RU2050387C1 - Sulfoacids of substituted n,n′-diphenyldiimides and dibenzimidazoles of 3,4,9,10-antantrontetracarboxylic acid as materials for forming superthin light- and thermostable gray color polarizing coatings - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: new compounds sulfoacids of substituted N,N′-diphenyldiimides or dibenzimidazoles of 3,4,9,10-antantrontetracarboxylic acid were synthesized by sulfonation of corresponding derivatives of 3,4,9,10-antantrontetracarboxylic acid or 1,1′- binaphthyl-4,4′,5,5′,8,8′ -hexacarboxylic acid at 80-130 C. Synthesized water-soluble dyes show capability to form lyotropic mesomorphic phase that allows to form superthin thermostable polarizing gray color coatings with high light stability (up to 7-8 points). EFFECT: enhanced quality of material. 1 tbl

Description

 The invention relates to new chemical compounds, namely, sulfonic acids of substituted N, N'-diphenyl diimides and dibenzimidazoles 3,4,9,10-antanthronetetracarboxylic acid (ATCC) of the general formula (I), which can be used as materials for the formation of ultrafine light - and heat-resistant polarizing coatings (PP) of gray color.

A O=

O O=

Известны дисульфокислоты дибензимидазолов 1,4,5,8-нафталинтетракарбоновой кислоты [1] N,N'-дифенилдиимидов [2] и дибензимидазолов [3] 3,4,9,10-перилентетракарбоновой кислоты, а также 3-хлориндантрона [4] которые могут быть использованы в качестве материалов для получения сверхтонких термостабильных (до 350^оС), светостойких (5-6 баллов) поляроидных пленок.

AO =

Oo =

Known disulfonic acids of dibenzimidazoles 1,4,5,8-naphthalene tetracarboxylic acid [1] N, N'-diphenyldiimides [2] and dibenzimidazoles [3] 3,4,9,10-perylenetetracarboxylic acids, as well as 3-chloroindantrone [4] which can be used as materials for ultrathin thermostable (up to 350 ^о С), light-resistant (5-6 points) polaroid films.

 However, these dyes provide selectivity of absorption in a strictly defined spectral region of 440-500 nm [1] 480-550 nm [2] 550-620 nm [3] 620-680 nm [4] and in order to obtain a gray polaroid film, it is necessary to use 3-4 dyes in a certain ratio, while the light fastness of the mixed dye does not exceed 5 points, which is insufficient for the use of polaroids in some areas of science and technology.

 The objective of the invention is the synthesis of sulfonic acids substituted N, N'-diphenyldiimides and dibenzimidazoles ATCC, which can be used as materials for the formation of ultrathin thermostable PP gray with high light resistance (up to 7-8 points).

R=H, Br, Cl, OH, Alk, OAlk
Cульфирование проводят в моногидрате, олеуме различной концентрации, смеси моногидрата или олеума с хлорсульфоновой кислотой при 80-130^оС.This problem is solved by sulfonation of the corresponding ATCC derivatives of the general formula (II) or 1,1'-binaphthyl-4,4 ', 5,5', 8,8'-hexacarboxylic acid (BGCC) of the general formula (III)

R = H, Br, Cl, OH, Alk, OAlk
Sulfonation is carried out in monohydrate, oleum of various concentrations, a mixture of monohydrate or oleum with chlorosulfonic acid at 80-130 ^about C.

 The obtained water-soluble dyes (I) have the ability to form a lyotropic liquid crystal (VFA) phase, which allows the formation of ultrathin thermostable gray PPs with increased light resistance (up to 7-8 points).

EXAMPLE EXAMPLE 1 10 ml of 15-20% strength oleum at 20-25 ^C. 2 g of N, N'-ATAC difenildiimida heated to 80-90 ^{° C} and stirred at this temperature to obtain a water-soluble sample for 6-7 hours. The reaction mixture was poured onto ice, the resulting precipitate was filtered off, washed with hydrochloric acid until no sulfate anions and dried at 80 ^° C to give 1.76 (69%) of the sulfonic acid I, a = a, R = H. IR spectrum (UR-20 device, tablets with KCl, cm ^-1 ): 1025, 1060, 1150-1200 (SO ₃ H), 1650, 1695 (С = О). Found, N 3.05; 3.23; S 7.50; 7.37. C ₃₈ H ₁₆ N ₂ O ₁₂ S ₂ ˙ 4H ₂ O. Calculated, N 3.38; S 7.74. Similarly, sulfonic acids N, N'-di- (4-butylphenyl), N, N'-di- (4-hydroxyphenyl), N, N'-di- (4-methoxyphenyl) and N, N'-di- ATCC (4-ethoxyphenyl) diimides (I, A = a). Instead of oleum, 97-100% sulfuric acid is also used at 115-125 ^о С.

PRI me R 2. In the conditions of example 1 from dibenzimidazole ATCC receive sulfonic acid of the formula I, A = b, R = H. Yield 88% IR spectrum (UR-20 device, tablets with KCl, cm ^-1 ): 1020, 1065, 1150-1200 (SO ₃ H), 1650, 1695 (C = O). Found, N 6.50; 6.75; S 8.0; 8.33; C ₃₈ H ₁₄ N ₄ O ₁₀ S ₂ ˙ 4H ₂ O. Calculated, N 6.81; S 7.79. Similarly, sulfonic acids of 4.4 '(3.3') dimethyl-, 4.4 '- (3.3') -dibromodibenzimidazole ATCC (I, A = b) are obtained.

