DE1670192A1 - Process for the preparation of chloro-s-triazines - Google Patents

Description

Ludwigshafen am Rhein, March 1st, 1967

Process for the preparation of chloro-s-triazines

This invention relates to a process for the preparation of chloro-s-triazines by reacting mercapto-s-triazines with chlorine.

It is known from Smolin and Rapoport, The Chemistry of Heterocyclic Compounds, Volume XII, pages 58 ff. (1959), cyanuric chloride under the conditions of a Grignard or Friedel-Crafts reaction to give 4,6-dichloro-s-triazines substituted in the 2-position or 6-chloro-s-triazines substituted in the 2- and 4-positions to implement. Following these procedures is only a limited number available from 2- or 2,4-substituted compounds; Compounds which have different substituents in the 2- and 4-positions wear, cannot be made.

4,6-Dihydroxy-s-triazines substituted in the 2-position are treated with phosphorus pentachloride (according to US Pat. No. 1,897,428), with thionyl chloride (according to US Pat. No. 2,691,018) or with dimethylformamide and phosgene (according to German patent specification 1 164 418) converted to the corresponding 4,6-dichloro-s-triazines. All three Process go from the difficult to access 4,6-dihydroxy-s-tri-

009884/2182 - 2 -

azines which are otherwise substituted in the 2-position.

It has now been found that chloro-s-triazines of the general formula

“T

Cl

I,

YY-

N N

in which R ₁ and R _{2 can be} identical or different and each have an aliphatic, araliphatic, cycloaliphatic, aromatic, heterocyclic radical, a hydroxy, alkoxy, aralkoxy, cycloalkoxy, aroxy or a Ν, Ν radical -disubstituted amino group, R ₁ can also stand for the chlorine atom, advantageously obtained when mercapto-s-triazines of the general formula

- R ₄ II, NN

where R _{2 has} the aforementioned meaning, R- denotes an aliphatic, araliphatic or aromatic radical, Eu has the aforementioned meaning of R ₁ and can also stand for the -8R ^ group, in which case R _{1 is} always the

009884/2162 "* ⁵ "

the

Chlorine atom, with chlorine in the presence of an inert under / reaction conditions solvent or suspension agent at a temperature between -20 and +200 ⁰ C is reacted.

Compared to the aforementioned procedures, the procedure follows the invention of partially more accessible starting materials and is simpler and more economical; Compounds with mutually different substituents in the 2- and 4-positions can be made. Eire is a larger number of 2-substituted 4,6-dichloro- and 2,4-dl-substituted 6-chloro-s-triazines manufacturable.

R ₁ ^and R ₂ in the chloro-s-triazines of the formula I and accordingly also Rj ₁ and R «in the Hercapto-s-triazines of the formula II can be allphatic, araliphatic , cycloaliphatic, aromatic or heterocyclic radicals bonded via a carbon atom as well Hydroxy, alkoxy, aralkoxy, cycloalkoxy, aroxy or Ν, Ν-disubstituted amino groups. The radicals and groups mentioned can be substituted by further groups or atoms which are inert under the reaction conditions. Such groups and atoms "can be halogen, nitro, amino, N- and Ν, Ν-substituted amino, cyano, carboxyl, carbamide, carboxylate, sulfonamide, alkylsulfonyl, sulfonic acid, hydroxy, alkoxy -, aralkoxy, cycloalkoxy, aroxy or acyl groups. R ₁ and R ^ can also stand for the chlorine atom. R ^ Irann also mean the -SR ^ group, in which case R _{1 is} always the chlorate. In formula II, R ^ can mean an aliphatic, araliphatic or cycloaliphatic radical; this r.estt

00SGS4 / 2.162 ₀ cf

can be replaced by other groups, such as the cyano or caralkoxy group, be substituted. During the implementation of the Mereapto-s-triazine with chlorine to the corresponding chloro-s-triazines, one or more of the aforementioned radicals can be used, provided they are not inert are substituted by chlorine.

