PL214617B1 - Photochromic N-[4-[(E)-phenylazo]phenyl]sulfonylobenzamide dyes and process for the preparation thereof - Google Patents

Description

(12) PATENT DESCRIPTION (19) PL (11) 214617 (13) B1 (21) Filing number: 394754 (22) Filing date: May 4, 2011 (51) Int.Cl.

C07C 245/08 (2006.01) C07C 311/15 (2006.01)

Photochromic N- [4 - [(E) -phenylazo] phenyl] sulfonylbenzamide dyes and the method of their preparation (73) Patent holder:

POLITECHNIKA WROCŁAWSKA, Wrocław, PL (43) Application was announced:

12.03.2012 BUP 06/12 (45) The following was announced about the grant of the patent:

30.08.2013 WUP 08/13 (72) Inventor (s):

MARIA LARKOWSKA, Wrocław, PL SONIA ZIELIŃSKA, Kędzierzyn-Koźle, PL STANISŁAW KUCHARSKI, Wrocław, PL (74) Representative:

item. stalemate. Anna Meissner

PL 214 617 B1

Description of the invention

The subject of the invention are photochromic N- [4 - [(E) -phenylazo] phenyl] sulfonylbenzamide dyes and a method of their preparation, which are used in optoelectronics and nonlinear optics, as well as in optical recording and reading of information.

There is known from the Polish patent description No. P 188699 a method for the preparation of new 4-sulfonamido-4- (N-methyl-N-alkyl) amino azobenzene derivatives, which consists in the N-substituted heteroaromatic moiety in the sulfonamide group of 4-aminobenzenesulfonamides, with an isoxazolyl or thiazolyl or pyrimidinyl moiety. is subjected to a diazotization reaction, preferably in a concentrated acetic acid medium, then the obtained diazonium salts are coupled with N-methyl-N-alkylanilines having 10 to 18 carbon atoms in the alkyl moiety, preferably in concentrated acetic acid or concentrated acid mixture acetic acid with 2-methoxy or 2-ethoxyethanol, in the presence of sodium acetate and at a temperature of 0 to 5 ° C, and the obtained 4-sulfonamido-4- (N-methyl-N-alkyl) aminoazobenzene derivatives with a heteroaromatic moiety are purified by crystallization from dioxane or a water-dioxane mixture. The compounds produced by the above-mentioned method show nonlinear optical properties and the ability to create monomolecular Langmuir layers on the water surface.

From another Polish patent application No. P 382162, a derivative of 3-amino-5-methylisoxazole is known, which is 3- (4'-N-methyl-N- (2-hydroxyethyl) phenylazo) -5-methylisoxazole, and a method of producing the new compound 3- (4'-N-methyl-N- (2-hydroxyethyl) phenylazo) -5-methylisoxazole, which consists in the diazotization of 3-amino-5-methylisoxazole and coupling the obtained diazonium salt with N-methyl-N- (2-hydroxyethyl) aniline. The invention also relates to the use of the new 3- (4'-N-methyl-N- (2-hydroxyethyl) phenylazo) -5-methylisoxazole for the preparation of transparent hybrid films. According to the above-mentioned invention, 3- (4'-N-methyl-N- (2-hydroxyethyl) phenylazo) -5-methylisoxazole is added with 3-isocyanatopropyltriethoxysilane, and then the addition product is formed directly from the reaction mixture into thin films.

It is known from the Polish patent application No. P 380843 a nonlinear-optical monomer named 3- (4'-N, N-di (2-hydroxyethyl) phenylazo) -5-methylisoxazole, as well as a method for producing a new compound, which consists in that 3-amino-5-methylisoxazole is diazotized with a mixture of concentrated sulfuric acid and aqueous sodium nitrate (III), and then the diazonium salt obtained is coupled with N, N-di (2-hydroxyethyl) aniline.

The photochromic N- [4 - [(E) -phenylazo] phenyl] sulfonylbenzamide dyes and the method of their preparation, which are the subject of the invention, have not been described in the literature.

The invention relates to the photochromic N- [4 - [(E) -phenylazo] phenyl] sulfonylbenzamide dyes of general formula I, wherein R is N- (2-hydroxy) ethyl (N-methyl) amino, N-ethyl (N- (2-hydroxy) ethyl) amino or bis (N- (2-hydroxy) ethyl) amino.

The invention also provides a process for the production of photochromic N- [4 - [(E) -phenylazo] phenyl] sulfonylbenzamide dyes of general formula I, wherein R is N- (2-hydroxy) ethyl (N-methyl) amino, N-ethyl (A- (2-hydroxy) ethyl) amine or bis (N- (2-hydroxy) ethyl) amine based on a two-stage process of obtaining an azo dye, where the first is the diazotization of N- (4-aminophenyl) sulfonylbenzamide with sodium III nitrate in an acidic environment at a temperature ranging from 0 to 5 ° C, then, in the second stage, the resulting diazonium salt is coupled in the form of 4- (benzoylsulfamoyl) -benzenediazonium chloride with aniline at a temperature not exceeding 5 ° C, and then the obtained product is separated out of the reaction mixture by neutralization and filtration.

