DE2551504A1 - SULFENAMIDE, THEIR PRODUCTION AND THEIR USE AS VULCANIZATION RETARDER - Google Patents

Description

Sulfenamides, their production and their use as vulcanization retarders __

The invention relates to sulfenamides, which by adding sulfonic acid amide-N-sulfenic chlorides to compounds with a or two olefinic double bonds are formed.

In the case of addition to olefins having a double bond, the sulfenamides according to the invention can be given the following general information Formula can be represented:

R-SO ₀ -

NS
t

C-C-Cl ι ι

R ₄ R ₅

(D

In this formula I mean:

R is a straight-chain or branched alkyl radical with 1-20 C atoms, a cycloalkyl radical with 5-7 carbon atoms, an aralkyl radical with 7-12 C atoms, an aryl radical with 6 or 10 C atoms, which is replaced by one or more alkyl radicals with 1-4 C atoms or by halogen atoms

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and Ci-Ot-alkoxy or nitro groups can be substituted or a remainder

NR ₇ '

where R ₀ and R _{7 are} identical or different and are alkyl radicals with 1-6 C atoms or together with the N atom form a six-membered heterocyclic ring system which contains a ring C atom.

Ri is a straight-chain or branched alkyl radical with 1-20 C atoms, a cycloalkyl radical with 5-7 carbon atoms, an aralkyl radical with 7-12 carbon atoms or an aryl radical with 6-10 carbon atoms, which by one or more alkyl radicals with 1-8 carbon atoms or substituted by halogen atoms and Ci-C4-alkoxy or nitro groups can,

R2-R5, identically or differently, H, a straight-chain or branched one Alkyl radical with 1-20 carbon atoms, a cycloalkyl radical which contains 5-7 ring G atoms and which by straight-chain or branched alkyl radicals with 1-12 carbon atoms can be substituted, an aryl radical with 6 or 10 ring carbon atoms, which by Alkyl radicals with 1-6 carbon atoms or by chlorine or bromine as well as cyano or nitro groups or aromatic acyl radicals with 7 or 11 carbon atoms can be substituted, furthermore a nitrile group, chlorine or bromine or aliphatic acyl radicals with 1-10 carbon atoms or aromatic acyl radicals with 7 or 11 carbon atoms, a carboxylic acid ester group with 1-4 carbon atoms in the alcohol component, an alkoxy radical containing 1-6 carbon atoms, straight-chain or branched alkyl radical, acyloxy radicals, their aliphatic radicals Carboxylic acid component 1-10 ß-atoms or aromatic carboxylic acid component Contains 7 or 11 carbon atoms or a heterocyclic radical with 5-10 ring carbon atoms, which apart from carbon still contain 1 or 2 oxygen, nitrogen or sulfur atoms and optionally by alkyl radicals with 1-6 carbon atoms or aryl radicals with

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6 or 10 C atoms can be substituted, or R2 together with R _{3 forms} a 4-12 membered alicyclic ring system optionally substituted by 1-12 C atoms containing alkyl or 6 or 10 C atoms containing aryl radicals or a heterocyclic ring system with 5-8 ring carbon atoms which, in addition to carbon, can also contain 1 or 2 oxygen, nitrogen or sulfur atoms.

Examples of the radical R include:

Methyl, ethyl, n-propyl, i-propyl, η-butyl, sec-butyl, n-octyl, i-octyl, dodecyl, stearyl or eicosyl radicals, furthermore cyclopentyl radicals , Cyclohexyl, cycloheptyl radicals or benzyl or naphthylmethyl radicals and phenyl, tolyl, xylyl, naphthyl-chlorophenyl, bromophenyl, dichlorophenyl, trichlorophenyl, methoxyphenyl, isopropoxyphenyl and nitrophenyl radicals. Further examples of R are Ν, Ν-dimethylamino, Ν, Ν-diethylamino, Ν, Ν-dipropylamino, N, N-dibutylamino, Ν, Ν-dihexylamino and oxydiethylenamino radicals. Preferably, R is ^C i-C4-alkyl radicals such as methyl, ethyl, propyl or butyl as well as aromatic radicals such as phenyl, p-tolyl, o-tolyl, and naphthyl, as well as for the ChIorphenyl Oxydiäthylenamino-, Ν, Ν-dimethylamino and N, N-diethylamino residue. The methyl, phenyl, p-tolyl, chlorophenyl, Ν, Ν-dimethylamino and N, N-diethylamino radicals are particularly preferred.

Examples of the rest of Ri include:

Methyl, ethyl, n-propyl, i-propyl, η-butyl, sec-butyl, n-octyl, i-octyl, dodecyl, stearyl or eicosyl radicals, furthermore Cyclopentyl, cyclohexyl and cycloheptyl radicals or benzyl or naphthylmethyl radicals as well as phenyl, tolyl, xylyl, Naphthyl, chlorophenyl, bromophenyl, dichlorophenyl, trichlorophenyl, Methoxyphenyl and nitrophenyl residues. Ri preferably represents Ci-C4-alkyl radicals such as methyl, ethyl, propyl and butyl as well as for aromatic radicals such as phenyl, tolyl, - chlorophenyl and naphthyl. The methyl and phenyl radicals are particularly preferred.

