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US3699122A - N-substituted acylamidosulfenyl chlorides and their method of preparation - Google Patents

N-substituted acylamidosulfenyl chlorides and their method of preparation Download PDF

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US3699122A
US3699122A US45902A US3699122DA US3699122A US 3699122 A US3699122 A US 3699122A US 45902 A US45902 A US 45902A US 3699122D A US3699122D A US 3699122DA US 3699122 A US3699122 A US 3699122A
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Gustave K Kohn
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Chevron USA Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/30—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/45—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups at least one of the singly-bound nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylaminosulfonamides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/24—Oxygen or sulfur atoms

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  • N-substituted acylamidosulfenyl chlorides formula of the wherein R is an alkyl group of from 1 to 10 carbon atoms or cycloalkyl group of from 3 to 10 carbon atoms, the alkyl or cycloalkyl groups being optionally substituted with halogen atoms and R is hydrogen, alkyl of from 1 to 10 carbon atoms or cycloalkyl of from 1 to 10 carbon atoms, the alkyl or cycloalkyl groups being optionally substituted with halogen atoms; with the proviso that R and R may be joined to form a linear alkylene radical of 3 to carbon atoms which is bound to the carbonyl and nitrogen to form a ring.
  • the compounds are prepared by reacting N-substituted carboxamines with sulfur dichloride.
  • the 'N-substituted acylamidosulfenyl chlorides are useful intermediates in the preparation of pest
  • the present invention is directed to N-substituted acylamidosulfenyl chlorides and their method of preparation.
  • the subject acyl'amidosulfenyl chlorides are useful intermediates in the preparation of pesticides.
  • N-substituted acylamidosulfenyl chlorides of the present invention may be represented by the formula:
  • R is alkyl of from 1 to carbon atoms, alkyl of from 1 to 10 carbon atoms substituted with halogen of atomic number 17 to 35 (chlorine or bromine), cycloalkyl of from 3 to 10 carbon atoms or cycloalkyl of from 3 to 10 carbon atoms substituted with halogen atoms of atomic number 17 to 35;
  • R is hydrogen, alkyl of l to 10 carbon atoms, alkyl of 1 to 10 carbon atoms substituted with halogen atoms of atomic number 17 to 35, cycloalkyl of 3 to 10 carbon atoms or cycloalkyl of 3 to 10 carbon atoms substituted with halogen atoms of [atomic number 17 to 35; with the proviso that R and R may be joined to form a linear alkylene radical of 3 to 5 carbon atoms which is bound to the carbonyl and nitrogen to form a ring.
  • the haloalkyl radical or halocycloalkyl radical
  • R is alkyl of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms substituted with 1 to 4 halogen atoms of atomic number 17 to 35, preferably 1 to 2 halogen atoms of atimic number 17 to 35, cycloalkyl of 3 to 6 corbon atoms or cycloalkyl of 3 to 6 carbon atoms substituted with 1 to 4 halogen atoms of atomic number 17 to 35, preferably 1 to 2 halogen atoms of atomic number 17 to 35; and R is hydrogen, alkyl of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms substituted with 1 to 4 3,699,122 Patented Oct.
  • R is alkyl of l to 4 carbon atoms or alkyl of l to 4 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35, preferably chlorine and R is hydrogen or alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35, preferably chlorine.
  • R and R may be joined to form a linear alkylene radical of 3 to 5 carbon which is bound to the carbonyl and nitrogen to form a ring.
  • the iacylamidosulfenyl chlorides in which R and R are joined to form a ring with the carbonyl and nitrogen may alternatively be represented by the formula:
  • R is a linear alkylene of 3 to 5 carbon atoms.
  • alkyl groups which R and R above may represent are methyl, ethyl, n-propyl, isopropyl, n-butyl, iso'butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, 2-methylbutyl, 3-methylphentyl, cyclopentyl, cyclohexyl, cyclooctyl, chloromethyl, 2-chloroethyl, 3-chloropropyl, 4-chloroamyl, 6-chlorohexyl, 2,6-dichlorocyclohexyl, 2,6-dibromocyc1ohexyl, 3-bromocyc1ohexyl, bromomethyl, 2-bromoethyl, 3-bromopropyl, etc.
  • Alkyl radicals which R and R taken together or R may represent are propylene, butylene and amylene.
