furan-7-yl-methylcarbamate

11 g (0.05 mol) of 2,3-65 dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate was dissolved in 70 ml of methylene chloride, then 5.2 g (0 0.05 mol) of sulfur dichloride was added to the solution with cooling, and 5 g (0.05 mol) of triethylamine were then added dropwise to

13

Table 4

649765

Ex. No.

Amine

R1

R2

H-NMR (8ppm value in CDCI3)

Elementary analysis Empirical formula Value found (Calculated value)

C (%) H (%) N (%)

34

^, ch2cn ™ \ ^ »3

CK-CH,

-ch2cn

^ ch3

-ch

^ ch3

81.28 (d, 6H)

81.42 (s, 6H) 83.00 (s, 2H)

83.43 (s, 3H) 84.34 (s, 2H) 83.3-4.1 (m, 1H) 86.5-7.2 (m, 3H)

C17H23N3O3S

58.23 6.59 12.21 (58.44) (6.64) (12.03)

35

^ / ch2cn hn j w

-ch2cn

• o

81.44 (s, 6H) 82.98 (s, 2H) 83.41 (s, 3H) 84.76 (s, 2H) 86.5-7.7 (m, 8H)

C20H21N3O3S

62.11 5.48 11.02 (62.65) (5.52) (10.96)

36

ch2cn htf ^

\ ^ C "3

-ch2cn

-f ^ ch3

81.47 (s, 6H) 82.33 (s, 3H) 83.00 (s, 2H) 83.39 (s, 3H) 84.80 (s, 2H) 86.5-7.5 (m, 7H)

C21H23N3O3S

63.51 5.79 10.31 (63.46) (5.83) (10.58)

37

j3h2ch2cn hn

^ chs

-ch2ch2cn

-ch3

81.46 (s, 6H) 82.5-2.9 (m, 2H) 83.00 (s, 2H) 83.17 (s, 3H) 83.0-3.5 (m, 2H) 83, 46 (s, 3H) 86.5-7.1 (m, 3H)

C16H21N303S

57.59 6.17 12.74 (57.30) (6.31) (12.53)

38

CH2CH2CN

<^ c „3 CH ^

ch3

-ch2ch2cn

/ ch3

-ch ch3

81.21 (d, 6H) 81.43 (s, 6H) 82.72 (t, 2H) 83.00 (s, 2H) 83.0-3.8 (m, 3H) 83.32 (s, 3H) 86.6-7.2 (m, 3H)

C18H25N3O3S

59.32 6.87 11.64 (59.49) (6.93) (11.56)

39

ch2ch2cn hn

Vn-Ci, Hg

-ch2ch2cn

-n-CijHg

80.7-2.0 (m, 7H) 81.44 (s, 6H) 82.5-2.9 (m, 2H) 82.98 (s, 2H) 82.9-3.5 (m, 4H) 83.37 (s, 3H) 86.5-7.0 (m, 3H)

C19H27N3O3S

60.64 7.41 11.25 (60.46) (7.21) (11.13)

40

/ ch2ch2cn hn

^ iso-CijHg

-ch2ch2cn

-iso-cijhg

80.90 (d, 6H) 81.43 (s, 6H) 81.7-2.2 (m, 1H) 82.69 (t, 2H) 82.96 (s, 2H) 83.0-3, 5 (m, 4H) 83.33 (s, 3H) 86.5-7.0 (m, 3H)

Ci9H27N303S

60.25 7.39 11.01 (60.46) (7.21) (11.13)

649765

14

Table 4 (continued)

Ex. No.

Amine

R1

R2

H-NMR (8ppm value in CDC13)

Elementary analysis Empirical formula Value found (Calculated value)

C (%) H (%) N (%)

41

ch2ch2cn

HN

n-C8H17

-ch2ch2cn

-n-CgHj7

80.7-2.0 (m, 15H) 81.47 (s, 6H) 82.6-2.9 (m, 2H) 83.01 (s, 2H) 83.0-3.5 (m, 4H) 83.40 (s, 3H) 86.5-7.0 (m, 3H)

C23H35N303S

63.59 8.31 9.54 (63.72) (8.14) (9.69)

