DD201968A5 - CARBAMATE DERIVATIVES INCLUDING INSECTICIDES, ANTIMILY OR NEMATOCIDE COMPOSITIONS - Google Patents

Abstract

The invention relates to the provision of carbamate derivatives of general formula (I) containing insecticidal, mitogenic or nematocidal compositions containing the carbamate derivatives of formula I as an active ingredient besides an acceptable adjuvant. It also relates to a method of controlling harmful insects, mites or nematodes using the preferred compositions.

Description

Carbamate derivatives containing insecticides . Anti-mite or nematocidal compositions and their use

Field of application of the invention

The invention is applicable in agriculture and horticulture and wherever harmful insects mites or nematodes are to be controlled.

In the present invention, the term "insecticides" further includes miticidal and non-insecticidal insecticides, and the terms "insects" include mites and nematodes other than insects, unless otherwise specified.

Characteristic of the known technical solution

It is known that certain carbamate derivatives have a high insecticidal activity and also in practical

3 5 7 8 4 O

Use are. However, many of these carbamate compounds are toxic to warm-blooded animals. In particular, has 2 3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate (hereinafter referred to carbofuran) have high insecticidal activity, but it is in practice

Application problematic because of its high toxicity to warm-blooded animals. Thus, if it were possible to produce carbamate compounds that are comparable to carbofuran in terms of insecticidal activity and yet have reduced toxicity to warm-blooded animals, such compounds would be very useful. In view of these considerations, various carbofuransulfenic compounds have been synthesized, and the relationships between their insecticidal activity and toxicity to wild-type strains have been studied. Thus, from BE-PS 817,517 2,3-dihydro-2 _/ 2-dimethylbenzofuran-7-yl N- (Ν, Ν-dibutylaminosulfenyl) -N-methyl-carbamate and from DE-OS 22 54 359 2 _/ 3-Dihydro-2,2-dimethylbenzofuran-7-yl N- (N-methyl-N-benzenesulfonylaminosulfenyl) -N-methyl-carbamate. However, these compounds do not yet meet the requirements for insecticidal activity, toxicity to warm-blooded animals and fish and the manufacturing process

 25

Object of the invention

The aim of the invention is to show novel carbamate compounds which are suitable for controlling insects and which have no or only low toxicity to warm-blooded animals and fish.

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Explanation of the essence of the invention

The object of the invention is to provide an effective control of insects, mites and nematodes by providing new insecticides. This object is achieved by carbamate compounds of general formula I.

(I)

In the formula I mean:

"...

1 o

R and R, which are the same or different, are each (1) -X-COOR, wherein X is an alkylene group having 1 to 6 carbon atoms and R is an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, or (2) -Y-CN, wherein Y represents an alkylene group having 1 to 6 carbon atoms;

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 phenyl group having 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 wherein Z is a carbonyl group or a sulfonyl group and R is 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.

3578 4 o

In the definition of the formula (I), the alkyl groups in the alkyl group, in the alkylene group and in the alkoxy group may be straight-chain or branched.

Preferred compounds are compounds of the formula (I ¹ )

ίο ^ J ^SN

in which mean:

^r5 τ ν

R and R , which may be the same or different, are each (1) -X'-COOR, where X ^{1 is} an alkylene radical

group having 1 to 2 carbon atoms and R is an alkyl group having 1 to 4 carbon atoms, which may be straight-chain or branched, or

(2) -Y'-CN, wherein Y ^{1 represents} an alkylene group having 1 to _x '2 carbon atoms;

2 ' ^:

R is an alkyl group having 1 to 6 carbon atoms

.25 or a cycloalkyl group having 3 to 6 carbon atoms.

The compounds of the formula (I) are novel compounds which have hitherto not been described in the literature. It was further stated that. the new compounds have superior insecticidal activities in the control and control of

S

£, * J * J f

agricultural or forest insect pests and harmful domestic insects and that they are in this effect comparable to carbofuran, which previously had the highest insecticidal activity. The compounds are resistant to a large number of harmful insects, mites and nematodes harmful to vegetables, trees, other plants and humans, such as Hemiptera , Lepidoptera , Loeoptera , Diptera , Thysanoptera , Orthoptera , Isopoda , Acarina , Tylenchida , and the like. effective. Examples of such. Insects, mites and nematodes are the following: Hemiptera

Nephotettix cincticeps Laodelphax " striatellus , Nilapar vata lugens

Myzus persicae , Aphis gossypii Nezara antennata, Nezara viridula

Spodoptera litura , Agrotis fucosa ,

Laphygmae exigua Adoxophyes orana

Chilo suppressalis , Ostrinia furnacalis , Cnaphalocrocis medi nalis

Plutella xylostella

Echinocnemus squameus , Lissorhoptrus oryzophilus Popillia japonica Henosepilachna vigintiocto punctata

(1) Deltocephalidae Noctuidae: (2) Delphacidae: Tortricidae: (3) Aphididae: Pyralidäe: (4) pentatomidae: Lepidoptera (D (2) (3)

(4) Plutellidae ;

Coleoptera

(1) Curculionidae :

(2) Scarabaeidae :

(3) Coccinellidae;

3-5 7 8 4

Diptera

(1) Muscidae :

(2) Cecidomyiidae :

(3) agromyzidae;

Musca domestica Aspondylia sp. Phytobia cepae

Thyaneoptera

Thrip idae;

Thrips tabaci , Scirtothrips dorsalis

Orthoptera '

Gryllotalpidae: Gryllotalpa africana

Isopoda

Armandillidae; , , Arynadillidium vulgaris

Acarina

Tetranychidae ;

Tetranychus telarius , Tetranychus urticae, Panonychus citri

Tylenchida

Heteroderidae:

Meloidogyne incognita

The toxicity of the carbamate derivatives according to formula (I) to warm-blooded animals is only one-fifth to one-hundredth of the toxicity of carbofuran. The present compounds have activity against the aforementioned organisms at any stage of their growth, and therefore can be used effectively for monitoring and control on fields, in forests and also in sanitary facilities.

The compounds of the formula (I)

2 35 78 4 O

are very easy to produce in high yields and with high purity and are therefore economically very advantageous. . '·.

Typical compounds of the formula (I) are those described in Examples 1 to 56. Particularly preferred compounds are the following:

, 2,3-Dihydro-2,2-dimethylbenzofuran-7-yl N- / N, N-bis (ethoxycarbonylmethyl) -aminosulfenyl 7-N-methyl-carbamate

2/3-Dihydro-2,2-dimethylbenzofuran-7-yl N- (N-methyl-N-ethoxycarbonylmethylaminosulfenyl) -N-methyl-carbamate

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

2,3-dihydro-2, 2-dimethylbenzofuran-7-yl N- (Nn-butyl-N-ethoxycarbonylethylaminosulfenyl) -N-methy1-carbamate 20

2/3-dihydro-2 ₇ 2-dimethylbenzofuran-7-yl N- (N-cyclohexyl-N-ethoxycarbonylethylaminosulfenyl) -N-methy1-carbamate

2,3-Dihydro-2,2-dimethylbenzofuran-7-yl N- (N-n-butyl-N-cyanoethylaminosulfenyl) -N-methyl-carbamate

The compounds of the formula (I) are

prepared by dissolving a compound of the general formula (II) 30

357

0-c-n;

.CH.

• η

(ID

10

with Schwefeldichlorxd using 2,3-dihydro-2, 2-dimethylbenzofuran-7-yl N- (chlorosulfenyl) -N-methylcarbamate of the formula (III)

CH

, CH.

o-c-n:

(III)

20

which is then reacted with an amine compound of the general formula (IV)

HN

(IV)

25

1 2

in which R and R have the meanings given above, is reacted.

30

The reaction of the compound of the formula (II) with sulfur dichloride can be carried out in the presence or in the absence of a solvent. Examples of suitable solvents are methylene chloride, chloroform, carbon tetrachloride

* ϊ? κ .ι α π -η λ

and similar halogenated hydrocarbons, and diethyl ether, · dibutyl ether, tetrahydrofuran, dioxane and similar esters. The ratio of the compound of the formula (II) to SCl ₀ is not particularly limited and can vary widely. In general, 1 to 2 moles and preferably about 1 to about 1.2 moles of the latter are employed per mole of the former. Preferably, the reaction is carried out in the presence of a basic compound. Examples of suitable basic Verbindüngen are triethylamine, tributylamine, Dimethy aniline, diethylaniline, ethylmorpholine and like tertiary amines, pyridine, d *, ß, ^ - Pikolin, lutidine, etc .. The basic compounds can be applied in an amount sufficient capture the hydrogen chloride formed by-product in the reaction. In general, 1 to 2 moles of the basic compound are used per mole of the compound of the formula (II). The reaction, which proceeds under cooling, at room temperature or under heating, is generally carried out at -70 to 50 ^° C., and 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, and then the compound (III) is reacted with an amine compound of the formula (IV).

