DE2128672A1 - - Google Patents

Description

OVERALL. WALTBtIBf

\. H.-J. WOlJf DR. JUR. HANS CHR. BEIL 623 FRANKFURT AM MAIN-HOCHST

Our No. 17 140

Chevron Research Company San Francisco, Ca!., V.St.A.

N-3-substituted acylamidosulfenyl chlorides and N-alkyl-N-chlorothiocarbamoyl chlorides and processes for their manufacture.

The present invention relates to N-substituted acylamidosulfenyl chlorides and N-alkyl-N-chlorothiocarbamoyl chlorides and processes for their manufacture. The compounds are valuable intermediate products for production of pesticides.

The compounds of the present invention can be represented by the following formula:

Il

R-N-C-Y

SCl

109851/1998

in which R is an alkyl radical with 1 to 10 carbon atoms which is optionally substituted by chlorine and / or bromine atoms or an optionally substituted by chlorine and / or bromine atoms cycloalkyl radical with 3 to 10 carbon atoms, preferably 5 to 10 carbon atoms and Y is a hydrogen or chlorine atom, an alkyl radical with 1 to 10 carbon atoms which is optionally substituted by chlorine and / or bromine atoms or a cycloalkyl radical with 3 to 10 carbon atoms which is optionally substituted by chlorine and / or bromine atoms represents, wherein R and Y together form a linear alkylene radical having 3 to 5 carbon atoms which is bonded to the carbonyl group and the nitrogen atom to form a ring. Preferably included the haloalkyl or halocycloalkyl radicals which can be represented by R and Y, 1 to 4 halo substituents, better still 1 to 2 halogen substituents.

R preferably denotes an alkyl radical with 1 to 6 carbon atoms, which is substituted by 0 to 4 chlorine and / or bromine atoms, preferably 1 to 2 chlorine and / or bromine atoms, halogen atoms with the number of atoms 17 to 35, or one by 0 to 4 Chlorine and / or bromine atoms, preferably 0 to 2 chlorine and / or bromine atoms, substituted cycloalkyl radical with 3 to 6 carbon atoms. If Y stands for a chlorine atom and R for a cycloalkyl radical, this cycloalkyl group should preferably contain 5 to 10 carbon atoms and optionally be substituted by halogen atoms or even better contain 5 to 6 carbon atoms and by 0 to 4 chlorine and / or bromine atoms be substituted.

109851/1998

In a preferred embodiment, R is an alkyl radical having 1 to ¹ I carbon atoms, which is substituted by 0 to 2 Halogenatorne with the atomic number 17 to 35 »preferably Chloratone.

Y is preferably a hydrogen or chlorine atom, an alkyl radical with 1 to 6 carbon atoms which is substituted by 0 to H chlorine and / or bromine atoms, preferably 0 to 2 chlorine and / or eromatic atoms, or a cycloalkyl radical with 3 to 6 carbon atoms , which is substituted by 0 to 4 chlorine and / or bromine atoms, preferably 0 to 2 chlorine and / or bromine atoms.

In a preferred embodiment, Y represents a hydrogen or chlorine atom or an alkyl radical with 1 to H carbon atoms which is substituted by 0 to 2 halogen atoms with the number of atoms from 17 to 35, preferably chlorine atoms.

R and Y can also together form a linear alkylene radical having 3 to 5 carbon atoms, which forms a ring is bonded to the carbonyl group and the nitrogen atom. The compounds where R and Y under Ring formation associated with the carbonyl group and the nitrogen atom can also be achieved by the following Formula can be represented:

in which R is a linear alkylene group having 3 to 5 carbon atoms.

109851/1990

Examples of alkyl or cycloalkyl groups, de £ L R and Y can represent are the methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, pentyl, hexyl, heptyl, Octyl, nonyl, decyl, 2-methylbutyl, 3-methylpentyl, Cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, chloromethyl, 2-chloroethyl ^, 3-chloropropyl, 4-chloramyl-, 6-chlorhexyl-, 2,6-dichlorocyclohexyl-, 2,6-di-bromocyclohexyl-, 3-broracyclohexyl-, bromomethyl-, 2-bromoethyl or 3-bromopropyl group.

Alkyl radicals which R and Y together or R can represent are the propylene, butylene and amylene groups.

