GB2084134A

GB2084134A - Insecticidal, miticidal and nematocidal dihydrobenzofuran aminosulphenyl carbabates

Info

Publication number: GB2084134A
Application number: GB8126286A
Authority: GB
Original assignee: Otsuka Chemical Co Ltd
Current assignee: Otsuka Chemical Co Ltd
Priority date: 1980-09-01
Filing date: 1981-08-28
Publication date: 1982-04-07
Also published as: GB2084134B; DE3134596C2; FR2489329B1; MY8600015A; CH649765A5; EG15897A; MA19260A1; IN155624B; AU7481281A; GR74353B; AU539995B2; SE8105139L; DE3134596A1; HU188690B; NZ198211A; FR2489329A1; AR230276A1; SE451327B

Abstract

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

Description

SPECIFICATION Carbamate derivatives, insecticidal, miticidal or nematocidal compositions containing the same, and process for preparing the same This invention relates to carbamate derivatives, insecticidal, miticidal or nematocidal compositions containing the derivatives as an active ingredient, a process for preparing such derivatives, and a method for controlling noxious insects1 mites or nematodes. In the present specification, the term "insecticidal" includes "miticidal" and "nematocidal" in addition to "insecticidal", and the term "insect(s)" includes "mite(s)" and "nematode(s)" in addition to "insect(s)", respectively, unless otherwise indicated.

It is known that some carbamate compounds have high insecticidal activity, and they include those actually in use. However, many of such carbamate compounds have the drawback of being toxic or warm-blooded animals. Above all, 2,3-dihydro-2,2-dimethyl benzofuran-7-yl N-methyl-carbamate (hereinafter referred to as "carbofuran", as generally called) is known to have high insecticidal activity, but it causes problems in practical use due to high toxicity to warm-blooded animals. Accordingly, if it is possible to prepare carbamate compounds which are comparable to carbofuran in insecticidal activity and yet have reduced toxicity to warm blooded animals, the compounds should be very useful.From this viewpoint, various carbofuran sulfenyl compounds have been synthesized, and the relation between their insecticidal activity and toxicity to warm-blooded animals is being investigated, with reports made on the results of investigations. For example, Belgian Patent 817,517 discloses 2,3-dihydro-2,2-dimethylbenzofu ran-7-yI N-(N,N-dibutylaminosulfenyl)-N-methyl-carbamate, and German Patent DT-OS 2,254,359 discloses 2,3dihydro-2,2-dimethyl benzofu ran-7-yl N-(N-methyl-N-benzenesulfonylaminosulfenyl)-N-methyl-carbamate.

These compounds nevertheless fail to fully fulfill the requirements in respect of insecticidal activity, toxicity to warm-blooded animal and to fish and manufacturing process.

We have conducted intensive research in an attempt to develop carbamate compounds which will fulfill all of such requirements and found that the contemplated objects can be achieved by compounds represented by the formula (I):

wherein R1 and R2, which may be the same or different, each represents (1) -X-COOR3, in which X represents an alkylene group having 1 to 6 carbon atoms, and R3 represents an alkyl group having 1 to 8 carbon atoms or a cycioalkyl group having 3 to 6 carbon atoms; or (2) -Y-CN, in which Y represents an alkylene group having 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 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; a phenyl group which may be substituted with a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; or -Z-R4, in which 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 benzyl group, an alkoxy group having 1 to 6 carbon atoms or a phenoxy group In the definition for the formula (I) above, the alkyl moiety in the alkyl group, alkylene group and alkoxy group may be straight chain or branched chain.

Compounds represented by the formula (I'):

wherein R1 and R2,, which may be the same or different, each represents (1) -X'-COOR3,, in which X' represents an alkylene group having 1 to 2 carbon atoms, and R3 represents an alkyl group having 1 to 4 carbon atoms which may be straight chain or branched chain; or (2) -Y'-CN, in which Y' represents an alkylene group having 1 to 2 carbon atoms; and R2 further represents an alkyl group having 1 to 6 carbon atoms which may be straight chain or branched chain, or a cycloalkyl group having 3 to 6 carbon atoms, are preferred in this invention.

Thus, this invention has been accomplished.

The compounds of the formula (I) are novel compounds which have not been disclosed in any literature and which have been discovered by us for the first time. We have found that the novel compounds have outstanding insecticidal activity or controlling effect on agricultural and forestry noxious insects and household noxious insects and are comparable in such effect to carbofuran which has the highest insecticidal activity heretofore known. The compounds are effective on a wide variety of noxious insects, mites and nematodes which are harmful to vegetables, trees, other plants and man, such as Hemiptera, Lepidoptera, Coleoptera, Diptera, Thysanoptera, Orthoptera, Isopoda, Acarina, Tylenchida, etc. Examples of these insects, mites and nematodes are as follows.

Hemiptera (1) Deltocephalldae: Nephotettix cincticeps (2) Delphacidae: Laodelphax striatellus, Nilaparvata lugens (3) Aphididae: Myzus persicae, Aphis gossypli (4) Pentatomidae: Nezara antennata, Nezara viridula Lepidoptera (1) Noctuidae:Spodoptera lltura, Agrotis fucosa, Laphygma exigua (2) Tortricidae: Adoxophyesorana (3) Pyralidae: Chilo suppressalis, Ostrinia furnacalis, Cnaphalocrocis medinalis (4) Plutellidae: Plutella xylostella Coleoptera (1) Curcullonidae: Echinocn em us squameus, Lissorh op trus oryzophilus (2) Scarabaeidae: Popillia japonica (3) Coccinellidae: Henosepilachna vigintioctopunctata Diptera (1) Muscidae: Musca domestica (2) Cedidomyiidae: Aspondylia sp.

(3) Agromyzidae: Phytobia cepae Thysanoptera Thripidae: Thrps tabaci, Scirtothrips dorsalis Orth op tera Gryllotalpidae: Gryllotalpa africana Isopoda Armandillidae: Armadillidium vulgare Acarina Tetranychidae: Tetranychus telarius, Tetranychus urticae, Pan on ychus citri Tylenchida Hetero deridae: Meloidogyne incognito The toxicity of the carbamate derivatives of the formula (I) to warm-blooded animals is as low as about 1/5 to about 1/100 the toxicity of carbofuran.The present compounds exhibit insecticidal activity or controlling effect on the above-mentioned organisms in any stage or a specific stage of their growth and are therefore effectively usable for controlling them in the fields of agriculture, forestry and sanitation.

The present compounds of the formula (I) are very easy to prepare with high purities in high yields and have great commercial advantages as will be described in detail later.

Typical of the compounds of the formula (I) are those as described in Examples 1 to 56 set forth hereinafter. Of these compounds, the following compounds are particularly preferred in this invention.

2,3-Dihydro-2,2-dimethyibenzofuran-7-yl N-[N,N-bis(ethoxycarbonyl methyl )aminosulfenyl]-N-methylcarbamate 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl N-(N-methyl-N-ethoxycarbonylmethylaminosu If enyl )-N-methyl- carbamate 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl N-(N-isopropyl-N-ethoxycarbonylethylaminosulfenyl)-N-methyl- carbamate 2,3-Dihydro-2,2-dimethyl benzofuran-7-yl N-(N-n-butyl-N-ethoxycarbonylethylaminosulfenyl)-N-methylcarbamate 2,3-Dihydro-2,2-dimethylbenzofuran.7-yl N-(N-cyclohexyl-N-ethoxycarbonylethylaminosulfenyl)-N methyl-carbamate 2,3-Dihydro-2,2-dimethylbenzofu ran-7-yl N-(N-n-butyl-N-cyanoethylaminosulfenyl)-N-methyl-carbamate The compounds of the formula (I) can be prepared, for example, by reacting a compound represented by the formula (all):

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

which is then reacted with an amine compound represented by the formula (IV):

wherein R1 and R2 are as defined above.