Examples of suitable amine compounds of the formula (IV) are those secondary amines of the formulas (V) to (IX)

30 X-COOR ³

2 3578 4 O

- ίο -

X-CN HN (VI)

J-COOR ³

^ (VII)

X "-COOR

JC-COOR ³

HN (VIII)

Y-CN

Y-CN

HN - (IX)

Y "-CN

In the formulas (V) to (IX), X, Y and R ³ , R ⁴ and R have the meanings given 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 containing a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms;

4 'or -Z'-R, wherein Z ^{1 is} a carbonyl group or a

235784 O

4 '

Sulfonyl group and R represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group, an alkoxy group having 1 to 6 carbon atoms or a phenoxy group (in which the alkyl group and the alkoxy group are straight-chain or branched

R has the same meaning as in R; X "has the same meaning as X and Y" has the same meaning as in Y.

Typical examples of amine compounds of the formula (V) are 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-sec-butylglycine ethyl ester. Nn-octylglycinoctyl 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, ethyl Nn-propylaminopropionate, methyl N-isopropylaminopropionate, ethyl N-isopropylaminopropionate, butyl N-isopropylaminopropionate / 2-ethylhexyl N-isopropylaminopropionate, methyl N-n-butylaminopropionate, ethyl Nn-butylaminopropionate, ethyl

IS N-isobutylaminopropionate, ethyl N-sec-butylaminopropionate, ethyl Nt-butylaminopropionate, ethyl N, n-amylaminopropionate, ethyl N-isoamylaminopropionate, ethyl N-n-hexylaminopropionate, ethyl N-cyclohexylaminopropionate, N-acetylglycine ethyl ester, N-chloroacetylaminoglycine ethyl

JO ester, N-propionylglycine ethyl ester, N-benzoylglycine ethyl ester, N- (4-chlorobenzoyl) glycine ethyl ester, N-tosylglycine ethyl ester and the like.

23578 A O

Examples of amine compounds 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, and the like.

Typical examples of amine compounds of the formula (VII) are methyliminodiacetate, ethyliminodiacetate, isopropyliminodiacetate, cyclohexyliminodiacetate, methyliminodipropionate / ethyliminodipropionate, 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 and the like.

Typical examples of amines of the formula (VIII) are methyl N-cyanomethylcarbamate, ethyl N-cyanomethylcarbamate, ethyl N-cyanoethylcarbamate, N-cyanomethylglycine ethylester, N-cyanoethylglycine ethylester, ethyl N-cyanomethylaminopropionate, ethyl N-cyanoethylaminopropionate and the like.

Typical examples of amines of the formula (IX) are iminodiacetonitrile, iminodipropionitrile and iminidibutyronitrile.

3 b 7 ο 4 U

The reaction of the compound of the formula (III) with the amine compound of the formula (IV) can be carried out in the presence or absence of a solvent. Any solvent suitable for the reaction of the compound of formula (II) with sulfur dichloride is also suitable for this reaction. The ratio of the compound of the formula (III) to the amine is not particularly limited and may vary widely. In general, about 1 to about 2 moles, preferably about 1 to about 1.2 moles, of the latter are used per mole of the former. Preferably, the reaction is also carried out in the presence of a basic compound, which may be one of the aforementioned. The basic compound is used in an amount sufficient to bind the hydrogen chloride by-produced in this reaction. In general, 1 to 2 moles, preferably 1 to 1.5 moles of the basic compound are used per mole of the compound (III). The reaction, which proceeds under cooling, at room temperature or under heating, is generally carried out at -20 to 50 ^° C., preferably 0 to 30 ^° C. The reaction time is generally about 10 to about 15 hours.

, The compounds thus obtained

Formula (I) can be readily isolated and purified by conventional methods of separation, e.g. by solvent extraction, recrystallization or chromatographic.

The compounds (I). Can be concentrated into emulsions, wettable powders, suspensions

35 78 4 O -

Suspensions, granules, fine particles, dusts, coating compositions, foam sprays, aerosols, in microcapsules, as impregnations for natural or synthetic materials, as fumigants or as concentrated preparations, which are used in small quantities.

For the emulsions, dispersions, suspensions and foams, various surfactants 10 can be used. Suitable nonionic surfactants are polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbital alkyl esters, sorbital alkyl esters, etc. Examples of suitable anionic surfactants are alkylbenzenesulfonates, alkylsulfosuccinates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylnaphthalenesulfonates, lignosulfonates, etc.

Solvents, diluents and carriers for the compounds are many organic solvents, aerosol propellants, natural minerals,

Plants, synthetic compounds, etc. Examples j; preferred organic solvents are benzene,

Toluene, xylene, ethylbenzene, chlorobenzene, alkylnaphthalene, dichloromethane, chloroethylene, cyclohexane, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohols, dimethylformamide, dimethylsulfoxide, acetonitrile, mineral oil fractions, etc. Examples of suitable aerosol propellants are propane, butane, halocarbons , Nitrogen, carbon dioxide, etc. Examples of suitable natural minerals are kaolin, talc, bentonite, diatomaceous earth, clay, montmorillonite, lime, calcite, pumice,

35 78 4 O

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

)

10 The Conditions of Formula (I) ·>

may be formulated into numerous preparations, such as those mentioned above, so that these preparations are considered as; Active ingredient contains an insecticidal, miticidal or nematoid-killing amount (e.g., about 0.1 to 95% by weight, preferably about 0.5 to about 90% by weight) of the compound. Depending on the intended application, the compositions may be used as such or diluted with a carrier or with water.

The invention is explained in more detail in the following examples.

25 Example 1

- (cyanomethyl) _ -aminosulfenyl 7-N-methyl-carbamate

11 g (0.05 mol) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate were dissolved in 70 ml of methylene chloride

2 35 78 4 O - ¹⁶ -

and 5.2 g (0.05 mol) of sulfur dichloride were added to the solution under cooling, and then 5 g (0.05 mol) of triethylamine were further added to the solution at 0 ^° C. The mixture was allowed to stand at this temperature for 2 hours Then, at the same temperature, a solution of 4.8 g (0.05 mol) of iminodiacetonitrile in 40 ml of tetrahydrofuran was added dropwise, and to the mixture was further added dropwise 5 g (0.05 mol) of triethylamine Stirred at 0 ⁰ C and then allowed to stand overnight at room temperature After 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 concentrated in vacuo to give an oily product, the nachezu consisted entirely of the desired product but contained a small amount of the starting material Yield: 13.8 g (79.8%).

To identify the product, a part thereof was purified by silica gel column chromatography using benzene / ethyl acetate (4: 1) as a solvent to obtain a crystal having a melting point of 94 to 95 ^° C.

25 NMR in chloroform-d ₁ : 6 1/48 ppm (s, 8H)

63.02 ppm (s, 2H)

, ₉ 6 3.50 ppm (s, 3H)

6 4.32 ppm (s, 4H) 6 6.6-7.2 ppm (m, 3H)

78 4

Elemental Analysis for C ₁₆ H ₁₃ N ₄ O ₃ S: (Molecular Weight 346.418)

Calculated%: C 55.36 H 5.31 N 16.05 Found%: 55.48 5.24 16.17

The product thus had the following formula

CH, _Λ 1 ^ Stn;

¹ CH ₂ CN CH ₃ ^ I "

Example 2 20

11 g (0.05 mol of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate were dissolved in 50 ml of chloroform and 5.2 g (0.05 mol) of sulfur dichloride were added to the solution while cooling 5 g (0.05 mol) of triethylamine were then added dropwise to the solution at 0 ^° C. The mixture was stirred at the same temperature for 2 hours and then a solution of 9.5 g (0.05 mol) was added. Ethyliminodiacetate in 20 ml of chloroform

2357 8 4 O - Ψ. ~

was added dropwise at the same temperature and then further 5 g. (0.05 mol) of triethylamine was added dropwise to the mixture. The mixture was stirred for 2 hours at 0 ⁰ C and then allowed to stand overnight at room temperature. After addition of 100 ml of chloroform, the reaction mixture was washed with 100 ml. Washed water three times. The chloroform layer was dried and concentrated in vacuo to give an oily product which consisted almost completely of the desired product but still contained small amounts of starting material. Yield: 15.9 g (72.3%).

