KR850000743B1 - Process for preparing carbamate derivatives - Google Patents

Abstract

Prepn. of a carbamate deriv. of formula (I) comprises reacting a compd. of formula (II) with sulfur dichloride to give 2,3-dihydro- 2,2-dimethyl-benzofuran-7-yl N-(chlorosulphenyl)-Nmethyl-carbamate of formula (III), and reacting (III) with an amine compd. of formula (IV). In the formulas, R1 and R2 are independently -X-COOR3 or -Y- CN; X and Y are each C1-6 alkylene; R3 is C1-8 alkyl or C3-6 cycloalkyl; R2 is also C1-8 alkyl, C3-6 cycloalkyl or -Z-R4; Z is carbonyl or sulphonyl; and R4 is C1-6 alkoxy or phenoxy (I) is useful as in secticides, miticides and nematocides against lepidoptera, coleoptera, etc.

Description

Method for preparing carbamate derivative

The present invention relates to a process for preparing carbamate derivatives useful as insecticides.

As used herein, the term "pesticide composition" refers to acaricide composition and nematicidal composition in addition to the pesticidal composition unless otherwise specified, and the term "pest" means mites and nematodes other than pests unless otherwise specified.

It is known that some carbamate compounds have a high pesticidal action and these compounds include practical use. However, most of these carbamate compounds have the drawback of being toxic to warm-blooded animals. In particular, 2,3-dihydro-2,2-dimethylbenzofuran-7-ylN-methyl-carbamate (hereinafter referred to as carbofuran) is known to have high insecticidal action, but since it is highly toxic to warm-blooded animals, There are many problems with using it. Thus, if a carbamate compound can be produced that is identical to carbofuran in pesticidal action and exhibits less toxicity to warm-blooded animals, this compound would be very useful. Various carbofuransulphenyl compounds have been synthesized from this point of view, and the results of investigating the relationship between insecticidal action and toxicity to warm-blooded animals have been reported. For example, Belgian Patent No. 817,517 describes 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N- (N, N-dibutylaminosulphenyl) -N-methyl-carbamate German publication 2,254,359 discloses 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N- (N-methyl-N-benzenesulfonyl-aminosulphenyl-N-methyl Carbamates are described, but these compounds do not fully meet the requirements for pesticidal action, toxicity to warm-blooded animals and fish, and methods of preparation.

The inventors of the present inventors have studied to develop a carbamate compound that can satisfy all these requirements, and found that the compound represented by the following general formula (I) can satisfy the above-mentioned requirements.

In the above formula,

R ¹ and R ² may be the same or different, and each represents -X-COOR ³ or -Y-CN- (where X represents an alkylene group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 1 to 8 carbon atoms) Or a cycloalkyl group having 3 to 6 carbon atoms, Y represents an alkylene group having 1 to 6 carbon atoms), or

R ² is also an alkyl group having 1 to 8 carbon atoms: a cycloalkyl group having 3 to 6 carbon atoms: a halogen atom, an alkyl group having 1 to 3 carbon atoms or a benzyl group: a halogen atom, which may be substituted with an alkoxy group having 1 to 3 carbon atoms, Phenyl group which may be substituted with an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms: or -ZR ⁴ (wherein Z represents a carbonyl group or a sulfonyl group, and R ⁴ represents 1 to 6 carbon atoms Alkyl group, phenyl group, benzyl group or alkoxy group or phenoxy group having 1 to 6 carbon atoms).

In the definition of general formula (I), the alkyl component in the alkyl group, alkylene group and alkoxy group may be linear or branched.

In this invention, the compound represented by the following general formula (I ') is preferable.

In the above formula,

R ¹ and R ² may be the same or different, each of -X'-COOR or -Y'-CN, wherein X 'represents an alkylene group having 1 to 2 carbon atoms, R ³ ' is a straight or branched carbon number Represents an alkyl group of 1 to 4, Y 'represents an alkylene group of 1 to 2 carbon atoms), or

R ² ′ also represents an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, which may be straight or branched. As a result, the present invention can be carried out.

The compound of general formula (I) is a novel compound first developed by the present inventors without being described in any conventional literature. This new compound has a pesticidal effect that is comparable to that of cabofuran, which has a high pesticidal effect and a pesticidal effect against pests in farming and forestry as well as domestic pests. The compound is, for example, Hemiptera, Lepidoptera, Coleopera, Diptera, Thysanoptera, Orthoptera, Isopoda ( Isopoda, Acarina, Tilennchida, etc. have a wide range of effects on pests, mites and nematodes that are harmful to vegetables, trees, plants and the human body. Examples of these pests, mites and nematodes are as follows.