42

^ ch2ch2cn hn

Xi>

-ch2ch2cn

"0

80.7-2.0 (m, 10H) 81.46 (s, 6H) 82.5-2.9 (m, 2H) 82.98 (s, 2H) 83.0-3.5 (m, 2H) 83.32 (s, 3H) 83.9-4.3 (m, 1H) 86.5-7.1 (m, 3H)

C21H29N303S

62.33 7.42 10.85 (62.51) (7.25) (10.42)

the solution between -10 and -5 ° C. The mixture was stirred at 0 ° C for 1 h, then at room temperature for 2 h. After cooling to -10 to -5 ° C, a solution of 8 g (0.05 mol) of N-propionylglycinethylester in 10 ml of tetrahydrofuran was added dropwise to the mixture, and 5 g (0.05 mol ) of triethylamine were added dropwise to this mixture. This was stirred at 0 ° C for 2 h, then left to stand overnight at room temperature. After adding 100 ml of methylene chloride, the reaction mixture was washed with 100 ml of water three times. The methylene chloride phase was dried, then concentrated in vacuo to give an oily product, which was almost entirely composed of the desired product, although containing small amounts of the starting materials and impurities. Yield: 14.3 g (69.8%).

For the identification of the product, a portion of it was purified by column chromatography on Silicagel, using a benzene / ethyl acetate mixture (9: 1) as solvent, so as to obtain crystals having a melting point of 108 to 109 ° C.

NMR in chloroform-d! : 5 l, 14ppm (t, 3H)

8 1.49 ppm (s, 6H)

8 3.02 ppm (s, 2H)

8 4.15 ppm (q, 2H) S 6.6-7.1 ppm (m, 3H)

8 1.23 ppm (t, 3H) 8 2.7-3.3 ppm (m, 2H) 8 3.48 ppm (s, 3H) 8 4.50 ppm (s, 2H)

Analysis for C19H26N206S: Calculated: C 55.59 H 6.38 Found: C 55.35 H 6.41 (Molecular Weight 410.499)

N 6.82% N 6.77%

It was thus confirmed that the product obtained had the following formula:

o-c-n;

-ch,

"S-K

, ch2cooc2hs -coch2ch3

Example 44:

Preparation of N- (N-ethoxycarbonyl-N-ethoxycarbonylmethylamino-sulfenyl) -N-2,3-dihydro-2,2-dimethylbenzo-furan-7-yl-methylcarbamate

11 g (0.05 mol) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate was dissolved in 70 ml of methylene chloride, then 5.2 g (0, 05 mol) of sulfur dichloride were added to the solution with cooling, and 5 g (0.05 mol) of triethylamine were then added dropwise to the solution between - 10 and - 5 ° C. The mixture was stirred at 0 ° C for 1 h, then at room temperature for 2 h. After cooling to -10 to -5 ° C, 8.8 g (0.05 mol) of N-ethoxycarbonylglycinethylester was added dropwise to the mixture, and 5 g (0.05 mol) of triethylamine were added to the mixture. was then added dropwise to this mixture. This was stirred at 0 ° C for 2 h, then 4 s left to stand overnight at room temperature. After adding 100 ml of methylene chloride, the reaction mixture was washed with 100 ml of water three times. The methylene chloride phase was dried, then concentrated in vacuo to give an oily product, which was almost entirely composed of the desired product 50 although containing small amounts of the starting materials and impurities. Yield: 18.2 g (84.7%).

For the identification of the product, a portion of it was purified by column chromatography on Silicagel, using a benzene / ethyl acetate mixture (4: 1) as solvent, so as to obtain a product oily.

NMR in chloroform-dt:

8 1.17 ppm (t, 6H) 8 2.94 ppm (s, 2H) 8 4.05 ppm (q, 2H) 8 4.41 ppm (s, 2H)

Analysis for Ci9H26N207S: Calculated: C 53.51 H 6.14 Found: C 53.82 H 6.19 (Molecular Weight 426.499)

8 1.44 ppm (s, 6H) 8 3.41 ppm (s, 3H) 8 4.15 ppm (q, 2H) 8 6.5-7.0 ppm (m, 3H)

N 6.57% N 6.44%

It was thus confirmed that the product obtained had the following formula:

15

649,765

CH2COOC2HS COOC2H5

Examples 45 to 52:

The compounds presented in Table 5 were prepared in the same manner as that described in Examples 43 and 44. The physical properties and the NMR data (in chloroform-d!) Of these compounds are also mentioned in Table 5.