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

NMR in chloroform-d ₁ : £ 1.24 PP ^ (t, 6H)

51/48 ppm (s, 6H)

20 63.02 ppm (s, 2H)

£ 3.42 ppm (s, 3H) £ 4.20 ppm (q, 4H) 64.28 ppm (s, 4H) 66.6-7.2 ppm (m, 3H) 25

Elemental analysis for C ₂₀ H ₂₆ N ₂ O ₇ S (molecular weight 440.526)

Calculated%: C 54 , 68 H 6 46 N- 6 38 Found %: 54 / 53 6 41 6 36

The product thus had the following formula:

2357

CH ₂ COOC ₂ H ₅ CH ₂ COOC ₂ H ₅

Examples 3 to

The compounds shown in Table 1 were prepared in the same manner as in Examples 1 or 2. The physical properties and NMR data (nuclear magnetic resonance spectrum) (in Chlorof orm-d ..) of the compounds are also shown in Table 1,

  Table 'j

R ¹

Elemental analysis

Viii if

Amin 1 ο H-NMR. empirical formula at R ¹ R ^ ^ cT value (ppm) Find (%) game in _CDCl3 / · (calculated(%)) No. C HN

.CH ₂ COOCH ₃ 'CH ₂ COOCH ₃

, CH ₂ C00- ('CH ₂ C00- (

-CH ₂ COOCH ₃

-CH ₂ COOCH ₃

-CH ₂ COO- ^

-CH ₂ C00- (

61.47 (s, 6H),

63.02 (s, 2H),

63.41 (s, 3H), 63.73 (s, 6H), 64.30 (s, 4H), 66.7-7.2 (m, 3H)

61.23 (d, 6H), 61.46 (s, 6H),

63.03 (s, 2H),

63.42 (s, 3H), 64.26 (s, 4H), 64.5-5.3 (m, IH), 66.6-7.2 (m, 3H)

C ₁₈ H ₂₄ N ₂ O ₇ S

52jll 5.91 6.63

(52,42) (5,87) (6,79)

C ₂₂ H ₃₂ N ₂ O ₇ S

56.35 (56.44)

6.91 (6.89)

5.86 (5 _f 98)

Continued table

example

Amin

CH ₂ COO- / H 5 HN-CH ₂ COO- / H

CH ₂ COO- / H

-CH ₂ COO

H-NMR

Value (ppm) in CDCl ₃ /

61.0-2.2 (in, 20H), 61.48 (s, 6H), 63.02 (s, 2H), 63.43 (s, 3H), 64 _f 28 (s, 4H), 64 , 5-5.1 (m, 2H), 66.7-7.2 (m, 3H)

Elemental analysis

empirical formula found (%) (calculated (%))

61,32 7,39 (61,29) (7,35)

4.95 (5.11)

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Example 6 Preparation

11 g (0.05 mol) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate was dissolved in 70 ml of methylene chloride, and to the solution was added 5.2 g (0.05 mol) with cooling. Sulfur dichloride was added dropwise to the solution at -10 to -5 ⁰ C 5 g (0.05 mol) of triethylamine. The mixture was stirred at 0 ^° C. for 1 hour and at room temperature for a further 2 hours. After cooling to -10 to -5 ⁰ C 10.9 g (0.05 mol) Diethyliminodipropionat was added dropwise to the mixture, and 5 g (0.05 mol) of triethylamine, which was also added dropwise. The resulting mixture was stirred for 2 hours at 0 ⁰ C and then allowed to stand overnight at room temperature. After adding 100 ml of methylene chloride, the reaction mixture was washed three times with 100 ml of water. The methylene chloride layer was dried and concentrated in vacuo to give an oily product which consisted almost completely of the desired product and contained only minor amounts of impurities. Yield: 16.9 g (72.2%).

For identification, a portion of the product was purified by silica gel column chromatography using benzene / ethyl acetate (5: 1) to obtain an oily product.

235784

- .23 -

NMR in chloroform: ($ 1.21 ppm (t, 6H)

£ 1.44 ppm (s, 6H)

.. ·· 02.67 ppm (t, 4H)

62.97 ppm (s, 2H)

63.37 ppm (s, 3H)

63.42 ppm (tm 4H)

64.04 ppm (q, 4H)

66.5-1.2 ppm (m, 3H)

Elemental analysis for C ₂₂ H ₃₃ N ₂ O ₇ S (molecular weight 468.58)

Calculated%: C 56 26 H 6 91 N 5, 52 Found %: 56 39 6 , 88 5, 98

The product thus had the following formula:

CH ₃

CH ₂ CH ₂ COOC ₂ H ₅ CH ₂ CH ₂ COOC ₂ H ₅

2 35 78 4 O

Example 7

11 g (0.05 mol) of 2, S-dihydro-dimethylbenzofuran-1-yl-N-methyl-carbamate were dissolved in 50 ml of chloroform and to the solution were added 5.2 g (0.05 mol) of sulfur dichloride with stirring and then added dropwise to the solution at -10 to -5 ° C 5 g (0.05 mol) of triethylamine. The mixture was stirred at 0 ^° C. for 1 hour and at room temperature for a further 1 hour. After cooling to -10 to -5 ° C, 6.2 g (0.05 mol) of iminodipropionitrile was added dropwise to the mixture, and then 5 g (0.05 mol) of triethylamine was added dropwise to the mixture. The mixture was stirred for 2 hours at 0 ⁰ C and then allowed to stand overnight at room temperature.

After adding 100 ml of chloroform, the reaction mixture was washed three times with 100 ml of water. The chloroform layer was dried and concentrated in vacuo to give an oily product containing almost completely the desired product besides small amounts of impurities. Yield: 12.2 g (65.2%).

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

35 78 4 0

- 25 -

NMR in chloroform: £ 1.43 ppm (s, 6H)

, 62.73 ppm (t, 4H) 62.97 ppm (s, 2H) 63.37 ppm (s, 3H) 6 3.43 ppm (t, 4H) ^ 6.5-7.2 ppm (m, 3H )

Elemental analysis for C ₁₃ H ₂₂ N ₄ O ₃ S (molecular weight 374.47) 10

Calculated%: C 57.91 H 5.79 N 15.04 Found%: 57.73. 5.92 14.96

The product thus had the formula 15

CH ₂ CH ₂ CN

Examples 8 to 11

The compounds in Table 2 were prepared as in Examples 6 or 7. The physical properties and NMR data (in chloroform-d-j) of these compounds are also shown in Table 2.

  Table '2

Il / CH ₃

S-N

example

Amin

.R "

/ CH ₂ CH ₂ CN

HN-CH ₂ CH ₂ CN

^ CH ₂ COOC ₂ H ₅

-CH ₂ COOC ₂ H ₅

^ CH ₂ CH ₂ COOC ₂ H ₅

HN-CH ₂ CH ₂ COOC ₂ H ₅

CH ₂ COOC ₂ H ₅

-CH ₂ COOC ₂ H ₅

• ν

Ri

R ₂

H-NMR.

Value (ppm) in CDCl3 J.

61,26 (t, 3H),. 61.47 (s, 6H), 62.6-3.1 (m, 2H), 63 _t 02 (s, 2H), 63.40 (s, 3H), 63.3-3.8 (m, 2H), 64.18 (s, 2H), 64.20 (q, 2H), 66.6-7 _t 2 (m, 3H)

61.23 (t,

61.45 (s,

62.70 (t,

63.00 (s,

63.39 (s,

63.40 (t, 64.09 (q, 64 _t 14 (s, 64 _t 55 (q,

, 66.5-7 _t 2

6H), 6H), 2H), 2H), 3H), 2H), 2H), 2H), 2H), (m, 3H)

Elemental analysis empirical formula found (%) (calculated (%))

C ₁₉ H ₂₅ N ₃ O ₅ S

55.89 (56 _f 01)

6,31 10,64 (6 _f 19) (10,31)

C ₂ IH ₃₀ N ₂ O ₇ S

55.94 (55.50)

_6T 79

6.05

(6 _f 65) (6,16)

Continued table

example

HN.

Amin

R ¹

H-NMR value (ppm) CDCl ₃ /

, CH ₂ CH ₂ CH ₂ COOC ₂ H ₅ 'CH ₂ COOC ₂ K ₅

-CH ₂ CH ₂ CH ₂ COOC ₂ H ₅ -CH ₂ COOC ₂ H ₅ 61.22 (t, 6H), 61.45 (s, 6H), 61.7-2.6 (m, 4H), 63 , 00 (s, 2H), 63,35 (t, 2H), 63,42 (s, 3H), 64,13 (q, 2H), 64,15 (s, 2H), 64,17 (q, 2H), 66.5-7.2 (m, 3H)

HN

CH ₂ CH ₃ , CHCOOC ₂ H ₅ "CH ₂ COOC ₂ H ₅

CH ₂ CH ₃

-CHCOOC ₂ H ₅

-CH ₂ COOC ₂ H ₅ 60.99 (t, 3H), 61.20 (t, 3H), 61.23 (t, 3H), 61.43 (s, 6H), 61.5-2.5 (m, 2H), 63.02 (s, 2H), 63.38 (s, 3H), 63.5-4.5 (m, 7H), 66.5-7.2 (m, 3H)

Elemental analysis

empirical: formula N. found (%) (calculated(%)) C H

55.94 (56.44)

6.93 (6.89)

6.25 (5.98)

C22H32N2O7S

56.53 6.78 5.81 (56.44) (6.89) (5.98)

2 3 5 7 8 4

- .23 -

Example 12

Preparation of 2,7-γ1_Ν- (N-butyl-N-ethoxycarbonylaminosulfenyl) _-N-me -

11 g (0.05 mol) of 2,3-pihydro-2/2-dimethylbenzofuran-7-yl N-methyl-carbamate was dissolved in 70 ml of methylene chloride and to the solution was added 5.2 g (0.05 mol Sulfur dichloride was added and then further added to the solution at -10 to -5 ° C dropwise 5 g (0.05 mol) of triethylamine. The mixture was stirred at 0 ^° C. for 1 hour and then at room temperature for a further 2 hours. After cooling to -10 to -5 ° C, 8.0 g (0.05 mol) of N-butylglycine ethyl ester was added dropwise to the mixture, and to the mixture was further added dropwise 5 g (0.05 mol) of triethylamine. The mixture was stirred for 2 hours at 0 ⁰ C and then allowed to stand overnight at room temperature. To

After adding 100 ml of methylene chloride, the reaction mixture was washed three times with 100 ml of water. The methylene chloride layer was dried and concentrated in vacuo to give an oily product which was almost entirely composed of the desired substance besides low

There was an amount of impurities. Yield: 15.7g

(76.6%).