EXAMPLE EXAMPLE 3. In 6 ml of chlorosulfonic acid at 20-25 ^{° C} was charged with 1.5 g of N, N'-di- (3-methylphenyl) diimide ATAC, 3 ml monohydrate, is heated ^to 85 ° C and stirred at 80-90 ^o C to water soluble samples for 11 hours. The sulfonation product is isolated as in example 1 to give 1.6 g (85%) of the sulfonic acid (I, a = a, R = 3-CH _3). IR spectrum (UR-20 device, tablets with KCl, cm ^-1 ): 1020, 1065, 1170-1205 (SO ₃ H), 1650, 1695 (C = O). Found, N, 2.90; 3.05; S 7.00; 7.23. C ₄₀ H ₂₀ N ₂ O ₁₂ S ₂ ˙ 4H ₂ O. Calculated, N 3.27; S 7.48. Similarly, sulfonic acids of N, N'-di- (4-butylphenyl), N, N'-di- (4-bromophenyl), N, N'-di- (4-chlorophenyl) diimides of ATCC (I, A = a ) Instead of monohydrate, a 15-20% oleum is also used.

Example 4. Under the conditions of Example 3, a sulfonic acid of the formula IA = b, R = 4-CH _{3 is} obtained in 87% yield of 4,4'-dimethyldibenzimidazole ATCC. IR spectrum (UR-20 device, tablets with KCl, cm ^-1 ): 1025, 1065, 1150-1200 (SO ₃ H), 1650, 1695 (C = O). Found, N 6.65; 6.35; S 7.82; 8.00. C ₄₀ H ₁₈ N ₄ O ₁₀ S ₂ ˙ 4H ₂ O. Calculated, N 6.58; S 7.54. Similarly, sulfonic acids of 4.4 '- (3.3') - dichloro-4.4 '(3.3') - dibromodibenzimidazole ATCC (I, A = b) are obtained.

PRI me R 5. In 10 ml of monohydrate at room temperature, load 2 g of N, N'-di- (4-methoxyphenyl) diimide BGCC and stirred at 100-115 ^about With water-soluble samples for 5 hours. The reaction mixture diluted with water, the precipitate is filtered off, washed with hydrochloric acid until there are no sulfate anions and dried at 80 ^about C. 2.12 g (90%) of sulfonic acid are obtained (I, A = a, R = 4-OCH ₃ ), IR spectrum ( UR-20 device, tablets with KCl, cm ^-1 ): 1030, 1065, 1150-1200 (SO ₃ H), 1655, 1695 (C = O). Found, N 2.90, 3.00; S 7.87, 7.83. C ₄₀ H ₂₀ N ₂ O ₁₄ S ₂ ˙ 4H ₂ O. Calculated, N 3.16; S 7.12. In a similar manner, sulfonic acid I, A = a, R = 4-OC ₂ H _{5 is} obtained.

PRI me R 6. In 100 ml of a 20% oleum at 20-25 ^about With load 35 g of dibenzimidazole BGCC and incubated at 110-115 ^about With for 7 hours. At the end of the reaction, the mass is diluted with water, the resulting precipitate is filtered off washed with hydrochloric acid and dried. Obtain 35.2 g (84%) of the compounds of formula I, A = b, R = H. The data of the infrared spectrum and elemental analysis coincide with those in example 2.

 Similarly, sulfonic acid of N, N'-diphenyldiimide ATCC (I, A = a) is obtained using N, N'-diphenyldiimide BGCC (III, A = a). The data of the IR spectrum and elemental analysis coincide with those in example 1.

 The method of obtaining polaroid films.

1 g of Dye purified from inorganic impurities is dissolved in 100 g of distilled water, the pH of the solution is adjusted to 6.0 by adding an alkali solution (ammonia), the solution is carefully filtered and gradually evaporated on a rotary evaporator to a solution weight of 11 g. A lyotropic liquid crystal phase is formed (LZHKF) a dye at a concentration of 9-11% LZHKF 0.25 ml of dye applied on a glass substrate 5x5 cm ^2, a second plate is placed on top and a circular motion LZHKF extend into a thin film, after which an upper plate rapidly dumped ayut from the bottom. The resulting thin oriented film after drying when stained has an intense gray color.

 Polaroid characteristics (degree of polarization, dichroic ratio) of the obtained films are determined by the polarization absorption spectra, which are measured in the range 350-700 nm on a Shimadzu spectrophotometer with a polaroid attachment. As a polaroid analyzer, a Nicole prism with an aperture of 20 mm is used.

 The output, elemental analysis data, and polaroid characteristics of the synthesized compounds are shown in the table.

As can be seen from the data presented in the table, the claimed compounds allow to obtain polaroid films with a very small layer thickness (0.5-0.6 microns), high thermal stability (up to 400 ^° C) and light fastness of 7-8 points, gray.

Claims (1)

Sulfonic acids of substituted N, N′-diphenyl diimides and dibenzimidazoles of 3,4,9,10-anthanthronetetracarboxylic acid of the general formula

Where

RH, Br, Cl, OH, AlK, OAlK,
as materials for the formation of ultrathin light and heat-resistant polarizing gray coatings.

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