DE2151895A1 - Mixts of benzothiazyl-2-sulphenamides and aryl sulphinic - amine salts - as vulcanisation accelerators - Google Patents

Abstract

The benzothiazyl-2-sulphenamides of gen. formula: and amine salts of aryl sulphinic acids of gen. formula: (where Ar is a phenyl gp. opt. substd. by Cl atoms and/or straight/branched chain 1-4C alkyl gps. R1 and R4 may be the same or different H, straight/branched chain 1-20C alkyl gps. opt. substd. with OH gps. or 1-4C alkoxy gps. or 3-6C alkenyl gps. 5-7C cycloalkyl gps. or 7-9C aralkyl gps. or may form together a ring contg. 5-7 ring members which may be interrupted by O or N the latter being substd. with lower alkyl gps. R4 being additionally where R3 may be 2-10C alkylene, cycloalkylene, dialkylaryl or may form a heterocycle with R1, R5 may be, besides R1, -R3-NH2+(R1). O2S Ar may form, together with R1, a 5-7 membered ring which may be interrupted by O or N, the latter being substd. with lower alkyl) are prod. by reacting with HNR1R2 (where R2 may be besides R1, -R3-NHR1) at -20 degrees C to 100 degrees C in non-reactive diluents/solvents.

Description

2-Arylsulfonylthio-benzothiazoles and their reaction with amines Benzothiazyl-2-sulfenamides and amine salts of arylsulfinic acids It is known that Benzothiazy1-2-sulfenamide accelerator for the vulcanization of natural and Represent synthetic rubbers (see manual for the rubber industry, page 296, 1971, paint factories Bayer AG, Leverkusen).

Amine salts of arylsulfinic acids are also used as vulcanization accelerators for the sulfur crosslinking of rubber, especially at higher vulcanization temperatures, known (see U.S. Patent 3,518,236).

The known processes for the preparation of benzothiazyl-2-sulfenamides generally involve an oxidation in which salts of 2-mercaptobentothiazole reacted in the presence of amines with an oxidizing agent, such as, for example, sodium chloride solution will. The use of oxidation-sensitive amines is part of such a procedural measure not possible.

In the industrial production of aryl sulfinates, in general by reducing aryl sulfochlorides with alkali sulfites, water-soluble ones fall Alkali salts. For the production of corresponding amine salts, it is necessary from to isolate the very unstable arylsulfinic acids from the alkali salts in order to obtain them then to convert with the amines into the desired salts.

It has now been found that mixtures of benzothiazyl-2-sulfenamides can be used and can produce amine salts of arylsulfinic acids in a simple manner, on the one hand the reaction takes place under mild, non-oxidative reaction conditions, so that one can also use oxidation-sensitive amines, on the other hand an intermediate one Isolation of the unstable arylsulfinic acids is avoided.

The invention thus provides a process for the preparation of benzothiazyl-2-sulfenamides of the general formula (III) and amine salts of arylsulphinic acids of the general formula (IV) in which Ar is a phenyl radical optionally substituted by chlorine atoms and / or straight-chain or branched alkyl groups with 1-4 carbon atoms, R1 and R4 are identical or different hydrogen, straight-chain or branched. Alkyl radicals with 1-20 carbon atoms, which are optionally substituted by hydroxyl groups or alkoxy groups with 1-4 carbon atoms, alkenyl radicals with 3-6 carbon atoms, cycloalkyl radicals with 5-7 carbon atoms and aralkyl radicals with 7-9 carbon atoms, R1 and R4 optionally represent a ring with 5-7 ring members, which can optionally be interrupted by oxygen or nitrogen, the nitrogen being substituted by lower alkyl groups, R4 still in which R3 also contains alkylene, cycloalkylene and dialkylaryl with 2-10 carbon atoms, in addition a heterocyclic ring can be closed via R1, and R5 as well as R1 represents, R1 and R5 can form a ring with 5-7 ring members, which can optionally be interrupted by oxygen or nitrogen, the nitrogen being substituted by lower alkyl groups, characterized in that 2-arylsulfonylthiobenzothiazoles of the general formula (I) with amines of the general formula (II) in which Ar and R1 have the meaning given above and R1, R2 in addition to R1 also denotes -R3 -NH, is reacted at temperatures from -20 to 1000 ° C. in inert solvents or diluents.

