GB1567057A

GB1567057A - Process for the manufacture of mixtures of anthraquinone compounds

Info

Publication number: GB1567057A
Application number: GB5315576A
Authority: GB
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1975-12-23
Filing date: 1976-12-20
Publication date: 1980-05-08
Also published as: BE849729A; FR2336449A1; FR2336449B1; JPS5280330A; DE2657996A1

Description

(54) PROCESS FOR THE MANUFACTURE OF MIXTURES OF ANTHRAQUINONE COMPOUNDS (71) We, CIBA GEIGY AG, a Swiss body corporate of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The invention provides a process for the manufacture of mixtures of anthraquinone compounds, the mixtures themselves and the use thereof for dyeing or printing textile material, in particular polyester material.

German patent specifications 445,269, 446,563 and 456,235 disclose processes for the manufacture of 1 ,5-dih droxyA,8-diaminoanthraquinone compounds which are arylated in 2-position, wherein 1,5-dihydroxy-4,8-diaminoanthraquinone-2 disulphonic acid is reacted in the presence of boric acid in concentrated sulphuric acid with phenols, naphthols or anisoles to yield addition products which, when they are subsequently treated with acids or alkalies, with attendant exchange of the suiphonic acid group in 2-position, are converted into the corresponding arylsubstituted compounds, and wherein the sulphonic acid group in 6-position can also be subsequently removed by reduction.Analogous reactions with thiophene and derivatives thereof are disclosed in German patent specification 1,184,878, and with chromane and similar compounds in German patent specification 1,278,639 and in DTOS 1,644,514. This reaction, viz. the arylation in ortho-position to the OH group of a 1,5-dihydroxy-4,8-diamino-anthraquinone compound, is known as the "R. E. Schmidt reaction" and is also described, for example, in "The Chemistry of Synthetic Dyes" by K. Venkataraman, Vol. III, 1970, page 407, and in "Chemie der organischen Farbstoffe" by Fritz Mayer, Vol. I, 1934, page 174.

The use of such ortho-substituted 1,5-dihydroxy-4,8-diamino-anthraquinone derivatives for dyeing polyamide fibres, cellulose esters and polyterephthalate fibres is also known from German patent specification 1,144,678 and US patent specification 3,265,460.

A radical change in the formulation of this R. E. Schmidt reaction came about through the publications of E.D. Pandhare, V.B. Patil, A.V. Rama Rao and K.

Venkataraman in the "Indian Journal of Chemistry", Vol.9(1971), pp. 1060--1063, and of M. C. Clark, T. J. Marley and P. A. Lowe in the "J. appl. Chem.

Biotechnol.", 1974, 24, pp. 343-348. With the aid of'H--NMR spectroscopy, these authors were able to prove conclusively that the arylation takes place in 3position, viz. in the ortho-position to the NH2 group of the 1,4-dihydroxy-4,8diaminoanthraquinone and not in the ortho-position to the OH group.

Such a reaction, which results in 1 ,5-dihydroxy-4,8-diamino-anthraquinone compounds, is also known from DT-OS 2,346,047.

It has now been found that the arylation of 1,5-dihydroxy-4,8diaminoanthraquinone-2-sulphonic acid or 1,5-dihydroxy-4,8diaminoanthraquinone-2,6-disulphonic acid with a mixture of compounds of phenols and/or phenol ethers which are substituted in the meta-position, or with a mixture of compounds of a phenol or phenol ether which is substituted in the metaposition and an aromatic or heterocyclic compound, under conditions of the known R. E.Schmidt reaction, viz. accompanied by the elimination of the suiphonic acid group in 2-position. results surprisingly and unexpectedly in a mixture of novel mono- and disulphonic acids one sulphonic acid group of which is in the external meta-substituted phenol radical in accordance with formula IV and can only be hydrolysed under specific conditions, whereas the other sulpho group, which is in the 6-position of the anthraquinone radical, can be reduced with alkali, by which means disperse mixtures of novel anthraquinone compounds are obtained, which are arylated in 3-position and wherein, surprisingly; the oxygen atom of the meta-substituted phenol derivative is also in the ortho-position to the C-C linkage of the phenol radical at the anthraquinone radical.In a mixture wherein the aromatic compound in accordance with formula IV represents a parasubstituted phenol radical, the oxygen atom of the phenol radical is also in the ortho-position to the C-C linkage. This reaction and the formation of an insolatable mixture of disulphonic acids is novel and, in the light of the known R. E.

