DE2027432C - Process for the preparation of sulfenamides of s-triazines - Google Patents

Description

in the Y for the groups
R ¹

- N

or - S - N

R ²

R ³

R ⁴

where R ¹ and R ^{2 are} identical or different and represent a hydrogen atom or an alkyl or alkeny radical with 1 to 18 carbon atoms each, optionally substituted by an alkoxy group with 1 to 4 carbon atoms or by a cyano group, a cycloalkyl radical with 5 to 8 carbon atoms, phenyl -, naphthyl, benzyl or naphthylmethyl radicals, R ³ and R ^{4 are} identical or different and represent an alkyl radical having 1 to 18 carbon atoms, a cycloalkyl radical having 5 to 8 carbon atoms or the benzyl radical, where R ^{3 can} also represent a hydrogen atom , and where R ¹ with R ² and / or R ³ with R ^{4 can} also be closed to form a piperidine, pyrrole, pyrrolidine, hexamethyleneimine or morpholine ring which is optionally mono- or disubstituted by an alkyl group having 1 to 4 carbon atoms Oxidation of amino-mercaptotriazines of the general formula II

R ¹

I. c

N N

I Il

X-C C-SH

N
in the X for the remainder - SH or

(H)

R ¹

• N

stands, with a hypochlorite in the presence of an amine of the general formula HI
R ³ .

H-N

wherein R ¹ to R * is as defined above, have characterized used daßmar per mercapto group in the starting compound I] is at least 1 MoI hypochlorite and oxidized in the presence of a polar organic solvent or suspending agent, or their Gemischet between about -10 and about 50 ⁰ C.

2. The method according to claim 1, characterized that the solvent used is N, N'-dimethylformamide or ethylene glycol

3. The method according to claims 1 or 2, characterized in that one works at a ^{temperature between about 0 and about 3O 3} C lying between.

4. The method according to claims 1, 2 or 3, characterized in that one 10- bi < 15% aqueous sodium or potassium hypochlorite solution used.

It is known to produce sulfenamides of s-triazines by oxidation of mercapto-s-triazines with a sodium hypochlorite solution in the presence of an amine> in water (patent specification 69 206 of the Office for Invention and Patents in East Berlin). However, the yields and the purity of the sulfenamides obtainable by this process could not be fully satisfactory.
It has now been found that Sulfenamidc

of the general formula I.

R ¹

R ²

N
j

Y \
NN

I Il

Y-C C-S-N

N _n /

R ³

in the Y door the groups

R ¹

R ³

- N

or - S —N

R ²

R ⁴

stands, where R ¹ and R ^{2 are} identical or different and are a hydrogen atom or an optional: alkyl or alkenyl radical substituted by an alkoxy group with 1 to 4 carbon atoms or by a cyano group with 1 to 18 carbon atoms, Cycloalkylrei * with 5 to 8 carbon atoms

Phenyl, naphthyl, benzyl or naphthylmethyl ^{radical, R 3} and R ^{4 are} identical or different and represent an alkyl radical with 1 to 18 carbon atoms, a cycloalkyl radical with 5 to 8 carbon atoms or the benzyl radical, where R ^{3 is} an additional Can denote hydrogen atom, and where R ¹ with R ^: and / or R ³ with R * also closed to form a piperidine, pyrrole, pyrrolidine, hexamethyleneimine or ίο morpholine ring optionally substituted once or twice by an ABcyl group with 1 to 4 carbon atoms can be, by oxidation of Amino-mercaptotriazinea of the general formula II

R ²

N
ι N /
N -SH X-C : i
C.
* ■ /
n ' or in the X for the leftovers -SH R ¹

(H)

R-

stands, with a hypochlorite in the presence of a Amine of the general formula III

R ³

H - N

(III)

R ⁴

40

where R ¹ to R ^{4 have} the meaning given above, can be produced if at least 1 mol of hypochlorite is used per mercapto group in the starting compound II and is oxidized in the presence of a polar organic solvent or suspending agent or mixtures thereof between about -10 and about 50.degree .