According to the invention, 2-arylsulfonylthiobenzothiazoles (I) are reacted with amines (II) to give benzothiazyl-2-sulfenamides and amine salts of arylsulfinic acids as follows: Suitable 2-arylsulfonylthio-benzothiazoles (I) are, for example

2-benzenesulfonylthio-benzothiazole, 2- (o-, m- or p-toluene sulfonylthio) -benzothiazoi, 2- (o-, m- or p-chlorobenzenesulfonylthio) -benzothiazole, 2- (2 ', 5'-dichlorobenzenesulfonylthio) -benzothiazole, 2- (3 ', 4'-dichlorobenzenesulfonylthio) -benzothiazole, 2- (3'-chloro-4'-methyl-benzenesulfonylthio) -benzothiazole, 2- (1,3'-dimethylbenzenesulfonylthio) -benzothiazole, 2- (pentamethylbenzenesulfonylthio) -benzothiazole, 2- (2'-Isopropyl-4'-methylbenzenesulfonylthio) -benzothiazole, 2- (4'-tert-butyl-4'-methylsulfonylthio) -benzOthiazole, and 2- (Pentachlorobenzenesulfonylthio) -benzothiazole.

Suitable amines (II) are e.g.

Ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, Dipropylamine, isopropylamine, diisopropylamine, n-, sec- and tert-butylamine, di- (n-, sec.- and tert.-) butylamine, 2-ethyl-hexylamine, di- (2-ethylhexyl) -amine, dodecylamine, Tetradecylamine, hexadecylamine, stearylamine, methyl-stearylamine; Allylamine, diallylamine; Ethylenediamine, N, N'-dimethylethylenediamine, 1,2-diaminopropane, 3-amino-1-methylamino-propane, 1,4-diamino-butane, 1,6-diaminohexane, 2-aminoethanol, methyl- (2-amino-ethyl) -ether, 2-methylaminoethanol, bis (2-hydroxyethyl) amine, 3-aminopropanol (1), methyl (3-aminopropyl) ether, 1-aminopropanol (2), Bis (2-hydroxypropyl) amine, 4-aminobutanol- (2); Cyclopentylamine, cyclohexylamine, Cycloheptylamine, N-methyl-cyclohexylamine, dicyclohexylamine, N- (2-hydroethyl) -cyclohexylamine, o-, m- and p-methylcyclohexylamine; Benzylamine, N-methylbenzylamine, dibenzylamine, o-, m- and p-xylylenediamine, 1-amino-2-phenylethane; 1,4-diamino-cyclohexane, hexahydro- (o-, m- and p-) xylylenediamine, pyrrolidine, piperidine, hexamethyleneimine, piperazine, N-methyl-piperazine, 2,5-dimethylpiperazine, morpholine, 2,6-dimethylmorpholine, 3,5-dimethylmorpholine.

Preference is given to 2-benzenesulfonylthiobenzothiazole and 2-toluenesulfonylthiobenzothiazole and 2-chlorobenzenesulfonylthiobenzothiazole with ammonia, diethylamine, diisopropylamine, tert-butylamine, cyclohexylamine, dicyclohexylamine and morpholine implemented.

The reaction of the mentioned 2-Arylsúlfonylthio-benzothiazole (I) with the amines (II) mentioned are carried out in inert solvents or diluents at -20 to 1000 -C, preferably at 0-500 C. As an inert solvent may be mentioned: aliphatic and aromatic, optionally chlorinated hydrocarbons, z. B. gasoline, benzene, carbon tetrachloride, low molecular weight aliphatic alcohols, z. B.

Methanol, ethanol, isopropanol, aliphatic or heterocyclic Ether, e.g. B. diethyl ether, dioxane, aliphatic ketones, e.g. B. acetone, methyl ethyl ketone. If appropriate, water-containing solvents or water can also be used will.

The order in which the reactants are brought together is generally any. Since the 2-Arylsulfonylthiobenzothiazole (I) however opposite Most amines are in solid form, it is advisable to use the compounds (I) to be submitted with the solvent or diluent and to add the amine (II).

The amounts used of the reaction components with respect to one another can likewise can be chosen at will. However, in order to achieve good yields with simple work-up achieve, the implementation of approximately stoichiometric amounts of (I) and (II) is preferred, i.e. about 2 moles of a compound of type (II) if it is primary or secondary Contains amino group, with 1 mole of the compound (I), or about 1 mole of a compound of type (II), if it contains two primary or secondary amino groups per molecule, with 1 mole of the compound (I).