Preferably, the coupling reaction is carried out in the presence of an aniline derivative selected from N- (2-hydroxy) ethyl (N-methyl) aniline, bis (N- (2-hydroxy) ethyl) aniline or N-ethyl (N- (2-hydroxy) -ethyl) aniline.

Preferably the diazotization reaction is carried out in a mixture of concentrated hydrochloric acid, water and glacial acetic acid containing from 6 to 10% by volume of concentrated hydrochloric acid and from 50 to 60% by volume of glacial acetic acid.

Preferably, the diazotization reaction is carried out in a mixture of hydrochloric acid and glacial acetic acid ₃ in an amount of from 5 to 7 cm ³ per 1 mmol of N- (4-aminophenyl) sulfonylobenzamidu.

Preferably, the diazotization reaction is carried out in a ratio of 1.15 to 1.25 moles of sodium nitrate (III) per mole of N- (4-aminophenyl) sulfonylbenzamide.

PL 214 617 B1

Preferably, the coupling reaction is carried out with a molar ratio of the diazonium salt to the corresponding aniline derivative ranging from 1: 1 to 10:11 mol / mol.

Preferably, the coupling product is precipitated with sodium acetate, potassium acetate, sodium carbonate or potassium carbonate.

Preferably the azo dyes obtained are purified by precipitating the azo dye from a solution of N, N-dimethylformamide, methanol, ethanol or pyridine with small portions of distilled water.

Preferably the azo dyes obtained are purified by precipitation of the azo dye from the pyridine solution with small portions of ice.

Preferably the azo dyes obtained are purified by crystallization from methanol.

The subject of the invention is illustrated in the example of the production of a photochromic dye.

P r z k ł a d 1

Preparation method of N- [4 - [(E) - [4- [2-hydroxyethyl (methyl) amino] phenyl] azo] phenyl] sulfonylbenzamide of general formula 1, wherein R is N- (2-hydroxy) ethyl (N-methyl) amino.

₃

To 1.00 g (3.62 mmol) A- (4-aminophenyl) sulfonylobenzamidu added 2.16 cm ^{3 of} concentrated hydrochloric acid and heated to 50 ° C in order to well disperse the amine. Then, while stirring continuously, 6.48 cm ^{3 of} water and 12.96 cm ^{3 of} glacial acetic acid are added. The mixture was cooled to 0 ° C in an ice water bath, is added dropwise while stirring writing _3, a solution of 0.30 g (4.30 mmol) of sodium nitrite III dissolved in 0.80 ^cm3 of distilled water so that the the temperature did not exceed 5 ° C. The mixture of the resulting diazonium salt is stirred for 20 minutes, after which time excess nitric acid III is removed with a saturated aqueous solution of sulfamic acid, checking the presence of nitric acid III with iodine starch paper. Then, the diazonium salt mixture is poured into cooled to 0 ° C a solution of ₃ 0.56 g (3.70 mmol) of N- (2-hydroxy) ethyl (N-methyl) aniline are dissolved in 5 cm ³ of water distillation ₃ lated collector. The mixture is stirred at 0 ° C for 15 hours, then poured into 50 cm ³ of distilled water and neutralized with a saturated aqueous solution of sodium acetate. The precipitated product is filtered under vacuum, washed several times with distilled water and dried at 50 ° C. The obtained N- [4 - [(E) - [4- [2-hydroxyethyl (methyl) amino] phenyl] azo] phenyl] sulfonylbenzamide is purified by crystallization from methanol. The product yield after purification is 90%.

₁

Characteristics of the obtained product: ¹ HNMR (solvent: DMSO-d6, TMS standard): 3.11 ppm (s, 3H, CH3 at the nitrogen atom), 3.54 ppm (t, 2H, CH2 at the hydroxyl group), 3.58 ppm (t, 2H, CH2 at the nitrogen atom), 4.80 ppm (s, 1H, OH), 6.84 ppm (d, 2H, CH in the benzene ring meta to the amino group), 7.48 ppm ( t, 2H, CH in the benzene ring in the ortho position to the carbonyl group), 7.62 ppm (t, 1H, CH in the benzene ring in the para position to the carbonyl group), 7.79 ppm (d, 2H, CH in the benzene ring meta to the amino group), 7.85 ppm (d, 2H, CH in the benzene ring in the ortho position to the carbonyl group), 7.91 ppm (d, 2H, CH in the benzene ring in the ortho position to the sulfonyl group), 8.11 ppm (d, 2H, CH in the benzene ring meta to the sulfonyl group) 12.63 ppm (s, 1H, NH).