Schmidt reaction, unexpected. It is also surprising that a novel mixture of disperse dyes is obtained by desuiphonation.

By means of a simple synthesis, the novel process thus makes it possible to obtain mixtures of blue disperse dyes which, compared with comparable known mixtures of dyes, have good fastness properties on, for example, polyester material.

The dyestuff mixtures of the present invention are also characterised by a good exhaustion capacity in the carrier method.

The process of the present invention for the manufacture of mixtures of anthraquinone compounds accordingly comprises reacting an anthraquinone compound of the formula III

wherein x is 1 or 2, in the presence of ortho-boric acid and concentrated sulphuric acid (96 to 100%), with a mixture of compounds of the formula IV

or with a mixture of a compound of the formula IV and a compound of the formula V H-A (V) at a temperature between 150 and +50"C, in particular between 0 and l00C, diluting the reaction mixture with water and heating it to approx. 80" to 1000C, whereby the sulphonic acid group of the compound of the formula III in 2-position is removed, and then desulphonating the resultant mixture which contains suiphonic acid groups. The reaction scheme shown hereinafter will illustrate this reaction sequence in more detail. The reaction mixture formed from the reaction of the compound of formula III with the compound mixture as defined herein is desulphonated, if x in formula III is 1, with an inorganic strong acid at a temperature between approx. 100" and 1200C by hydrolysis, to yield accordingly the mixture of compounds of the formula I or the mixture of the compounds of the formula I and II.Where x is 2 in the compound of formula III, there are two ways of desulphonating the mixture which contains sulphonic acid groups, viz. on the one hand hydrolysing the sulpho group present in the external phenol radical in 3position with an inorganic strong acid to give a mixture of monosulphonic acids with a sulphonic acid group in 6-position and then reducing this mixture with alkali to give the mixture of compounds I or I and II, or vice versa, reducing the mixture which contains sulphonic acid groups to give a mixture of monosulphonic acids, whereby the sulphonic acid group in 6-position is eliminated, and hydrolysing the mixture which contains the sulphonic acid group in the external phenol radical in 3position with a strong inorganic acid to give the mixture of compounds I or I and II.

Examples of strong inorganic acids are hydrochloric and orthophosphoric acid. However, particularly good results are obtained with concentrated sulphuric acid, in particular with a 40 to 70%, preferably 55 to 60%, aqueous sulphuric acid.

The alkaline reduction is carried out in known manner, for example with sodium hydrosulphite in ammoniacal medium or in the presence of sodium hydroxide. However, it is also possible to carry out the reduction with glucose in alkaline medium.

The following scheme will serve to illustrate the reaction course: REACTION SCHE:ME

HR? 0 0111 Mixture of: CIporr Mixture of: --- on (l\r) ,~(HOJS + or OR Z/ Mixture of: lV + H - A (V) (HO3S (III) R2 t /50311 ZI SO H BN ab bA S) IlH Xl(N 3S X ; optionally -A desulphonation by / \ (x2) desulphonation by hydrolysis (it2) / \ alkaline reduction a OH H 1 1 R (x) R.Y 2 oW 2 i rl (dh 0r i p + optionally -A re Sr C > ' m desulphonation ion desulphonation by alkaline reductiono mixture of I o g / hydrolysis H of I+II Br1I 1 )lIl)wA NO O X R RO O N I (I) 2 (1I) In the above formulae, the symbols have the following meanings: Y represents a linear or branched alkyl group of 1 to 5 carbon atoms, R represents a hydrogen atom, an unsubstituted or substituted alkyl group of 1 to 5 carbon atoms, or the cyclohexyl group, and each of R, and R2 independently represents a hydrogen atom, the methyl, ethyl or isopropyl group, and A represent an aromatic or heterocyclic radical.

An alkyl group of 1 to 5 carbon atoms represented by Y is for example the methyl group, the ethyl group, the n-propyl and iso-propyl group, the n-butyl, sec.butyl or tert.-butyl group.

