SE451327B - - Google Patents

Description

451,327 have been investigated and the results of these surveys have been reported. Belgian Patent 817 517 discloses, for example, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N- (N, N-dibutylaminosulphenyl) -N-methyl-carbamate and German Patent DT-OS 2,254,359 indicates 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- & (N-methyl-N-benzenesulfonylaminosulphenyl) -N-methyl-carbamate.

However, these compounds do not meet the requirements regarding n insecticidal activity and toxicity to warm-blooded animals and fish and with regard to the manufacturing process.

According to the present invention, intensive research has been directed to the development of carbamate compounds which meet all of these requirements, it being found that the intended objects can be achieved using compounds having the general formula (I): CH CH wherein R 1 and R 2, which may be the same or different, each represents (1) -X-COOR 3, wherein X represents an alkylene group having 1-6 carbon atoms, and R 3 represents an alkyl group having 1-8 carbon atoms or a cycloalkyl group having 3-6 carbon atoms; or (2) -Y-CN, wherein Y represents an alkylene group having 1-6 carbon atoms; and wherein R 2 further represents an alkyl group having 1-8 carbon atoms; a cycloalkyl group having 3-6 carbon atoms; a benzyl group which may be substituted by a halogen atom; a phenyl group which may be substituted by a halogen atom, an alkyl group having 1-3 carbon atoms or an alkoxy group having 1-3 carbon atoms; or -Z-R 4, wherein Z represents a carbonyl group or a sulfonyl group and R 4 represents an alkyl group having 1-6 carbon atoms, a phenyl group, an alkoxy group having 1-6 carbon atoms or a phenoxy group. In the definition of formula (I) above, the alkyl moiety of the alkyl group, the alkylene group and the alkoxy group may be straight or branched.

Compounds of formula (I '): R 1' cH / (p) CH wherein R 1 'and R 2I, which may be the same or different, each represent (1) -X'-COOR 3', wherein X 'represents an alkylene group having 1 - 2 carbon atoms and R 3 'represents an alkyl group having 1-4 carbon atoms, which may be straight or branched; or (2) -Y'-CN, wherein Y 'represents an alkylene group having 1-2 carbon atoms: and wherein R 2' further represents an alkyl group having 1-6 carbon atoms or a cycloalkyl group having 3-6 carbon atoms, is preferred according to the invention. The objects according to the invention have thus been achieved.

The compounds of formula (I) are novel compounds not previously described in the literature and discovered according to the invention. It has been shown that the new compounds have excellent insecticidal activity or effect for controlling pests in agriculture and forestry as well as pests in the household and are comparable in this effect with carbofuran, which has the highest insecticidal activity known to date. The associations are active against a variety of different pests, mites and nematodes, which are harmful to vegetables, trees, other plants and humans, e.g. Hemiptera, Lepidoptera, Coleoptera, Diptera, Thysanoptera, Orthoptera, Isopoda, Acarína, Tylenchída, etc.

Examples of these insects, mites and nematodes are the following: 451 327 Hemigtera (l) Deltocephalidae: Nephotettix cincticeps (2) Delphacidae: Laodelphax striatellus, Nilaparvata lugens (3) Aphidídae: Myzus persicae, Aphis gossyparae (4) viridula Legidogtera (l) Noctuidae: Spodoptera litura, Agrotis fucosa, Laphygma exiqua (2) Tortricidae: Adoxophyes orana (3) Pyrálídae: Chilo suppressalis, Ostrinia furnacalis, Cnaphalocrocis medinalis (4) Plutoleocidae: 4 Lissorhoptrus oryzophilus (2) Scarabaeidae: Popillia japonica (3) Coccinellidae: Henosepilachna vigintioctopunctata Digtera (l) Muscidae: Musca domestica (2) Cecidomyiidae: Aspondylia sp. (3) Agromyzidae: Phytobia cepae Thysanogtera Thripidae: Thrips tabaci, Scirtothrips dorsalis Orthogtera Gryllotalpidae: Gryllotalpa africana Isogoda Armandillidae: Armadillidium vulgare Acarina Tetranychidae: Tetranychus telarius, Tetranychus urticae, Panonychus citri Tylenchida heteroderidae: Meloidogyne incognita f) 451,327 toxicity of karbamatderívaten of formula (I) for warm-blooded animals is as low as about 1/5 to about 1/100 of the toxicity of carbofuran. The compounds according to the invention show insecticidal activity or effect for controlling the above-mentioned organisms in each stage or a specific stage of their growth and they are thus effectively useful for controlling them in agriculture and forestry as well as for sanitary purposes.

The compounds of formula (I) are very easy to prepare with a high degree of purity and in high yields and show commercial advantages which are described in detail below.

Typical compounds of formula (I) are those described in Examples 1-52 below. Of these compounds, the following are particularly preferred according to the invention: 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- / N, N-bis (ethoxycarbonylmethyl) aminosulphenylph-N-methylcarbamate, 2,3- dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-methyl-N-ethoxycarbonylmethylaminosulphenyl) -N-methylcarbamate, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N -isopropyl-N-ethoxycarbonylethylaminosulphenyl) -N-methylcarbamate, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (Nn-butyl-N-ethoxycarbonylethylaminosulphenyl) -N-methylcarbamate, 2, 3-Dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-cyclohexyl-N-ethoxycarbonylethylaminosulphenyl) -N-methylcarbamate, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (Nn -butyl-N-cyano-ethylaminosulphenyl) -N-methyl-carbamate.

The compounds of formula (I) may be prepared, for example, by giving a compound having the formula (II): O H o-c-N: 3 - CH 3 I H (II) CH 2. _. to react with sulfur dichloride to give 2,3-dihydro--2,2-dimethylbenzofuran-7-yl-N- (chlorosulphenyl) -N- methyl carbamate having the formula (III): CH2 L SC2 C12 JO CH3 which is then reacted with an amine compound having the formula (IV): R1 HN '// \ R2 (IV) wherein R1 and R2 have the meaning given above.

The reaction of the compound of formula (II) with sulfur dichloride can be carried out in the presence or absence of a solvent.

Examples of useful solvents are methylene chloride, chloroform, carbon tetrachloride and similar hydrocarbon halides, as well as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane and similar ethers. The proportions between the compound of formula (II) and SC12 are not particularly limited, but a wide range thereof can be used. Usually 1 ~ 2 moles are used, preferably about 1 to about 1.2 moles of the latter per mole of the former. The reaction is preferably carried out in the presence of a basic compound. Examples of useful basic compounds are triethylamine, tributylamine, dimethylaniline, diethylaniline, ethyl-morpholine and similar tertiary amines, pyridine, æv4, γ = picoline, lutidine, etc. The basic compound may be used in an amount sufficient to capture it. hydrogen chloride formed HA in the reaction as a by-product. Usually 1-2 moles of the basic compound are used per mole of compound of formula (II).

The reaction, which proceeds under cooling, at room temperature or during heating, is usually carried out at -70 to 5000, preferably about -10 to about 30 ° C. The reaction time is about 2 to about 7 hours, preferably about 3 to about 5 hours. The compound (III) is then reacted with an amine compound having the formula (IV).

Examples of useful amine compounds of formula (IV) are the secondary amines represented by formulas (V) to (IX): 3 x-coon / HN (v) \ "R Y-CN HN (VI) \ * R 3 / // x-coon HN (VII) \\ ~ x "-cooR3" 3 HN (VIII) \ * \ Y-cN // Y-CN HN \\\ (Ix) Y "-cm In formulas (V) to (IX) X, Y and R 3 have the meaning given above; R represents an alkyl group having 1-8 carbon atoms; a cycloalkyl group having 3-6 carbon atoms; a benzyl group which may be substituted by a halogen atom; a phenyl group which may be substituted by a halogen atom, an alkyl group having 1-3 carbon atoms or an alkoxy group having 1-3 carbon atoms; Z'-R ', wherein Z' represents a carbonyl group or a sulfonyl group and R4 'represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a alkoxy group having 1-6 carbon atoms or a phenoxy group (wherein the alkyl group or alkoxy group may be straight or branched); 3 R3 has the same meaning as R; X "has the same meaning as X; and Y "has the same meaning as Y.

Representative examples of amine compounds of formula (V) are the following: N-methylglycine methyl ester, N-methylglycine ethyl ester, N-methylglycine butyl ester, N-ethylglycine ethyl ester, Nn-propyl = glycine ethyl ester, N-isopropylglycine ethyl ester, Nn-butylglycine ethyl ester N-sec-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-phenylglycine ethyl ) glycine ethyl ester, N- (4-methoxyphenyl) glycine ethyl ester, ethyl N-methylaminopropionate, ethyl Nn-propylaminopropionate, methyl N-isopropylaminopropionate, ethyl N-isopropylaminopropionate, butyl N-isopropylaminopropionate, 2-N-isopropylaminopropionate isopropylaminopropionate, methyl-Nn-butylaminopropionate, ethyl-Nn-butylaminopropionate, ethyl-N-isobutylaminopropionate, ethyl-N-sec-butylaminopropionate, ethyl-Nt-butylaminopropionate, ethyl-Nn-amyl-aminopropionate -N-isoamylaminopropionate, ethyl-Nn-hexylaminopro pionate, ethyl N-cyclohexylaminopropionate, N-acetylglycine ethyl ester, N-chloroacetylaminoglycine ethyl ester, N-propionylglycine ethyl ester, N-benzoylglycine ethyl ester, N- (4-chlorobenzoyl) -glycine ethyl ester, N-tethyl ester, etc.