P r z k ł a d 2

Preparation method of N- [4 - [(E) - [4- [ethyl (2-hydroxyethyl) amino] phenyl] azo] phenyl] sulfonylbenzamide of general formula 1, wherein R is N-ethyl (N- (2 -hydroxy) ethyl) amino.

₃

To 1.00 g (3.62 mmol) of N- (4-aminophenyl) sulfonylobenzamidu added 1.30 cm ^{3 of} concentrated hydrochloric acid and heated to 50 ° C in order to well disperse the amine. Then, while stirring continuously, 9.50 cm ^{3 of} water and 10.80 cm ^{3 of} glacial acetic acid are added. The mixture was cooled to 0 ° C in an ice water bath, is added dropwise while stirring writing _3, a solution of 0.29 g (4.16 mmol) of sodium nitrate (III) dissolved in 0.80 ^cm3 of distilled water. so that the temperature does not exceed 5 ° C. The mixture of the resulting diazonium salt is stirred for 20 minutes, after which time excess nitric acid is removed with a saturated aqueous solution of sulfamic acid. checking the presence of nitric acid with iodine starch paper. Then, the diazonium salt mixture is poured into cooled to 0 ° C a solution of ₃ (0.66 g, 3.98 mmol), N-ethyl (N- (2-hydroxy) ethyl) aniline are dissolved in 5 cm ³ of methanol. Ca ₃ The reaction was stirred at 2.5 ° C for 15 hours and then poured into 50 cm ³ of distilled water and neutralized with saturated aqueous potassium carbonate. The precipitated product is filtered under vacuum, washed several times with distilled water and dried at 50 ° C. The obtained N- [4- (E) [4- [ethyl (2-hydroxyethyl) amino] phenyl] azo] phenyl] sulfonylbenzamide is purified by dissolving it in a little pyridine and then precipitation of the azo dye with small portions of distilled water. The product yield after purification is 92%.

PL 214 617 B1 ₁

Characterization of the obtained product: ^{1 2} H NMR (solvent: DMSO-d6, TMS standard): 1.13 ppm (t, 3H, CH3 in the ethyl group), 3.57 ppm (m, 6H, CH2), 4.81 ppm (s, 1H, OH), 6.84 ppm (d, 2H, CH in the benzene ring meta to the amino group), 7.48 ppm (t, 2H, CH in the benzene ring in the ortho position to the carbonyl group), 7.62 ppm (t, 1H, CH in the benzene ring in the para position to the carbonyl group), 7.79 ppm (d, 2H, CH in the benzene ring in the meta position to the amino group), 7.85 ppm (d, 2H , CH in the benzene ring ortho to the carbonyl group), 7.91 ppm (d, 2H, CH in the benzene ring in the ortho position to the sulfonyl group), 8.11 ppm (d, 2H, CH in the benzene ring in the meta position to the sulfonyl group) 12.62 ppm (s, 1H, NH).

P r z k ł a d 3

Preparation method of N- [4 - [(E) - [4- [bis (2-hydroxyethyl) amino] phenyl] azo] phenyl] sulfonylbenzamide of general formula 1, wherein R is bis (N- (2-hydroxy ) ethyl) amino.

₃

To 1.00 g (3.62 mmol) of N- (4-aminophenyl) sulfonylobenzamidu added 1.80 cm ^{3 of} concentrated hydrochloric acid and heated to 50 ° C in order to well disperse the amine. Then, while stirring continuously, 8.00 cm ^{3 of} water and 11.80 cm ^{3 of} glacial acetic acid are added. The mixture was cooled to 0 ° C in an ice water bath, is added dropwise while stirring writing _3, a solution of 0.31 g (4.52 mmol) of sodium nitrate (III) dissolved in 0.80 ^cm3 of distilled water. so that the temperature does not exceed 5 ° C. The mixture of the resulting diazonium salt is stirred for 20 minutes, after which time the excess nitric acid is removed with a saturated aqueous solution of sulfamic acid, checking the presence of nitric acid with iodine starch paper. Then, the diazonium salt mixture is poured into cooled to 0 ° C a solution of ₃ (0.66 g, 3.62 mmol) of bis (N- (2-hydroxy) ethyl) aniline are dissolved in 5 cm ³ of methanol. The whole ₃ is stirred at 5 ° C for 15 hours, then poured into 50 cm ³ of distilled water and neutralized with a saturated aqueous solution of sodium carbonate. The precipitated product is filtered under vacuum, washed several times with distilled water and dried at 50 ° C. The obtained N- [4 - [(E) - [4- [bis (2-hydroxyethyl) amino] phenyl] azo] phenyl] sulfonylbenzamide is purified by dissolving it in a little ethanol and then precipitation of the azo dye with small portions of distilled water. The product yield after purification is 91%.

