Carbamate derivatives and insecticidal, miticidal or nematocidal compositions containing 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 insects, 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, umless 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-dimethylbenzofuran-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-dimethylbenzofuran-7-yl N-(N,N-dibutylaminosulfenyl)-N-methyl-carbamate, and German Patent DT-OS 2,254,359 discloses 2,3-dihydro-2,2-dimethylbenzofuran-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): ##STR2## wherein R.sup.1 and R.sup.2, which may be the same or different, each represents (1) --X--COOR.sup.3, in which X represents an alkylene group having 1 to 6 carbon atoms, and R.sup.3 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 R.sup.2 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--R.sup.4, in which Z represents a carbonyl group or a sulfonyl group, and R.sup.4 represents an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, 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, 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'): ##STR3## wherein R.sup.1' and R.sup.2', which may be the same or different, each represents (1) --X'--COOR.sup.3', in which X' represents an alkylene group having 1 to 2 carbon atoms, and R.sup.3' 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 R.sup.2' 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) Deltocephalidae: Nephotettix cincticeps
(2) Delphacidae: Laodelphax striatellus, Nilaparvata lugens
(3) Aphididae: Myzus persicae, Aphis gossypii
(4) Pentatomidae: Nezara antennata, Nezara viridula
Lepidoptera
(1) Noctuidae: Spodoptera litura, Agrotis fucosa, Laphygma exigua
(2) Tortricidae: Adoxophyes orana
(3) Pyralidae: Chilo suppressalis, Ostrinia furnacalis, Cnaphalocrocis medinalis
(4) Plutellidae: Plutella xylostella
Coleoptera
(1) Curculionidae: Echinocnemus squameus, Lissorhoptrus oryzophilus
(2) Scarabaeidae: Popillia japonica
(3) Coccinellidae: Henosepilachna vigintioctopunctata
Diptera
(1) Muscidae: Musca domestica
(2) Cecidomyiidae: Aspondylia sp.
(3) Agromyzidae: Phytobia cepae
Thysanoptera
Thripidae: Thrips tabaci, Scirtothrips dorsalis
Orthoptera
Gryllotalpidae: Gryllotalpa africana
Isopoda
Armandillidae: Armadillidium vulgare
Acarina
Tetranychidae: Tetranychus telarius, Tetranychus urticae, Panonychus citri
Tylenchida
Heteroderidae: Meloidogyne incognita
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-dimethylbenzofuran-7-yl N-[N,N-bis(ethoxycarbonylmethyl)aminosulfenyl]-N-methyl-carbamate
2,3-Dihydro-2,2-dimethylbenzofuran-7-yl N-(N-methyl-N-ethoxycarbonylmethylaminosulfenyl)-N-methylcarbamate
2,3-Dihydro-2,2-dimethylbenzofuran-7-yl N-(N-isopropyl-N-ethoxycarbonylethylaminosulfenyl)-N-methylcarbamate
2,3-Dihydro-2,2-dimethylbenzofuran-7-yl N-(N-n-butyl-N-ethoxycarbonylethylaminosulfenyl)-N-methylcarbamate
2,3-Dihydro-2,2-dimethylbenzofuran-7-yl N-(N-cyclohexyl-N-ethoxycarbonylethylaminosulfenyl)-N-methylcarbamate
2,3-Dihydro-2,2-dimethylbenzofuran-7-yl N-(N-n-butyl-N-cyanoethylaminosulfenyl)-N-methyl-carbamate
The compounds of the formula (I) can be prepared, for example, by reacting a compound represented by the formula (II): ##STR4## with sulfur dichloride to form 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(chlorosulfenyl)-N-methyl-carbamate represented by the formula (III): ##STR5## which is then reacted with an amine compound represented by the formula (IV): ##STR6## wherein R.sup.1 and R.sup.2 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, dibutyl ether, tetrahydrofuran, dioxane and like ethers, etc. The proportions of the compound of the formula (II) and SCl.sub.2 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, .alpha.,.beta.,.gamma.-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.degree. to 50.degree. C., preferably about -10.degree. to about 30.degree. 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 the formula (IV) are those secondary amines represented by the formulae (V) to (IX): ##STR7## In the formulae (V) to (IX), X, Y, and R.sup.3 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'--R.sup.4', in which Z' represents a carbonyl group or a sulfonyl group, and R.sup.4' represents an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, 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, 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); R.sup.3" has the same meaning as in R.sup.3 ; 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-methylglycine butyl ester, N-ethylglycine ethyl ester, N-n-propylglycine ethyl ester, N-isopropylglycine ethyl ester, N-n-butylglycine ethyl ester, N-isobutylglycine ethyl ester, N-sec-butylglycine 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 N-methylaminopropionate, ethy N-n-propylaminopropionate, methyl N-isopropylaminopropionate, ethyl N-isopropylaminopropionate, butyl N-isopropylaminopropionate, 2-ethylhexyl N-isopropylaminopropionate, methyl N-n-butylaminopropionate, ethyl N-n-butylaminopropionate, ethyl N-isobutylaminopropionate, ethyl N-sec-butylaminopropionate, ethyl N-t-butylaminopropionate, ethyl N-n-amylaminopropionate, ethyl N-isoamylaminopropionate, ethyl N-n-hexylaminopropionate, 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-tosylglycine ethyl ester, etc.
Representative examples of the amine compound of the formula (VI) are N-methylaminoacetonitrile, N-ethylaminoacetonitrile, N-n-propylaminoacetonitrile, N-isopropylaminoacetonitrile, N-n-butylaminoacetonitrile, N-isobutylaminoacetonitrile, N-benzylaminoacetonitrile, N-phenylaminoacetonitrile, N-(4-methylphenyl)aminoacetonitrile, N-methylaminopropionitrile, N-n-propylaminopropionitrile, N-isopropylaminopropionitrile, N-n-butylaminopropionitrile, N-isobutylaminopropionitrile, N-sec-butylaminopropionitrile, 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, N-phenoxycarbonylglycine ethyl ester, ethyl N-ethoxycarbonylmethylaminopropionate, ethyl 4-(ethoxycarbonylmethylamino)butyrate, ethyl 2-(ethoxycarbonylmethylamino)butyrate, ethyl N-ethoxycarbonylaminopropionate, etc.