The reaction of the compound of the formula (II) with sulfur dichloride may be conducted in the presence or absence of a solvent. Examples of useful solvents are methylene chloride, chloroform, carbon tetrachloride and like hydrocarbon -halides, and diethyl ether, dibuty ether, tetrahydrofuran, dioxane and like ethers. The proportions of the compounds of the formula (II) and SCCP are not particularly limited but are widely variable suitably. Usually 1 to 2 moles, preferably about 1 to about 1.2 moles, of the latter is used per mole of the former. Preferably the reaction is conducted in the presence of a basic compound. Examples of useful basic compounds are triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine and like tertiary amines, pyridine, a, ss, y-picoline, lutidine, etc.The basic compound may be used in an amount sufficient to capture the hydrogen chloride to be produced by the reaction as a by-product. Usually 1 to 2 moles of the basic compound is used per mole of the compound of the formula (II). The reaction, which proceeds with cooling, at room temperature or with heating, is carried out usually at -70 to 50"C, 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 subsequently reacted with an amine compound of the formula (IV).

Examples of useful amine compounds of formula (IV) are those secondary amines represented by the formulae (V) to (IX)

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

Representative examples of the amine compound of the formula (V) are N-methylglycine methyl ester N-methylglycine ethyl ester, N-methyiglycine butyl ester, N-ethylglycine ethyl ester, N-n-propylglycine ethyl ester, N-isopropylglycine ethyl ester, N-n-butylglycine ethyl ester, N-isobutyl-glycine ethyl ester, N-secbutylglycine ethyl ester, N-n-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 ester, N-(3-methylphenyl)glycine ethyl ester, N-(4-methoxyphenyl)glycine ethyl ester, ethyl Nmethylaminopropionate, ethyl N-n-propylaminopropionate, methyl N-isopropylaminopropionate, ethyl N-isopropylaminopropionate, butyl N-isopropylaminopropionate, 2-ethylhexyl Nisopropylaminopropionate, methyl N-n-butylaminopropionate, ethyl N-n-butylaminopropionate, ethyl Nisobutylaminopropionate, ethyl N-sec-butylaminopropionate, ethyl N-t-butylaminopropionate, ethyl N-namylaminopropionate, ethyl N-isoamylaminopropionate, ethyl N-n-hexylaminopropionate, ethyl Ncyclohexylaminopropionate, N-acetylglycine ethyl ester, N-chloroacetylaminoglycine ethyl ester, Npropionylglycine ethyl ester, N-benzoylglycine ethyl ester, N-(4-chlorobenzoyl)glycine ethyl ester, Ntosylglycine ethyl ester, etc.

Representative examples of the amine compound of the formula (VI) are N-methylaminoacetonitrile, N-ethylaminoacetonitrile, N-n-propylaminoacetonitrile, N-isopropylaminoacetonitrile, N-nbutylaminoacetonitrile, N-isobutylaminoacetonitrile, N-benzylaminoacetonitrile, N-phenylaminoacetonitrile, N-(4-methylphenyl)aminoacetonitriie, N-methylaminopropionitrile, N-n-propylaminopropionitrile, Nisopropyiaminopropionitrile, N-n-butylaminopropionitrile, N-isobutylaminopropionitrile, N-secbutylaminopropionitrile, N-octylaminopropionitrile, N-cyclohexylaminopropionitrile, etc.

Representative examples of the amine compound of the formula (VII) are methyl iminodiacetate, ethyl iminodiacetate, isopropyl iminodiacetate, cyclohexyl iminodiacetate, methyl iminodipropionate, ethyl iminodipropionate, N-methoxycarbonylglycine ethyl ester, N-ethoxycarbonylglycine ethyl ester, Nphenoxycarbonylglycine ethyl ester, ethyl N-ethoxycarbonylmethylaminopropionate, ethyl 4 (ethoxycarbonylmethylamino)butyrate, ethyl 2-(ethoxycarbonyl methylamino)butyrate, ethyl Nethoxycarbonylaminopropionate, etc.

Representative examples of the amine compound of the formula (VIII) are methyl Ncyanomethylcarbamate, ethyl N-cyanomethylcarbamate, ethyl N-cyanoethylcarbamate, Ncyanomethylglycine ethyl ester, N-cyanoethylglycine ethyl ester, ethyl N-cyanomethylaminopropionate, ethyl N-cyanoethylaminopropionate, etc.

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

The reaction of the compound of the formula (III) with the amine compound of the formula (IV) may be conducted in the presence or absence of a solvent. Any of the solvents useful for reacting the compound of the formula (II) with sulfur dichloride is usable for this reaction. The proportions of the compound of the formula (III) and the amine are not particularly limited but are widely variable suitably. Usually about 1 to about 2 moles, preferably about 1 to about 1.2 moles, of the latter is used per mole of the former. It is preferable to conduct this reaction also in the presence of a basic compound, which can be any one of those already mentioned. The basic compound may be used in such an amount that is sufficient to capture the hydrogen chloride to be formed by the reaction as a by-product. Usually 1 to 2 moles, preferably 1 to 1.5 moles, of the basic compound is used per mole of the compound (III). The reaction, which proceeds with cooling, at room temperature or with heating, is carried out usually at -20 to 50"C, preferably 0 to 300C. The reaction time is usually about 10 to about 15 hours.

The compound of this invention represented by the formula (I) and thus obtained can be easily isolated and purified by a usual method of separation, such as solvent extraction, recrystallization or chromatography.

The compounds (I) of this invention can be formulated into emulsions, wettable powders, suspensions, concentrated suspensions, granules, fine particles, pellets, dusts, coating compositions, foam sprays, aerosols, microcapsule compositions, impregnants to be applied to natural or synthetic materials, fumigants, concentrated preparations to be applied in small amounts, etc.

Various surfactants are usable for the preparations of 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, alkyl sulfosuccinates, alkyl sulfates, polyoxyethylene alkylether sulfates, alkylnaphthalene sulfonates, lignin sulfonates, etc.

Solvents, diluting agents and carriers for the present compounds include various organic solvents, aerosol propellants, natural minerals, vegetables, synthetic compounds, etc. Examples of preferred organic solvents are benzene, toluene, xylene, ethylbenzene, chlorobenzene, alkylnaphthalenes, 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 propellants are propane, butane, hydrocarbon halides, nitrogen, carbon dioxide, etc. Examples of useful natural minerals are kaolin, talc, bentonite, diatomaceous earth, clay, montmorillonite, chalk, calcite, pumice, dolomite, etc. Examples of useful vegetables are coconut shells, tobacco stalks, sawdust, etc.

Exemplary of useful synthetic compounds are alumina, silicates, sugar polymers, etc. Also useful are adhesives, such as carboxymethyl cellulose, gum arabic, polyvinyl alcohol, polyvinyl acetate, etc. The preparations can be colored with organic or inorganic dyes.

The compounds (I) of this invention are formulated into various preparations, such as those exemplified above, so that the preparations contain, as an active ingredient, an insecticidally, miticidally or nematocidally effective amount (e.g., about 0.1 to about 95% by weight, preferably about 0.5 to about 90% by weight) of the compound. Depending on the application contemplated, such preparations are used as such, ores diluted with a carrier or water.

The present invention will be described below in greater detail with reference to the following examples.

Example 1 Preparation of 2,3-dihydro-2,2-dimethylbenzofu ran-7-yl N-[N,N-bis(cyanomethyl )aminosu lfenylj-N- methyl-carbamate.