The arylsulfonylthiobenzothiazoles required as starting material (I) are partly new compounds. Their production can e.g. through implementation of benzothiazyl-2-sulfenchloride with alkali or amine salts of arylsulphinic acids in suitable solvents or diluents, such as benzene, toluene, chlorobenzene, Methylene chloride, chloroform, carbon tetrachloride, di-, tri- or tetrachloroethane, Tri- and tetrachlorethylene, etc. take place. For a more detailed characterization of this implementation Examples 1 - 3 serve.

It is not necessary to isolate the benzothiazyl-2-sulphene chloride in the meantime. Prepared by introducing chlorine into a solution or suspension of dibenzothiazyl-2,2'-disulfide or of 2-mercaptobenzothiazole in the above-mentioned solvents or diluents, 3enzothiazyl-2-sulfen chloride can be obtained without isolation with the alkali metal or amine sulfinates convert in the reaction mixture, for example: The mixture according to the invention of sulfenamide (III) and aryl sulfinate (IV) can be used as a vulcanization accelerator mixture for the sulfur crosslinking of natural and / or synthetic rubbers.

If necessary, the two connections can be made in a simple manner be separated from each other, since the salts (IV) are readily soluble in water, while the sulfenamides (OIL) have practically no water solubility. Both classes of compounds can therefore also be used separately as vulcanization accelerators insert. Should the need for sulfenamides continue to be greater than that for amine arylsulfinates, so the latter can wholly or partially instead of the alkali aryl sulfinates for the Production of the 2-arylsulfonylthiobenzothiazoles required as starting material (I) can be used.

For a more detailed explanation of the method according to the invention are used following examples: Example 1 Preparation of 2-benzenesulfonylthio-benzothiazole a) 166 g (0.5 mol) of dibenzothiazyl-2,2'-disulfide are dissolved in 1000 ml of carbon tetrachloride suspended. 40 g (0.55 mol) of chlorine are passed into this suspension at 20.degree.-300.degree a. The mixture is heated to 700 ° C. for 30 minutes, cooled to 700 ° C. and at 10-200 C with 164 g (1 mol) of sodium benzenesulfinate added. Leave for 3 hours Stir at 20 - 300 C, suck off the solid components and wash them to remove of sodium chloride with water. The water-insoluble reaction product is made from acetonitrile recrystallized.

Yield: 202 g: 66% of theory beige crystals Afp. 93-94OC C13HgN02S3 MW 307 calc .: C 50.81 H 2.93 N 4.56 0 10.42 S 31.27 found: C 51.2 H 3.13 N 4 * 4 0 10.5 S 31.1 b ) 83.5 g (0.5 mol) of 2-mercapto-benzothiazole are suspended in 600 ml of benzene. 40 g (0.55 mol) of chlorine are passed into this suspension at 20.degree.-300.degree. The mixture is refluxed until evolution of HCl has ceased. After cooling to 0 ° C., 90 g (0.55 mol) of sodium benzene sulfinate are introduced at 0 ° -200 ° C., this mixture is stirred for 2 hours at 20 ° -300 ° C. and the solid components are filtered off with suction. The filtrate is evaporated in vacuo at 500 ° C./15 mm, and the residue (140 g) is recrystallized from 250 ml of acetonitrile.

Yield: 120 g: 78% of theory beige crystals m.p. 93-940C The product is identical to that obtained under a).

c) The same product is also obtained if instead of sodium benzenesulfinate the morpholine, tert. Butylamine or diethylamine salt of benzenesulfinic acid is used.

Example 2 In a manner analogous to that described under 1a) to 1c), if alkali or amine salts of p-toluenesulfinic acid are used instead of the benzenesulfinates mentioned, the following is obtained: 2-p-toluenesulfonylthio-benzothiazole: C14N11N02S3 MG 321 beige crystals, m.p. 1360cd calc .: C 52.34 H 3.43 N 4.36 0 9.97 S 29.91 found: C 52.3 H 3.3 N 4.6 0 9, 2 S 30.07 The corresponding m- and o-toluenesulfonyl compounds are prepared in the same way.

Example 3 In a manner analogous to that described under 1a) to 1c), 2-p-chlorobenzenesulfonylthio-benzothiazole is obtained when using the alkali or amine salts of p-chlorobenzenesulfinic acid C1DH8ClN02S3 MW 341.5 light yellow crystals, m.p. 1380 C calc .: C 45.68 H 2.34 C1 10.39 N 4.10 0 9.37 S 28.11 found: C 46, o H 2.6 C1 9.8 N 4.3 0 9.0 S 28.2 The corresponding m- and o-chloro-benzenesulfonyl compounds and benzenesulfonyl compounds which have several chlorine atoms and / or alkyl groups are prepared in the same way.