Ex. No.

Amine r1

r2

h-nmr (Sppm value in CDCI3)

Elementary analysis Empirical formula Value found (Calculated value)

c (%) h (%) n (%)

45

^ ch2cooc2h5

hn

"s, c0ch2CJI

-ch2c00c2h5

-cocn2ci

81.21 (t, 3h) 51.46 (s, 6h) 52.98 (s, 2h) 53.40 (s, 3h) 54.05 (q, 2h) 54.36 (s, 2h) 54, 67 (s, 2h) 55.6-7.0 (m, 3h)

cI8h23n206c1s

49.98 5.17 6.43 (50.17) (5.38) (6.50)

46

ch2cooc2h5

hn, „

\ o- ^ 3

-ch2cooc2h5

51.18 (t, 3h) 51.41 (s, 6h) 52.87 (s, 3h) 52.91 (s, 2h) 54.06 (q, 2h) 54.60 (s, 2h) 56, 5-7.0 (m, 3h) 57.1-7.7 (m, 5h)

c23h26n2o6s

60.54 5.61 6.02 (60.25) (5.72) (6.11)

47

^ .ch ^ ooc ^ s hn

-ch2cooc2h5

-co ^ yc,

51.21 (t, 3h) 51.46 (s, 6h) 52.93 (s, 3h) 52.95 (s, 2h) 54.07 (q, 2h) 54.56 (s, 2h) 56, 5-7.0 (m, 3h) 57.1-7.6 (m, 4h)

C23H25N2OaClS

56.53 5.37 5.49 (56.04) (5.11) (5.68)

48

^ / ch2c00c2h5

hn s02- ^ ^ -ch3

-ch2cooc2h5

-so2- ^ ~ ^ -ch3

51.18 (t, 3h) 51.46 (s, 6h) 52.37 (s, 3h) 52.96 (s, 2h) 53.48 (s, 3h) 54.02 (q, 2h) 54, 58 (s, 2h) 56.5-7.9 (m, 7h)

c23h28n2o7s2

54.04 5.57 5.24 (54.31) (5.55) (5.51)

49

^, CH2c00c2hs hn cooch3

-ch2cooc2h5

-cooch3

51.19 (t, 3h) 51.46 (s, 6h) 52.97 (s, 2h) 53.43 (s, 3h) 53.74 (s, 3h) 54.07 (q, 2h) 54, 42 (s, 2h) 56.5-7.1 (m, 3h)

CI8h24n207s

52.15 5.64 6.66 (52.42) (5.87) (6.79)

649765

16

Table 5 (continued)

Ex. No.

Amine

R1

R2

H-NMR (Sppm value in CDC13)

Elementary analysis Empirical formula Value found (Calculated value)

C (%) H (%) N (%)

50

// CH2C00C2H5 HN

\ oo ^ 3

-CH2C00C2H5

-coo-f ^)

81.19 (t, 3H) 81.44 (s, 6H) 82.95 (s, 2H) 83.50 (s, 3H) 84.05 (q, 2H) 84.52 (s, 2H) 86, 5-7.4 (m, 8H)

C23K26N2O7S

57.97 5.61 5.78 (58.22) (5.52) (5.90)

51

^, ch2ch2cn

HN

C00C2H5

-ch2ch2cn

-cooc2h5

81.30 (t, 3H) 81.46 (s, 6H) 82.63 (t, 2H) 82.97 (s, 2H) 83.40 (s, 3H) 83.95 (t, 2H) 84, 16 (q, 2H) 86.5-7.0 (m, 3H)

c18h23n3o5s

55.16 5.93 10.31 (54.95) (5.89) (10.68)

52

, ch2ch2cooc2h5

HN

C00C2H5

-ch2ch2cooc2h5

-cooc2h5

81.17 (t, 3H) 81.32 (t, 3H) 81.46 (s, 6H) 82.57 (t, 2H) 82.98 (s, 2H) 83.40 (s, 3H) 83, 7-4.4 (m, 6H) 86.5-7.0 (m, 3H)

C20H28N2O7S

54.33 6.29 6.51 (54.54) (6.41) (6.36)

Examples of preparations according to the invention are now given below. These compositions are applicable to all the compounds of formula (I) according to the invention, an appropriate composition being usable for a particular application. The compositions which are presented only by way of illustration, and the proportions of the active compound, of the organic solvent, of the surfactant and of the support are variable according to the applications. In some cases, the nature of the organic solvent, of the surfactant, of the support, etc., can also be modified. The percentages are all given by weight.