Representative examples of the amine compound of the formula (VIII) are methyl N-cyanomethylcarbamate, ethyl N-cyanomethylcarbamate, ethyl N-cyanoethylcarbamate, N-cyanomethylglycine 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.degree. to 50.degree. C., preferably 0.degree. to 30.degree. C. 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 carbon 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, or as 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-dimethylbenzofuran-7-yl N-[N,N-bis(cyanomethyl)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 70 ml 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.degree. 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 ml 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 0.degree. C. for 4 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 ml of methylene chloride, the reaction mixture was washed with 100 ml of water three times. The methylene chloride layer was dried 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.degree. to 95.degree. C. was obtained.
______________________________________NMR in chloroform-d.sub.1 :.delta. 1.48 ppm (s, 6H) .delta. 3.02 ppm (s, 2H).delta. 3.50 ppm (s, 3H) .delta. 4.32 ppm (s, 4H).delta. 6.6-7.2 ppm (m, 3H)Elemental Analysis: C H NFound (%): 55.36 5.31 16.05Calcd. for C.sub.16 H.sub.18 N.sub.4 O.sub.3 S: 55.48 5.24 16.17(molecular wt. 346.418)______________________________________
Thus, the product was confirmed to have the following formula: ##STR8##
EXAMPLE 2
Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N,N-bis(ethoxycarbonylmethyl)aminosulfenyl]-N-methylcarbamate
A 11 g quantity (0.05 mole) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate was dissolved in 50 ml 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 0.degree. C. 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 ml 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 0.degree. C. for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 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 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-d.sub.1 :.delta. 1.24 ppm (t, 6H) .delta. 1.48 ppm (s, 6H).delta. 3.02 ppm (s, 2H) .delta. 3.42 ppm (s, 3H).delta.4.20 ppm (q, 4H) .delta. 4.28 ppm (s, 4H).delta. 6.6-7.2 ppm (m, 3H)Elemental Analysis: C H NFound (%): 54.68 6.46 6.38Calcd. for C.sub.20 H.sub.28 N.sub.2 O.sub.7 S: 54.53 6.41 6.36(molecular wt. 440.526)______________________________________
Thus, the product was confirmed to have the following formula: ##STR9##
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-d.sub.1) of these compounds are also shown in Table 1.
TABLE 1__________________________________________________________________________ ##STR10## Elemental Analysis Empirical Formula Found Value H-NMR (Calculated Value)Example [.delta. Value (ppm) C H NNo. Amine R.sup.1 R.sup.2 in CDCl.sub.3 ] (%) (%) (%)__________________________________________________________________________ ##STR11## CH.sub.2 COOCH.sub.3 CH.sub.2 COOCH.sub.3 .delta.1.47 (s, 6H), .delta.3.02 (s, 2H), .delta.3.41 (s, 3H), .delta.3.73 (s, 6H), .delta.4.30 (s, 4H), .delta.6.7-7.2 (m, C.sub.18 H.sub.24 N.sub.2 O.sub.7 S 52.115.916.63 (52.42)(5.87)(6.79)4 ##STR12## ##STR13## ##STR14## .delta.1.23 (d, 6H), .delta.1.46 (s, 6H), .delta.3.03 (s, 2H), .delta.3.42 (s, 3H), .delta.4.26 (s, 4H), .delta.4.5-5.3 (m, 1H), .delta.6.6-7.2 (m, C.sub.22 H.sub.32 N.sub.2 O.sub.7 S 56.36.915.86 (56.40)(6.89)(5.98)5 ##STR15## ##STR16## ##STR17## .delta.1.0-2.2 (m, 20H), .delta.1.48 (s, 6H), .delta.3.02 (s, 2H), .delta..43 (s, 3H), .delta.4.28 (s, 4H), .delta.4.5-5.1 (m, 2H), .delta.6.7-7.2 (m, C.sub.28 H.sub.40 N.sub.2 O.sub.7 S 61.32 7.394.95 (61.29) (7.35)(5.11)__________________________________________________________________________
EXAMPLE 6
Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N,N-bis(ethoxycarbonylethyl)aminosulfenyl]-N-methylcarbamate
A 11 g quantity (0.05 mole) 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 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.degree. to -5.degree. C. The mixture was stirred at 0.degree. C. for one hour and further at room temperature for 2 hours. After cooling to -10.degree. to -5.degree. 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.degree. C. for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 ml of methylene chloride, the reaction mixture was washed with 100 ml of water three times. The methylene chloride layer was dried 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-d.sub.1 :.delta. 1.21 ppm (t, 6H) .delta. 1.44 ppm (s, 6H).delta. 2.67 ppm (t, 4H) .delta. 2.97 ppm (s, 2H).delta. 3.37 ppm (s, 3H) .delta. 3.42 ppm (t, 4H).delta. 4.04 ppm (q, 4H) .delta. 6.5-7.2 ppm (m, 3H)Elemental Analysis: C H NFound (%): 56.26 6.91 5.52Calcd. for C.sub.22 H.sub.32 N.sub.2 O.sub.7 S: 56.39 6.88 5.98(molecular wt. 468.58)______________________________________
Thus, the product was confirmed to have the following formula: ##STR18##
EXAMPLE 7
Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N,N-bis(cyanoethyl)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 ml 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.degree. to -5.degree. C. The mixture was stirred at 0.degree. C. for one hour and further at room temperature for one hour. After cooling to -10.degree. to -5.degree. 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 mixture was stirred at 0.degree. C. for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 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 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%).
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-d.sub.1 :______________________________________.delta. 1.43 ppm (s, 6H) .delta. 2.73 ppm (t, 4H).delta. 2.97 ppm (s, 2H) .delta. 3.37 ppm (s, 3H).delta. 3.43 ppm (t, 4H) .delta. 6.5-7.2 ppm (m, 3H)______________________________________Elemental Analysis: C H N______________________________________Found (%): 57.91 5.79 15.04Calcd. for C.sub.18 H.sub.22 N.sub.4 O.sub.3 S: 57.73 5.92 14.96(molecular wt. 374.47)______________________________________
Thus, the product was confirmed to have the following formula: ##STR19##
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-d.sub.1) of these compounds are also shown in Table 2.