R can represent an unsubstituted alkyl group in accordance with the definition of Y. However, this alkyl group can be substituted for example by CN, OH or C1-C4-alkoxy groups, or R is a radical of the formula B-Z, wherein B represents a QCH2)n or a CH2)2-0CH2)2 group in which n is 2 to 8 and Z represents a CN or COOH group.

In preferred compounds, Y represents the methyl group, R represents a hydrogen atom or the methyl group, each of R1 and R2 represents a hydrogen atom and x is 2.

The mixture of the compounds of the formula IV or the mixture of the formulae IV and V and also the final mixture of compounds of the formulae I or I and II, is in the weight ratio 1:99 to 99:1.

It will be readily understood that the starting mixture of compounds of the formulae IV or IV and V can also consist of more than two compounds within the definition of these compounds, so that the end product is also composed of correspondingly more components.

The compounds of the formula V are aromatic and heterocyclic compounds.

As examples of aromatic compounds there may be mentioned: phenol and derivatives thereof, or substituted phenols, such as those which are mono- or polysubstituted by halogen, in particulr chlorine, bromine and fluorine; by lower alkyl; by hydroxy or lower alkoxy. Substituted or unsubstituted naphthol, such as a- or B-naphthol, may also be mentioned as examples of aromatic compounds.

The heterocyclic compounds are, for example, thiophene, substituted thiophenes, such as methylthiophene, chromanes and chromenes. The following compounds have proved particularly interesting:

A particularly useful mixture consists of a 2-mixture of the compounds of the formula IV, wherein on the one hand Y represents the CH3 group and R represents a hydrogen atom, and on the other hand, each of Y and R represents the CH3 group.

From the reaction of the compound of the formula III with the mixture of the compounds of the formulae IV and V, small amounts of isomeric by-products are formed in such a way that the meta-substituted phenol derivatives (IV) are attached in the para-position to the oxygen atom to the anthraquinone structure.

In this connection, not only the mixtures of the final, desulphonated products, i.e. the disperse anthraquinone compounds of the formula I

optionally together with the compounds of the formula II

are claimed, but also the mixtures of intermediate anthraquinones which are formed prior to desulphonation having sulphonic acid groups, such as mixtures of anthraquinones of the formula

optionally together with compounds of the formula

the mixtures of anthraquinone compounds of the formula

optionally together with the compounds of the formula

and the mixtures of anthraquinone compounds of the formula

optionally together with the compounds of the formula

In all these compounds, the symbols Y, R, R1, R2 and A have the meanings initially assigned to them.

The compounds of the formulae III, IV and V are known. For example, those of the formula III, wherein x is 2, are obtained on the lines of the method described by J. Houben in "Die Anthracene und die Anthraquinone", G. Thieme Verlag, Leipzig, 1929, pp. 44748, or of the method of DT-OS 2,231,514, or of that of British patent application No. 52234/75, Serial No. 1527528. The compounds of the formula III, wherein x is 1, are obtained for example by the desulphonation of 1,5 dihydroxy-t,8-diaminoanthraquinone-2,6-disulphonic acid to give 1,5-dihydroxy4,8-diaminoanthraquinone-2-sulphonic acid in accordance with the particulars in Friedlander, Vol. 19, page 2001 (1934) or Vol. 21, page 1038(1937).

The intermediates which contain a sulphonic acid group in the metasubstituted phenol radical, and which are formed in the process of this invention prior to desulphonation to give the final compounds, are novel and their constitution has been conclusively proved by 'H--NMR and 3CNMR spectra.

These intermediates are used on the one hand by desulphonation for obtaining mixtures of disperse dyes and on the other for dyeing and printing organic material, in particular textile material, which can be dyed with acid dyes, for example natural polyamide, such as wool and silk, and synthetic polyamide.

The mixtures of novel anthraquinone compounds of the formula I or I and II which can be obtained according to the invention are blue dyes which, by themselves, or preferably in the form of aqueous suspensions, are suitable chiefly for dyeing and printing synthetic and regenerated man-made fibres, for example for dyeing and printing cellulose esters, cellulose triacetate, synthetic polyamide, polyurethane, and, in particular, linear polyester, fibres, chiefly polyethylene tetrephthalate fibres. In the exhaustion and continuous processes, dyeings of good to very good fastness properties, such as fastness to light, sublimation, thermofixing and wet treatments, are obtained on these materials. The textiles can be in any form of make-up, for example fibres or wovens.