Preparation example 1:

60% Emulsion:

Compound of Example 25 60.0%

Polyoxyethylenenonylphenyl ether 10.0%

Xylene 30.0%

Preparation example 2:

50% Emulsion:

Compound of Example 12 Polyoxyethylenesorbitan monooleate Sorbitan monooleate

Xylene

Cyclohexanone Preparation example 3: 20% Emulsion:

Compound of Example 22 Polyoxyethylenalkylether Xylene

Petroleum ether

50.0% 6.5% 3.5% 30.0% 10.0%

20.0% 5.0% 45.0% 30.0%

In each of the preparation examples 1 to 3, the ingredients were mixed uniformly and dissolved so as to obtain the desired emulsion.

Preparation example 4:

90% Wettable powder:

Compound of Example 1 Sodium Ligninesulfonate 40 Clay

Preparation example 5:

50% Wettable powder:

Compound of Example 21 45 Alkyl sulfate

Naphthalenesulfonic acid and formaldehyde condensate Kaolin so talc alkyl phosphate Talc

Preparation example 6:

30% Wettable powder:

Compound of Example 30 55 Alkylbenzenesulfonate

Sodium ligninsulfonate

White carbon

Clay

60

90.0% 3.0% 7.0%

50.0% 30.0%

10.0% 5.5% 3.5% 1.0%

30.0% 3.0% 2.0% 15.0% 50.0%

In each of Preparation Examples 4 to 6, ingredients were mixed uniformly with stirring using a Shinagawa type mixer. The mixture was then finely pulverized using a sample mill or a ball mill to obtain the desired wettable powder.

Preparation example 7: 5% Powder:

Composed of Example 46

5.0%

17

649,765

Land of diatomaceous earth 10.0%

Talc 85.0%

Preparation example 8:

2% Powder:

Wettable powder from Preparation Example 5 4.0%

Clay 95.8%

0.2% isopropyl phosphate

Preparation example 9:

0.5% Powder:

Wettable powder from Preparation Example 6 1.7%

100.3% clay

In each of the preparation examples 7 to 9, the ingredients were mixed uniformly with stirring using a mixer of the Shinagawa type in order to obtain the desired powder.

Preparation example 10:

20% Granule:

Wettable powder from Preparation Example 5 40.0%

Dolomite 60.0%

These ingredients were mixed uniformly, then a 2% aqueous solution of carboxymethylcellulose was added to the mixture in an amount of 15 parts by weight per 100 parts by weight of the mixture, and the resulting mixture was kneaded completely. The mixture was then granulated using a granulator and finely cut, then dried. Thus, the desired granule was obtained.

Preparation example 11:

10% Granule:

Compound of Example 40 10.0%

Sodium dodecylbenzenesulfonate 0.5%

Sodium ligninsulfonate 2.0%

Infusoria land 27.5%

Bentonite 60.0%

40

These ingredients were mixed evenly, and water was added to the mixture. The mixture obtained was kneaded completely, then put into granules using a granulator. The product thus granulated was finely cut, and dried in order to obtain the desired granule. 45

Preparation example 12:

3% Granule:

Compound of Example 8 3.0%

Polyvinyl alcohol 3.0%

Clay 94.0%

The same technique as in Preparation Example 11 was repeated in order to obtain the desired granule.

Examples of tests are given below. 55

Test example 1:

10 third instar larvae (instar) of the cutworm or caterpillar (cutworm) of tobacco (Spodoptera lituraj were placed on a cabbage (a young plant of one month) planted in a pot, and an emulsion at 60 50% of the compound to be tested was diluted to a specific concentration and applied to the leaves of the plant to completely wet it. The test compound for each specific concentration was tested on two pots. 3 d later, the larvae were observed in as regards their mortality, the results obtained being collated in Table 6, which also presents the results obtained with respect to control groups and groups not treated for comparison.

