DE1670236A1 - Process for the preparation of phosphatriazines - Google Patents

Description

Process for the preparation of phosphatriazines It has been found that new phosphatriazines of the general formula I, in which X and Y are oxygen or sulfur, R1 is hydroxyl or an optionally substituted O-alkyl-, S-alkyl-, NH-alkyl-, N (alkyl) 2-, O-aryl-, S-aryl-, N-alkyl -Aryl or NH-aryl group, R is an optionally substituted alkyl or aryl group and R2 is hydrogen, an optionally substituted aliphatic or aromatic radical, obtained by phosphoric acid or thiophosphoric acid halides of the general formula II, in which Z denotes halogen, in particular chlorine or bromine, X has the meaning given above and R, in addition to the meaning given above, can also denote halogen, preferably chlorine or bromine, with imino-bis-carbimidic acid esters or imino-bis-carbimidic acid thioesters of the general formula III, in which R, R2 and Y have the meaning given above, in the presence of hydrogen halide binding agents, preferably in a liquid medium, and, if R1 is halogen, the resulting phosphatriazine of the general formula IV, in which X, Y, Z, R and R2 have the meaning given above, with compounds of the general formula V, H-R1 (V) in which R1 has the meaning given above, in the presence of halogen-hydrogen binding agents, preferably in a liquid Medium, implements.

If the substituent R contains one or two alkyl groups, then have these preferably 1 to 18 carbon atoms. You can still use inert substituents, for example, carry halogens, alkoxy, nitrile, carbon ester, aryl, aroxy groups. The alkyl radicals of the DialkylcLrnlnogr. lppe can be the same or different. Contains the substituent R1 is an aromatic hydrocarbon radical, it is preferred up to 10 carbon atoms. He can also have inert substituents, z. B. alkyl, aryl, halogen, alkoxy, aroxy, nitrile, carbonamide, carbon ester or Nitro groups, wear.

The alkyl radicals R and R2 are preferably those having 1 to 8 carbon atoms into consideration. They can also contain inert substituents, such as halogens, alkoxy, Nitrile groups.

Aromatic hydrocarbon radicals R and R2 preferably contain up to to 10 carbon atoms in the ring system and can also have inert substituents, for example halogens, alkyl, aryl, alkoxy, aroxy, nitrile, carbonamide, carbon ester, Carry alkyl mercapto, aryl mercapto, sulfonic acid ester, amide, acyl groups.

Examples of phosphoric acid or phosphoric acid used as starting materials Thiophosphoric acid halides are phosphorus oxychloride, phosphorus oxybromide, thiophosphoryl chloride, Dichlorothiophosphoric acid, phosphoric acid methyl ester dichloride, phosphoric acid 2-bromoethyl ester dichloride, Phosphoric acid 2-ethylhexyl ester dichloride, phosphoric acid decyl ester dichloride; Phosphoric acid- (4-methoxyphenyleter dichloride, phosphoric acid α-naphthyl ester dichloride; phosphoric acid diethylamide dichloride, Phosphoric acid dodecylamide dichloride, phosphoric acid bis (2-chlorithyl) amide dichloride, Phosphoric acid B-naphthylamide dichloride; Thiophosphoric acid O-ethyl ester dichloride, Thiophosphoric acid O-phenyl ester dibromide; Thiophosphoric acid S-butyl ester dichloride, Thiophosphate S- (4-chlorophenyl ester) dichloride; Dithiophosphoric acid trichloromethyl ester dichloride ; Dithiophosphoric acid phenyl ester dichloride; Thiophosphoric acid benzylamide dichloride, Thiophosphoric acid (N-methyl-anilide) dichloride.

Examples of the starting compounds used in the process of this invention Imino-bis-carbimidic acid esters or thioesters to be used are imino-bis-carbimidic acid ß, ß, ß-trichloroethyl ester or phenyl ester, dimethyldithiobiuret, tert-butylimino-bis-carbimidic acid phenyl ester, Phenylimino-bis-carbimidic acid (4-methyl) -phenyl ester.

Examples of the general compounds used as starting materials Formula V are water, n-propanol, cyclohexanol, stearyl alcohol, 3-methoxyphenol, n-butyl mercaptan, thiophenol, N-methyl-α-naphthylamine, diethylamine, laurylamine.

The implementation of the starting materials II and III is expedient in one inert organic solvents carried out, in the presence of hydrogen halide binding Means.