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Examples of the radicals R2 - R ₅ include:

H, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, Octyl, dodecyl, stearyl, eicosyl, cyclopentyl, cyclohexyl, cycloheptyl, Methylcyclohexyl, dodecylcyclohexyl, phenyl, tolyl, xylyl, tert-butylphenyl, hexylphenyl, chlorophenyl, bromophenyl, cyanophenyl, Nitrophenyl, acetylphenyl, benzoylphenyl, naphthyl, cyan, Chlorine, bromine, methoxycarbonyl, ethoxycarbonyl, isobutoxycarbonyl, Methoxy, ethoxy, isopropoxy, acetoxy, butyroxy, benzoyloxy, naphthoyloxy, 5-oxo-pyrrolidinyl, carbazolyl. Preferably stand R2-R5 for H, straight-chain or branched alkyl radicals with 1-ΐβ C atoms such as methyl, ethyl, propyl, butyl, octyl, dodecyl and stearyl and phenyl, with only up to 2 radicals from the group R2 and R3 should preferably be phenyl. Most notably R2-R5 are preferably H, straight-chain or branched alkyl radicals with 1-8 carbon atoms such as methyl, ethyl, propyl, butyl, octyl and the radical R3 also represents phenyl.

Examples in which R2 together with R3 forms a k - 12-membered alicyclic or a 5-8 ring C-atom containing heterocyclic ring system include:

Cyclobutyl, cyclopentenyl, cyclohexyl, methylcyclohexyl, dodecyl cyclohexyl, phenylcyclohexyl, naphthylcyclohexyl, cycloheptyl, Cyclododecyl, norbornyl, indenyl, tetrahydrofuranyl, Tetrahydropyranyl, dihydrobutadiene sulfonyl, 1,2-diphenylpyrazolidinyl and the hexahydrophthalic anhydride radical, preferably cyclohexyl, methylcyclohexyl, norbornyl, indenyl and the hexahydrophthalic anhydride radical, cyclohexyl and norbornyl being very particularly preferred.

Another object of the invention relates to production above sulfenamides by addition of sulphonic acid amide-N-sulfenchlorides to compounds with 1 or 2 olefinic double bonds, preferably with 1 double bond.

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The sulphonic acid amide-N-sulfenchloride required as starting material are described in DT-AS 1 101 407 and DT-AS 1 156 403. The connection not mentioned in the interpretative documents genes can be easily produced by the methods specified there.

The sulfonic acid amide-N-sulfene chlorides have the formula

R-SO ₉ -NS-Cl

R ₁
in which R and R _{1 have} the definition already listed.

You need a second starting material

1. acyclic compounds with 1 or 2 olefinic double bonds, which contain 2 to 22 carbon atoms, preferably 2-10 carbon atoms and which optionally contain cycloalkyl radicals containing 5-7 ring carbon atoms can be substituted. The acyclic compounds with 1 or 2 olefinic double bonds can also be substituted by 6 or 10 ring carbon atoms containing aryl radicals, by alkyl radicals with 1-6 carbon atoms or by Chlorine or bromine as well as cyano or nitro groups or by aromatic acyl radicals with 7 or 11 carbon atoms can be substituted. Further substituents of the acyclic olefins are: chlorine, bromine, nitrile groups, aliphatic acyl radicals containing 1-10 carbon atoms or aromatic acyl radicals with 7 or 11 carbon atoms, a carboxylic acid ester group with 1-4 carbon atoms in the alcohol component, an alkoxy radical with 1-6 carbon atoms containing straight-chain or branched alkyl radical and an acyloxy radical, the aliphatic carboxylic acid component of which contains 1-10 carbon atoms or the aromatic carboxylic acid component contains 7 or 11 carbon atoms and also a heterocyclic radical with 5-10 ring carbon atoms, which, in addition to carbon, also contains 1 or 2 oxygen, nitrogen or sulfur atoms and possibly through alkyl radicals may be substituted with 1-6 carbon atoms or aryl radicals with 6 or 10 carbon atoms.

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2. Cyclic olefins with 4-12 ring carbon atoms, which may be through 1-12 C-atoms containing alkyl or 6 or 10 C-atoms Aryl radicals can be substituted.

3. Heterocyclic olefins with 5-8 ring carbon atoms, which except Carbon can also contain 1 or 2 oxygen, nitrogen or sulfur atoms.

