GB2051110A

GB2051110A - 1,1-binaphthyl-4,4',5,5',8,8'- Hexacarboxylic Acid Derivatives, Method for Preparing Same and Their Use

Info

Publication number: GB2051110A
Application number: GB8015596A
Authority: GB
Original assignee: Individual
Current assignee: Individual
Priority date: 1979-05-10
Filing date: 1980-05-12
Publication date: 1981-01-14
Also published as: DE3017935C2; GB2051110B; FR2456102A1; DE3017935A1; CH655824GA3; FR2456102B1

Abstract

There are disclosed 1,1'- binaphthyl-4,4',5,5',8,8'- hexacarboxylic acid derivatives having the following general formula: <IMAGE> wherein R1 is hydrogen, a halogen or an alkyl group; wherein when X is oxygen, Y is hydrogen, an alkyl group, a cycloalkyl group or an aryl group containing at least one substituent selected from a halogen, an alkyl group and an alkoxy group; and wherein when X is nitrogen, Y is <IMAGE> where R2 is hydrogen, a halogen or an alkyl group, X being linked with Y with the formation of a benzimidazole cycle. There is also disclosed a method of preparing such derivatives, the use thereof for the synthesis of asymmetric derivatives of 3,4,9,10- perylenetetracarboxylic acid, as well as for dyeing and printing of textile materials.

Description

SPECIFICATION 1,1 '-Binaphthyl-4,4',5,5',8,8'-Hexacarboxylic Acid Derivatives, Method for Preparing Same and Their Use The present invention relates to the art of organic dyestuffs and, more specifically, to novel compounds-i ,1 '-binaphthyl-4,4',5,5t,8,8'-hexacarboxylic acid derivatives, a method for preparing said compounds and their use.

The compounds according to the present invention pertain to a new class of water-soluble dyestuffs forming, directly on the fibre, water insoluble asymmetric derivatives of perylenetetracarboxylic acid; they are useful in dyeing and printing of textile materials.

Known in the art are symmetric derivatives of 1,1 '-binaphthyl-4,41,5,5',8,8'-hexacarboxylic acid, in particular diimides or dibenzimidazoles which are obtained by condensation of 1,1 '-binaphthyl 4,4',5,5',8,8'-hexacarboxylic acid dianhydride with amines or ortho-diamines (cf. USSR Inventor's Certificate No. 366705). Dip'midges of 1,1 '-binaphthyl-4,4'-5,5',8,8'-hexacarboxylic acid dye textile materials to various shades of red colour, while dibenzimidazoles of 1,1 '-binaphthyl-4,4',5,5',8,8'- hexacarboxylic acid dye textile materials to blue and blue-violet colours. The resulting dyeings are fast to all kinds of processing and light.

It is an object of the present invention to broaden the colour range of the dyestuffs.

In accordance with the present invention; this object is accomplished by the provision of novel derivatives of 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid having the following general formula:

wherein R1 is hydrogen, a halogen, an alkyl, with X being oxygen, Y is hydrogen, an alkyl, a cycloalkyl, an aryl containing at least one substituent: a halogen, an alkyl, an alkoxy; with X being nitrogen, Y is

wherein R2 is hydrogen, a halogen, an alkyl, Y being linked to X with the formation of a benzimidazole cycle.

The compounds of the above-given formula are yellow crystalline substances non-melting to the temperature of 3000C, sparingly soluble in water, but forming salts well soluble in water upon interaction with basic compounds. The compounds according to the present invention also are dyestuffs for textile materials and dye same to various shades of violet colour.