₁

Characteristics of the product obtained: ¹ HNMR (solvent: DMSO-d6, TMS standard): 3.43 ppm (t, 8H, CH2), 4.86 ppm (s, 2H, OH), 6.84 ppm (d, 2H, CH in the benzene ring meta to the amino group), 7.48 ppm (t, 2H, CH in the benzene ring in the ortho position to the carbonyl group), 7.62 ppm (t, 1H, CH in the benzene ring in the para position to carbonyl group), 7.79 ppm (d, 2H, CH in the benzene ring meta to the amino group), 7.85 ppm (d, 2H, CM in the benzene ring ortho to the carbonyl group), 7.91 ppm (d, 2H, CM in the benzene ring ortho to the sulfonyl group), 8.11 ppm (d, 211, CH in the benzene ring meta to the sulfonyl group) 12.62 ppm (s, 1H, NH).

Claims (17)

Patent claims 1. Photochromic N- [4 - [(E) -phenylazo] phenyl] -sulfonylbenzamide dyes of general formula I, in which R is N- (2-hydroxy) ethyl (N-methyl) amino, N-ethyl (N - (2-hydroxy) ethyl) amino or bis (N- (2-hydroxy) ethyl) amino. 2. A method for the production of photochromic N- [4 - [(E) -phenylazo] phenyl] sulfonylbenzamide dyes of general formula I, in which R is N- (2-hydroxy) ethyl (N-methyl) amino, N-ethyl (N- (2-hydroxy) ethyl) amino or bis (N- (2-hydroxy) ethyl) amino, characterized in that in the first one the diazotization of N- (4-aminophenyl) sulfonylbenzamide is carried out with sodium III nitrate in an acidic environment in temperature ranging from 0 to 5 ° C, then in the second stage, the resulting diazonium salt is coupled in the form of 4- (benzoylsulfamoyl) -benzenediazonium chloride with aniline at a temperature not exceeding 5 ° C, and then the obtained product is separated from reaction mixture by neutralization and filtration. 3. The method according to p. 2. The process of claim 2, characterized in that the coupling reaction is carried out in the presence of an aniline derivative selected from N- (2-hydroxy) ethyl (N-methyl) aniline, bis (N- (2-hydroxy) ethyl) aniline or N-ethyl (N- (2-hydroxy) ethyl) aniline. PL 214 617 B1 4. The method according to p. The process of claim 2, wherein the diazotization reaction is carried out in a mixture of concentrated hydrochloric acid, water and glacial acetic acid containing from 6 to 10% by volume of concentrated hydrochloric acid and from 50 to 60% by volume of glacial acetic acid. 5. The method according to p. 2, characterized in that the diazotization reaction is carried out in a mixture of ₃ is not hydrochloric acid and glacial acetic acid in an amount of from 5 to 7 cm ³ per 1 mmol of N- (4-aminophenyl) sulfonylobenzamidu. 6. The method according to p. The process of claim 2, wherein the diazotization reaction is carried out in a ratio of 1.15 to 1.25 moles of sodium nitrate (III) per mole of N- (4-aminophenyl) sulfonylbenzamide. 7. The method according to p. 2. The method of claim 2, wherein the coupling reaction is carried out with a molar ratio of the diazonium salt to the corresponding aniline derivative ranging from 1: 1 to 10:11 mol / mol. 8. The method according to p. The process of claim 2, wherein the coupling product is precipitated with sodium acetate. 9. The method according to p. The process of claim 2, wherein the coupling product is precipitated with potassium acetate. 10. The method according to p. The process of claim 2, wherein the coupling product is precipitated with sodium carbonate. 11. The method according to p. The process of claim 2, wherein the coupling product is precipitated with potassium carbonate. 12. The method according to p. A process according to claim 2, characterized in that the azo dyes obtained are purified by precipitating the azo dye from the solution of N, N-dimethylformamide with small portions of distilled water. 13. The method according to p. A process according to claim 2, characterized in that the azo dyes obtained are purified by precipitating the azo dye from the methanol solution with small portions of distilled water. 14. The method according to p. The process of claim 2, wherein the azo dyes obtained are purified by precipitating the azo dye from the ethanol solution with small portions of distilled water. 15. The method according to p. The process of claim 1, wherein the azo dyes obtained are purified by precipitating the azo dye from the pyridine solution with small portions of distilled water. 16. The method according to p. A process according to claim 2, characterized in that the obtained azo dyes are purified by precipitation of the azo dye from the pyridine solution with small portions of ice. 17. The method according to p. The process of claim 2, characterized in that the obtained azo dyes are purified by crystallization from methanol.