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

2 3578 k O

NMR in chloroform-d-j: 6 0.6-1.9 ppm (m, 7H)

61.22ppm (t, 3H)

ppm (t, 3H) -

6 1.44 ppm (s, 6H)

6 3.03 ppm (s, 2H)

6 3.30 ppm (t, 2H)

6 3.42 ppm (s, 3H)

6 4.14 ppm (s, 2H)

(S 4.13 ppm (q, 2H) 6 6.5-7.2 ppm (m, 3H)

Elemental analysis for

{Mw. 410.54)

Calculated%: C 58 39 H 7 , 41 N 6 75 Found %: 58 52 7 / 37 6 83

The product thus had the following formula:

CH

o-c-n;

CH ₉ COOC ₇ Hr CH ₂ CH ₂ CH ₂ CH ₃

235 78 4 O-

Example 13

Preparation von_2 _i 3-dihydro ^ 2 _j: 2-dimethylbenzofuran-7-yl N- (N-

11 g (0.05 mol) of 2,3-dihydroc ~ 2,2-dimethylbenzofuran-7-yl N-methyl-carbamate were dissolved in 70 ml of methylene chloride and to the solution were added 5.2 g while cooling

(0.05 mol) of sulfur dichloride and then to the solution at -10 to -5 ° C was added dropwise 5 g (0.05 mol) of triethylamine. The mixture was stirred at 0 ^° C. for 1 hour and then at room temperature for a further 2 hours. After cooling to -10 to -5 ° C, 9 g (0.05 mol) of N-phenylglycine ethyl ester was added dropwise to the mixture and to the mixture was added 5 g (0.05 mol) of triethylamine. The mixture was stirred at ⁰ C for 2 h and then allowed to stand at room temperature overnight. After addition of 100 ml

Methylene chloride, the reaction mixture was washed three times with 100 ml of water. The methylene chloride layer was dried and concentrated in vacuo to give an oily product. A benzene / hexane mixture (1: 1) was added to the oily product, with

stalle-failed. The precipitated crystals were

filtered off and the mother liquor was concentrated to give an oily product, which was then cooled to give crystals. The crystals thus obtained were recrystallized from diethyl ether,

whereby 13.4 g (yield: 62.3%) of white crystals having a melting point of 92 to 93 ° C was obtained.

78 4 O

NMR in chloroform-d.j: ($ 1/15 ppm (t, 3H)

6 1.46 ppm (s, 6H)

0 3.00 ppm (s, 2H)

(S 3.32 ppm (s, 3H)

6 4.12 ppm (q, 2H)

0 4.76 ppm (s, 2H) 66.5-7.2 ppm (m, 8H)

Elemental ^analysis for ^C 22 ^H 26 ^N 2 ° 5 ^S ( ^molecular weight 430.53)

Calculated%: C 61 / 11 H 6 / 15 N 6 / 49 Found %: 61 , 38 6 / 09 6 / 51

The product thus had the following formula:

235784 O Examples 14 to 32

- 32 -

The compounds shown in Table 3 were prepared in the same manner as in Examples 12 or 13. The physical properties and NMR data (in chloroform-d ₁ ) of the compounds are also shown in Table 3.

Table 3

example

Amin

H-NMR.

Value (ppm) in CDCl ₃ /

Elemental analysis empirical formula found (%) (calculated {%) )

14

15

HN.

, CH ₂ COOC ₂ H ₅ 'CH ₃

-CH ₂ COOC ₂ H ₅

-CH ₃

HN

CH ₂ COOC ₂ H ₅ / CH ₃

CH

-CH ₂ COOC ₂ H ₅

-CH

CH ₃

.CH ₃ 'CH ₃

61,24 (t, 3H),

61.47 (s, 6H), 63.02 (s, 2H), 63.17 (s, 3H),

63.48 (s, 3H), 64.10 (s, 2H),

64.17 (q, 2H), 66.6-7.2 (m, 3H)

61,16 (d, 6H),

61.18 (t, 3H), 61.43 (s, 6H), 62.94 (s, 2H), 63.29 (s, 3H), 63.1-3.7 (m, IH), 64 _f OO (q, 2H), 64.02 (s, 2H), 66.5-7.0 (m, 3H)

C17H24N2O5S

55.61 (55.43)

6.45 (6.56)

C ₁₉ H ₂₈ N ₂ O ₅ S

7.83 (7.61)

57 _f 34 7,15 7,17 (57,56) (7,12) (7,07)

Continuation Table 3

example

Amin

R '

^ CH ₂ COOC ₂ H ₅ 16 HN-CH ₂ COOC ₂ H ₅

^ CH ₂ COOC ₂ Hs 17 HN-CH ₂ COOC ₂ H ₅

-Hl-C ₈ H ₁ 7

^ CH ₂ COOC ₂ H ₅ 18 HN-CH ₂ COOC ₂ H ₅

H-NMR

Value (ppm) in CDCl ₃ /

60 _t 8-1.8 (m, 8H), 61.22 (t, 3H), 61.45 (s, 6H), 62.97 (s, 2H), 62.9-3.3 (m, IH), 63.30 (s, 3H), 64.03 (s, 2H), 64.08 (q, 2H), 66.7-7.1 (m, 3H).

60.7-1.8 (m, 18H), 61.45 (s, 6H), 62.97 (s, 2H), 63.1-3.5 (m, 2H), 63.36 (s, 3H) , 64.01 (s, 2H),

64.07 (q, 2H), 66.6-7.2 (m, 3H)

60.7-2.4 (m, 14H), 61.43 (s, 6H), 62.93 (s, 2H), 63.32 (s, 3H), 64.06 (q, 211),

64.08 (s, 2H), 66 _f 6-7.2 (m, 3H)

Elemental analysis empirical formula found (%) "(calculated (%))

C ₂₀ H ₃₀ N ₂ O ₅ S

58.55 7.25 6.91

(58,52) (7,37) (6,83)

C ₂ I ₁ H ₃₈ N ₂ O ₅ S

61.53 8 _f ll (61.78) (8.21)

6.24 (6.00)

C ₂₂ H ₃₂ N ₂ O ₅ S

60.95 7.42 6.51

(60,53) (7,39) (6,42)

Continuation Table 3

example

Amin

R ¹

^ CH ₂ COOC ₂ H ₅ 19 HN-CH ₂ COOC ₂ H ₅

/ CH ₂ COOC ₂ H ₅ 20 HN-CH ₂ COOC ₂ H ₅

/ CH ₂ COOC ₂ H ₅ 21 HN-CH ₂ COOC ₂ H ₅

CH ₃

Elementary analysis empirical formula

H-NMR (T, 3H) > C found ⁽ %) 5, 63 (S, 6H) (calculated ( ^: %)) (5, 30) fö value (ppm) (S, 2H) H N in CDC1 ₃ _7 (S, 3H) 8H) 62 C ₂₃ H ₂₈ N ₂ O ₅ S 61, (S, 2H) (62 61 (Q, 2H) » , 04 6,39 ⁶ r 62 (S, 2H) , 15) (6,35) (6 _r 63 > (M, 63 (T, 3H) 69 64 (S, 6H) » 6 , 85) 64 (S, 2H) (6, 66 (S, 3H) 3H), 58 C ₂₃ H ^ N ₂ O ₅ CJtS 61 (S, 2H) 4H) (57 £ 61 (Q, 2H) , 01 5,54 63 (S, 2H) , 67) (5,68) 63 ', 2 gn, 63 f, 5 (in, 64 (T, 3H) » .19 64 (S, 6H) _r 30) 66 (S, 3H) 67 (S, 2H) 7H) 61 C ₂₃ H ₂₈ N ₂ O ₅ S 61 (S, 3H) (62 61 (Q, 2H) , 84 6,42 62 (S, 2H) , 15) (6 _f 35) 63 .7-7,5 (M, 63 64 64 66 _t 22 40 1 ⁹⁷ 24 , 82 , 11 t ¹⁵ , 5-7 25 , 42 , 04 ⁴² , 92 , 21 , 23 »7-i , 2- 17 48 _t 35 , 05 40 , 18 80