Representative examples of the amine compound of formula (VI) are the following: N-methylaminoacetonitrile, N-ethylaminoacetonitrile, Nn-propylaminoacetonitrile, N-isopropylaminoacetonitrile, Nn-butylaminoacetonitrile, N-isobutylaminylaminoacetonitrile, 4-methylphenyl) -aminoacetonitrile, N-methylaminopropionitrile, Nn-propylamino-3! propionitrile, N-isopropylaminopropionitrile, Nn-butylaminopropionitrile, N-isobutylaminopropionitrile, N-sec-butylaminopropionitrile, N-octylaminopropionitrile, N-cyclohexylaminopropyl, pionitrile, etc. are the following: methyliminodiacetate, ethyliminodiacetate, isopropyliminodiacetate, cyclohexyliminodiacetate, methyliminodipropionate, ethyliminodipropionate, N-methoxycarbonylglycine ethyl ester, N-ethoxycarbonylglycinethyl ester, N-phenoxycarbonyl, N-phenoxycarbonyl butyrate, ethyl 2- (ethoxycarbonylmethylamino) butyrate, ethyl N-ethoxycarbonylaminopropionate, etc.

Representative examples of amine compounds of formula (VIII) are the following: methyl N-cyanomethylcarbamate, ethyl N-cyanomethylcarbamate, ethyl N-cyanoethylcarbamate, N-cyanomethylglycine ethyl ester, N-cyanoethylglycine ethyl ester, ethyl-N-amopropionate , ethyl N-cyanoethylaminopropionate, etc.

Representative examples of amine compounds of formula (IX) are the following: iminodiacetonitrile, iminodipropionitrile, iminodibutyronitrile, etc.

The reaction between the compound of formula (III) and the amine compound of formula (IV) may be carried out in the presence or absence of a solvent. Any solvent useful for the reaction between the compound of formula (II) and sulfur dichloride is useful for this reaction. The proportions between the compound of formula (III) and the amine are not particularly limited but a wide range is useful. Usually about 1 to about 2 moles are used, preferably about 1 to about 1.2 moles of the latter per mole of the former.

It is also preferred to carry out this reaction in the presence of a basic compound, which may be any of the above.

The basic compound can be used in an amount sufficient to capture the hydrogen chloride formed in the reaction as a by-product. Usually 1 to 2 moles are used, preferably 1 to 1.5 moles of the basic compound per mole of compound of formula (III). The reaction, which proceeds under cooling, at room temperature or during heating, is usually carried out at -20 to 50 ° C, preferably 0-30 ° C.

The reaction time is usually about 10 to about 15 hours. The compound of the invention of formula (I) thus prepared can be readily isolated and purified by commonly used separation methods, e.g. solvent extraction, recrystallization or chromatography.

The compounds (I) of the invention may be formulated into emulsions, wettable powders, suspensions, concentrated suspensions, granules, fine particles, pellets, powders, coating compositions, foam sprays, aerosols, microcapsule compositions, impregnating agents for application to natural or synthetic materials, smoking agents, concentrated preparations for application in small quantities, etc.

Various surfactants are useful for preparing such emulsions, dispersions, suspensions and foams. Examples of useful nonionic surfactants are polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, sorbitan alkyl esters, etc. Examples of useful anionic surfactants are alkylbenzenesulfonates, alkylsulfosuccinates, alkylsulfanesulfonyls, alkylethanesulfonylalkylates, etc.

Solvents, diluents and carriers for the compounds of the invention include a variety of organic solvents, aerosol propellants, natural minerals, vegetables, synthetic compounds, etc. Examples of preferred organic solvents are benzene, toluene, xylene, ethylbenzene, chlorobenzene, alkylnaphthalene, dichloromethane, dichloromethane chloroethylene, cyclohexane, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohols, dimethylformamide, dimethyl sulfoxide, acetonitrile, fractions of mineral oils, etc. Examples of useful aerosol fuels are propane, butane, hydrocarbon halides, useful nitrogen, minerals, minerals, etc. are kaolin, talc, bentonite, diatomaceous earth, clay, montmorillonite, chalk, calcite, pumice, dolomite, etc. Examples of useful vegetables are coconut shells, tobacco stalks, sawdust, etc. Examples of useful synthetic compounds are f), alumina , silicates, sugar polymers, etc. You can also use glues, such as carboxymethylce cellulose, gum arabic, polyvinyl alcohol, polyvinyl acetate, etc. The preparations can be dyed with organic or inorganic dyes.

The compounds (I) of the invention may be formulated into various preparations, such as those exemplified above, so that the preparations contain as active ingredient an effective amount as insecticidal, miticidal or nematocidal (eg about 0.1 to about 95% by weight). , preferably about 0.5 to about 90% by weight) of the compound. Depending on the intended use, the preparations were used as such or diluted with a carrier or with water.

The invention is further described by the following examples.

Example 1

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- [N, N-bis (cyanomethyl) aminosulphenyl] -N-methylcarbamate 11 g (0.05 mol) 2,3-dihydro-2 .2-Dimethylbenzofuran-7-yl-N-methyl carbamate was dissolved in 70 ml of methylene chloride, 5.2 g (0.05 mol) of sulfur dichloride was added to the solution under cooling and 5 g (0.05 mol) of triethylamine was added. then dropwise to the solution at 0 ° C. The mixture was stirred at the same temperature for 2 hours, a solution of 4.8 g (0.05 mol) of iminoacetonitrile in 40 ml of tetrahydrofuran was then added dropwise to the mixture at the same temperature and 5 g (0.05 mol) of triethylamine was further added dropwise. - show to the mixture. The resulting mixture was stirred at 0 ° C for 4 hours and then allowed 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 layer was dried and then concentrated in vacuo to give an oily product which consisted almost exclusively of the desired product even though it contained small amounts of the starting materials. Yield: 13.8 g (79.8%).

To identify the product, a portion thereof was purified by silica gel column chromatography using benzene / ethyl acetate (4: 1) as solvent, crystals being added. .. .. ......._._._. ~. A melting point of 94-9 ° C was obtained.

NMR in chloroform-dl: δ 1.48 ppm (S, sn) 53.02 ppm (S, zu) δ 3.50 ppm (s, 3H) δ 4.32 ppm (s, 4H) δ 6.6-7 , 2 ppm (m, 3H), Elemental analysis: CHN Found (%) 55.36 5.31 16.05 Calculated for C 16 H 18 N 4 O 3 S 55.48 5.24 16.17 (molecular weight 346.418) It was thus found that the product had the following formula: 0 ll CH S ocN // /, CH, 5'N ~ 0 „* cn2cN / \ l CHZCN CH3 Example 2.

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl- -N- [N, N-bis (ethoxycarbonylmethyl) aminosulphenyl] -N-methylcarbamate 11 g (0.05 mol) 2,3-dihydro- 2,2-Dimethylbenzofuran-7-yl-N-methylcarbamate was dissolved in 50 ml of chloroform, 5.2 g (0.05 mol) of sulfur dichloride was added to the solution under cooling and 5 g (0.05 mol) of triethylamine was added further dropwise. to the solution at 0 ° C.

The mixture was stirred at the same temperature for two hours, a solution of 9.5 g (0.05 mol) of ethyl iminodiacetate in 20 ml of chloroform was then added dropwise to the mixture at the same temperature and 5 g (0.05 mol) of triethylamine was further added. dropwise to the mixture. The resulting mixture was stirred at 0 ° C for 2 hours and then allowed 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 layer was dried and then concentrated in vacuo to give (3 451 327 13 g of an oily product which consisted almost exclusively of the desired product even though it contained small amounts of the starting materials. Yield: 1.59 g (72.3%).

To identify the product, a small portion thereof was purified by silica gel column chromatography using benzene / ethyl acetate (4: 1) as the solvent to give an oily product.

NMR in chloroform-d: 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, Ppm (q, 4H) δ 4.28 ppm (s, 4H) δ 6.6-7.2 ppm (m, 3H) Elemental analysis: CHN Found (%) 54.68 6.46 6.38 Calculated for C 2 OH 28 N 2 O 7 S 54,53 6,41 6,36 (molecular weight: 440,526) Thus it was found that the product had the following formula: 0 || m3 o-c-N / cnzcooczns \ S_N / CH 30 0 \ c flzcoocz fl s CH3 Examples 3-5.