Regarding the standards used here, it should be noted that that compounds in which Y is a hydrogen atom or is optionally substituted by halogen atoms Represents alkyl or cycloalkyl group, as acylamidosulfenyl chlorides are referred to, while compounds in which Y is a chlorine atom as carbamoyl chlorides are designated.

Typical acylamidosulfenyl chlorides represented by the formula below are: N-methylformamidosulfenyl chloride, N-Ethylformamidosulfenyl chloride, N-propylformamidosulfenyl chloride, N-butylformamidosulfenyl chloride, N-chloroethylformamidosulfenyl chloride, N-2-chloroethylformamidosulfenyl chloride, N-2-chloropropylformamidosulfenyl chloride, N-bromomethylformamidosulfenyl chloride, N-cyclopropylformamidosulfenyl chloride, N-cyclobutylformamidosulfenyl chloride, N-cyclohexylformamidosulfenyl chloride, N-Methylacetamidosulfenylc ^ lorid, N-Ethylacetamidosulfenyl chloride, N-Propylacetamidosulf-

109851/1990

fenylchlorid, N-Butylacetamidosulfenylchlorid, N-methy1-chloracetamidosulfenylchlorid, N-Methylbromacetamidosulfenylchlorid, N-Methylpropionamidosulfenylchlorid, N-Äthylpropionamidosulfenylchlorid, N-Chlormethylpropionamidosulfenylchlorid, N-methyl-3, -d ichlorpropionamidosulfenylchlorid, N-methyl-2,3-dibrompropion _v amidosulfenylchlorid, N-Butylpropionamidosulfenylchlorid, N-MethyIbutyramidosulfenylchlorid, N-Äthylbutyjframidosulfenylchlorid, N-Cyclohexylbutyramidosulfenylchlorid, N-Isopropylbutyramidosulfenylchlorid, N-Methylvaleramidosulfenylchlorid, N-Methy1-3 "4.5 trichlorvaleramidosulfenylchlorid, N-Chlormethylcaproamidosulfenylchlorid, N-ethyl-6,7-dichlorönanthamidosulfenylchlorid, N-methylcapry1-amidosulfenyl chloride, N-methylcyclohexanoamidosulfenyl chloride, N-methy1-2-chlorocyclopentanoamidosulfenyl chloride, N-thiochloropyrrolidone, N-thiochloropiperidone, N-thiochlorocaprolactam.

Examples of suitable carbamoyl chlorides, which according to produced by the process according to the invention are: N-methyl-N-chlorothiocarbamoyl chloride, N-ethyl-N-chlorothiocarbamoyl chloride, N-n-propyl-N-chlorothiocarbamoyl chloride, H-n-Butyl-N-chlorothiocarbaraoyl chloride, N-isopropyl-iJ-chlorothiocarbamoyl chloride, M-n-pentyl-N-chlorothiocarbamoyl chloride, N-chloromethyl-N-chlorothiocarbamoyl chloride, N-bromomethyl-N-chlorothiocarbamoyl chloride, N-cyclopentyl-N-chlorothiocarbamoyl chloride, N-cyclohexyl-N-chlorothiocarbamoyl chloride, N-halocyclohexyl-N-chlorothiocarbamoyl chloride.

The compounds of the invention are made by reaction of sulfur dichloride with a suitable compound

109851/1998

manufactured. To prepare compounds in which Y is a hydrogen atom or optionally through Halogen atoms means substituted alkyl or cycloalkyl radical, is the sulfur dioxide with a? reonoalkylated Amide or a lactam implemented. This conversion is represented by the chemical equation below explained:

Q - 0

H It

R-NH-CY 4- SCl- * RNCY + HCl (I)

SCl

in which R and Y have the meanings given above, but where Y is not chlorine. It is desirable stoichiometric proportions of the reagents or an excess of sulfur dichloride up to as feed a molar ratio of 4: 1 to be used.

The reaction temperature for reaction (I) is im generally not critical and is usually within a range from -50 to 100.degree. C., preferably -20 to 60 ° C. The pressure is also non-critical and is usually atmospheric or autogenic. The reaction time is generally 0.25 to 5 hours.

The reaction (I) Ttfird is generally in the presence of a inert solvent, such as dichloromethane, Diethyl ether, tetrahydrofuran, dimethylformamide, dioxane or acetonitrile. In general, each reagent is mixed separately with a solvent, and then that will be the amide and preferably a halon

109851/1998

mixture containing hydrogen acceptor slowly Stir to the mixture containing the sulfur dichloride admitted. The fen ^ e of the solvent should be about equal to your weight of sulfur dichloride oiler in one! "tight up to five times the weight of the same to be available. The solvent for the amide-halo-hydrogen acceptor mixture should also be in the same or up to five times the amount of weight both be present.

