Patented Apr. 7, 1953 2,634,291 UNITED STATES PATENT OFFICE 2,634,291 PRIMARY AND SECONDARY ALKYL SULFENYLTRITHIOCARBONATES Philip M. Arnold, Bartlesville, Okla., assignor to Phillips Petroleum Company, a corporation of Delaware No Drawing. Application November 13, 1951. Serial No. 256,119 - 3 Claims. (CI. 260-545) 1. The following examples are specific illustra The present invention relates to a new class of tions of the preparation of one of the novel Com organic sulfur compounds, and more particularly pounds of this invention, but the procedure de to novel compounds having the general formula, Scribed therein may be considered as exemplary SSR of that applicable to the preparation of the other members of the class of primary and secondary N SSR dialkyl sulfenyl trithiocarbonates described. in which R is a primary or secondary alkyl group. A Solution of n-butylsulfenyl chloride in iso The new compounds are the primary and secon pentane was prepared in a one liter, three necked 10 flask equipped with a stirrer, a Dry-Ice cooled dary dialkyl sulfenyl trithiocarbonates, and are condenser, a heating Inantle, and a chlorine inlet derivatives of trithiocarbonic acid, H2CS3, in bubbler. Di - n - butyldisulfide and isopentane Which the hydrogen atoms have been replaced were charged to the flask using approximately by the alkyl sulfenyl groups, RS-, wherein S is connected with the the alkyl group at a primary 1200 ml, of isopentane per mol of disulfide. The 5 solution was heated until the isopentane refluxed or a secondary carbon atom. vigorously. The heating mantle was removed The new compounds of the present invention and agitation started. ... One mol of chlorine (71 may be prepared by the reaction of an alkali tri grams) per gram mol of disulfide was added. thiocarbonate with a primary or secondary alkyl The resulting normal butyl Sulfenyl chloride So sulfenylhalide in accordance with the equation 20 lution was used immediately after preparation. SM SSR An aqueous solution of sodium trithiocarbonate was prepared by reacting sodium sulfide With SacC -- 2RSX - S=C carbon disulfide in the presence of Water, as SM SSR described in U. S. Patent 2,221,796. The solu where. M is sodium or other alkali metal, R. tion was prepared in a one liter, three necked is a primary or secondary alkyl radical, and flask. The flask was equipped with a Stirrer, a X is chlorine or other halogen. The reaction Dry-Ice cooled condenser, and provisions for con may be carried out at room temperature or at ducting the reaction in a nitrogen atmosphere. somewhat higher temperatures, preferably in the Approximately one gram molecular weight of presence of a Suitable inert Solvent Such as a sodium sulfide nonahydrate and 100 ml. of water paraffin hydrocarbon. In general, it is preferred were charged to the flask. The slurry was stirred that R be a primary or Secondary alkyl radical 20 minutes to saturate the water. Based on the having from 1 to 12 carbon atoms, in Order to sodium sulfide, a 10 per cent excess of carbon give products having a preferred chain length and disulfide was added, and the reaction mixture Was molecular weight. stirred approximately 16 hours at room tempera The primary and secondary alkyl Sulfenyl 35 ture. As the reaction proceeded, the sodium Sull halides are readily prepared by halogenation of fide gradually went into solution and the Water primary or secondary alkyl mercaptains or disul phase changed from colorless to yellow and finally fides, care being taken to avoid simultaneous to deep red. After completing the reaction, the halogenation of the alkyl group. The alkali tri excess carbon disulfide was removed by heating thiocarbonates are prepared by the reaction of 40 the solution to 140°F., and the concentration of an alkali metal sulfide with carbon disulfide. sodium trithiocarbonate in the resulting aqueous The new compounds in question are of particu solution was calculated from the weight of car lar interest as lubricating oil additives, rubber bon disulfide which had reacted. Based on the vulcanization agents, and as flotation agents in sodium sulfide charged, a 92 mole per cent yield the separation of Ores. They also can be em 45 of sodium trithiocarbonate was obtained. Sodium trithiocarbonate was also prepared by ployed in polymerization recipes wherein syn the method of Yoeman, J. Chem. Soc., 119, 40 thetic elastomers are produced. These novel pri (1921), whereby sodium ethylate is converted to mary and secondary compounds have good de sodium hydrosulfide with hydrogen Sulfide, and foliation properties, and show Some nematocidal 50 carbon disulfide is added to the alcoholic Solu activity. The use of the new compounds dis tion of sodium hydrosulfide to obtain the Sodium closed and claimed herein as nematocides is Set trithiocarbonate. Using the literature procedure forth in detail and claimed in the copending a 74 mol per cent yield (based on the sodium application of Roy E. Stansbury et al., Serial used) of the dry salt was obtained. No. 323,509, filed December 1, 1952, for Trithio 55 The reaction of normal butyl sulfenyl chloride carbonates as Nematocides. 