The object of the present invention is also accomplished by the provision of a method for preparing derivatives of 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid, wherein, according to the present invention, 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid anhydride is treated with sodium hydroxide or potassium hydroxide; the resulting hexapotassium or hexasodium salt of 1 ,1 '-binaphthyl- 4,4',5,5',8,8'-hexacarboxylic acid is condensed upon heating at reflux at a pH of from 6.3 to 6.8 which is maintained by adding a mineral or organic acid, with ortho-phenylenediamines of the general formula:

wherein R1 is hydrogen; a halogen, an alkyl; the resulting benzimidazole-1 ,1 '-binaphthyl4,4',5,5',8,81- hexacarboxylic acid anhydride of the general formula:

wherein R1 is hydrogen, a halogen, an alkyl; is recovered and condensed with an amine of the formula: R3-NH2 wherein R3 is hydrogen, an alkyl, a cycloalkyl, and aryl containing at least one substituent: a halogen, an alkyl, an alkoxy; or with ortho-phenylenediamines of the formula:

wherein R2 is hydrogen, an alkyl, a halogen; in an excess of said amine, in water or in an organic solvent, followed by isolation of the desired product.

To improve quality of the product, it is advisable to isolate benzimidazole-1,1 '-binaphthyi 4,4',5,5',8,8'-hexacarboxylic acid anhydride of formula (IV) by alkalinization of the reaction mass to a pH value of from 9.0 to 9.5.

The present invention also relates to the use of the novel derivatives of 1 ,1 '-binaphthyl- 4,4',5,5',8,8'-hexacarboxylic acid.

One of the applications is a process for producing derivatives of 3,4,9,1 O-peryienetetracarboxylic acid, wherein according to the present invention 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid derivatives of formula (I) are treated with a reducing agent which comprises sodium hydrosulphite or rongalite in an alkaline medium, this being followed by oxidation to give, as a result, the above mentioned asymmetric derivatives of the general formula:

wherein R1 is hydrogen, a halogen, an alkyl; with X being oxygen, Y is hydrogen, an alkyl, a cycloalkyl, an aryl containing at least one substituent: a halogen, an alkyl, an alkoxy; at X being nitrogen Y is

wherein R2 is hydrogen, a halogen, an alkyl; Y being linked to X with the formation of a benzimidazole cycle.

The resulting derivatives of 3,4,9,1 O-perylenetetracarboxylic acid can be used as pigments.

Another application of the derivatives of the general formula (I) according to the present invention is the process for dyeing textile materials, wherein, according to the present invention, the textile material is impregnated with an aqueous alkaline solution of compounds of the general formula (I) in the presence of a reducing agent which is sodium hydrosulphite or rongalite, followed by oxidation to give asymmetric derivatives of 3,4,9,1 O-perylene tetracarboxylic acid of formula (VI) on the material.

Still another application of the derivatives of 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid is the process for printing of textile materials, wherein according to the present invention onto the material a printing paste is applied consisting of derivatives of 1,1 '-binaphthyl-4,4',5,5',8,8'hexacarboxylic acid according to formula (I), an alkaline agent, a reducing agent such as sodium hydrosulphite or rongalite, whereafter the material is subjected to a heat-treatment with a subsequent oxidation to give asymmetric derivatives of 3,4,9,1 O-perylenetetracarboxylic acid of the general formula (VI).

The method for preparing derivatives of 1 ,1 -bi 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid according to the present invention is carried out in the following manner.

The process is conducted in two stages. I n the first stage there is produced benzimidazole-1 1' binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid anhydride of the formula (IV). In the second stage the resulting compound is condensed with amines or ortho-phenylenediamines different from those employed in the first stage. The first stage of the process is performed as follows.

1.1 '-Binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid anhydride is converted to hexapotassium or hexasodium salt by dissolution in an aqueous solution of an alkali; this salt is condensed with orthophenylenediamines of formula (III) at a pH of from 6.3 to 6.8. At a pH below 6.3 the yield of corresponding dibenzimidazoles of 1,1 '-binaphthyl- 4,4',5,5',8,8'-hexacarboxylic acid is sharply increased, while at pH above 6.8 the reaction proceeds but very slowly.

The reaction is completed substantially within 15 hours at the boiling point (107-1 080C). The predetermined pH value is maintained by the addition of a mineral acid or an organic acid.