Such olefins are, for. E.g .: ethylene, propylene, n-butylene, i-butylene, n-pentene, 2,3-dimethyl-l-butene, 2,2,4-trimethyl-3-pentene, 2,2,4-trimethyl-4-pentene, 2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene, tripropylene, tetrapropylene, 2,4,4,6,6- Pentamethyl-1-heptene, tetraisobutylene, butadiene, isoprene, 2,3-di-

methylbutadiene, chloroprene, styrene, a-methylstyrene, divinylbenzene, Diisopropenylbenzene, syllables, vinyl chloride, allyl chloride, Allyl bromide, methallyl chloride, methallyl bromide, vinylidene chloride, Trichlorethylene, 2,3,4-trichloro-l-butene, l, j5-dichloro-2-butene, l-bromo-2-butene, acrylonitrile, crotononitrile, 1,4-dicyanobutene- (2), Methacrylonitrile, vinyl-methy! Ketone, mesityl oxide, methylbutenone, Acrylic acid methyl ester, acrylic acid ethyl ester, methacrylic acid methyl ester, methacrylic acid ethyl ester, crotonic acid methyl ester, Oleic acid ethyl ester, maleic acid methyl ester, fumaric acid ethyl ester, Vinyl isopropyl ether. Vinyl isobutyl ether, vinyl acetate, Allyl acetate, 1,2-diacetoxypropene, l, l-diacetoxy-2-propene, cyclobutene, cyclopentene, cyclohexene, methylcyclohexene, Dodecylcyclohexene, cycloheptene, cyclooctene, cyclododecene, pinene, norbornene, camphene, indene, dihydronaphthalene, cyclohexadiene, norbornadiene, Vinylcyclohexene, ethylidene norbornene, dicyölopentadiene, Cyclopentadiene, dihydrofuran, butadiene sulfone, 2-ethoxy-dihydropyran, Tetrahydrophthalic anhydride, 1,2-diphenyl-A ^ -pyrazoline.

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The inventive implementation of sulfonic acid amide-N-sulfenchloride with the olefins can take place in solution or without a solvent. Suitable solvents are those with the sulfonic acid amide-N-sulfene chlorides do not respond, such as B. methylene chloride, chloroform, carbon tetrachloride, trichloroethane, tetrachloroethane, Chlorobenzene, dichlorobenzene, toluene, nitrobenzene, dioxane, tetrahydrofuran. Such solvents are preferred used in which the production of sulfonic acid amide-N-sulfenchloride takes place, such as B. chlorinated aliphatic hydrocarbons.

In the reaction, one uses per mole of sulfonic acid amide-N-sulfene chloride 1-1.2 moles of monoolefin, preferably 1 mole of monoolefin or 0.5-1 mole diolefin, preferably 0.5 mole diolefin. The reaction temperature is in the range from -20 to + 60 ° C., preferably in the range from 0 ° to 4o °. The reaction pressure is in the range from 1 to 6 bar, preferably at normal pressure.

The order in which the components are added to the reaction mixture can be selected as desired. Preferably one poses first and brings a solution of the sulfonic acid amide-N-sulfene chloride into this, without first isolating the sulfonic acid amide-N-sulfene chloride, the olefin. Liquid olefins are generally in pure form or as solutions, solid olefins in general. added as solutions while gaseous olefins are introduced into the reaction mixture. The reaction products are isolated one according to known methods. They are generally colorless and odorless, liquid or solid compounds.

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Using this process, for example, the following new sulfur amides being represented:

N-2-chloroethylthio-methanesulfonic acid methylamide, N-2-chloro-2-methyl-ethylthio-methanesulfonic acid-ethylamide, N-2-chloro-2,2-dimethyl-ethylthio-methanesulfonic acid-methylamide, N-2-chloro-l, l-dimethyl-ethylthio-methanesulfonic acid-methylamide, N ^ -Chlor ^ -isopropyl ^ -methyl-ethylthio-ethanesulfonic acid-butylamide, N-2-chloro-l, l, 2-trimethyl-ethylthio-propanesulfonic acid methylamide, N-2-chloroethylthio-methanesulfonic acid anilide, N-2-chloro-2-butylthiomethanesulphonic acid anilide, N-2-chloro-2-bromomethyl-l-methyl-ethylthio-methanesulphonic acid-p-chloroanilide,

N-2-chloro-1-chloromethyl-ethylthio-hexanesulfonic acid anilide, N-2-chloro-2-phenyl-ethylthio-methanesulfonic acid anilide, N-2-chloro-2-phenyl-ethylthio-stearylsulfonic acid-p-nitro-anilide N-2-chloro-cyanoethylthio-ethanesulfonic acid-m-methoxy-anilide, N-2-chloro-acetyl-ethylthio-hexanesulfonic acid-n-octylamide, N-2-chloro-carbethoxy-ethylthio-benzenesulfonic acid methylamide, N-2-chloro-cyclopentylthiobenzenesulfonic acid anilide, N-2-chloro-cyclohexylthio-p-toluene-sulfonic acid-methylamide, N-2-chloro-ethylthio-p-toluene-sulfonic acid-methylamide, N-2-chloro-2-methyl-ethylthio-p-toluenesulfonic acid anilide, N-2-chloro-l-methyl-ethylthio-p-toluenesulfonic acid-methylamide, N-2-chloro-2,2-dimethyl-ethylthio-p-toluenesulfonic acid methylamide, N-2-chloro-l, l-dlmethyl-ethylthio-p-toluenesulfonic acid methylamide, N-2-chloro-l, l, 2-trimethyl-ethylthio-p-toluenesulfonic acid methylamide,

