US2466276A - Manufacture of thiocarbamyl chlorides - Google Patents

Manufacture of thiocarbamyl chlorides Download PDF

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Publication number
US2466276A
US2466276A US645233A US64523346A US2466276A US 2466276 A US2466276 A US 2466276A US 645233 A US645233 A US 645233A US 64523346 A US64523346 A US 64523346A US 2466276 A US2466276 A US 2466276A
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grams
thiuram
chlorine
reaction
sulfur
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US645233A
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Edmond J Ritter
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Sharples Chemicals Inc
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Sharples Chemicals Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
    • C07D295/21—Radicals derived from sulfur analogues of carbonic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators

Definitions

  • the present invention rests upon the discovery that the thiocarbamyl chlorides can be made by the relatively simple procedure of chlorinating the corresponding thiuram sulfides.
  • the thiuram sulfides which can be treated most effectively in practice of the invention may be represented by the following formula:
  • R1, R2, R3 and R4 are hydrocarbon substituents.
  • R1, R2, R3 and R4 may be either alkyl or aryl substituents, but R2 and R4 will ordinarily be alkyl substituents in cases in which R1 and R3 are aryl substituents.
  • the symbols R1 and R2 may represent between them a single polymethylene radical such as pentamethylene, and the symbols R3 and R4 another such radical.
  • the compounds which may be successfully chlorinated in practice of the invention include tetra-alkyl, symmetrical di-alkyl-di-aryl, and di-polymethylene thiuram sulfides.
  • the temperature at the beginning of the chlorination procedure is 75 C., this temperature may rise to 82 C., for example, during introduction of the chlorine.
  • the flask may then be immersed in a water bath maintained at 40 C. and chlorination continued until the theoretically necessary quantity of chlorine has been added, the temperature being maintained between and C. during this continued chlorination.
  • the reaction product is preferably maintained at a temperature between 50 and C. for two hours or longer to permit sulfur and a trace of amine hydrochloride to precipitate.
  • the product may then be filtered at a temperature of 52 0., and the filtrate distilled under vacuum to yield di-ethyl thiocarbamyl chloride of a high degree of purity.
  • chlorination of various substituted thiuram sulfides such as represented by the above formula and equation may be accomplished by direct treatment of the liquid or melted thiuram sulfide, just as in the case of the tetra-ethyl thiuram disulfide discussed above, it will be desirable in many instances to suspend or dissolve the particular thiuram sulfide to be treated in a suitable solvent or diluent which is relatively inert under the conditions of the reaction.
  • the thiuram sulfide maybe suspended in carbon tetrachloride or dissolved in benzene or chloroform, and then subjected to chlorination by introduction of a stream of gaseous chlorine or other chlorinating agent providing free chlorine.
  • the chlorination reaction may be performed upon thiuram sulfides of various degrees of sulfur content.
  • Thiuram mono-sulfides, tri-sulfides or tetra-sulfides may, for example, be chlorinated in the same manner as the corresponding disulfides, the only difference in chlorination of these other sulfides being that, in the case of the mono-sulfide, only a single molecule of the desired thiocarbamyl chloride is formed by the chlorination, and in the case of triand tetrasulfides, a larger quantity of sulfur is liberated incident to formation of two molecules of thiocarbamyl chloride from a single molecule of the thiuram sulfide than is the case in chlorination of the disulfide.
  • Example I 402 grams (1.36 moles) of tetra-ethyl thiuram disulfide were dispersed in 800 ml. of carbon tetrachloride. 96.5 grams (1.36 moles) of chlorine gas were bubbled into the resulting suspension over a period of about minutes, the temperature rising from 32 C. to 67 C. during this interval. By the time 49 grams of chlorine had been added, the remaining tetra-ethyl thiuram disuliide had become dissolved, with the result that a clear, reddish brown solution was formed. When 76 grains of chlorine had been added, the solution became cloudy due to formation of free sulfur. At the conclusion of the chlorination, sulfur was precipitated by cooling the reaction mixture on an ice bath.
  • This material was distilled at 113 C. at 10 mm. Hg. pressure. Analysis showed 23.31% Cl, 8.89% N, 21.01% S. compared to theoretical values of 23.4% C1, 9.2%% N, and 21.1% S. The total yield was 402 grams or 98%.
  • Example II 1118 grams (4.65 moles) of tetramethyl thiuram disulfide were dispersed in 3 liters of carbon tetrachloride. 3305 grams 1.65 moles) of chlorine gas were bubbled into the resulting suspension during a period of three hours, the temperature rising from 25 C. to 65 C. during this chlorination. No external cooling was provided. The chlorination reaction resulted in formation of a relatively clear, deep orange solution. Toward the end of the reaction, the solution became milky, due to precipitation of sulfur. The flask containing the reaction product was immersed overnight in a water bath maintained at 10 0., and the product was decanted from the large mass of sulfur thus precipitated.
  • Example III 296 grams (0.73 mole) of tetra-butyl thiuram disulfide were dissolved in 500 ml. of carbon tetrachloride. grams (0.73 mole) of chlorine gas were bubbled into the resulting suspension over a period or 20 minutes. The temperature rose from C. to 45 C. during introduction of the first 26 grams of chlorine, and the flask was then immersed in an ice bath and the reaction completed by introduction of the remaining 26 grams of chlorine to the reaction mixture maintained at about 30 C. Upon removal of free sulfur and solvent as in the preceding examples, a dark brown filtrate of crude di-butyl thiocarbamyl chloride weighing 260 grams (87% of theory) was obtained.
