DE3017935A1 - 1,1'-BINAPHTHYL-4,4 ', 5,5', 8,8'-HEXACARBONIC ACID DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE SYNTHESIS OF ASYMMETRIC 3,4,9,10-PERYLENTETRACARBONIC ACID DERIVATIVES AND FOR THE STERBEROXIDE - Google Patents

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

SHIP ν. FDNER STREHL SCHOBEL-HOPF EBBINGHAUS FINCK

description

The present invention relates to the field of organic dyes, more particularly, it relates to new compounds, 1,1'-binaphthyl-4,4 ¹ , 5,5 ', 8,8'-hexacarboxylic acid derivatives, a process for their preparation and their use .

The compounds according to the invention belong to a new class of water-soluble dyes, which directly the fiber is water-insoluble asymmetric perylenetetracarboxylic acid derivatives form, and are used for dyeing and printing textiles.

Symmetrical 1,1'-binaphthy1-4,4 ·, 5,5 ', 8,8'-hexacarboxylic acid derivatives, for example diimides or dibenzimidazoles, which can be obtained by condensation of 1,1'-binaphthy1-4,4' are known , 5,5 ', e ^' - hexacarboxylic acid dianhydride with amines or ortho-diamines (SU-PS 366 705). The diimides of 1,1 »- binaphthyl-4,4 ', 5,5', 8,8 · -hexacarboxylic acid give the textiles various red hues, while the dibenzimidazoles of 1,1 · -binaphthyl-4,4 ¹ , 5,5 ', 8,8 · -hexacarboxylic acid dye textile fabrics blue and blue-violet.

The colors obtained have high resistance to all Types of treatments and light.

The invention was based on the object that Expand the range of dyes.

The proposed 1,1'-binaphthyl-4,4 ¹ , 5,5 ', 8,8'-hexacarboxylic acid derivatives according to the invention have the following

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general formula on

where R ^ is hydrogen, halogen, alkyl, where X = oxygen, Y is hydrogen, alkyl, cycloalkyl, aryl, which contains at least one substituent such as halogen, alkyl, alkoxy group, where X = nitrogen, Y is

> \ U (II), in which R _{2 is} hydrogen, halogen, alkyl, where Y and X are linked to one another and form a benzimidazole ring.

Preferably alkyl is lower alkyl of 1 to 5 carbon atoms. Cycloalkyl is preferably a group with 5 to 7, in particular with 6, carbon atoms. At the expression Aryl is mainly the phenyl radical, i.e. a mononuclear radical, but also the naphthyl group can be envisaged; Those compounds which have 1 to 3 substituents in the phenyl radical are preferred have, in particular one. Halogen is preferably understood to mean chlorine and bromine, in particular chlorine. the

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The alkoxy group is preferably one having 1 to 5 carbon atoms.

The compounds of the above formula are yellow crystalline substances which cannot be melted up to a temperature of 30O ⁰ C, are poorly soluble in water and when reacted with basic agents form salts which are readily soluble in water. The compounds according to the invention are dyes for textiles and give them various purple hues.

The invention also relates to a process for the preparation of 1,1 ^l -binaphthyl-4,4 ', 5,5', 8,8'-hexacarboxylic acid derivatives, in which, according to the invention, the 1,1'-binaphthyl- 4,4 ', 5,5', 8,8 · -hexacarboxylic acid anhydride treated with potassium hydroxide or sodium hydroxide, the resulting hexapotassium salt or hexasodium salt of 1,1'-binaphthy 1-4,4'-, 5, -5 ', 8 , 8'-hexacarboxylic acid with boiling at a pH of 6.3 to 6.8, which is maintained by adding a mineral or organic acid, with ortho-phenylenediamines of the general formula

in which R _{1 is} hydrogen, halogen, alkyl, condensed, the benzimidazole-1,1'-binaphthy1-4,4 ', 5,5', 8,8'-hexecarboxylic anhydride obtained of the general formula

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IV

wherein R- is hydrogen, halogen, alkyl, separates and with an amine of the general formula R-, - NHp, in which R, for hydrogen, alkyl, cycloalkyl, aryl, the at least contains a substituent such as halogen, alkyl, alkoxy group, or with ortho-phenylenediamines of the general formula

wherein Rp is hydrogen, halogen, alkyl, in one Excess of the amine mentioned, condensed in water or an organic solvent and then the end product isolated.

To increase the quality of the product, it is advisable to use the benzimidazole-1,1'-binaphthy1-4,4 ', 5,5', 8,8'-hexacarboxylic anhydride of the general formula IV by alkalizing the reaction mass to a pH of 9.0 to 9.5 to separate.