TABLE 2__________________________________________________________________________ ##STR20## Elemental Analysis Empirical Formula Found Value H-NMR (Calculated Value)Example [.delta. Value Cppm) H NNo. Amine R.sup.1 R.sup.2 in CDCl.sub.3 ] (%) (%) (%)__________________________________________________________________________ ##STR21## CH.sub.2 CH.sub.2 CN CH.sub.2 COOC.sub.2 H.sub.5 .delta.1.26 (t, 3H), .delta.1.47 (s, 6H), .delta.2.6-3.1 (m, 2H), .delta.3.02 (s, 2H), .delta.3.40 (s, 3H), .delta.3.3-3.8 (m, 2H), .delta.4.18 (s, 2H), .delta.4.20 (q, 2H), .delta.6.6-7.2 (m, C.sub.19 H.sub.25 N.sub.3 O.sub.5 S 55.89.3110.64 (56.01)(6 .19)(10.31)9 ##STR22## CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5 CH.sub.2 COOC.sub.2 H.sub.5 .delta.1.23 (t, 6H), .delta.1.45 (s, 6H), .delta.2.70 (t, 2H), .delta.3.00 (s, 2H), .delta.3.39 (s, 3H), .delta.3.40 (t, 2H), .delta.4.09 (q, 2H), .delta.4.14 (s, 2H), .delta.4.55 (q, 2H), .delta.6.5-7.2 (m, C.sub.21 H.sub.30 N.sub.2 O.sub.7 S 55.94.796.05 (55.50)(6. 65)(6.16)10 ##STR23## CH.sub.2 CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5 CH.sub.2 COOC.sub.2 H.sub.5 .delta.1.22 (t, 6H), .delta.1.45 (s, 6H), .delta.1.7-2.6 (m, 4H), .delta.3.00 (s, 2H), .delta.3.35 (t, 2H), .delta.3.42 (s, 3H), .delta.4.13 (q, 2H), .delta.4.15 (s, 2H), .delta.4.17 (q, 2H), .delta.6.5-7.2 (m, C.sub.22 H.sub.32 N.sub.2 O.sub.7 S 55.94.936.25 (56.40)(6. 89)(5.98)11 ##STR24## ##STR25## CH.sub.2 COOC.sub.2 H.sub.5 .delta.0.99 (t, 3H), .delta.1.20 (t, 3H), .delta.1.23 (t, 3H), .delta.1.43 (s, 6H), .delta.1.5-2.5 (m, 2H), .delta.3.02 (s, 2H), .delta.3.38 (s, 3H), .delta.3.5-4.5 (m, 7H), .delta.6.5-7.2 (m, C.sub.22 H.sub.32 N.sub.2 O.sub.7 S 56.53.785.81 (56.40)(6. 89)(5.98)__________________________________________________________________________
EXAMPLE 12
Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N-butyl-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 ml 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.degree. to -5.degree. C. The mixture was stirred at 0.degree. C. for one hour and further at room temperature for 2 hours. After cooling to -10.degree. to -5.degree. 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.degree. C. for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 ml of methylene chloride, the reaction mixture was washed with 100 ml of water three times. The methylene chloride layer was dried 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: 15.7 g (76.6%).
For the identification of the product, a portion thereof was purified by silica gel column chromatography, using hexane/ethyl acetate (4:1) as the solvent, whereby an oily product was obtained.
______________________________________NMR in chloroform-d.sub.1 :______________________________________.delta. 0.6-1.9 ppm (m, 7H) .delta. 1.22 ppm (t, 3H).delta. 1.44 ppm (s, 6H) .delta. 3.03 ppm (s, 2H).delta. 3.30 ppm (t, 2H) .delta. 3.42 ppm (s, 3H).delta. 4.14 ppm (s, 2H) .delta. 4.13 ppm (q, 2H).delta. 6.5-7.2 ppm (m, 3H)______________________________________Elemental Analysis: C H N______________________________________Found (%): 58.39 7.41 6.75Calcd. for C.sub.20 H.sub.30 N.sub.2 O.sub.5 S: 58.52 7.37 6.83(molecular wt. 410.54)______________________________________
Thus, the product was confirmed to have the following formula: ##STR26##
EXAMPLE 33
Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N-phenyl-N-ethoxycarbonylmethylaminosulfenyl)-N-methylcarbamate
A 11 g quantity (0.05 mole) 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 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.degree. to -5.degree. C. The mixture was stirred at 0.degree. C. for one hour and further at room temperature for 2 hours. After cooling to -10.degree. to -5.degree. C., 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 was further added dropwise to the mixture. The resulting mixture was stirred at 0.degree. C. for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 ml of methylene chloride, the reaction mixture was washed with 100 ml of water three times. The methylene chloride layer was dried 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.degree. to 93.degree. C.
______________________________________NMR in chloroform-d.sub.1 :______________________________________.delta. 1.15 ppm (t, 3H) .delta. 1.46 ppm (s, 6H).delta. 3.00 ppm (s, 2H) .delta. 3.32 ppm (s, 3H).delta. 4.12 ppm (q, 2H) .delta. 4.76 ppm (s, 2H).delta. 6.5-7.5 ppm (m, 8H)______________________________________Elemental Analysis: C H N______________________________________Found (%): 61.11 6.15 6.49Calcd. for C.sub.22 H.sub.26 N.sub.2 O.sub.5 S: 61.38 6.09 6.51(molecular wt. 430.53)______________________________________
Thus, the product was confirmed to have the following formula: ##STR27##
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-d.sub.1) of these compounds are also shown in Table 3.