  • Typical acylamidosulfenyl chlorides represented by the above formula are: N-methyl formamidosulfenyl chloride, N-ethyl formamidosulfenyl chloride, N-propyl formamidosulfenyl chloride, N-butyl formamidosulfenyl chloride, N-chloromethyl formamidosulfenyl chloride, N- 2-chloroethyl formamidosulfenyl chloride, N-2-chlor0- propyl formamidosulfenyl chloride, N-bromomethyl formamidosulfenyl chloride, N-cyclopropyl formamidosulfenyl chloride, N-cyclobutyl foramidosulfenyl chloride, N-cyclohexyl formamidosulfenyl chloride, N-methyl acetamidosulfenyl chloride, N-ethyl acetamidosulfenyl chloride, N-propyl
  • acylamidosulfenyl chloride of this invention may be prepared by reacting sulfur dichloride with a monoalkylated amide or a lactam. This reaction is illustrated by the following chemical equation:
  • R and R are as previously defined. It is desirable .to use stoichiometric proportions of the reactants or an excess of the sulfur dichloride reactant, up to, e.g. 4: 1. mole ratio.
  • reaction temperature in general is'not critical and will usually be in the range of 50 to 100 0, preferably 20 to 60 C.
  • the pressure is not critical and will usually be atmospheric or autogenous.
  • Reaction time will generally be from A hr. to 5 hours.
  • the reaction will generally be carried out in the presence of an inert solvent such as dichloromethane, diethylether, tetrahydrofuran, dimethylformamide, dioxane, acetonitrile, and the like.
  • an inert solvent such as dichloromethane, diethylether, tetrahydrofuran, dimethylformamide, dioxane, acetonitrile, and the like.
  • each of the reactants will be admixed separately with a solvent and then the mixture containing the amide and preferably a hydrogen halide acceptor will be added slowly with stirring to the mixture containing the sulfur dichloride.
  • the amount of solvent should be equal to or up to five times the weight of the sulfur dichloride.
  • the solvent for the amide-halide acceptor mixture should be equal to or up to five times the weight of both.
  • the sulfur dichloride should be added in high purity, for example greater than 98% purity. It is frequently desirable to have a small amount of an inhibitor such as tributyl phosphate or triethylphosphate present with the sulfur dichloride in order to maintain the high purity.
  • an inhibitor such as tributyl phosphate or triethylphosphate
  • the reaction is preferably carried out in the presence of a mild hydrogen halide acceptor. At least stoichiometric amounts of acceptor should be used. Soluble tertiary amines such as pyridine'and trialkylamines, e.g., triethylamine and tributylamine are preferred.
  • the acylamidosulfenyl chlorine can generally be recovered from the reaction mixture by stripping any excess sulfur dichloride, filtering ofi? the salt formed between the hydrogen halide acceptor and the HCl, evaporating the solvent and the product purified as by distillation or recrystallization.
  • the compounds of the present invention are useful intermediates in the preparation of pesticides.
  • the compounds of the present invention may be used to produce aryl N-(N'-alkylacylamidothio)-N-alkyl carbamates which have pesticidal, particularly insecticidal activity.
  • These compounds are prepared by the reaction of an N- alkyl acylamidosulfenyl chloride with an aryl N-alkyl carbamate.
  • m-sec-butylphenyl N-(N- methylacetamidothio)-N-methy1 carbamate may be prepared by reacting N-methyl acetamidosulfenyl chloride of the present invention with m-sec-butylphenyl N-methyl carbamate according to the general chemical reaction scheme:
  • Example 1 up in petroleum ether and the remaining salt filtered. The petroleum ether was then evaporated and the product distilled. The fraction boiling at 39 C./05 mm. was analyzed. This analysis showed:
  • N-methyl chloroacetamidosulfenyl chloride was prepared as follows:
  • the oily liquid product was analyzed in the infrared. There was a medium strong peak between 18 and 19p. Distillation should be avoided, or carefully performed, to prevent violent decomposition of the N-trichloro pyrollidone.
  • R is alkyl of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35, cycloalkyl of from 3 to 6 carbon atoms or cycloalkyl of from 3 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35;
  • R is hydrogen, alkyl of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35, cycloalkyl of 3 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35 with the proviso that R and R may be joined to form a linear alkylene radical of 3 to carbon atoms which is bound to the carbonyl and nitrogen to form a ring.
  • R is alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted with 1 to 2 chlorine atoms; R is hydrogen, alkyl of 1 to 4 carbon atoms or alkyl of l to 4 carbon atoms substituted with 1 to 2 chlorine atoms.