N-2-chloro-cyclohexylthio-p-toluenesulfonic acid-p-chloroanilide, N-2-chloro-cycloheptylthio-benzenesulfonic acid-stearylamide, N-2-C! Chloro-cyclooctylthio-benzylsulphonic acid methylamide, N-2-chloro-ethylthio-benzylsulphonic acid anilide, N-2-chloro-norbornylthiocyclohexylsulfonic acid methylamide, N-2-chloro-norbornylthio-p-toluenesulfonic acid methylamide, N-2-chloro-indanylthio-p-toluenesulfonic acid methylamide,

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N-2-chloro-indanylthio-methanesulphonic acid anilide,

N-2-chloro-A ^ -cyclopentenylthio-napththalenesulfonic acid-methylamide, N-2-chloro-cyGlododecylthio-napththalenesulfonic acid anilide, N ^ -Chlor-tetrahydropyranylthio-methanesulfonic acid-methylamide, N-2-chloro-ethylthio-dimethylamine-sulfonic acid-methylamide, N-2-chloro-ethylthio-diethylamine-sulfonic acid anilide, N-2-chloro-norbornyl-thio-dimethylamino-sulfonic acid anilide, N-2-chloro-cyclohexylthiodipropylamine-sulfonic acid anilide, N-2-chloro-2-phenyl-ethylthiodimethylamino-sulfonic acid anilide, N ^ -Chlor ^ -methyl-ethylthiodimethylamino-sulfonic acid anilide, N-2-chloro-l-methyl-ethylthio-dimethylamino-sulfonic acid anilide, N ^ -Cfalor ^^ - dimethyl-ethylthio-dimethylamino-sulfonic acid anilide, N ~ 2-chloro-l, l-dimethyl-ethylthio-dimethylamino-sulfonic acid anilide.

Furthermore, addition products of sulfonic acid-N-sulfene chlorides to compounds with two olefinic double bonds, such as. B. butadiene, isoprene, 2, j5-dimethylbutadiene, chloroprene, Divinylbenzene, diisopropenylbenzene, cyclohexadiene, norbornadiene, vinylcyclohexene, ethylidene norbornene, dicyclopentadiene, cyclopentadiene .

The addition of sulfonic acid amide-N-sulfene chlorides to compounds with two olefinic double bonds generally leads to geraischen structural isomeric mono- and bis-sulfenamides. Also can here just as in the case of compounds with an olefinic double bond, the addition of the sulfonic acid amide-N-sulfene chloride in the sense the rule of Markovnikov as well as the opposite of this rule. The separation of such mixtures is technical Application, such as B. not required as a vulcanization retarder.

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The present invention also includes the use of the new sulfenamides as vulcanization retarders during manufacture and processing of mixtures based on natural or synthetic rubber.

Surprisingly, it was found that the invention Sulfenamides, in particular, as vulcanization retarders in known production and processing of mixtures containing natural or synthetic rubber can be used.

Suitable rubbers for the production and processing of mixtures based on natural or synthetic Rubber are e.g. natural rubber or synthetic rubber-like polymers, e.g. from conjugated diolefins such as butadiene, Dimethylbutadiene, chloroprene, isoprene and its homologues are obtained, or copolymers conjugated in this way Diolefins with polymerizable vinyl compounds such as styrene, <£ -Methylstyröl, acrylonitrile, methacrylonitrile, acrylates, methacrylates, as well as terpolymers of ethylene, propylene and at least one non-conjugated diene such as dicylopentadiene, 5-ethylidene-2-norbornene or 1,4-hexadiene.

The retarders to be used according to the invention can be used in the Rubber are mixed in in the usual way, for example on a rolling mill or in an internal mixer, they will preferably added before or simultaneously with the addition of the other ingredients. However, you can also be the last Mixture constituent are added.

The amount of the retarders according to the invention should be 0.05-5.0 % And preferably 0.1-1.5% by weight of the rubber.

