CS237330B2 - Processing of aminosulphenylchloride derivatives - Google Patents

Abstract

NEW MATERIAL:The compound of formulaI[R1 and R2 are -X-COOR3 or -Y-CN (X and Y are 1-6C alkylene; R3 is 1-8C alkyl; excluding the case that both X and Y are methylene); when one of R1 and R2 is -X-COOR3 or -Y-CN, the other may be 1-8C alkyl, benzyl, etc.]. EXAMPLE:N-Acetyl-N-ethoxycarbonylmethylaminesulfenyl chloride. USE:The compound has high reactivity, reacts easily with various groups such as -NH2, -SH, etc., and is useful as an intermediate raw material for various reactions. PROCESS:The compound of formulaIcan be prepared by reacting the amine derivative of formula II with S2Cl2 or SCl2 in the absence of solvent or in a proper solvent, in the presence of a basic compound (e.g. triethylamine, etc.) at -20-+50 deg.C for 1-2hr.

Description

are prepared by reacting the corresponding amino compound with sulfur trichloride to form a bisaminodisulfide derivative, followed by chlorination with the chlorinating agent. The compounds of formula I are useful as intermediates in the preparation of carbamates having an insecticidal, acaricidal or nematicidal effect.

The invention relates to a process for the preparation of novel aminosultonyl chloride derivatives useful as intermediates in the preparation of carbamates having an insecticidal, acaricidal or nematicidal effect.

The aminosulfenyl chloride derivatives according to the process of the invention can be represented by the general formula (I) wherein:

R ^l and R ² are the same or different · represents (1) a group of formula -X-COOR ³ wherein 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 cycloalkyl containing 3 to 6 carbon atoms; or (2) a group of the formula -Y-CN, wherein Y is an alkylene group having 1 to 6 carbon atoms; and

R ^{2 is} additionally C 1 -C 8 alkyl; (C 3 -C 6) cycloalkyl; a benzyl group optionally substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; phenyl optionally substituted with halogen, C 1 -C 3 alkyl or C 1 -C 3 alkoxy; or a group of the formula —Z — R ⁴ wherein Z is carbonyl or sulfonyl and R ⁴ is C 1 -C 6 alkyl, phenyl optionally substituted with C 1 -C 3 alkyl or halogen, C 1 -C 3 alkoxy carbon atoms or phenoxy.

These derivatives have not yet been described in the literature and are therefore novel compounds.

In the definition of the individual symbols in formula (I), the alkyl radical in the alkyl, alkoxy and alkylene radicals may have a straight or branched chain.

The compounds of formula I are highly reactive and can readily react with groups such as -NH _2, -SH, -OH, etc. Therefore these compounds are useful as intermediates in various reactions. For example, a compound of formula I may be reacted with 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N-methylcarbamate to give 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N- Of (N, N-disubstituted aminosulfenyl) -N-methylcarbamate.

The latter class of compounds exhibits an insecticidal effect.

The present invention provides a process for the preparation of aminosulfenyl chloride derivatives of formula (I), which is characterized by reacting an amino compound of formula (IV):

R ¹ and R ² are as defined above, with sulfur trichloride to form the bisaminodisulfide derivative of general formula V (V) wherein:

R ¹ and R ² are as defined above, after which the obtained bisaminodisulfide derivative of the general formula V is chlorinated with a chlorinating agent.

The procedure is illustrated by the following reactions 3 and 4, j, + NH ₉ ci _Q ² r2 ^{X 2} (3) chlorination _ r * ² _9> NS-C ⁽⁴⁾

Reaction 3 may optionally be carried out in the presence of a solvent or in a two-phase system consisting of solvent and water. Examples of solvents that may be used include halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichlorethylene, m-ethylchloroform, etc .; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, etc .; hydrocarbons such as n-pentane, n-hexane, n-heptane, cyclohexane, etc .; and aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, etc. In reaction 3, the ratio of the amount of the compound of formula (IV) to the sulfur trichloride is not particularly limited and can be varied quite widely. Typically, about 0.5 moles of sulfur trichloride is used per mole of compound of formula IV. Reaction 3 is preferably carried out in the presence of a basic compound.

The basic compounds which can be used are the amine compounds which serve as starting materials. Other examples of basic compounds include tertiary amines such as triethylamine, tributylamine, dimethylaniline, diethylaniline, ethylmorpholine, etc .; and pyridines such as pyridine, picoline, lutidine, etc. On the other hand, when the reaction is carried out in a two-phase system consisting of solvent and water, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. may be used as the basic compound.