  • R is alkyl of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35, cycloalkyl of from 3 to 6 carbon atoms, cycloalkyl of from 3 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35
  • R is hydrogen, alkyl of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35, cycloalkyl of 3 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35; with the proviso that R and R may be joined to form a linear alkylene radical of 3 to 5 carbon atoms which is bound to the carbonyl and nitrogen to form

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Abstract

N-SUBSTITUTED ACYLAMIDOSULFENYL CHLORIDES OF THE FORMULA

R-N(-SCL)-CO-R1

WHEREIN R IS AN ALKYL GROUP OF FROM 1 TO 10 CARBON ATOMS OR CYCLOALKYL GROUP OF FROM 3 TO 10 CARBON ATOMS, THE ALKYL OR CYCLOALKYL GROUPS BEING OPTIONALLY SUBSTITUTED WITH HALOGEN ATOMS AND R1 IS HYDROGEN, ALKYL OF FROM 1 TO 10 CARBON ATOMS OR CYCLOALKYL OF FROM 1 TO 10 CARBON ATOMS, THE ALKYL OR CYCLOALKYL GROUPS BEING OPTIONALLY SUBSTITUTED WITH HALOGEN ATOMS; WITH THE PROVISO THAT R AND R1 MAY BE JOINED TO FORM A LINEAR ALKYLENE RADICAL OF 3 TO 5 CARBON ATOMS WHICH IS BOUND TO THE CARBONYL AND NITROGEN TO FORM A RING. THE COMPOUNDS ARE PREPARED BY REACTING N-SUBSTITUTED CARBOXAMINES WITH SULFUR DICHLORIDE. THE N-SUBSTITUTED ACYLAMIDOSULFENYL CHLORIDES ARE USEFUL INTERMEDIATES IN THE PREPARATION OF PESTICIDES.

Description

United States Patent O ABSTRACT OF THE DISCLOSURE N-substituted acylamidosulfenyl chlorides formula of the wherein R is an alkyl group of from 1 to 10 carbon atoms or cycloalkyl group of from 3 to 10 carbon atoms, the alkyl or cycloalkyl groups being optionally substituted with halogen atoms and R is hydrogen, alkyl of from 1 to 10 carbon atoms or cycloalkyl of from 1 to 10 carbon atoms, the alkyl or cycloalkyl groups being optionally substituted with halogen atoms; with the proviso that R and R may be joined to form a linear alkylene radical of 3 to carbon atoms which is bound to the carbonyl and nitrogen to form a ring. The compounds are prepared by reacting N-substituted carboxamines with sulfur dichloride. The 'N-substituted acylamidosulfenyl chlorides are useful intermediates in the preparation of pesticides.
FIELD OF THE INVENTION The present invention is directed to N-substituted acylamidosulfenyl chlorides and their method of preparation. The subject acyl'amidosulfenyl chlorides are useful intermediates in the preparation of pesticides.
DESCRIPTION OF THE INVENTION The N-substituted acylamidosulfenyl chlorides of the present invention may be represented by the formula:
wherein R is alkyl of from 1 to carbon atoms, alkyl of from 1 to 10 carbon atoms substituted with halogen of atomic number 17 to 35 (chlorine or bromine), cycloalkyl of from 3 to 10 carbon atoms or cycloalkyl of from 3 to 10 carbon atoms substituted with halogen atoms of atomic number 17 to 35; R is hydrogen, alkyl of l to 10 carbon atoms, alkyl of 1 to 10 carbon atoms substituted with halogen atoms of atomic number 17 to 35, cycloalkyl of 3 to 10 carbon atoms or cycloalkyl of 3 to 10 carbon atoms substituted with halogen atoms of [atomic number 17 to 35; with the proviso that R and R may be joined to form a linear alkylene radical of 3 to 5 carbon atoms which is bound to the carbonyl and nitrogen to form a ring. Preferably the haloalkyl radical or halocycloalkyl radical will contain 1 to 4 halogen substituents, more preferably 1 to 2 halogen substituents.
Preferably R is alkyl of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms substituted with 1 to 4 halogen atoms of atomic number 17 to 35, preferably 1 to 2 halogen atoms of atimic number 17 to 35, cycloalkyl of 3 to 6 corbon atoms or cycloalkyl of 3 to 6 carbon atoms substituted with 1 to 4 halogen atoms of atomic number 17 to 35, preferably 1 to 2 halogen atoms of atomic number 17 to 35; and R is hydrogen, alkyl of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms substituted with 1 to 4 3,699,122 Patented Oct. 17, 1972 "ice halogen atoms of atomic number 17 to 35, preferably 1 to 2 halogen atoms of atomic number 17 to 35, cycloalkyl of 3 to 6 carbon atoms of cycloalkyl of 3 to 6 carbon atoms substituted with 1 to 4 halogen atoms of atomic number 17 to 35, preferably 1 to 2 halogen atoms of atomic number 17 to 35.