The reaction (I) is preferably carried out in the presence of a mild hydrogen halide acceptor. At least stoichiometric amount of acceptor should be used. Soluble tertiary amines such as Pyridine and trialkylamines, partly 3. Triethylandn and tributylaxnin are preferred.

The acylamidosulfenyl chloride can generally by Stripping off the excess sulfur dichloride, filtering off that formed from hydrogen halide acceptor and HCl Salt, evaporation of the solvent and cleaning of the product, for example by distillation or recrystallization, obtained from the reaction mixture will.

The compounds in which Y represents a chlorine atom, i.e. the carbamoy! Chlorides of the present invention, are produced by reacting an isocyanate with SCl according to the following equation:

0 dd

Λ - il = C = 0 + SCl ₉ * R-II-C-Cl (II)

SCl

1 0 9 8 5 1/1 S 9 8

in which R has the meaning given above. The molar ratio of the sulfur dichloride to the isocyanate should be at least 1: 1. The "sulfur dichloride" is available in excess "preferential prices."

The reaction (II) can be carried out in the presence of a suitable inert organic solvent or without a solvent be performed. It is preferable to use a low boiling point solvent that is easy can be removed by wiping at low temperature. To the examples of suitable solvents include: dichloromethane, diethyl ether, tetrahydrofuran and dimethylfuran. The solvent is used in an amount sufficient to dissolve the reagents. In general, it is sufficient to use about 25 to 200 ml of solvent to be used for every 0.1 mole of isocyanate. The use of 50 to 100 ml is preferred.

The reaction (II) of isocyanate and sulfur dichloride can be carried out in the presence of a suitable catalyst, such as, for example, dibutyltin dilaurate, tetraethylammonium chloride or triethylamine. The preferred catalyst is tetraethylammonium chloride. Although the reaction takes place without a catalyst, the use of a catalyst is preferred. In general, about 1 to 50 weight range -.% Catalyst, based on the isocyanate from. Preferably, the catalyst is removed before the carbamoyl chloride is isolated or the in situ reaction with a suitable reagent to prepare the insecticide, which is described below, is carried out.

10 9 8 5 1/19 9 8

The reaction (CU) is preferably carried out at one temperature from -50 to 10OG ° C and at ambient or autogenous pressure. The reaction time is generally between 0.25 and 72 hours, usually between 0.33 and 24 hours.

The carbamoyl chloride from reaction (II) can by Stripping off the sulfur dichloride and then distilling the desired product from the mixture be won. If the catalyst is insoluble, the carbamoyl chloride can be removed by stripping off the sulfur dichloride, Filtering off the insoluble catalyst and subsequent evaporation of the low-boiling solvent be won.

In the above reactions (I) and (II) the sulfur in pure a state as possible should, for example, in a purity above 95%, preferably over 98% _t be added. It is often desirable that a small amount of an inhibitor such as tributyl phosphate or triethyl phosphate be present along with the sulfur dichloride in order to maintain the high degree of purity.

The compounds according to the invention are valuable intermediate products in the production of pesticides. Thus, the compounds in which Y is a hydrogen atom or an alkyl or cycloalkyl group optionally substituted by halogen atoms can be used for the preparation of aryl-N- (N ^f -alkylacylamidothio) -N-alkyl carbamates, which are a pesticidal, in particular

109851/1098

have a special insecticidal effect »These compounds are made by reacting an N-Alkylacylamidosulfenylchlorids made with an aryl N-alkyl carbamate. For example, m-sec-butylphenyl-IT-CN'-methylacetamidothioO-N-methyl-carbamate by reacting the N-Methylacetamidosulfenylchlorids according to the invention with m-sec-Butylphenyl-N-methylcarbamate according to the following general chemical reaction scheme will:

O O

I! Il

- O - C - NH- + CH, - N - C - CH,

CH ₃ SCl

CH ₃ -CH-CH ₂ -CH ₃

0 _CH

Il / 3

-O -C-N 0 + HCl

SNC- CH, t J

CH ₃ -CH-CH ₂ -CH _{3 CH}

Compounds in which Y is chlorine, ie carbamoyl chlorides, can be used to prepare, for example, N-alkyl-N-chlorocycloalky! Thioureas which have a pesticidal, in particular herbicidal, action. These compounds are prepared by reacting an N-alkyl-N-chlorothiocarbamoyl chloride with a cyclic unsaturated hydrocarbon and then with ammonia or an amine. For example, N-methyl-N- (2-chlorocyclohexylthio) -N ^f -phenyl-

109851/1998

- li -

Urea by reacting N-methyl-N-chlorothiocarbamoyl chloride according to the invention with cyclohexane and further reaction of the product obtained with aniline according to the the following general reaction scheme can be prepared:

- Ii - C - Cl +

3Gl

CH, - N - C - Cl J t

Cl

It

CH ^ -N-C-Cl +

ti

-NH-C-N '

HCl

The present invention is explained in more detail using the following examples:

example 1

N-methylformamidosulfenyl chloride was obtained by reacting il-methylformamide and sulfur dichloride in the presence of Dichloromethane and triethylamine produced.

10 9 8 5 1/19 9 8

80 g of SCIp were placed in a flask with 150 ml of dichloromethane given. The mixture was cooled in an ice bath and then added dropwise with 23 g of N-methylformamide and 40 g of triethylamine, which were dissolved in about 100 ml of dichloromethane, added.

The triethylamine hydrochloride salt, which results from the hydrogen halide acceptor and HCl formed was filtered off and the dichloromethane was evaporated. The product was taken up in petroleum ether and the remaining salt was filtered off. The petroleum ether was then evaporated and the product was distilled. The fraction boiling at 39 ° C / 0.5 mm was analyzed, namely as follows:

Calculated Found

Cl % 28.23 31.88 S % 25.5 26.60

The proton magnetic resonance and infrared spectra also confirmed the structure.

Example 2

N-Methylacetamidosulfenyl chloride was prepared as follows:

268 g of freshly distilled sulfur dichloride stabilized with tributyl phosphate and 500 ml of dichloromethane were cooled to -10 ° C. in a dry ice bath. A mixture of 142 g of N-Ilethylacetamide and 154 g of pyridine in 200 ml of dichloromethane was then added in the course of five hours with stirring. The temperature was kept between -10 and 0 ° C. After the addition was finished, another

109851/1998

The mixture was stirred at a temperature of 0 ^° C. for an additional hour. The solid residue was filtered off, the dichloromethane was evaporated and the product was taken up in hexane which was then evaporated. The liquid product was analyzed. The elemental analysis had the following results:

Calculated Found

Cl % 22.98 23.04 S % 25.42 27.35.

Example 3

rl-methylchloroacetamidosulfenyl chloride was prepared as follows:

134 g of stabilized with tributyl phosphate, freshly distilled SCIP in 300 ml of dichloromethane were placed in a Tr okkeneisbad cooled to -10 ⁰ C. A mixture of 100 g of N-methylchloroacetamide, 73> 5 g of pyridine and 150 ml of dichloromethane was slowly added. The temperature was kept between -10 ° and 0 ° C. during the addition time of 45 minutes. The mixture was allowed to warm during about two hours to room temperature, then gave 250 ml of hexane added and the mixture was cooled again to 0 ⁰ C. The .feste residue was removed and the hexane was stripped from the solution, so that a thick got dark oil. N-methylchloroacetamidosulfenyl chloride was obtained by distillation and had a boiling point of 68 ^° C. at 1.5 mm. Nuclear magnetic resonance analysis as well as infrared analysis helped confirm the structure.

109851/1998

Example 4

Preparation of N-Äthylformamidosulfenylchlorid: A solution of 176 g of freshly distilled sulfur dichloride, containing a small amount of tributyl phosphate as a stabilizing agent, in 250 ml dichloromethane was added at 10 ⁰ C over one hour with a solution of 100 g N-Äthylformamid, in 108 g Pyridine and 200 ml of dichloromethane were added. The resulting mixture was stirred for an additional hour. 200 ml of hexane were then added, and the insoluble residue was filtered off ^{at 0 ° C.} The piltrate was evaporated under reduced pressure to obtain 173 g of an oily liquid. This material was distilled and the fraction with boiling point at 25-30 ^° C. under a pressure of 0.5 mm was taken as the product. The nuclear magnetic resonance spectrum agreed with the specified structure. The elemental analysis had the following results:.

