CS218495B1 - Method of preparation of derivatives of the 1,1-diantrimide - Google Patents

Description

A process for preparing the Ι, Ι-dianthrimide derivatives of the general formula

wherein X denotes a benzamide group at the 4 ', 5' or 8 'position and Y denotes NHz or R8, respectively. benzamide group by reacting diaminoanthraquinone with 1-halo-benzamidoanthraquinone in an organic solvent at a temperature of 150 to 210 ° C in the presence of a copper catalyst and the resulting aminobenzainidodianthrimide, respectively. further with benzoyl chloride.

The present invention relates to a process for the preparation of se, Γ-dianthrimide derivatives used as blanks for the preparation of vat dyes from 1,4-diaminoanthraquinone or its leukoderivative, which is condensed with 1-halogen-4,5- or 3-diaminoanthraquinone. 8-Benzamidoanthraquinones.

Significant dianthrimides include, for example, 4-amino-4'-benzamido-1,1'-dianthrimide or 4-amino-5'-benzamido-1,1'-dianthrimide, which are semi-finished products for the preparation of vat dyes, referred to in the Color Index as Vat Black 27 (CI 69005) and Vat Brown 3 (CI 69015).

The vat dye referred to as Vat Black 27 can generally be prepared by two methods. Conventionally described and used process starts with Ι, Γ-dianthrimide prepared by reaction of 1-aminoanthraquinone with 1-chloranthraquinone, which is further nitrated, reduced, benzoylated and carbazolyzed.

A second possible procedure has been found in the literature only without a specific description of the embodiment. For example, U.S. Pat. No. 3,230,232, describing a method for carrying out carbazolization, discloses that 1-amino-4-benzamidoantlirachlnone can be condensed with 1-chloro-4-benzamidoanthraquinone in a solvent in the presence of copper. In vat brown known as Vat Brown 3, 1-amino-4-benzamidoanthraquinone is condensed with 1-chloro-5-benzamidoanthraquinone.

It has now been found that said dyes can be obtained more efficiently by the process of the invention. Process for the preparation of the Ι, Γ-dianthrimide derivatives of the general formula I

O

(i) where X represents a benzamide group at the 4 ', 5' or 8 'position and Y represents an NH 2 or a benzamide group, according to the invention, the compound of formula II

wherein Y is NH 2, optionally in the form of a leukoderivative, is reacted with 1-halobenzamidoanthraquinone of formula III

wherein X is as defined above and Z is Cl or Br, optionally prepared in situ, in an organic solvent at a temperature of 150 to 210 ° C in the presence of a copper catalyst, a hydrogen chloride reactant and a molar ratio of compound II or its leukoderivative to halogensamidoanthraquinone greater than or equal to 1, and the resulting 1-amino-4 ', 5' and 1-amino-4 ', 5', respectively. The 8´-benzamido-1,1'-dianthrimide of formula IV is optionally further reacted with benzoyl chloride.

The resulting benzamido or dibenzamido derivative is further cyclized to the corresponding dibenzamidocarbazole, which is a dye.

1-Halogen-4-benzamidoanthraquinone, for example 1-chloro-4-benzoylaminoanthraquinone, can be prepared either by benzoylating 1-chloro-4-aminoanthraquinone or by chlorination of 1-benzoylaminoanthraquinone. Thionyl chloride, sulfuryl chloride or chlorine are useful as chlorinating agents for 1-aminoanthraquinone or 1-benzoylaminoanthraquinone, the amino group being protected, for example, by the formation of dimethylformamidinium complex. Similarly, bromo derivatives can be prepared.

The process according to the invention brings the following advantages:

- eliminates the need for nitro groups reduction by either a health and ecologically unsuitable sulphide or scarce reducing sugars in vat black - eliminates the need to prepare monobenzoylated diaminoanthraquinones, which does not run uniformly and is accompanied by difficult filterability of the reaction mixture reduce the laboriousness of production - starting material is clizarine and not more difficult to access anthraquinone-1-sulfonic acid, which requires catalytic presence of mercury for its preparation.