Hemiptera

(1) Deltocephacidae: Nephotettix cincticeps

(2) Delphacidae: Laodelphax striatellus, Nilaparyata lugens

(3) Aphididae: Myzus persice, Apis gossypii

(4) Pentatomidae: Nezara antennata, Nezara viridula

Lepidoptera

(1) Noctuidae: Spodoptera litura, Agrotis fucosa, Laphygma exigua

(2) Tortricidae: Adoxophyes orana

(3) Pyralidae: indeed Chilo suppressalis. Austrian Furnalis, Cnaphalocrocis medinalis,

(4) Plutellidae: Plutella xylostella

Coleoptera

(1) Curculionidae: Echinocne-Scuameus (Echinocn-

emus squameus), Lissohoptrus oryzophilus

(2) Scarabaeidae: Popillaia japoncia

(3) Cocinillide (Coccinelledae): Henosepilachna vigitioctopunctata

Diptera

(1) Muscidae: Musca donestica

(2) Cecidomyiidae: Aspondylia SP.

(3) Agromyzidae: Phytobia cepae

Thysanoptera

Tripidae: Tripps tabaci, Scirtothrips dorsalis

Orthoptera

Gryllotalpidae: Gryllotalpa africana

Isopoda

Armandillidae: Armadillidium vulgare

Acarina

Tetranychidae: Tetrauchus telarius, Tetrachuus utricae, Panonichus citri

Tylenchida

Heteroderidae: Melodidogyne incognita

The toxicity of carbamate derivatives of general formula (I) to warm-blooded animals is about 1/5 to about 1/100 times that of carbofuran toxicity. The compound exhibits pesticidal or control effects in the growth phase or in certain growth stages of the organism.

The compounds of formula (I) of the present invention are very easy to prepare in high yields of high purity and also have many commercial advantages, as described in detail below.

Representative examples of the compound of general formula (I) include the compounds illustrated in Examples 1 to 56 described below. Among these compounds, the following compounds are particularly preferred in the present invention.

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

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

2,3-dihydro-2,2-dimethylbenzofuran-7-yl N- (N-isopropyl-N-ethoxycarbonylethylaminosulphenyl) -N-methyl-carbamate

2,3-dihydro-2,2-dimethylbenzofuran-7-yl N- (N-n-butyl-N-ethoxycarbonylethylaminosulphenyl) -N-methyl-carbamate

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

2,3-dihydro-2,2-dimethylbenzofuran-7-yl N- (N-n-butyl-N-cyanoethylaminosulphenyl) -N-methyl-carbamate

The compound of the general formula (I) according to the present invention is reacted with sulfur dichloride and a compound of the general formula (II) to give 2,3-dihydro-2,2-dimethyl-benzofuran- of general formula (III) It can be prepared by producing 7-yl N- (chlorosulphenyl) -N-methyl-carbamate and then reacting with an amine compound of the general formula (IV).

In the above general formula

R ¹ and R ² are as defined above.

Compounds of formula (II) are well known [The Merk Index, 10th edition, Rahway 1983, page 250, 1786], as cabofuran, for example prepared by the methods described in US Pat. No. 3,474,170. Can be.

The reaction of the compound of formula (II) with sulfur dichloride may be carried out in the presence or absence of a solvent. Examples of useful solvents include methylene chloride, chloroform, carbon tetrachloride and similar hydrocarbon halides and diethyl ether, dibutyl ether, tetrahydrofuran, dioxane and similar ethers. The ratio of the compound of formula (II) and SCl ₂ can be widely used without particular limitation. Usually 1 to 2 moles, preferably about 1 to about 1.2 moles of SCl ₂ are used per mole of the compound of formula (II). The reaction is preferably carried out in the presence of a basic compound. Examples of useful basic compounds include triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine and similar tertiary amines, pyridine, α, β, γ-picolin, lutidine and the like. The basic compound is used in a sufficient amount so that hydrochloric acid is produced by the reaction as a by-product. Normally 1 to 2 moles of basic compound are used per mole of compound of formula (II). The reaction of cooling to room temperature or heating is usually carried out at -70 ° C to 50 ° C, preferably at about -10 ° to about 30 ° C. The reaction time is about 2 to about 7 hours, preferably about 3 to about 5 hours. Next, compound (III) is reacted with an amine compound of general formula (IV).

Compounds of general formula (IV) are N-substituted amino acid esters, which may be prepared by known methods [Jikken Kagaku Koza ("Experimental Chemistry Course"), pp. 507-508, Japan), Examples of the amine compound are secondary amines represented by general formula (V) to general formula (IX).

In the above general formula

X, Y and R ³ are as defined above,

R is 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 halogen atom, 1 carbon atom Or a phenyl group which may be substituted with an alkyl group of 3 to 3 or an alkoxy group having 1 to 3 carbon atoms, or -Z'-R ⁴ , wherein Z represents a carbonyl group or sulfonyl group, and R ⁴ represents 1 to 6 carbon atoms Alkyl group, phenyl group, benzyl group, alkoxy group or phenoxy group having 1 to 6 carbon atoms, wherein alkyl group and alkoxy group may be straight or branched chain),

R ³ "has the same meaning as in R ³ ,

X "has the same meaning as in X,

Y "has the same meaning as in Y.