The compounds listed in Table 1 below are prepared in the same manner as in Examples 1 or 2. Physical data and NMR data (in chloroform-dl) for these compounds are also given in Table 1. 451 327 14 Note ~. ~ | ß.mm. ^ = ~ .sv Hm | m. «@ .Amm .mv m ~ .mm mou ~ = u, / ^ ~ H.mv ^ mm. ~ v ^ m ~ .Hmv. ^ = m .mv mm.mm N 1 N 1 2. m mm. «mm.N ~ m. ~ m .ñmw .mv ~ o.nm Qom: U omv = m \\ _. ^ = m .mv m« .Hm oou ~ = u mo ~ = m: = m ~ u. ^ = @ N .ev ~. ~ «Q. ~ m ^ = m .Ev ~ .ß | m.mm .QS .av needle fi â. ^ = <.mv mN .mm ^ mm.mv ^ mm.mv ^ om.mmv. ^ = m .mv ~ <.mm mm.m Hm.m mm.mm. ^ = ~ .mv ~ o.mm V.0oo ~ = m, /. ^ = m .mv m «.Hm v | oou ~ = m | v | oou ~ = m | \\ z = v mmo ~ z ~ m = -u. ^ = m .mv m ~ .Hm vfoou ~ = u ^ = m .Ev ~. ~ | ~ .mm. ^ = m .mv @ ~. «m ^ mN.mv ^ ~ m.mv ^ ~ m. ~ mv. ^ = m .mv m ~ .mm mm.m Hm.m HH.Nm. ^ = fi .mv H «.mm m = Qoou ~ = m . ^ = ~ .mv No.mm m = UooU ~ = m | m = Uo @ U ~ = m «~ wz = m m.m ~ z. ~ = m.m. ^ = m .mv .m.Hm m = mmom ~ = m ^ Nv ^ Nv. ^ Nv 1 |. . ||| 2 = U vmmmnm mm Hm = me <H = .xn ^ mwHw> vmnxwnwmv Q & avw®Hm> | @_ N wmnmä uwcnøm mzzš ||| HmaHow 4 mwwmnmumu fl wåwam: |; Q m = U wa \ I / Wznm /, Q m = u \ .z «ø | om = o = Q vx" H .Swnmü 451 327 15 Example 6.

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- - [N, N-bis (ethoxycarbonylethyl) aminosulphenyl] -N-methylcarbamate 11 g (0.05 mol) 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 was added to the solution under cooling and 5 g (0.05 mol) of triethylamine were further added dropwise to solution at -10 to -5 ° C. The mixture was stirred at 0 ° C for one hour and further at room temperature for 2 hours. After cooling to -10 to -5 ° C, 10.9 g (0.5 mol) of ethyl iminodipropionate was added dropwise to the mixture and 5 g (0.05 mol) of triethylamine was added dropwise thereto. The resulting mixture was stirred at 0 ° C for 2 hours and then allowed 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 layer was dried and then concentrated in vacuo to give an oily product, which consisted almost exclusively of the desired product even if small amounts of impurities were present. Yield: 16.9 g (72.2%).

To identify the product, a small portion thereof was purified by silica gel column chromatography using benzene / ethyl acetate (5: 1) as the solvent to give an oily product.

NMR in chloroform-dl: § 1.21 ppm (t, 6H) δ 1.44 ppm (s, 6H) § 2.67 ppm (t, 4: a) 52.97 ppm (s, 2: a) § 3.37 ppm (s, 3H) ¿3.42 ppm (t, 4H) § 4.04 ppm (q, 4H) 86.5-7.2 ppm (m, 3H) Elemental analysis: ICHN Found (%) Calculated for C 22 H 32 N 2 O 7 S: 56.39 6.88 _ 5.98 (molecular weight: 468.58) The product was thus found to have the following formula:. _. .__.....-.,.,. - - .w v x rn »n-u-t-c r- 451 527 16 3 o-c-N” ”/, cn2cH2cooc2H5 0“ \ cH2cH2cooc2H5 CH, Example 7.

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N-: [N, N-bis (cyanoethyl) aminosulphenyl] -N-methylcarbamate 11 g (0.05 mol) 2,3-dihydro-2 , 2-dimethylbenzofuran-7-yl-N-methylcarbamate was dissolved in 50 ml of chloroform, 5.2 g (0.05 mol) of sulfur dichloride was added to the solution under cooling and 5 g (0.05 mol) of triethylamine was further added dropwise to the solution at -io to -5 ° c. The mixture is stirred at 0 ° C for one hour and further at room temperature for one hour. After cooling to -10 to -5 ° C, 6.2 g (0.05 mol) of iminodipropionitrile was added dropwise to the mixture and 5 g (0.05 mol) of triethylamine was then added dropwise to the mixture. The resulting mixture was then stirred at 0 ° C for 2 hours and then allowed 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 layer was dried and concentrated in vacuo to give an oily product which consisted almost exclusively of the desired compound even though it contained small amounts of impurities. Yield: 12.2 g (65.2%).

To identify the product, a small portion thereof was purified by silica gel column chromatography using benzene / ethyl acetate (4: 1) as the solvent to give an oily product.

NMR in chloroform-d: 1 β] δ 43 ppm (s, 6H) 52.73 ppm (t, 4H) δ 2.97 ppm (S, za) 53.37 ppm (S, ss) 33.43 ppm ( t, 4H) δ 6.5-7.2 ppm (m, 3H) Elemental analysis: CHN Found (%): 57.9l 5.79 15.04 Calculated for CHNOS: 57.73 5.92 14.96 18 22 4 3 (In 451 327 17 (molecular weight: 374.47) It was thus found that the product had the following formula: 1 | cH3 ,, cH2cH2cN X0 \ \ cH2cH2cN css l / ExemBel 8-ll.

The compounds listed in Table 2 below were prepared in the same manner as in Example 6 or 7. The physical properties and NMR data (in chloroform-dl) of these compounds are also listed in Table 2.

..-.... Ma.- .......-........... 451 327 l8 Én .Ev N Ktm. E, »n. ^ = ~ .Vv mm.v @. ^ = ~ .Mv vH.v @ .G5 .E 3.2 .ÉN Jv ov2 n - u ^ = n mv mm mv ^ @ H. @ v ^ m @. @ v ^ om.mmv. ^ = ~ .mv Q = .m @ ... Qm 2 .... .v92 .så .av 2.3 måuoøuåu /. ^ = @ .mv m «. ~ @ m = ~ UooQ ~ = u »m = ~ voou ~ = U ~ = u | \\ z = Q mßowzomvväo .sä Jv 2.3 åwuoouåuåu ^ = «.ev ~. ~ | @. @@. ^ = ~ .vv o ~ .v @. ^ = ~ .mv æH. <@. ^ = ~. ev wm | m.mv. ^ = m .mv ov.mv ^ Hm. @ Hv ^ m ~. @ v WHo.vmv. ^ = ~ .mv ~ on @ N <@. O fi flfi. @ @ w.mm . ^ = ~ .Ev ~ .m | @. ~ Vm = ~ QQoQ = U, /. ^ = @ .Mv ~ «.Hv m = ~ voou ~ = @ | zQ ~ = Q ~ = u- 2: w mmomzm fl zm fi u. ^ = m .uv @ ~ .vv zU ~ = Q ~ mQ \ ñ fl v ^ Nv ^ Nv. . z = U vmauau H Na Hm = .E <H: xm = m mumm ^ s @@ vwwHm> | @_ Ü fl hwwxv QÜCCDW MZZII lllduëudulmw fl m fl mñüií 1 |. : ö 2 / am zw // = u .m \\ z | U | om = Q = 0 "__ A m <.__ 451 327 ^ = ~ .Ev ~ .ß | m.mm. ^ = ~ .ev m. «| m.mm. ^ = ~ .mv wm.mm. ^ = N .mv ~ o.mm. ^ = N .ev m. ~ | mH @ m = ~ uoou ~ = u // ^ mm. mv ^ mm.mv ^ om.mmv. ^ = m .mv m «.Hm 2: Am.mw ~ .m nm.mm. ^ = m .mv m ~ .Hm m = ~ uoom ~ = U» m = ~ uoou = U | m = ~ oQ ° o =% \\ HH. ^ = m .mv o ~. fi m _ mmo ~ z ~ m = ~ NQ _. ^ = ~ .mv mm. @ mm = uN = um = u ~ = u ^ = m .av ~. ~ | m.mm 9. ^ = ~ .mv ~ H. «m 1. ^ = ~ .mv mH.« m. ^ = ~ .vv mH. «m . ^ = fl .mv ~ <.mm. ^ = N .mv m fl. mm ^ wm.mv ^ mm.mv ^ @ «. mmv. ^ = ~ .mv @ o.mm m ~ .m ~ mm« m .mm. ^ m «.Ev m. ~ | ~ .Hm m N Û N ~ NN m = ~ moom ~ = u, / 7. OH. ^ = m .mv m <. ~ @ = Qoo @ N = u1 . = u@ou.=o: Q: ul; m> o ~ zNm = -m. ^ = m .mv -. ~ mm = ~ uoom ~ = o ~ mm ~ = o \\ ^ Nv ^ Nv ^ Nv 2 __ 0 Hmmunu M Na Hz = «: <.uc.xm ^ mm ~ m> mmcxmmmmv @ a @ vm @ mm> -m_ wøHw> umccsm zzz | =.

HÜEHOMH MMHHHWEN mæ fl mcmnmucmâm fi m 451 327 zo Example 12.

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-butyl-N-ethoxycarbonylaminosulphenyl) -N-methylcarbamate 11 g (0.05 mol) 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 was added to the solution under cooling and 5 g (0.05 mol) of triethylamine were further added dropwise to the solution. at -10 to -5 ° C. The mixture was stirred at 0 ° C for one hour and further at room temperature for 2 hours; After cooling to -10 to -s ° C, 8.0 g (0.05 mol) of N-butylglycnecyl ester was added dropwise to the mixture and 5 g (0.05 mol) of triethylamine was then added further dropwise to the mixture. The resulting mixture was stirred at 0 ° C for 2 hours and then allowed 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 layer was dried and then concentrated in vacuo to give an oily product which consisted almost exclusively of the desired product even though a small amount of impurities was present.

Yield: 15.7 g (76.6%).

To identify the product, a small portion thereof was purified by silica gel column chromatography using the benzene / ethyl acetate (4: 1) as solvent to give an oily product.