The invention also relates to the use of the

1,1'-binaphthyl-4,4 ', 5,5', 8,8'-hexakarbon- according to the invention

0 3 0 0 4 7/0885

acid derivatives.

One of the variants of the use is the use for the production of 3,4,9,10-perylenetetracarboxylic acid derivatives by, according to the invention, the 1,1'-binaphthyl-4,4 ¹ , 5,5 *, 8,8'-hexacarboxylic acid derivatives of the general Formula I treated with a reducing agent, such as sodium hydrogen sulfite or Rongalite, in an alkaline medium with subsequent oxidation, whereby the said asymmetric derivatives of the general formula

VI

wherein R ^ is hydrogen, halogen or alkyl; at X = Oxygen Y is hydrogen, alkyl, cycloalkyl or aryl, which has at least one substituent such as halogen, alkyl or contains the alkoxy group; where X = nitrogen Y for

II

where R _{2 is} hydrogen, halogen or alkyl, where Y and X are linked to one another and form a benzimidazole ring.

The 3,4,9,10-perylene tetracarboxylic acid derivatives obtained

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ORIGINAL INSPECTED

can be used as pigments.

Another variant of the use of the derivatives of the general formula I according to the invention is for dyeing Textiles, according to the invention, the material with an aqueous alkaline solution of compounds of the general Formula I in the presence of a reducing agent, sodium hydrogen sulfite or Rongalite, soaked with subsequent Oxidation, which results in asymmetric 3,4,9,10-perylenetetrakarvonic acid derivatives of the general on the material Form Formula VI.

Another variant of the use of the 1,1'-binaphthyl-4,4 ', 5,5', 8,8'-hexacarboxylic acid derivatives is a process for printing textiles by applying, according to the invention, a printing paste, the 1,1'-binaphthyl-4,4 ', 5,5'-8,8'-hexacarboxylic acid derivatives, to the textile of the general formula I, an alkaline agent, a reducing agent, sodium hydrogen sulfide or Rongalit, contains, applies, then subjected to a heat treatment and then oxidized, whereby 3 »4,9,10-perylenetetracarboxylic acid derivatives asymmetric on the textile of formula VI.

The process for the preparation of 1,1'-binaphthyl-4,4 ', 5,5', StS'-hexacarboxylic acid derivatives according to the invention is carried out as follows.

The procedure is carried out in two stages. In the first stage, benzimidazole-1,1'-binaphthy1-4,4'-5,5 ', 8,8'-hexacarboxylic anhydride is obtained of the general formula IV. In the second stage, the compound obtained is condensed with amines or o-phenylenediamines, which are of the first stage used are different.

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The first stage of the process is carried out as follows.

The 1,1 ^f -Binaphthy1-4,4 ', 5 ₁ 5 ·, 8.8 ^% -hexacarboxylic anhydride is converted into the hexasodium salt or hexapotassium salt by dissolving in aqueous alkali solution, which with o-phenylenediamines of the general formula III at pH Value of 6.3 to 6.8 is condensed. At a pH of below 6.3, the yield of the corresponding dibenzimidazole-1,1 ^l -binaphthyl-4,4 ^f , 5.5 * | 8 »8 * -hexacarboxylic acids increases sharply, while at a pH above 6, If the pH value is 8, the reaction is extremely slow.

The reaction is practically over after 15 minutes at the boiling point (10 ° to 108 ° C.). The said pH is Maintained by adding a mineral or organic acid.

The addition of salts (NaCl or KCl) causes the benzimidazole-1,1 * -binaphthyl-4,4 ^l , 5 »5 ^l » 8 »8 ^f -hexacarboxylic acid or its derivatives to precipitate, which increases the yield leads to product. When the reaction mass is made alkaline to a pH of 9.0 to 9.5, the benzimidazole-1,1'-binaphthyl-4,4 ·, 5.5 ·, 8.8 · hexacarboxylic acid goes into solution, while the dibenzimidazole -1,1'-binaphthyl-4 _l 4 ^t , 5 »5 ^l 18 | 8 '~ n ^e xacarboxylic acid (by-product) remains in the precipitate and can be separated off by filtration. Benzimide * · azole-1,1'-binaphthyl-4,4 *, 5,5 ', 8,8 * -hexacarboxylic acid enhydride of the general formula IV is separated from the filtrate by acidic acids.

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In the second stage, the compound of the general formula IV which has been separated off is condensed with a Amine of the general formula R ^ - NHp, where B ^ is hydrogen, Alkyl, cycloalkyl, aryl, which contains at least one substituent such as halogen, alkyl, alkoxy group, stands, or with o-phenylenediamines of the general formula V in an excess of the amine mentioned, in water or an organic solvent such as acetic acid, dimethylformamide, trichlorobenzene.

