Патент USA US3065136код для вставки
United States Patent Office 3,@55,l27 Patented Nov. 20, 1962 1 2 3,065,127 of either said monochloride or said nitrile, and analyses by both physical and chemical methods show the pres ence in said reaction product of the elements chlorine and sulfur and of the cyano (-CN) radical. We have found, PESTICAL ACRYLONETRILE REACTEUN PRQDUCTS Samuel Ailen Heininger, §t. Louis, Mo., and Gail H. Birum, Dayton, ()hio, assignors to Monsanto Chemical Company, St. Louis, Mo, a corporation of Delaware N0 Drawing. @riginai application Oct. to, 1%7, Ser No. 690,423, now Patent No. 2,993,037, dated Juiy 18, 1961. Divided and this application Dec. 22, 1960, tier. No. 77,486 5 Claims. (Cl. 167—-22) This invention provides novel compositions of matter on the other hand, that when one mole of‘ sulfur mono chloride is treated under the same conditions with only one mole—rather than two moles—-of acrylonitrile, most of said monochloride is recovered unchanged, and the very small amount of higher boiling product which is obtained decomposes upon standing for a short time un , der atmospheric conditions. Since formation of the present complex mixture of obtained by reaction of acrylonitrile with sulfur monochlo sulfur~containing nitriles consumes approximately two ride. The invention also provides biological toxicants in moles of acrylonitrile per mole of the sulfur monochlo which said compositions are employed as the essential 15 ride, these reactants are advantageously present in stoichi toxicant ingredients. ometric proportions. However, an excess of the acrylo According to the invention, the presently provided novel reaction products are prepared by simply contacting sul~ nitrile may be used if desired to serve, e.g., as a reaction fur monochloride with at least two molar equivalents of wise be employed. Such suitable materials include, e.g., diluent. acrylonitrile, and allowing the resulting mixture to stand Extraneous inert solvents or diluents may like— carbon tetrachloride, chloroform, ethylene dichloride, di at ordinary or increased temperatures until reaction is completed. This can be readily ascertained, e.g., by not oxane, ether, etc. While the reaction will take place Without application of external heat, it is accelerated by moderate heating. Temperatures of, say, 25° C. to 180° ing cessation in change of color and/ or viscosity and/or refractive index of the reaction mixture. The present re C., and preferably of from 40° C. to 100° C., are em action products are believed to be mixtures of organic, 25 ployed. The use of catalysts is generally not necesesary, sulfur-containing chloro-nitriles and diverse decomposi~ tion products thereof. The reaction mixture components although acid catalysts and acidic reaction media may be employed. Since acrylonitrile is readily polymerizable, are dii?c‘ult to separate, but the presently provided com plex reaction products are of intrinsic utility, e.g., as an inhibitor of polymerization may be included in the reaction mixture, particularly when operating at the high microbiological toxicants, etc. It is believed that the reaction of sulfur monochloride with two molar equivalents of acrylonitrile probably pro ceeds with the primary formation of isometric chloro cyano disul?des, thus: er temperatures. The reaction may also be facilitated by conducting it under superatmospheric pressure. The time required to complete the reaction will de pend, of course, on other operational conditions, e.g., tem perature, pressure, presence or absence of diluent and/or 35 catalyst, reactant quantities, details of apparatus, etc. The reaction may be conducted batch-wise or by continuous procedures. Conveniently, the course of the reaction may be fol lowed by observing the change in color of the reaction mixture. As the reaction proceeds, the color of the re action mixture gradually darkens, usually changing from a clear yellow to a deep or brownish red by‘ the time all of the sulfur monochloride is reacted. On completion of 45 the reaction, the 2:1 acrylonitrile-sulfur monochloride re_ action product may be isolated by conventional methods, e.g., by evaporation of any solvents, by washing and/or decantation to remove unreacted acrylonitrile, etc. Some of the product of (I) and/or (11) may decom pose as reaction proceeds to give a chloro cyano mono sul?de, thus: (III) cicnzclin-crv S OICHzICHON l CICH2CH—CN CICHQCHGN To the best of our knowledge, the presently provided 50 reaction products of sulfur monochloride with acryloni_ trile are complex mixtures of isomeric saturated and un saturated sulfur-and chlorine-containing cyano com pounds. The constituents are di?