The rubber mixtures to be treated contain the usual additives required for vulcanization, such as vulcanizing agents and accelerator. The vulcanizing agent, e.g., sulfur, can be in the conventional amount, generally in an amount

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0.2-5.0% by weight of the rubber is used for vulcanization will. Examples of accelerators that may be mentioned are: thiazoles, such as 2-mercaptobenzothiazole or dibenzothiazyl disulfide, Sulfenamides, such as benzothiazyl-2-cyclohexylsulfenamide, benzthia-2-tert.butylsulfenamide or benzthiazylsulfenmorpholide, guani-r dine, such as diphenylguanidine or di-o-tolylguanidine, dithiocarbamates, like diethyldithiocarbamic acid zinc and thiurams, like Tetramethylthiuram disulfide or tetramethylthiuram monosulfide.

Mixtures of accelerators can also be used. The accelerators are generally used in amounts from 0.05 to 7 % By weight of the rubber used.

The rubber mixture can also contain other known auxiliaries, for example active or inactive fillers such as chalk or soot, antioxidants, antiozonants, waxes, pigments, zinc oxide, Fatty acids such as stearic acid or processing oils.

The rubber can be vulcanized by heating to the usual temperatures, preferably to a temperature between 120 and 170 ^° C., but it is also possible to work at higher or lower temperatures.

The following examples illustrate the invention without, however, wishing to restrict it. The in the tables of the application examples Unless otherwise stated, the values given are parts by weight based on 100.0 parts by weight Rubber.

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Application example:

The following mixes were produced on a mixing mill:

Mixture No. 1 2 5 k 5 6

Natural rubber 100 100 100 100 100 100

Zinc oxide 5.0 5.0 5.0 5.0 5.0 5.0

Stearic acid 5.0 5.0 5.0 5.0 5.0 5.0

Aromatic mineral “ _{ς pc} - pe pe pe oc oil softener '° ^{>D>0> 0} ' ° * °

Napththenischer _{? C} - _{? [} - _pc - _{? C} - _{p (} - _{p (} -Mineral oil softener- '° ⁱ⁰ ' ° '° ^{> 0} > ° maker

phenyl-p-pheny- ^x '° ^X ' ^DL '° ^x > ° ^{XtD x} ' ° lenediamine

Sulfur 2.5 2.5 2.3 2.5 2.5 2.5

N-cyclohexyl-2-

benzthiazolyl- o, 5 o, 5 o, 5 o, 5 o, 5 o, 5 sulfenamide

A - o, 5-

B o, 5 - -

C - - - 0.5

D - - - o, 5

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A = mixture of 70 % N-2-chloro-2-methyl-ethylthio-p-toluenesulfonic acid methylamide and 30 % N-2-chloro-l-methyl-ethylthio-p-toluenesulfonic acid methylamide (according to preparation example no.15)

B = N-2-chloro-norbornylthio-dimethylaminosulfonic acid anilide (after Production example No. 6)

C = mixture of 50 % N-2-chloro-2,2-dimethyl-ethylthio-p-toluenesulfonic acid methylamide and 50 % N-2-chloro-l, l-dimethylethylthio-p-toluenesulfonic acid methylamide (according to preparation example no. 14).

D = N-S-chloro-cyclohexylthio-p-toluenesulfonic acid methylamide (after Production example No. 17)

E = N-2 - (^ lor-2-phenyl-ethylthio-p-toluenesulfonic acid methylamide (according to Production Example No. 13)

The mixtures obtained were used to determine the retarding effect of the mixed-in sulfenamides according to the invention with the aid of a linear shear volcanic meter, BAYER system (see H. Kramer, Gummi-Asbest-Kunststoffe 23 No. 1/1970, p. 22 ff) The test methods are as follows:

Scorch time (t _g ): In analogy to the Mooney Scorch Time

(DIN 53524) determined: time determined from the volcano curve until the curve rises by 20 mm above the minimum.

Fully cured time (tg _Q ) : Time to reach 90 % of the

Maximum value of the volcanic curve.

: Maximum of the volcanic meter display, based on the minimum (Fa) of the volcanic meter curve (see DIN 53529).

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Tabel:

Mixture vulcanization no. delay

Scorch

time (min.)

b. l3o ° C b. 14o ° C

Vulcanization at 14o ° C t90 (min) Fa / Pe (ram)

1 without 23.3 11.5 26.9 83 2 A. 35.0 17.8 34.9 86 3 B. 35.2 18.6 34.5 84 4th C. 33.4 17.2 34.4 84 VJl D. 33.8 16.9 32.8 84 6th E. 30.0 16.6 32.0 85

The values - especially the vulcanization times - leave clearly recognize that it is with the tested sulfenamides according to the invention to vulcanization retarders, which are relative have strong effect.

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Manufacturing examples:

The structures of the compounds are clearly defined by their nuclear magnetic resonance and mass spectra.