The addition of salts (NaCI or KCI) facilitates precipitation of benzimidazole-1,1 '-binaphthyl4,4',5,5',8,8'-hexacarboxylic acid or its derivatives, thus increasing its yield. Upon alkalinization of the reaction mass to the Ph of 9.0 to 9.5, benzimidazole of 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid passes into solution, whereas dibenzimidazole of 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid (by-product) remains in the precipitate and can be separated by filtration. From the filtrate, benzimidazole-1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid anhydride of formula (IV) is recovered by acidification.

In the second stage the recovered compound of the general formula (IV) is condensed with an amine of the general formula: R3-NH2, wherein R3 is hydrogen, an alkyl, a cycloalkyl, an aryl containing at least one substituent: a halogen, an alkyl, an alkoxy, or with ortho-phenylenediamines of the general formula (V) in an excess of the above-mentioned amine, in water or in an organic solvent such as acetic acid, dimethylformamide, trichlorobenzene. The thus prepared dyestuffs are separated from the reaction mass by conventional techniques, for example by filtration.

Dyeing of textile materials, for example cotton, lin, viscose, staple, acetate, polyamide materials with the dyes of the present invention is effected in an alkaline medium upon the action of reducing agents such as sodium hydrosulphite or rongalite, followed by oxidation to convert the derivatives of 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid to corresponding symmetric derivatives of 3,4,9,10perylenetetracarboxylic acid with the formation of dyeings of red-violet, violet and blue-violet colours with various shades on the material.

The dyestuffs according to the present invention are employed for printing on textile materials by way of application, onto the material, of a printing ink containing the derivatives of the general formula (I), an alkaline agent, a thickener, a reducing agent-sodium hydrosulphite or rongalite, whereafter the material is dried, kept in the atmosphere of saturated steam at a temperature of from 101 to 1 050C and subjected to oxidation.

Corresponding asymmetric derivatives of 3,4,9,1 O-perylenetetracarboxylic acid can be obtained from the dyestuffs according to the present invention not only on fibre, but in a reaction apparatus as well, and they can be employed as they are, for example as pigments. It should be noted that the resulting asymmetric derivatives of 3,4,9,10-perylenetetracarboxylic acid are novel compounds hitherto unknown in the literature. Their preparation from 3,4,9,1 O-perylenetetracarboxylic acid dianhydride is very difficult.

The dyestuffs according to the present invention have a number of advantages over the existing violet vat dyestuffs such as vat violet 9 (Colour Index 60005) and vat violet 1 (Colour Index 60010).

Solubility of the dyestuffs according to the present invention substantially simplifies their use, makes it possible to avoid non-uniformity of dyeing; furthermore, in the use of such dyes the rate of consumption of alkaline and reducing agents are considerably reduced (by 2-6 times) as compared to vat dyestuffs; there is no need in the manufacture of special preparative forms imminent in vat dyestuffs. It should be also noted that the dyestuffs according to the present invention give dyeings non-sensitive to water drops.

For a better understanding of the present invention, some specific examples are given hereinbelow by way of illustration.

Example 1 12.05 g (0.023 g-mol) of a 92% 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid anhydride and 8 g of caustic soda are dissolved in 75 ml of water, heated to reflux and maintained for 30 minutes.

There are added 17.5 g of sodium chloride and 2.7 g (0.025 g-mol) of ortho-phenytenediamine.

Thereafter, the reaction mass is acidified with a 15% solution of hydrochloric acid to pH=6.3, and allowed to stand for 1 5 hours at the temperature of 1 080C and pH of from 6.3 to 6.8. The pH value is maintained by the addition of a 1 5% solution of hydrochloric acid. On completion of the residence the mass is alkaiinized to the pH of 9.0 and dibenzimidazole-1 ,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid is filtered off. Anhydride of benzimidazole 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid is recovered from the filtrate by acidifying with acetic acid in the amount of 6.41 g (46.3% by weight).

After recrystallization from acetic acid anhydride there are obtained 6.00 g (43.3% by weight) of the product.