Continued table

example

22

23

24

Amin

/ CH ₂ COOC ₂ H ₅ HN-CH ₂ COOC ₂ H ₅

(/ \ VOCH3

CH ₂ CH ₂ COOC ₂ H ₅

HN _Na -CH ₂ CH ₂ COOC ₂ H ₅

/ ^CH3 CH

CH ₃

HN

/ CH ₂ CH ₂ COOCH ₃

-CH ₂ CH ₂ COOCH ₃

CH ₃

^ CH ₃ -CH CH ₃ -CH CH ₃ H-NMR 3H), Elemental analysis found (% ) K) 6H), empirical formula. (calculated(% ) CaJ 2H), H N. CTS 2 3H), C23H28N2O6S "^ R ^ 3H), C GO 2H), , 31 6,22 6.11 - // M-OCH ₃ 2H), 99) (6,13) (6.08) \ / / / CH ₃ . £ S value (ppm) (m, 7H) 60 in CDC1 ₃ _7 3H), (59, "I, 6H), 61 6H), 63 2H), C ₂₀ H ₃₀ N ₂ O ₅ S I 63 2H), U) σ \ 63 3H), , 43 7.29 6.65 I 64 (m, 3H), , 52) (7,37) (6.83) 63 2H), 58 66 (m, 3H) (58, 61 6H), 61 6H), 61 2H), 62 2H), Ci9H ₂₈ N ₂ O ₅ S 63 (m, 3H), 63 3H), , 01 7,32 7 * 11 63 3H), , 56) (7 _f 12) (7.07) 64 (m, 3H) 58 66 (57 61 61 62 62 63 63 63 66 _f 15 48 , 02 , 31 , 76 t ¹⁷ _c 70 t ⁷ " ⁷ 121 , 23 I ⁴⁷ , 78 , 04 40 , 2-3 .12 , 6-7 , 18 , 43 , 68 99 , 0-3 ., 31 , 51 , 5-7 (T, (S, (S, (S, (S, (Q, (S, « ⁴ (T, (D, (S, (T, (S, (S, ⁸ (Q, 2 (D, (S, (T, (S, f (S, (B,

Continuation Table 3

In, play

Amin

H-NMR.

Value (ppm) in CDC1 ₃ _7

Elemental analysis

empirical formula found (%) (calculated (%))

25

HN

CH2CH2COOC4H9

-CH2CH2COOC4H9

, CH ₃ ^S CH ₃

CH ₃

HN

CH ₂ CH ₂ COO Vv / ^

-CH ₂ CH ₂ COO

CH

CH ₂ CH ₂ COOC ₂ H ₅

HN-CH ₂ CH ₂ COOC ₂ H ₅ -11-C4H9

^ n-Ci ₁ Hg

From 60.6 to 1.8 (m, 7H), 61.17 (d, 6H), 61.42 (s, 6H), 62 _t 65 (t, 2H);

62.94 (s, 2H), 63.31 (s, 3H), 63.0-3.6 (m, 3H), 63.7-4.1 (m, 2H), 66.5-7.0 (m, 3H)

60.6-1.8 (m, 15H), 61.16 (d, 6H), 61.42 (s, 6H), 62.68 (t, 2H), 62.98 (s, 2H), 63 , 0-3.6 (m, 3H), 63.33 (s, 3H), 63.6-4.1 (τη, 2Η), 66.5-7.0 (m, 3H)

60.7-1.8 (m, 10H), 61.41 (s, 6H), 62.4-2.8 (m, 2H),

62.95 (s, 2H), 63 _{ 33 (s, 3H), 63.1-3.4 (m, 4H), 63.97 (q, 2H), 66.6-7 _t 2 (m, 3H)

60.48 7.69 (60.25) (7.82)

63 _f 45 8.62 (63 _t 13) (8,56)

6,13 (6,39)

5.49 (5.66)

C ₂ 1Η3 ₂ N ₂ O ₅ S

59.01 7.38 6 _t 79

(59,42) (7,60) (6,60)

Continued table

example

Amin

'R ¹

^ .CH ₂ CH ₂ COOCH ₃ 28 HN-CH ₂ CH ₂ COOCH ₃

-U-Ci ₁ Hg

CH ₂ CH ₂ COOC ₂ Hs 29 HN-CH ₂ CH ₂ COOC ₂ H ₅

sec- CjjHg

.CH ₂ CH ₂ COOC ₂ H ₅

ISO-Ci ₁ Hg

-CH ₂ CH ₂ COOC ₂ H ₅ -IsO-Ci ₁ Hg

, 0 (m, 7H), empirical formula ' found ( %) " • 6.53 CO H-NMR (S. 6H), (calculated( %)) (6.60) cn (T, 2H), H N. (S, 2H), C C20H30N2O5S - ^ , 7 (m, 4H), ^> (S, 3H), , 79 7,14 6.66 // $ value (ppm) (S, 3H), 58 _f 52) (7,37) (6.83) in CDCl3_ / r ° (in, 3H) (58 CD 60.6-2 ,8th (m, 11H), 6.63 61.45 (S, 6H), (6.60) 62.66 (T, 2HJ, 62.97 (S, 2H), C21H32N2O5S I 62.9-3 , 7 (m, 3H), to (» 63.35 (S, 3H), , 62 7.71 I 63.54 (Q. 211) 59 , 42) (7 _f 60) 66.5-7 , 0 (m, 3H) (59 60.6 to 1 (D, 6H), 61.42 (T, 3H), 62.66 (S, 6H), 62.96 2 (m, IH), C ₂₁ H ₃₂ N ₂ OsS 63.0-3 (T, 2H), 63.31 (S, 2H), _r 71 7.54 63,95 , 6 (m, 4H), 59 , 42) (7,60) 66.6-7 (S, 3H), (59 60.84 (Q. 2H), 61.18 ti (m, 3H) 61.42 61.6-2 62.70 62.97 63.1-3 63.37 64.04 66.5-7

Continuation Table 3

example

Amin

 : v

H-NMR

Value (ppm) in CDCl ₃ /

Elemental analysis empirical formula found (%) (calculated (%)) CHN

XH ₂ CH ₂ COOC ₂ H ₅ 31 HN-CH ₂ CH ₂ COOC ₂ H ₅

^ nC ₆ H ₁₃

-11-C ₆ H ₁ 3

/ CH ₂ CH ₂ COOC ₂ H ₅ 32 - HN-CH ₂ CH ₂ COOC ₂ Hs

60 _t 7-2.0 (m, 14H), 61.46 (s, 6H),

62.63 (t, 2H), 62.98 (s, 2H), 62.9-3.6 (m, 4H), 63.35 (s, 3H), 63.97 (q, 2H), 66, 5-7.0 (m, 3H)

60.9-2.0 (m, 10H), 61.17 (t, 3H), 61.43 (s, 6H),

62.64 (t, 2H),

62.94 (s, 2H), 63.0-3.6 (m, 3H), 62.97 (s, 3H),

63.95 (q, 2H), 66.5-7.1 (m, 3H)

C ₂₃ H ₃₆ N ₂ O ₅ S

60.85 8.11 (61 _t 04) (8.02)

61.59 (61 _f 31)

7.49 (7.61)

6.32 (6,19)

6.09 (6.22)

235784 "O

Example 33

Preparation von_2 33DihYdro _{i-2 i-2} dimethYlben2ofuran-7-γ1_Ν- (N-tertbutyl-N CYanomethYlaminosulfenYl ^ -N-methylcarbamate

11 g (0/05 mol) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate were dissolved in 70 ml of methylene chloride and to it were added 5.2 g (0.05 mol) of sulfur dichloride while cooling and dropwise at -10 to -5 ⁰ C 5 g (0.05 mol) of triethylamine. The mixture was stirred at 0 ^° C. for an hour and then at room temperature for a further 2 hours. After cooling to -10 to -5 ⁰ C, 5.6 g (0.05 mol) of N-Butylaminoacetonitril was added dropwise to the mixture and continue to 5g (0.05 mol ·) of triethylamine likewise dropwise. The mixture was stirred for 2 hours at 0 ⁰ C and then allowed to stand overnight at room temperature. After adding 100 ml of methylene chloride, the reaction mixture was washed three times with 100 ml of water. The methylene chloride layer was dried and evaporated in vacuo to give an oily product which consisted almost completely of the desired product besides small amounts of impurities. Yield: 13.0 g (71.4%)

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

2-3 5 7 8.4 O

NMR in chloroform-d ₁ : £ 0.1-2.0 ppm (m, 7H)

61/42 ppm (s, 6H) S 2.92 ppm (s, 2H) 02.9-3.5 ppm (m, 2H) 03.33 ppm (s, 3H) 64.01 ppm (s, 2H) 6 6.5-7.1 ppm (m, 3H)

Elemental analysis for C 1 H ₂₅ N ₃ O ₃ S (molecular weight 363,488)

Calculated%: C 59 19 H 7 , 02 N 11 / 69 Found %: 59 / 48 6 / 92 11 , 56

The product thus had the formula:

o-c-n:

.CH.

'S-N.