A 11 g quantity (0.05 mole) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate was dissolved in 70 mt of methylene chloride, 5.2 g (0.05 mole) of sulfur dichloride was added to the solution with cooling, and 5 g (0.05 mole) of triethylamine was further added 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 mole) of iminodiacetonitrile in 40 mt of tetrahydrofuran was then added dropwise to the mixture at the same temperature, and 5 g (0.05 mole) of triethylamine was further added dropwise to the mixture. The resulting mixture was stirred at 0C for 4 hours and thereafter allowed to stand overnight at room temperature.With addition of 100 mt of methylene chloride, the reaction mixture was washed with 100 mt of water three times. The methylene chloride layer was dried and then concentrated in a vacuum to give an oily product, which was almost entirely composed 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 thereof was purified by silica gel column chromatography, using benzene/ethyl acetate (4:1) as the solvent, whereby a crystal having a melting point of 94 to 95"C was obtained.

NMR in chloroform-dl: 61.48 ppm (s, 6H) 6 3.02 ppm (s, 2H) 53.50 ppm (s, 3H) 54.32 ppm (s, 4H) 6 6.6-7.2 ppm (m, 3H) Elemental Analysis: C H N Found (%): 55.36 5.31 16.05 Calcd.forC16Hl8N403S: 55.48 5.24 16.17 (molecularwt. 346.418) Thus, the product was confirmed to have the following formula:

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

A 11 g quantity (0.05 mole) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate was dissolved in 50 me of chloroform, 5.2 g (0.05 mole) of sulfur dichloride was added to the solution with cooling, and 5 g (0.05 mole) of triethylamine was further added dropwise to the solution at OOC. The mixture was stirred at the same temperature for 2 hours, a solution of 9.5 g (0.05 mole) of ethyl iminodiacetate in 20 me of chloroform was then added dropwise to the mixture at the same temperature, and 5 g (0.05 mole) of triethylamine was further added dropwise to the mixture. The resulting mixture was stirred at OOC for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 me of chloroform, the reaction mixture was washed with 100 me of water three times. The chloroform layer was dried and then concentrated in a vacuum 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%).

For the identification of the product, a portion thereof was purified by silica gel column chromatography, using benzene/ethyl acetate (4:1) as the solvent, whereby an oily product was obtained.

NMR in chloroform-d1: 61.24 ppm (t, 6H) 6 1.48 ppm (s, 6H) 6 3.02 ppm (s, 2H) 6 3.42 ppm (s, 3H) 6 4.20 ppm (q, 4H) 6 4.28 ppm (s, 4H) 6 6.6-7.2 ppm (m, 3H) Elemental Analysis: C H N Found (%): 54.68 6.46 6.38 Calcd. for C20H28N207S: 54.53 6.41 6.36 (molecularwt. 440.526) Thus, the product was confirmed to have the following formula:

Examples 3 to 5 The compounds shown in Table 1 below were prepared in the same manner as in Example 1 or 2. The physical properties and NMR data (in chloroform-d1) of these compounds are also shown in Table 1. TABLE 1

Example Amine R1 R2 H-NMREl Elemental Analysis No. [# Value (ppm) Empirical Formula in CDCl3] Found Value C H N (Calculated Value) (%) (%) (%) 81,47(s,6H), C18H24N2O7S 3 # -CH2COOCH3 -CH2COOCH3 83.02(s,2H), 83.41(s,3H), 52.11 5.91 6.63 83.73(s,6H), (52.42) (5.87) (6.79) 84.30(2,4H), 86.7-7.2(m,3H) 81.23(d,6H), C2H32N2O7S 4 # -CH2COO- > -CH2COO- > 81,46(s,6H), 83.03(s,2H), 56.35 6.91 5,86 83.42(s,3H), (56.40) (6.89) (5.98) 84.26(s,4H), 84,5-5,3(m,1H), 86.6-7.2(m,3H), 81.0-2.2(m,20H), C28H40N2O7S 81.48(2,6H), 5 # # # 83.02(s,2H) 61,32 7.39 4.95 83.43(s,3H), (61.29) (7.35) (5.11) 84.28(s,4H), 84.5-5.1(m,2H), 86.7-7.2(m,3H) Example 6 Prenaration of 2,3-dihydro-2,2-dimethylhenzofuran-7-yl[N-N-his@@@@@@@@@@@@@@@@@@@@@@@@ N-methyl-carbamate A 11 g quantity (0.05 mole) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate was dissolved in 70 me of methylene chloride, 5.2 g (0.05 mole) of sulfur dichloride was added to the solution with cooling, and 5 g (0.05 mole) of triethylamine was further added dropwise to the solution at -10 to -5 C. The mixture was stirred at O"C for one hour and further at room temperature for 2 hours.After cooling to - 10 to -5 C, 10.9 g (0.05 mole) of diethyl iminodipropionate was added dropwise to the mixture, and 5 g (0.05 mole) of triethylamine was further added dropwise to the mixture. The resulting mixture was stirred at 0 C for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 me of methylene chloride, the reaction mixture was washed with 100 me of water three times. The methylene chloride layer was dried and then concentrated in a vacuum 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 the identification of the product, a portion thereof was purified by silica gel column chromatography, using benzene/ethyl acetate (5:1) as the solvent, whereby an oily product was obtained.

NMR in chloroform-d1: 61.21 pm(t,6H) 51.44ppm(s,6H)- 6 2.67 ppm (t, 4H) 6 2.97 ppm (s, 2H) 6 3.37 ppm (s, 3H) 6 3.42 ppm (t, 4H) 6 4.04 ppm (q, 4H) 6 6.5-7.2 ppm (m, 3H) Elemental Analysis C H N Found (%): 56.26 6.91 5.52 Calcd. for C22H32N207S: 56.39 6.88 5.98 (molecular wt. 468.58) Thus, the product was confirmed to have the following formula:

Example 7 Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N-[N,N-bis(cyanoethyl)aminosulfenylj-N-methyl- carbamate A 11 g quantity (0.05 mole) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate was dissolved in 50 me of chloroform, 5.2 g (0.05 mole) of sulfur dichloride was added to the solution with cooling, and 5 g (0.05 mole) of triethylamine was 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 one hour.After cooling to -10 to - 5"C, 6.2 g (0.05 mole) of iminodipropionitrile was added dropwise to the mixture, and 5 g (0.05 mole) of triethylamine was further added dropwise to the mixture. The resulting mixtured was stirred at 0 C for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 me of chloroform, the reaction mixture was washed with 100 me of water three times. The chloroform layer was dried and then concentrated in a vacuum 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%).