Found, %: C 69.50; 69.40; H 2.57, 2.58; N 5.23, 5.05 C32H,4N208.

Calculated, %: C 69.32; H 2.55; N 5.05.

Thereafter, 6.00 g (0.108 g-mol) of anhydride of benzimidazole 1,1 '-binaphthyl-4,4',5,5',8,8'- hexacarboxylic acid are charged into 75 ml of cyclohexylamine, kept for 3 hours at reflux. Then the reaction mass is cooled and poured into 1 50 ml of a 1 5% hydrochloric acid. The precipitate is filteredoff, washed with water and dried to give 6.48 g (94% by weight) of N-cyclohexylimide of benzimidazole-1,1 '-binaphthyl- 4,4',5,5',8,8'-hexacarboxylic acid. Recrystallization is effected from dimethylformamide.

Found, %: N 6.25; 6.50. C38H25N307.

Calculated, %: N 6.61.

Then 0.2 g of the resulting N-cyclohexylamide of benzimidazole-1 ,1 '-binaphthyl-4,4',5,5',8,8'hexacarboxylic acid is dissolved in 100 ml of a 1% of caustic soda, 1 g of sodium hydrosulphite is added thereto and into the reaction mixture a sample of cotton fabric weighing 5 g is immersed. The dyeing solution is heated to the temperature of 800C and kept at this temperature for about one hour.

Then the fabric sample is washed with cold water until a bright violet dyeing is formed thereon.

A mixture consisting of 1.00 g of N-cyclohexylimide of benzimidazole-1 ,1 '-binaphthyl4,4',5,5',8,8'-hexacarboxylic acid, 4.0 g of glycerol, 30 g of starch-trogacannth thickener, 5.0 g of potassium carbonate, 5.0 g of rongalite and 5 ml of water is applied onto a cotton fabric and dried.

The dried fabric is kept in the atmosphere of saturated steam at a temperature of from 101 to 1 050C for 5 minutes, whereafter the fabric is oxidized, thoroughly washed with water, soaped depending on the vat dye type. A bright violet dyeing remains on the fabric.

To a solution of 4.00 g of N-cyclohexylimide of benzimidazole-1 ,1 '-binaphthyl-4,4',5,5',8,8'hexacarboxylic acid in 100 ml of a 5% solution of caustic soda, added with 2-3 g of sodium hydrosulphite, maintained at the temperature of 800C about one hour. The solution of the leucocompound is oxidized by purging air therethrough for two hours. The precipitate is filtered-off, washed with a 1% soda solution, then with water and dried. There are obtained 2.62 g (76.2%) of Ncyclohexylimide of benzimidazole-3,4,9,1 0-perylenetetracarboxylic acid.

Found, %: N 7.85, 7.70. C36H23N3O3.

Calculated, %: N 7.72.

Example 2 2.00 g (0.0036 g-mol) of benzimidazole-1 ,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid anhydride produced as in Example 1 are suspended in 1 5 ml of dimethylformamide added with 7.00 g of p-bromoaniline and refluxed at the temperature of 1 530C for two hours. After cooling there is added 5 ml of water the residue is filtered-off, washed with 60% aqueous dimethylformamide and dried to give 2.00 g (78.2% by weight) of N-(4-bromophenyl)-imide of benzimidazole-1 ,1 '-binaphthyl4,4',5,5',8,8'-hexacarboxylic acid. Crystallization is effected from acetic an hydride.

Found, %: Br 11.00, 11.28. C38H12BrN3O7.

Calculated, %: Br 11.28.

The resulting compound is employed for dyeing and printing in a manner similar to that described in Example 1.

N-(4-bromophenyl)-imide of benzimidazole-3,4,9,10-perylenetetracarboxylic acid is obtained in a manner similar to that described in example 1 with the yield of 70% by weight.

Found, %: N 6.85; 6.90. C36H,8BrN303.

Calculated, %: N 6.80.