NMR in chloroform-d: 50, sl, 9 ppm (nnmm) 51.22 ppm (t, 3: a) 51.44 ppm (s, 6H) δ 3.03 ppm (s, 2H) 53.30 ppm (t, 2H) δ 3.42 ppm (s, 3H) 64.14 ppm (s, 2H) δ 4.13 ppm (q, 2H) δ 6.5-7.2 ppm (m, 3H) Elemental analysis : CHN ä Found (%): 58.39 7.41 6.75 Calculated for C 2 OH 3 ON 2 O 5 S: 58.52 7.37 6.83 (molecular weight: 410.54) The product was thus found to have the formula: 451 327 21 o | | / cns O_C_N \ / cnzcooczus CH: o * CHZCHZCHZACHS cns Example 13.

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- - (N-phenyl-N-ethoxycarbonylmethylaminosulphenyl) -N-methylcarbamate 11 g (0.05 mol) 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 was added to the solution under cooling and 5 g (0.05 mol) of triethylamine were further added dropwise to the solution at 10 to -5 ° C. The mixture was stirred at 0 ° C for one hour and further at room temperature for 2 hours. After cooling to -10 DEG to -5 DEG C., 9 g (.mu.mol) of N-phenylstyrene were added dropwise to the mixture and 5 g (0.05 mol) of triethylamine were further added dropwise to the mixture. The resulting mixture was stirred at 0 ° C for 2 hours and then allowed to stand overnight at room temperature. After adding 100 ml of methylene chloride, the reaction mixture was washed with 10 ml of water three times. The methylene chloride layer was dried and then concentrated in vacuo to give an oily product.

A mixture of benzene and hexane (Izl) was added to the oily product, whereby crystals precipitated. The crystals thus precipitated were filtered off and the mother liquor was concentrated to obtain an oily product, which was then cooled to obtain crystals. The crystals thus obtained were recrystallized from diethyl ether to give 13.4 g (yield: 62.3%) of white crystals, m.p. 92-9300.

NMR in chloroform-d: δ 1.15 ppm (t, 3H) δ, 1.46 ppm (s, 6H) δ, 100 ppm (s, zu) 53.32 ppm (s, an) 34.12 ppm (q, za) 34.76 ppm (s, zn) 86.5-7.5 ppm (m, 8H) 451 327 22 Elemental analysis: CHN Found (%): 61.11 6.15 6.49 Calculated for C 22 H 26 N 2 O 5 S : 61.38 6.09 6.51 (molecular weight: 430.53) It was thus found that the product had the following formula: an- CH3 Example gel 14-32.

The compounds listed in Table 3 below were prepared in the same manner as in Example 12 or 13. Physical data and NMR data (in chloroform-dl) for these compounds are also given in Table 3. q »451 327 23 Ill: tiïuuá- 1.1 ... ._ 1212 .__ ^ = m .sv @ .ß-m.mm. ^ = N .mv ~ o. . ^ = ~ _vv m @ .mm. ^: fl .sv ~ .m | H. ~ m. ^ = fi .mv m ~ .nm ^ ~ o. ~ v ^ ~ H. ~ v ^ mm. ~ mv . ^ = ~ .mv «m. ~ mm = v, / m = u ,, = m, ~ H. ~ m ~. ~« m.ßm. ^: m .mv m «.Hm: ul m = ~ uQou ~ = u | m = u \\ 1 // Ev md. ^ = m .mv mv.Hm m = u \\. \\ mmo ~ zm ~ = mvu. ^ = @ .mv v fi. Hm mmmuooummu ^ = @, Ev ~. ~ | m.mm. ^ = ~ .mv> H. . ^ = ~ .mv QH, mm v _. ^ = n .mv m «.nm ^ Hm. ~ v ^ mn.mv ^ mm.mmv. ^ = m .mv ~ H.mm mw. ~ m«. @ ~ m.mm. ^ = ~ .mv ~ o.mm ~ = u, / .Em .mv 3.3 351 m = ~ uooo ~ vvu | z: .ä mmo ~ z: ~ =>. v. ^ = m .mv «~ .Hm m = ~ Q @ ou ~ = u \\ ^ Nv ^ Nv ^ Nv z = u Zvnvou .H vv: då. ucám ñwønw> umšxwum fl v fi vëavwwum> nwvv NH Ümqhwwxw äw flflfl h MZZII ixu fl ummmw xwww fi øsm mæam fl mhnøucwëwam ~ = Wzlm / o fi x \ z | @ | © Sö __. Q m fl à fi <ë ^ = m .ev ~. ~ | M.vm. ^ = ~ .Mv æo.vm. ^ = N .mv m @ .mm ^ ~ «.mv ^ mm. ~ V ^ mm.omv . ^ = fi .mv -.mm ~ mm ~ v. ~ nm.om. ^ = ~ .mv mm. ~ @. ^ = m .mv mv.Hw mmo ~ z ~ m = -u. ^ = m ~ .av v. ~ | ~ .0 @ Amn .Ev ~. ~ «m.mm. ^ = ~ .mv ßo.vm. ^ = ~ .mv Ho.vm. ^ = n .mv mm.mm ^ oo. mv ^ v ~ .wv ^ æß. ~ vv. ^ = ~ .ev mm | Am @ «~ .m ... m nm.Hm. ^ = ~ .mv ~ m.Nm,. ^ = m .mv mm .Hm mmo ~ zmm = mmu. ^ = WH .Ev w.ñ | ~ .cm 24 ^ = m .av H.ß! ~ .Mm. ^ 1 ~ .vv mo.vm. ^ = ~ .Mv ~ o . «M. ^ = N .mv om.mm. ^ = H .Ev n. ~ | @. ~ M ^ fl w. @ V ^ ~ m. ~ V ^ ~ m.wnv. ^ = ~ .Mv ~ @ .N @ v @ .mm ~. ~ Mm. @ M. ^ = M .mv mv. ~ M _. ^ = ~ .Mv ~ N.Hm mmo ~ z ° m = ° ~ u. ^ = W .sv w.H1w.ov 451 327 ß vzmol fl l Q :: u | umm | m = ~ uoou ~ = u | 2: m = ~ Uoou ~ = U \\ ~: z? = / M = ~ ooou ~ = v | \\ z = m = ~ uoou ~: u .m =: U | uom // mz fl uooumzul z = m = ~ uoøu ~ = Q \\ æ fi ß fl ua 451 327 ^ om.mv ^ m ~ .mv ^ mH. ~ vv mm.m ~ vm vw.Hv mmONZæNImNU ^ mw.mv ^ æm.mv. ^ ~ m.ßmv mm.n «mm Ho.mm n mmvmo ~ z- = m ~ u ^ Q fl. vv ^ m ~ .mv ^ mH. ~ mv ~ mv m ~ .m vo. ~ m mmo ~ zm ~ = m ~ o ^ = ~ .ev n.ß | ~ .mm. ^ = N. ^ = ~. ^ = ~. ^ = ~. ^ = n. ^ = m. ^ = m nww QÜQ .m9 amv .mv .ww näw oælë malë omïmw moámv mm. Nwv mw fi üv: nån ^ = m .ev m.ß- ~. ~ V. ^ = M .ev N.ß | ~ .mm. ^ = ~ .Mv m ~ .vm. ^ = ~ .Mv HN.vm. ^ = ~ .mv Nm. ~ m. ^ = m .mv N «.m @. ^ = ~ .mv vo.m @. ^ = m .mv ~«. ~ m. ^ = m .mv m ~. Hm ^ = m .sv m.> - m.mm. ^ = ~ .Mv mH.vm _ ^ = ~ .mv H ~ .vm. ^ = ~ .Mv ~ m.mv. ^ = M .mv «~ .mm. ^ = ~ .mv »m. ~ @. ^ = m .mv Qm.Hm. ^ = m .mv -. ~ m NEO! ~ = u | m: ~ ooou ~ = u- mmmuooommu- m = ~ uoou ~ = u1 mmm z = HN m = ~ vooo ~ = U \\ «o-Aï1í @ Y ~ = u // z = om m = ~ UoQU ~ = u \\ ~ = u // z = mv m = ~ uoou ~ = U \\ 451 327 26 ä., ... v ^ ~ 0. ~ v ^ NH. ~ v ^ mm. ~ mv HH. ~ Nm .. Ho.mm mmo ~ zm ~ = m_Q ^ mm.mv ^ ~ m. ~ V ^ ~ m.mmv mm.mm ~. ~ M «.mm mmomzmm = m ~ o ^ mo.mv ^ mH.mv ^ mm.mmv HH.m -.m ~ m.Om mmomzm ~ = m ~ Q ^ = m .Ev ñ. ~ | m.mm. ^ = m .mv Hw.mm. ^ = m .mv Hm.mm. ^ = m .av mm | o. ~ m. ^ = ~. ^ = ~. ^ = m. ^ = m nmà .uu lmí .vv mo. ~ w æo.Nw m «.Hw æ fl. Hw ^ = m .Ev ~. ~ | M.mm. ^ = ~ .Mv ~ H.mm. ^ = M .av mm | ~ .mm. ^ = M .mv m «.mm. ^ = ~ .Mv mo.mm. ^ = ~ .mv m ~. ~ m. ^ = m .mv ß «.Hm. ^ = m .mv m ~ .Hm. ^ = m .mv fi ~. Hm ^ = ~ .av m. ~ | ~ .mm. ^ = ~ .mv ° ~ .mm. ^ = ~ .mv ßm.mm. ^ = m .mv m ~ .mm. ^ = m .mv Hm.mm. ^ = ~ .mv ~ o.mm . ^ = m .mv w «. ~ m. ^ = m .mv mH.Hm m = U m = Q \\ mmm mmm m = uo \ /: ul moi m = Uoou ~ = u ~ mu | mm ~ uooU ~ = u ~ = u | m = ~ uoou ~ mU | .ï hv mmuff mm m = o \\ m = uøou ~ = u ~ = u \\ Z: vw m = u // = U mmu \\ // \\ z = m ~ m = ~ uoou ~ = u ~ = um = uø z = NN m = ~ UQoo ~ = u \\ 451 327 80.3 26.2 Sïamv @ ß.v wm. ~ Ho.mm mmo ~ z ~ m = _ ~ u ^ @@. mv ^@m.æv ^m~.m@vm «.m ~ @ .mm« .m @ 7 2 mmowv fi wlv fl mmv ^ @ ~. @ v ^ ~ m. ~ v ^m~.o@v ~ Hv @@. ~ w «.o @ mmo ~ z, mz-U ^ = m .Ev ~. ~ | @. @@. ^ = ~ .vv ~ @ .m @. ^ = «.Ev« .n | Hn @. ^ = m .mv -. ~ @. ^ = ~ .mv m @. ~ @. ^ = ~ .Ev m. ~ | «. ~ v. ^ = @ .mv ~ v..v ^ = Q ~ .Ev wH | ~. o @ ^ = m .Ev o. ~ | n. @@. ^ = ~ .ev A. «| @ .m @. ^ mm .mv nm.n @. ^ = m .Ev @ .m- °. n @. ^ = ~ .mv w @. ~ @. ^ = ~ .uv w @. ~ @. ^ = @ .mv ~ v.Hv. ^ = @ .vv @H. fi @ ^ = mH .Ev @ .H - @. Ov m = om = o Amm .ev 0. ^ = ~ .Ev H. ^ = M .Ev Q. ^ = M. ^ = N. ^ = ~. ~ -M. @@. «- ~ .mv .m | om @ .mv H ~. ~ @ .Mv« @. ~ @ .Uv m @. ~ V. ^ = @ .Mv ~ «. ~ @. ^ = @ .Vv ~ H . ~ @. ^ = ~ .Ev wH - @. O @ m = U // m = Q mzzUlül: UI: Un 315 | = / m = ~ Qoo0 ~ = u ~ mQ | \\ z = m = ~ @ oou ~ = u ~ = u m = U, / mo mIU \ / \ / \ «fi oou ~ = u ~ mu | \\ z = \ (»w | oou ~ = o ~ = um = u wwmu m = u // \\ @ = vQoou ~ = u ~: U« z = @ = «@ oQu ~ = o ~ = Q NN mm 451 527 28 ^ o @. @ v ^ o @. ~ v ^ ~ «.mnv mw.m Qm.N Hß.mm mmONZNmIHNU ^ om.wv ^ o @. ~ v ^ ~« .mmv nm.m Hm .ß No.mm mmONZNmE ~ NU ^ nw.ev ^ ~ m. ~ v ^ ~ m.mmv @@. @ «fi. ~ @ ß.wn wnoNzcm = o ~ u ^ = n .ev H.ß | m . @@. ^ = ~ .vv «o.« @. ^ = m .mv ßm.m @. ^ = «.av @ .m | Hm @. ^ = ~ .mv ~ m. ~ @. ^ = ~ .uv @ ~. ~ @. ^ = H .ev ~. ~ | @ .H @. ^ = @ .wv N «.H @. ^ =« .Uv æH.H @. ^ = @ .vv « wQ @ ^ = m .ev @. ~ | @. @@. ^ = N .vv n @ .mw. ^ = m .mv fl m.m @. ^ = @ .ev ~ .m | om @. ^ = N .wv @ m. ~ @. ^ = ~ .Vv @@. ~ @. ^ = @ .Mv ~ <.H @. ^ = ~ H .Ev wH | @ .o @ ^ = m .ev o. ~ «M. @@. ^ = M .mv« mm @. ^ = ~ .Mv mm.m @. ^ = «.Ev> .fl | @. ~ @. ^ = N .mv ß @. ~ @ . ^ = N .vv @ v. ~ @. ^ = @ .Mv m <.H @ .Amß .Ev c. ~ 1 @. @@ mI: Ul0mwl m == U | U @ w | m == u1 = | mm = u | ° w fl // m = ~ @ ooo ~ = O ~ mO | z = m = Nuoou ~ = u ~ = o \\ mmfuluuw / m = ~ uoou ~ = 0 ~ mu | \\ z = m = ~ uQQu ~ = o ~ = u @ =: o | = // m = uooo ~ = u ~ = u | \\ z = ~ = uooo ~ = u ~ = u om mm ww ïš. ... E . (. 1 .....:. 1 .: 451 327 ^ -. @ V ^ H @. ~ V _^H~.~@v mo. @ @ «. ~ Mm. ~ @ OJ 2 wmo ~ z: m = m ~ u ^ @ H. @ v ^ ~ o.mv ^ «oH @ v ~ m. @ ~ H. @ mw. @@ mmø ~ z @ m = -u ^ = ~ .ev ~. ~ | n. @@. ^ = ~. ^ = m .vv mm.m @ .mv ~ @. ~ @ _ Én .Ev mm | o.mm. ^ = ~. ^ = N. ^ = @ .Ñ = m .mv «@. ~ @ .UV <@. ~ @ .Mv m« .H @ .UV ~ HH @. ^ MQ ~ .Ev o. ~ | @ .O @ ^ = m .ev o.ß1m. @@. ^ = ~. ^ = M .vv ~ @ .m @ .mv mn.m @. ^ = «.Ev @ .m | °. ~ @. ^ = ~. ^ = N. ^ = @ .Wv wm.N @ .UV n @. ~ @ .Mv @«. Fi @ .fi mq fi. EV o. ~ | ~. ° @ m ~ = m UIGI m = ~ Uoou ~ = u ~ = U | \\ zm Nm m = ~ uoou ~ = u ~ = u n ~ = @ U | =, / m = ~ UooQ ~ = @ ~ = U | 2: Hm m = ~ UooQ ~ = QN = Qx \ 451 327 30 Example 33.