Still more preferably R is alkyl of l to 4 carbon atoms or alkyl of l to 4 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35, preferably chlorine and R is hydrogen or alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35, preferably chlorine.
R and R may be joined to form a linear alkylene radical of 3 to 5 carbon which is bound to the carbonyl and nitrogen to form a ring. The iacylamidosulfenyl chlorides in which R and R are joined to form a ring with the carbonyl and nitrogen may alternatively be represented by the formula:
wherein R is a linear alkylene of 3 to 5 carbon atoms.
Representative alkyl groups which R and R above may represent are methyl, ethyl, n-propyl, isopropyl, n-butyl, iso'butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, 2-methylbutyl, 3-methylphentyl, cyclopentyl, cyclohexyl, cyclooctyl, chloromethyl, 2-chloroethyl, 3-chloropropyl, 4-chloroamyl, 6-chlorohexyl, 2,6-dichlorocyclohexyl, 2,6-dibromocyc1ohexyl, 3-bromocyc1ohexyl, bromomethyl, 2-bromoethyl, 3-bromopropyl, etc.
Alkyl radicals which R and R taken together or R may represent are propylene, butylene and amylene.
Typical acylamidosulfenyl chlorides represented by the above formula are: N-methyl formamidosulfenyl chloride, N-ethyl formamidosulfenyl chloride, N-propyl formamidosulfenyl chloride, N-butyl formamidosulfenyl chloride, N-chloromethyl formamidosulfenyl chloride, N- 2-chloroethyl formamidosulfenyl chloride, N-2-chlor0- propyl formamidosulfenyl chloride, N-bromomethyl formamidosulfenyl chloride, N-cyclopropyl formamidosulfenyl chloride, N-cyclobutyl foramidosulfenyl chloride, N-cyclohexyl formamidosulfenyl chloride, N-methyl acetamidosulfenyl chloride, N-ethyl acetamidosulfenyl chloride, N-propyl acetoamidosulfenyl chloride, N-butyl acetamindosulfenyl chloride, N-methyl chloroacetamidosulfenyl chloride, N-methyl bromoacetamidosulfenyl chloride, N-methyl propionamidosulfenyl chloride, N- ethyl propionamidosulfenyl chloride, N-chloromethyl propionamidosulfenyl chloride, N-methyl 3,3-dichloropropionamidosulfenyl chloride, N-methyl-2,3-dibromopropionamidosulfenyl chloride, N-butyl propionamidosulfenyl chloride, N-methyl butyramidosulfenyl chloride, N- ethyl butyramidosulfenyl chloride, N-cyclohexyl buty-ramidosulfenyl chloride, N-isopropyl butyrarnidosulfenyl chloride, N-methyl valeramidosulfenyl chloride, N- methyl 3,4,S-trichlorovaleramidosulfenyl chloride, N- chloromethyl caproamidosulfenyl chloride, N-ethyl 6,7- dichloroenanthamidosulfenyl chloride, N-methyl caprylamidosulfenyl chloride, N-methyl cyclohexanoamidosulfenyl chloride, N-methyl 2-chlorocyclopentanoamidosulfenyl chloride, N-thiochloro pyrrolidone, N-thiochloro piperidone, N-thiochloro caprolactam.
The acylamidosulfenyl chloride of this invention may be prepared by reacting sulfur dichloride with a monoalkylated amide or a lactam. This reaction is illustrated by the following chemical equation:
wherein R and R are as previously defined. It is desirable .to use stoichiometric proportions of the reactants or an excess of the sulfur dichloride reactant, up to, e.g. 4: 1. mole ratio.
- The reaction temperature in general is'not critical and will usually be in the range of 50 to 100 0, preferably 20 to 60 C. Likewise the pressure is not critical and will usually be atmospheric or autogenous. Reaction time will generally be from A hr. to 5 hours.
The reaction will generally be carried out in the presence of an inert solvent such as dichloromethane, diethylether, tetrahydrofuran, dimethylformamide, dioxane, acetonitrile, and the like. Generally each of the reactants will be admixed separately with a solvent and then the mixture containing the amide and preferably a hydrogen halide acceptor will be added slowly with stirring to the mixture containing the sulfur dichloride. The amount of solvent should be equal to or up to five times the weight of the sulfur dichloride. Likewise the solvent for the amide-halide acceptor mixture should be equal to or up to five times the weight of both.