Example 3 In 40 ml of glacial acetic acid there are introduced 2.00 g (0.0036 g-mol) of benzimidazole-1 1' binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid anhydride prepared as in Example 1 and 1.50 g (0.0105 g-mol) of 4-chloro-1 ,2-phenylenediamine and refluxed for 6 hours, cooled; the precipitate is filtered-off and washed with water and then dried to give 2.03 g (83.3% by weight) of 5"(6")chlorodibenzimidazole-1 , 1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid. The product is crystallized from a 1% solution of sodium bicarbonate.

Found, %: Cl 5.30; 5.27: N 8.28, 8.50. C36H,5CIN402.

Calculated, %: Cl 6.21; N 9.81.

Example 4 Into 40 ml of a 25% aqueous solution of ammonia there are added 2.00 g (0.0036 g-mol) of benzimidazole-1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid anhydride prepared as in Example 1, heated to reflux and maintained for two hours, filtered-off and dried to give 1.50 g (75% by weight) of benzimidazole-1 ,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid imide. The resulting compound is crystallized from dimethylformamide.

Found, /0: N 7.63; 7.68. C32H,5N307.

Calculated, %: N 7.59.

Dyeing and printing with the use of the thus-prepared compound are effected in a manner similar to that described in Example 1 hereinbefore.

Benzimidazole-3,4,9,1 0-perylenetetracarboxylic acid imide is produced following the procedure described in Example 1 with the yield of 96.0% by weight.

Found, %: N 9.00, 9.10. C30H13N303.

Calculated, %: N 9.07.

Example 5 To the aqueous suspension of 5.57 g (0.01 g-mol) of benzimidazole-1,1 '-binaphthyl4,4',5,5',8,8'-hexacarboxylic acid anhydride prepared as in Example 1 there is added 1.3 ml (0.012 gmol) of m-toluidine and maintained for 10 hours. The precipitate is filtered-off, dissolved in 30 ml of a 1% alkali solution, then acidified with a concentrated hydrochloric acid. The precipitate is filtered-off, washed with water and dried. There are obtained 4.50 g (70% by weight) of N-(3-tolyl)-imide of benzimidazole-1 ,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid. The product is crystallized from acetic anhydride.

Found, %: N 6.42, 6.45. C39H2,N307.

Calculated, %: N 6.52.

Dyeing and printing with the resulting compound are effected in a manner similar to that described in Example 1.

N(3-tolyl)-imide of benzimidazole-3,4,9,1 0-perylene-tetracarboxylic acid is prepared following the procedure similar two that described in Example 1 with the yield of 87.1so by weight.

Found, %: N 7.07; 6.79. C37H1gN3O3.

Calculated, %: N 7.59.

Example 6 To an aqueous suspension of 5.57 g (0.01 g-mol) of benzimidazole-1 ,1 '-binaphthyl4,4',5,5',8,8'-hexacarboxylic acid anhydride prepared as in Example 1 at the temperature of 200C there are added 1.48 g (0.012 g-mol) of p-xylidine and maintained at reflux for 10 hours. The precipitate is filtered-off, dissolved in 30 ml of a 1% solution of sodium hydroxide, acidified with a concentrated hydrochloric acid. The precipitate is filtered-off, washed with water and dried.

There are obtained 4.28 g (65% by weight) of N-(2,4dimethylphenyl)-imide of benzimidazole1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid which is crystallized from dimethylformamide.

Found, %: N 6.28,6.30. C40H23N307.

Calculated, %: N 6.38.

N-(2,4-dimethylphenyl)imide of benzimidazole-3,4,9, 1 O-perylene tetracarboxylic acid is produced in the yield of 85.0% by weight in a manner similar to that described in Example 1.

Found,%: N 7.45, 7.35. C38H2,N303.

Calculated, %: N 7.40.

Example 7 12.05 g (0.023 g-mol) of a 92% 1,1 '-binaphthyl-4,4'-5,5',8,8'-hexacarboxylic acid and 1 1.2 g of caustic soda are dissolved in 75 ml of water, heated to reflux and maintained for 30 minutes.