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-methyl-N-cyanomethylaminosulphenyl) -N-methylcarbamate 11 g (0.05 mol) of 2,3-dihydro-2, 2-Dimethylbenzofuran-7-yl-N-methyl-Carbamate was dissolved in 70 ml of methylene chloride, 5.2 g (0.05 mol) of sulfur-Dichloride were added to the solution under cooling and 5 g (0.05 X mol) of triethylamine was further added dropwise to the solution at -1o to -s ° c. The mixture is stirred at 0 ° C for one hour and further at room temperature for 2 hours: After cooling to -10 to -SOC, 5.6 g (0.05 mol) of N-butylaminoacetonitrile were added dropwise to the mixture and 5 g (0, 05 mol) of triethylamine was added further dropwise to the mixture. The resulting mixture was stirred at 0 ° C for two hours and then allowed 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 layer was dried and then concentrated in vacuo to give an oily product, which consisted almost exclusively of the desired product even if small amounts of impurities were present. Yield: 13.0 g (71, 4%). To identify the product, a portion was purified on silica gel column chromatography using benzene / ethyl acetate (5: 1) as a solvent to give an oily product.

NMR in chloroform-dl: δ 0.7-2.0 ppm (m, 7H) δ 2.92 ppm (S, ZH) 53.33 ppm (s, 3H) 56.5-7.1 ppm (m, 3H ) Δ 1.42 ppm (s, 6H) δ 2.9-3.5 ppm (m, 2H) g 4.01 ppm (s, 2H) Elemental analysis: CHN Found (%) = I 59.19 7, Calculated for C 18 H 25 N 3 O 3 S: 59.48 6.93 11.56 (molecular weight 363.488) Thus, the product was found to have the following formula: (LL. 451 327 CH CH 3 Example gel 34-42.