TABLE 3__________________________________________________________________________ ##STR28## Elemental Analysis Empirical Formula Found Value H-MNR (Calculated Value)Example [.delta. Value Cppm) H NNo. Amine R.sup.1 R.sup.2 in CDCl.sub.3 ] (%) (%) (%)__________________________________________________________________________14 ##STR29## CH.sub.2 COOC.sub.2 H.sub.5 CH.sub.3 .delta.1.24 (t, 3H), .delta.1.47 (s, 6H), .delta.3.02 (s, 2H), .delta.3.17 (s, 3H), .delta.3.48 (s, 3H), .delta.4.10 (s, 2H), .delta.4.17 (q, 2H), .delta.6.6-7.2 (m, C.sub.17 H.sub.24 N.sub.2 O.sub.5 S 55.61.457.83 (55.43)(6. 56)(7.61)15 ##STR30## CH.sub.2 COOC.sub.2 H.sub.5 ##STR31## .delta.1.16 (d, 6H), .delta.1.18 (t, 3H), .delta.1.43 (s, 6H), .delta.2.94 (s, 2H), .delta.3.29 (s, 3H), .delta.3.1-3.7 (m, 1H), .delta.4.00 (q, 2H), .delta.4.02 (s, 2H), .delta.6.5-7.0 (m, C.sub.19 H.sub.28 N.sub.2 O.sub.5 S 57.34.157.17 (57.56)(7. 12)(7.07)16 ##STR32## CH.sub.2 COOC.sub.2 H.sub.5 sec-C.sub.4 H.sub.9 .delta.0.8-1.8 (m, 8H), .delta.1.22 (t, 3H), .delta.1.45 (s, 6H), .delta.2.97 (s, 2H), .delta.2.9-3.3 (m, 1H), .delta.3.30 (s, 3H), .delta.4.03 (s, 2H), .delta.4.08 (q, 2H), .delta.6.7-7.1 (m, C.sub.20 H.sub.30 N.sub.2 O.sub.5 S 58.55.256.91 (58.52)(7. 37)(6.83)17 ##STR33## CH.sub.2 COOC.sub.2 H.sub.5 n-C.sub.8 H.sub.17 .delta.0.7-1.8 (m, 18H), .delta..45 (s, 6H), .delta.2.97 (s, 2H), .delta.3.1-3.5 (m, 2H), .delta.3.36 (s, 3H), .delta.4.01 (s, 2H), .delta.4.07 (q, 2H), .delta.6.6-7.2 (m, C.sub.24 H.sub.38 N.sub.2 O.sub.5 S 61.53.116.24 (61.78)(8. 21)(6.00)18 ##STR34## CH.sub.2 COOC.sub.2 H.sub.5 ##STR35## .delta.0.7-2.4 (m, 14H), .delta..43 (s, 6H), .delta.2.93 (s, 2H), .delta.3.32 (s, 3H), .delta.4.06 (q, 2H), .delta.4.08 (s, 2H), .delta.6.6-7.2 (m, C.sub.22 H.sub.32 N.sub.2 O.sub.5 S 60.95.426.51 (60.53)(7. 39)(6.42)19 ##STR36## CH.sub.2 COOC.sub.2 H.sub.5 ##STR37## .delta.1.22 (t, 3H), .delta.1.40 (s, 6H), .delta.2.97 (s, 2H), .delta.3.24 (s, 3H), .delta.3.82 (s, 2H), .delta.4.11 (q, 2H), .delta.4.15 (s, 2H), .delta.6.5-7.6 (m, C.sub.23 H.sub.28 N.sub.2 O.sub.5 S 62.04.396.63 (62.15)(6. 35)(6.30)20 ##STR38## CH.sub.2 COOC.sub.2 H.sub.5 ##STR39## .delta.1.25 (t, 3H), .delta.1.42 (s, 6H), .delta.3.04 (s, 2H), .delta.3.42 (s, 3H), .delta.3.92 (s, 2H), .delta.4.21 (q, 2H), .delta.4.23 (s, 2H), .delta.6.7-7.2 (m, 3H), .delta.7.2-7.5 (m, C.sub.23 H.sub.27 N.sub.2 O.sub.5 ClS 58.015.545.69 (57.67)(5 .68)(5.85)21 ##STR40## CH.sub.2 COOC.sub.2 H.sub.5 ##STR41## .delta.1.17 (t, 3H), .delta.1.48 (s, 6H), .delta.2.35 (s, 3H), .delta.3.05 (s, 2H), .delta.3.40 (s, 3H), .delta.4.18 (q, 2H), .delta.4.80 (s, 2H), .delta.6.7-7.5 (m, C.sub.23 H.sub.28 N.sub.2 O.sub.5 S 61.84.426.19 (62.15)(6. 35)(6.30)22 ##STR42## CH.sub.2 COOC.sub.2 H.sub.5 ##STR43## .delta.1.15 (t, 3H), .delta.1.48 (s, 6H), .delta.3.02 (s, 2H), .delta.3.31 (s, 3H), .delta.3.76 (s, 3H), .delta.4.17 (q, 2H), .delta.3.70 (s, 2H), .delta.6.7-7.4 (m, C.sub.23 H.sub.28 N.sub.2 O.sub.6 S 60.31.226.11 (59.99)(6. 13)(6.08)23 ##STR44## CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5 ##STR45## .delta.1.21 (t, 3H), .delta.1.23 (d, 6H), .delta.1.47 (s, 6H), .delta.2.78 (t, 2H), .delta.3.04 (s, 2H), .delta.3.40 (s, 3H), .delta.3.2-3.8 (m, 3H), .delta.4.12 (q, 2H), .delta.6.6-7.2 (m, C.sub.20 H.sub.30 N.sub.2 O.sub.5 S 58.43.296.65 (58.52)(7. 37)(6.83)24 ##STR46## CH.sub.2 CH.sub.2 COOCH.sub.3 ##STR47## .delta.1.18 (d, 6H), .delta.1.43 (s, 6H), .delta.2.68 (t, 2H), .delta.2.99 (s, 2H), .delta.3.0-3.5 (m, 3H), .delta.3.31 (s, 3H), .delta.3.51 (s, 3H), .delta.6.5-7.1 (m, C.sub.19 H.sub.28 N.sub.2 O.sub.5 S 58.01.327.11 (57.56)(7. 12)(7.07)25 ##STR48## CH.sub.2 CH.sub.2 COOC.sub.4 H.sub.9 ##STR49## .delta.0.6-1.8 (m, 7H), .delta.1.17 (d, 6H), .delta.1.42 (s, 6H), .delta.2.65 (t, 2H), .delta.2.94 (s, 2H), .delta.3.31 (s, 3H), .delta.3.0-3.6 (m, 3H), .delta.3.7-4.1 (m, 2H), .delta.6.5-7.0 (m, C.sub.22 H.sub.34 N.sub.2 O.sub.5 S 60.48.696.13 (60.25)(7. 