CH ₂ CN

o CH ^ CH ~

235784 O

Examples 34 to 43

- 4-2 -

The compounds in Table 4 were prepared as in Example 33. The physical data and the NMR data (in chloroform) of the compounds are also shown in Table 4.

  Table '4

example

Amin

, CH ₂ CN

HN

-CH ₂ CN

-CH

CH

-CH ₃ ^ CH ₃

CH ₃

, CH ₂ CN HN '

-CH ₂ CN

36

H/

CH ₂ CN

-CH ₂ CN

CH ₃

H-NMR.

Value (ppm) in CDCl ₃ /

61,28 (d, 6H),

61.42 (s, 6H), 63.00 (s, 2H),

63.43 (s, 311), 64.34 (s, 2H), 63.3-4.1 (m, IH), 66.5-7.2 (in, 3H)

61.44 (s, 6H), 62.98 (s, 2H), 63.41 (s, 3H), 64.76 (s, 2H), 66.5-7.7 (m, '8H)

61.47 (s

62.33 (s

63 _f 00 (s

63.39 (s

64.80 (s

6H), 3H), 2H), 3H), 2H),

66.5-7.5 (ro, 7H)

Elemental analysis empirical formula found (%) (calculated (%))

58 _t 23 6.59 12.21 (58.44) (6.64) (12.03)

C ₂₀ H ₂₁ N ₃ O ₃ S

62.11 (62.65)

5.48 (5.52)

11.02 (10.96)

C ₂₁ H ₂₃ N ₃ O ₃ S

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

Continuation Table 4

example

37

Amin

HN

^ CH ₂ CH ₂ CN

-CH ₂ CH ₂ CN

-CH ₃

, CH ₂ CH ₂ CN 38 HIf "" - CH ₂ CH ₂ CN

-CH

/ CH ₃

CH ₃

CH ₃

CH ₂ CH ₂ CN 39 HN ^. -CH ₂ CH ₂ CN

Elementary analysis empirical formula

H-NMR , 46 (Β, 6H) » C found ( %) N. 74 , 5-2 , 9 (M, 2H), (calculated (%)) 53) 00 (S, 2H) H ^ <Γ value (ppm) 17 (A. 3H) > 57 C ₁₆ H ₂₁ N ₃ O ₃ S 12 in CDCl3 J , 0-3 , 5 (M, 2H), (57, (12, 61 ; 46 (S, 311) » 59 6,17 62 , 5-7 ,1 (in, 3H) 30) (6,31) 63 , 21 (D, 6H) > 64 63 , 43 (S, 6H) » 56) 63 72 (T, 2H) t 63 00 (S, 2H) » 59, CieH ₂ 5N ₃ O ₃ S Hf 66 , 0-3 ⁸ (in, 3H), (59, (11, 61 , 32 (S, 3H) I 32 6,87 61 , 6-7 2 (M, 3H) 49) (6 _t 93) 62 63 63 63 66

60 _f 7-2.0 (in, 7H), 61.44 (s, 6H), 62.5-2.9 (m, 2H), 62.98 (a, 2H), 62.9-3, 5 (m, 4H), .63.37 (s, 3H), 66.5-7.0 (ro, 3H)

60 _t 64 7.41 (60.46) (7.21) (11.13)

11.25

Continuation Table 4

example

No..

Amin

41 HN

CH ₂ CH ₂ CN UC ₈ Hj7

CH ₂ CH ₂ CN

42 HN

^ CH ₂ CH ₂ CN HN-CH ₂ CH ₂ CN

iso-CijHg

-CH ₂ CH ₂ CN

-UC ₈ H ₁₇

-CH ₂ CH ₂ CN

H-NMR

Value (ppm) in CDCl ₃ /

60.90 (d, 6H), 61.43 (s, 6H), 61.7-2.2 (m, IH), 62.69 (t, 2H), 62.96 (s, 2H), 63.0 -3.5 (m, 4H), 63.33 (s, 3H), 66.5-7.0 (m, 3H)

60.7-2.0 (m, 15H), 61.47 (s, 6H), 62.6-2.9 (τη, 2Η), 63.01 (s, 2H), 63.0-3, 5 (m, 4H), 63.40 (s, 3H), 66.5-7.0 (m, 3H)

60.7-2.0 (m, 10H), 61.46 (s, 6H), 62.5-2.9 (m, 2H), 62.98 (s, 2H), 63.0-3, 5 (m, 2H), 63.32 (s, 3H), 63.9-4.3 (m, IH), 66.5-7.1 (m, 3H)

Elemental analysis

empirical formula found (%) (calculated (%)) CHN

^C 19 ^H 27 ^N 3 ° 3 ^S

60,25 7,39 11,01 (60,46) (7,21) (11,13)

C23H35N3O3S ·· - ;.

63.59 8.31 9.54

(63,72) (8,14) (9,69)

62,33 7,42 10,85 (62,51) (7,25) (10,42)

35 78 4 O

Example 43

N-methy_l carbamate

11 g (0.05 mol) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate were dissolved in 70 ml of methylene chloride and thereto were added, while cooling, 5.2 g (0.05 mol).

Sulfur dichloride and further dropwise 5 g (0.05 mol) of triethylamine at -10 to -5 ⁰ C. The mixture was stirred for 1 hour at 0 ⁰ C and two more hours at room temperature. After cooling to -10 to -5 ° C, a solution of 8 g (0.05 mol) of N-propionylglycine in 10 ml of tetrahydrofuran was added dropwise, and also dropwise 5g (0.05 mol) of triethylamine. The mixture was stirred for 2 hours at 0 ⁰ C and then allowed to stand overnight at room temperature. After addition of 100 ml of methylene chloride

The reaction mixture was washed three times with 100 ml of water. The methylene chloride layer was dried and concentrated in vacuo to give an oily product almost completely from the desired product besides small amounts of the starting material

and impurities existed. Yield: 14.3 g (69.8%).

To identify the product, a part thereof was purified by silica gel column chromatography using benzene / ethyl acetate (9: 1) as a solvent to obtain crystals having a melting point of 108 to 109 ^° C.

2 35 7

NMR in chloroform d: 61.14 ppm (t, 3H)

01.23 ppm (t, 3H) ί 1.49 ppm (s, 6H) 02.7-3.3 ppm (m, 2H) 6 3.02 ppm (s, 2H) (S 3.48 ppm (s , 3H) 4.15 ppm (g, 2H) ci.50 ppm (s, 2H) 06.6-7.1 ppm (m, 3H)

Elemental analysis for

(Molecular weight 410,499)

Calculated%: C 55, 35 H 6 , 41 N 6 / 77 Found %: 55, 59 6 , 38 6 , 82

The product thus had the following formula:

CH

O-C-N.

.CH ₃

s-s:

'COCH ₂ CH ₃

35 78 4 O

Example 4 4

- 43 -

N- (N-ethoxvcarbonYl-N-ethoxYcarbonYlmethvlaminosul-

11 g (0.05 mol) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-diethyl-carbamate were dissolved in 70 ml of methylene chloride and 5.2 g (0.05 mol) of sulfur dichloride were added to the solution With cooling, and then added at -10 to -5 ⁰ C 5 g (0.05 mol) of triethylamine added dropwise. The mixture was stirred at 0 ^° C. for 1 hour and at room temperature for 2 more hours. After cooling to -10 to -5 ⁰ C, 8.8 g (0.05 mol N-Ethoxycarbonylglycinethylester were dropwise added to the mixture, and also added dropwise 5 g (0.05 mol) of triethylamine. The mixture was for 2 hours at 0 ⁰ After addition of 100 ml of methylene chloride, the reaction mixture was washed three times with 100 ml of water The methylene chloride layer was dried and concentrated in vacuo to give an oily product which was almost completely from the desired Product but with minor amounts of impurities and starting material Yield: 18.2 g (84.7%).

For identification, a part thereof was purified by silica gel column chromatography using benzene. Ethyl acetate (4: 1) was purified as a solvent to give an oily product.

78 4

NMR in chloroform-d

£ 1.17 ppm (t, 6H)

6i , 44 ppm (s, 6H)

£ 2.94 ppm (s, 2H)

£ 3.41 ppm (s, 3H)

6 4.05 ppm (q, 2H)

£ 4.15 ppm (q, 2H)

6 4.41 ppm (s, 2H)

6 6.5-7.0 ppm (m, 3H)

Elemental analysis for C.

(Molecular weight 426,499)

Calculated%: C 53 82 H 6 19 N 6 44 Found %: 53 51 6 , 14 6 67

The product thus had the following formula:

o-c-n;

.CH ₃

? S n;

.CH ₂ COOC ₂ H ₅ 'COOC ₂ H ₅ ,

35 7 8 Λ Ο

Examples 45 to 52

- 50 -

The compounds in Table 5 were obtained as in Examples 43 or 44. The physical properties and NMR data (in chloroform-d-) of these compounds are also shown in Table 5.

• Table 5

example

Amine H NMR.