Representative examples of the amine compound of general formula (V) include N-methylglycine methyl ester, N-methylglycine ethyl ester, N-methylglycine butyl ester, N-ethylglycine ethyl ester, Nn-propylglycine ethyl ester, N- Isopropylglycine ethyl ester, Nn-butylglycine ethyl ester, N-isobutylglycine ethyl ester, N-tert-butylglycine ethyl ester, Nn-octylglycine ethyl ester, N-cyclohexylglycine ethyl ester, N-benzyl glycine 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 -Methylcyphenyl) glycine ethyl ester, ethyl N-methylaminopropionate, ethyl Nn-propylaminopropionate, methyl N-isopropylaminopropionate, ethyl Nn-isopropylamino Propionate, Butyl N-isopropylaminopropionate, 2-ethylhexyl N-isopropylaminopropionate, methyl Nn-butylaminopropionate, ethyl Nn-butylaminopropionate, ethyl N-isobutyl Aminopropionate, ethyl N-tert-butyl-aminopropionate, ethyl N-tert-butylaminopropionate, ethyl Nn-amylamino propionate, ethyl N-isoamylaminopropionate, ethyl Nn-hexylaminopropionate, ethyl N-cyclohexylaminopropionate, N-acetylglycine ethyl ester, N-cycloacetylaminoglycine ethyl ester, N-propionylglycine ethyl ester, N-benzoylglycine ethyl ester, N -(4-chlorobenzoyl) glycine ethyl ester, N-tosylglycine ethyl ester and the like.

Representative examples of the amine compound of general formula (VII) include methyl iminodiacetate, ethyl iminodiacetate, isopropyliminodiacetate, cyclohexyliminodiacetate, methyl iminodipropionate, ethyl iminodipropionate, N -Methoxycarbonylglycineethyl ester, N-ethoxycarbonylglycine ethyl ester, N-phenoxycarbonylglycine ethyl ester, ethyl N-ethoxycarbonylmethylaminopropionate, ethyl 4-ethoxycarbonylmethyl Amino) butyrate, ethyl 2- (ethoxycarbonylmethylamino) butyrate, ethyl N-ethoxycarbonylaminopropionate, and the like.

Representative examples of the amine compound of formula (VIII) include methyl N-cyanomethylcarbamate, ethyl N-cyanomethylcarbamate, ethyl N-cyanomethylcarbamate, N-cyanomethylglycine ethyl ester, N Cyanoethylglycine ethyl ester, ethyl N-cyanomethylaminopropionate, ethyl N-cyanoethylaminopropionate, and the like.

Representative examples of the amine compound of general formula (IX) include iminodiacetonitrile, iminodipropionitrile, iminobutyronitrile and the like.

The reaction between the compound of formula (III) and the amine compound of formula (IV) may be carried out in the presence or absence of a solvent. Both the compound of formula (II) and the solvent useful for the reaction of this sulfur chloride can be used in the present reaction. The ratio of the compound of formula (III) to the amine can be used widely without particular limitation. Usually, 1 to 2 moles, preferably 1 to 1.2 moles of amine are used per mole of the compound of formula (III). This reaction is preferably carried out in the presence of a basic compound, and any basic compound can be used as described above. The basic compound is used in a sufficient amount such that hydrochloric acid is produced by the reaction as a by-product. Normally 1 to 2 moles, preferably 1 to 1.5 moles of basic compound are used per mole of compound of formula (III). The reaction of cooling to room temperature or heating is usually carried out at -20 ° C to 50 ° C, preferably 0 ° to 30 ° C. The reaction time is usually about 10 to about 15 hours.

The compounds of the present invention represented by general formula (I) can be easily separated and purified by conventional separation methods such as, for example, solvent extraction, recrystallization or chromatography.

Compound (I) of the present invention is used in emulsions, wetting agents, suspending agents, thickening suspensions, granules, granules, pellets, powders, coating compositions, foam spraying agents, aerosols, microcapsule compositions, saturating agents used in natural or synthetic materials. It can be formulated in the form of a fumigant, a concentrated preparation used in small amounts.

Various types of surfactants are useful for preparing emulsions, dispersants, suspending agents and foaming agents. Examples of useful nonionic surfactants are polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, sorbitan alkyl esters, and the like. Examples of useful anionic surfactants include alkylbenzenesulfonates, alkylsulfosuccinates, alkylsulfates, polyoxyethylene alkyl ether sulfates, alkyl naphthalene sulfonates, lignin sulfonates and the like.