82)(6.39)26 ##STR50## ##STR51## ##STR52## .delta.0.6-1.8 (m, 15H), .delta..16 (d, 6H), .delta.1.42 (s, 6H), .delta.2.68 (t, 2H), .delta.2.98 (s, 2H), .delta.3.0-3.6 (m, 3H), .delta.3.33 (s, 3H), .delta.3.6-4.1 (m, 2H), .delta.6.5-7.0 (m, C.sub.26 H.sub.42 N.sub.2 O.sub.5 S 63.45.625.49 (63.13)(8. 56)(5.66)27 ##STR53## CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5 n-C.sub.4 H.sub.9 .delta.0.7-1.8 (m, 10H), .delta..41 (s, 6H), .delta.2.4-2.8 (m, 2H), .delta.2.95 (s, 2H), .delta.3.33 (s, 3H), .delta.3.1-3.4 (m, 4H), .delta.3.97 (q, 2H), .delta.6.6-7.2 (m, C.sub.21 H.sub.32 N.sub.2 O.sub.5 S 59.01.386.79 (59.42)(7. 60)(6.60)28 ##STR54## CH.sub.2 CH.sub.2 COOCH.sub.3 n-C.sub.4 H.sub.9 .delta.0.6-2.0 (m, 7H), .delta.1.45 (s, 6H), .delta.2.66 (t, 2H), .delta.2.97 (s, 2H), .delta.2.9-3.7 (m, 4H), .delta.3.35 (s, 3H), .delta.3.54 (s, 3H), .delta.6.5-7.0 (m, C.sub.20 H.sub.30 N.sub.2 O.sub.5 S 58.79.146.66 (58.52)(7. 37)(6.83)29 ##STR55## CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5 sec-C.sub.4 H.sub.9 .delta.0.6-1.8 (m, 11H), .delta..42 (s, 6H), .delta.2.66 (t, 2H), .delta.2.96 (s, 2H), .delta.3.0-3.7 (m, 3H), .delta.3.31 (s, 3H), .delta.3.95 (q, 2H), .delta.6.6-7.0 (m, C.sub.21 H.sub.32 N.sub.2 O.sub.5 S 59.62.716.53 (59.42)(7. 60)(6.60)30 ##STR56## CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5 iso-C.sub.4 H.sub.9 .delta.0.84 (d, 6H), .delta.1.18 (t, 3H), .delta.1.42 (s, 6H), .delta.1.6-2.2 (m, 1H), .delta.2.70 (t, 2H), .delta.2.97 (s, 2H), .delta.3.1-3.6 (m, 4H), .delta.3.37 (s, 3H), .delta.4.04 (q, 2H), .delta.6.5-7.1 (m, C.sub.21 H.sub.32 N.sub.2 O.sub.5 S 59.71.546.63 (59.42)(7. 60)(6.60)31 ##STR57## CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5 n-C.sub.6 H.sub.13 .delta.0.7-2.0 (m, 14H), .delta..46 (s, 6H), .delta.2.63 (t, 2H), .delta.2.98 (s, 2H), .delta.2.9-3.6 (m, 4H), .delta.3.35 (s, 3H), .delta.3.97 (q, 2H), .delta.6.5-7.0 (m, C.sub.23 H.sub.36 N.sub.2 O.sub.5 S 60.85.116.32 (61.04)(8. 02)(6.19)32 ##STR58## CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5 ##STR59## .delta.0.9-2.0 (m, 10H), .delta..17 (t, 3H), .delta.1.43 (s, 6H), .delta.2.64 (t, 2H), .delta.2.94 (s, 2H), .delta.3.0-3.6 (m, 3H), .delta.2.97 (s, 3H), .delta.3.95 (q, 2H), .delta.6.5-7.1 (m, C.sub.23 H.sub.34 N.sub.2 O.sub.5 S 61.59.496.09 (61.31)(7. 61)(6.22)__________________________________________________________________________
EXAMPLE 33
Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N-butyl-N-cyanomethylaminosulfenyl)-N-methyl-carbamate
A 11 g quantity (0.05 mole) 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 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.degree. to -5.degree. C. The mixture was stirred at 0.degree. C. for one hour and further at room temperature for 2 hours. After cooling to -10.degree. to -5.degree. 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.degree. C. for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 ml of methylene chloride, the reaction mixture was washed with 100 ml of water three times. The methylene chloride layer was dried 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: 13.0 g (71.4%).
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-d.sub.1 :______________________________________.delta. 0.7-2.0 ppm (m, 7H) .delta. 1.42 ppm (s, 6H).delta. 2.92 ppm (s, 2H) .delta. 2.9-3.5 ppm (m, 2H).delta. 3.33 ppm (s, 3H) .delta. 4.01 ppm (s, 2H).delta. 6.5-7.1 ppm (m, 3H)______________________________________Elemental Analysis: C H N______________________________________Found (%): 59.19 7.02 11.69Calcd. for C.sub.18 H.sub.25 N.sub.3 O.sub.3 S: 59.48 6.93 11.56(molecular wt. 363.488)______________________________________
Thus, the product was confirmed to have the following formula: ##STR60##
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-d.sub.1) of these compounds are also shown in Table 4.