  • Example IV 148 grams (0.5 mole) of tetra-ethyl thiuram disulfide were suspended in 500 m1. of carbon tetrachloride. 67.5 rams (0.5 mole) of sulfuryl chloride were dissolved in 100 ml. of carbon tetrachloride, the resulting solution was added to the suspension of tetra-ethyl thiuram clisulfide over a period of 25 minutes during continued stirring of the reaction mixture. The resulting chlorination reaction was exothermic, the temperature rising from 25 C. to 36 C. during the course of the reaction. The stirring was continued for additional minutes at room temperature, with slow evolution of sulfur dioxide. The material was then heated with a low flame for 30 minutes and refluxed for one hour, and allowed to stand overnight at room temperature. About 2 grams of amorphous sulfur was filtered from the product.
  • Example V 208 grams (1.0 mole) of tetra-methyl thiuram mono-sulfide were dispersed in 675 ml. of carbon tetrachloride. 76 grams (1.56 mole) of chlorine gas were bubbled into the resulting suspension over a period of one hour, and the temperature rose from 23 C. to 50 C. during the course of the chlorination. During introduction of the last half of the theoretical quantity of chlorine, the solution resulting from the chlorination already accomplished was placed on an ice bath, with the result that the chlorination was completed at a temperature of about 40 C. A large quantity of sulfur precipitated at the end of the reaction. Upon removal or" sulfur and solvent as in previous examples, 132.5 grams (53% of theory) of dimethyl thiocarbarnyl chloride were obtained.
  • Example VI 152 grams (0.5 mole) of tetra-methyl thiuram tetra-sulfide Were dispersed in 500 ml. of carbon tetrachloride. 35.5 grams (0.5 mole) of chlorine gas were bubbled in over a period of 20- minutes, with a resultant rise in temperature from 23 C. to 52 C.
  • This example presented a contrast to the chlorination of tetra-ethyl thiuram disulfide, as in the preceding examples, in that a clear solution was not obtained at'any time during the course of the reaction of the present example, due to splitting out of free sulfur. Solvent and sulfur were removed as-in preceding examples, and the resulting di-methyl thiocarbamyl ch1o-,
  • Example VII 148 grams (0.5 mole) of tetra-ethyl thiuram disulfide were dissolved in 500 ml. of benzene. 35.5 grams (0.5 mole) of chlorine gas were bubbled in over a 15 minute interval, the temperature rising from 25 C. to 60 C. Upon removal of sulfur and solvent, 142 grams (93.8% of theory) of crude di-ethyl thiocarbamyl chloride were obtained.
  • Example VIII 148 grams (0.5 mole) of tetra-ethyl thiuram disulfide were dissolved in 500 ml. of chloroform. 67.5 grams (0.5 mole) of sulfur monochloride were dissolved in 100 ml. of chloroform and the resulting solution was added to the tetra-ethyl thiuram disulfide solution over a period of minutes, with continued stirring. The temperature rose from 21 C. to 45 C. during introduction of the sulfur monochloride. The resulting solution was refluxed for one hour at 62 C. and then cooled and filtered. Upon purification as in preceding examples, 119 grams (79% yield) of crude di-ethyl thiocarbamyl chloride were obtained as a light brown crystalline material, M. P. 47-495 C.
  • Example X 148 grams (0.5 mole) of tetra-ethyl thiuram disulfide were placed in a flask which was immersed in a hot water bath until the tetra-ethyl thiuram sulfide had melted. No solvent was added. Chlorine gas was bubbled into the melted material intermittently over a period of minutes until about half of the theoretically required amount of chlorine had been added. The temperature rose from 75 C. to 82 C. during this period. The flask was now immersed in a water bath maintained at 40 C., and introduction of chlorine was resumed until the theoretically required amount of chlorine had been added, the temperature of the melted product being kept between 50 C. and 60 C. during this completion of the chlorination reaction.
  • Example XI 192 grams (0.5 mole) of di-pentamethylene thiuram tetra-sulfide were dispersed in 700 ml. of carbon tetrachloride. 38 grams (0.53 mole) of chlorine gas were bubbled in over a minute interval, and the temperature rose from 23 C. to 48 C. during this chlorination. A cloudy precipitate was present throughout the course of the reaction, due to splitting out of free sulfur.
  • Example XIV 151 grams of tetra-ethyl thiuram disulfide, 114 grams of phosphorus pentachloride and '75 grams of phosphorus oxychloride were placed in a flask equipped with a reflux condenser and heated by means of a water bath. After being maintained at a temperature of 95-100 C. for 3 hours the material was distilled under vacuum, 202.5 grams of yellow oil being taken overhead. The residue, crude diethyl thiocarbamyl chloride, which melted at 46-48 C. amounted to 48.1 grams. This corresponded to a yield of 53.5%.
  • di-ethyl thiocarbamyl chloride the process comprising contacting under substantially non-aqueous conditions tetraethyl thiuram disulfide with chlorine until reaction occurs between said thiuram sulfide and said chlorine to effect splitting of said thiuram sulfide and formation of di-ethyl thiocarbamyl chloride.
  • cals' and taken collectively represent a single polymethylene radical and in which R3 and taken individually represent one of a group consisting of alkyl radicals and aryl radicals and taken collectively represent a single polymeth 8 ylene radical, and continuing the action of said chlorinating agent until splitting of said thiuram sulfide occurs with the formation of substituted thiocarbamyl chloride.
  • each of R1, R2, R3 and R4 is an alkyl radical containing from 1 to 4 carbon atoms.
  • chlorinating agent is chlorine, in which a; has a value of from 1 to 4, and in which each of R1, R2, R3 and R4 is an alkyl radical containing from 1 to 4 carbon atoms.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US645233A 1946-02-02 1946-02-02 Manufacture of thiocarbamyl chlorides Expired - Lifetime US2466276A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2767212A (en) * 1952-08-02 1956-10-16 Pennsylvania Salt Mfg Co N-substituted thiocarbamyl chloride perchlorides
US2870204A (en) * 1955-03-25 1959-01-20 American Cyanamid Co Preparation of phosphonothioic dichlorides, tetrachlorophosphoranes, and phosphonic dichlorides
US3332658A (en) * 1965-02-15 1967-07-25 Jerome H Lemelson Mold construction and method