Solvents, diluents and carriers that can be used in the compounds of the present invention include various types of organic solvents, aerosol promoters, natural minerals, vegetables, synthetic compounds, and the like. Examples of preferred organic solvents are benzene, toluene, xylene, ethylbenzene, chlorobenzene, alkylnaphthalene, dichloromethane, chloroethylene, cyclohexane, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohol, dimethyl formamide , Dimethyl sulfoxide, acetonitrile, mineral oil fractions, and the like. Examples of useful aerosol propellants include propane, butane, hydrocarbon halides, nitrogen, carbon dioxide, and the like. Examples of useful natural ores include caroline, talc, bentonite, diatomaceous earth, clay, montmorillonite, chalk, calcite, pumice, dolomite and the like. Examples of useful plants are coconut husks, tobacco, sawdust and the like. Examples of useful synthetic compounds are alumina, silicates, sugar polymers and the like. Useful synthetic compounds with good adhesion include carboxymethyl cellulose, gum arabic, polyvinyl alcohol, polyvinyl acetate, and the like. These formulations can be colored with organic or inorganic dyes. Compound (I) of the present invention may be formulated in various formulations as described above as active ingredients so that the formulation can contain an effective amount (about 0.1 to 95% by weight) in a pesticidal, acaricidal or nematicidal manner. Can be mad. Such agents are used with or diluted with a carrier or water.

The following describes the invention in more detail by way of examples.

Example 1

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

Dissolve 11 g (0.05 mole) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate with 70 ml of methylene chloride and cool 5.2 g (0.05 mole) of sulfur dichloride To this solution while 5 g (0.05 mol) of triethylamine are added dropwise at 0 ° C. The mixture was stirred at 0 ° C. for 2 hours, then 4.8 g (0.05 mole) of iminodiacetonitrile solution in 40 ml of tetrahydrofuran was added dropwise to the mixture at 0 ° C., then 5 g (0.05 mole) of triethyl Add more amine. The resulting mixture is stirred at 0 ° C. for 4 hours and then left at room temperature overnight. 100 ml of methylene chloride is added and the reaction mixture is washed three times with 100 ml of water. Drying the methylene chloride layer and then concentrating in vacuo yielded an oily product consisting almost of the desired product, although a small amount of starting material was included. Yield 13.8 g (79.8%).

To identify the product, a portion of this product is purified by silica gel column chromatography using benzene / ethyl acetate (4: 1) as solvent to give crystals having a melting point of 94 ° to 95 ° C.

NMR of chloroform-d ₁ : δ1.48 ppm (s, 6H), δ3.02ppm (s, 2H), δ3.50ppm (s, 3H), δ4.32ppm (s, 4H), δ6.6 to 7.2ppm (m, 3 H)

Elemental analysis: C ₁₆ H ₁₈ N ₄ O ₃ S (molecular weight 346.418)

C H N

Found (%): 55.36 5.31 16.05

Calculation: 55.48 5.24 16.17

As a result, the product was confirmed to have the following structural formula.

Example 2

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

Dissolve 11 g (0.05 mole) of 2,3-dihydro-2,3-dimethylbenzofuran-7-yl N-methyl-carbamate with 50 ml of chloroform and cool 5.2 g (0.05 mole) of sulfur dichloride To this solution while 5 g (0.05 mol) of triethylamine are added dropwise at 0 ° C. The mixture was stirred at the same temperature for 2 hours, 9.5 g (0.05) mole of ethyl iminodiacetate solution in 20 ml of chloroform was added dropwise to the dimixture at the same temperature, followed by further dropwise addition of 5 g (0.05 mole) of triethylamine. do. The resulting mixture was stirred at the same temperature for 2 hours, 9.5 g (0.05 mole) of ethyl iminodiacetate solution in 20 ml of chloroform was added dropwise to the mixture at the same temperature, and then 5 g (0.05 mole) of triethylamine was added. Add it down. The resulting mixture is stirred at 0 ° C. for 2 hours and then left at room temperature overnight. 100 ml of chloroform is added and the reaction mixture is washed three times with 100 ml of water. The chloroform layer is dried and then concentrated in vacuo to yield an oily product which contains a small amount of starting material but consists almost of the desired product. Yield: 15.9 g (72.3%).

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

NMR of Chloroform-d ₁ :

δ 1.24 ppm (±, 6H), δ 1.48 ppm (s, 6H), δ 3.02 ppm (s, 2H), δ 3.42 ppm (s, 3H), δ 4.20 ppm (t, 4H), δ 4.28 ppm ( s, 4H), δ 6.6 to 7.2 ppm (m, 3H)

Elemental analysis: C ₂₀ H ₂₈ H ₂ O ₇ S (Molecular Weight 440.526)

C H N

Found (%): 54.68 6.46 6.38

Calculation: 54.53 6.41 6.36

As a result, the product was confirmed to have the following structural 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 (chloroform-d ₁ ) of this compound are also shown in Table 1.