(1> value (ppm) in CDClO / ·

Elemental analysis empirical formula found (%) (calculated (%))

45

HN

46

, CH ₂ COOC ₂ H ₅ TOCH ₂ CA,

-CH ₂ COOC ₂ H ₅

-COCH ₂ Ci,

CH ₂ COOC ₂ H ₅

-CH ₂ COOC ₂ H ₅

CO

61,21 (t, 3H),

61.46 (s, 6H),

62.98 (s, 2H),

63.40 (s, 3H),

64.05 (q, 2H), 64.36 (s, 2H), 64.67 (s, 2H), 65.6-7 ^ 0 (m, 3H)

61.18 (t, 3H),

61.41 (s, 6H), 62 ', 87 (s, 3H), 62.91 (s, 2H),

64.06 (q, 2H), 64.60 (s, 2H), 66.5-7.0 (m, 3H), 67.1-7.7 (m, 5H)

C ₁₈ H ₂₃ N ₂ O ₆ C) IS

49.98 5.17 6.43

(50,17) (5 _; 38) (6,50)

C23H26N2O6S

60.54 (60.25)

5.61 (5.72)

6.02 (6.11)

Continuation Table 5

example

Amin

R ¹

, CH ₂ COOC ₂ H ₅ HN ^ -CH ₂ COOC ₂ H ₅

CO

, CH ₂ COOC ₂ H ₅

HN

-CH ₂ COOC ₂ H ₅

SO ₂ - // ^ V-CH ₃

^ CH ₂ COOC ₂ H ₅

HN-CH ₂ COOC ₂ H ₅

^ COOCH ₃

-COOCHi

H-NMR

Value (ppm) in CDCl ₃ /

61.21 (t, 3H), 61.46 (s, 6H), 62.93 (s, 3H),

62.95 (s, 2H), 64.07 (q, 2H), 64.56 (a, 2H), 66.5-7.0 (m, 3H), 67.1-7.6 (m, 4H)

61.18 (t, 3H), 61.46 (s, 6H), 62.37 (a, 3H),

62.96 (s, 2H), 63.48 (a, 3H), 64.02 (q, 2H), 64.58 ( _S , 2H), 66.5-7.9 (m, 7H)

61.19 Ct, 3H), 61.46 (s, 6H),

62.97 (a, 2H), 63.43 (s, 3H), 63.74 (s, 3H), 64.07 (q, 2H), 64.42 (s, 2H), 66.5-7.1 (m, 3H)

Elemental analysis empirical formula found (%) (calculated (%))

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

C ₂₃ H ₂₈ N ₂ O ₇ S ₂

54.04 5.57 5.24 (54.31) (5 _; 55) (5.51)

C ₁₈ H ₂₄ N ₂ O ₇ S

52.15 5.64 6.66

(52,42) (5,87) (6,79)

Continued table

example

51

Amin

, CH ₂ COOC ₂ H ₅

HN

-CH ₂ COOC ₂ H ₅

.CH ₂ CH ₂ CN COOC ₂ H ₅

-CH ₂ CH ₂ CN

-COOC ₂ H ₅

XH ₂ CH ₂ COOC ₂ H ₅

HN-CH ₂ CH ₂ COOC ₂ H ₅

^ COOC ₂ H ₅

-COOC ₂ H ₅

19 (T, 3H), Elemental analysis found ( Q- "O / , 78 , 44 (S, 6H), (Calculated ^ "O / / 90) 95 (S, 2H), empirical formula · H N 50 (S, 3H), ^C 23 ^H 26 ^N 2 ° 7 ^S H-NMP , 05 2H), , 52 (S! 211) C , 97 5.61 5, , 5-7 > v (m, 8H) , 22) (5,52) I 30 (T, 3H), , 31 ^ cT value (τ , 46 (S, 6H), 57 _r 68) , 63 (T, 2H), (58 J ⁹⁷ (S, 2H), C ₁₈ H ₂₃ N ₃ O ₅ S 40 (S, 3H), dpm) 95 (T, 2H), , 16 5.93 10 in CDC1 ₃ _7 16 (Q, 2H), _; 95) (5,89) ι (10, 61, , 5-7 (m, 3H) 61 I ¹⁷ (T, 311) 55 , 51 62 , 32 (T, 3H), (54 , 36) 63 , 46 (S, 6H), ' 64 J ⁵⁷ (T, 2H), ^C 20 ^H 28 ^N 2 ° 7 ^S 64 (S, 2H), 66 40 (S, 311) , 33 6.29 6 61 , 7-4 , 4 (m, 6H), , 54) (6,41) (6 61 , 5-7 Ί ° (m, 3H) 62 54 62 (54 63 63 64 66 61 61 61 62 62 63 63 66

2 3578 A O

In the following, preparation examples are shown. These formulations are applicable to all compounds of the invention and a suitable formulation is applicable to a particular application. The formulations are shown for purposes of description only and the proportions of active ingredients, organic solvents, surfactants and carriers can be varied as desired. In some cases, the kinds of the organic solvent, the surfactant, the carrier, etc., may also be changed. The percentages are all by weight.

Preparation Example 1

Compound of Example 25 60.0%

Polyoxyethylene nonylphenyl ether 10.0%

Xylene - 30.0%

Preparation Example 2

Compound of Example 12 50.0%

Polyoxyethylene sorbitol monooleate 6.5%

Sorbitol monooleate 3.5%

Xylene. 30.0%

Cyclohexanone 10.0%

· 3 5 7 8 L Π

Preparation Example 3

20% emulsion

Compound of Example 22 20.0%

Polyoxyethylene alkyl ether 5.0%

Xylene 45.0%

Petroleum ether 30.0%

In all of the above-mentioned Preparation Examples 1 to 3, the ingredients are thoroughly mixed to obtain the desired emulsion.

Exemplary preparation 4

90 _% - i2es_anfeuchtbares_Pulver

Compound of Example 1 90.0%

20 sodium lignosulfonate 3.0%

Volume . 7.0%

Formulation Example 5 50% - xaes_enfeuchtbares powder

Compound of Example 21 50.0%

Alkyl sulfate 30.0%

Condensate of naphthalenesulfonic acid

and formaldehyde. 10.0%

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Alkyl phosphate. 5.5%

Kaolin 3.5%

Talc 1.0%

Preparation Example 6

30 _% - i2es_anfeuchtbares_Pulver

Compound of Example 30 30.0%

Alkylbenzenesulfonate · 3.0%

Sodium lignosulfonate 2.0%

white carbon 15.0%

Sound 50.0%

In each of Preparation Examples 4 to 6, the ingredients were thoroughly mixed using a Shinagawa type mixer. The mixture was then pulverized in a ball mill or the like to obtain a wettable powder.

25 Preparation Example 7

Compound of Example 46 5.0%

Diatomaceous earth 10.0%

Talc 85.0 ..%

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- .57-

Preparation Example 8

wettable powder from preparation example 5 4.0% clay 95.8% isopropyl phosphate 0.2%

Preparation Example 9

moistenable powder from preparation

Example 6 1.7%

Sound 100.3%

In Preparation Examples 7 to 9, the ingredients were thoroughly mixed using a Shinagawa type mixer to obtain the desired dust.

Preparation Example 1 0

wettable powder of preparation example 5 40.0 dolomite. '60.0

35 78 4 O

These ingredients were uniformly mixed, and to the mixture, in an amount of 15 parts by weight per 100 parts by weight of the mixture, a 2% aqueous solution of carboxymethyl cellulose was added, and the mixture was thoroughly kneaded. The mixture was then granulated in a granulator and the granules were crushed to obtain the desired granules.

Preparation Example 11

Compound of Example 40 10.0%

Sodium dodecylbenzenesulfonate 0/5%

Sodium lignosulfonate 2%

.Diatome earth 27/5%

Bentonite 60 _# 0%

These ingredients were thoroughly mixed and water was added to the mixture. The resulting mixture was thoroughly kneaded and then granulated using a granulator. The granulated product thus obtained was crushed and dried to obtain the desired granules.

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Preparation Example 12

3 _% - i2es_Granulat

Compound of Example 8. 3.0%

Polyvinyl alcohol '3.0%

Sound 94.0%

The procedure of Preparation Example 11 was repeated under **> to obtain the desired granule

 10

In the following, experimental examples are shown.

Experimental Example 1

Ten-third instar larvae of the tobacco cutting worm ( Spodoptera litura ) were placed on a herb (one-month-old plants) in a pot and a 50% emulsion of the compound to be tested was in each concentration indicated applied the leaves of the plant with complete moistening of the same. The test compound was in the indicated concentrations in each case in two

Töpfenausprobiert. Three days later, the larvae were examined for mortality with the result shown in Table 6. Table 6 also shows the results obtained for comparison with an untreated group.

2.3578 4 O

Table 6

Test compound Mortality (%)

(Example No.) ~ ~ ~~. \ '.

