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United States Patent Office 3,454,590 United States Patent Office Patented July 8, 1969 2 3,454,590 New compounds that can be produced by the process BENZOTHAZO-LE-2-SULFNAMIDES are benzothiazole-2-sulfinamides where R and R in the Alan Jeffrey Neale, Llangollen, Wales, and Terence above formula each represent an aliphatic or cyclo James Rawlings, Penicuik, Scotland, assignors to aliphatic group and the total number of carbon atoms Monsanto Chemicals Limited, London, England, in R and R' is at least four, and sulfinamides where R a British company No Drawing. Filed June 1, 1967, Ser. No. 642,717 and R are linked to form a saturated cyclic system with Claims priority, application Great Britain, June 17, 1966, the nitrogen atom. 27,184/66 The invention includes a process in which a new com nt. C. C07d 91/44, 29/34 pound as defined above is employed as an accelerator U.S. CI. 260-306.6 3 Claims O for the Vulcanization of rubber. Sulfinamides that can be produced by oxidation of the corresponding sulfenamides in the process defined above ABSTRACT OF THE DISCLOSURE can also be obtained by reaction of a benzothiazole-2-sul finyl halide with an appropriate amine. In particular, sul This disclosure is benzothiazole-2-sulfinamides of the 5 finamides in which the sulfinamide grouping is represented formula by the formula: S N R R C-S-N -s-N Né y 20 R. can be obtained by reaction of the sulfinyl halide with where R and R' are each an aliphatic or cycloaliphatic an amine having the formula HNRR. This process for group or R and R' are linked to form a saturated cyclic the production of a benzothiazole-2-sulfinamide comprises System with the nitrogen atom. The benzothiazole-2-sul 25 the reaction of a benzothiazole sulfinyl halide with finanides are prepared by the action on the correspond ammonia or an amine. The compound 2-morpholino-sul ing benzothiazole-2-sulfenamide of an aqueous solution finylbenzothiazole prepared by this process is a useful of an alkali metal hypohalite containing at least one mole accelerator. The compound is claimed in the copending of hypohalite per mole of Sulfenamide. The compounds application of Robert H. Campbell and Alfred B. Sul can also be prepared by reacting a benzothiazole sulfinyl 30 livan, Ser. No. 642,712, filed June 1, 1967. halide With ammonia or an amine. The benzothiazole-2- The oxidation process of the invention can be applied Sulfinamides are useful vulcanization accelerators for to the production of benzothiazole-2-sulfinamide itself rubber. and also to the production of sulfinamides in which the nitrogen atom carries a single substituent, for example BACKGROUND OF THE INVENTION 35 N-alkyl and N-cycloalkyl benzothiazole-2-sulfinamides. In the sulfinamides where the nitrogen atom is doubly The invention pertains to new compounds useful as substituted as shown in the above formula, the aliphatic vulcanization accelerators for rubber and processes for groups from which R and R' can be selected include alkyl making the compounds. The applicable U.S. patent clas groups, generally those containing from 1 to 20 carbon sifications are 260-306.6 and 260.779. 40 atoms having either straight or branched chains, and more The compounds of this invention are delayed action especially alkyl groups containing from 2 to 12 carbon accelerators, i.e., an increase in scorch time is shown in atoms, for example ethyl, isopropyl, Sec.-butyl, n-amyl, vulcanizing rubber using the compounds of this invention. hexyl, octyl, nonyl, and dodecyl groups. R and R' may Mingasson's U.S. Patent 2,585,155, 1952, assigned to also be selected from substituted alkyl groups, for example Societe Anonyme de Matieres Colorantes et Produits 45 halogen, cyano, or aryl-substituted alkyl groups such as Chimiques Francolor, Paris, France, a French company, for instance cyanoethyl and benzyl. discloses N,N-dimethylbenzothiazole-2-sulfinamide as a Where a group R and R' is cycloaliphatic, it is usually vulcanization accelerator. The benzothiazole - 2 - sulfin one containing from 5 to 7 carbon atoms in the ring. The amides of this invention show a greater degree of delayed preferred groups are cycloalkyl and alkylcycloalkyl action than N,N-dimethylbenzothiazole-2-sulfinamide. 50 groups, for example cyclopentyl, cyclohexyl, or methyl SUMMARY OF THE INVENTION cyclohexyl, although substituents, as exemplified above This invention relates to compounds that are useful for instance, may be present. as vulcanization accelerators and to processes for their Instances of benzothiazole sulfinamides where R and production. R" are linked and form a saturated cyclic system with the The compounds are benzothiazole-2-sulfinamides, and nitrogen atom, are those in which -NRR' represents a according to the present invention Such a compound can piperidino or substituted piperidino group, or a hexa be produced by the action on the corresponding benzo methyleneimino group. thiazole - 2 -sulfenamide of an aqueous solution of an The benzothiazole-2-sulfinamides that can be produced alkali metal hypohalite containing at least one mole of 60 by the process of the invention include, moreover, mem hypohalite per mole of Sulfenamide. bers where the benzene nucleus carries one or more Sub The process is particularly valuable for the production stituents. Such a substituent can be, for example a halogen of benzothiazole-2-sulfinanides in which the sulfinamide atom, especially chlorine or bromine, a nitro group, an grouping is represented by the formula: alkyl group, or an alkoxy group. 