The sulfur dichloride should be added in high purity, for example greater than 98% purity. It is frequently desirable to have a small amount of an inhibitor such as tributyl phosphate or triethylphosphate present with the sulfur dichloride in order to maintain the high purity.
The reaction is preferably carried out in the presence of a mild hydrogen halide acceptor. At least stoichiometric amounts of acceptor should be used. Soluble tertiary amines such as pyridine'and trialkylamines, e.g., triethylamine and tributylamine are preferred.
The acylamidosulfenyl chlorine can generally be recovered from the reaction mixture by stripping any excess sulfur dichloride, filtering ofi? the salt formed between the hydrogen halide acceptor and the HCl, evaporating the solvent and the product purified as by distillation or recrystallization.
The compounds of the present invention are useful intermediates in the preparation of pesticides. Thus the compounds of the present invention may be used to produce aryl N-(N'-alkylacylamidothio)-N-alkyl carbamates which have pesticidal, particularly insecticidal activity. These compounds are prepared by the reaction of an N- alkyl acylamidosulfenyl chloride with an aryl N-alkyl carbamate. Thus for example, m-sec-butylphenyl N-(N- methylacetamidothio)-N-methy1 carbamate may be prepared by reacting N-methyl acetamidosulfenyl chloride of the present invention with m-sec-butylphenyl N-methyl carbamate according to the general chemical reaction scheme:
' The present invention can be more fully understood by reference to the following examples.
Example 1 up in petroleum ether and the remaining salt filtered. The petroleum ether was then evaporated and the product distilled. The fraction boiling at 39 C./05 mm. was analyzed. This analysis showed:
Calculated (percent): Cl, 28.23; S, 25.5. Found (percent): Cl, 31.88; S, 26.60.
The proton magnetic resonance spectra and infrared spectra further confirmed the structure.
Example 2 N-methyl acetamidosulfenyl chloride was prepared'as follows:
268 g. of freshly distilled sulfur dichloride stabilized with tributyl phosphate and 500 m1. of dichloromethane was cooled in a Dry Ice bath to l0 C. Then a mixture of 142 g. of N-methylacetamide and 154 g. of pyridine in 200 ml. of dichloromethane was added with stirring over a period of 5 hours. The temperature was maintained between 10 and 0 C. Stirring was continued for one hour after addition at a temperature of 0 C. The solid residue was removed by filtration, dichloromethane was evaporated and the product taken up in hexane which was then evaporated. The liquid product was analyzed. Element analysis was as follows:
Calculated (percent): S, 22.98; Cl, 25.42. Found (percent): S, 23.04; Cl, 27.35.
Example 3 N-methyl chloroacetamidosulfenyl chloride was prepared as follows:
134 g. of freshly distilled SC1 stabilized with tributylphosphate in 300 ml. of dichloromethane was cooled in a Dry Ice bath to 10 C. A mixture of g. of N-rnethylchloroacetamide, 73.5 g. of pyridine and ml. of dichloromethane was slowly added. Temperature was maintained between l0 and 0 C. during the addition time of 45 minutes. The mixture was then allowed to Warm to room temperature over about 2 hours, then 250 ml. of hexane was added and the mixture again cooled to 0 C. The solid residue was removed and the solution was stripped of hexane to give a thick dark oil. N-methyl chloroacetamidosulfenyl chloride was recovered by distillation and had a boiling point of 68 C. at 1.5 mnnNuclear magnetic resonance analysis and infrared analysis helped confirm the structure.
Example 4 Preparation of N-ethyl formamidosulfenyl chloride:
To a solution of 176 g. of freshly distilled sulfur dichloride containing a small amount of tributyl phosphate stabilizer, in 250 ml. of dichloromethane at 10 C. There was added over a period of 1 hour a solution of 100 g. of N-ethyl formamide, 108 g. of pyridine and 200 ml. of dichloromethane. The resulting mixture was stirred for an additional hour. Then 200 ml. of hexane was added and the soluble residue removed. by filtration at 0 C. The filtrate was evaporated under reduce pressure to give 173 g. of an oily liquid. This material was distilled and the fraction having a boiling point of 25-30 C. at 0.5 mm. pressure was taken as the product. An NMR spectra was consistent with the structure assigned. Elemental analysis gave the following results:
Calculated (percent): S, 22.97; Cl, 25.40. Found (percent): S, 22.58; Cl, 25.85.