The solvents used in the context of the invention Process are used, they are those that are miscible with water and also able to dissolve the starting triazine in at least small amounts. From the size of the Solvent power also depends on the amount of solvent or solvent mixture to be used away.

The solvents include in particular ketones, ethers, alcohols, glycols, acid amides and sulfones. The use of tert is particularly advantageous. Butanol, methyl ethyl ketone, formamide, dimethyl sulfoxide, tetramethylene sulfone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, tetrahydrofuran, N-methylpyrrolidone, acetone, methanol, ethanol, diethylene glycol, triethylene glycol _{or dioxane, N-methylamido-dimamide, N-1} -methyl-acetamide, N-methyl-1-methyl-acetamide, N-methyl-1-methyl-acetamide. N, N'-dimethylformamide or ethylene glycol are preferably used. The amines used can also act as solvents.

Examples of amines that can be used in the context of the invention are methylamine, diniethylamine, ethylarain, Diethylamine, iso-propylamine, di-iso-propylamine, tert-butylamine, cyclohexylamine, Morpholine, piperidine, benzylimine, pyrrole, pyrrolidine.

It is advisable to carry out the oxidation in the presence of 1 to 5 moles of the amine per SH group.

An aqueous sodium or potassium hypochlorite solution can advantageously be used for the oxidation will. This should preferably be 10 to 15%, but lower concentrations are also possible, for example up to about 3%, useful.

When carrying out the method according to the invention, it is possible, for example, to proceed as follows: that one submits the amine dissolved in a solvent or solvent mixture and into this Solution the mercapto-s-triazine. which is also in a solvent or solvent mixture is dissolved, added dropwise with stirring. Simultaneously with this dropping in, the aqueous alkali metal hypochlorite solution also becomes added from a separate vessel. The inlet speeds should be be regulated in such a way that the two solutions are ended at the same time.

But Ls is also possible, only part of the amine and add the remaining portion of the amine aer the abovementioned solution of mercapto-s-triazine and drop this mixture. Here, too, there is a coordination of the inlet speeds expedient.

However, it is advantageous to use the mercapto-s-triazine or the bis-mercapto-s-triazine together with the amine to be submitted in an organic solvent or solvent mixture and the alkali hypochlorite solution with stirring.

It is particularly favorable in general in that Maintain mixture temperatures between about 0 and about 30 C during the reaction.

According to the process according to the invention, the sulfenamides can be obtained in high yields and high purity can be obtained. They can be used as accelerators in the vulcanization of natural or synthetic Rubber are used.

The invention is illustrated in more detail by the following examples. The sulfenaimd contents were after O. Foss, Acta formerly scand., 1 (1947) 307, definitely.

example 1

10 g of cyclohexylamine (0.1 mol) are placed in 20 ml of dimethylformamide in a multi-necked flask. At 25 to 30 "C the solution of 20 g of 2 - amino - 4 - diethylamine ^ - 6 - mercapto - s - triazine (0.1 mol) and JOg cyclohexylamine in 100ml dimethylformamide added dropwise. At the same time, the aqueous solution is left in a second dropping funnel of sodium hypochlorite (77.9 g with 10.51% NaClO = 0.11 mol) flow in.

The inflow speeds are coordinated so that the additions end at the same time are. A finely crystalline precipitate separates out immediately when the components are added. The mixture is stirred for a further 2 hours, filtered off and washed

did

with distilled water and petroleum ether, and dries 16 hours at 40 ° C over calcium chloride in a vacuum.

Yield: 91% (27 g);

F .: 101 to 102 ⁰ C;

Sulfur content: found 10.70,10.63%;

theoretical: 10.82%.

Sulfenamide content: 96.2.96.1%.