NMR in chloroform-d1: 8 1.43 ppm (5, 6H) 82.73 ppm (t, 4H) 82.97 ppm (s, 2H) 6 3.37 ppm (s, 3H) 6 3.43 ppm (t, 4H) 6 6.5-7.2 ppm (m, 3H) Elemental Analysis: C H N Found (%): 57.91 5.79 15.04 Calcd. for C18H22N403S: 57.73 5.92 14.96 (molecular wt. 374.47) Thus, the product was confirmed to have the following formula:

Examples 8 to 11 The compounds shown in Table 2 below were prepared in the same manner as in Example 6 or 7. The physical properties and NMR data (in chloroform-d1) of these compounds are also shown in Table 2. TABLE 2

Example Amine No. R1 R2 H-NMR Elemental Analysis [# Value (ppm) Empirical Formula in CDCl3] found Value (Calculated Value) C H N (%) (%) (%) 81.26(t,3H), C19H25N3O5S 8 # -CH2CH2CN -CH2COOC2H5 81,47(s,6H), 82,6-3.1(m,2H), 55.89 6.31 10.64 83.02(s,2H), (56.01) (6.19) (10.31) 83.40(s,3H), 83,3-3.8(m,2H), 84.18(s,2H), 84.20(q,2H), 86.6-7.2(m,3H) 81.23(t,6H), C21H30N2O7S 9 # -CH2CH2COOC2H5 -CH2COOC2H5 81,45(s,6H), 82.70(t,2H), 55.94 6.79 6.05 83.00(s,2H), (55.50) (6.65) (6.16) 83.39(s,3H), 83.40(t,2H), 84.09(q,2H), 84.14(s,2H), 84.55(q,2H), 86.5-7.2(m,3H) (cont'd)

Example Amine R1 R2 H-NMR Elemental Analysis No. [# Value (ppm) Empirical Formula in CDCl3] Found Value (Calculated Value) C H N (%) (%) (%) 81.22(t,6H), C22H32N2O7S 10 # -CH2CH2CH2COOC2H5 -CH2COOC2H5 81,45(s,6H), 81.7-2,6(m,4H), 55.94 6.93 6.25 83.00(s,2H), (56.40) (6.89) (5.98) 83.35(t,2H), 83,42(s,3H), 84.13(q,2H), 84.15(s,2H), 84.17(q.2H), 86.5-7.2(m,3H) 80.99(t,3H), C2H32N2O7S 81.20(t,3H), 11 # # -CH2COOC2H5 81.23(t,3H), 56.53 6.78 5.81 81.43(s,6H), (56.40) (6.89) (5.98) 81,5-2,5(m,2H), 83.02(s,2H), 83.38(s,3H), 83.5-4,5(m,7H), 86,5-7.2(m,3H), Example 12 Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N-butyl-N-ethoxycarbonylaminosulfenyl )-Nmethyl-carbamate A 11 g quantity (0.05 mole) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate was dissolved in 70 mt of methylene chloride, 5.2 g (0.05 mole) of sulfur dichloride was added to the solution with cooling, and 5 g (0.05 mole) of triethylamine was further added dropwise to the solution at -10 to -5"C. The mixture was stirred at OOC for one hour and further at room temperature for 2 hours.After cooling to - 10 to -5 C, 8.0 g (0.05 mole) of N-butylglycine ethyl ester was added dropwise to the mixture, and 5 g (0.05 mole) of triethylamine was further added dropwise to the mixture. The resulting mixture was stirred at 0 C for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 me of methylene chloride, the reaction mixture was washed with 100 mt of water three times. The methylene chloride layer was dried and then concentrated in a vacuum to give an oily product, which was almost entirely composed of the desired product although containing small amounts of impurities.

Yield: 15.7g (76.6%).

NMR in chloroform-d1: 50.6-1.9 ppm (m,7H) 61.22 ppm (t,3H) 5 1.44 ppm (s, 6H) 6 3.03 ppm (s, 2H) 53.30 ppm (t, 2H) 6 3.42 ppm (s, 3H) 54.14 ppm (s, 2H) 54.13 ppm (q, 2H) ä 6.5-7.2 ppm (m, 3H) Elemental Analysis: C H N Found (%): 58.39 7.41 6.75 Calcd.forC20H30N205S: 58.52 7.37 6.83 (molecularwt.410.54) Thus, the product was confirmed to have the following formula:

Example 13 Preparation of 2,3-dihydro-2,2-dimethylbenzofu ran-7-yl N-(N-phenyl-N-ethoxycarbonylmethylamino- sulfenyl)-N-methyl-carbamate A 11 g quantity (0.05 mole) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate was dissolved in 70 mt of methylene chloride, 5.2 g (0.05 mole) of sulfur dichloride was added to the solution with cooling, and 5 g (0.05 mole) of triethylamine was further added dropwise to the solution at -10 to -50C. The mixture was stirred at 0 C for one hour and further at room temperature for 2 hours.After cooling to -10 to --50C, 9 g (0.05 mole) of N-phenylglycine ethyl ester was then added dropwise to the mixture, and 5 g (0.05 mole) of triethylamine as further added dropwise to the mixture. The resulting mixture was stirred at 0 C for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 mt of methylene chloride, the reaction mixture was washed with 100 mt of water three times. The methylene chloride layer was dried and then concentrated in a vacuum to give an oily product. A benzene-hexane (1:1) mixture was added to the oily product, whereby crystals were precipitated. The thus-precipitated crystals were then filtered off, and the mother liquor was concentrated to give an oily product, which was subsequently cooled to obtain crystals.The thus-obtained crystals 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-d1: 81.15ppm(t,3H) 81,46ppm(s,6H) 83.00ppm(s,2H) 83.32ppm(s,3H) 84.12ppm(q,2H) 84.76ppm(s,2H) â 6.5-7.5 ppm (m, 8H) Elemental Analysis: C H N Found(%): 61.11 6.15 6.49 Calcd. for C22H26N205S: 61.38 6.09 6.51 (molecularwt. 430.53) Thus, the product was confirmed to have the following formula:

Examples 14 to 32 The compounds shown in Table 3 below were prepared in the same manner as in Example 12 or 13. The physical properties and NMR data (in chloroform-di) of these compounds are also shown in Table 3. TABLE 3

Example Amine R1 R2 H-MNR Elemental Analysis No. [# Value (ppm) Empirical Formula in CDcl3] Found Value (Calculated Value) C H N (%) (%) (%) 81.24(t,3H), C17H24N2O6S 14 # -CH2COOC2H5 -CH3 81,47(s,6H), 83.02(s,3H), 55.61 6.45 7.83 83.17(s,3H), (55.43) (6.56) (7.61) 83.48(s,3H), 84.10(s,2H), 84.17(q.2H), 86.6-7.2(m,3H) 81.16(d,6H), C19H28N2O5S 15 # -CH2COOC2H5 # 81.18(t,3H), 81,43(s,6H), 57.34 7.15 7.17 82.94(s,2H), (57.56) (7.12) (7.07) 83.29(s,3H), 83.1-3,7(m,1H), 84.00(q.2H), 84.02(s,2H), 86.5-7.0(m,3H) (cont'd)

Example Amine R1 R2 H-NMR Elemental Analysis No. [# Value (ppm) Empirical Formula in CDCl3] Found Value (Calculated Value) C H N (%) (%) (%) 80.8-1.8(m,8H), C20H30N2O5S 16 # -CH2COOC2H5 - sec-C4H9 81.22(t,3H), 81.45(s,6H), 58.55 7.25 6.91 82.97(s,2H), (58.52) (7.37) (6.83) 82.9-3.3(m,1H), 83.30(s,3H), 84.03(s,2H), 84.08(q,2H), 86.7-7.1(m,3H) 80.7-1.8(m,18H), C24H38N2O5S 17 # -CH2COOC2H5 - n -C8H17 81.45(s,6H), 82.97(s,2H) 61.53 8.11 6.24 83.1-3.5(m,2H), (61.78) (8.21) (6.00) 83.36(s,3H), 84.01(s,2H), 84.07(q,2H), 86.6-7.2(m,3H) 80.7-2.4(m,14H), C22H32N2O5S 18 # -CH2COOC2H5 # 81.43(s.6H), 82.93(s,2H), 60.95 7.42 6.51 83.32(s,3H), (60.53) (7.39) (6.42) 84.06(q,2H), 84.08(s,2H), 86.6-7.2(m,3H) (cont'd)