The dyes obtained are separated from the reaction mass in a manner known per se, for example by Filtration, ab.

The dyeing of textiles, for example cotton, linen, viscose, rayon, acetate, polyamide fibers, with the dyes according to the invention takes place in an alkaline medium with the action of reducing agents - sodium hydrogen sulfite or Rongalite - with subsequent oxidation, where the 1, Convert 1'-binaphthyl-4,4 ¹ -5 »5 '» 8 »8'-hexacarboxylic acid derivatives into the corresponding asymmetric 3 | 4,9> 10-perylenetetracarboxylic acid derivatives with the formation of red-violet, violet and blue-violet colors of various shades.

The dyes according to the invention are used to print substances by applying a printing ink, the derivatives, to the substance of the general formula I, an alkaline agent,

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a thickener containing a reducing agent such as sodium hydrogen sulfite or rongalite, then applies the Fabric dries, holds in the atmosphere of saturated steam at a temperature of 101 to 105 ° 0 and oxidizes. The corresponding asymmetric 3,4,9,10-perylene- ■ ueurakarbonsäurederivate can from the dyes according to the invention not only on the fibers, but also in one Reaction apparatus received and used independently, for example as pigments · It should be established that the asymmetric 3,4,9 »10-perylenetetracarboxylic acid derivatives which are formed represent new products that are not described in the literature. Your manufacture from 3,4,9,10-perylenetetracarboxylic acid dianhydride is extreme difficult.

The dyes according to the invention have a number advantages over the violet vat dyes available in the range, for example vat Violet 9 (O.I. 60005) and vat Violet 1 (CI. 60010) · The solubility of the dyes according to the invention make theirs considerably easier Use, makes it possible to avoid uneven coloring. In addition, the use of these dyes decreases significantly (by 2 to 6 times) the consumption of the alkaline and reducing agents compared to the vat dyes There is no need to prepare special commercial forms, as are customary for vat dyes. It should also be noted that the invention

0 30047/08 8 5

.Dyestuffs produce colorations that are imperceptible to water are.

In order to better understand the present invention The following concrete examples are given below for their implementation.

Example 1.

12.05 g (0.023 mol) of anhydride of 92% strength 1,1 ^f -binaphthyl-4,4 ', 5,5', δ, 8'-hexacarboxylic acid and 8 g of caustic soda are dissolved in 75 ml of water and heated Reflux and hold for 30 minutes. 17.5 g of sodium chloride and 2.7 g (0.025 mol) of o-phenylenediamine are added. It is acidified with 15% hydrochloric acid to a pH of 6.3 and held for 15 hours at a temperature of 108 ^° C. and a pH of 6.3 to 6.8. The pH is maintained by adding a 15-6 strength hydrochloric acid solution. Then the pH is adjusted to 9 »0

The dibenzimidazole-1,1'-binaphthyl-4,4 ·, 5 * 5 * »8,8« - hexacarboxylic acid is filtered off. Benzimidazole-1,1'-binaphthyl-4,4 ', 5.5 ^f -8,8'-hexacarboxylic anhydride in an amount of 6.41 g (46.3 percent by weight) is separated from the filtrate by acidifying with acetic acid. After recrystallization from acetic acid anhydride, 6.00 g (43.3 percent by weight) of product are obtained.

Found, ^: G 69.50? 69.4O ₅ H 2.57; 2.5ö; N 5.23? 5.05,

Calculated,%: C, 69.32; H 2.55} N 5.05 Then 6.00 g (0.0108 mol) of benzimidazole-1,1'-binaphthyl-4,4 ', 5,5', 8,8'-hexacarboxylic anhydride are added in 75 ml

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Cyclohexylamine. The mixture is heated to reflux for 3 hours. The reaction mass is cooled and poured into 150 ml of 15% hydrochloric acid. The deposited precipitate is filtered off, washed with water and dried. 6.48 g (94 percent by weight) of benzimidazole-1 ~, 1'-binaphthyl-4,4 ', 5 »5 ^{« »8» 8 f} hexacarboxylic acid-N-cyclohexylimide are obtained.

It is recrystallized from dimethylformamide.

Found, %% N 6.25; 6.50; G ₃₂ H ₂₅ N ₃ O ₇ .

Calculated, ^: 6.61.

0.2 g of the benzimidazole-1, I ¹ -binaphthyl-4, 4 ', 5.5 ^f »8,8'-hexacarboxylic acid-N-cyclohexylimide obtained is then taken, dissolved in 100 ml of 1% sodium hydroxide solution, brought 1 g of sodium hydrogen sulfite and dips a cotton fabric sample weighing 5 g. It is heated to a temperature of 80 ^° C. and held for about 1 hour. The tissue sample is then washed with cold water up to. Education on a brilliant purple color. .