Example 2

40 g (0.4 mol) of cyclohexylamine and 30 ml of dimethyl ίο formamide are placed in a multi-necked flask. At 25 to 30 ° C, the solution of 22 g of 2-diethylamino-4,6-bis-mercapto-s-triazine (0.1 mol) in 100 ml of dimethylformamide was added dropwise. At the same time, the aqueous solution is allowed to pass through a second dropping funnel of 0.22 mol of sodium hypochlorite (155.8 g with 10.51% NaClO) flow.

Both inflow speeds are coordinated so that the additions end at the same time are. A finely crystalline precipitate separates out. The mixture is stirred for a further 2 hours.

The contents of the flask are poured into 1000 ml of ice water and the excess amine with stirring 0.18 mol hydrochloric acid (about In) neutralized. It is filtered off, with water and then with petroleum ether washed. It is dried at 40 ° C. in vacuo over calcium chloride.

Yield: 79.2% (32.5 g):

F .: 80 to 82 C;

Sulfur content: found: 15.43, 15.77%;

theoretical: 15.62%.

Sulfenamide content: 93.4.94.9%.

Example 3

In a three-necked flask (1000 ml) 10 g of cyclohexylamine (0.1 MrIi and 30 ml of dimethylformamide submitted. In this mixture at 25 to 30 C, the solutions of 25.5 g of 2,4-bis-diethylamino-o-mercapto-s triazine and 10 g of cyclohexylamine in 100 ml of dimethylformamide at the same time as 86 g aqueous sodium hypochlorite solution (9.53% NaClO = 0.11 mol) from two dropping funnels with stirring admitted.

The Zuflußgeschwindigkei ^f s are coordinated so the additions IASS at the same time are finished.

It is allowed to react for 1 hour, rinsed in 1000 ml of ice water, neutral! iert (pH = 8) with about 1 normal Hydrochloric acid, sucks off. Washed with distilled water and dried at 30 "C in a vacuum over calcium chloride.

Yield: 99.1% (32 g);

F .: 44 to 46 C;

Sulfur content: found: 9.41, 9.30%;

theoretical: 9.12%.

Sulfenamide content: 97.1, 97.77 ", ..

Example 4

40 g of cyclohexylamine and 30 ml of dimethylformamide are placed in a multi-necked flask. The solution of 22.7 g of 2-ethylamino-4-diethylamino-6-mercapto-s-triazine (0.1 mol) in 100 ml of dimethylformamide and 82.6 are simultaneously added dropwise to this mixture with stirring at 15 to 20 ° C g aqueous sodium hypochlorite solution _ί 9.02% = 0.1 mol).

The inflow rates of the two solutions are adjusted so that the additions end at the same time are. It is stirred for 1 hour, rinsed in ice water, neutralized with hydrochloric acid (about In) (pH = 8), the precipitate is filtered off, washed with water and at 4OC in vacuo over calcium chloride

dried.
Yield: 31.2 g (96.6%);

F-100 to 101 C;

Sulfur content: found: 10.08, 10.10%;

theoretical: 9.91%.
Sulfenamide content: 97.4, 96.4%.

Example 5

70 g of 2 4 - bis - ethylamino - 6 - mercapto - s - triazine (ΟΪΜοΙ) are in 100 ml of dimethylformamide and 35 g of cyclohexylamine (0.35 mol) suspended. With stirring at 25 to 30 ° C with 150 g of aqueous Sodium hypochlorite solution (7.4% NaClO = 0.15MoI) oxidized. The mixture is stirred for 1 hour, the precipitate is filtered off and washed with distilled water and Petrolatum.

It is dried at 4 ° C. i vacuum over (a'aumchloriJ Πιο substance is light after drying yellow "egg".

Yield: 91 "o (27 μ);

F .: 90 to 93 C;

Schwefelten.ilt: Findings: 10.15%:
theoretical: 10.81%.

Suifenamidgehall: 95.5. 92.9%.