Example R1 R2 H-NMR Elemental Anslysis No. [# Value (ppm) Empirical Formula in CDCl3] Found Value (Calculated Value) C H N (%) (%) (%) 81.22(t,3H), C23H28N2O5S 19 # -CH2COOC2H5 # 81.40(s,6H), 82.97(s,2H), 62.04 6.39 6.63 83.24(s,3H), (62.15) (6.35) (6.30) 83.82(s,2H), 84.11(q.2H), 84.15(s,2H), 86.5-7,6(m,8H), 81.25(t,3H), C23H27N2O5ClS 20 # -CH2COOC2H5 # 81.42(s,6H), 83.04(s,2H), 58.01 5.54 5.69 83.42(s,3H), (57.67) (5.68) (5.85) 83.92(s,2H), 84.21(q.2H), 84.23(s,2H), 86.7-7.2(m,3H), 87.2-7.5(m,4H), 81.17(t,3H), C23H28N2O5S 21 # -CH2COOC2H5 # 81,48(s,6H), 82.35(s,3H), 61.84 6.42 6.19 83.05(s,2H), (62.15) (6.35) (6.30) 83.40(s,3H), 84.18(q,2H), 84.80(s,2H), 86.7-7.5(m,7H) (cont'd)

Example Amine R1 R2 H-NMR Elemental Analysis No. [# Value (ppm) Empirical Formula in CDCl3] Found Value (Calculated Value) C H N (%) (%) (%) 81.15(t,3H), C28H28N2O5S 22 # -CH2COOC2H5- # 81,48(s,6H), 83.02(s,2H), 60.31 6.22 6.11 83.31(s,3H), (59.99) (6.13) (6.08) 83.76(s,3H), 84.17(q,2H), 83.70(s,2H), 86.7-7.4(m,7H) 81.21(t,3H), C20H30N2O5S 23 # -CH2CH2COOC2H5 # 81.23(d,6H), 81,47(s,6H), 58.43 7.29 6.65 82.78(t,2H), (58.52) (7.37) (6.83) 83.04(s,2H), 83.40(s,3H), 83.2-3,8(m,3H), 84.12(q,2H), 86.6-7.2(m,3H) 81.18(d,6H), C20H30N2O5S 24 # -CH2CH2COOC2H5 # 81.43(s,6H), 82,68(t,2H), 58.01 7.32 7.11 82.99(s,2H), (57.56) (7.12) (7.07) 83.0-3,5(m,3H), 83.31(s,3H), 83.51(s,3H), 86.5-7.1(m,3H) (cont'd)

Example Amine R1 R2 H-NMR Elemental Analysis No. [#Value (ppme) Empirical Formula in CDCl3] Found Value (Calculated Value) C H N (%) (%) (%) 806-1.8(m,7H), C22H34N2O5S 25 # -CH2CAH2COOC2H5 # 81.17(d,6H), 81,42(s,6H), 60.48 7.69 6.13 82.65(t,2H), (60.25) (7.82) (6.39) 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) 80.6-1,8(m,15H), C26H42N2O5S 26 # -CH2CH2COO-# # 81.16(d,6H), 81.42(s,6H), 63.45 8.62 5.49 82.68(t,2H), (63.13) (8.56) (5.66) 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), 80.7-1.8(m,10H), C21H32N2O5S 27 # -CH2CH2COOC2H5 - n -C4H9 81.41(s,6H), 82.4-2.8(m,2H), 59.01 7.38 6.79 82.95(s,2H), (59.42) (7.60) (6.60) 83.33(s,3H), 83.1-3.4(m,4H), 83.97(q.2H), 86.6-7.2(m,3H) (cont'd)

Example Amine R1 R2 H-NMR Elemental Analysis No. [# Value(ppm) Empirical Formula in CDCl3] Found Value (Calculated Value) C H N (%) (%) (%) 80.6-2.0(m,7H), C20H30N2O5S 28 # -CH2CH2COOCh3 - n -C4H9 81.45(s,6H) 82.66(t,2H), 58.79 7.14 6.66 82.97(s.2H), (58.52) (7.37) (6.83) 82.9-3.7(m,4H), 83.35(s,3H), 83.54(s,3H), 86.5-7.0(m,3H) 80.6-1.8(m,11H), C21H32N2O5S 29 # -CH2CH2COOC2H5 -Sec-C4H9 81.42(s,6H), 82.66(t,2H), 59.62 7.71 6.53 82.96(s,2H), (59.42) (7.60) (6.60) 83.0-3.7(m,3H), 83.31(s,3H) 83.95(q,2H), 86.6-7.0(m,3H) 80.84(d,6H), C21H32N2O5S 30 # -CH2CH2COOC2H5 - iso-C4H9 81.18(t,3H), 81.42(s,6H), 59.71 7.54 6.63 81.6-2.2(m,1H), (59.42) (7.60) (6.60) 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) (cont'd)

Example Amine R1 R2 H-NMR Elemental Analysis No. [# Value(ppm) Empirical Formula in CDCl3] Found Value (Calcualted Valte) C H N (%) (%) (%) 80.7-2.0(m,14H), C23H36N2O5S 31 # -CH2CH2COOC2H5 - n -C6H15 81.46(s,6H), 82.63 (t,2H), 60.85 8.11 6.32 82.98(s,2H), (61.04) (8.02) (6.19) 82.9-3,6(m,4H), 83.35(s,3H), 83.97(q.2H), 86.5-7.0(m,3H) 80.9-2.0(m,10H), C23H34N2O5S 32 # -CH2CH2COOC2H5 # 81.17(t,3H), 81,43(s,6H), 61.59 7.49 6.09 82.64(t,2H), (61.31) (7.61) (6.22) 82.94(s,2H), 83.0-3,6(m,3H), 82.97(s,3H), 83.95(q,2H), 86.5-7.1(m,3H) Example 33 Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N-butyl-N-cyanomethylaminosulfenyl)-Nmethyl-carbamate A 11 g quantity (0.05 mole) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate was dissolved in 70 me of methylene chloride, 5.2 g (0.05 mole) of sulfur dichloride was added to the solution with cooling, and 5 g (0.05 mole) of triethylamine was 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-5 C,5,6 g (0.05 mole) of N-butylaminoacetonitrile was added dropwise to the mixture, and 5 g (0.05 mole) of triethylamine was further added dropwise to the mixture. The resulting mixture was stirred at 0 C for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 me of methylene chloride, the reaction mixture was washed with 100 me of water three times. The-methylene chloride layer was dried and then concentrated in a vacuum to give an oily product, which was almost entirely composed of the desired product although containing small amounts of impurities.

Yield: 13.0g (71.4%).

