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Ice . Patented Feb 2,824,890 ice ._ Patented Feb. 25, 1958 2 fenyl chloride, 3,4-dichlorobenzenesulfenyl chloride, 2,5 2,824,890 dichlorobenzenesulfenyl chloride, 2,4,5-trichlorobenzene sulfenyl chloride, 2-bromo-3,4-dichlorobenzenesulfenyl AlDDUCTS 6F HALQGENATED BENZENE SUL FENYL HALmES AND VINYL ESTERS AND bromide, 2,3,4,5 -tetrachlorobenzenesulfenyl chloride, PROCESS pentachlorobenzenesulfenyl chloride, etc. The vinyl esters useful in preparing the products of Samuel Alien Heininger and Gail H. Birurn, Dayton, this invention are the esters of saturated aliphatic car Ohio, assignors to Monsanto Chemical Company, St. boxylic acids of from 1 to 6 carbon atoms. Such esters Louis, Mo, a corporation of Delaware can be obtained, e. g., by the addition of acetylene to No Drawing. Application February 21, 1957 10 the. corresponding acids. Vinyl acetate is the preferred Serial No. 641,491 ester for the preparation of the present products; other vinyl esters which may be reacted with the sulfenyl halide 8 Claims. (Cl. 260-488) in accordance with this invention include, e. g., vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl n This invention relates to ester products and more par hexanoate, etc. ticularly to the products of the reaction of vinyl esters The new ester products are prepared by reacting a of carboxylic acids with halogenated aromatic sulfenyl halobenzenesulfenyl halide as de?ned above with one of halides. the presently useful vinyl esters to form a reaction prod In accordance with this invention, a halobenzenesul uct comprising compounds containing sulfur atoms and fenyl halide is reacted with the vinyl ester of an aliphatic 20 carboxylate radicals, where by a carboxylate radical is carboxylic acid to produce a complex reaction product here meant a radical of the form comprising compounds containing sulfur atoms and car boxylate radicals. The reaction involves equimolecular amounts of the sulfenyl halide and vinyl ester reactants, and is believed to proceed with the formation of an adduct, 25 where R represents the organic radical attached to the as illustrated by the following equation: carbonyl carbon atom. The process of the invention 0 appears to involve the reaction of equimolecular amounts‘ N of sulfenyl halide and vinyl ester, but if desired an ex @sx + onFonoon —-> cess of the more readily available component may be 30 present in the reaction mixture to serve, e. g., as a 're action diluent. In accordance with the present process, the two reaction components are contacted for a time such as to produce a reaction product comprising com ACE-J pounds containing both sulfur atoms and carboxylate it radicals. The rapidity of the reaction varies greatly where X represents chlorine or bromine, R represents depending on the reactants chosen, and may be suf a lower alkyl radical, containing from 1 to 6 carbon ?ciently exothermic to require cooling and/or diluents atoms, and n represents an integer of from 1 to 5. to moderate the violence of the reaction or may not The position of the halophenylthio radical and of the reach completion until after a period of re?uxing at halogen atom derived from the sulfenyl halide radical 40 elevated temperatures. Suitable inert solvents or dil uents which may be employed in the reaction mixture are not known with certainty, and for this reason the if desired include hydrocarbons such as benzene or above non-commital formula is used. While the forma hexane, halogenated solvents such as chloroform or tion of a-halo-?-thioalkyl esters in certain related re ethylene dibromide, oxygenated solvents free of active actions has been reported, our experiments have shown 4:5 that the various types of sulfenyl halides dilfer greatly hydrogen, e. g., ether or dioxane, etc. A particularly in reactivity; thus, unsaturated compounds react with a preferred class of solvents are anhydrous organic car haloaryl sulfenyl halide which do not undergo reaction boxylic acids and especially glacial acetic acid, since with a nitroaryl sulfenyl halide or with a halogenated this solvent also has the advantage of acting as a catalyst for the reaction. Mixtures of glacial acetic acid and alkanesulfenyl halide such as perchloromethyl mercaptan, 50 and which may react differently with a halogenated al an inert solvent such as ethylene dichloride may also kanesulfenyl halide than with a halogenated aromatic be used as a reaction medium if desired. sulfenyl halide. The nature of the ole?nic addend also To accelerate the rate of reaction when desired, heat a?ects the product of reaction with a given sulfenyl ing and catalysts are employed. Suitable temperatures for carrying out the reaction comprise, e. g., any tem halide, certain ole?nic compounds yielding well-de?ned 55 individual adducts as products, whereas