Example 6

20g 2-Am'io-4-diethylamino-6-mercapto-s-triazine (0.1 mol) are suspended in 20 g of cyclohexanone 10.2 mol) and 100 ml of dimethyl sulfoxide. At 25 C. 74 g of aqueous sodium hypochlorite solution (10.9% NaCl = 0.11 mol) are slowly added dropwise with stirring. 200 ml of water are added, the mixture is filtered and dried at 40 ° C. in vacuo over calcium chloride.

Yield: 91% (27 g);

F .: 102 to 105 ^° C;

Sulfur content: found: il, 23%;
theoretical: 10.82%.

Sulfenamide content: 83.8, 85.2%.

Example 7

22.7 g of 2-ethylamino-4-diethylamino-6-mercpptos-triazine (0.1 mol) are dissolved in 100 ml of cold ethylene glycol. This solution is added dropwise with stirring simultaneously with 84 g of aqueous sodium hypochlorite solution (8.8% NaClO = 0.1 mol) from a second Dropping funnel to a mixture of 30 g of diisopropylamine (0.3 mol) and 30 ml of ethylene glycol at a temperature of about 10 ° C.

The mixture is stirred for 1 hour, poured into 1000 ml of ice water, the excess amine is neutralized with 1 normal Hydrochloric acid, filtered off and dried at 40 ° C. in vacuo over calcium chloride.

Yield: 95% (31 g);

M.p .: 72 bL 76 ° C;

Sulfur content: found: 10.00%;
theoretical: 9.82%.

Sulfenamide content: 94.4, 92.2%.

Example 8

The procedure is as in the previous examples. The raw materials, the processing quantity of the Reactants, the yields and the analysis results are summarized in Tables 1 and 2 below. The stated positions of the substituents relate to the end product.

- Ver R ¹ R ² QH, 7th Substituents 2,027,432 R ¹ R ⁴ H 1-C ₃ H ₇ H CH ₂ · C ₆ H, Triazine S. 8th approach • search in 2 position QH ₅ R ² H CH ₂ • C ₆ H ₅ (Mole) Solvent*) No. QH ₅ QH ₅ in 4 position Table 1 H C ₆ H ₁ , Piperidino 0.10 ml 1 H QH ₅ R ¹ C ₂ H ₅ H C ₆ H ₁ , 0.10 130 DMF ClO- 2 H H C ₂ H, H C ₆ H ₁ , 0.10 Amine 160 DMF (MoI) 3 H H C ₂ H ₅ C ₂ H ₅ H C ₆ H ₁ , 0.10 (Mole) ! 30 DMr 0.11 4th H H C ₂ H ₅ C ₂ H, H QH ₁ , 0.10 0.20 130 DMF 0.15 5 H H C ₂ H ₅ C ₂ H, H C ₆ H ₁ , 0.10 0.25 130 DMF 0.10 6th H QH ₅ C ₂ H ₅ C ₂ H, H C ₆ H ₁ , 0.10 0.20 200 DMF 0.10 7th H C ₂ H ₅ C ₂ H ₅ C ₂ H, H C ₆ H ₁ , 0.10 0.40 130 DMF 0.11 8th H H C ₂ H ₅ C ₂ H, H C ₆ H _n 0.10 0.20 100 DMSO 0.25 9 H H C ₂ H ₅ C ₂ H, H C ₆ H _n 0.10 0.30 100 DMF 0.10 10 H H C ₂ H ₅ C ₂ H, H C ₆ H _n 0.10 0.40 120 DMF 0.11 11th H H H C ₂ H, H C ₆ H _n 0.10 0.20 160 DMF 0.15 12th H C ₂ H, H C ₂ H, H C ₆ H ₁₁ 0.10 0.35 UODMF OiO 13th H C ₂ H, H H H C ₆ H ₁₁ 0.10 0.20 250 DMF 0.15 14th H C ₂ H, H H H tert. C ₄ H ₉ 0.20 0.22 130 DMF 0.10 15th H CH ₃ H C ₂ H ₅ Morpholines » 0.10 0.20 230 DMF 0.15 16 H C ₄ H ₉ H C ₂ H ₅ 0.10 0.30 130 DMF 0.10 17th H C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ 0.05 0.30 130ethylene
glycol
80 DMF 0.20 18th H C ₂ H ₅ (CH ₂ ), • OCH ₃ 0.05 0.40 80 DMF 0.10 19th H C ₂ H ₅ (CH ₂ ), • OCH ₃ 0.10 0.20 100 DMF 0.10 20th ♦) DMF = H C ₂ H, 0.30 0.05 DMSO = H 0.10 0.05 H 0.10 0.10 Dimethylformamide. 0.20 ' Dimethyl sulfoxide.