A mixture consisting of 1.00 g benzimidazole-1.1 ^f b inaphthyl-4.4 ^f , 5.5 ^f , 8.8'-hexacarboxylic acid-ir-cyclohexylimide, 4.0 g glycerine _# 30 g starch tragacanth -Thickener, 5.0 g potassium carbonate, 5.0 g Rongalit and 5 & 1 water, are applied to a cotton fabric and dried.

The dried fabric is kept in the atmosphere of saturated steam at a temperature of 101 to 105.degree 5 minutes, then oxidizes the fabric, rinses carefully Water and finished according to the type of, vat substances. It behind-

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a brilliant purple color remains on the fabric.

2 to 3 g of sodium hydrogen sulfite are added to a solution of 4.00 g of benzimidazole-1,1'-binaphthyl-4,4 ^f , 5 »5 ^l » 8.8 ^l -hexacarboxylic acid-N-cyclotiexylimide in 100 ml of 5% sodium hydroxide solution and holds at a temperature of 80 ⁰ G for about 1 hour. The solution of the leuco compound is oxidized by blowing through this air for about two hours. The precipitate is filtered off, washed with 1% sodium carbonate solution, then with water and dried. 2.62 g (76.2 percent by weight) of benzimidazole-3,4,9,1O-perylenetetracarboxylic acid N-cyclohexylimide are obtained.

Found,%: N 7.85; 7.70. G ₃₆ H ₂₃ N ₃ O ₃ .

Calculated,%: N 7.72.

Example 2 »

2.00 g (0.0036 mol) of the benzimidazole-1,1'-binaphthy1-4,4 ', 5,5', 8,8'-hexacarboxylic acid anhydrides obtained according to Example 1 are suspended in 15 ml of dimethylformamide, 7, 00 g of p-bromoaniline and heated to reflux at a temperature of 153 ° C for two hours. After cooling, 5 nil water is added, the envy is filtered off, washed with 60% aqueous dimethylformamide and dried. This gives 2.00 g (78.2 weight percent) benzimidazole-1,1 ^{f-binaphthyl-4,4} ', 5,5', 8,8 ^f -hexakarbonsäure-N- (4-bromophenyl) imide. It is crystallized from acetic anhydride.

Found, %: Br 11.00; 11.28.

Calculated,%: Br 11.28.

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The compound obtained is used for dyeing and Printing of textile materials analogous to that described in example 1 «

Benzimidazole-3 »4.9» 10-perylenetetracarboxylic acid-N- (4-bromophenyl) imide is obtained analogous to that described in Example 1 in a yield of 70 percent by weight.

Found,%: Κ 6.85; 6.90. C ₃₆ H ₁₀ BrIi ₃ O-.

Calculated,%: N 6.80.

Example 3 »

2.00 g (0.0036 mol) of benzimidazole-1,1 ^f -binaphthyl-4,4.5 »5 '» 8,8'-hexacarboxylic acid anhydride, obtained according to Example 1 and 1, are placed in 40 ml of glacial acetic acid , 50 g (0.0105 ωοΐ) 4-chloro-1,2-phenylenediamine and heated to reflux for 6 hours, cooled, the precipitate filtered off, washed with water and dried. 2.03 g (83.3 Percent by weight) 5 ⁿ (6 ^H ) -chlorodibenzimidazole-1 _f 1'-binaphthyl-4,4 ^l , 5f5 ^t -8,8'-hexacarboxylic acid. The compound obtained is crystallized from 1% :. Sodium Bicarbonate Solution · Found, %: Cl 5.30; 5.27; N 8.28; 8.50.

Calculated, % i Cl 5.36; N 8.48.

The dyeing and printing using the compounds obtained is carried out analogously to Example 1.

Analogous to that described in Example 1 is ma n 5 · '(6 · ^f) -chloro-3,4,9,10-dibenzimidazole perylente tr akarb oic acid in a yield of 75 percent by weight.

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ORIGINALINSPECTED

Found, %% Cl 6.25; 6.30; N 9.75} 9.80.

Calculated, % x Cl 6.21; N 9.81.

Example 4.

2.00 g (0.0036 mol) of benzimidazole-i ^ '- binaphthyl ^^ ¹ ^^ ¹ -d _? 8'-hexacarboxylic anhydride, obtained according to Example 1, heated to reflux, held for two hours, filtered off, dried and obtained 1.50 g (75 percent by weight) of benzimidazole-1,1'-binaphthyl-4,4 ¹ , 5 * 5 ', ö ^' - hexacarboximide.