Basic compounds may be used in an amount sufficient for capturing ^one of the hydrogen chloride to be released during the reaction as a byproduct. Usually about 1 to about 10 moles are used, preferably about 1 to about 10 moles. 5 moles of basic compound per mole of compound of formula IV. The reaction may be carried out with cooling, at room temperature or with heating. It is generally carried out at a temperature of from -20 ° C to about 50 ° C, preferably from 0 ° C to 40 ° C. The reaction time varies depending on the basic compound used, but is usually about 1 to about 2 hours. The bisaminodisulfide derivative of formula (V) thus obtained can be purified and then used, or the reaction solution can be washed with water, dried and then used directly for the next reaction.

Reaction 4 may optionally be carried out in the presence of a solvent. Any suitable solvent for reaction 3 may be used. Examples of chlorinating agents which may be used include chlorine, sulfuryl chloride, etc. The ratio of the amount of the compound of formula V to the chelating agent is not particularly limited and may vary. quite a wide range. Typically, about 0.5 to about 5 moles, preferably 0.5 to about 1.5 moles, of chlorinating agent are used per mole of compound of formula (V). (VIII) (IX) heating. In general, the reaction is carried out at a temperature of from -20 ° C to about 50 ^° C, preferably from -10 ° C to 30 ° C. The reaction is complete in about 1 to about 2 hours.

The compounds of formula IV are known.

Examples of useful amino compounds of formula (IV) include secondary amines of formulas (VI) to (X)

X — COOR ³ / HN \

R

Y — CN

HN \

R

X — COOR ³

HN \

X “—COOR ³ “

X — COOR ³

HN \ Y — CN

Y — CN

HN \ Y “—CN

In formulas VI to X, they have groups

Y, Y and R3 are as defined above,

R represents an alkyl group having from 1 to 8 carbon atoms; A cycloalkyl group having 3 to 6 carbon atoms; benzyl optionally substituted with halogen, C 1 -C 3 alkyl or C 1 -C 3 alkoxy; phenyl optionally substituted with halogen, C 1 -C 3 alkyl or C 1 -C 3 alkoxy; or a group of formula Z'-R 4 ', wherein Z' is carbonyl or sulphonyl and R ⁴ represents an alkyl group having 1 to 6 carbon atoms, phenyl, benzyl, alkoxy of 1 to 6 carbon atoms or a phenoxy group (which may have alkyl and alkoxy are straight or branched chain);

R ³ 'has the same meaning as R ³ ,

X ”has the same meaning as X and

Y 'has the same meaning as Y.

Representative examples of amino compounds of formula VI are (X)

With N-methylglycine methyl ester, N-methylglycine ethyl ester, N-methylglycine butyl ester, N-ethylglycine ethyl ester, N-propylglycine ethyl ester, N-isopropylglycine ethyl ester, N-butylglycine ethyl ester, N-isobutylglycine ethyl ester, N-sec.butyl ester _: -octylglycine, ethyl ester of N-cyclohexylglycine, ethyl ester of N-benzylglycine, ethyl ester of N- (4-methylbenzyl) glycine, ethyl ester of N- (4-sulfobenzyl) glycine, ethyl ester of N-phenylglycine, ethyl ester of N- (3- methylphenyl) glycine, N- (4-methoxyphenyl) glycine ethyl ester, N-methoxycarbonylglycine ethyl ester, N-ethoxycarbonylglycine methyl ester, N-ethoxycarbonylglycine ethyl ester, N-ethoxycarbonylglycine ethyl ester, N-phenoxy ethyl N-phenoxy ethyl ester, N-phenoxy ethyl ester, -propylaminopropionate, methyl-N-isopropylaminopropionate, ethyl-N-isopropylaminopropionate, butyl-N-isopropylaminopropionate, 2-ethythexyl-N-isopropropylaminopropionate (> metat, methyl-N-butylaminopropionate, ethyl-N-butyropinate) ethyl-N-isobutylaminopropionate, ethyl-N-sec-butylaminoproponate, ethyl-N-t-britylpropionate. ethyl-N-amylaminopropionate, ethyl-N-lsoamylaminorropionate, ethyl-1-N-hexylaminoproponate, ethyl-N-cyclohexylaminoproponate, ethyl-N-ethoxycarbonylaminoropropionate, N-acetylglycine ethyl ester, ethyl N-chloroacetyl ester. N-propionylglycine, .....

ethyl ester of N-benzoylglycine, ethyl ester of N- (4-chlorobenzoyl) glycine, ··· ethyl ester of N-tosylglycine, etc. ·.

