RU2001122813A - The method of producing simple azoiminoesters and esters of azo carboxylic acids and new mixed esters of azo carboxylic acids - Google Patents

Claims (26)

1. A method of producing azoimino ether hydrochlorides, comprising reacting azonitrile with alcohol and hydrochloric acid in an aromatic solvent, with a molar ratio R = HCl / azonitrile greater than 2 if the alcohol is methanol, and greater than 3 if the alcohol is ethanol or a higher alcohol. 2. The method according to claim 1, in which azonitrile is formed in situ by reacting the corresponding hydrazonitrile with chlorine. 3. The method according to claim 1 or 2, in which the solvent is selected from the group consisting of toluene, chlorobenzene, xylene and benzene. 4. The method according to claim 2, in which the solvent is chlorobenzene. 5. The method according to any one of claims 1 to 4, in which the alcohol is ethanol. 6. The method according to any one of claims 1 to 4, in which the alcohol used is a mixture of alcohols. 7. The method according to claim 6, in which the mixture contains methanol. 8. The method according to claim 6 or 7, in which the mixture contains methanol and ethanol. 9. The production method according to any one of claims 1 to 8, in which the azoimino ether hydrochloride corresponds to the formula II

in which R ₁ , R ₂ , R ₃ and R ₄ , identical or different, are independently selected from the group consisting of the following substituents: straight or branched C ₁ -C ₉ -alkyls (mainly C ₁ -C ₄ ), unsubstituted or substituted by one or more substituents selected from hydroxyl, C ₁ -C ₆ alkoxy, halogen; C ₃ -C ₆ cycloalkyl unsubstituted or substituted by one or more substituents selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, hydroxy, halogen; C ₇ -C ₁₂ arylalkyl unsubstituted or substituted by one or more substituents selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, hydroxy, halogen; C ₇ -C ₁₂ aryls unsubstituted or substituted by one or more substituents selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, hydroxy, halogen; moreover, at least one of the combinations of R ₁ -R ₂ and R ₃ -R ₄ may form an aliphatic cycle; R and R ', identical or different, are independently selected from the group consisting of straight or branched aliphatic C ₁ -C ₁₀ radicals, mainly C ₁ -C ₄ . 10. The production method according to claim 9, in which R and R 'in the formula II are different from each other and selected from normal aliphatic C ₁ -C ₄ radicals. 11. The production method according to claim 9 or 10, in which R ₁ , R ₂ , R ₃ and R ₄ in the formula II are C ₁ -C ₄ -alkyl groups. 12. A method of producing esters of azocarboxylic acids, including the synthesis of hydrochlorides of simple azoiminoesters by the method defined in any one of claims 1 to 11, and the hydrolysis of the thus obtained hydrochlorides of simple azoiminoesters in the presence of water. 13. The production method according to item 12, in which the hydrolysis is carried out by gradually adding water to the reaction mixture or by pouring the reaction mixture to water at a temperature of 15-50 ° C, preferably 25-35 ° C. 14. The production method according to item 12, in which, after synthesis, the azoimino ether hydrochloride is separated by filtration, washed with an organic solvent, and then hydrolyzed by gradually adding the filtered precipitate to water at a temperature of 15-50 ° C, mainly 25-35 ° C. 15. A method of preparing a liquid composition of esters of azocarboxylic acids, including the synthesis of hydrochlorides of azoimino ethers according to claims 6, 7, 8, 9 or 10, hydrolysis of the salts thus obtained in the presence of water and the selection of an organic phase containing acid esters. 16. The production method according to clause 15, in which in the first stage of the reaction, the heaviest alcohol is introduced into the interaction, and then, in the second stage of the reaction, the least heavy alcohol is introduced. 17. A liquid composition of esters of azocarboxylic acids, which can be obtained by the method according to item 15 or 16. 18. The liquid composition of esters of azocarboxylic acids according to 17, which is liquid at a temperature of from -20 to + 20 ° C. 19. The liquid composition of azocarboxylic acid esters according to claim 17 or 18, comprising a first symmetric ester of a first alcohol, a second symmetric ester of a second alcohol and a mixed ester of these first and second alcohols. 20. The azocarboxylic acid ester liquid composition of claim 19, wherein said first symmetric ester is a symmetric acid methyl ester, said second symmetric ester is a symmetric acid ethyl ester and said mixed ester is an acid methyl ester. 21. A method for producing polymerization initiators, comprising the synthesis of azocarboxylic acid esters by the method according to any of claims 12-16 and, if necessary, converting these esters into initiators by conventional methods. 22. Salts of mixed azoimino ethers corresponding to formula II ’

in which R ₁ , R ₂ , R ₃ and R ₄ , identical or different, are independently selected from the group consisting of the following substituents: straight or branched C ₁ -C ₉ -alkyls (mainly C ₁ -C ₄ ), unsubstituted or substituted by one or more substituents selected from hydroxyl, C ₁ -C ₆ alkoxy, halogen; C ₃ -C ₆ cycloalkyls unsubstituted or substituted by one or more substituents selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, hydroxy, halogen; C ₇ -C ₁₂ arylalkyls unsubstituted or substituted by one or more substituents selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, hydroxy, halogen; C ₇ -C ₁₂ aryls unsubstituted or substituted by one or more substituents selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, hydroxy, halogen; moreover, at least one of the combinations of R ₁ -R ₂ and R ₃ -R ₄ may form an aliphatic cycle; R and R 'are different from each other and independently selected from the group consisting of normal or branched aliphatic C ₁ -C ₁₀ radicals, mainly C ₁ -C ₄ radicals. 23. Azoimino ether salts according to claim 22, wherein in formula II 'R is methyl and R ₁ is ethyl. 24. Azoimino ether salts according to claim 22 or 23, wherein, in the formula II ′, R ₁ , R ₂ , R ₃ and R ₄ are C ₁ -C ₄ alkyl groups. 25. Mixed esters of azo carboxylic acids of formula III ’

in which R ₁ , R ₂ , R ₃ , R ₄ , R and R 'are defined in paragraphs 22-24, provided that the mixed ester of azocarboxylic acid is not methyl butyl isobutyrate. 26. A method of producing azoguanyl derivatives, comprising the preparation of azoamino ether hydrochlorides by the method according to any one of claims 1 to 11 and the interaction of the latter with ammonia or amine in the presence of alcohol.