Calculated Found

S % 22.97 22.58

Cl % 25.40 ■ 25.85

Example 5

Production of N-thiochloropyrrolidone: 20.6 g of freshly distilled sulfur dichloride were in Dissolved 100 ml of dichloromethane, which contained a small amount of tributyl phosphate as a stabilizing agent. to this solution became a solution of 8.5 g of pyrrolidone

109851/1998

and 10.2 g of triethylamine in 100 ml of dichloromethane. The mixture thus obtained was filtered, and the filtrate was removed by evaporation under reduced pressure concentrated. The resulting precipitate was filtered off and the oily liquid product became in the infrared spectrum analyzed. A medium strong peak was between 18 and 19 / u. A distillation should be avoided or carried out carefully to avoid violent decomposition of the N-trichloropyrrolidone.

Example 6

Preparation of M-methyl-N-chlorothiocarbamoyl chlorides: (a) 14.3 g of methyl isocyanate (molecular weight = 57.05) and 5 g of tetraethylammonium chloride were dissolved in 100 ml of dichloromethane. 25.8 g of sulfur dichloride with a purity of over 98 % were added dropwise. The reaction was slightly exothermic. The reaction mixture turned yellow in about 15 minutes. The dichloromethane was evaporated and the product was separated from the tetraethylammonium chloride salt by hexane extraction. The hexane was now evaporated and the product was distilled. The fraction boiling at 32 - 35 ° C / 0.2 mm was chemically analyzed for N-methyl-N-chlorothiocarbamoyl chloride:

% Calculated Found N % 8.75 8.12 Cl % 44.31 44.18 S. 20.04 19.68

109851/1998

Infrared analysis as well as proton magnetic resonance analysis were used to confirm the structure. (b) 11.4 g of methyl isocyanate (0.2 mol) and 52 g of sulfur dichloride (0.5 mol) with a purity of over 98 % were mixed without a catalyst. The reaction vessel was left to stand for eight days at ambient temperature. Excess sulfur dichloride was stripped from the product and the product was distilled. The boiling point was 37 ° C under a pressure of 0.5 mm. The chemical analysis of the N-methyl-N-chlorothiocarbamoyl chloride had the following result:

Calculated Found N % 8.75 8.34 Cl % 44.4 45.0 S % 20.04 19.95

(c) 14.3 g of methyl isocyanate and 25.8 g of sulfur dichloride were reacted without a catalyst and without exposure to light. After 28 days the reaction mixture turned yellow. N-methyl-N-chlorothiocarbamoyl chloride was obtained.

Example 7

(a) Preparation of N-n-Butyl-N-chlorothiocarbamoyl chloride:

19.8 g of n-butyl isocyanate and 20.6 g of sulfur dichloride were placed in an ampoule without a catalyst and reacted in sunlight. The reaction mixture turned colored yellow. The analysis showed the formation of N-n-butyl-N-ehlorothiocarbamq * yl chloride at.

109 851/199 8

(b) The same reagents as in Example 7 (a) were added in approximately the same amounts to a pressure tube which was sealed and placed in a boiling water bath for six hours. At the end of this period the reaction mixture was orange _a and after standing for about two days the product turned yellow. Analysis of the stripped product indicated Nn-butyl-N-chlorothiocarbamoyl chloride:

Found found

N % 6.93 6.68 Cl % 35.08 35.23 S % 15.87 15.62

(c) 19.8 g of n-butyl isocyanate and 5 g of tetraethylammonium chloride were dissolved in 100 ml of dichloromethane. 20.6 g of sulfur dichloride were slowly added dropwise. After about 15 minutes the reaction mixture turned yellow. The dichloromethane was evaporated. The product was taken up in hexane and separated from the catalyst. The hexane was then evaporated. One received N-n-Butyl-N-chlorothiocarbamoyl chloride.

Other reactions similar to the reactions of Examples 6 and 7 were carried out in the presence of solvents such as for example dimethylfuran and tetrahydrofuran, and in the presence of catalysts such as dibutyltin dilaurate and tetraethylamine carried out.