There are added 17.5 g of sodium chloride, 3.56 g (0.025 g-mol) of 4-chloro-1 2- phenylenediamine, acidified with a 30% aqueous solution of acetic acid to the pH of 6.5. The reaction mixture is maintained for 15 hours at the temperature of 1080C and pH of from 5.6 to 6.8. the required pH value is maintained by the addition of a 1 5% solution of hydrochloric acid. On completion of the residence the reaction mass is alkalinized to the pH of 9.3, dichlorodibenzimidazole-1 ,1 '-binaphthyl4,4',5,5',8,8'-hexacarboxylic acid is filtered-off, 5"-chlorobenzimidazole-1 , 1 '-binaphthyl- 4,4',5,5',8,8'-hexacarboxylic acid anhydride is separated from the filtrate by acidification with acetic acid; the product amount is 4.88 g (35% by weight).

Found, %: C 64.77, 64.89; H 2.66, 2.66; N 4.75, 4.90. C32H13CIM208.

Calculated, %: C 65.53, H 2.23; N 4.76.

Found, %: Cl 6.09; 6.10.

Calculated, %: Cl 6.09.

Into 34 ml of butylamine there are introduced 4.88 g (0.00334 g-mol) of 5"chlorobenzimidazole-1 ,1 '-binaphthyl-4,4',5,5',8,8'-hexachlorocarboxylic acid anhydride, heated to reflux and maintained for 3 hours. Then the reaction mass is cooled and poured into 73 ml of a 1 5% hydrochloric acid. The precipitate is filtered-off and dried to give 4.98 g (93% by weight) of Nbutyiimide of 5"-(6")-chlorobenzimidazole-1 ,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid.

Recrystallization is effected from dimethylformamide.

Found, %: N 5.47, 5.50. C36H22C1N3O7.

Calculated, %: N 5.38.

Dyeing and printing by means of the thus prepared compound is effected following the procedure described in Example 1 hereinbefore.

N-Butylimide of 5"-(6")-chlorobenzimidazole-3,4,9, 1 O-perylenetetracarboxylic acid is prepared as described in Example 1 in the yield of 95% by weight.

Found, %: N 7.60, 7.65; Cl 6.42, 6.45. Q4H20ClN3Q.

Calculated, %: N 7.58, Cl 6.40.

Example 8 Into 14 ml of butylamine there are introduced 2.00 g (0.0036 g-mol) of benzimidazole-1 ,1 '- binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid anhydride prepared as in Example 1. The reaction mixture is maintained at reflux for 3 hours, The precipitate is filtered-off, dried to give 2.55 g (95% by weight) of butylimide of benzimidazole-1 ,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid which is then recrystallized from dimethylformamide.

Found, %: N 5.70, 5.62. C36H23N307.

Calculated, %: N 5.64.

Dyeing and printing by means of the resulting compound are effected as described in Example 1.

N-Butylimide of benzimidazole-3,4,9,10-perylenetetracarboxylic acid is prepared in a manner similar to that described in Example 1 in the yield of 95% by weight.

Found, %: N 7.79, 8.10. C34H2,N303.

Calculated, %: N 8.09.

Example 9 12.05 g (0.023 g-mol) of a 92% 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid and 8 g of caustic soda are dissolved in 75 ml of water, heated to reflux and maintained for 30 minutes at this temperature, then added with 1 7.5 g of sodium chloride and 3.05 g of 4-methyl-1,2phenylenediamine. The reaction mixture is acidified with a 15% solution of hydrochloric acid to pH of 6.8, kept for 15 hours at the temperature of 1 080C and pH of 6.8. The required pH value is maintained by the addition of a 1 5% solution of hydrochloric acid. On completion of the residence, the reaction mass is alkalinized to the pH of 9.5; the product, i.e. dimethylbenzimidazole-1 ,1 '-binaphthyl4,4',5,5',8,8'-hexacarboxylic acid, is separated by filtration.From the filtrate 5"-(6")- methylbenzimidazole-1 ,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid anhydride is isolated by acidification with acetic acid; the product yield is 5.49 g (37.3% by weight).