The reaction is carried out in an organic solvent medium in the presence of a copper catalyst and reagents binding reaction hydrogen chloride at temperatures of 150 to 210 ° C, the molar ratio of 1,4-diaminoanthraquinone to 1-halogen-4,5 or 1,4-diaminoanthraquinone used. The 8-benzamidoanthraquinone is greater than or equal to 1, preferably 1 to 1.3.

Copper powder, cuprous oxide, cuprous acetate and optionally other salts may be used as the copper catalyst, the amount of which may be from 5 to 20 mol%, per 1-halogen-4,5 or 1-halogen. 8-Benzamidoanthraquinone.

Sodium or potassium carbonates, bicarbonates or acetates, or alkaline earth, magnesium and calcium koy oxides may be used as reagents for binding the reaction hydrogen chloride in a 0.5- to 7-fold molar excess.

The reaction medium is composed of inert organic solvents of higher boiling point, such as nitrobenzene, o-nitrotoluene, o-dichlorobenzene and the like, preferably operating with a small volume of solvent.

The preparation of the starting 1-halogen-4- (or 5 or 8-) benzamidoanthraquinones in which halogen is chlorine or bromine can be carried out in such a way that condensation of 1,4-diaminoanthraquinone can be coupled without isolation of 1-halogen-4- (or 5- or 8-) benzamidoanthraquinones, thereby further enhancing the convenience of the process. Similarly, without isolation of the dlanthrimide of formula (I), benzoylation of the free amino group can be carried out directly in the reaction medium. Both benzoylation and carbazolization are carried out by conventional methods

The principle of the invention is illustrated in the following examples (percentages are by weight):

Example 1

500 g of nitrobenzene, 36 g of 1-chloro-46 are placed in a reaction vessel equipped with a stirrer, a descending condenser and a thermometer.

-benzoylaminoanthraquinone (92%), 28 g 1,4-diaminoanthraquinone (96%), 15 g anhydrous soda, 5 g fused sodium acetate and 1 g copper bronze. The reaction mixture is heated to 200-205 ° C over 3 hours and maintained for 10 hours until the starting 1-chloro-4-benzoylaminoanthraquinone disappears. The reaction mixture is cooled to 80 DEG C., diluted with 450 g of ethanol and the product is filtered off with suction, washed with ethanol and dried. 53 g of a product suitable for further processing into a black vat dye are obtained.

Example 2

Reaction mixture 500 g o-dichlorobenzene,

40.5 g of 1-bromo-4-benzoyl-aminoanthraquinone (95% content), 28 g of 1,4-diaminoanthraquinone (96% content), 25 g of sodium bicarbonate and 3 g of copper acetate are heated to boiling for 8 hours. After treatment analogously to Example 1, 52 g of product are obtained, from which a vat dye is prepared by benzoisolation in sulfuric acid, coloring 2 to 3 degrees redder than the Ostanthrene olive type R.

Example 3

According to the procedure of Example 1, 4-amino-5-benzamido-1,1'-dianthrimide in an amount of 28 g of 1,4-diaminoanthraquinone and 36.5 g of 1-chloro-5-benzoylaminoanthraquinone is prepared in an amount of

52.5 g, giving benzylation and carbazolization a vat brown of suitable color.

Example 4

In 80 g of nitrobenzene, 26 g of 1-amino-4-chloroanthraquinone (prepared by chlorination of 1-aminoanthraquinone dimethylformamidium complex and decomposition of the 1-amino-4-chloroanthraquinone dimethylformamidium complex formed) are heated and heated to 100 [deg.] C. of benzoyl chloride and the suspension is heated to 125 degrees C. After 3 hours of reaction, the disappearance of the starting material is checked by chromatography and, if necessary, the reaction is completed by adding additional benzoyl chloride and heating.