The invention is illustrated by the following Examples, in which the parts are by weight.

Example 1.

21.5 parts of 1 ,5-dihydroxy-4,8-diaminoanthraquinone-2,6-disulphonic acid are dissolved at 450C in a solution of 21.6 parts of ortho-boric acid in 400 parts of 96% sulphuric acid. After the mixture has cooled to 50--8.OC, a mixture in the ratio of 50:50 of 6.5 parts of m-cresol and 7.3 parts of m-cresol methyl ether is added dropwise. The reaction mass is then poured into 1000 parts of ice-water and the mixture is heated for 2 hours to the boil. After the mixture has cooled, the precipitate which has formed is collected with suction and washed neutral with a 10% aqueous solution of sodium chloride.The filter residue contains a mixture composed of approx. 95% of the disulphonic acid of the formulae

and approx. 5% of the monosulphonic acid of the formulae

Without being dried, this mixture is stirred in 750 parts of water, neutralised with sodium hydroxide solution and, after addition of 40 parts of a 25% aqueous solution of ammonia, heated to 900--920C and reduced in the course of 1 hour with a 10% aqueous solution of hydrosulphite. The precipitate is collected with suction, washed neutral with water, and dried.The reaction mixture contains approx. 95% of the monosulphonic acid of the formulae

and approx. 5% of the dye of the formulae

This crude mixture is stirred in 1000 parts of a 60% solution of sulphuric acid of 1100C. After the batch has cooled, the precipitate which has formed is poured into 1000 parts of ice-water, collected with suction, washed free of acid and dried to give a very good yield of a blue powder which contains the following 4 dyes:

approx.95%

approx .5% From a finely divided aqueous dispersion, this dye mixture exhausts in reddish blue shades onto fibres and wovens made of polyethylene terephthalate and cellulose triacetate. The dyeings are of very good wet- and light-fastness.

Similarly good dye mixtures with good tinctorial properties are obtained by using mixtures of the components I and 2 listed in the following table instead of the mixture of m-cresol and m-cresol methyl ether in the ratio 50:50 used in this Example. The shades obtained on polyester textile material are indicated in the final column of the table.

Table

Example | Componcnt I Component 2 | Shade on No l I polyester 2 I 2 OH -0H blue CH3 3 | OH (3 0CH3 CI{ 4 3 tH3H II 5 AOH CH OH fi CH3 3 1 6 (;H OH OC21I5 I 6 OH \--J 3 Cll3 8 TOUCH3 l94H I.

3 0Cl13

Example Component 1 Component 2 Shade on No. Component 1 V ~ OCH3 2 polyester 9 C\ SOCH, CH3' 011 blue 10 3 > Cz O f 3 2 CH'3 OH 11011 ~ 011 II CR3 12 OH 11 CR3 ClI3 13 ≈> Ull OH 1 CR3 14 C OH (%$i)lj)CC1111122 rl CR3 CH, CI13 > OR Q%/ycII 2C112-01 blue 17 C1 112 CH3 C1 112 CII Example 18.

The procedure of Example 1 is repeated using a mixture of 4.3 parts of mcresol, 4.9 parts of m-cresol methyl ether and 3.8 parts of phenol instead of the mixture of m-cresol and m-cresol methyl ether, to yield as intermediate a mixture consisting of the disulphonic acids of the formulae

and the monosulphonic acids of the formulae

Removal of the sulpho groups with sodium hydrosulphite and 60% sulphuric acid as indicated in Example 1 gives the following dye mixture in very good yield: approx. 30% of the dye of the formula

approx. 30% of the dye of the formula

approx. 35% of the dye of the formula

and approx. 5% of the dyes of the formulae

From a finely divided aqueous dispersion, this dye mixture exhausts onto polyester fibres in blue shades of very good fastness properties.

Example 19.

1 part of the mixture of disperse dyes obtained in Example I is ground wet with 2 parts of a 50% aqueous solution of the sodium salt of diphenylmethanedisulphonic acid and dried.

This dye preparation is stirred with 40 parts of a 10% aqueous solution of the sodium salt of N-benzyl-y-heptadecylbenzimidazole-disulphonic acid and 4 parts of a 40% solution of ascetic acid are added. A dyebath of 4000 parts is prepared therefrom by dilution with water.