Found, %: C 69.52, 69.60; H 2.77, 2.78; N 4.90, 4.97. C35H,6N208.

Calculated, %: C 69.72; H 2.84; N 4.93.

Thereafter 5.49 g (0.0983 g-mol) of 5"(6")-methylbenzimidazole-1 ,1 '-binaphthyl- 4,4',5,5',8,8'-hexacarboxylic acid anhydride are charged into 28 ml of p-phenetidine, maintained at the temperature of 1 500C for two hours, cooled and poured onto 85 ml of a 1 5% solution of hydrochloric acid. The precipitate is filtered-off, washed with water and dried to give 6.73 g (91% by weight) of N-(ethoxyphenyl)-imide of 5"(6")-methylbenzimidazole-1,1'-binaphthyl-4,4',5,5',8,8'- hexacarboxylic acid which is crystallized from acetic anhydride.

Found, %: N 6.03, 6.15. C41H2sN3 ss Calculated, %: N 6.11.

Dyeing and printing by means of the thusLprepared compound is effected following the procedure described in the foregoing Example 1.

N-4-ethoxyphenylimide of 5"(6")-methylbenzimidazole-3,4,9,1 0-perylenetetracarboxylic acid is produced following the procedure of Example 1 with the yield of 80% by weight.

Found, %: N 6.85, 7.00. C39H23N304.

Calculated, %: N 7.03.

Example 10 The process is carried out in a manner similar to that described in Example 9, except that the first condensation is effected using 4-ethyl- 1 ,2-phenylenediamine. There is obtained N-(4-ethoxyphenyl)imide of 5"(6")-ethylbenzimidazole 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid.

Found, %: N 6.05, 60.1. C42H27N308.

Calculated, %: N 5.99.

Dyeing and printing are effected following the procedure of Example 1. N-(4-ethoxyphenyl)-imide of 5"(6")-ethylbenzimidazole-3,4,9,1 O-perylenetetracarboxylic acid is prepared as in Example 1, the yield is 80% by weight.

Found, %: N 6.90, 6.95. C40H25N3O4.

Calculated, %: N 6.87.

Example 11 The process is carried out following the procedure of Example 7, except that the first condensation is effected using 4-bromo-1 ,2-phenylenediamine.

Dyeing and printing are performed as in Example 1.

Butylimide of 5"(6")bromobenzimidazole-3,4,9,1 O-perylenetetracarboxylic acid is prepared following the procedure similar to that of Example 1; the product yield is 90.0% by weight.

Found, %: N 7.25, 7.115; Br 13.25, 13.30. C34H20BrN3O3.

Calculated, %: N 7.02, Br 13.35.

Example 12 To 40 ml of a 25% aqueous solution of methylamine there are charged 2.00 g (0.0036 g-mol) of benzimidazole 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid anhydride prepared as in Example 1, heated to reflux and maintained for two hours, then filtered, dried to give 1.64 g (80%) of Nmethylimide of benzimidazole-1 ,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid. The product is crystallized from acetic an hydride.

Found, %: N 7.35, 7.40. C33H,7N307.

Calculated, %: N 7.40.

Dyeing and printing is effected as described in the foregoing Example 1.

N-Methylimide of benzimidazole-3,4,9,1 0-perylenetetracarboxylic acid is prepared as described in Example 1, the yield is 97.0% by weight.

Found, %: N 8.90, 8.85. C3,H,sN303.

Calculated, %: N 8.81.

Claims

1. 1,1 '-Binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid derivatives having the following general formula:

wherein R, is hydrogen, a halogen or an alkyl group; wherein when X is oxygen, Y is hydrogen, an alkyl group, a cycloalkyl group or an aryl group containing at least one substituent selected from a halogen, an alkyl group and an alkoxy group; and wherein when X is nitrogen, Y is

where R2 is hydrogen, a halogen or an alkyl group, Xbeing linked with Y with the formation of a benzimidazole cycle.