The hydrogen halide binding agents used are, for example Alkali hydroxides, carbonates, amides, but especially tertiary amines such as triethylamine, Triisopropylamine, ethyldiisopropylamine or pyridine. For splitting off 1 mol of hydrogen halide In general, 1 to 2 1/2 times the stoichiometric amount of the acid-binding agent is used By means of a.

As inert organic solvents, for. B. benzene, toluene, chlorobenzene, Tetrahydrofuran, dioxane, acetone, methylene chloride, carbon tetrachloride, petroleum ether or mixtures thereof.

The starting materials are preferably added in a molar ratio for the reaction 1: 1 together. In general, a temperature range of -50 ° to + 80 ° C is chosen, especially from -300 to + 30 ° C.

The reaction increases depending on the components used, the temperatures and the solvent used generally takes from 20 minutes to 24 hours. The end products of general formula I are generally stable compounds, which in the cases where the end product precipitates, by suction with washing with Water, in those cases where it initially remains in solution, by concentrating the solvent, Treating the residue with water and then filtering off with suction can be isolated.

Phosphatriazines of the general formula IV, which are on the phosphorus atom Contain halogen, on the other hand, are very reactive and can only be found in substance isolate when in the absence of water using inert solvents worked up.

Substances obtained in this way can then be converted into phosphatriazines in a second stage of the general formula I are implemented. However, it is beneficial to take the phosphatriazines of the general formula IV without isolation immediately with the compounds of the general Formula V to continue to implement, whereby one expediently already at the beginning one for the Total Reaktton uses a sufficient amount of the hydrogen halide binding agent.

One uses the phosphatriazines of the general formula IV with the compounds of the general formula V expediently in a molar ratio of 1: 1 to 1:10, where the inert organic solvents and hydrogen halide-binding solvents already described above Agent used and generally in the presence of 1 to 2 1/2 times stoichiometric Amount of acid scavenger will work. For the implementation one chooses advantageous a temperature range from -50 ° to + 80 ° C, in particular from -30 ° to + 30 ° C. the The end products of the general formula I thus obtained are worked up as described above.

The compounds serve as valuable precursors, e.g. B. for dyes, and as additives for plastics, e.g. B. as a flame retardant.

The parts given in the examples are parts by weight.

Example 1 To 8.15 parts of dimethyldithiobiuret in 50 parts of benzene are added within 20 minutes at 0 to 5 ° C. 7065 parts of phosphorus oxytrichloride. After stirring for 20 minutes at 0 to 5 ° C., 19.35 parts of ethyldiisopropylamine are added added and the mixture stirred for 1 hour at -20 to 23 ° C, then be 40 parts of methanol were added, the now clear solution at 20 ° to 25 ° C. for 30 minutes After stirring and then concentrated in vacuo. The residue is mixed with 75 parts of water stirred out, the Niedersohläg then sucked off, washed with water and dried. 95 parts (805% of theory) of 1-methoxy-3,5-dimethylmeroapto-4H-1-phospha-2,4,6-triazine are obtained -1-oxide. The compound melts at 193 ° to 194 ° C.

Example 2 To the solution of 8.15 parts of dimethyldithiobiuret in 50 parts of benzene are added dropwise at 0 to 5 ° C. 7.65 parts of phosphorus oxytrichloride.

After stirring for 20 minutes at 0 ° to 5 ° C., 15.2 parts of triethylamine are added added and the mixture stirred at 20 ° to 23 ° C for 1 hour. After the addition of -40 parts of ethanol becomes the solution after stirring for 10 minutes at room temperature concentrated in vacuo. The residue is mixed with 75 parts of water, 10 minutes stirred well and then vacuumed off. After washing with water and drying 10.8 parts (85% of theory) 1-ethoxy-3, 5-dimethylmercapto-4H-1-phospha-2 are obtained, 4-6 triazine-1-oxide with a melting point of 178 ° to 180 ° C.

Example 3 To 8.15 parts of dimethyldithiobiuret in 75 parts of benzene 15 parts of phosphoric acid ethyl ester dichloride are added at 0 to 5 ° C.

After stirring for 30 minutes at 0 to 5 ° C., 12.9 parts of ethyldiisopropylamine are added was added dropwise and the mixture was stirred for 3 hours at room temperature. After narrowing the solution in vacuo, the residue is stirred with 80 parts of water. That I 01 which separates out is separated from the water and rubbed with a little ethyl acetate brought to crystallization. You get 6.4 parts (50.5 / of the theory) of the already Compound obtained in Example 2 with a melting point of 176 to 179 ° C.