The compound obtained is crystallized from dimethylformamide

Found, %: N 7 »63; 7.68. C ₃₂ H ₁₅ N ₃ O ₇ .

Calculated,%: N 7.59.

The dyeing and printing using the compound obtained is carried out analogously to Example 1.

Benzimidazole-3 »4.9» 10-perylenetetracarboximide is obtained analogously to that described in Example 1 in a yield of 96.0 percent by weight

Found, % i Έ 9.00; 9.10. C ₃₀ H ₁₃ N ₃ O ₃ .

Calculated, % i N 9.07

Example 5 »

An aqueous suspension of 5 »57 g (0.01 mol) of benzimidazole-1,1» -binaphthyl-4,4 ¹ , 5.5 *, 8.8 ^f -hexacarboxylic anhydride, obtained according to Example "1, is added 1, 3 ml (0.012 mol)

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m-toluidine and lasts for 10 hours. The precipitate is filtered off, dissolved in 30 ml of 1% strength alkali solution, then acidified with concentrated hydrochloric acid. 4.50 g (70 percent by weight) of benzimidazole-1,1'-binaphthyl-4,4 ¹ »5.5 ', 8th , 8 ^l -hexacarboxylic acid-N- (3-tolyl) imide. It is crystallized from acetic anhydride.

Found, % in N 6.42; 6.45. ^G ^ ^E 2 ^/ \ ^S 3 ° 7 ' Calculated,%: N 6.52 *

The dyeing and printing using the compound obtained is carried out analogously to Example 1.

Benzimidazole-3,4,9 »10-perylene-tetracarboxylic acid-N- (3-tolyl) imide is obtained analogously to that described in Example 1 in a yield of 87 »1 percent by weight.

Found,%: N 7.07; 6.79. C-oH ^ oNq ⁰ * - Calculated,%: N 7 »59 *

Example 6.

A suspension of 5.57 S (0.01 mol) of benzimidazole-1.1 ^l -binaphthyl-4 _f 4 ^l , 5 »5 ^l » 8.8 ^l -hexacarboxylic anhydride, obtained according to Example 1, is added to water at a temperature of 20 ⁰ C. 1.48 g (0.012 mole) of p-xylidine to Bückfluß and heated to 10 hours. The precipitate is filtered off, dissolved in 30 ml of 1% strength solution of sodium hydroxide and acidified with concentrated hydrochloric acid. The precipitate is filtered off, washed with water and dried.

4.28 g (65 percent by weight) of benzimidazole -1,1'-binaphthyl-4,4 ♦, 5,5 *, 8,8 »-hexacarboxylic acid-N- (2,4-dimethylphenyl) imide, which is crystallized from dimethylformamide

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ORIGINAL INSPECTED

Found, % t N 6.28; 6.30. C ₄₀ H ₂ -N ₃ O ₇ .

Calculated,%: N 6.38.

Benzimidazole-3,4,9i1O-perylenetetracarboxylic acid-N- (2,4-dimethylphenyl) imide is obtained analogously to that described in Example 1 in a yield of 85.0 percent by weight.

Found, % t N 7.45; 7,35- C ₃₀ H ₂₁ N ₃ O _3.

Calculated,%: N 7.40.

Example 7 »

12.05 g (0.023 mol) 92% 1,1'-binaphthyl-4,4 ', 5,5', ö, 8'-hexacarboxylic acid and 11.2 g of caustic potash are dissolved in 75 ml of water on, heat to simmering and hold for 30 minutes.

17.5 g of sodium chloride, 3.56 g (0.025 mol) of 4-chloro-12-phenylenediamine are added, the mixture is acidified to a pH of 6.5 with 30% strength aqueous aqueous acid solution, and the mixture is kept at 108 ° for 15 hours C and a pH of 6.5 to 6.8. The older pH is maintained by adding 15% hydrochloric acid. It is then made alkaline to a pH of 9.3, the dichlorodibenaiaidaaol- 1,1'-binaphthyl-4,4 ', 5,5', 8,8 ^f -hexacarboxylic acid is filtered off and the filtrate is separated off by acidification with acetic acid the 5 "-chlorobenzimidazole-1,1'-binaphthyl-4,4 ·, 5, 5 ', 8» 8 ^t -nexacarboxylic acid anhydride in an amount of 4.88 g (35 percent by weight).

Found, %% C 64.77; 64.89; H 2.66; 2.66; N 4.75; 4.90. C ₃₂ H ₁₃ ClN ₂ O ₀ .

Calculated C 65.53; H 2.23; N 4.76.