2,684,291 3. 4. With sodium trithiocarbonate was carried out in chlorides are more reactive, particularly those a one liter, three necked flask equipped with a having 1 to 3 carbon atoms, it is desirable to use stirrer, a Dry-Ice cooled condenser and a drop an anhydrous reaction medium and avoid the ping funnel. After completing the addition of presence of Water in the reaction mixture. Other the two solutions, in each case, the two phase 5 alkali metal Salts such as potassium, and other mixture was stirred vigorously for 30 to 60 min halides Such as the fluoride and bromide may be utes. The two phases were then separated, the used instead of the Sodium Salt and the chloride, Water phase discarded, and the oil phase was respectively. washed with water and desiopentanized by heat This application is a continuation-in-part of ing to 130 F. at one mm. Hg preSSure. In each 10 my copending application Serial No. 766,438 filed case two mols of n-butyl sulfenyl chloride were August 5, 1947, issued Nov. 13, 1951, as U. S. used per mol of sodium trithiocarbonate. Patent 2,574,457, which claims the tertiary alkyl It was found that rapid addition of n-butyl Sulfenyl trithiocarbonates. sulfenyl chloride to the aqueous trithiocarbonate, I claim: or reverse addition (addition of trithiocarbonate 5 1. An alkyl Sulfenyl tithiocarbonate having to n-butylsulfenyl chloride) very significantly the general formula. favored the reaction, indicating that the presence SSR of an excess of the Sulfenyl chloride in the re Sa-C action mixture is desirable. Reaction of n-butylsulfemyl chloride with sodium trithiocarbonate to form di-n-butylsulfenyl trithiocarbonate Approxi Run No Method of Preparing Conc.Na2CS3 of centMole Yield Per- ofER, Crude mateof Adding Tine V. Na2CS3 Solution Sol. of Crude Product Sulfenyl (Percent) Product (no.20) Chloride d (Min.) 1------------------ NaOC5-2S--CS2------- 50 75 . 5230 30 2"----------------- Na2S.9H2O.--H2O.--CS:------ 36.6 91.7 . 590 (b) 3------------------ Na2S-9H2O--O--CS3------ 36.6 93.7 1.5928 were8 Attempts unsuccessful. to remove di-n-butyl disulfide, thought to be a possible inpurity, from the crude product essentially no overheadAt amaterial. pottemperature of 275 F. (1 mm.) decomposition occurred, and there was b Trithiocarbonate added to sul?enyl chloride. Analysis of crude di-n-butylsulfenyl trithio wherein R, is an alkyl radical selected from the carbonate from Run. No. 3: group consisting of primary and secondary alkyl Percent Carbon: Calculated.---------------------------------------------- 87.77 radicals having no more than 12 carbon atoms. Found-------------------------------------------------- 37.90 40 2. A di(primary alkyl sulfenyl) trithiocar Percent hydrogen: bonate having no more than 12 carbon atoms in Calculated.---------------------------------------------- 6.29 each alkyl group. PercentFound.--------------------'n Sulfur: r n - m - w - - - - - - - - - - - - - w - - - - - - - 6.99 3. Di-n-butylsulfenyl trithiocarbonate. Calculated.------ --- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 55.94 Found (by difference).--------------------------------- 55. Refractive Index, ni-------------------------------------- 1.5928 Density, dao'----------------------------------------------- 36 45 PHILIP M. ARNOLD. In a similar manner, other primary and sec REFERENCES CATED ondary alkyl Sulfenyl trithiocarbonates may be prepared by the reaction of Sodium trithiocar The following references are of record in the bonate with other primary and secondary alkyl file of this patent: sulfenyl chlorides. Examples are: methyl, ethyl, 50 UNITED STATES PATENTS n-propl, isopropyl, isobutyl, Sec-butyl, the various Number Name Date primary and Secondary pentyl, hexyl, heptyl, etc., 1,659,396 Douglass ---------- Feb. 14, 1928 Sulfenyl chlorides. Since the lower sulfenyl 2,574,457 Arnold ------------ Nov. 13, 1951 .