2. A 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid derivative according to Claim 1, substantially as herein described in any of the foregoing Examples.

3. A method of preparing a 1,1 '-binaphthyl-4A',5,5',8,8'-hexacarboxylic acid derivative according to Claim 1, wherein 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid anhydride is treated with potassium hydroxide or sodium hydroxide, and the resulting hexapotassium or hexasodium salt of 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid is condensed upon heating at reflux and at a pH of from 6.3 to 6.8 maintained by the addition of a mineral or an organic acid with an orthophenylenediamine of the formula:

wherein R, is hydrogen, a halogen or an alkyl group, the resulting benzimidazole-1 ,1 '-binaphthyl4,4',5,5',8,8'-hexacarboxylic acid anhydride of the formula::

wherein R, is hydrogen, a halogen or an alkyl group, being recovered and condensed with an amine of the general formula R3-NH2 wherein R3 is hydrogen, an alkyl group, a cycloalkyl group or an aryl group containing at least one substituent selected from a halogen, an alkyl group and an alkoxy group, or with an ortho-phenylenediamine of the general formula:

wherein R2 is hydrogen, a halogen or an alkyl group, in an excess of the amine, in water or in an organic solvent, followed by isolation of the desired product.

4. A method as claimed in Claim 3, wherein the isolation of benzimidazole-1 ,1 '-binaphthyl4,4',5,5',8,8'-hexacarboxylic acid anhydride of formula (IV) is effected by alkalinization of the reaction mass to a pH value of from 9.0 to 9.5.

5. A method of preparing a 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid derivative according to Claim 3, substantially as herein described in any of the foregoing Examples.

6. A method of preparing an asymmetric derivative of 3,4,9, 1 O-perylenetetracarboxylic acid, wherein a 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid derivative of formula (I) as claimed in Claim 1 is treated with a reducing agent in an alkaline medium, followed by oxidation to give the asymmetric derivative of the formula:

wherein R, is hydrogen, a halogen or an alkyl group; and wherein when X is oxygen, Y is hydrogen, an alkyl group, a cycloalkyl group or an aryl group containing at least one substituent selected from a halogen, an alkyl group and an alkoxy group, and wherein when X is nitrogen, Y is

wherein R2 is hydrogen, a halogen or an alkyl group, Y being linked to X with the formation of a benzimidazole cycle.

7. A method as claimed in Claim 6, wherein the said reducing agent is sodium hydrosulphite or rongalite.

8. A method of preparing an asymmetric derivative of 3,4,9,1 0-perylene-tetracarboxylic acid according to Claim 6, substantially as herein described in any of the foregoing Examples.

9. A process for dyeing a textile material, wherein the material is impregnated with an aqueous alkaline solution of a 1,1 '-binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid derivative of formula (I) as claimed in Claim 1 in the presence of a reducing agent, followed by oxidation, with the formation of an asymmetric derivative of 3,4,9,1 O-perylenetetracarboxylic acid of formula (VI) as claimed in Claim 6 on the textile material.

1 0. A process as claimed in Claim 9, wherein the said reducing agent is sodium hydrosulphite or rongalite.

11. A process for dyeing a textile material according to Claim 9, substantially as herein described in any of the foregoing Examples.

12. A process for printing a textile material, wherein a printing paste comprising a 1,1' binaphthyl-4,4',5,5',8,8'-hexacarboxylic acid derivative of formula (I) as claimed in Claim 1, an alkaline agent and a reducing agent, is applied onto the material, and the material is then heat-treated and oxidized with the formation of an asymmetric derivative of 3,4,9,1 0-perylenetetracarboxylic acid of formula (VI) as claimed in Claim 6 on the textile material.

1 3. A process as claimed in Claim 12, wherein the said reducing agent is sodium hydrosulphite or rongalite.

14. A process for printing a textile material according to Claim 12, substantially as herein described in any of the foregoing Examples.