Found, % i Cl 6.09; 6.10. Calculated,%; 6.09.

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4.68 g (0.00334 mol) of 5 "-chlorobenzimidazole-1,1'-binaphthyl-4,4 ·, 5.5 ·, Ö, Ö'-hexacarboxylic acid anhydride are introduced into 34 ml of butylamine, the mixture is heated to reflux and Lasts 3 hours. The reaction mass is then cooled and poured onto 73 inl of 15% hydrochloric acid. The precipitate which has separated out is filtered off, dried and obtained .4.90 g (93%) 5 "(6 ^M ) - -Chlorobenzimidazole- 1,1'-binaphthyl-4,4 ', 5 »5' ♦ β, ü'-hexacarboxylic acid-N-butylimide. After recrystallization from dimethylformamide:

Found,%: N 5.47; 5.50. O ₃₆ H ₂₂ GlN ₃ O ₇

Calculated, %; N 5.38.

The inking and printing using the obtained Connection is made in the same way as in example 1.

Analogously to that described in Example 1, 5 "(6") -chlorobenzimidazole-3,4,9,1O-perylenetetracarboxylic acid is obtained -N-bitylimide in a yield of 95 percent by weight.

Found,%: N 7.60; 7.65. Gl 6.42; 6.45. G ₃₈ H ₂₀ GlN ₃ O ₃ .

Calculated,%: N 7.58; Cl 6.40.

Example 8.

2.00 g (0.0036 mol) of benzimidazole-1,1 ^f -binaphthyl-4,4 *, 5,5 * ^, S'-hexacarboxylic anhydride, obtained according to Example 1, are placed in 14 ml of butylamine and heated Reflux 3 hours. The reaction mass is cooled and poured into 30 dlL of 15% strength hydrochloric acid. The deposited precipitate is filtered off, dried and 2.55 g is obtained

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(95 percent by weight) benzimidazole-1,1'-binaphthyl-4,4 ', 5,5 ¹ -8,8'-hexacarboxylic acid-N-butyliiiiid. It is converted from dimethylformamide.

Found, % t 5.70; 5.62. C ₃₅ H ₂ -NO ₇ .

Calculated,%: K 5.64.

The dyeing and printing using the compound obtained is carried out analogously to Example 1.

Benzimidazole-3,4,9 »10-perylenetetracarboxylic acid-N-butylimide is obtained analogously to that described in Example 1 in a yield of 95 percent by weight.

Found, % t N 7.79; ö, 10. C ₃₄ H ₂₁ N ₂ O ₃ .

Calculated, %% N 8.09.

Example 9 «

12.05 g (0.023 mol) of 92% strength 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 lasts 30 minutes. 17 »5 6 sodium chloride and 3.05 g ^ -Methyl-i ^ -phenylenediamine are added, acidified with 15% hydrochloric acid to a pH of 6.8, held at 108 ⁰ C and pH 6 for 15 hours, 8th. The pH is maintained by adding 15% hydrochloric acid. Then basified to a pH of 9.5, filtered Dimethyldibenzimidazol-1,1-binaphthyl-4,4 ^1, 5 * 5 * | 8,8' hexakarbon acid and separates from the filtrate by acidification with acetic acid ^lf 5 (6 ^H) -Methylbenzimidazol ^{1,1-f-binaphthyl-4,4} ', 5,5 * - 8,8'-hexakarbonsäureanhydrid in an amount of 5 »49 g (37» 3 weight per cent) ·

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Found, % i C 69.52; 69.60; H 2 _t ? 7i 2.70; N 4.90;

4.97. G ₃ ^ ₁₆ If ₂ O ₈

Calculated,%: G 69i72; H 2.84; N 4.93

Then one brings 5.49 g (0.0903 mol) 5 "(6") -Methylbenzimidazol-1,1'-binaplithyl-4,4 ¹ , 3 * 5 * , 8,8 ^f -hexacarboxylic anhydride in 28 ml p- Phenetidine, kept at a temperature of 150 ° C for two hours, cooled and poured into 85 ml of 15% hydrochloric acid. The deposited precipitate is filtered off, washed with water and dried. 6.73 S (91 percent by weight) 5 "(6 ^M ) -methylbenzimidazole-1,1 ^f -binaphthyl-4» 4 ^f , 5 »5 '» 8,8'-hexacarboxylic acid-N (4-ethoxyphenyl) - imide, which is crystallized from acetic anhydride · Found, % ·. N 6.03; 6.15. C ₄₁ H ₂₅ N ₃ O ₀ .

Calculated,%: N 6.11.

The dyeing and printing using the compound obtained is carried out analogously to Example 1.