‘icultly separable, and the composition of the present mixture of reaction products 55 has not been precisely established. The presently ob tained reaction products have bacteriostat and fungistat properties and are useful as the active constituents of Either the chloro cyano disul?des or the chloro cyano microbiological toxicant compositions. As will be shown monosul?des may undergo some dehydrochlorination. The identity of any one of the possible isomeric chloro cyano disul‘?des or sul?des or their dehydrohalogenation hereinafter, at concentrations of as low as, say, 10 ppm. products has proved impossible to establish; hence, we do not wish to be bound by the above speculative struc tures. ‘ That the present products result from the reaction of 65 one mole of the sulfur monochloride with two moles of acrylonitrile is evident from consumption of these reac tants in the 1:2 ratio. Thus, the ‘reaction product ob they entirely prevent growth of a variety of bacteria and fungi. The reaction product of this invention can be used as a preservative, e.g., in leather, paper and fabrics, or in paints and varnishes to render them proof against mildew or fungus attack. The present reaction products may further be used as nematocides, insecticides, herbicides, etc. They are also of utility as chemical intermediates whereby the cyano radical thereof is converted to the carboxylic --COOH radical. the chlorine radical replaced by other radicals, tained by heating, at, say, 50° C. to 60° C. a mixture of e.g., alkoxy, amino, phosphinyl, or phosphate radicals, one mole of sulfur monochloride and two moles of acrylo 70 and the sul?de or disul?de radicals converted by oxida nitrile has a bOiling point and refractive index above that tion into sulfoxides or sulfones. 3,065,127 3 Trichoderma sp. T-l ATCC 9645 ______ __ No growth The present invention is further illustrated, but not lim— Chaetomium globosum USDA l032.4_____. No growth ited, by the following examples: Example 1 Aspergillus oryzae ATCC 10196 ________ __ No growth The lowest concentration at which no growth occurred was 1:l00,000 for the following organisms: Into a 500 ml. ?ask, there was placed 138 g. (1.0 mole) of sulfur monochloride (S2Cl2), 150 ml. of carbon tetra chloride and 106 g. (2.0 moles) of acrylonitrile. The Micr0c0ccus pyogenes var. aareus ATCC whole was heated with stirring, at a temperature of 6538 _____________________________ __ No growth ture under partial vacuum to remove solvent and ma terial boiling up to 34° C./0.2 mm., gave as residue 126 g. of a very viscous liquid which was converted to a Fo‘mes annosus FPL 517 ______________ __ No growth Mycobacterium plzlci—St. Louis ________ __ No growth 60° C. for three hours, allowed to stand overnight at room temperature, and then heated again at 55—60° C. 10 Proteus vulgaris-Lambert _____________ __ No growth Penicilliam expansam IPC 126 _________ __ N0 growth for one hour. Distillation of the resulting reaction mix TrichophytOn mentagrophytes ATCC 9129-- No growth Hormisciam gelatinosum FPL 595 ______ __ Ceratostomclla pilz'fera ATCC 8713 ____ __ red, resinous product upon cooling. 15 Claa'osporium lzerbaram ATCC 6506 ____ __ A portion of the resinous product was extracted with Alternaria tenuis ATCC 11612 _________ __ a benezeneehexane mixture and the resulting solution Myrothecium verracaria ATCC'9095 ____ __ evaporated to dryness to give a benzene extract (A) and No No No N0 No growth growth growth growth growth Bacillus subtilis-Lambert _____________ __ No growth a benzene-insoluble portion (8). infra-red analysis of (A) and (B) after evaporation of all solvents showed 20 Stemphylium sarcinaeforme-——U. of lll_____ No growth Monolinia fracticola-U. of I11 _________ __ No growth CEN absorption at 2360 cm.—1 for both (A) and (B). Pscudomonas phaseolic0la—USDA ______ __ No growth Also, for both (A) and (B) the -—C—Cl linkage was in~ dicated at about 720 cmfl. Elemental analyses showed It will be readily seen from the above that the present the presence of chlorine and sulfur in both (A) and (B). acrylonitrile-sulfur monochloride reaction product is effec 25 tive in suppressing the growth of both gram negative and Example 2 gram positive bacteria as well as that of various fungi and To a mixture consisting of 138 g. (1.0 mole) of sulfur molds. At concentrations which are somewhat higher than monochloride and 150 ml. of carbon tetrachloride, there those required for the prevention of microbiological was gradually added 106 g. (2.0 moles) of acrylonitrile. growth, the present 2:1 acrylonitrile-sulfur monochloride The whole was brought to a temperature of 55° C. and 30 reaction products possess herbicidal and insecticidal ac maintained at this temperature for 10 minutes. It was then allowed to stand overnight at room temperature and then heated again to 60-70“ C. until evolution of some hydrogen chloride was noted. The reaction mixture was tivity. secticides or herbicides, the present reaction products are advantageously employed in the form of suspensions then cooled and the carbon tetrachloride stripped there or emulsions. from in vacuo to 50° C./13 mm. The residue was taken up with benzene and acetone and all solvents and unre acted sulfur monochloride were stripped o? by distilling acrylonitrile-sulfur monochloride reaction product, solu on the total weight of the emulsion are useful. ble in benzene and insoluble in acetone and analyzing as follows: H _____ ___. ________________________ __ 1.51 The word “oil” is here used to designate any organic liquid which is insoluble in water. Emulsifying agents which may be employed are those used in the art for the preparation Percent C ________________________________ __ 20.49 Percent Cl ________________________________ __ 26.12 Since the reaction products are effective bacteriostats and fungistats when employed in very small concentrations, commercial toxicants comprising the re action products may contain only minor proportions there of. Oil-in-water emulsions containing, say, from 0.001% to 0.1% by weight of the present reaction products based up to a pot temperature of 70° C./0.5—1.0‘ mm. There was thus obtained as residue 143 g. of the red, glassy 2:1 Percent ' When used either as microbiological toxicants or as in 45 of oil-in-water emulsions, e.g., long-chained alkylbenzene sulfonates, polyalkylene glycols, long-chain alkyl sulfo succinates, etc. For these and related biological toxi~ cant purposes, the reaction products may be incorporated into inert carriers generally. Thus they may be mixed Example 3 50 with solid carriers such as clay, talc, pumice and ben This example describes microbiological evaluation of tonite to give toxicants dusts. We have found, however, the 2:1 acrylonitrile-sulfur monochloride reaction prod that the emulsions possess an improved tendency to adhere not of Example 2. to the treated surfaces so that less of the active ingredient, A 1.0% solution of said reaction product was prepared i.e., the acrylonitrile-sulfur monochloride reaction prod in acetone and added to sterile melted nutrient agar to give uct, is required when applied in the emulsion form. an 0.1% (1 part of reaction product per 1,000 parts of This application is a division of our copending applica agar) concentration of the test compound. This was tion, Serial No. 690,423, ?led October 16, 1957, now further diluted with additional melted agar to give US. Patent No. 2,993,037. 1:10,000 and 1:100,000 dilutions of said reaction product What we claim is: in the agar. The various solutions were then respectively 60 l. A composition effective against bacteria and fungi poured into Petri dishes and allowed to harden. Plates comprising an oil-in-water emulsion of a complex mix thus prepared were inoculated with the test organisms ture of compounds containing carbon, hydrogen, sulfur, shown below and the inoculated plants were incubated chlorine and cyano radicals, said mixture having been for 48 hours at a temperature of 25° C. Inspection of obtained by the reaction of one mole of sulfur monochlo the inoculated plates at the end of that time showed the ride with two moles of acrylonitrile at a temperature of Percent N ________________________________ __ 7.24 Percent S _________________________________ __ 4563 lowest concentration at which no growth occurred to be 1: 10,000 for the following organisms: 25° C. to 100° C. 2. A composition effective against bacteria compris Streptococcus faecalz's ATCC 9790 ______ __ No growth ing an oil-in-water emulsion of a bacteriostatic quantity Bacillus cereus var. mycoides IPC 509_____ N0 growth of a complex mixture of compounds containing carbon, hydrogen, sulfur, chlorine and cyano radicals, said mix Cornyebactcriam diphtcriae ATCC 296____ No growth Bacterium ammoniagenes ATCC 6871____ No growth Erwinia atroseptica ATCC 7404 ________ __ Salmonella typhosa-Hopkins Strain ____ __ Aspergillus niger IPC 144 _____________ __ Memnoniella echinata ATCC 9597 ______ __ No No No No growth growth growth growth ture having been obtained by the reaction of one mole of sulfur monochloride with two moles of acrylonitrile at a temperature of 25° C. to 100° C. 3. A composition effective against fungi comprising an oil-in~water emulsion of a fungistatic quantity of a 5 3,065,127 complex mixture of compounds containing carbon, hydro gen, sulfur, chlorine and cyano radicals, said mixture having been obtained by the reaction of one mole of sulfur monochloride with two moles of acrylonitrile at a temperature of 25° C. to 100° C. 4. The method of inhibiting the growth of fungi and bacteria which comprises exposing them to a growth-in hibiting quantity of a composition comprising as the es sential effective ingredient a complex mixture of com pounds containing carbon, hydrogen, sulfur, chlorine and cyano radicals, said mixture having been obtained by the reaction of one mole of sulfur monochloride with two moles of acrylonitrile at a temperature of 25° C. to 100° C. 5. The method of inhibiting the growth of fungi which 15 comprises exposing them to a growth-inhibiting quan 6 'ty of a composition comprising as the essential effective ingredient a complex mixture of compounds containing carbon, hydrogen, sulfur, chlorine and cyano radicals, said mixture having been obtained by the reaction of one mole of sulfur monochloride with two moles of acrylo nitrile at a temperature of 25° C. to 160° C. 6‘. The method of inhibiting the growth of bacteria which comprises exposing them to a growth-inhibiting quantity of a composition comprising as the essential ef fective ingredient a complex mixture of compounds con taining carbon, hydrogen, sulfur, chlorine and cyano radi cals, said mixture having been obtained by the reaction of one mole of sulfur monochloride with two moles of acrylonitrile at a temperature of 25° C. to 100° C. No references cited.