Example 6

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

11 g (0.05 mole) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate are dissolved in 70 ml of methylene chloride and 5.2 g (0.05 mole) of sulfur dichloride To this solution is added while cooling and 5 g (0.05 mol) of triethylamine are added dropwise at -10 ° to -5 ° C. The mixture is stirred at 0 ° C. for 1 hour and then further at room temperature for 2 hours. After cooling the mixture to −10 ° C. to −5 ° C., 10.9 g (0.05 mole) of diethyl iminodipropionate is added dropwise followed by further dropwise addition of 5 g (0.05 mole) of triethylamine. The resulting mixture is stirred at 0 ° C. for 2 hours and then left at room temperature overnight. The reaction mixture is washed three times with 100 ml of water while 100 ml of methylene chloride is added. Drying the methylene chloride layer and concentrating in vacuo yields an oily product consisting of a small amount of impurities but consisting almost of the desired product. Yield: 16.9 g (72.2%).

To identify the product, some of this product is purified by silica gel column chromatography using benzene / ethyl acetate (5: 1) as solvent to give an oily product.

NMR of Chloroform-d ₁ :

δ 1.21 ppm (t, 6H), δ 1.44 ppm (s, 6H), δ 2.67 ppm (t, 4H), δ 2.97 ppm (s, 2H), δ 3.37 ppm (s, 3H), δ 3.42 ppm (t , 4H), δ 4.04 ppm (q, 4H), δ 6.5 to 7.2 ppm (m, 3H)

Elemental analysis: C ₂₂ H ₃₂ N ₂ O ₇ S (Molecular weight 468.58)

TABLE 1

As a result, the product was confirmed to have the following structural formula.

Example 7

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

11 g (0.05 mole) of 2, 3-dihydro-2, 2-dimethylbenzofuran-7-yl N-methyl-carbamate are dissolved in 50 ml of chloroform and 5.2 g (0.05 mole) of sulfur dichloride are cooled To the solution, while 5 g (0.05 mol) of triethylamine are added dropwise at -10 ° C to -5 ° C. The mixture is stirred at 0 ° C. for 1 hour and then further at room temperature for 1 hour. After cooling the mixture from -10 [deg.] To -5 [deg.] C., 6.2 g (0.05 mole) of iminodipropionitrile are added dropwise to the mixture followed by further dropwise addition of 5 g (0.05 mole) of triethylamine. The resulting mixture is stirred and stirred at 0 ° C. for 2 hours and then left at room temperature overnight. The reaction mixture is washed three times with 100 ml of water by addition of 100 ml of chloroform. The chloroform layer is dried and then concentrated in vacuo to give a small amount of impurities but almost the desired product. Yield: 12.2 g (65.2%)

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

NMR of Chloroform-d ₁ :

δ 1.43 ppm (s, 6H), δ 2.73 ppm (t, 4H), δ 2.97 ppm (s, 2H), δ 3.37 ppm (s, 3H), δ 3.43 ppm (t, 4H), δ 6.5 to 7.2 ppm (m, 3 H)

Elemental analysis: C ₁₆ H ₂₂ N ₄ O ₃ S (Molecular weight 374.47)

As a result, the product was confirmed to have the following structural formula.

TABLE 2

[Examples 8 to 11]

The compounds shown in Table 2 were prepared in the same manner as in Example 6 or 7. Physical properties and NMR data (chloroform-d ₁ ) of this compound are also shown in Table 2.

Example 12

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

11 g (0,05 A mol) of 2, 3-dihydro-2, 2-dimethylbenzofuran-7-yl N-methyl-carbamate are dissolved in 70 ml of methylene chloride, and 5.2 g (0,05 mol) of After adding sulfur dichloride to the solution, 5 g (0.05 mol) of triethylamine are added dropwise at -10 ° to -5 ° C. The mixture is stirred at 0 ° C. for 1 hour and then further at room temperature for 2 hours. After cooling the mixture from -10 [deg.] To -5 [deg.] C., 8.0 g (0.05 mole) of N-butylglycine ethyl ester is added dropwise to the mixture followed by further dropwise addition of 5 g (0.05 mole) of triethylamine. The resulting mixture is stirred at 0 ° C. for 2 hours and then left at room temperature overnight. The methylene chloride layer is dried and then concentrated in vacuo to yield an oily product which contains a small amount of impurities but consists almost of the desired product. Yield 15.7 g (76.6%).