Example 4 Cleavage of 2-benzenesulfonylthio-benzothiazole with diethylamine to the diethylamine salt of benzenesulfinic acid (a) and benzothiazyl-2-diethylsulfenamide (b) a) 20.7 g (0.1 mol) of 2-benzenesulfonylthio-benzothiazole in 200 ml of benzene 14.6 g (0.2 'mol) of diethylamine are added at 20-300 ° C. The reaction mixture is stirred for 3 hours at 20-300 ° C., evaporated in vacuo at 400 ° C./15 mm, colorless crystals remaining: Yield: 19 g = 88.4% of theory. brownish crystals, m.p. 60-620 ° C 10H17N ° 2S MG 215 calc .: C 55.82 H 7.91 N 6.51 0 14.88 S 14.88 found: C 55.5 H 7.9 N 6.4 0 15.0 S 15, 2 b) The petroleum ether filtrate is evaporated in vacuo at 400 ° C./15 mm, an oil remaining: 20 Yield 21 g = 88.3% of theory. brownish oil nD: 1.6195 C11H14N2S2 MW 238 calcd .: C 55.50 H 5.85 N 11.75 S 26.90 found: C 55.4 H 5.6 N 11.4 S 26.8 Example 5 Cleavage of 2-benzenesulfonylthio-benzothiazole with cyclohexylamine to the cyclohexylamine salt of benzenesulfinic acid (a) and benzothiazyl-2-cyclohexylsulfenamide (b): a) 30.7 g (0.1 mol) of 2-benzenesulfonylthio-benzothiazole in 200 ml of benzene are added at 20-400 ° C. with 20 g (0.2 mol) cyclohexylamine: added. The mixture is stirred for 3 hours at 20-400 ° C., the undissolved components are filtered off with suction and washed with benzene.

Yield: 23 g = 96% of theory colorless crystals m.p. 193-1950 C. C12H19N02S MW 241 calc .: C 59.75 H 7.88 N 5.81 0 13.28 S 13.28 found: C 59.8 H 8.1 N 5.8 0 13.3 S 13.3 Das The filtrate is evaporated in vacuo at 500 ° C./15 mm, and the residue is recrystallized from acetonitrile.

Yield: 23 g = 96% of theory colorless crystals m.p. 1010 C.

C13H16N2S2 MW 240 calc .: C 65.0 H 6.66 N 1i, 68 S 26.66 found: C 64.7 H 6.8 N 11.4 S 26.4 c) The original reaction mixture is evaporated without isolation of the two cleavage products, a colorless powder with a melting point of 156-1640 is obtained C, which receives components a) to b) in approximately equal parts.

Example 6 In an analogous manner, using tert. Butylamine instead of cyclohexylamine in Example 5 with a yield of about 90 each % of th.

a) the tert. Butylamine salt of benzenesulfinic acid, m.p. 190-1930C C10H17N ° 2 MW 215 calc .: C 55.82 H 7.91 N 6.51 0 14.88 S 14.88 found: C 56.6 H 8.1 N 6.5 0 14.4 S 14, 8 b) and benzothiazyl-2-tert-butylsulfenamide, m.p. 102-1040 C C11H14N2S2 MW 238 calc .: C 55.50 tI 5.85 N 11.75 S 26.90 found: C 55.6 H 5.9 N 11.5 S 26.7 c) analogous to 5c) with a yield of about 95%, a component mixture of equimolar proportions of a + b.

Example 7 In an analogous manner, using dicyclohexylamine is obtained instead of cyclohexylamine in Example 5 with yields of about 90% of theory each.

a) the dicyclohexylamine salt of benzenesulfinic acid, melting point 149-1510 ° C C18H29N02S -MG 323 calc .: C 66.87 H 8.98 N 4.33 0 9.91 S 9.91 found: D 66.3 H 8.9 N 4.4 0 9.9 S 10.0 b) and benzothiazyl-2-dicyclohexylsulfenamide, m.p. 97-980 C C19H26X2S2 MW 346 calc .: C 62.60 H 7.14 N 7.66 S 17.60 found: C 62.5 H 7.0 N 7.5 -S 17.4 c) analogous. 5c) a component mixture of equimolar proportions of a + b with a yield of about 95%.