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE386936C (de) * 1921-12-09 1923-12-19 Kalle & Co Ag Verfahren zur Darstellung von Halogenderivaten des Lupinins
US1610216A (en) * 1925-02-25 1926-12-07 Du Pont Production of vulcanized rubber and accelerators therefor
DE462418C (de) * 1926-10-31 1928-07-11 Silesia Ver Chemischer Fabrike Verfahren zur Darstellung von Thiuramdisulfiden
US1782111A (en) * 1925-08-04 1930-11-18 Naugatuck Chem Co Method of manufacturing tetra-alkylated thiuramdisulphides
US1796977A (en) * 1931-03-17 Sigkjeents
US1798588A (en) * 1926-05-28 1931-03-31 Roessler & Hasslacher Chemical Process for the preparation of tetra-methyl-thiuram polysulphides
US2375083A (en) * 1943-08-05 1945-05-01 Monsanto Chemicals Preparation of disulphides

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1796977A (en) * 1931-03-17 Sigkjeents
DE386936C (de) * 1921-12-09 1923-12-19 Kalle & Co Ag Verfahren zur Darstellung von Halogenderivaten des Lupinins
US1610216A (en) * 1925-02-25 1926-12-07 Du Pont Production of vulcanized rubber and accelerators therefor
US1782111A (en) * 1925-08-04 1930-11-18 Naugatuck Chem Co Method of manufacturing tetra-alkylated thiuramdisulphides
US1798588A (en) * 1926-05-28 1931-03-31 Roessler & Hasslacher Chemical Process for the preparation of tetra-methyl-thiuram polysulphides
DE462418C (de) * 1926-10-31 1928-07-11 Silesia Ver Chemischer Fabrike Verfahren zur Darstellung von Thiuramdisulfiden
US2375083A (en) * 1943-08-05 1945-05-01 Monsanto Chemicals Preparation of disulphides

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2767212A (en) * 1952-08-02 1956-10-16 Pennsylvania Salt Mfg Co N-substituted thiocarbamyl chloride perchlorides
US2870204A (en) * 1955-03-25 1959-01-20 American Cyanamid Co Preparation of phosphonothioic dichlorides, tetrachlorophosphoranes, and phosphonic dichlorides
US3332658A (en) * 1965-02-15 1967-07-25 Jerome H Lemelson Mold construction and method

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