Example 13

Preparation of 2, 3-dihydro-2, 2-dimethylbenzofuran-7-yl N- [N-phenyl-N-ethoxycarbonylmethylaminosulphenyl] -N-methyl-carbamate

11 g (0.05 mole) of 2, 3-dihydro-2, 2-dimethylbenzofuran-7-yl N-methyl-carbamate are dissolved in 70 ml of methylene chloride and 5.2 g (0.05 mole) of sulfur dichloride To this solution is added with cooling followed by further dropwise addition of 5.2 g (0.05 mol) of triethylamine at -10 ° to -5 ° C. The mixture is stirred at 0 ° C. for 1 hour and then further at room temperature for 2 hours. After cooling the mixture from -10 [deg.] To -5 [deg.] C., 9 g (0.05 mole) of N-phenylglycine ethylester is added dropwise, followed by further dropwise addition of 5 g (0.05 mole) of triethylamine. The resulting mixture was stirred at 0 ° C. for 2 hours and then left at room temperature overnight. The reaction mixture is washed three times with 100 ml of water while 100 ml of methylene chloride is added. The methylene chloride layer is dried and then concentrated in vacuo to give an oily product. A benzene-hexane (1: 1) mixture is added to this oily product to precipitate crystals. This precipitated crystals are filtered off and the mother liquor is concentrated to give an oily product which is then cooled to give crystals. Recrystallization of the obtained crystals with diethyl ether afforded 13.4 g (yield: 62.3%) of white crystals having a dew point of 92 ° to 93 ° C.

NMR of Chloroform-d ₁ :

δ 1.15 ppm (t, 3H), δ 1.46 ppm (s, 6H), δ 3.00 ppm (s, 2H), δ 3.32 ppm (s, 3H), δ 4.12 ppm (Q, 2H), δ 4.76 ppm (s , 2H), δ 6.5 to 7.5 ppm (m, 8H)

Elemental Analysis C ₂₂ H ₂₆ N ₂ O ₅ S (Molecular Weight 430.53)

t

t

As a result, the product was confirmed to have the following structural 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 (chloroform-d ₁ ) of this compound are also shown in Table 3 below.

TABLE 3

Example 33

Preparation of 2, 3-dihydro-2, 3-dimethylbenzofuran-7-yl N- [N-butyl-N-cyanomethylaminosulphenylmethyl] -N-carbamate

11 g (0.05 mol) of 2, 3-dihydro-2, 2-dimethylbenzofuran-7-yl N-methyl-carbamate are dissolved in 70 ml of methylene chloride and 5.2 g (0.05 mol) of sulfur dichloride are cooled To this solution while 5 g (0.05 mol) triethylamine is added dropwise at -10 [deg.] To -5 [deg.] C. The mixture is stirred at 0 ° C. for 1 hour and then further at room temperature for 2 hours. After cooling the mixture from -10 [deg.] To -5 [deg.] C., 5.6 g (0.05 mole) of N-butylaminoacetonitrile was added dropwise, followed by further 5 g (0.05 mole) of triethylamine. The resulting mixture is stirred at 0 ° C. for 2 hours and then left at room temperature overnight. The reaction mixture is washed three times with 100 ml of water while 100 ml of chloroform is added. Drying the methylene chloride layer and then concentrating in vacuo yielded an oily product consisting of a small amount of impurities but consisting almost of the desired product. Yield 13.0 (71.4%).

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

NMR of Chloroform-d ₁ :

δ 07 to 2.0 ppm (s, 7H), δ 1.42 ppm (s, 6H), δ 2.92 ppm (s, 2H), δ 2.9 to 3.5 ppm (m, 2H), δ 3.33 ppm (s, 3H), δ 4.01 ppm (s, 2H), δ 6.5 to 7.1 ppm (m, 3H)

Elemental analysis: C ₁₉ H ₂₆ N ₂ O ₆ S (molecular weight 363.488)

C H N

Found (%): 59.19 7.02 11.69

Calculation: 59.48 6.93 11.56

As a result, the product was confirmed to have the following structural formula.

[Examples 34 to 42]

The compound shown in Table 4 was prepared in the same manner as in Example 33. Physical properties and NMR data (chloroform-d ₁ ) of this compound are shown in Table 4 below.

TABLE 4

Example 43

Preparation of 2, 3-dihydro-2, 2-demethylbenzofuran-7-yl N- [N-propionyl-N-ethoxycarbonylmethylaminosulphenyl] -N-methyl-carbamate

11 g (0.05 mole) of 2, 3-dihydro-2, 2-dimethylbenzofuran-7-yl N-methyl-carbamate are dissolved in 70 ml of methylene chloride and 5.2 g (0.05 mole) of this sulfur chloride To this solution is added with cooling followed by further dropwise addition of 5 g (0.05 mol) of triethylamine at -10 ° to -5 ° C. The mixture is stirred at 0 ° C. for 1 hour and then further at room temperature for 2 hours. After cooling the mixture from -10 [deg.] To -5 [deg.] C., 8 g (0.05 mol) of N-propionylglycine ethyl ester in 10 ml of tetrahydrofuran was added dropwise to the mixture followed by 5 g (0.05 mol) of triethylamine. More drop. The resulting material is stirred at 0 ° C. for 2 hours and then left at room temperature overnight. The reaction mixture is washed three times with 100 ml of water while 100 ml of ethylene chloride is added. The methylene chloride layer was dried and then concentrated in vacuo to yield an oily product which contained a small amount of starting material but consisted almost of the desired product. Yield: 14.3 g (69.8%).