Preferred starting mercapto-s-triazines, which are converted to the preferred chloro-s-triazines with the corresponding radicals R ₁ and Rp, are those in whose formulas R ₂ and R ^ are identical or different and each represents an alkyl radical 1 to 6 carbon atoms, which can be substituted by halogen, aroxy groups with 6 to 10 carbon atoms, alkoxy groups with 1 to 4 carbon atoms or acyl groups with up to 4 carbon atoms, an alkenyl radical with 2 to 4 carbon atoms, which can optionally be substituted by a heterocyclic radical , an aralkyl group with 7 to 10 carbon atoms, a cycloalkyl group with 5 to 12 carbon atoms, an aryl group with 6 to 14 carbon atoms, which can be substituted by chlorine and / or nitro, oxo, amino or alkoxy groups with 1 to 6 carbon atoms can, a heterocyclic radical with 1 or 2 5- or 6-membered ring and with 1 or 2 nitrogen, oxygen and / or sulfur atoms as a ring member he in one or both rings, a hydroxyl group, an alkoxy group with 1 to 6 carbon atoms, an aroxy group with 6 to 14 carbon atoms or an N, N-dialkylamino group, the two alkyl groups with 1 to 6 carbon atoms each being the same or different and optionally also can be linked to one another via a carbon, oxygen, nitrogen or sulfur atom.

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Ru can also mean the chlorine atom or the -SR, group. In the preferred starting materials of the formula II, R denotes an alkyl radical having 1 to 6 carbon atoms, which may optionally be substituted by a cyano or carbalkoxy group having 2 to 5 carbon atoms, a benzyl or cyclohexyl radical.

For example, the following mercapto-s-triazines can be used as starting materials: 4,6-Dimercapto-s-triazines, which in the 2-position are the methyl, Ethyl, propyl, isopropyl, butyl, chloromethyl, trichloromethyl, 2-oxo-propyl, cyclohexyl, benzylphenyl, 4-chlorophenyl, 2,4-dichlorophenyl? 4-methoxyphenyl-, 4-nitrophenyl-, 4-aminophenyl-, Benzyl-, phenoxymethyl-, ß-methoxyäthyliOG-naphthyl, 'ß-naphthyl-, Anthraquinonyl- (2) -, anthraquinonyl- (1) -, 1-nitroanthraquinonyl- (2) -, 1-chloroanthraquinonyl- (2) -, 1-amino-4-nitro-anthraquinonvi- (2) -, 1-aminoanthraquinonyl- (2) -, puryl- (2) -, pyridyl- (3) -, thienyl- (2) -, 5,6-Benzocoumarinyl- (5) -, ß-Puryl- (2) -vinyl group carry j 6-mercapto-s-triazines, which are the same in the 2- and 4-positions or carry various of the aforementioned groups. The aforementioned mercapto-s-triazines can be methyl, ethyl, benzyl or cyclohexylmercapto-s-triazines or corresponding 4,6-disubstituted mercapto-s-triazines.

For the chlorination of the mereapto-s-triazines, gaseous chlorine is generally used, but liquid chlorine can also be used. Chlorine can be used in a stoichiometric amount or in excess, preferably in a 5- to 20-fold excess. the The speed of the chlorine flow can be varied as desired. Appropriately, the chlorine storm before the implementation traces of

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- 6 - 1670192 OZ 24 736 Water, ζ.Β », removed by desiccant.

The reaction is carried out in the presence of one of the reaction conditions inert solvent or suspending agent carried out. Suitable solvents or suspending agents are e.g. chlorinated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, trichlorethylene, tetrachlorethylene, carboxylic acids such as glacial acetic acid; aromatic solvents such as trichlorobenzene or nitrobenzene. They can be used alone or in a mixture, expediently work with a 5- to ^ O-fold excess, based on the Amount by weight of mercapto-s-triazine.

The reaction can be carried out as follows: In the solution or suspension of the mercapto-s-triazine is introduced at a temperature between -20 and +200 ⁰ C, usually between 20 to 8o ° C, chlorine. During the reaction time, which is generally 10 minutes to 28 hours, the distribution of the chlorine stream in the reaction medium can be improved by any mixing method, for example by stirring. After the reaction has ended and the reaction mixture has possibly cooled to room temperature, the chloro-s-triazine produced can be separated off from the reaction medium by filtering off or by precipitation with petroleum ether, η-hexane or cyclohexane. If appropriate, the solvent can also be distilled off first and the chloro-s-triazine can be obtained from the residue by urrystallization, for example in ethanol or benzene.

The compounds which can be prepared by the process of the invention are valuable starting materials for dyes.