The compounds shown in Table 4 below were prepared in the same manner as in Example 33. Physical data and NMR data (in chloroform-dl) for these compounds are also given in Table 4. ..... - _ .. ...-. T ,,., 451 327 32 CK: Ö m. Ssxm. E,. ^ = ~ .Mv oæ.mm ^ mm.oHv ^ mm.mv ^ @ «. Mmv HM = m Umw mm.mm m = m ~ n.ø ~ m ~ .m fl m.mm = ~ m @ o.mm m = u zumzul 2: mm an .l ^ = ~ mv mn mm mmomzm ~ = _ ~ u. ^ = m .mv ß «.Hm zm ~ = U \\ ^ = m .av ~. ~ - m.mm ^ vm. @ mv ^ ~ m.mv ^ mm. ~ mv U ^ = ~ Hmw m ~ .vm ~ o.H fi w <.m HH. ~ m ^ = mm ~ m.mm zummul z = mm mm _ ~ om U ^ = ~ mmv wm. ~ @ N \\ m Q z = Q ^ = m mv vv Hm zu: U ^ = m .av ~. ~ 1m. @ m .mia .Ev HÃNlMÜmw mSU,. ^ = ~ .mv vm. «m ,, = Q ^ mo. ~ Hv ^ vm.mv ^« m.mmv. ^ = m Hmv m <.mm m = m, / mm = m \\ ff H ~. ~ H @ m. @ M ~ .wm Uv = N .mß oo.m @ m \\ mu | zu_ = u | \\ z = mm = mm ~ «.Hm mo N mmomzm ~ => vu. ^ = m .mv m ~ .Hm zu: U fi xv ^ Nv ^ Nv z = Q vmmcnø H x Hm = Hs <.am lll fl üqmc» uwnxmummv ^ Em fi vvm ~ uum> | w_ N mw »w> mmcssm všziv HmEHou xm fl u fl a fi mvil .ll - mšummmumucmëm fi m. v! wz / \ o \ \\ z-m, / _ 1% ZIUIO m __: u w ._ c <.r 451 327 33 And. mm. ^ mm.AHv ^ mm.mv ~ mm.mmv qo.HH ßæ.w Nm.mm Anm. eß. väv ^ H ~. ~ v ^ m «.omv av ~ m. ~ mm.om mmOmZßN = mHO mmomzmm = mvo Nav ^ Hm.mv ^ om. ~ mv NH ßv.m mm.ßm mmcmz. ~ = m_u ^ = m .ev o. ~ | m.mm. ^ = m .mv ~ n.mm. ^ = «.ev m. ~« m. ~ @. ^ = N .mv @ m. ~ @. ^ = ~. av m. ~ -m. ~ m. ^ = m .mv mm.vm. ^ = ~ .Ev o. ~ - ~ .om ^ = m .ev ~ .ß »m.mm .fl mm .mv ~ m. ~ m. ^ = m .Ev mm-Q.mm. ^ = ~ .mv oQ.mm. ^ = ~ .mv -. ~ m. ^ = m .mv ~ «.vm. ^ = m .mv H ~ .vm ^ = m .sv H.ß-m.mm. ^ = m .mv mm. ~ m. ^ = ~ .Ev m. ~ | o. ~ m. ^ = ~ .mv .-. nm. ^ = ~ .mv o @ .mm. ^ = ~ .sv m. ~ «m. ~ m. ^ = m .mv v <.vm mzzoln 1 / m = mv- = | zQ ~ = u ~ = 0- N \\ z = zu = u ~ = o mmm 35 Wvö / @ w = o | zu ~ = o ~: u | mmu \\ z = m: Q zU ~ = u ~ = u m = m // m = U | = U ~ = u ~ = u- zm zm ~ = u ~ = u \\ mm am ßm 451 327 34 ^ ~ <. @ Hv ^ m ~. ~ V ^mm.~@v nw.oH ~ «. ~ mm. ~ @ mmOmZmNm ~ NO ^ mm.mv ^ mH.mv ^ -. mmv «mm mm.m mm.mm mmomzmm = m ~ u ^ nH.HHv ^ H ~. ~ v ^ @«. @ mv HQ. HH mm.ß mN.cm mmOmZß ~ Sm ~ O ~ = m .ev H. ~ | m.mm. ^ = M .sv m. «| M.mm .fi zn .mv ~ m.mm. ^ = ~. ev m.m1o.nm. ^ = N .mv wm. ~ m. ^ = ~ .av m. ~ | m. ~ m. ^ = m .mv m «.Hm. ^ mo ~ .ev oN | ~. om ^ = m .Ev o. ~ | m.mm. ^ = n .mv @ «. mm. ^ =« .sv mm | o.mm. ^ = ~ .mv Ho.m @. ^ = ~ .ev m. ~ | @. ~ m. ^ = m .mv ~ m.Hm. ^ mmH .av o. ~ | ~. @ m ^ = m .ev o. ~ | m.mm. ^ = n .mv mm .mm. ^ = m .ev nm | c.mm. ^ = ~ .mv @ m. ~ m. ^ = ~ .mv mm.N @. ^ = H .av ~. ~ | ~ .Hm. ^ = @ .mv m «.H @. ^ = m .mv Q @ .om ß ~ = mUlS | m =, O; mmm «zu ~ = u ~ = u | \\ z = Nq .zu ~ = u ~ = u ß ~ mmOlG. / zo ~ = o ~ = o | z = Hm š38Sö \ m == u | omm // zu ~ = @ ~ = v | Z: om so ~ = QN = o \\ 451 327 35 Example 43.

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- - (N-propionyl-N-ethoxycarbonylmethylaminosulphenyl) -N-methylcarbamate 11 g (0.05 mol) 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 was added to the solution under cooling and 5 g (0.05 mol) of triethylamine were further added dropwise to solution The mixture was stirred at -10 DEG to -5 DEG C. The mixture was stirred at 0 DEG C. for one hour and further at room temperature for 2 hours. After cooling to -10 to -SOC, a solution of 8 g (0.05 mol) of N-propionylglycine ethyl ester in 10 ml of tetrahydrofuran was added dropwise to the mixture, and 5 g (0.05 mol) of triethylamine was added further dropwise to the mixture. The resulting mixture was stirred at 0 ° C for 2 hours and then allowed 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 layer was dried and then concentrated in vacuo to give an oily product which consisted almost exclusively of the desired product even though it contained small amounts of starting materials and impurities. Yield: 14.3 g (69.8%).

To identify the product, a portion thereof was purified by silica gel column chromatography using benzene / ethyl acetate (9: 1) as a solvent to give crystals, m.p. 100 DEG-100 DEG.

NMR in chloroform-dl: 51.14 ppm (t, an) δ 1.49 ppm (s, 6H) 53.02 ppm (s, 211) δ 54.15 ppm (q, 214) δ 6.6- 7.1 ppm (m, 3H) 51.23 ppm (t, 3H) 82.7-3.3 ppm (m, 2H) g 3.48 ppm (s, 3H) 34.50 ppm (s, 23-) Elemental analysis: CHN Found (%): 55.35 6.41 6.77 Calculated for C 19 H 26 N 2 O 6 S: 55.59 6.38 6.82 (molecular weight: 4110, 499) - .. mpf-p. "451 327 36 The product was found thus have the formula: H * 'CH3 cs cooc H \ S_ \ I / * Z 2 5 7 ,; CH- O \\ ° cocH2cH3 CH- 0 ((111 Example 44.

Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-ethoxycarbonyl-N-ethoxycarbonylmethylaminosulphenyl) -N-methylcarbamate 11 g (0.05 mol) 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 was added to the solution under cooling and 5 g (0.05 mol) of triethylamine were added further dropwise to the solution at -io to -s ° c. The mixture is stirred at 0 ° C for one hour and further at room temperature for 2 hours. After cooling to -10 to -5 ° C, 8.8 g (0.05 mol) of N-ethoxycarbonylglycine ethyl ester was added dropwise to the mixture and 5 g (0.05 mol) of triethylamine was added further dropwise to the mixture. The resulting mixture was stirred at 0 ° C for 2 hours and then allowed 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 layer was dried and concentrated in vacuo to give an oily product which consisted almost entirely of the desired product even though small amounts of starting materials and impurities were present. Yield: 18.2 g (84.7%).

To identify the product, a portion thereof was purified by silica gel column chromatography using benzene / ethyl acetate (4: 1) as a solvent to give an oily product. NMR in chloroform-dl: δ 1.17 ppm (t, 6H δ ', 1.44 ppm (s, 6H) ¿' 2.94_PPm (S, 2H) ¿'3.4l ppm (S, 3H) 451 327 37 54.05 ppm (q, za) 84.41 ppm (s, ZH) δ 4115 ppm (q: ZH) δ 6.5 ~ 7.0 ppm (m, 3H) Elemental analysis: CHN Found (%): 53, 82 6.19 6.44 Calculated for C 19 H 26 N 2 O 7 S: 53.51 6.14 6.57 (molecular weight: 426.499) It was thus found that the product had the following formula: O u, cn3 O'C'N \ 2 CH_ SN ° \ 0 \ cooc, H5 CH3 /, CH COOCZHS Exemgel 45-52.

The compounds listed in Table 5 below were prepared in the same manner as in Examples 43 or 44. Physical data and NMR data (in chloroform-dl) for the compounds are also given in Table 5..-....._... _. ,,. 451 327 38 ^ = m .ev ß. ~ | H. ~ m. ^ = M .ev o. ~ | M.mm. ^ = ~ .Mv Qm.mm. ^ = ~ .Mv mc.

^ ~ H.mv ^ ~ ß.mv ^m~.Q@v H ^ = ~ Umw Hm.Nm auf / ~ o. @ ~ M.m mm.om ^ = m m mm Nm @v | m = ~ Uo @ U ~ = m | z = mm. ^ = m .mv H <.Hm _, \\ mmo ~ zm ~ = m ~ u. ^ = m .mv wH.Hm m = ~ UooU ~ = Q ^ = m .ev o. ~ | m.mm. ^ = ~ .mv ~ m.mm. ^ = ~ .mv @m. «@. ^ = ~ .mv mo.mm ^ Qm.mv ^ mm.mv. ^ -. mmv. ^ = m .mv @ <. mm N m <.m ~ mm mm.mm. ^ = ~ .mv mm. ~ m mm = Uom / I. ^ = m .mv m «. fi m mu ~ = Uou- m = ~ moou ~ = u | \\ z = mv mmumc ~ zm ~ mm_u. ^ = ~ .mv -.Hm m: ~ Uoou ~ = u ... v š cs _. z .-: _ f: ... v -Sono m Nm .Hm såå n: xm Jm fl nwï, umcxwuwmv _- Gššv muuwtfï wwum> uwccam «: z¿.