Analogously to that described in Example 1, 5 "(6") methylbenzimidazole-3,4,9,1O-perylenetetracarboxylic acid is obtained -N-4-ethoxyphenylimide in a yield of 80 percent by weight.

Found,%: N 6.85; 7 »00; C ₃ UH ₂₃ N ₃ O ₄ .

Calculated, %: N 7, .03

Example 10.

The process is carried out analogously to Example 9, man however, leads to the first condensation with 4-ethyl-1,2-phenylenediamine by.

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5 "(6") ~ ethylbenzimidazole-1,1'-binaphthyl- -4.4 *, 5.5 '» ^{Ö.8 f} -hexacarboxylic acid-N- (4-ethoxyphenyl) imide · N 6.05 found ; 6.01 · O ₄₂ H ₂₇ N ₃ Og.

Calculated, % s N 5 * 99

The dyeing and printing are carried out in the same way as in Example 1.

Analogously to Example 1, 5 ^lf (6 ") -ethylbenzimidazole-3,4,9» 10-perylenetetracarboxylic acid-N- (4-ethoxyphenyl) -imide are obtained in a yield of 80 percent by weight. Found, % t N 6.90; 6.95 · ^ ο ^ Λ ⁰ / ^ Calculated,% s N 6.87.

Example 11 «

The process is carried out analogously to Example 7, man however, leads to the first condensation with 4-bromo-1,2-phenylenediamine by.

The dyeing and printing are carried out in the same way as in Example 1,

Analogously to Example 1, 5 "(6") ~ bromobenzimidazole-3i4 »9i10-perylene-tetracarboxylic acid butylimide is obtained in a yield of 90.0 percent by weight.

Found, % t N 7.25; 7,115; Br 13.25; 13.30. C ₃₄ H ₂₀ BrN ₃ O ₃ .

Calculated, %; N 7.02; Br 13.35.

Example 12.

2.00 g (0.0036 mol) of benzimidazoles, 1'-binaphthyl-4,4 ¹ -5,5 ', 8,8'-hexacarboxylic acid anhydride, obtained according to Example 1, are placed in 40 ml of 25% strength aqueous solution of methylamine , one, heated to reflux, held for two hours, filtered off and dried. 1.64 g (80%) of benzimidazole-1,1 ^f -bi-

Q300A7 / 0885

naphthyl-4,4 ', 515 ¹ JU ₁ O ¹ -hexacarboxylic acid eN-methylimide. The compound obtained is crystallized from acetic anhydride.

Rounded, % in N 7.35; 7.40. C ₃₃ H ₁₇ N ₃ O ₇ .

Calculated,% s ET 7.40.

The dyeing and printing are carried out in the same way as in Example 1.

Benzimidazole-3,4,9,10- is obtained analogously to Example 1 -perylenetetracarboxylic acid-N-methylimide in a yield of 97.0 percent by weight.

Found, % t N 8.9Oj 8.85. G ₃₁ H ₁₅ N ₃ O ₃ .

Calculated,%: Ή 8.81.

- / '0 30047/0885

Claims (4)