Representative. examples of the amino compounds of formula VII are N-methylaminoacetonitrile, N-ethylaminoacetonitrile, N-n-propylaminoacetonitrile,

N-n-butylaminoacetonitrile, N-isobutylaminoacetonitrile,

N-phenylaminoacetonetril,

N- (4-ethylphenyl) aminoacetonitrile, N-methylaminopropionitrile, N-propylaminopropionitrile, Nds-propylaminopropionitrile, N-butylaminopropionitrile, N-isobutylaminopropionitrile, N-sec-butylaminopropionitrile methyl, N-octylaminopropion, N-cyanomethylcarbamate, ... ethyl N-cyanoethylcarbamate etc.

Representative examples of amino compounds of formula (VIII ') are:

methyliminodiacetate, ethyliminodiacetate, isorrochlorylimmodiacetate, butyliminodetate, rentyliminodiacetate, hexyllminodiacetate, cycllorropyliminodiactate, cyclopentylminodiacetate, cyclohexyliminodiacetate, methyliminodipropionate, ethyliminodipropionate, ethyliminodipropionate, β-ethoxylaminomethyl-β-ethoxylaminomethyl-N-ethoxycarbonyl ethyl 2- (ethoxycarbonylmethylamino) butyrate etc.

Representative examples of amino compounds of formula (IX) are:

ethyl ester. N-cyanomethylglycine, ethyl ester of N-cyanoethylglycine, ethyl-N-cyanomethylaminoproplonate, ethyl-N-cyanoethylaminopropionate, etc.

Representative examples of amino compounds of formula X. are iminodiacetonitrile, iminodlpropionitrile, iminodlbutyronitrile, etc.

The following examples explain in more detail the preparation of the compounds of formula I.

Example 1

Preparation of N-n-butyl-N-ethoxycarbonylbenzylaminosulfenyl chloride. ·.

Dissolve 1,4 g (0,01 mol) of sulfur trichloride in 50. ml · carbon tetrachloride. and to the resulting solution. 3.5 g (0.02 mol) of ethyl N-butylaminopropionate and 2 g (0.02 mol) of triethylamine were added to each other. 0 ° C to 5 ° C. After completion of the drop of these substances, the resultant is obtained. the mixture is stirred for one hour. and then the reaction solution. wash three times. in each case 50 ml of water. The carbon tetrachloride layer was dried over sodium sulfate, filtered, and then the carbon tetrachloride solution was recooled with stirring to 0. After cooling, 1.4 g (0.01 mol) of sulfuryl chloride were added to the mixture while cooling, and the mixture was stirred for 1 hour the same temperature. The reaction solution was concentrated under reduced pressure to an oily product. Yield: 4.5 g (93.8%).

The NMR spectrum in _CDCl3 of this oily product · exhibits these. values:

δ 0.7 to 2.0 ppm (m, 7H), δ 2.70 ppm (t, 2H), δ 3.43 ppm (t, 2H), δ 1.26 ppm (t, 3H), <5 3.25 ppm (t, 2H);

4.08 ppm (q, 2 H).

NMR analysis shows that this oily product contains a small amount of bisaminodisulfide but nevertheless confirms that the product has a structure corresponding to the formula

CH2CH2COOC2H5

Cl — S — N \

⁴ CH2CH2CH2CH3

Example 2

Preparation of Ndsopropyl-N-ethoxycarbonyl-ethylaminosulfenyl chloride

3.2 g (0.02 mol) of ethyl N-isopropylaminopropionate are dissolved in 30 ml of n-hexane and 50 ml of 5% aqueous sodium hydroxide solution are added. After cooling the mixture to 5 ° C, 1.4 g (0.01 mol) of sulfur trichloride dissolved in 50 ml of n-hexane was added dropwise, and the resulting solution was stirred at the same temperature for one hour. After completion of the reaction, the n-hexane layer was separated, washed with water and then dried. The n-hexane layer was then stirred again with cooling and 1.4 g (0.01 mol) of sulfuryl chloride was added dropwise. The mixture was stirred for one hour and then concentrated by evaporation of n-hexane under reduced pressure. An oily product is obtained. Yield: 4.1 g (91%).

NMR spectrum in CDC1 ₃ of this oil showed the following values:

1.23 ppm (t, 3H);

2.77 ppm (t, 2 H),

4.06 ppm (q, 2H);

1.26 ppm (d, 6H), <5 3.0-3.8 ppm (m, 3H).