TABLE 4__________________________________________________________________________ ##STR61## Elemental Analysis Empirical Formual H-NMR Found ValueExample [.delta. Value (ppm) (Calculated Value)No. Amine R.sup.1 R.sup.2 in CDCl.sub.3 ] C (%)H (%)N__________________________________________________________________________ (%)34 ##STR62## CH.sub.2 CN ##STR63## .delta.1.28 (d, 6H), .delta.1.42 (s, 6H), .delta.3.00 (s, 2H), .delta.3.43 (s, 3H), .delta.4.34 (s, 2H), .delta.3.3-4.1 (m, 1H), .delta.6.5-7.2 (m, C.sub.17 H.sub.23 N.sub.3 O.sub.3 S 58.236.5912.21 (58.44)(6.64)(12.03)35 ##STR64## CH.sub.2 CN ##STR65## .delta.1.44 (s, 6H), .delta.2.98 (s, 2H), .delta.3.41 (s, 3H), .delta.4.76 (s, 2H), .delta.6.5-7.7 (m, C.sub.20 H.sub.21 N.sub.3 O.sub.3 S 62.115.4811.02 (62.65)(5.52)(10.96)36 ##STR66## CH.sub.2 CN ##STR67## .delta.1.47 (s, 6H), .delta.2.33 (s, 3H), .delta.3.00 (s, 2H), .delta.3.39 (s, 3H), .delta.4.80 (s, 2H), .delta.6.5-7.5 (m, C.sub.21 H.sub.23 N.sub.3 O.sub.3 S 63.515.7910.31 (63.46)(5.83)(10.58)37 ##STR68## CH.sub.2 CH.sub.2 CN CH.sub.3 .delta.1.46 (s, 6H), .delta.2.5-2.9 (m, 2H), .delta.3.00 (s, 2H), .delta.3.17 (s, 3H), .delta.3.0-3.5 (m, 2H), .delta.3.46 (s, 3H), .delta.6.5-7.1 (m, C.sub.16 H.sub.21 N.sub.3 O.sub.3 S 57.596.1712.74 (57.30)(6.31)(12.53)38 ##STR69## CH.sub.2 CH.sub.2 CN ##STR70## .delta.1.21 (d, 6H), .delta.1.43 (s, 6H), .delta.2.72 (t, 2H), .delta.3.00 (s, 2H), .delta.3.0-3.8 (m, 3H), .delta.3.32 (s, 3H), .delta.6.6-7.2 (m, 3H) C.sub.18 H.sub.25 N.sub.3 O.sub.3 S 59.326.8711.64 (59.49)(6.93)(11.56)39 ##STR71## CH.sub.2 CH.sub.2 CN n-C.sub.4 H.sub.9 .delta.0.7-2.0 (m, 7H), .delta.1.44 (s, 6H), .delta.2.5-2.9 (m, 2H), .delta.2.98 (s, 2H), .delta.2.9-3.5 (m, 4H), .delta.3.37 (s, 3H), .delta.6.5-7.0 (m, C.sub.19 H.sub.27 N.sub.3 O.sub.3 S 60.647.4111.25 (60.46)(7.21)(11.13)40 ##STR72## CH.sub.2 CH.sub.2 CN iso-C.sub.4 H.sub.9 .delta.0.90 (d, 6H), .delta.1.43 (s, 6H), .delta.1.7-2.2 (m, 1H), .delta.2.69 (t, 2H), .delta.2.96 (s, 2H), .delta.3.0-3.5 (m, 4H), .delta.3.33 (s, 3H), .delta.6.5-7.0 (m, 3H) C.sub.19 H.sub.27 N.sub.3 O.sub.3 S 60.257.3911.01 (60.46)(7.21)(11.13)41 ##STR73## CH.sub.2 CH.sub.2 CN n-C.sub.8 H.sub.17 .delta.0.7-2.0 (m, 15H), .delta.1.47 (s, 6H), .delta.2.6-2.9 (m, 2H), .delta.3.01 (s, 2H), .delta.3.0-3.5 (m, 4H), .delta.3.40 (s, 3H), .delta.6.5-7.0 (m, C.sub.23 H.sub.35 N.sub.3 O.sub.3 S 63.598.319.54 (63.72)(8.14)(9.69)42 ##STR74## CH.sub.2 CH.sub.2 CN ##STR75## .delta.0.7-2.0 (m, 10H), .delta.1.46 (s, 6H), .delta.2.5-2.9 (m, 2H), .delta.2.98 (s, 2H), .delta.3.0-3.5 (m, 2H), .delta.3.32 (s, 3H), .delta.3.9-4.3 (m, 1H), .delta.6.5-7.1 (m, C.sub.21 H.sub.29 N.sub.3 O.sub.3 S 62.337.4210.85 (62.51)(7.25)(10.42)__________________________________________________________________________
EXAMPLE 43
Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N-propionyl-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 ml 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.degree. to 31 5.degree. C. The mixture was stirred at 0.degree. C. for one hour and further at room temperature for 2 hours. After cooling to -10.degree. to -5.degree. C., a solution of 8 g (0.05 mole) of N-propionylglycine ethyl ester in 10 ml of methylene chloride 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.degree. C. for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 ml of methylene chloride, the reaction mixture was washed with 100 ml of water three times. The methylene chloride layer was dried 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.degree. to 109.degree. C. were obtained.
______________________________________NMR in chloroform-d.sub.1 :.delta. 1.14 ppm (t, 3H) .delta. 1.23 ppm (t, 3H).delta. 1.49 ppm (s, 6H) .delta. 2.7-3.3 ppm (m, 2H).delta. 3.02 ppm (s, 2H) .delta. 3.48 ppm (s, 3H).delta. 4.15 ppm (q, 2H) .delta. 4.50 ppm (s, 2H).delta. 6.6-7.1 ppm (m, 3H)Elemental Analysis: C H N______________________________________Found (%): 55.35 6.41 6.77Calcd. for C.sub.19 H.sub.26 N.sub.2 O.sub.6 S: 55.59 6.38 6.82(molecular wt. 410.499)______________________________________
Thus, the product was confirmed to have the following formula: ##STR76##
EXAMPLE 44
Preparation of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N-ethoxycarbonyl-N-ethoxycarbonylmethylaminosulfenyl)-N-methyl-carbamat
A 11 g quantity (0.05 mole) 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 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.degree. to -5.degree. C. The mixture was stirred at 0.degree. C. for one hour and further at room temperature for 2 hours. After cooling to -10.degree. to -5.degree. C., 8.8 g (0.05 mole) of N-ethoxycarbonylglycine 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.degree. C. for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 ml of methylene chloride, the reaction mixture was washed with 100 ml of water three times. The methylene chloride layer was dried 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%).