Example 4 4 7, 65 parts of phosphorus oxytrichloride are used at 0 to 3 ° C added dropwise to 8.15 parts of dimethyldithiobiuret in 50 parts of benzene. After 30 minutes After stirring at 0 to 5 ° C, 19.35 parts of ethyldiisopropylamine are added and the mixture was held at 20-25 ° C for 40 minutes. After adding 11.1 parts n-Butanol is stirred for 2 hours at room temperature and then in vacuo constricted. The residue is stirred with 100 parts of water, the precipitate Sucked off, washed with water and dried.

12.2 parts (82% of theory) of 1-butoxy-3, 5-dimethylmercapto-4H-1-phospha-2 are obtained, 4,6-triazine-1-oxide. The compound crystallizes with 1 mole of H2O; she melts at 97 to 98 ° C.

Example 5 To the mixture of 8, 15 parts of dimethyldithiobiuret and 12.9 parts of ethyldiisopropylamine in 70 parts of methylene chloride are added at 0 to 3 ° C 10.5 parts of phosphoric acid phenyl ester dichloride. It will be at 20 to 1 hour 25 ° C and then stirred for 3 hours at 30 to 35 ° C, then the clear solution 5 ° C cooled, stirred with 100 parts of ice water and the methylene chloride layer severed. After drying over Na, the methylene chloride is distilled off in vacuo. The residue is recrystallized from a mixture of dimethylformamide and acetone. 13.7 parts (91% of theory) of 1-phenoxy-3, 5-dimethylmercapto-4H-1-phospha-2 are obtained, 4,6-triazine-1-oxide with a melting point of 207 to 208 ° C.

Example 6 8, 15 parts of dimethyldithiobiuret in 50 parts of benzene at 0 to 2 ° C with 7.65 parts of phosphorus oxytrichloride. After 30 minutes Stirring at 20 to 25 ° C, 15.2 parts of triethylamine are added and the mixture Stirred at 45 to 50 ° C. for 1 hour. After adding 50 parts of water Stirred for a further 20 minutes at room temperature and then the precipitate is filtered off with suction. After washing with water and acetone and subsequent drying, 8 is obtained 3 parts (74% of theory) 1-oxy-3, 5-dimethylmercapto-4H-1-phospha-2, the compound melts at 274 to 275 ° C.

Example 7 7, 65 parts of phosphorus oxytrichloride are added dropwise at 0 to 3 ° C to the mixture of 8.15 parts of dimethyldithiobiuret and 19.35 parts of ethyldiisopropylamine. After stirring for 2 hours at 20 to 30 ° C, 20 parts of a 40 wt. % strength aqueous diethylamine solution was added dropwise. After 2 hours, it is concentrated in vacuo and the residue was stirred up with 100 parts of water. Crystallize when standing in the cold from this solution 7 parts (50% of theory) 1-diethylamino), 5-dimethylmercapto-4H-1-phospha-2J4J6-triazine-1-oxide. After recrystallization from ethyl acetate, the compound melts at 180 to 181 ° C.

Claims (2)

Claims 1. Process for the preparation of new phosphatriazines of the general formula I, in which X and Y are oxygen or sulfur, R1 is hydroxyl or an optionally substituted O-alkyl-, S-alkyl-, NH-alkyl-, N (alkyl) 2-, O-aryl-, S-aryl-, N-alkyl -Aryl or NH-aryl group, R is an optionally substituted alkyl or aryl group and R2 is hydrogen, an optionally substituted aliphatic or aromatic radical, characterized in that phosphoric acid or thiophosphoric acid halides of the general formula II. in which Z denotes halogen, in particular chlorine or bromine, X has the meaning given above and R1, in addition to the meaning given above, can also denote halogen, preferably chlorine or bromine, with imino-bis-carbimidic acid star or imino-bis-carbimide-thioester general formula III, in which R, R2 and Y have the meaning given above, in the presence of hydrogen halide binding agents, preferably in a liquid medium, and, if R is halogen, the resulting phosphatriazine of the general formula IV, in which X, Y, Z, R and R2 have the meaning given above, with compounds of the general formula V, H-R1 (V) in which R has the meaning given above, in the presence of hydrogen halide binding agents, preferably in a liquid medium. implements. 2. Phosphatriazines of the general formula I, in which X and Y are oxygen or sulfur, RI is hydroxyl, halogen or an optionally substituted O-alkyl-, S-alkyl-, NH-alkyl-, N (alkyl) 2-, 0-aryl-, S-aryl-, N -Alkyl-acyl or NH-aryl group, R denotes an optionally substituted alkyl or aryl group and R2 denotes hydrogen or an optionally substituted aliphatic or aromatic radical.