From N, N '~ dithio-bis (dimethylaminosulphonic anilide), a solution of Ν, Ν-dimethylaminosulphonic anilide-N ^ -sulfenchlorid in carbon tetrachloride is prepared according to the instructions in DT-AS 1 101 407. The stoichiometric amount of the olefin is added dropwise to the freshly prepared solution of the sulfenic chloride or the stoichiometric amount of the olefin is introduced in gaseous form or a solution of the olefin in carbon tetrachloride is added dropwise. The mixture is stirred for 3 hours at room temperature and the solvent is evaporated i. Vac. away. Solid residues are recrystallized, free liquid residues under high vacuum at a bath temperature of 50 ⁰ C of volatiles. In this way, for example, the addition products with the following olefins are obtained:

Example No. Olefin M.p. . 82-83 ° C, Sulfenamide Ι C 51.8 (348.5) from cyclohexane N 7.6 S 18.4 1 Cyclohexene Yield colored needles 51.6 6.0 Cl 10.2 8.0 18.9 Ci ₄ H ₂ 94 % d. Th. 5.8 9.5 Cyclo- Ber: 1ClN ₂ O ₂ S ₂ N 8.1 Found: C 48.2 H. 8.6 M.p. 48.1 cream-colored.crystalline S 17.3 2 Styrene hexane . 77-81 ⁰ C, a '92 "# d. Th. 17.6 , Yield (370.5) Ci ₀ Hi ₉ CIN ₂ O ₂ S ₂ I 5.1 Cl 9.6 Ber: 5.1 8.8 Found:

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Olefin fio 2551504 Sulfenamide (322.5) Cyclo- (308.9) 11.5 N 9.1 S 20.7 (360.9) 9.8 N 7.8 S 17.7 Example no. Isobutylene , color. 5.9 Cl d. Th. 5.5 cl 11.5 9.1 21.7 5.8 Cl 9.7 7 ² I 17.0 3 M.p. 84-85 ° C hexane, yield 88.5 % 5.7 5.6 brown oil, yield 99 # d. Th. 5.5 Ci ₂ Hi ₉ ClN ₂ O ₂ S ₂ , color. 11.0 N 8.7 S 19.9 Ci ₅ H ₂ IClN ₂ O ₂ S ₂ Ber: C 44.6 H. 5 82 fo d. 11.0 8.6 19.4 Ber: C 49.8 H. Found: 44.7 (29 ^, 5) Cyclo- Found: 48.5 Ethylene Mp. 91-93 ⁰ C. 5.1 Cl , Th. 4th hexane, yield 5.0 Ci ₀ Hi ₅ CIN ₂ O ₂ S ₂ brown oil, educ. 95 ° / 12.0 N 9.5 S 21.8 Ber: C 4o.7 H 12.0 9.7 22.0 Gef: 4l, o i d. Th. Propylene 37 % Markovnikov and 63 % Antimarkovnikov vji -Adduct ChHi ₇ CIN ₂ O ₂ S ₂ Ber: C 42.7 H. Found: 42.1 Norbornene 6th

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From Ν, Ν'-dithio-bis- (methanesulfonic acid anilide) one makes after the Regulation in DT-AS 1 101 407 a solution of methanesulphonic acid anilide-N-sulfen chloride in carbon tetrachloride and reacts this with the olefins as described above. You get for example the addition products with the following olefins:

Example No. Olefin Sulfenamide 7th Cyclohexene Melting point 106 ° C., color crystals. from cyclohexane
Yield 8 * 1.5 % d. Th.
Ci ₃ Hi ₈ Cl NO ₂ S ₂ (319.9) 8th In the brown oil, yield 99 % of theory Th.
Ci ₆ HIeClNO ₂ S ₂ (353.5) 9 Isobutylene M.p. 86 ° -88 ° C, color crystals. from isoprop.
Yield: 73 $ d. Th.
CnHIeClNO ₂ S ₂ (293.5) 10 Styrene Mp. 137-138 ° C, color crystals. from isoprop.
Yield 77.5 % d. Th.
Ci ₅ HIeClNO ₂ S ₂ (3 ^ 1.9) 11 Cyclopentene brown oil, yield 93 % of theory Th.
Ci ₂ HIeClNO ₂ S (305.5) 12th N orb ornadi en brown resin, yield 97 $ d. Th.
C ₂ IH ₂₄ Cl ₂ N ₂ S ₄ O ₄ (567.6)

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ft

From bis (p-toluenesulfonic acid methylamido) disulfide (Schffip. 1Ό5 from methanol) a solution of p-toluenesulfonic acid methylamide-N-sulfenchloride (melting point 67 ^{0) is prepared by the process described in DT-AS 1 101 407} C) in carbon tetrachloride and reacts this with the olefins as described above. For example, the addition products with the following olefins are obtained:

Example No. Olefin Suli'enamid f> 11 12, Th • 3 , 9 S. 18th , 0 N » 4th S. 20th N 4, 7th N 5, 8th S. 21 Styrene yellow oil, yield 91.5 11. 10, 3 , 9 17th , 3 4, 20th 5, 7th 5, 0 21 Ci ₆ Hi ₈ ClNO ₂ S ₂ (355.9) 10 d. N 1 to one Kr is ; al] Calc .: C 54.0 H 5.1 Cl 9 50 % Markovnikov and $ 50 a. & Antimarkovnikov- Th. Found: 54.6 5.2 d. Adduct lü Isobutylene yellow oil, yield 92 % 7o % Markovnikov and 3o \ CiiHieCINOaSa (293.5) , 0 , 6 ,8th 12, 0 S. 22 ₃ Adduct Calc .: C 45.0 H 5.5 Cl , 9 , 5 , 7 , 2 11 1 21 Ci ₂ Hi ₈ ClNO ₂ S ₂ (307.9) Found: 46.1 5.6 Th , 0 Calc .: C 46.9 H 5.9 Cl yellow oil, the slow Th % Antimarkovnikov- I. Found: ^ 7.3 6.0 solidified, yield 93 % d. ,8th yellow oil, yield 93 % C10H14CINO2S2 (279.8) 3 15th Propylene Calc .: C 43.0 H 5.1 Cl ,1 .br < Found: 43.7 5.2 , 9 8th 0 16 Ethylene

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Example no. Olefin Sulfenamide? RF Π 504 s 19.2 Mp. 107-110 ⁰ C, colorless crystals, 8th S 17.5 17th Cyclohexene yellow oil that slowly becomes one Crystal- 18.8 Yield: 55.0 # d. Th. 9 17.3 solidified pulp, yield. 94 # d. Th. Ci ₇ Hi ₈ ClNO ₂ S ₂ - (567.5) Ci ₄ H ₂₀ CINO ₂ S ₂ (355.9) Ber: C 55.5 H 4.9 Cl 9.7 N 5, Ber: C 50.5 H 6.0 Cl 10.6 N 4, 2 Found: 55.8 4.9 9.6 3, t, 2 s 19.1 Found: 50.9 6.2 10.6 4, 5 S 20.0 brown oil, educ. 93 # d. Th. 19.0 18th Cyclopentene Mp. 60 ° -65 ° C. from cyclohexane 19.5 Ci ₄ H ₂₂ ClNO ₂ S ₂ (335.5) Yield 70 % d. Th. Calc .: C 50.1 H 6.6 Cl 10.6 N 4 Ci ₃ Hi ₈ ClNO ₂ S ₂ (519.9) Found: 51.2 6.7 9.5 * Calcd: C 48.9 H 5.7 Cl 11.1 N 4. , 4 S 21.5 Found: 49.2 5.4 10.4 4 , 4 20.4 19th Norbornadiene brown resin, yield. 96 # d. Th. C ₂₃ H ₂₈ Cl ₂ N ₂ O ₄ S ₄ (659.5) Calcd: C 46.4 H 4.7 Cl 11.9 N 4 , 7 Found: 47.5 5.0 11.6 4 , 7 20th In the 21 I.
2,3-dimethyl 1-butene

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BSD no. Olefin ι Norbornene Sulfenamide 94 < t d. Th. 4.4 S 19.9 22nd 2-methyl-2- brown oil, educ. , 5) 4.9 19.5 buten CIaH ₂₀ ClNO ₂ S ₂ (321 Cl 11.1 N Calc .: C 48.6 H 6.2 10.1 trans style
ben Oef: 48.8 6.2 97 p % d. Th. 4.1 S 18.5 23 brown oil, educ. , 9) 4.4 18.4 Ci5H ₂₀ ClNO ₂ S ₂ (345 Cl 10.3 N the end ISO Calc .: C 52.1 H 5.8 9.7 Get: 52.3 6.5 color] L. Krist. 24 M.p. 132-135 ° C,
prop. . Th. Yield: 32.5 ^ d , 0) C12H22CINO2S2 (432

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Claims (10)