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-d.sub.1 :.delta. 1.17 ppm (t, 6H) .delta. 1.44 ppm (s, 6H).delta. 2.94 ppm (s, 2H) .delta. 3.41 ppm (s, 3H).delta. 4.05 ppm (q, 2H) .delta. 4.15 ppm (q, 2H).delta. 4.41 ppm (s, 2H) .delta. 6.5-7.0 ppm (m, 3H)Elemental Analysis: C H N______________________________________Found (%): 53.82 6.19 6.44Calcd. for C.sub.19 H.sub.26 N.sub.2 O.sub.7 S: 53.51 6.14 6.57(molecular wt. 426.499)______________________________________
Thus, the product was confirmed to have the following formula: ##STR77##
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-d.sub.1) of these compounds are also shown in Table 5.
TABLE 5__________________________________________________________________________ ##STR78## Elemental AnalysisEx- Empirical Formulaam- H-NMR Found Valueple [.delta. Value (Calculated Value)No. Amine R.sup.1 R.sup.2 in CDCl.sub.3 ] C (%)H (%)N__________________________________________________________________________ (%)45 ##STR79## CH.sub.2 COOC.sub.2 H.sub.5 COCH.sub.2 Cl .delta.1.21 (t, 3H), .delta.1.46 (s, 6H), .delta.2.98 (s, 2H), .delta.3.40 (s, 3H), .delta.4.05 (q, 2H), .delta.4.36 (s, 2H), .delta.4.67 (s, 2H), .delta.6.5-7.0 (m, C.sub.18 H.sub.23 N.sub.2 O.sub.6 ClS 49.985.17 6.43 (50.17)(5.38)(6.50)46 ##STR80## CH.sub.2 COOC.sub.2 H.sub.5 ##STR81## .delta.1.18 (t, 3H), .delta.1.41 (s, 6H), .delta.2.87 (s, 3H), .delta.2.91 (s, 2H), .delta.4.06 (q, 2H), .delta.4.60 (s, 2H), .delta.6.5-7.0 (m, 3H), .delta.7.1-7.7 (m, C.sub.23 H.sub.26 N.sub.2 O.sub.6 S 60.54.616.02 (60.25)(5. 72)(6.11)47 ##STR82## CH.sub.2 COOC.sub.2 H.sub.5 ##STR83## .delta.1.21 (t, 3H), .delta.1.46 (s, 6H), .delta.2.93 (s, 3H), .delta.2.95 (s, 2H), .delta.4.07 (q, 2H), .delta.4.56 (s, 2H), .delta.6.5-7.0 (m, 3H), .delta.7.1-7.6 (m, C.sub.23 H.sub.25 N.sub.2 O.sub.6 ClS 56.535.375.49 (56.04)(5 .11)(5.68)48 ##STR84## CH.sub.2 COOC.sub.2 H.sub.5 ##STR85## .delta.1.18 (t, 3H), .delta.1.46 (s, 6H), .delta.2.37 (s, 3H), .delta.2.96 (s, 2H), .delta.3.48 (s, 3H), .delta.4.02 (q, 2H), .delta.4.58 (s, 2H), .delta.6.5-7.9 (m, C.sub.23 H.sub.28 N.sub.2 O.sub.7 S.sub.2 54.045.575.24 (54.31)(5.55)(5.51)49 ##STR86## CH.sub.2 COOC.sub.2 H.sub.5 COOCH.sub.3 .delta.1.19 (t, 3H), .delta.1.46 (s, 6H), .delta.2.97 (s, 2H), .delta.3.43 (s, 3H), .delta.3.74 (s, 3H), .delta.4.07 (q, 2H), .delta.4.42 (s, 2H), .delta.6.5-7.1 (m, C.sub.18 H.sub.24 N.sub.2 O.sub.7 S 52.15.646.66 (52.42)(5. 87)(6.79)50 ##STR87## CH.sub.2 COOC.sub.2 H.sub.5 ##STR88## .delta.1.19 (t, 3H), .delta.1.44 (s, 6H), .delta.2.95 (s, 2H), .delta.3.50 (s, 3H), .delta.4.05 (q, 2H), .delta.4.52 (s, 2H), .delta.6.5-7.4 (m, C.sub.23 H.sub.26 N.sub.2 O.sub.7 S 57.97.615.78 (58.22)(5. 52)(5.90)51 ##STR89## CH.sub.2 CH.sub.2 CN COOC.sub.2 H.sub.5 .delta.1.30 (t, 3H), .delta.1.46 (s, 6H), .delta.2.63 (t, 2H), .delta.2.97 (s, 2H), .delta.3.40 (s, 3H), .delta.3.95 (t, 2H), .delta.4.16 (q, 2H), .delta.6.5-7.0 (m, C.sub.18 H.sub.23 N.sub.3 O.sub.5 S 55.16.9310.31 (54.95)(5 .89)(10.68)52 ##STR90## CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 .delta. 1.17 (t, 3H), .delta.1.32 (t, 3H), .delta.1.46 (s, 6H), .delta.2.57 (t, 2H), .delta.2.98 (s, 2H), .delta.3.40 (s, 3H), .delta.3.7-4.4 (m, 6H), .delta.6.5-7.0 (m, C.sub.20 H.sub.28 N.sub.2 O.sub.7 S 54.33.296.51 (54.54)(6. 41)(6.36)__________________________________________________________________________
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 10.0Xylene 30.0______________________________________
PREPARATION EXAMPLE 2
______________________________________50% Emulsion:Compound of Example 12 50.0%Polyoxyethylene sorbitan monooleate 6.5Sorbitan monooleate 3.5Xylene 30.0Cyclohexanone 10.0______________________________________
PREPARATION EXAMPLE 3
______________________________________20% Emulsion:Compound of Example 22 20.0%Polyoxyethylene alkyl ether 5.0Xylene 45.0Petroleum 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 3.0Clay 7.0______________________________________
PREPARATION EXAMPLE 5
______________________________________50% Wettable powder:Compound of Example 21 50.0%Alkyl sulfate 30.0Condensate of naphthalenesulfonic acid 10.0and formaldehydeAlkyl phosphate 5.5Kaolin 3.5Talc 1.0______________________________________
PREPARATION EXAMPLE 6
______________________________________30% Wettable powderCompound of Example 30 30.0%Alkylbenzenesulfonate 3.0Sodium lignin sulfonate 2.0White carbon 15.0Clay 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 10.0Talc 85.0______________________________________
PREPARATION EXAMPLE 8
______________________________________2% Dust:______________________________________Wettable powder of Preparation 4.0%Example 5Clay 95.8Isopropyl phosphate 0.2______________________________________
PREPARATION EXAMPLE 9