NMR in chloroform-d1: 80.7-2.0 ppm (m, 7H) 61.42 ppm (s, 6H) 6 2.92 ppm (s, 2H) 6 2.9-3.5 ppm (m, 2H) 6 3.33 ppm.(s, 3H) 6 4.01 ppm (s, 2H) 66.5-7.1 ppm (m, 3H) Elemental Analysis: C H N Found (%): 59.19 7.02 11.69 Calcd. for C18H25N3O3S: 59.48 6.93 11.56 (molecular 363.488) Thus, the product was confirmed to have the following formula:

Examples 34 to 42 The compounds shown in Table 4 below were prepared in the same manner as in Example 33.The physical properties and NMR data (in chloroform-di) of these compounds are also shown in Table 4. TABLE 4

Example Amine R1 R2 H-NMR Elemental Analysis No. [# Value (ppm) Empirical Formula in CDCl3] Found Value (Calculated Value) C H N (%) (%) (%) 81.28(d,6H), C17H23N3O3S 34 # -CH2CN # 81,42(s,6H), 83.00(s,2H), 58.23 6.59 12.21 83.43(s,3H), (58.44) (6.64) (12.03) 84.34(s,2H), 83.3-4.1(m,1H), 86.5-7.2(m,3H) 81.44(s,6H), C20H21N3O3S 35 # -CH2CN # 82.98(s,2H), 83.41(s,3H), 62.11 5.48 11.02 84.76(s,2H), (62.65) (5.52) (10.96) 86.5-7.7(m,8H) 81,47(s,6H), C21H23N3O3S 36 # -CH2CN # 82.33(s,3H), 83.00(s,2H), 63.51 5.79 10.31 83.39(s,3H), (63.46) (5.83) (10.58) 84.80(s,2H), 86.5-7.5(m,7H) (cont'd)

Example Amine R1 R2 H-NMR Elemental Analysis No. [# Value (ppm) Empirical Formula in CDCl3] Found Value (Calculated Value) C H N (%) (%) (%) 81.46(s,6H), C16H21N3O3S 37 # -CH2CH2CN -CH3 82.5-2.9(m,2H), 83.00(s,2H), 57.59 6.17 12.74 83.17(s,3H), (57.30) (6.31) (12.53) 83.0-3,5(m,2H), 83.46(s,3H), 86.5-7.1(m,3H) 81.21 (d,6H), C18H25N3O3S 38 # -CH2CH2CN # 81.43(s,6H), 82.72(t,2H), 59.32 6.87 11.64 83.00(s,2H), (59.49) (6.93) (11.56) 83.0-3,8(m,3H), 83.32(s,3H), 86.6-7.2(m,3H) 80.7-2.0(m,7H), C19H27N3O3S 39 # -CH2CH2CN -n-C4H9 81.44(s,6H), 82.5-2.9(m,2H), 60.64 7.41 11.25 82.98(s,2H), (60.46) (7.21) (11.13) 82.9-3.5(m,4H), 83.37(s,3H), 86.5-7.0(m,3H) (cont'd)

Example Amine R1 R2 H-NMR Elemental Analysis No. [# value(ppm) Empirical Formula in CDCl3] Found Value (Calculated Value) C H N (%) (%) (%) 80.90(d,6H), C19H27N3O3S 40 # -CH2CH2CN -iso-C4H9 81.43(s,6H), 82.69(t,2H), 60.25 7.39 11.01 82.96(s,2H), (60.46) (7.21) (11.13) 83.0-3,5(m,4H), 83.33(s,3H), 86.5-7.0(m,3H) 80.7-2.0(m,15H), C23H35N3O3S 41 # -CH2CH2CN -n-C8H17 81.47(s,6H), 82.6-2.9(m,2H), 63.59 8.31 9.54 83.01(s,2H), (63.72) (8.14) (9.69) 83.0-3,5(m,4H), 83.40(s,3H), 86.5-7.0(m,3H) 80.7-2.0(m,10), C21H29N3O3S 42 # -CH2CH2CN # 81.46(s,6H), 82.5-2.9(m,2H), 62.33 7.42 10.85 82.98(s,2H), (62.51) (7.25) (10.42) 83.-3.5(m,2H), 83.32(s,3H), 83.9-4,3(m,1H), 86.5-7.1(m,3H) Example 43 Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N-propionyl-N-ethoxycarbonylmethylamino- sulfenyl)-N-methyl-carbamate A 11 g quantity (0.05 mole) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate was dissolved in 70 me of methylene chloride, 5.2 g (0.05 mole) of sulfur dichloride was added to the solution with cooling, and 5 g (0.05 mole) of triethylamine was further added dropwise to the solution at -10 to -50C. 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, a solution of 8 g (0.05 mole) of N-propionylglycine ethyl ester in 10 m of tetrahydrofuran was added dropwise to the mixture, and 5 g (0.05 mole) of triethylamine was further added dropwise to the mixture. The resulting mixture was stirred at 0 C for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 me of methylene chloride, the reaction mixture was washed with 100 me of water three times.The methylene chloride layer was dried and then concentrated in a vacuum 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 thereof was purified by silica gel column chromatography, using benzene/ethyl acetate (9:1) as the solvent, whereby crystals having a melting point of 108 to 109"C were obtained.

NMR in chloroform-d1: 61.14 ppm (t 3H) 6 1.23 ppm (t, 3H) 61.49 ppm (s, 6H) ä 2.7-3.3 ppm (m, 2H) 6 3.02 ppm (s, 2H) 6 3.48 ppm (s, 3H) 64.15 ppm (q, 2H) 6 4.50 ppm (s, 2H) 66.6-7.1 ppm (m, 3H) Elemental Analysis: C H N Found (%): 55.35 6.41 6.77 Calcd. for C19H26N206S: 55.59 6.38 6.82 (molecularwt. 410.499) Thus, the product was confirmed to have the following formula:

Example 44 Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N-ethoxycarbonyl-N-ethoxycarbonylmethylaminosulfenyl)-N-methyl-carbamate A 11 g quantity (0.05 mole) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate was dissolved in 70 me of methylene chloride, 5.2 g (0.05 mole) of sulfur dichloride was added to the solution with cooling, and 5 g (0.05 mole) of triethylamine was further added dropwise to the solution at -10 to --5"C. The mixture was stirred at O"e for one hour and further at room temperature for 2 hours.After cooling to - 10 to -50C, 8.8 g (0.05 mole) of N-ethoxycarbonylglycine ethyl ester added dropwise to the mixture, and 5 g (0.05 mole) of triethylamine was further added dropwise to the mixture. The resulting mixture was stirred at 0 C for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 me of methylene chloride, the reaction mixture was washed with 100 me of water three times. The methylene chloride layer was dried and then concentrated in a vacuum 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: 18.2 g (84.7%).

NMR in chloroform-d1: # 1.17 ppm(t,6H) # 1.44 ppm (s,6H) 82.94 ppm (s, 2H) 83.41 ppm (s, 3H) 6 4.05 ppm (q, 2H) #4.15 ppm (q, 2H) #4.41 ppm (s, 2H) 86.5-7.0 ppm (m, 3H) Elemental Analysis: C H N Found (%): 53.82 6.19 6.44 Calcd. for C19H26N2O7S; 53.51 6.14 6.57 (molecularwt. 426.499) Thus, the product was confirmed to have the following formula:

Example 45 to 52 The compounds shown in Table 5 below were prepared in the same manner as in Example 43 or 44.The physical properties and NMR data (in chloroform-d1) of these compounds are also shown in Table 5. TABLE 5

Example Amine R1 R2 H-NMR Elemental Analysis No. [# Value (ppm) Empirical Formula in CDCl3] Found Value (Calculated Value) C H N (%) (%) (%) 81.21 (t,3H), C18H23N2O6ClS 45 # -CH2COOC2H5 -COCH2C 81,46(s,6H), 82.98(s,2H), 49.98 5.17 6.43 83.40(s,3H), (50.17) (5.38) (6.50) 84.05(q,2H), 84.36(s,2H), 84.87(s,2H), 85.6-7.0(m,3H) 81.18(t,3H), C23H26N2O6S 46 # -CH2COOC2H5 # 81.41(s,6H), 82.87(s,3H), 60.54 5.61 8.02 82.91(s,2H), (60.25) (5.72) (6.11) 84.06(q,2H), 84.60(s,2H), 86.5-7.0(m,3H), 87.1-7.7(m,5H) (cont'd)