(Continuation)

yield F. Analysis of the sulfenamide theoretical,% S. Ver
search % ⁰ C Schwerelgehall 9.12 found No. 99 44 to 46 found, % 9.91 97.1 1 87 98 to 99 9.39 9.91 93.9 2 94 94 to 96 9.93 9.91 96.0 3 97 98 to 99 10.14 10.82 99.2 4th 91 101 to 102 10.09 10.82 96.2 5 71 98 10.67 10.86 92 ^ 6th 95 98 to 102 10.60 10.82 96.6 7th 91 102 to 105 10.95 10.82 83.8 8th 91 90 to 93 11.:3 10.82 95.5 9 97 95 to 98 10.15 11.95 101.8 ίο 93 121 to 123 10.76 11.95 93.1 11th 88 126 to 128 11.95 13.34 100.6 12th 79 176 to 178 11.75 13.34 85.6 13th 93 190 11.79 10.70 89.5 14th 84 86 to 88 13.16 10.26 91.9 15th 92 149 to 152 10.90 9.82 88.4 16 95 72 to 76 10.27 9.55 94.4 17th 69 74 to 76 04/10 9.03 93.6 18th 93 113 to 116 9.03 10.52 84.1 19th 98 113 to 117 9.00 83.3 20th 10.41

Sulfenamidgchalt

theoretically. %

97.7 93.8 93.9 98.3 96.1 93.6 94.8 85.2 92.9

100.7 87.2 89.5 92.4 884

Table 2

10

R ¹ in R ² 2 closure Substitution R ⁴ C ₆ H ₁₁ H tert. QH ₉ Triazine At in approach ClO " Ver
search QH, in 4- and 6-position C ₆ H ₁₁ H C ₆ H ₁₁ (Mot) (Mole) (Mole) No. C ₂ H, H Morpholino H Q ₁ H ₁ , 0.1 0.4 0.22 1 C ₂ H, H 0.4 1.6 0.80 2 C ₂ H, 0.1 0.4 0.20 3 H 0.1 0.4 0.20 4th H 0.1 0.4 0.20 5 C ₂ H, 0.1 0.4 0.20 6th C ₂ H, C ₂ H, R ¹ solvent QH, Dimethyl
formamide / ml C ₂ H, 130 H 300 130 130 130 130

(Continuation)

yield F. Analysis of the sulfcnamide theoretical,% Sulfenamidgchalt theoretical,% attempt
No. % ⁰ C Switch 15.62 found, % 94.9 79 80 to 82 rounded,% 15.62 93.4 91.9 1 80 78 to 80 15.60 16.59 92.3 91.5 2 73 132 to 134 15.98 17.88 88.3 93.7 3 47 98 to 101 16.77 16.76 92.8 92.6 4th 79 105 to 108 18.76 18.08 94.2 86.0 5 96 181 to 184 16.61 86.3 6th 17.46

Claims (1)

Patent claims: 1. Process for the preparation of sulfenamides of the general formula I. R ² N
YC Il C — S —N R ³