Table 6

35

Test compound (example N °)

Mortality (%)

Active ingredient concentration (ppm)

2000

1000

500

1

100

80

65

2

100

70

60

3

100

80

65

4

100

70

60

5

100

80

65

6

100

75

60

7

100

75

60

8

100

80

75

9

100

90

80

10

100

85

75

11

100

80

70

12

100

90

75

13

100

90

75

14

100

90

75

15

100

90

75

16

100

85

65

17

100

80

60

18

100

90

75

19

100

85

65

20

100

85

65

21

100

90

75

22

100

85

65

23

100

85

70

24

100

85

75

25

100

90

75

26

100

80

60

27

100

90

75

28

100

90

75

29

100

80

60

30

100

85

65

31

100

80

60

32

100

80

65

33

100

90

75

34

100

90

75

35

100

80

65

36

100

80

65

37

100

85

70

38

100

90

75

39

100

90

75

40

100

85

75

41

100

80

65

42

100

85

70

43

100

85

70

44

100

90

75

45

100

90

75

46

100

85

70

47

100

80

65

48

100

80

65

49

100

90

75

50

100

80

65

51

100

85

70

52

100

85

70

Control*

80

60

35

Untreated

-

0

-

* 1-Naphthyl-N-methyl carbamate used as a control.

649765

18

Test example 2:

An emulsion of specified concentration was prepared from a wettable powder 50% of the test compound and applied to the leaves of paddy or unhulled rice (young plant of one month) planted in a pot in order to completely wet it . After the emulsion was dried, the jar was covered with a mesh cage, into which ten adult female green rice leafhopper (Nepho-tettix cincticeps) were introduced. The compound of each specified composition was tested on two jars. 3 d later, the insects were observed with regard to their mortality, the results obtained being collated in table 7, which also presents the results obtained with regard to control groups and groups not treated for comparison.

Table 7

Test compound (example N °)

Mortality (%)

Active ingredient concentration (ppm)

800

400

200

1

100

85

50

2

100

85

45

3

100

85

45

4

100

70

40

5

100

80

45

6

95

75

55

7

90

70

50

8

95

85

60

9

100

90

60

10

100

90

60

11

95

80

55

12

100

90

65

13

100

90

65

14

100

90

65

15

100

90

65

16

100

90

65

17

95

75

55

18

100

90

65

19

100

80

60

20

100

80

60

21

100

90

65

22

100

80

60

23

100

85

55

24

100

90

60

25

100

90

65

26

100

75

55

27

100

90

65

28

100

90

65

29

100

75

45

30

100

80

60

31

100

75

55

32

100

75

55

33

100

90

70

34

100

90

65

35

95

75

60

36

95

75

60

37

100

85

65

38

100

90

70

39

100

90

70

40

100

85

70

41

95

75

60

42

100

85

65

43

100

85

60

44

100

90

70

45

100

90

65

Table 7 (continued)

Test compound (example N °)

Mortality (%)

Active ingredient concentration (ppm)

800

400

200

46

100

90

65

47

95

75

60

48

95

75

60

49

100

90

70

50

95

75

60

51

100

85

65

52

100

85

65

75

50

25

Control*

0

0

0

Untreated

-

0

-

* 2-Isopropoxy-phenyl-N-methyl carbamate was used as a control.

Test example 3:

Granules containing 10% of the test compound were mixed, in a specified amount, with soil contaminated with larvae of southern root-knot nematode (Meloidogyne incognita) and tomato plants were immediately transplanted into this soil. A month later, the roots of the plants were observed for the formation of nodules. Two test areas, 2 x 2 m2 each, were used for the compound as being applied in each of the specified amounts. The degree of nodule formation was determined according to the criteria given below, the results being collated in Table 8. For comparison, Table 8 also presents the results obtained in control surfaces and untreated surfaces.