65 DESCRIPTION OF THE PREFERRED g R EMBODIMENTS Specific examples of benzothiazole-2-sulfinamides that --NC R can be obtained by the process of the invention are: where R and R' are each an aliphatic or cycloaliphatic 70 N-methyl-N-cyclohexyl benzothiazole-2-sulfinamide group or where R and R' are linked to form a saturated N,N-diisopropyl benzothiazole-2-sulfinamide cyclic system with the nitrogen atom. N,N-diisobutyl benzothiazole-2-sulfinamide 3,454,590 3 4 N,N-dicyclohexyl benzothiazole-2-sulfinamide rubber concerned, for example a temperature in the range 2-hexamethyleneiminosulfinylbenzothiazole 135°-155° C. where the composition is based on natural N,N-diisopropyl-6-chlorobenzothiazole-2-sulfinamide, and rubber, or a temperature in the range of 140°-160 C. N,N-dicyclohexyl-6-ethoxybenzothiazole-2-sulfinamide. where the composition is based on a styrene-butadiene rubber. In practice, the oxidation process of this invention is The amount of accelerator used depends on a number usually conducted by adding the aqueous Solution of of factors, including for example the type of rubber and alkali metal hypohalite to a dispersion or Solution of the the use for which the vulcanized product is required. The benzothiazole sulfenamide in an inert liquid dispersion amount is, however, usually within the range 0.3 to 5 or solvent medium. This can be water but is preferably a parts by weight, and more especially within the range 0.3 water-miscible organic solvent. Water-miscible Solvents O to 2 parts by weight, per 100 parts by weight of rubber, that can be used include alcohols, ketones, glycols and for example 0.5, 1.0 and 1.5 parts by weight. dioxane, the alcohols, especially methanol, being generally Conventional amounts of other additives referred to preferred. as Preferred reaction temperatures for the oxidation are above can be used. within the range 30° to 80° C. The optimum depends Ol 5 This invention is illustrated by the following examples: the particular benzothiazole-2-sulfenamide that is oxidized, Example 1 but is often within the range 35 to 50 C. When using This example describes the production of N,N-dicyclo methanol as the water-miscible solvent, it is sometimes hexylbenzothiazole-2-sulfinamide by oxidation of N,N-di convenient to conduct the process under reflux at the boil 20 cyclohexylbenzothiazole - 2 - sulfenamide using sodium ing point. hypochlorite. The hypohalite is employed in at least the stoichiometric 150 grams of a 15% by weight aqueous solution of so quantity required for oxidation of the Sulfenamide to the dium hypochlorite containing 0.3 mole of NaOCl were sulfinamide, but not usually in amounts exceeding three gradually added during a period of 10 minutes to a sus times this quantity. Good results are obtained using from 25 pension of 48.3 grams (0.15 mole) of N,N-dicyclohexyl 1.5 to 2.5 moles of hypohalite per mole of sulfenamide. benzothiazole-2-sulfenamide in 300 cc. of boiling meth Sodium hypochlorite is the alkali metal hypohalite nor anol. Boiling was continued for one hour, and then the mally employed in practice, although hypochlorites of mixture was cooled to 0° C. By filtration, there were re other alkali metals, for instance potassium and lithium, covered 64 grams of a brown solid, most of which was and the alkali metal salts of other hypohalous acids, for 30 extracted into benzene leaving 16 grams of insoluble instance hypobromous acid, are functionally satisfactory. material. The benzene solution was washed thoroughly The commercial aqueous solution of sodium hypochlorite with water and then dried using sodium sulfate. The ben containing nominally about 15% by weight NaOCl (in Zene was removed at 50° C. in vacuo to give 40 grams of practice usually from 12 to 16% by weight) is quite suit a brown oil which solidified on standing. Crystallization able and is in fact preferred to more dilute Solutions. 35 of this solid from ethanol gave 26 grams of unchanged The benzothiazole-2-sulfinyl halides, which have not N,N-dicyclohexylbenzothiazole-2-sulfenamide. The etha hitherto been described and are useful in the second proc nolic mother liquors were evaporated giving a brown oil ess of the benzothiazole-2-sulfinamides of this invention, which on crystallization from 60-80 petroleum ether can be obtained by the reaction of a thionyl halide with yielded 5.5 grams of N,N-dicyclohexylbenzothiazole-2- an alkylbenzothiazole-2-sulfinate.
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