Claims η) I sulfenamides can be prepared by adding sulphonic acid amide ^ N-sulfenchloride of the formula R-SOp-NS-Cl
R ₁ in the R is a straight-chain or branched alkyl radical with 1-20 carbon atoms, a cycloalkyl radical with 5-7 carbon atoms, an aralkyl radical with 7-12 carbon atoms, an aryl radical with 6 or 10 carbon atoms, which is replaced by one or more alkyl radicals may be substituted by 1-4 C atoms or by halogen atoms and C ₁ -C ^ alkoxy or nitro groups, or a radical R ₇ where Rg and Ry are identical or different and are alkyl radicals with 1-6 C atoms or together with the N atom form a six-membered heterocyclic ring system which a ring contains C atom, and R _{1 is} a straight-chain or branched alkyl radical with 1-20 carbon atoms, a cycloalkyl radical with 5-7 carbon atoms, an aralkyl radical with 7-12 carbon atoms or an aryl radical with 6-10 carbon atoms, which is replaced by one or more Alkyl radicals with 1-8 C atoms or by halogen atoms and C ₁ -C ^ -AIkOXy- or nitro groups mean * on compounds with an olefinic double bond. 2) Sulfenamides according to claim 1 can be prepared by addition of sulfonic acid amide-N-sulfehchlorides of the formula according to Claim 1 of compounds with an olefinic double bond. Le A 16 836 - 21 - 709820/1042 3) Sulfenamides according to claim 1 can be prepared by addition of sulfonic acid amide-N-sulfene chlorides of the formula according to Claim 1 of compounds with two olefinic double bonds. 4) Sulfenamides according to claim 1 can be prepared by addition of sulfonic acid amide-N-sulfenic chlorides of the formula according to claim at a) acyclic compounds with one or two olefinic double bonds, which have 2 to 22 carbon atoms and can optionally be substituted by 5-7 ring carbon atoms containing cycloalkyl groups, 6 or 10 ring carbon atoms containing aryl radicals, which in turn are optionally _{substituted by C 1} -C 6 alkyl, chlorine, bromine, cyano, nitro or by aromatic acyl radicals having 7 or 11 carbon atoms; Chlorine, bromine, nitrile, C - C ₁₀ containing aliphatic acyl radicals, aromatic acyl radicals with 7 or 11 carbon atoms, carboxylic acid ester groups with 1-4 carbon atoms in the alcohol component, alkoxy with 1-6 carbon atoms in the straight-chain or branched one Alkyl group, acyloxy radical with 1-10 carbon atoms in the aliphatic carboxylic acid component or 7 or 11 carbon atoms in the aromatic carboxylic acid component, heterocyclic radical with 5-10 ring carbon atoms, which also has 1 or 2 oxygen, nitrogen or Contains sulfur atoms and in turn can optionally be _{substituted by C 1} -C 6 alkyl or by C ₆ or C 10 aryl, b) cyclic olefins with 4-12 ring carbon atoms, which can optionally be substituted _{by C 1} -C ₁₂ alkyl or Cg or C _{10 aryl} or c) heterocyclic olefins with 5-8 ring carbon atoms, which also have 1 or 2 oxygen, nitrogen or May contain sulfur atoms. Le A 16 836 - 22 - 709820/1042 5) Process for the preparation of sulfenamides according to claim 1, characterized in that per mole of sulfonic acid amide-N-sulfen chloride of the formula according to claim 1 1.2-1 mol of a compound with an olefinic double bond at temperatures accumulates from -20 to + 60 ° C. 6) A process for preparing SuIfenamiden according to claim 1, characterized in that per mole of N-sulphonamide sulfenchlorid of formula according to claim 1 0.5-1 moles of a compound having two olefinic double bonds at temperatures of -20 to +60 ⁰ C attaches. 7) Process for the preparation of sulfenamides according to claim 1, characterized in that sulfonic acid amide-N-sulfenchloride of the formula according to claim 1 with a) acyclic compounds with one or two olefinic double bonds, which have 2 to 22 carbon atoms and can optionally be substituted by 5-7 ring carbon atoms containing cycloalkyl groups, 6 or 10 ring carbon atoms containing aryl radicals, which in turn are optionally _{substituted by C 1} -C 6 alkyl, chlorine, bromine, cyano, nitro or by aromatic acyl radicals having 7 or 11 carbon atoms; Chlorine, bromine, nitrile, C ₁ -C _10- containing aliphatic acyl radicals, aromatic acyl radicals with 7 or 11 carbon atoms, carboxylic acid ester groups with 1-4 carbon atoms in the alcohol component, alkoxy with 1-6 carbon atoms in the straight-chain or branched one Alkyl group, acyloxy radical with 1-10 carbon atoms in the aliphatic carboxylic acid component or 7 or 11 carbon atoms in the aromatic carboxylic acid component, heterocyclic radical with 5-10 ring carbon atoms, which also has 1 or 2 oxygen, nitrogen or sulfur atoms contains and in turn can optionally be _{substituted by C 1} -C 6 alkyl or by C ₆ or C 10 aryl, Le A 16 836 - 23 - 70982Π / 1042 b) cyclic olefins with 4-12 ring carbon atoms, which can optionally be substituted by C ₁ -C ₁₂ alkyl or Cg or C ^ _{0 aryl} or c) heterocyclic olefins with 5-8 ring carbon atoms, which can also contain 1 or 2 oxygen, nitrogen or sulfur atoms, at temperatures from -20 to +60 ⁰ C implemented. 8) Vulcanization retarders for natural and synthetic rubber consisting of sulfenamides according to claim 1. 9) Process for the vulcanization of natural or synthetic rubber, characterized in that in addition to the customary additives required for vulcanization as vulcanization retarders sulfenamides according to claim 1 in amounts of 0.05 to 5.0% by weight, based on rubber. 10) Natural or synthetic rubber composition containing sulfenamides according to claim 1. 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