IN! .Hmšuowfämñq - ll ...-._ m.w.wmrmwmß fl m fi aiw | fl ww | \. _ || fl @ _ mmu _ NM / wwzlmff 9 ZIUIÖ mru __ 451 327 39 ^ mw. @ v ^ ~ w.mv @@. @ <@. m mßOm2: NIæ ~ U ^ ¿m.mV ^ mm.mv «~ .M ~ mm NmßONZmNEmNU ^ æ @ .mv ^ H ~ .wv @«. M ~ nm m «u @ o ~ zm ~ = m ~ u ^ ~«. ~ Mv mH. ~ M ^ Hm.wmv ^ «O.omv nm.om Amn .ev ~ .ß | m. @@. ^: ~. ^ = ~. ^ = M. ^ = M. ^ = ~. ^ = @. ^ = ~ Qmè 47% amy nmí * Wu »mv AU¶ ~ <. <@ ~ o.« u «~ .m @ n« .m @ Nm. ~ @ o «.H @ mH.H @ ^ m ~“ ev @. ~ | m . @@. ^ = ~. ^ = ~. ^ = fi. ^ = ~ .fi zm. ^: ®. ^ = m .m9 QÜ% am? -m% nmå -W @ .U @ mm. «m No.« @ æ «.mw ma.N @ ßm.N @ w« .H @ æ fl. Hm ^ = «.ev @ .ß« ~. ~ @. ^ = fi .ev o.> | m. @@. ^ = N. ^ = ~. ^ = ~. ^ = ~. ^ = @. ^ = n awv .www -WQ umw »mv QUV wm. «W ßo.« W mo.Nm nm.N @ o <.Hm fi w. Fi w m = u au m = o @ ov | NOml Oux m = ~ uoou ~ = u | mm ~ uQou ~ mu | m = ~ Qooo ~ mQ | m = uL @ í1 @ v «~ øw // ä * mmuooo @ wz = @ <m = ~ ooou ~ = U æ <\ m = ~ @ 0ou ~ = u ao. / 1: v av // z: \\ ßq m = ~ uoou ~ = u .lïzšï-.II 1 f., Ii .. 451 327 a., .3 ^ vm. @ V ^ H «.vv ^« m. «mv ~ mv m ~ .vm ~ .vm mßo ~ zm ~ = ° ~ u ^ w @ .oHv ^ mw.mv ^ mm.« mv o Hn.oH m @ .m @ fi. mm a .. .mmomzm ~ = w_U ^ o @ .mv ^ ~ m.mv ^ -. æmv @ ~ .n H @ .m ~ @. ~ m WNÛNZQNZMNO fi mm .ev Q. ~ 1m.v @. ^ = v .ev « . «- ~ .m @. ^ = M .mv o« .m @. ^ = ~ .Mv æ @. ~ @. ^ = ~ .Uv ~ m. ~ @. ^ = @ .Mv @ «. H @. ^ = m .vv -.H @ .ñmm .uv ßH.H @ ^ = fi .sv o. ~ | m. @@. ^ = ~ .vv @H. «@. ^ = ~ .uv mm .m @. ^ = m .mv @ «. m @. ^ = ~ .mv ~ m. ~ @. ^ = ~ .vv m @. ~ @. ^ = @ .mv v« .H @. ^ m ~ .Uv o ~ .H @ ^ = @ .ev «.ß | n.vv. ^ = ~ .Mv Nn.« V. ^ = ~ .Vv no. «@. ^ = ~ .Mv cm. Fl @ . ^ = ~ .mv n @. ~ @. ^ = v .mv «« .H @. ^ = m .uv @ HH @ m = ~ UQou | m = ~ uoou | OOUI _ m = ~ QooQ // m = ~ UooU ~ = u ~ = u | \\ z = Nm m = ~ uoou ~ = u ~ = u m = ~ vooQ, / zU ~ = v ~ = U | \\ z = Hm zuwmuwmu oouf / m = ~ uoou ~ = U1. z = if m = ~ uøouN = u \\ N 451 327 Preparation examples according to the invention are given below. These regulations apply to all associations according to the invention; a suitable composition is useful for a particular purpose. The instructions given below are intended only to illustrate the use and the proportions between the active component, organic solvent, surfactant and carrier can be varied as desired. In some cases, the types of organic solvent, surfactant, carrier, etc. can also be changed.

The percentages all relate to the weight.

Preparation Example 1. 60% Emulsion: Compound of Example 25 Polyoxyethylene nonylphenyl ether Xylene Preparation Example 2. 50% Emulsion: Compound of Example 12 Polyoxyethylene sorbitan monooleate Sorbitan monooleate Xylene Cyclohexanone Preparation Example 3. 20% emulsion: Compound of Example 22 Polyoxyethylene 0% 10.0 30.0 50.0% 6.5 3.5 30.0 10.0 20.0% 5.0 45.0 30.0 In one of the preparation examples 1-3, the components were mixed uniformly. and dissolved to obtain the desired emulsion. - = - | -n-. ~ v-ar -. ~ w -_- 451 327 42 Preparation Example 4. 90% wettable powder Compound of Example 1 90.0% Sodium lignin sulfonate 3.0 Clay 7.0 Preparation Example 5 50% wettable powder Compound of Example 21 50.0 Alkyl sulphate 30.0 Condensate of naphthalene sulfonic acid and formaldehyde 10.0 Alkyl phosphate 5.5 Kaolin 3.5 Talc 1.0 Preparation example 6. 30% wettable powder Compound in Example 30 30.0% Alkylbenzene sulfonate 3.0 Sodium lignin sulfonate 2.0 White carbon 15.0 Clay 50.0 In each of Preparation Examples 4-6, the components were mixed uniformly with stirring using a type mixer. Shinagawa ". The mixture was then pulverized using a test mill or a ball mill to obtain the desired wettable powder.

Preparation Example'7. 5% powder: Compound according to Example 46 5.0% Diatomaceous earth 10.0 Talc 85.0 (101 wF F !! 451 327 43 Preparation Example 8. 2% powder: Wettable powder according to Preparation Example 5 4.0% Clay 95.8 Isopropyl phosphate 0.2 Preparation Example 9. 0.5% Powder: Precious Powder of Preparation Example 6 1.7% Clay 98.3 In each of Preparation Examples 7-9, the components were mixed uniformly with stirring using a Shinagawa type mixer. "to obtain the desired powder.

Preparation Example 10. 20% granules: Wettable powder according to Preparation Example 5 40.0% Dolomite 60.0 These components were mixed uniformly, 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 kneaded carefully. The mixture was then granulated using a granulator and comminuted, after which it was allowed to dry. In this way the desired granules were obtained.

Preparation Example ll. 10% granules: Compound of Example 40 10.0% Sodium dodecylbenzenesulfonate 0.5 Sodium lignin sulfonate 2 Diatomaceous earth 27.5 Bentonite '60, o These components were mixed uniformly and water was added to the mixture. The resulting mixture was carefully kneaded and then granulated using a granulator. The product so granulated was pulverized and dried to obtain the desired granules.

Preparation Example 12. 3% granules: Compound of Example 8 3.0% Polyvinyl alcohol 3-0 Clay 94.0 The procedure of Preparation Example 11 was repeated to obtain the desired granules.

Test example is given below: Test example l. 10 larvae of the tobacco worm (Spodoptera litura) in the third stage of development between two instincts (third-instar) were placed on a charcoal plant (one month old plant) present in a pot, and a 50% - The emulsion of the compound to be tested was diluted to a specified concentration and the leaves of the plant were applied to full wetting. The test compound at each specified concentration was tested on two pots. Three days later, the larvae were checked for killing and the results obtained are given in Table 6, which also indicates results obtained with control groups and untreated groups for comparison. f? .fl ñ d Test compound (ex. no.) l 2 45 Table 6 Mortality (%) Concentration of active component (ppm) 2,000 1,000 500 100 _ 80 65 100 70 60 100 S0 65 100 70 60 100 80 65 100 75 60 100 75 60 100 80 75 100 90 80 100 85 75 100 80 70 100 90 75 100 90 75 100 90 75 100 90 75 100 85 65 100 80 60 100 90 75 100 85 65 100 85 65 100 90 75 451 327 451 327 Table 6 ( cont.) bl KJ b] -F> 46 90 S0 90 90 80 80 80 90 90 80 85 90 90 85 80 85 v? f) 451 327 47 Table 6 (continued) 44 100 90 75 45 100 90 75 46 l00_ 85 70 47 100 S0 65 48 100 S0 65 49 100 90 75 S0 100 80 65 51 100 SS 70 S2 100 SS 70 Control * 80 60 35 A ** 90 75 45 Untreated O * 1-naphthyl-N-methylcarbamate was used as a control. ** (2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-N-methylcarbamoyl) - (methoxy-N'-n-butylcarbamoyl) sulfide.

Testexemgel 2.

An emulsion of specified concentration was prepared from a 50% wettable powder of the compound to be tested and applied to the leaves of rice seedlings (one month old seedlings) in a pot until full wetting of the leaves. When the emulsion dried, the pot was covered with a net cage, in which 10 adult female Nephotettix cincticeps were released. Each compound at each indicated concentration was tested on two pots. Three days later, the insects were checked for killing and the results are given in Table 7, which also contains results obtained with control groups and untreated control groups for the sake of comparison. 451 327 48 Table 7 Mortality (%) Concentration of active component (ppm) Test compound §QQ ÅQQ ZQQ ¿9x 'no') 100 ss 50 2 100 ss 45 3 100 ss 45 4 100 70 40 5 100 so 45 _6 95 75 55 7 90 70 50 8 95 85 50 9 100 90 60 10 100 90 50 ll 95 80 55 12 100 90 65 13 100 90 65 14 100 90 65 15 100 90 es lö 100 90 65 17 95 75 ss 18 '100 90 es _ 19 100 S0 60 .gu H Table 7 (fcrts.) Lx) J> b! 4 ..