Degree of nodule formation:

0:

0%

1:

up to 25%

2:

up to 50%

3:

up to 75%

4:

up to 100%

Table 8

Test compound (example N °)

Degree of nodule formation

Quantity of granules applied (kg / 10 a)

100

50

20

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

0

1

2

16

0

1

3

5

10

15

20

25

30

35

40

45

50

55

60

65

19

649,765

Table 8 (continued)

Table 9 (continued)

Degree of training

Test compound (example N °)

nodules

Quantity of granules applied (kg / 10 a)

100

50

20

17

0

1

3

18

0

1

2

19

0

1

2

20

0

1

3

21

0

1

2

22

0

1

3

23

0

1

2

24

0

1

25

0

1

2

26

0

1

2

27

0

1

2

28

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

1

39

0

1

40

0

1

1

41

0

1

3

42

0

1

2

43

0

1

2

44

0

1

45

0

1

2

46

0

1

2

47

0

1

3

48

0

1

3

49

0

1

50

0

1

3

51

0

1

2

52

0

1

2

Control*

2

4

4

Untreated

-

4

-

Test compound

LDS0

Test compound

LDS0

(example N °)

(P-g / g)

(example N °)

(M-g / g)

5

7

54.0

34

16.7

8

24.6

35

65.6

9

31.7

36

59.3

10

46.0

37

11.8

11

93.9

38

17.5

10

12

16.7

39

13.7

13

12.5

40

37.9

14

9.9

41

54.6

15

33.0

42

46.0

16

44.4

43

14.4

15

17

42.3

44

16.2

18

32.5

45

29.2

19

22.2

46

33.2

20

61.9

47

57.8

21

10.4

48

58.6

20

22

45.2

49

15.7

23

44.3

50

34.7

24

38.6

51

45.3

25

50.1

52

54.3

26

64.7

Control*

22.5

25

27

13.8

30

* 2-Isopropoxyphenyl-N-methyl-carbamate.

Test example 5:

The compounds of formula (I) according to the invention have been tested on male mice with regard to their acute toxicity by oral administration. Table 10 presents the LD50 values determined by the Litchfield-Wilcoxon method from the mortality observed on the seventh day. Table 10

* Bis- (2-chloro-1-methylethyl) ether.

Test example 4:

The test compound was dissolved in a predetermined amount of acetone. The solution was diluted to different concentrations and applied locally to house flies (Musca domestica). Table 9 presents the LD50 values determined by the Probit method from the mortality observed 24 h later.

Table 9

Test compound ld50

Test compound ld50

(example N °)

(pg / g)

(example N °)

(M-g / g)

1

21.3

28

17.7

2

58.8

29

22.5

3

40.0

30

23.8

4

28.9

31

33.1

5

75.6

32

32.7

6

38.3

33

9.1

Test compound ld50

Test compound ld50

(example N °)

(mg / kg)

(example N °)

(mg / kg)

1

58

28

89

40

2

140

29

120

3

145

30

133

4

122

31

135

5

90

32

107

6

135

33

103

45

7

75

34

95

8

105

35

95

9

158

36

70

10

115

37

65

11

93

38

125

50

12

125

39

110

13

115

40

103

14

120

41

105

15

110

42

88

16

110

43

43

55

17

69

44

128

18

135

45

80

19

108

46

105

20

75

47

95

21

105

48

80

60

22

88

49

105

23

113

50

95

24

77

51

88

25

123

52

125

26

150

Control*

5.6

65

27

105

* 2,3-Dihydro-2,2-dimethyl-7-benzofuran-7-yl N-methylcarbamate.

R

Claims (20)