To identify the product, some of this product was purified by silica gel column chromatography using benzene / ethyl acedate (9: 1) as solvent to give crystals having a melting point of 108 ° to 109 ° C.

NMR of Chloroform-d ₁ :

δ 1.14 ppm (t, 3H), δ 1.23 ppm (t, 3H), δ 1.49 ppm (s 6H), δ 2.7-3.3 ppm (m, 2H), δ 3.02 ppm (s, 2H), δ 3.48 ppm ( s, 3H), δ 4.15 ppm (q, 2H), δ 4.50 ppm (s, 2H), δ 6.6-7.1 ppm (m, 3H)

Elemental analysis: C ₁₉ H ₂₆ N ₂ O ₆ S (Molecular Weight 410.499)

As a result, the product was confirmed to have the following structural formula.

Example 44

Preparation of 2, 3-dihydro-2, 2-dimethylbenzofuran-7-yl N- [N-ethoxycarbonyl-N-ethoxycarbonylmethylaminosulfayl] -N-methyl-carbamate

11 g (0.05 mole) of 2, 3-dihydro-2, 2-dimethylbenzofuran-7-yl N-methyl-carbamate are dissolved in 70 ml of methylene chloride and 5.2 g (0.05 mole) of this sulfur chloride To this solution is added with cooling followed by further dropwise addition of 5 g (0.05 mol) of triethylamine at -10 ° to -5 ° C. The mixture is stirred at 0 ° C. for 1 hour and then further at room temperature for 1 hour. After cooling the mixture to −10 ° to −5 ° C., 8.3 g (0.05 mole) of N-ethoxycarbonylglycine ethyl ester is added dropwise to the mixture followed by 5 g (0.05 mole) of triethylamine. . The resulting mixture is stirred at 0 ° C. for 2 hours and then left at room temperature overnight. The reaction mixture is washed three times with 100 ml of water while 100 ml of methylene chloride is added. Drying the methylene chloride layer and concentrating in vacuo yields an oily product consisting of a small amount of starting material and impurities but consisting almost of the desired product. Yield 18.2 g (84.7%).

To identify the product, a portion of this product is purified by silica gel column chromatography using benzene / ethyl acetate (4: 1) as solvent to give an oily product. NMR of chloroform -d ₁ ;

δ 1.17 ppm (t, 6H), δ 1.44 ppm (s, 6H), δ 2.94 ppm (s, 2H), δ 3.41 ppm (s, 3H), δ 4.05 ppm (q, 2H), δ 4.15 ppm (q , 2H), δ 4.41 ppm (s, 2H), δ 6.5-7.0 ppm (m, 3H)

Elemental analysis: C ₁₉ H ₂₆ N ₂ O ₇ S (Molecular Weight 426.499)

As a result, the product was confirmed to have the following structural formula.

[Examples 45 to 52]

The compounds shown in Table 5 were prepared in the same manner as in Example 43 or 44. Physical properties and NMR data (chloroform-d ₁ ) of this compound are shown in Table 5 below.

TABLE 5

Formulation examples of the present invention are as follows.

These examples are applicable to all compounds of the invention: suitable examples are applicable only in special cases. These examples are described for the purpose of explanation only, and the ratio of the active ingredient, the organic solvent, the surfactant, and the carrier may be variously used as necessary. In some cases, the type of the organic solvent, the surfactant, and the carrier can be changed. Where% is weight percent.

Production Example 1

60% Emulsion:

Compound of Example 25 60.0% xylene 30.0

Polyoxyethylene nonyl phenyl ether 10.0%

Production Example 2

50% Emulsion:

Compound 50.0% xylene 30.0 of Example 12

Polyoxyethylene sorbitan monooleate 6.5 cyclohexanone 10.0

Sorbitan Monooleate 3.5

Production Example 3

20% Emulsion:

Compound of Example 22 20.0% xylene 45.0

Polyoxyethylene alkyl ether 5.0 petroleum ether 30.0

In the case of Formulation Examples 1 to 3, the ingredients are uniformly mixed and dissolved to give the desired emulsion.

Production Example 4

90% Hydration:

Compound of Example 1 90.0% Clay 7.0

Sodium Lignin Sulfonate 3.0

Production Example 5

50% hydration:

Compound 50.0% Alkyl Phosphate 5.5%

Alkyl sulfate 30.0 kaolin 3.5

Condensate of naphthalenesulfonic acid and formaldehyde 10.0 Talc 1.0

Production Example 6

30% Hydration:

Compound 30.0% White Carbon 15.0% of Example 30

Alkylbenzenesulfonate 3.0 clay 50.0

Sodium Lignin Sulfonate 2.0

For Formulation Examples 4-6, the ingredients are stirred and mixed uniformly using a Shinagawa-type mixing mixer. The mixture is finely ground using a sample mill or ball mill to yield the desired wetting agent.