Example 5 Preparation of N-thiochloro pyrollidone:
Freshly distilled sulfur dichloride, 20.6 g., was dissolved in 100 ml. of dichloromethane containing a small amount of tributyl phosphate stabilizer. To this solution there was added a solution of 8.5 g. of pyrollidone and 10.2 g. of
triethylamine, dissolved in 100 ml. of dichloromethane.-
The resulting mixture was filtered, and the filtrate was concentrated by evaporation under reduced pressure. The thereby formed precipitate was removed by filtration, and
the oily liquid product was analyzed in the infrared. There was a medium strong peak between 18 and 19p. Distillation should be avoided, or carefully performed, to prevent violent decomposition of the N-trichloro pyrollidone.
As will be evident to those skilled in the art, various modifications on this invention can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.
I claim:
1. Compound of the formula wherein R is alkyl of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35, cycloalkyl of from 3 to 6 carbon atoms or cycloalkyl of from 3 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35; R is hydrogen, alkyl of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35, cycloalkyl of 3 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35 with the proviso that R and R may be joined to form a linear alkylene radical of 3 to carbon atoms which is bound to the carbonyl and nitrogen to form a ring.
2. Compound of claim 1 wherein R is alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted with 1 to 2 chlorine atoms; R is hydrogen, alkyl of 1 to 4 carbon atoms or alkyl of l to 4 carbon atoms substituted with 1 to 2 chlorine atoms.
3. Compound of claim 2 wherein R is methyl or ethyl and R is hydrogen, methyl or chloromethyl.
4. Compound of claim 1 wherein R and R are joined to form a linear alkylene radical of 3 carbon atoms.
5. The method of preparation of the compound of the formula o R-N-ii-R wherein R is alkyl of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35, cycloalkyl of from 3 to 6 carbon atoms, cycloalkyl of from 3 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35 R is hydrogen, alkyl of 1 to 6 carbon atoms, alkyl of 1 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35, cycloalkyl of 3 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms substituted with 1 to 2 halogen atoms of atomic number 17 to 35; with the proviso that R and R may be joined to form a linear alkylene radical of 3 to 5 carbon atoms which is bound to the carbonyl and nitrogen to form a ring, which comprises reacting in the presence of a hydrogen halide acceptor a monoalkylated amide or lactem with sulfur dichloride according to the reaction:
References Cited UNITED STATES PATENTS 6/1971 Fuchs 260-482 OTHER REFERENCES Chem. Abs. -4061 (1964). Chem. Abs. 57-13771 (1962). Sullivan et al. Int. J. Sulfur Chem. A, l, 207 (1971).
ALEX MAZEL, Primary Examiner J. A. NARCAVAGE, Assistant Examiner US. Cl. X.R.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3997605A (en) * 1975-05-19 1976-12-14 The Goodyear Tire & Rubber Company Preparation of formamide compounds
US4006231A (en) * 1973-07-12 1977-02-01 The Regents Of The University Of California N-aminosulfenylated derivatives of carbofuran
US4134913A (en) * 1975-05-07 1979-01-16 The Upjohn Company Amidosulfenyl chloride intermediates
US4159281A (en) * 1971-10-15 1979-06-26 Chevron Research Company N-Chlorothio ureas
US4338450A (en) * 1975-12-01 1982-07-06 Union Carbide Corporation Carbamate-sulfenyl-carbamoyl fluoride compounds
US4595769A (en) * 1975-12-01 1986-06-17 Union Carbide Corporation Carbamate-sulfenyl-carbamoyl fluoride compounds
US4642353A (en) * 1982-04-28 1987-02-10 Ciba-Geigy Corporation Photocrosslinkable polymers having thioetherimidyl side groups

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4159281A (en) * 1971-10-15 1979-06-26 Chevron Research Company N-Chlorothio ureas
US4006231A (en) * 1973-07-12 1977-02-01 The Regents Of The University Of California N-aminosulfenylated derivatives of carbofuran
US4134913A (en) * 1975-05-07 1979-01-16 The Upjohn Company Amidosulfenyl chloride intermediates
US3997605A (en) * 1975-05-19 1976-12-14 The Goodyear Tire & Rubber Company Preparation of formamide compounds
US4338450A (en) * 1975-12-01 1982-07-06 Union Carbide Corporation Carbamate-sulfenyl-carbamoyl fluoride compounds
US4595769A (en) * 1975-12-01 1986-06-17 Union Carbide Corporation Carbamate-sulfenyl-carbamoyl fluoride compounds
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