109851/1998

Claims (8)

'- 18 - Claims: 1. N-Substituted Acylarnidosulfenylchloride and Π-Alkyl-N-chlDrizfthiocarbamoylchloride the general formula: ir R -NCY
t SCl - in which R is an alkyl radical with 1 to 10 carbon atoms substituted by 0 to 4 chlorine and / or bromine atoms or a cycloalkyl radical with 3 to 10 carbon atoms substituted by 0 to 4 chlorine and / or bromine atoms and Y is a hydrogen or chlorine atom, one by 0 alkyl radical with 1 to 10 carbon atoms substituted by H chlorine and / or bromine atoms or a cycloalkyl radical with 3 to 10 carbon atoms substituted by 0 to H chlorine and / or bromine atoms, where R and Y together also represent a linear alkylene radical with 3 to 5 carbon atoms can form, which is bonded to the carbony group and the nitrogen atom with ring formation. · 2. Compounds according to claim 1, characterized in that R of the formula one through 0 to 4 chlorine and / or Bromine atoms substituted alkyl radical with 1 to 6 carbon atoms or one by 0 to 4 chlorine and / or Bromine atom-substituted cycloalkyl radical having 5 to 10 carbon atoms and Y represents a chlorine atom. 3. Compounds according to claim 1, characterized in that R of the formula is a through 0 to h chlorine and / or bromine atoms substituted alkyl radical with 1 to "Koh-109851/1998 lenstoffatomen or one through 0 to 4 chlorine and / or Bromine atoms-substituted cycloalkyl radical with 3 to 6 Carbon atoms and Y is a hydrogen or chlorine atom, one by 0 to 4 chlorine and / or bromine atoms substituted alkyl radical with 1 to 6 carbon atoms or one with 0 to 4 chlorine and / or bromine atoms represents substituted cycloalkyl radical having 3 to 6 carbon atoms, where R and Y together also a linear alkyl structure with 3 to 5 carbon atoms can form, which is bonded to the carbonyl group and the nitrogen atom to form a ring. 4. Compounds according to claim 1, characterized in that R of the formula one by ο to 2 chlorine and / or bromine atoms substituted alkyl radical with 1 to 4 carbon atoms and Y is a hydrogen or Chlorine atom or an alkyl radical with 1 to 4 carbon atoms substituted by 0 to 2 chlorine and / or bromine atoms atot ^ nn represents. 5. Compounds according to claim 1, characterized in that R of the formula is a methyl or butyl radical and Y represent a chlorine atom. 6. Compounds according to claim 1, characterized in that R of the formula is a methyl or ethyl radical and Y represents a hydrogen atom, a methyl or a chloromethyl radical or R and Y together form a linear alkyl radical with 3 carbon atoms. 7. Process for the preparation of the η-substituted acylamidosulfenyl chlorides of formula I, in which R is an alkyl 10 9 8 5 1/19 9 8 rest with 1 to 10 carbon atoms, one by chlorine and / or bromine atoms substituted alkyl radical with 1 to 10 carbon atoms, a cycloalkyl radical with 3 to 10 carbon atoms or a cycloalkyl radical with 3 to 10 which is substituted by chlorine and / or urine atoms Carbon atoms and Y denotes a hydrogen atom, an alkyl radical having 1 to 10 carbon atoms, a alkyl radical with 1 to 10 carbon atoms substituted by chlorine and / or bromine atoms, a cycloalkyl radical with 3 to 10 carbon atoms or a cycloalkyl radical substituted by chlorine and / or bromine atoms represents having 3 to 10 carbon atoms, wherein R and Y together can also form a linear alkylene radical having 3 to 5 carbon atoms, which under Ring formation is bonded to the carbonyl group and the nitrogen atom, characterized in that one Reacts monoalkylated amide or lactam in the presence of a hydrogen halide acceptor with sulfur dichloride. 8. Process for the preparation of the N-alkyl-N-chbr ^ rthiocarbamoylchloride of formula I, in which R is an alkyl radical with 1 to 10 carbon atoms, a chlorine and / or bromine atoms-substituted alkyl radical with 1 to 10 carbon atoms, a cycloalkyl radical with 5 to 10 carbon atoms or a cycloalkyl radical with 5 to 10 substituted by chlorine and / or bromine atoms Is carbon atoms and Y is a chlorine atom, characterized in that one is an isocyanate of the formula R-M = C = O, where R has the above meaning, is reacted with sulfur dichloride. For Chevron Research Company San Francisco, CaI., V.St.A. 10 9 8 51/19 9 8 / j tf (Dr H.A. Wolff) Lawyer