Concentration of active ingredient (ppm) 2 »000 1.000 500

1 100 80 65 2 100 70 60 3 100 80 65 4 100 70 60 5 100 80 65 6 100 75 60 7 100 75 60 8th 100 80 75 9 100 90 80 10 100 85 75 11 100 80 70 12 100 90 75 13 100 90 75 14 100 90 75 15 100 90 75 16 100 85 65 17 100 80 60 18 100 90 75 19 100 85 65 20 100 85 65 21 100 90 75

235 78 4 O - »-

Continuation Table 6

Test compound mortality

(Example No.) Concentration. , , Part 2,000 1,000 85 active inventory (ppm) 500 22 100 85 65 23 100 85 70 24 · 100 90 75 25 100 80 75 26 100 90 60 27 100 90 75 28 100 80 75 29 100 85 60 30 100 80 65 31 100 80 60 32 100 90 ⁶⁵ 33 100 90 75 34 100 80 75 35 100 80 65 36 100 85 65 37 100 90 70 38 100 90 75 39 100 85 75 40 100 80 " 75 41 100 85 65 42 100 85 70 43 100 70

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Continuation Table 6

test compound Sterblii 90 quality (%; (Example No.) Concentration of part 2,000 1,000 90 active stock (ppra) 500 44 100 85 75 45 100 80 75 46 100 80 70 47 100 90 65 48 100 80 65 49 100 - 85. 75 50 100 85 65 51 100 60 70 52 100 O 70 Control* 80 35 untreated

i-Naphthyl-N-methyl-carbamate was used as a control.

2-35 7

- 63 -

Experimental Example 2 .

An emulsion of each concentration was prepared from a 50% wettable powder of the compound to be tested and applied to the leaves of 1-month-old paddy rice seedlings planted in a pot with complete humidification of the leaves. After drying the emulsion, the pot was covered with a reticulated cage into which 10 female, adult green rice leafhopper ( Nephotettix cincticeps ) were added. The compound to be tested in each case at a specific concentration was tried on two pots. Three days later, the mortality of the insects was determined and the results are shown in Table 7, which also shows the results for a control group and for an untreated group.

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Table 7

Test compound Mortality (%)

(Example No.) Concentration of active ingredient (ppm)

1 2 3 4 S 6 7 8 9

10 11 12 13 14 15 16 17 18 19 20 21

2000 1, 000 500 100 85 50 100 85 45 100 85 45 100 70 40 100 80 ' 45 95 75 55 90 70 50 95 85 60 100 90 60 100 90 60 95 80 55 100 90 65 100 90 65 100 90 65 100 90 65 100 90 65 95 75 55 100 90 65 100 80 60 100 80 60 100 90 65

2 3578 Λ Ο

Continuation Table 7

Test compound mortality

(Example No.) Concentration of part 2,000 1,000 80 active inventory (ppm) 500 22 100 85 60 23 100 90 55 24 100 .90 60 25 100 75 65 26 100 90 55 27 100 90 65 28 100 75 65 29 100 80 45 30 100 75 60 31 100 75 55 32 100 90 55 33 100 90 70 34 100 75 65 35 , 95 75 60 36 95 85 60 37 100 90 65 38 100 90 70 39 100 85 70 40 100 75 .70 41 95 85 60 42 100 65

78 4 Continuation Table

Test compound (Example No.)

Mortality (%)

Concentration of active ingredient (ppm) 2,000 1,000 500

43 100 85 60 44 100 90 70 45 100 90 65 46 100 90 65 47 95 75. 60 48 95 75 60 49 100 90 ' 70 50 95 75 60 si 100 85 65 52 100 85 65 Control* O O O untreated O

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

235 78 4 O

Experimental Example 3

- 67 -

Granules containing 10% of the compound to be tested were specifically mixed with soil contaminated with larvae of southern root-knot nematodes ( Meloidogyne incognita ) and tomato seedlings were immediately planted in this soil. One month later, the roots of the plants were examined for nodule formation. Two test areas of 2 χ 2 m ² each were used for the compound used in a certain amount. The degree of knot formation was evaluated according to the criteria given below and the results are shown in Table 8. For comparison, Table 8 also includes the results obtained on a control area and the results obtained on an untreated area.

Degree of sound formation j: 20

0: 0% to 25 1: to to' 50 2: to to 75 3: to

4: up to 100%

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Table 8

Test compound Degree of knot formation (Example No.) _Quantity of applied granules

(kg / 10 ares)

100 50 20

1 2 3 4 5 6 7 8 9.

10 11 12

0 1 2 0 2 3 0 2 3 0 2 3 0 2 3 1 2 3 1 3 3 1 1 2 0 1 . 2 0 1 2 1 2 3 0 1 2

2357

Continuation Table 8

Test compound Degree of knot formation (Example No.) Quantity of applied granules

(10 kg / Ar)

100 50 20

13 0 1 2 14 0 1 2 15 0 1 2 16 O 1 3 17 0 1 3 18 0 1 2 19 0 1 2 20 0 1 3 21 0 1 2 22 0 1 3 23 0 1 2 24 0 0 1 25 0 1 * 2 26 0 1 2 27 0 1 2 28 0 0 1 29 0 1 2 30 0 1 2 31 0 2 3 32 0 2 3 33 0 0 .1

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-7G-

Continuation Table 8

Test compound Degree of knot formation (Example No.) Quantity of applied granules

(10 kg / Ar)

100 50 20

35 0 1 3 36 0 1 3 37 0 1 2 38 0 0 1 39 0 0 1 40 0 1 1 41 0 i 3 42 0 1 ·· "2 43 0 1 44 0 0 1 45: ο 1 2 46 ο 1 2 47 0 1 3 48 0 1 3 49 0 0 1 50 0 1 3 51 0 1 2 52 0 1 2 Control* 2 4 4 untreated 4

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

2357 8 4 0

Experimental Example 4

- 71-

The compounds to be tested were dissolved in a predetermined amount in acetone. The solution was diluted to various concentrations and applied locally to house flies ( Musca domestica ). Table 9 shows the LD ₅ ,, values determined by the 24-hour mortality probit method.

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Table 9

Test Compound ^ ^d 5q (Example No.) (Mg / kg)

1 21.3 2 58.8 3 40.0 4 28.9 5 75.6 6 38.3 7 54.0 δ 24.6 9 31 ·, 7. 10 46.0 11 93.9 12 16.7 13 12.5 14 9.9 15 33.0 16 44.4 17 42.3 18 32.5 19 22.2 20 61.9 21 10.4 22   , 45.2

23 5?

O -

73. -

Continuation Table 9

Test compound (Example No.) LD ₅₀ (yig / kg) 23 44 y 3 24 38.6 25 50jl 26 64j.7 27 13.8 28 17.7 29 22.5 30 23.8 31 33.1 32 32.7 33 34 16.7 35 65.6 36 59.3 37 11.8 38 17.5 39 13.7 40 37.9 41 · 54 j6 42 .46,0 43 14.4

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Continuation Table 9

Test compound (Example No.) LD ₅₀ (yug / kg) 44 16.2 45 29.2 46 33 y 2 47 57 _V 8 48 58 ^ 6 49 15.7 50 34.7 51 45.3 52 54.3 Control*" 22.5

2-1sopropoxypheny1-N-methyl-carbamate was used as a control.

235 78 4 0

Experimental Example 5

- 75-

The compounds of the invention were tested in male mice for acute toxicity by oral administration. Table 10 shows the LD j- _Q values calculated from the 7th day mortality by the Litchfield-Wilcoxon method.

235 78 4 O

Table 10

Test compound (Example No.) (Mg / kg) 1 58 2 140 3 • 145 4 122 5 90 6 135 7 75 8th 105 9 158 10 115 11 93 12 125 13 115 14 120 15 110 16 110 17 69 "18 ·. 135 19 108 20 75 21 105. 22 88

35 78 4 O

Continuation Table 10

Test compound (Example No.) LD5O (mg / kg) 23 113 24 77 25 123 26 150 27 1os 28 89 29 120 30 133 31 135 32 107 33 103 34 95 35 95 36 70 37 65 38 125 39 110 40 103 41 105 42 88 43 43

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Continuation Table 10

Test compound (Example No.) LE> 50 (mg / kg) 44 128 45 80 46 105 47 95 48 80 49 105 50 95 51 88 52 125 Control* .... 5 _r 6

♦ 2,3-Dihydro-2,2-dimethyl-7-benzofuran-7-yl N-methylcarbamate was used as a control

Claims (2)

1. Insecticidal antimicrobial and nematocidal composition containing carbamate derivatives, characterized in that they contain an effective amount of at least one compound of the general formula (I) in which mean: 12 R and R, which are the same or different, are each (1) -X-COOR, wherein X is an alkylene group having 1 to 6 carbon atoms and R is an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms; or (2j - "'Y-CN ¹ V wherein -Y represents an alkylene group having 1 to 6 carbon atoms; Γ 'τη 0 j' f \ - 30 OIL / lJ 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 phenyl group having 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 wherein Z is a carbonyl group or 4 represents a sulfonyl group and R contains 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, and a suitable adjuvant. , 2. A method for controlling harmful insects, mites or nematodes, characterized in that applying an effective amount of the composition according to _: Item 1.