649765 2 1. Carbamate derivative represented by the general formula (I): 0 ru o-c-n .ch, (ii) »/ CH3 o-c-n; ^ r-1 • s-n, "R (I) with sulfur dichloride, to form N- (chlorosulfenyl) -N-methylcarbamate of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl of io formula (III): in which R1 and R2, identical or different, each represent: 1) a —X — COOR3 group, in which X represents an alkylene group having from 1 to 6 carbon atoms, and R3 represents an alkyl group having from 1 to 8 atoms or a cycloalkyl group having 3 to 6 carbon atoms, or 2) a —Y — CN group, in which Y represents an alkylene group having from 1 to 6 carbon atoms, and R2 also represents an alkyl group having 1 to 8 carbon atoms; a cycloalkyl group having 3 to 6 carbon atoms; a benzyl group, which may be substituted with a halogen atom, an alkyl group having from 1 to 3 carbon atoms or an alkoxy group having from 1 to 3 carbon atoms; a phenyl group, which may be substituted with a halogen atom, an alkyl group having from 1 to 3 carbon atoms or an alkoxy group having from 1 to 3 carbon atoms, or —Z — R4, in which Z represents a group carbonyl or a sulfonyl group, and R4 represents an alkyl group having from 1 to 6 carbon atoms, a phenyl group, a benzyl group, an alkoxy group having from 1 to 6 carbon atoms or a phenoxy group. 2. Carbamate derivative according to claim 1, represented by formula (I), in which X represents an alkylene group having 1 or 2 carbon atoms, and R3 represents an alkyl group having from 1 to 4 carbon atoms which can be straight or branched chain, and Y represents an alkylene group having 1 or 2 carbon atoms and R2 represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. 3. 2,3- Dihydro-2,2-dimethylbenzofuran-7-yl N- [N, N-bis (ethoxycarbonylmethyl) aminosulfenyl] -N-methyl-carbamate according to claim 1 or claim 2. 4. N- (N-methyl-N-ethoxycarbonylmethylaminosulfenyl) -N-2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate according to claim 1 or claim 2. 5. N- (N-isopropyl-N-ethoxycarbonylethylaminosulfenyl) -N-2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate according to claim 1 or claim 2. 6. N- (N-n-butyl-N-ethoxycarbonylethylaminosulfenyl) -N-2,3-dihydro-2,2-dimethylbenzofuran-7-yl 2,3-dihydro-2,2-dimethylbenzofuran according to claim 1 or claim 2. 7. N- (N-cyclohexyl-N-ethoxycarbonylethylaminosul-fenyl) -N-methyl-carbamate of 2,3-dihydro-2,2-dimethylbenzo-furan-7-yl according to claim 1 or claim 2. 8. N- (N-n-butyl-N-cyanoethylaminosulfenyl) -N-methylcarba-mate of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl according to claim 1 or claim 2. 9. An insecticide, miticide or nematocide composition comprising an insecticide, miticide or nematocide effective amount of the carbamate derivative of formula (I) according to claim 1 as active ingredient. 10. The insecticide, miticide or nematocide composition according to claim 9, comprising an insecticide, miticide or nematocide effective amount of the carbamate derivative of formula (I) according to claim 2 as an active ingredient. 11. Process for the preparation of the carbamate derivative of formula (I) according to claim 1, characterized in that a compound of formula (II) is reacted: ch ch o-c-n: • C.H3 • sc £ (iii) 20 then reacting this compound of formula (III) with an amine of formula (IV): HN y \ R1 (IV) R2 wherein R1 and R2 are as defined in claim 1. 12. Method according to claim 11, characterized in that 1 to 2 mol of sulfur dichloride per mole of the compound of formula (II) is used. 13. Method according to claim 11, characterized in that the reaction of the compound of formula (II) with sulfur dichloride is carried out in the presence of a solvent. 14. Method according to claim 13, characterized in that the solvent is chosen from methylene chloride, chloroform, Carbon tetrachloride, diethyl ether, dibutyl ether, tetrahydrofuran and dioxane. 15. Method according to claim 11, characterized in that the reaction of the compound of formula (II) with sulfur dichloride is carried out in the presence of a basic compound. 16. Method according to claim 15, characterized in that the basic compound is chosen from triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine, pyridine, a, ß, y-picoline and lutidine. 17. Method according to claim 11, characterized in that 45 that about 1 to 2 mol of the amine of formula (IV) are used per mole of the compound of formula (III). 18. Method according to claim 11, characterized in that the reaction of the compound of formula (III) with the amine of formula (IV) . is carried out in the presence of a solvent. 19. Method according to claim 18, characterized in that the solvent is chosen from methylene chloride, chloroform, carbon tetrachloride, diethyl ether, dibutyl ether, tetrahydrofuran and dioxane. 20. Method according to claim 11, characterized in that 55 reaction of the compound of formula (III) with the amine of formula (IV) is carried out in the presence of a basic compound. 21. The method of claim 20, characterized in that the basic compound is chosen from triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine, py- 60 ridine, a, ß, y-picoline and lutidine. 22. Process for the destruction of harmful insects, mites or nematodes by applying to them a carbamate derivative of formula (I) according to claim 1. 23. The method of claim 22 by applying the derivative 65 of carbamate of formula (I) according to claim 2. 3 649,765