Once the benzoylation is complete, 27 g of 1,4-diaminoanthraquinone, 15 g of anhydrous soda, 5 g of sodium acetate and 1 g of copper bronze are added at a temperature below 100 ° C. Condensation was performed by heating to 200 ° C for 10-14 hours according to the disappearance of 1-chloro-4-benzoylaminoanthraquinone, which was checked by thin layer chromatography. After completion of the reaction, the mixture was cooled to 100 ° C, 10 g of benzoyl chloride was added dropwise and heated to 125-130 ° C. This temperature is maintained for about 3 hours. It is then distilled off with nitrobenzene in vacuo. Carbazolization in sulfuric acid yields a vat black coloring in

218493 shade 2 to 3 degrees yellower and darker than the product obtained with intermediate insulation. The consumption of 1-aminoanthraquinone is 0.21 g per 1 g of dye in a type strength.

EXAMPLE 5 g of 1-aminoanthraquinone (97 percent) was heated to 100 DEG C. in 80 g of nitrobenzene, 15 g of benzoyl chloride was added dropwise, and the reaction was completed by heating to 165 DEG C. for 2 hours. 1 g of anhydrous aluminum chloride, 0.5 g of cuprous chloride and 25 g of sulfuryl chloride were added to the reaction mixture, and the reaction mixture was stirred at 70 [deg.] C. for 5 hours, then an additional 12.5 g of sulfuryl chloride was added. this temperature repeats.

Chlorination is complete within 12 hours. Unreacted chlorinating agent is then distilled off at an elevated temperature of 85-100 ° C, 27 g of 1,4-diaminoanthraquinone, 15 g of anhydrous soda, 5 g of sodium acetate and 1 g of copper bronze are added. The further procedure corresponds to the description given in Example 4. The prepared vat black dyeed cotton in the same shade as the product prepared according to Example 4. The consumption of the starting 1-aminoanthraquinone is 0.29 g per 1 g of commercial-type dye.

Example 6

50 g of nitrobenzene and 29 g of 1,4-leukodiaminoanthraquinone (calculated on 100% product) were charged to a reaction vessel equipped with a stirrer, descending condenser and thermometer, and heated to 130 ° C with stirring for 3 hours to distill off all the water. If the leukodiaminoanthraquinone is used in the form of an aqueous paste, it is heated with particular caution in the temperature range of 95 to 120 ° C. After addition of 0.25 g piperidine and heating to 150 ° C, this temperature is maintained for a further 1-2 hours. 36 g of 1-chloro-4-benzoylaminoanthraquinone (92% content), 15 g of anhydrous soda, 5 g of sodium acetate and 1 g of copper bronze are then introduced.

The reaction mixture was heated to 200-205 ° C over 3 hours and held for 10 hours until completion of the reaction. The reaction mixture was cooled to 100 ° C, 10 g of benzoyl chloride was added dropwise and heated to 125-130 ° C. It is maintained at this temperature for 3 hours. The nitrobenzene is distilled off with steam, the reaction mixture is filtered and the product is dried. This gives 53 g of a blank suitable for further processing into Vat Black 27 vat dye.

Example 7

The procedure of Example 6 was repeated except that instead of distilling off nitrobenzene, 4,4'-dibenzamido-1,1'-dianthrimide was isolated after benzoylation by diluting the nitrobenzene reaction mixture at 80 ° C with 450 g of ethyl alcohol and filtering the product off with suction. , washed with ethyl alcohol and dried.

Claims (1)

A process for the preparation of the 1,1'-dianthrimide derivatives of the formula I wherein X is a benzamide group at the 4 ', 5' or 8 'position and Y is NHa or a benzamide group, characterized in that the compound of formula II wherein Y is NH 2 or in the form of a leukoderivative, it is reacted with 1-halobenzamidoanthraquinone of formula III wherein X is as defined above and Z is Cl or Br, optionally prepared in situ, in an organic solvent at a temperature of 150 to 210 ° C in the presence of a copper catalyst; If the reaction of hydrogen chloride and at a molar ratio of compound II or its leukoderivative to halobenzamidoanthraquinone greater than (IV) exceeds 8'-benzamido-1,1'-dianthrimide of the formula IV, it is optionally further reacted with benzoyl chloride in molar ratio at least one.