Example Amine R1 R2 H-NMR Elemental Analysis No. [# Value (ppm) Emplrical Formula in CDCl3 Found Value (Calculated Value) C H N (%) (%) (%) 81.21(t,3H), C23H25N2O6ClS 47 # -CH2COOC2H5 # 81,46(s,8H), 82.93(s,8H), 56.53 5.37 5.49 82.95(s,2H), (56.04) (5.11) 5.68) 84.07(q,2H), 84,56(s,2H), 86.5-7.0(m,3H), 87.1-7.6(m,4H) 81.18(t,3H), C23H28N2O7S2 48 # -CH2COOC2H5 # 81.46(s,6H), 82.37(s,3H), 54.04 5.57 5.24 82.96(s,2H), (54.31) (5.55) (5.51) 83.48(s,3H), 84.02(q,2H), 84.58(s,2H), 86.5-7.9(m,7H) 81.19(t,3H), C18H24H2O7S 49 # -CH2COOC2H5 -COOCH2 81,46(s,6H), 82.97(s,2H), 52.16 5.64 6.56 83.43(s,3H), (52.42) (5.87) (6.79) 83.74(s,3H), 84.07(q,2H), 84.42(s,2H), 86.5-7.1(m,3H) (cont'd)

Example Amine R1 R2 H-NMR Elemental Analysis No. [# Value (ppme) Empirical Formula in CDECl3] Found Value (calculated Valued) C H N (%) (%) (%) 81.19(t,3H), C23H26N2O7S 50 # -CH2COOC2H5 # 81,44(s,6H), 82.95(s,2H), 57.97 5.61 5.78 83.50(s,3H), (58.22) (5.52) (5.90) 84.05(q,2H), 84.52(s,2H), 86.5-7.4(m,8H) 81.30(t,3H), C18H23N3O5S 51 # -CH2CH2CN -COOC2H5 81,46(s,6H), 82.63(t,2H), 55.16 5.93 10.31 82.97(s,2H), (54.95) (5.89) (10.58) 83.40(s,3H), 83.95(t,2H), 84.16(q,2H), 86.5-7.0(m,3H) 81.17(t,3H), C20H28N2O7S 52 # -CH2CH2COOC2H5 -COOC2H5 81.32(t,3H), 81.46(s,6H), 54.33 6.29 6.51 82.57(t,2H), (54.54) (6.41) (6.36) 82.98(s,2H), 83.40(s,3H), 83,7-4,4(m,6H), 86.5-7.0(m,3H) Preparation Examples of this invention are given below. These prescriptions are applicable to all the compounds of this invention; a suitable prescription is usable for a particular application. The prescriptions are shown only for illustrative purposes, and the proportions of the active component, organic solvent, surfactant and carrier are variable as desired. In some cases, the kinds of organic solvent, surfactant, carrier, etc., can also be changed. The percentages are all by weight.

Preparation Example 1 60% Emulsion: Compound of Example 25 60.0% Polyoxyethylene nonylphenyl ether 10.0 Xylene 30.0 Preparation Example 2 50% Emulsion: Compound of Example 12 50.0% Polyoxyethylene sorbitan monooleate 6.5 Sorbitan monooleate 3.5 Xylene 30.0 Cyclohexanone 10.0 Preparation Example 3 20% Emulsion: Compound of Example 22 20.0% Polyoxyethylene alkyl ether 5.0 Xylene 45.0 Petroleum ether 30.0 In each of Preparation Examples 1 to 3, the ingredients were uniformly mixed and dissolved to obtain the desired emulsion.

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 sulfate 30.0 Condensate of naphthalenesulfonic acid 10.0 and formaldehyde Alkyl phosphate 5.5 Kaolin 3.5 Talc 1.0 Preparation Example 6 30% Wettable powder: Compound of Example 30 . 30.0% Alkylbenzenesulfonate 3.0 Sodium lignin sulfonate 2.0 White carbon 15.0 Clay 50.0 In each of Preparation Examples 4 to 6, the ingredients were uniformly mixed with stirring using a Shinagawa-type mixer. The mixture was then finely pulverized using a sample mill or ball mill to obtain the desired wettable powder.

Preparation Example 7 5% Dust: Compound of Example 46 5.0 Diatomaceous earth 10.0 Talc 85.0 Preparation Example 8 2% Dust: Wettable powder of Preparation 4.0 Example 5 Clay 95.8 Isopropyl phosphate 0.2 Preparation Example 9 0.5% Dust: Wettable powder of Preparation 1.7% Example 6 Clay 100.3 In each of Preparation Examples 7 to 9, the ingredients were uniformly mixed with stirring using a Shinagawa-type mixer to obtain the desired dust.

Preparation Example 10 20% Granule: Wettable powder of Preparation 40.0% Example 5 Dolomite 60.0% These ingredients were uniformly mixed, a 2% aqueous solution of carboxymethyl cellulose 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 thoroughly kneaded. The mixture was then granulated using a granulator and finely cleaved, followed by allowing it to dry. Thus, the desired granule was obtained.

Preparation Example ii 10% Granule: Compound of Example 40 10.0% Sodium dodecylbenzenesulfonate 0.5 Sodium lignin sulfonate 2 Diatomaceous earth 27.5 Bentonite 60.0 These ingredients were uniformly mixed, and water was added to the mixture. The resulting mixture was thoroughly kneaded, and then granulated using a granulator. The thus-granulated product was finely cleaved and dried to obtain the desired granule.

Preparation Example 12 3% Granule: Compound of Example 8 3.0% Polyvinyl alcohol 3.0 Clay 94.0 The same procedure as in Preparation Example 11 was repeated to obtain the desired granule.

Test Examples are given below.

Test Example 1 Ten third-instar larvae of tabacco cutworm (Spodoptera litura) were placed on a cabbage (one-month-old seedling) planted in a pot, and a 50% emulsion of the compound to be tested was diluted to a specified concentration and applied to the leaves of the plant to fully wet them. The test compound of each specified concentration was tested on two pots. Three days later, the larvae were checked for mortality, with the result listed in Table 6, which also shows the results achieved for control groups and untreated groups for comparison.

TABLE 6 Test Compound Mortality (%) (Example No.) Concentration of Active Ingredient (ppm) 2,000 1,000 500 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 (cont'd) Test Compound Mortality (%) (Example No.) Concentration of Active Ingredient (ppm) 2,000 1,000 500 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 (cont'd) Test Compound Mortality (%) (Example No.) Concentration of Active Ingredient (ppm) 2,000 1,000 500 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 O 1 -Naphthyl-N-methyl-carbamate was used as the control.

Test Example 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 paddy rice (one-month-old seedlings) planted in a pot to fully wet the leaves. After the emulsion had been dried, the pot was covered with a net cage, into which 10 femal adults of green rice leafhopper (Nephotettix cincticeps) were released. The compound of each specified concentration was tested on two pots. Three days later, the insects were checked for mortality, with the result listed in Table 7, which also shows the results achieved for control groups and untreated groups for comparison.

TABLE 7 Test Compound Mortality (%) (Example No.) Concentration of Active Ingredient (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 (cont'd) Test Compound Mortality (%) (Example No.) Concentration of Active Ingredient (ppm) 800 400 200 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 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 Control* 75 50 25 0 0 0 Untreated O *2-lsopropoxyphenyl-N-methyl-carbamate was used as the control.

Test Example 3 Granules containing 10% of the compound to be tested were mixed, in a specified amount, with soil contaminated with larvae of southern root-knot nematode (Meloidogyne incognita), and tomato seedlings were immediately transplanted in the soil. One month later, the roots of the plant were checked for the formation of nodules. Two test areas, 2 x 2 m2 each, were used for the compound as applied in each specified amount. The degree of formation of the nodules was determined according to the criteria given below, with the result shown in Table 8. For comparison, Table 8 also shows the results achieved in control areas and untreated areas.