I »49 100 100 100 100 100 100 100 100 100 100 100 95 95 100 100 100 100 100 100 100 100 100 451 327 451 327 * Jc Table 7 (continued) 52 Control * A ** Untreated 2-isopropoxyphenyl-N-methylcarbamate was used such as control. (2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-N-methylcarbamoyl) - (methoxy-N'-n-butylcarbamoyl) sulfide. 50 100 100 95 95 100 100 lOO 75 85 65 65 60 70 60 65 65 25 35 vw UI i! W (\ 451 327 51 Test Example 3.

Granules containing 10% of the compound to be tested were mixed in specified amount with soil contaminated with larvae of the nematode Meloidogyne incognita and tomato plants were immediately transferred to the soil. One month later, the roots of the plants were checked for nodule formation.

Two test areas, 2 x 2 m2 each, were used for the compound to be tested in the specified amount. The degree of nodule formation was determined according to the criteria given below with the result given in Table 8. For the sake of comparison, Table 8 also contains data regarding results obtained in control areas and untreated areas.

Degree of nodule formation: 0: 0% 1: up to 25% 2: up to 50% 3: up to 75% 4; up to 1oo æ Degree of modulus formation Hanged added Testföreniny granules (kg / 10 a) (ex. no.) ___ 100 âg gg 1 0 1 2 2 0 2 3 S 0 Z 3 4 O 2 3 SO 2 3 6 1 2 3 7 1 3 3 8 1 1 2 9 0 1 2 10 O 1 2 11 1 2 3 12 0 1 2 451 327 Table 8 (cont.) 52 lx) IQ fx) IQ h) [U b) FJ Q! Lil 451 327 53 Table 8 (fort¿ ._ \ ___ 35 0 1 3 36 D 1 3 37 0 1 2 33 0 O 1 3: 0 O 1 40 O 1 l ~ l 0 l 3 12 D l 2 45 0 1 2 44 0 0 1 45 0 1 2 26 0 l 2 h "0 l 3 l8 Û l 3 49 0 0 1 50 0 1 3 51 O l 2 52 0 l 2 Control * 2 4 4 Untreated 4 x Bis (2- chloro-1-methylethyl) ether was used as control 451 327. ....... ~. <- ¶f. 54 Testexemgel 4.

The compound to be tested was dissolved in a predetermined amount of acetone. The solution was diluted to different concentrations and applied topically to housefly (Musca domestica). Table 9 lists LDSO values, which were determined according to the Probit method on the basis of mortality 24 hours later.

Table 9 f »Test compound LD (ex- no.) 50 JAg / g) 1 21.3 2 58.8 3 ¿0.0 4 28.9 5 75.6 6 38.3 7 54.0 3 24.6 9 31.7 10 46 0 11 93 9 12 16 7 13 12 5 14 9 9 15 33 0 rl G \ 42- 4 :.

J .. 451 327 55 Table 9 (fort§¿) _ 17 12 3 13 32 5 19 22 2 10 61 9 31 10.4 32 45 2 23 44 3 24 38 b 35 50 1 35 64.7 37 13.8 33 17 7 39 22 s 30 23 S 31 33 l 33 32.7 33, 9.1 34 16.7 35 6: 6 S6 59 3 37 ll 8 SS 17 5 39 1 "7 Ö (fl \ 1 O 451 327 56 Table 9 (cont.) 1.1 54 Ö 42 16.0 _, 3 14.1 44 45 29.2 _15 33 2 -7 57.8 _18 53.6 49 15.7 50 34.7 51 45.3 52 54.3 Control ”22 .sx 2-isopropoxyphenyl-N-methylcarbamate was used as control Testexemgel 5.

Compounds of the invention were tested on male mice for acute toxicity by oral administration. Table 10 shows LDSO values determined according to Litchfield-Wilcoxon with respect to mortality on the 7th day. (1): w. 451 327 57 Table 10 Test compound LDSO (mg / kg) (ex. No.) 1 58 2 140 3 145 4 122 5 90 6 135 T 75 3 105 9 158 10 113 11 93 12 125 13 115 14 120 15 110 16 110 17 69 18 135 19 108 20 TS Zl 105 22 S8 Xx) UI F '| _n b! 451 327 Table lO (cont.) IQ U1 Id Û \ I.) \ lk) 03 IJ iQ UI 4'- Lu U1 UI C \ bl \ l L: SC (n 1D 58 105 95 'in § _- \ 59 Table 10 (continued) LS SO 49 105 50 95 51 SS 52 125 Control x 5.6 X 2,3-dihydro-2,2-dimethyl-7-benzofuran-7-yl-N-methyl-carbamate was used as control 451 327. ..-.-, _.

Claims (23)

451 327 60 PATENT REQUIREMENTS A carbamate derivative, characterized in that it has the general formula (I): C 143 s N \ R 2 m about wherein R 1 and R 2, which may be the same or different, each represent (1) -X -COOR 3, wherein X represents an alkylene group having 1-6 carbon atoms, and R 3 represents an alkyl group having 1-8 carbon atoms or a cycloalkyl group having 3-6 carbon atoms: or (2) -Y-CN, wherein Y represents an alkylene group having 1- 6 carbon atoms; and wherein R 2 further represents an alkyl group having 1-8 carbon atoms; a cycloalkyl group having 3-6 carbon atoms; a benzyl group which may be substituted by a halogen atom; a phenyl group which may be substituted by a halogen atom, an alkyl group having 1-3 carbon atoms or an alkoxy group having 1-3 carbon atoms; or -Z-R 4, wherein Z represents a carbonyl group or a sulfonyl group and R 4 represents an alkyl group having 1-6 carbon atoms, a phenyl group, an alkoxy group having 1-6 carbon atoms or a phenoxy group. Carbamate derivative according to claim 1, characterized in that it has the formula (I '): o || cH o-c-Ní 5,111 'u.) cn O I S-N \ 2, 3 \ R cH 4) * / fl lr FF; wherein R 1 'and R 2', which may be the same or different, each represent (1) -X'-COORBI, wherein X 'represents an alkylene group having 1-2 carbon atoms and R 31 represents an alkyl group having 1-4 carbon - atoms which may be straight or branched; or (2) -Y'-CN, wherein Y 'represents an alkylene group having 1-2 carbon atoms; and R 2 'further represents an alkyl group having 1-6 carbon atoms or a cycloalkyl group having 3-6 carbon atoms. 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-N1 [N, N-bis (ethoxycarbonylmethyl) aminosulphenyl] -N-methylcarbamate according to claim 1 or 2. 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-methyl-N-ethoxycarbonylmethylaminosulphenyl) -N-methylcarbamate according to claim 1 or 2. 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-isopropyl-N-ethoxycarbonylethylaminosulphenyl) -N-methylcarbamate according to claim 1 or 2. 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-n-butyl-N-ethoxycarbonylethylaminosulphenyl) -N-methylcarbamate according to claim 1 or 2. 2,3-Dihydro-2,2-dimethylbenxfuran-7-yl-N- (N-cyclohexyl--N-ethoxycarbonylethylaminosulphenyl) -N-methylcarbamate according to claim 1 or 2. 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl-N- (N-n-butyl-N-cyanoethylaminosulphenyl) -N-methylcarbamate according to claim 1 or 2. 9. An insecticidal, miticidal or nematocidal composition, characterized in that it contains an insecticidal, miticidal or nematocidal effective amount of the carbamate derivative according to claim 1 as an active ingredient and a carrier. 451 327 62 mun-f_en ...- 10. An insecticidal, miticidal or nematocidal composition, characterized in that it contains an insecticidal, miticidal or nematocidal effective amount of the carbamate derivative according to claim 2 as an active ingredient and a carrier. i 'vi 11. ll. Process for the preparation of the carbamate derivative according to claim 1, claim 1, characterized in that a compound having the formula (II): , 2-dimethylbenzofuran-7-yl-N- (chlorosulphenyl) -N-methylcarbamate having the formula (III): on CH- and N-. H cus O / \ \ scz _ (I) which is then reacted with an amine compound having the formula (IV): 1 / R HN (IV) \ R meaning. 451 327 63 12. A process according to claim 11, characterized in that 1 to 2 moles of sulfur dichloride are used per mole of the compound of formula (II). 13. A process 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. A process according to claim 13, characterized in that said solvent is methylene chloride or chloroform. 15. A process 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. A process according to claim 15, characterized in that said basic compound is triethylamine. 17. A process according to claim 11, characterized in that about 1 to about 2 moles of the amine compound of formula (V) are used per mole of compound of formula (III). 18. A process according to claim 11, characterized in that the reaction of the compound of formula (III) with the amine compound of formula (IV) is carried out in the presence of a solvent. 19. A process according to claim 18, characterized in that said solvent is methylene chloride or chloroform. 20. A process according to claim 11, characterized in that the reaction of the compound of formula (III) with the amine compound of formula (IV) is carried out in the presence of a basic compound. 451 327 64 21. A process according to claim 20, characterized in that said basic compound is triethylamine. Use of the carbamate derivative according to claim 1 for controlling harmful insects, mites and nematodes. Use of the carbamate derivative according to claim 2 for controlling harmful insects, mites and nematodes. 1 l vm-: uin-u-n- * m ål) A11. ., _ «\\