others result in perature from below room temperature up to tempera~ the formation of a complex reaction product comprising tures below the decomposition temperature of the re mixtures of unsaturated materials and compounds having action mixture constituents. Acid catalysts are useful in accelerating the present reaction; in addition to the the elementary analytical composition of adducts, these organic carboxylic acid catalysts mentioned above, there adducts appearing to be present in the form of mixed 60 may alternatively be used Friedel-Crafts catalysts such isomers. In the present instance, the product of reaction of as aluminum trichloride or boron trifluoride complexes. a. halobenzene sulfenyl halide with a vinyl ester of an Pressure variation may also be utilized to facilitate con~ aliphatic carboxylic acid presents difficulties in the isola ducting the reaction if desired. Since the present vinyl esters may be susceptible to tion and characterization thereof, and we prefer not to 65 be bound by speculation as to its precise nature. thermal polymerization, the reaction may, if desired, be The presently-preferred sulfenyl halides are benzene conducted in the presence of polymerization inhibitors. sulfenyl bromides and chlorides, wherein the benzene Examples of suitable inhibitors are hydroquinone, the ring is substituted by from 1 to 5 chlorine and/ or bromine monomethyl ether of hydroquinone, etc. The time required to accomplish the reaction depends atoms. Exemplary of presently useful halobenzenesul 70 fenyl halides are p-chlorobenzenesulfenyl chloride, p on functional factors such as the reactivity of the vinyl bromobenzenesulfenyl chloride, 2,4-dichlorobenzenesul ester and the sulfenyl halide, the temperature of the 2,824,890 4 reaction,‘thepresencev or absence of catalysts, .etc. Re such as Micrococcus pyogenes var.‘ aureus,_ Salmonella action rates and times of reaction may also vary con typhosa, etc. 7 I siderably, depending on details of apparatus and other For use‘ as a pesticide, the present compounds may be operational conditions. By modi?cation of, the appara employed as constituents of organicsolutionsr'aqueous‘ ' tus, continuous-procedures may be‘substituted, for the dispersions and emulsions, or -dusting formulations pre batch-type operations described below. ’ pared by mixing the toxic compounds with an inert ?nely Conveniently the course of the reaction is followed by divided 'powdenj They maybe employed as disinfect: * observing the change in colorrof the reaction mixture. ing and. preserving agents in the textile industry for Sulfenyl halides are generally a deep red shade; as the preserving fabrics or for-disinfecting bandage material, - reaction PIOC€CdS,'th8 601s; of the reaction mixture 10 instruments, the skin, surfaces such as ?oors and walls generally lightens, gradually becoming a clear. yellow or , and the like, and’ also for disinfecting and preserving orangeshade by the time all of the sulfenyl halide has cosmetics andiiutrient substances; 7 ' reacted. , On completion of ,the reaction, the product It is also contemplated that the presently provided sul— may be isolated ‘by removing solvents and unreacted fur-containing' reaction products, of vinyl esters of car components by. procedures such as’ decantation, evaporae 15 boxylic. acids with halogenated» aromatic sulfenyl'halides tion or distillation. It is to be noted that elevated dis may be converted by‘ oxidation _ (e. vg.,_ with ‘hydrogen . tillation temperatures appear to promote , dehydroi ' peroxide in acetic acid, potassium pe . anganate, chromic ~ chlorination ofthe present products, andtheuse of ‘such acid, etc.) into thecorresponding sulfoxides and sulfonesr. elevated temperatures should be avoided unless the'de A 'WhiléQ the ‘invention has been illustrated withreference hydrohalogenated product is the object of the synthesis. to particularpreferred embodiments thereof, it will be '_ As exemplary of the process of the invention,'_there appreciated "that variations‘can ‘be made without’ de V is described the following non-limiting exemplary op partingfrom'the spirit andrscope of the invention. eration. ' ' ' ‘ " ‘ What, isicla'imed is:' ' ' . ‘V t ' ' Example 7 7 V, ,_, ,7 1'. Thef'method which comprises contacting a sulfenyl 25 To 17.2 g; (0.2 mole) of freshly-distilled vinyl ace halidese'lected fromv the'cla‘ss consisting of benzene tate mixed with 100 ml. of glacial acetic acid was added sulfenyl ibromides'iand" chlorides 'wherein the benzene 35.9 g. (0.2 mole) of p-chlorobenzenesulfenyl chloride. ring of?said'i‘henzenesulfenyl bromides 'and chlorides is There ‘was ‘an immediate exothermic reaction,; raising the substituted .byf-fr’om’. lltoiS halogen atoms selected from ‘ chlorine‘and ‘bromine. atoms, .with va vinyl ‘ester
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