Example 8 Cleavage of 2-benzenesulfonylthio-benzothiazole with morpholine 30.7 g (0.1 mol) of 2-benzosulfonylthio-benzothiazole in 200 ml of benzene are mixed with 17.4 g (0.2 mol) of morpholine at 5-100 ° C. The mixture is stirred for 2 hours at 20-300 ° C. and evaporated in vacuo at 500 ° C./15 mm. The residue melts at 65 to 800 C and contains an equimolar mixture of about 96% of theory in each case. from: a) the morpholine salt of benzenesulfinic acid and b) benzothiazole-2-sulfenmorpholide. Treating the residue with water gives an aqueous solution of a), while b) remains solid. Evaporation of the aqueous solution also gives a) in solid form: a) C10H15N ° 3S MW 229, m.p. 71-74 ° C Yield: 92% calc .: C 52.40 H 6.55 N 6.11 0 20.96 S 13.97 found: C 51.90 H 6, 7 N 6.0 0 21.7 S 13.5 b) C11H12N20S2 MW 252, m.p. 85-870C Yield: 96 56 calc .: C 52.4 H 4.7 N 11.1 0 6.4 S 25.4 found: C 52.2 H 4.5 N 10, 8 0 6.2 S 25.2 Example 9 Cleavage of 2-benzenesulfonylthio-benzothiazole with ethylenediamine 30.7 g (0.1 mol) of 2-benzenesulfonylthio-benzothiazole in 200 ml of benzene are mixed with 6 g (0 , 1 mol) ethylenediamine added. The mixture is stirred for 4 hours at 20.degree.-30.degree. C., then evaporated in vacuo at 400.degree. C./15 mm. A mixture of equimolar amounts of a) the ethylenediamine salt of benzenesulfinic acid and b) the N, N'-ethylenebis (benzthiazyl-2-sulfenamide) is obtained. By treating the mixture with water, an aqueous solution of a) is obtained while b) remains firmly behind. Evaporation of the aqueous solution also gives a) in solid form: a) C14H20N204S MW 344 Yield: 91% colorless crystals mp 1950, C calc .: C 48.84 H 5.81 N 8.14 0 18.60 S 18.60 found: C 47.4 H 5, -9 N 8 , 6 0 18.5 S 17.9 b) C16H14N4S4 MW 390 beige crystals m.p. 115-1170 C yield: 90% calc .: C 49.23 H 3.59 N 14.36 S 32.82 found: C 49.5 H 3.9 N 13.7 3 33.1 Example 10 In an analogous manner, when 1,6-hexamethylenediamine is used instead of ethylenediamine in Example 9, a mixture which can be separated into: a) the hexamethylenediamine salt of benzenesulfinic acid is obtained in an equally good yield C18H28N2O4S2 MW 400 colorless crystals m.p. 1490 C yield: 86% calc. C 54.00- H 7.00 N 7.00 0 16.00 S 16.00 found: C 54.4 H 7.1 N 7 , 0 0 16.1 S 15.8 b) and the N, N'-hexamethylene-bis (benzothiazyl-2-sulfenamide) C20H22N4S4 MW 446 beige crystals m.p. 87 ° C yield: 85% calc .: C 53.81 H 4.93 N 12.56 S 28.70 found: C 53.9 H 5.3 N 12.2 S 27 , 9 In an analogous manner, but without isolation of the corresponding benzenesulfinic acid, amine salts were prepared in good yields: Example 11 N, N'-1,4-diaminocyclohexyl-bis- (benzothiazyl-2-sulfenamide) C20H20N454 FT MG 444 colorless crystals melting point 2070 C Yield: 92% of theory

Calc .: C 54.05 H 4.51 N 12.61 S 28.83 Found: C 54.1 H 4.7 N 12.6 S 28.1 In an analogous manner, but without isolating the corresponding benzenesulfinic acid amine salts, were prepared: Example 12 Benzothiazyl-2-allylsulfenamide C10H10N2S2 MG 222 brown oil Yield: 97% of theory

Calc .: C 54.05 H 4.51 N 12.01 S 28.83 Found: C 53.0 H 4.6 N-11.4 S 27.8 Example 13 Benzothiazyl-2-diallylsulfenamide C13H14N2S2 MG 262 brown oil Yield: 97% of theory

Calc .: C 59.54 H 5.34 N 10.69 S 24.43 Found: C 59.9 H 5.5 N 10.6 S 24.7 Example 14 Cleavage of 2-benzenesulfonylthio-benzothiazole with ammonia to give the ammonium salt the benzenesulfinic acid and benzothiazyl-2-sulfenamide In the suspension of 30.7 g (0.1 mol) 2-benzenesulfonylthiobenzothiazole in 200 ml benzene are heated to 10-200C Introduced 4 g (0.24 mol) of ammonia. The mixture is stirred at 20-300 ° C. for 4 hours and mixed with 200 ml of water.