NMR analysis shows that this oily product contains a small amount of bisaminodisulfide but nevertheless confirms that the product has a structure corresponding to the formula:

CH ₂ CH ₂ COCO ₂ H ₅ /

Cl-S-N _CH3 \ /

CH \

CH3

Examples 3 to 27

The compounds listed in Table 1 were prepared according to the procedures described in Examples 1 a

2. The NMR daaa (in CDCl 3) of these compounds are also listed in Table 1.

Example number

Table 1

Structure·

NMR (in CDCl 3) ppm δ

CH9COOC9H5 / ''

Cl — S — N \

CH2CH2CH2CH3

0.7-2.0 (m, 7H),

1.29 (t, 3H);

3.31 (t, 2H).

4.05 (s, 2H).

4.16 (q, 2 H).

CH ₂ C OOC ₂ H ₅

1.26 [t, CH]

2.34 (s, 3H);

4.13 (q, 2H);

4.59 (s, 2H).

6.9 to d, 5 µm, CH 2].

1.18 (T СН))

3.67 ((5, С3 ^) »

4.08 (q, 2H);

4.46 (s, 2H).

6.9 a and d, 5 m, CH) ·

CH ₂ COOC ₂ H ₅

Cl-S-N

1.29 (t, 3H);

4.19 (q, 2H).

4.53 (s, 2H).

7.1 to 7.8 (m, 5H).

NMR (in CDCl 3) ppm δ

Example number

Structure

CH ₂ COOC ₂ H ₅

Cl-S- N ^ so ₂ -

CH ₃

1.26 (t, 3H);

2.45 (s, 3H);

4.16 (q, 2H).

4.38 (s, 2H).

7.2 to 8.0 (m, 4H).

CH ₂ COOC ₂ H ₅

Cl — S — N \

COOCH3

1.28 (t, 3H);

3.81 (s, 3H);

4.17 (q, 2H).

4.36 (s, 2 H).

CH-) COOC ₂ Hr,

Cl — S — N \

COOC ₂ H ₅

1.27 (t, 3H);

1.33 (t, 3H);

4.16 (q, 2H).

4.25 (q, 2H).

4.39 (s, 2 H).

/ СН ₂ СООС ₂ Н ₅

Cl-S-N? COO

1.30 (t, 3H);

4.15 (q, 2H).

4.48 (s, 2H).

6.9 to 7.6 (m, 5H).

Cl—

CH ₂ COOC ₂ Hr

S — N \ ch ₂ ch ₂ cn

1.30 (t, 3H);

2.89 (t, 2H).

3.65 (t, 2H).

4.20 (s, 2H).

4.26 (q, 2 H).

ch ₂ cn /

Cl-S-N _CH3 \ /

CH \

CH3

1.33 (d, 6H);

3.3-3.9 (m, 1H);

4.32 (s, 2 H).

CH-, CN

Cl — S — N \

СН ₂ СН ₂ СН ₂ СН ₃

CH ₂ CH ₂ COOC ₂ H ₅

Cl — S — N \

CH ₂ CH ₂ CH ₃

0.7-2.0 (m, 7H),

3.22 (t, 2H).

4.05 (s, 2 H).

CH ₂ CH ₂ COOC ₂ H ₅ /

Cl-S-N _CH3 \ /

CH \

CH ₃

0.93 (t, 3H);

1.24 (t, 3H);

1.4-2.2 (m, 2H);

2.68 (t, 2H).

3.20 (t, 2H).

3.43 (t, 2 H),

4.06 (q, 2 H).

1.23 (t, 3H);

1.26 (d, 6H);

2.77 (t, 2H).

3.0-3.8 (m, 3H), 4.06 (q, 2H).