Production Example 7

5% powder:

Compound of Example 46 5.0% Diatomaceous Earth 10.0%

Talc 85.0

Production Example 8

2% powder:

Wetting Agent 4.0% Isopropyl Phosphate 0,2% of Preparation Example 5

Clay 95.8

[Example 9 of Manufacturing]

0.5% powder:

Hydration 1.7% Clay 100.3% of Preparation Example 6

In Preparation Examples 7 to 9, the above ingredients were uniformly mixed using a mixing mixer in the form of Shinagawa to obtain the desired powder.

Production Example 10

20% of granules:

Hydration 40.0% Dolomite 60.0% of Preparation Example 5

The components are uniformly mixed and an aqueous solution of 2% carboxymethyl cellulose 2% is added to the mixture at 15 parts by weight per 100 parts by weight of the mixture and the resulting mixture is kneaded completely. The mixture is granulated using a granulator, finely divided and dried. As a result, the desired granules are obtained.

Production Example 11

10% granules:

Compound 10.0% Diatomaceous Earth 27.5% of Example 40

Sodium Dodecylbenzenesulfonate 0.5 Bentonite 60.0

Sodium Lignin Sulfonate 2

The components are mixed uniformly and water is added to the mixture. The resulting mixture is thoroughly kneaded and then granulated using a granulator. The granular product is finely divided and dried to obtain the desired granules.

Production Example 12

3% granules:

Compound of Example 8 3.0% clay 94.0%

Polyvinyl Alcohol 3.0

The desired granules can be obtained by repeating the same method as in Preparation Example 11. Test Examples are as follows.

[Test Example 1]

Tobacco larvae (Spofoptera litura). 3/10 larvae are transplanted into pot-planted cabbage (one month after seeding) and the 50% emulsion of the compound to be tested is diluted to a certain concentration and completely soaked to the leaves of the cabbage. Each specific concentration of test compound is tested on two ports. Three days later, the larvae were counted and shown in Table 6. The results show a comparison between the control and the untreated group.

TABLE 6

1-Natyl-N-carbamate was used as a control.

[Test Example 2]

A certain concentration of emulsion is prepared from 50% of the hydrous compound to be tested so that the leaves of the rice planted in the pot (one month after sowing seeds) are wetted. After drying the emulsion, 10 female adult Nepthotettix cincticepes are released by covering the pot with a net. Each specific concentration of compound is tested on two ports. Insects killed after 3 days were examined and shown in Table 7. The results show a comparison between the control and the untreated group.

TABLE 7

2-isopropoxyphenyl-N-methylcarbamate was used as a control.

[Test Example 3]

Granules containing 10% of the compound to be tested are mixed with soil contaminated with an appropriate amount of western larval nematode (Meloidgtne incognita) larvae. After one month, examine the root nodules formed on the roots of the plant.

Two test zones of 2x2m2 are used as compounds with specific amounts. The formation range of the root nodule can be determined based on the criteria of Table 8. Table 8 also shows a comparison between the control and untreated areas.

Root nodule formation range

0: 0% 3: 75% or less

1: 25% or less 4: 100% or less

2: 50% or less

TABLE 8

Bis (2-chloro-1-methylethyl) ether was used as a control.

[Test Example 4]

The compound to be tested is dissolved in a predetermined amount of acetone. This solution is diluted to various concentrations and applied locally to Mnsca domestica. Table 9 shows the LD ₅₀ values measured by four days after the probit method (probit method).

TABLE 9

2-isopropoxyphenyl-N-carbamate was used as a control.

[Test Example 5]

The compound of the present invention is applied to male rats to investigate the toxicity for oral administration. Table 10 shows the mortality rate of the LD ₅₀ value by the Richfield Wilcoxon method after 17 days.

TABLE 10

2, 3-dihydro-2, 2-dimethyl-7-benzofuran-7-yl N-methyl-carbamate was used as a control.

Claims (1)

The compound of formula (II) is reacted with sulfur dichloride to give 2, 3-dihydro-2, 2-dimethyl-benzofuran-7-yl N- (chlorosulphenyl) -N of formula (III) A method of preparing a carbamate derivative of formula (I), characterized in that -methyl-carbamate is produced and then reacted with an amine compound of formula (IV).

R in the above general formula^OneAnd R²May be the same or different and each is -X-COOR³Or -Y-CN wherein X represents an alkylene group having 1 to 6 carbon atoms, R³Represents an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, and Y represents an alkylene group having 1 to 6 carbon atoms), or R²Is also an alkyl group having 1 to 8 carbon atoms; A cycloalkyl group having 3 to 6 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; 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-R⁴Wherein Z represents a carbonyl group or a sulfonyl group, and R⁴Represents 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.