Degree of formation of nodules 0: 0% 1: Upto25% 2: Up to 50% 3: Up to 75% 4: Upto10O% TABLE 8 Test Compound Degree of Formation (Example No.) of Nodules Amount 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 17 0 1 3 18 0 1 2 19 0 1 2 20 0 1 3 (cont'd) Test Compound Degree of Formation (Example No.) of Nodules Amount of Granules Applied (kg/10 a) 100 50 20 21 0 1 2 22 0 1 3 23 0 1 2 24 0 0 1 25 0 1 2 26 0 1 2 27 0 1 2 28 0 0 1 29 0 1 2 30 0 1 2 31 0 2 3 32 0 2 3 33 0 0 1 34 0 0 1 35 0 1 3 36 0 1 3 37 0 1 2 38 0 0 1 39 0 0 1 40 0 1 1 41 0 1 3 42 0 1 2 43 0 1 2 44 0 0 1 45 0 1 2 46 0 1 2 47 0 1 3 48 0 1 3 49 0 0 1 (cont'd) TABLE 6 (Cont'd) Test Compound Mortality (%) (Example No.) Concentration of Active Ingredient (ppm) 2,000 1,000 500 50 0 1 3 51 0 1 2 52 0 1 2 Control* 2 4 4 Untreated 4 *Bis (2-chloro-1 -methylethyl)ether was used as the control.

TestExample4 The compound to be tested was dissolved in a predetermined amount of acetone. The solution was diluted to various concentrations and locally applied to house fly (Musca domestica). Table 9 shows LD50 values determined by the Probit method from the mortality 24 hours later.

TABLE 9 Test Compound LD50 (Example No.) ( g/g) 1 21.3 2 58.8 3 40.0 4 28.9 5 75.6 6 38.3 7 54.0 8 24.6 9 31.7 10 46.0 11 93.9 12 16.7 13 12.5 14 9.9 15 33.0 16 44.4 17 42.3 18 32.5 19 22.2 20 61.9 21 10.4 22 45.2 23 44.3 24 38.6 25 50.1 26 64.7 27 13.8 28 17.7 29 22.5 (cont'd) Test Compound LD50 (Example No.) (llg/g) 30 23.8 31 33.1 32 32.7 33 9.1 34 16.7 35 65.6 36 59.3 37 11.8 38 17.5 39 13.7 40 37.9 41 54.6 42 46.0 43 14.4 44 16.2 45 29.2 46 33.2 47 57.8 48 58.6 49 15.7 50 34.7 51 45.3 52 54.3 Control* 22.5 *2-lsopropoxyphenyl-N-methyl-carbamate was used as the control.

Test Examples Compounds of this invention were tested on male mice for acute toxicity by oral administration. Table 10 shows LD50 values determined by the Litchfield-Wilcoxon method from the mortality on the seventh day.

TABLE 10 Test Compound LD50 (Example No.) (mg/kg) 1 58 2 140 3 145 4 122 5 90 6 135 7 75 8 105 9 158 10 115 11 93 12 125 13 115 14 120 15 110 16 110 17 69 18 135 19 108 20 75 21 105 22 88 23 113 24 77 25 123 26 150 27 105 28 89 29 120 (cont'd) Test compound LD50 (Example No.) (mg/kg) 30 133 31 135 32 107 33 103 34 95 35 95 36 70 37 65 38 125 39 110 40 103 41 105 42 88 43 43 44 128 45 80 46 105 47 95 48 80 49 105 50 95 51 88 52 125 Control* 5.6 *2,3-Dihydro-2,2-dimethyl-7-benzofuran-7-yl N-methyl-carbamate was used as the control.

Claims

1. A carbamate derivative represented by the formula (I):

wherein R1 and R2, which may be the same or different, each represents (1) -X-COOR3, in which X represents an alkylene group having 1 to 6 carbon atoms, and R3 represents an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms; or (2)-Y-CN, in which Y represents an alkylene group having 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 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; a phenyl group which may be substituted with a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; or -Z-R4 in which 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 benzyl group, an alkoxy group having 1 to 6 carbon atoms or a phenoxy group.

2. A carbamate derivative represented by the formula (I'):

wherein R1' and R2, which may be the same or different, each represents (1) -X'-COOR3,, in which X' represents an alkylene group having 1 to 2 carbon atoms, and R3 represents an alkyl group having 1 to 4 carbon atoms which may be straight chain or branched chain; or (2) -Y'-CN, in which Y' represents an alkylene group having 1 to 2 carbon atoms; and R2 further 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.

4. 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl N-(N-methyl-N-ethoxycarbonylmethylaminosulfenyl)-Nmethyl-carbamate.

5. 2,3-Dihydro-2,2-dimethylbenzofu ran-7-yl N-(N-isopropyl-N-ethoxycarbonylethylaminosulfenyl)-Nmethyl-carbamate.

6. 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl N-(N-n-butyl-N-ethoxycarbonylethylaminosulfenyl )-Nmethyl-carbamate.

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

8. 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl N-(N-n-butyl-N-cyanoethylaminosulfenyl)-N-methylcarbamate,

9. An insecticidal, miticidal or nematocidal composition comprising an insecticidally, miticidally or nematocidally effective amount of the carbamate derivative according to Claim 1 as an active ingredient.

10. An insecticidal, miticidal or nematocidal composition comprising an insecticidally, miticidally or nematocidally effective amount of the carbamate derivative according to Claim 2 as an active ingredient.

11. A process for preparing the carbamate dericative according to Claim 1, which comprises reacting a compound represented by the formula (all):

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

which is then reacted with an amine compound represented by the formula (IV):

wherein R' and R2 are as defined in Claim 1.

12. A process according to Claim 11, wherein one to 2 moles of sulfur dichloride is used per mole of the compound of the formula (II).

13. A process according to Claim 11, wherein the reaction of the compound of the formula (II) with sulfur dichloride is carried out in the presence of a solvent.

14. A process according to Claim 13, wherein said solvent is one selected from methylene chloride, chloroform, carbon tetrachloride, diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane.

15. A process according to Claim 11, wherein the reaction of the compound of the formula (II) with sulfur dichloride is carried out in the presence of a basic compound.

16. A process according to Claim 15, wherein said basic compound is one selected from triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine, pyridine, cur, a, '3,y-picoline, and lutidine.

17. A process according to Claim 11, wherein about 1 to about 2 moles of the amine compounds of the formula (IV) is used per mole of the compound of the formula (III).

18. A process according to Claim 11, wherein the reaction of the compound of the formula (III) with the amine compound of the formula (IV) is carried out in the presence of a solvent.

19. A process according to Claim 18, wherein said solvent is one selected from methylene chloride, chloroform, carbone tetrachloride, diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane.

20. A process according to Claim 11, wherein the reaction of the compound of the formula (III) with the amine compound of the formula (IV) is carried out in the presence of a basic compound.

21. A process according to Claim 20, wherein said basic compound is one selected from triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine, pyridine, a, '3,y-picoline, and lutidine.

22. A method for controlling noxious insects, mites or nematodes applying thereto the carbamate derivative according to Claim 1.

23. A method for controlling noxious insects, mites or nematodes by applying thereto the carbamate derivative according to Claim 2.

24. A process according to claim 11, substantially as hereinbefore described in any one of Examples 1 to 52.

25. A carbamate derivative when prepared by a process according to any one of Claims 11 to 21 and 24.

26. A carbamate derivative substantially as hereinbefore described in any one of Examples 1 to 52.

27. A composition according to Claim 9, substantially as hereinbefore described in any one of Preparation Examples 1 to 12.