SHIP ν. FÜNER STRtHL SCHÜBEL-HOPF EBBINGHAUS FINCK MARIAHILFPLATZ 2 Λ 3, MDNCHEN BO POSTAL ADDRESS: POST BOX 65 0160, D-BOOO MDNCHEN QB Grlgorij Nikolaevitsch Voroschcov Natalia Nikolaevna Masanova NikolaJ Borisovich Feldbljum Vasilij Ivanovitsch Alekseev Vadim Alekseevitsch Schigalevski ^ Georgij Georgievitsch Solomatin Olga Igorevna Schulepova Galina Georgievna Chaitun née Zezikova Nadezhda Vladimirovna Gordeeva. born Tschernjavaja SO PROFESSIONAL REPRESENTATIVE BEFORE THE EUROPEAN PATENT OFFICE KARL LUDWIQ SCHIFF (1O64-1Q78) DIPL..CHEM, DR. ALEXANDER V. FÜNER DIPL. INQ. PETER STREHL DIPL. CHEM. DR. URSULA SCHÜBEL-HOPF DIPL. INQ. DIETER EBBINGHAUS DR. INQ. DIETER FINCK TELEPHONE (O8B) 4B9OB4 TELEX B-aaoeB AURO D TELEQRAMS auromarcpat Munich DEA-21099 May 9, 1980 1,1 «-ßINAHiTHYL-4,4 ', 5,5', 0, S'-HEXAEARBONSACID DERIVATIVES, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE FOR
SYOTHESIS OF ASYMMETRIC 3,4,9,10-HERYLENTETRACARBONIC ACID DERIVATIVES AND FOR DYING AND PRINTING TEXTILE FABRICS PATENT CLAIM (Ti 1,1'-binaphthyl-4 _f 1 ^l , 5.5 * ₉ H, 8 '-liexakarbonsäxire derivatives, characterized in that they have the following general formula COOH UODC 030047/0885 where E ,. stands for hydrogen, halogen, alkyl, for X - oxygen, Y stands for hydrogen, alkyl, cycloalkyl, aryl, which contains at least one substituent such as halogen, alkyl, alkoxy group, for X = nitrogen, Y stands for 7) (II) ι where E _{2 is} hydrogen, halogen, alkyl, where Y and X are linked to one another and form an ßenzimidazole ring. 2. Process for the preparation of 1,1'-binaphthy 1-4,4 -'- ^l 5i5'ö, 8'-iiexakarboxylic acid derivatives according to claim 1, characterized in that one 1) the 1.1 ^l - ± JinaphT; hyl-4.4 ^t , 5.5 ', οίβ'-hexacarboxylic acid anhydride treated with potassium hydroxide or sodium hydroxide, 2) the hexasodium salt of 1,1'-binaphthyl-4,4 ', 5,5' »8,8'-hexacarboxylic acid obtained in step (1) with boiling at a pH of 6.3 to 6.8, which can be achieved by adding a Mineral or organic acid is maintained with ortho-phenylenediamines of the general formula III, where E _{1 is} hydrogen, halogen, alkyl, condensed, 3) the benzimidazole-1,1'-binaphthyl-4 ₁ 4 * _t 5t5 * »& * & * -hexakarbonsäureannyarid of the general formula obtained in sture (2) 0300A7 / 0885 HOOG IV. wherein R ,. represents hydrogen, halogen, alkyl, separates and with an amine of the general formula S ~ - KH «, in which R., for hydrogen, alkyl, cycloalkyl, aryl, the at least contains a substituent such as ijalogen, alkyl, alkoxy group, or with ortho-phenylenediamines of the general formula V. where R, - is hydrogen, halogen, alkyl, condensed, wherein the condensation is carried out in an excess of said amine, in water or an organic solvent; will, 4) isolate the final product. 3. Process for the preparation of 1,1'-binaphthy1-4,4'-i? i5 '»6,8' -hexacarboxylic acid derivatives according to Claim 2, characterized in that the isolation des benzimidazole-1,1'-binaphthyl-4,4 ', 5,5 *, d, 6'-hexakarbon- 030047/0885 ORIGINAL INSPECTED acid anhydride of the general formula IV by alkalizing the mass is carried out to a pH of 9.0 to 9.5. 4. Process for the production of asymmetric 3,4,9,10- -Perylenetetracarboxylic acid-.Uerivate, thus marked refuses that one 1) 1,1-binaphthyl-4,4 ', 5,5 *, 8,8'-hexacarboxylic acid deri- vate according to claim 1, which have the general formula I, with a reducing agent such as sodium hydrogen sulfite or Rongalit, treated in an alkaline medium, 2) oxidizes the compounds obtained in step (1), 3) the mentioned asymmetric derivatives of the general M nen i'ormel N 0 = C VI wherein E ^ is hydrogen, halogen, alkyl; where X = oxygen Y is hydrogen, alkyl, Cyc Io alkyl, aryl, which has at least one substituent such as halogen, alkyl, alkoxy group contains, means; where X = nitrogen Y for wherein R _{2 is} hydrogen, halogen, alkyl, where 030047/0885 ORIGiNAL INSPECTED Y and X are linked together and form a benzimidazole ring form, receive. 5. A method for dyeing textile materials, d a by ch characterized in that one 1) the material with an aqueous alkaline solution of the compounds according to claim 1, the 1,1'-binaphthyl-4,4 ¹ , -5,5 ', 8,8'-hexacarboxylic acid derivatives of the general formula I ₁ in the presence of Sodium hydrogen sulfite or rongalite as
Soaked reducing agent, 2) the dyed textile oxidizes, 3) then the asymmetric 3,4,9,10-perylenetetracarboxylic acid derivatives of formula VI. 6. Method for printing textiles, thereby marked that one 1) on the textile a printing paste containing 1,1 · -Binaphthyl-4,4 ¹ , 5, 5 ', 8,8' -hexacarboxylic acid derivatives according to claim 1 of
general formula I, an alkaline agent, a reducing agent, sodium hydrogen sulfite or rongalite, applies, 2) subjected to heat treatment, 3) oxidized, and 4) 3,4,9,10-perylenetetracarboxylic acid derivatives asymmetric thereon of formula VI. 030047/0885