______________________________________0.5% Dust:______________________________________Wettable powder of Preparation 1.7%Example 6Clay 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 5Dolomite 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 11
______________________________________10% Granule:______________________________________Compound of Example 40 10.0%Sodium dodecylbenzenesulfonate 0.5Sodium lignin sulfonate 2Diatomaceous earth 27.5Bentonite 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 3.0Clay 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 tobacco 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______________________________________ Mortality (%) Concentration ofTest Compound Active Ingredient (ppm)(Example No.) 2,000 1,000 500______________________________________1 100 80 652 100 70 603 100 80 654 100 70 605 100 80 656 100 75 607 100 75 608 100 85 759 100 90 8010 100 85 7511 100 80 7012 100 90 7513 100 90 7514 100 90 7515 100 90 7516 100 85 6517 100 80 6018 100 90 7519 100 85 6520 100 85 6521 100 90 7522 100 85 6523 100 85 7024 100 85 7525 100 90 7526 100 80 6027 100 90 7528 100 90 7529 100 80 6030 100 85 6531 100 80 6032 100 80 6533 100 90 7534 100 90 7535 100 80 6536 100 80 6537 100 85 7038 100 90 7539 100 90 7540 100 85 7541 100 80 6542 100 85 7043 100 85 7044 100 90 7545 100 90 7546 100 85 7047 100 80 6548 100 80 6549 100 90 7550 100 80 6551 100 85 7052 100 85 70Control* 100 80 60Untreated 0______________________________________ *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 female 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______________________________________ Mortality (%) Concentration ofTest Compound Active Ingredient (ppm)(Example No.) 800 400 200______________________________________1 100 85 502 100 85 453 100 85 454 100 70 405 100 80 456 95 75 557 90 70 508 95 85 609 100 90 6010 100 90 6011 95 80 5512 100 90 6513 100 90 6514 100 90 6515 100 90 6516 100 80 6017 95 75 5518 100 90 6519 100 80 6020 100 80 6021 100 90 6522 100 80 6023 100 85 5524 100 90 6025 100 90 6526 100 75 5527 100 90 6528 100 90 6529 100 75 4530 100 80 6031 100 75 5532 100 75 5533 100 90 7034 100 90 6535 95 75 6036 95 75 6037 100 85 6538 100 90 7039 100 90 7040 100 85 7041 95 75 6042 100 85 6543 100 85 6044 100 90 7045 100 90 6546 100 85 6547 95 75 6048 95 75 6049 100 90 7050 95 75 6051 100 85 6552 100 85 65Control* 0 0 0Untreated 0______________________________________ *2-Isopropoxyphenyl-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.times.2 m.sup.2 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: Up to 25%,2: Up to 50%, 3: Up to 75%,4: Up to 100%______________________________________
TABLE 8______________________________________ Degree of Formation of Nodules Amount of GranulesTest Compound Applied (kg/10 a)(Example No.) 100 50 20______________________________________1 0 1 22 0 2 33 0 2 34 0 2 35 0 2 36 1 2 37 1 3 38 1 1 29 0 1 210 0 1 211 1 2 312 0 1 213 0 1 214 0 1 215 0 1 216 0 1 317 0 1 318 0 1 219 0 1 220 0 1 321 0 1 222 0 1 323 0 1 224 0 0 125 0 1 226 0 1 227 0 1 228 0 0 129 0 1 230 0 1 231 0 2 332 0 2 333 0 0 134 0 0 135 0 1 336 0 1 337 0 1 238 0 0 139 0 0 140 0 1 141 0 1 342 0 1 243 0 1 244 0 0 145 0 1 246 0 1 247 0 1 348 0 1 349 0 0 150 0 1 351 0 1 252 0 1 2Control* 2 4 4Untreated 4______________________________________ *Bis(2-chloro-1-methylethyl)ether was used as the control.
TEST EXAMPLE 4
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 LD.sub.50 values determined by the Probit method from the mortality 24 hours later.
TABLE 9______________________________________Test Compound LD.sub.50(Example No.) (.mu.g/g)______________________________________1 21.32 58.83 40.04 28.95 75.66 38.37 54.08 24.69 31.710 46.011 93.912 16.713 12.514 9.915 33.016 44.417 42.318 32.519 22.220 61.921 10.422 45.223 44.324 38.625 50.126 64.727 13.828 17.729 22.530 23.831 33.132 32.733 9.134 16.735 65.636 59.337 11.838 17.539 13.740 37.941 54.642 46.043 14.444 16.245 29.246 33.247 57.848 58.649 15.750 34.751 45.352 54.3Control* 22.5______________________________________ *2-Isopropoxyphenyl-N--methyl-carbamate was used as the control.
TEST EXAMPLE 5
Compounds of this invention were tested on male mice for acute toxicity by oral administration. Table 10 shows LD.sub.50 values determined by the Litchfield-Wilcoxon method from the mortality on the seventh day.
TABLE 10______________________________________Test Compound LD.sub.50(Example No.) (mg/kg)______________________________________1 582 1403 1454 1225 906 1357 758 1059 15810 11511 9312 12513 11514 12015 11016 11017 6918 13519 10820 7521 10522 8823 11324 7725 12326 15027 10528 8929 12030 13331 13532 10733 10334 9535 9536 7037 6538 12539 11040 10341 10542 8843 4344 12845 8046 10547 9548 8049 10550 9551 8852 125Control* 5.6______________________________________ *2,3-Dihydro-2,2-dimethyl-7-benzofuran-7-yl-methyl-carbamate was used as the control.

Number	Date	Country
56-85093	Jun 1981	JPX
56-85094	Jun 1981	JPX
56-124422	Aug 1981	JPX
56-124423	Aug 1981	JPX

Carbamate derivatives and insecticidal, miticidal or nematocidal compositions containing the same

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