Example number Structure NMR (in CDC1 ₃₎ 8 ppm CH ₂ CH ₂ COOCH ₃ 0.7-2.0 (m, 7H), of 2.62 (t, 2H). 16 Cl — S — N 3.17 (t, 2H). \ 3.36 (t, 2H). CH ₂ CH ₂ CH ₂ CH ₃ 3.58 (s, 2H). '' 7 ^r ^ · CH ₂ CH ₂ COOC ₂ H ₅ 0.87 (d, 6H); of 1.34 (t, 3H); 17 Cl — S — N CH ₃ 1.6 to 2.2 (m, 1H), \ / 2.74 (t, 2H). CH, CH 4.13 (q, 2H). \ CH; j 2.95-3.6 (m, 4H). CH ₂ CH ₂ COOC ₂ H ₅ 1.26 (t, 3H); of 1.39 (s, 9H); 18 Cl — S — N 2.76 (t, 2H). \ 3.53 (t, 2 H), C (CH3) ₃ 4.14 (q, 2 H). CH ₂ CH ₂ COOC ₂ H ₅ 0.6 to 2.0 (m, 14H), of 2.62 (t, 2H). 19 Dec Cl — S — N 3.19 (t, 2H). \ 3.39 (t, 3H); CH2CH2CH2CH2CH2CH3 4.02 (q, 2H). oh _? ch ₂ cooc _? h ₅ 0.8-2.3 (m, 10H), 20 May / í í of 0 1.24 (t, 3H); Cl-S-N. / \ 2.65 (t, 2 H), \ ^H / 2.8-3.5 (m, 3H), 4.06 (q, 2H). ch ₂ ch ₂ cn 0.91 (d, 6H); of 1.7 to 2.5 (m, 1H), 21 Cl — S — N CH ₃ 2.5-3.2 (m, 4H), \ from CH ₂ CH CH ₃ 3.39 (t, 2 H). ch ₂ ch ₂ cn 1.35 (s, 9H); of 2.85 (t, 2H). 22nd Cl-S-N \ C (CH3) ₃ 3.57 (t, 2 H). CH9CH9CN 2.94 (t, 4H); of 3.68 (t, 4 H). 23 Cl — S — N \ ch ₂ ch ₂ cn 1.26 (t, 3H); CH2CHJCOOC2H5 2.75 (t, 2H). / 3.35 (t, 3H); 24 ^CI ' ^S ' ^N 2 CH ₂ ZZ 3.94 (s, 2H). 4.16 (q, 2H). ^í \ = / 6.9 to 7.5 (m, 5H).

37'3 30

NMR (in CDCl 3) ppm δ

Example number

Structure _Z CH2CH2COOC2H5

Cl-S-N

CH2CH2COOC2H5

'X'

1.24 (t, 3H);

2.74 (t, 2H).

3.33 (t, 2H).

4.01 (s, 2H).

4.14 (q, 2H); 7.0-7.8 (m, 4H).

1.24 (t, 3H);

2.73 (t, 2H).

3.35 (t, 2H).

4.11 (q, 2H), 7.0-7.5 (m, 5H).

Claims (9)

OBJECT OF INVENTION 1. A process for the preparation of aminosulfenyl chloride derivatives of the formula I by reacting an amino compound of the formula IV R1 R1 \ \ N-S-Cl (AND) NH / R ² R2 where - each of the symbols where (IV) ^R1 and R2, which are identical or different, represents (1) a group of formula -X-obecného- COOR 3 wherein X represents an alkylene group having 1 to 6 carbon atoms and ^{R t} is an alkyl group containing 1-8 carbon atoms or cycloalkyl having 3 to 6. -. carbon atoms; or (2) a group of the formula -Y-CN, wherein Y is an alkylene group containing 1 to 6 carbon atoms; and R ² furthermore represents C further ob si ^ hi ^; ^ IIci 1-8 carbon atoms; and cycloalkyl having from 3 to 6 carbon atoms; a benzyl group optionally substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; phenyl optionally substituted. 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 ⁴ wherein Z is carbonyl or sulfonyl and R 4 is - (C 1 -C 6) -alkyl, phenyl optionally substituted by C 1 -C 3 -alkyl or halogen, alkoxy-containing 1 to 3 carbon atoms or a phenoxy group, characterized in that it is left R ¹ - and - R ² are as defined above, with sulfur trichloride to form the bisaminodisulfide derivative of general formula V R'LR · \ / N — S — S — Ν (V) / \ R2R2 where R1 and ^R2 are as defined above, whereafter the obtained bisaminodisulfidový derivative of the formula V chlorinated with chlorinating agent. 2. A process according to claim 1 wherein the reaction of the amino compound of formula IV with sulfur trichloride is carried out in the presence of a solvent. 3. The process according to claim 1, wherein the reaction of the amino compound of general formula IV with sulfur trichloride is carried out in a two-phase system consisting of solvent and water. 4. The process of claim 1 wherein the reaction of the amine compound of formula IV with sulfur trichloride is carried out in the presence of a basic compound. 5. The method of claim 1, wherein: u wherein the reaction of the amino compound of formula IV with sulfur trichloride is carried out at a temperature of from -20 to 50 ° C for a period of from 1 hour to 2 hours. 6. A process according to any one of claims 1 to 5, wherein 0.5 moles of sulfur trichloride per mole of amino compound of formula IV is used. 7. The process of claim 1 wherein the chlorination is carried out in the presence of a solvent. 8. The process of claim 1 wherein the chlorination is carried out at a temperature of from -20 ° C to 50 ° C for a period of from 1 to 2 hours. 9. A process according to claim 1, wherein from 0.5 to 5 moles of chlorinating agent is used per mole of bisaminodisulfide derivative of formula (V).