The remaining solid product is filtered off with suction, it provides the benzothiazyl-2-sulfenamide Another crystal fraction of this compound is obtained by evaporation the benzene layer. The ammonium salt is obtained by evaporating the aqueous layer of benzenesulfinic acid. Both substances are produced with a yield of about 80 96 d.Th.

and are identical to the products manufactured by processes known from the literature: If, instead of the 2-benzenesulfonylthio-benzothiazole used in Examples 4 to 11 above, the 2-p-toluenesulfonylthiobenzothiazole or 2-p-chlorobenzenesulfonylthio-benzothiazole described in Examples 2 and 3 are used, the same sulfenamides and the following are obtained Amine salts of p-toluenesulfinic acid or p-chlorobenzenesulfinic acid: diethylamine p-toluenesulfinic acid p-toluenesulfinic acid cyclohexylamine p-toluenesulfinic acid tert-butylamine p-toluenesulfinic acid dicyclohexylamine p-toluenesulfinic acid ammonium p-toluenesulfinic acid p-toluenesulfinic acid p-toluenesulfinic acid ammonium p-toluenesulfinic acid p-toluenesulfinic acid p-toluenesulfinic acid p-toluenesulfinic acid p-toluenesulfinic acid p-toluenesulfinic acid p-toluenesulfinic acid p-toluenesulfinic acid p-toluenesulfinic acid p-toluenesulfinic acid p-toluenesulfinic acid p-toluenesulfinate -Chlorbenzenesulfinsaures diethylamine p-Chlorbenzenesulfinsaures Cyclohexylamine p-Chlorbenzenesulfinsaures tert. -Butylamine p-chlorobenzenesulfinic acid, dicyclohexylamine, p-chlorobenzenesulfinic acid, morpholine, p -chlorobenzenesulfinic acid, allylamine, p-chlorobenzenesulfinic acid, diallylamine and the ammonium salt of p-chlorobenzenesulfinic acid.

Claims (5)

Patent claims: (1) ') Process' for the preparation of benzothiazyl-2-sulfenamides of the general formula (III) and amine salts of arylsulphinic acids of the general formula (IV) in which Ar is a phenyl radical optionally substituted by chlorine atoms andl or straight-chain or branched alkyl groups with 1 - 4 carbon atoms, R1 and R4 are identical or different hydrogen, straight-chain or branched alkyl radicals with 1 - 20 carbon atoms, which are optionally substituted by hydroxyl groups or alkoxy groups with 1 - 4 Carbon atoms are substituted, alkenyl radicals with 3-6 carbon atoms, cycloalkyl radicals with 5-7 carbon atoms and aralkyl radicals with 7-9 carbon atoms, R1 and R4 can form a ring with 5-7 ring members, which can optionally be interrupted by oxygen or nitrogen, where the nitrogen is substituted by lower alkyl groups, R4 still in which R3 still represents alkylene, cycloalkylene and dialkylaryl with 2-10 carbon atoms, in addition a heterocyclic ring can be closed via R1, R5 in addition to R1 still represents, R1 and R5 can form a ring with 5-7 ring members, which can optionally be interrupted by oxygen or nitrogen, the nitrogen being substituted by lower alkyl groups, characterized in that 2-arylsulfonylthiobenzothiazoles of the general formula (I) with Amines of the general formula (IT) in which Ar and R1 have the meaning given above, and 'R2, in addition to R1, also denotes -R3-NH-, is reacted in inert solvents or diluents at temperatures from -20 to 100 ° C 2.) Process according to claim 1, characterized in that 2-benzenesulfonylthiobenzothiazole, 2-toluenesulfonylthiobenzothiazole and 2-chlorobenzenesulfonylthiobenzothiazole with ammonia, diethylamine, diisopropylamine, tert. -Butylamine, cyclohexylamine, dicyclohexylamine and morpholine are implemented. 3.) The method according to claim 1, characterized in that the compounds of the general formula (IV) for the preparation of the compound of the general formula (I) can be used. 4.) The method according to claim 1, characterized in that in addition the compounds of the general formula (III) and (IV) by different water solubility be separated. 5.) Use of the compounds of the general formula (III) and ( IV) as a vulcanization accelerator mixture.