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The parts given in the examples are parts by weight.

example 1

Dry chlorine is passed into the mixture of 4.98 parts of 2-phenyl-4,6-dimethylmercapto-1,3,5-triazine and 80 parts of carbon tetrachloride at 30.degree. To 40.degree. C. for 5 hours. Then the mixture is concentrated under reduced pressure. The residue is recrystallized from cold ethanol. 4.02 parts (89 % of theory) of 2-phenyl-4,6-dichloro-1,3 # 5-triazine with a melting point of 119 ° to 121 ° C. are obtained.

Example 2

At 40 to 5O ⁰ C is passed under stirring for 8 hours dry chlorine in the mixture of 6.36 parts of 2- (2 ^l, 4'-dichloro) phenyl-4,6-dimethylmercapto-1,3,5-triazine ~ and 80 parts carbon tetrachloride. The mixture is cooled and filtered. This gives 4.49 parts (76% of theory) of 2- (2 ^L, 4 ^L-dichloro) phenyl-4,6-dichloro-1,3,5-triazine of Pp. 112-113 ° C.

Example 3

At 6o to 65 ⁰ C for 7 hours dry chlorine is passed into the mixture of 8.5 parts of 2- (1'-nitro) -anthraquinonyl- (2 ') - 4,6-dimethylmercapto-1,3,5- tria2in, 70 parts of chloroform and 30 parts of trichlorobenzene. After the mixture has cooled, it is filtered off and the filter material is washed with benzene. 7.23 parts (90 % of theory) of 2- (1 ¹ ^ l
1,3,5-triazine, mp. 302 bit 304 ° C.

003884/2162

Example 4

In a suspension of 7 * 88 parts of 2- (1'-amino) -anthraquinonyj- (2 ') -4,6-dimethylmercapto-1,3,5-triazine in 70 parts of chloroform at 6o to 65 ⁰ C dry chlorine is initiated. After 5 hours, the mixture is allowed to cool to room temperature, filtered off, the piltered material is washed with benzene and dried. 5 * 4-3 parts (67 % of theory) 2- (1 ^l -Amlno-4 ¹ -chloro) -anthraquinonyl- (2 ') · 4,6-dichloro-1,3,5-triazine of melting point are obtained . 252 to 254 ⁰ C.

Example 5

In a solution of 8.78 parts of 2- (1'-amino-4'-nitro) -anthraquinonyl- (2 ^l ) -4,6-dimethylmercapto-1,3,5-triazine in 200 parts of chloroform is at 60 to Introduced 65 ⁰ C for 3 hours dry chlorine. Thereafter, about 160 parts of chloroform are distilled off under reduced pressure and 80 parts of cyclohexane are added. The mixture is filtered off and the pilter material is washed with cyclohexane and dried. 8 parts (96 % of theory) of 2- (1'-amino-4'-nitro) -anthraquinonyl- (2 ') -4,6-dichloro-1,3,5-triazine of pp. 278 to 280 are obtained ° C.

Example 6

At 50 to 60 ^° C., dry chlorine is passed into the solution of 6.9 ^ parts of 2- (3'-nitro) -phenyl-4-morpholino-6-ethylraercapto-1,3,5-triazine in 80 for 6 hours Share chloroform. After the chloroform has been distilled off under reduced pressure, the residue is recrystallized from a little benzene. 6 parts (93 % of theory) of 2- (3'-nitro -) - phenyl-4-inorpholino-6-chloro-1,3,5-triazine with a melting point of 206 ° to 208 ° C. are obtained. -Q-

009884/2162

Claims (1)

Process for the preparation of chloro-s-triazines of the general formula - R. in which R ₁ and Rp can be the same or different "'and each have an aliphatic, araliphatic, cycloaliphatic, aromatic, heterocyclic radical, a hydroxy, alkoxy, aralkoxy, cycloalkoxy, aroxy or an N, N-disubstituted amino group, R ₁ can also stand for the chlorine atom, characterized in that mercapto-s-triazines of the general formula where Rp has the aforementioned meaning, R denotes an aliphatic, araliphatic or cycloaliphatic radical, Rk has the aforementioned meaning of R ₁ and, moreover, also for the 009884/2162 - 10 - -Srv group may be, in which case R ₁ is always the chlorine atom, is reacted with chlorine in the presence of an inert under the reaction conditions solvent or suspension agent at a temperature between -20 and +200 ⁰ C. BADISCHE ANILIN- & SODA-FABRIK AG 009884/2162