100 parts of a cleansed polyester fabric is put into this bath at 500 C, the temperature is raised in the course of half an hour to 1200--1300C and dyeing is carried out for 1 hour in a closed vessel at this temperature. The fabric is subsequently thoroughly rinsed. A strong, reddish blue dyeing of excellent fastness to light and sublimation is obtained.

Some of the individual anthraquinones of formula I, and the method of making them, as claimed per se in our copending application as (Serial No. 1532048) 52138/76.

WHAT WE CLAIM IS: 1. A process for the manufacture of a mixture of anthraquinone compounds containing at least one compound of the formula I

wherein Y represents a linear or branched alkyl group of 1 to 5 carbon atoms, R represents a hydrogen atom, an unsubstituted or substituted alkyl group of 1 to 5 carbon atoms, or the cyclohexyl group, each of R, and R2 independently represents a hydrogen atom, the methyl, ethyl or isopropyl group, and optionally at least one compound of the formula II

wherein R, and R2 are as defined in formula I and A represents an aromatic or heterocyclic radical, which process comprises reacting an anthraquinone compound of the formula III

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. and approx. 5% of the dyes of the formulae From a finely divided aqueous dispersion, this dye mixture exhausts onto polyester fibres in blue shades of very good fastness properties. Example 19.

wherein R, and R2 are as defined in formula (I) and x is 1 or 2, in the presence of ortho-boric acid and concentrated sulphuric acid having a concentration of at least 96% by weight, with a mixture of compounds of the formula IV

wherein R and Y are as defined in formula (I), or with a mixture of compounds of the formula IV and of the formula V H-A (V) wherein A is as defined in formula (II) at a temperature between-150C and 50"C., diluting the reaction mixture with water and heating it to approximately 80" to 1000 C. whereby the sulphonic acid group of the compound of formula (III) in 2-position is removed and desulphonating the resultant mixture which contains sulphonic acid groups.

2. A process according to claim 1, wherein the desulphonation of the mixture containing sulphonic acid groups obtained from the reaction of the compound of the formula III with the mixture of the compounds of the formula IV or IV and V is carried out by hydrolysis with a strong inorganic acid, at 1000 to 1200C. and by a reduction with alkali or vice versa.

3. A process according to claim I or 2, wherein the mixture of the formula IV or IV and V is used in the weight ratio of 1:99 to 99:1.

4. A process according to claim 1, 2 or 3, which comprises the use of a compound of the formula IV, wherein Y represents the methyl group and R represents a hydrogen atom or the methyl group.

5. A process according to claim 1, 2, 3 or 4, which comprises the use of one of the following compounds as compound of the formula V:

6. A process according to claim 1, wherein the compound of the formula III is reacted with mixture of two compounds of the formula IV.

7. A process according to claim 1, substantially as herein described.

8. A mixture of anthraquinones comprising at least one compound of formula I and optionally at least one compound of formula II, as defined in claim 1, when manufactured by a process according to any preceding claim.

9. A mixture of anthraquinone compounds containing sulphonic acid groups, when prepared in the course of a process according to any of claims 1 to 7 prior to the final desulphonation.

10. A mixture of anthraquinone compounds of formula I, or of anthraquinone compounds of formulae I and II,

wherein Y represents a linear or branched alkyl group of 1 to 5 carbon atoms, R represents a hydrogen atom, an unsubstituted or substituted alkyl group of 1 to 5 carbon atoms or the cyclohexyl group, each of R, and R2 independently represents a hydrogen atom, the methyl, ethyl or isopropyl group, and A represents an aromatic or heterocyclic radical.

11. A mixture of anthraquinone compounds of the formulae

and optionally

12.A mixture of anthraquinone compounds of the formulae

and optionally

wherein Y represents a linear or branched alkyl group of 1 to 5 carbon atoms, R represents a hydrogen atom, an unsubstituted or substituted alkyl group of 1 to 5 carbon atoms or the cyclohexyl group, each of R1 and R2 independently represents a hydrogen atom, the methyl, ethyl or isopropyl group, and A represents an aromatic or heterocyclic radical

13.A mixture of anthraquinone compounds of the formulae

and optionally

14. A mixture of anthraquinone compounds according to claim 10, wherein the weight ratio in the mixture of the compounds of the formula I by themselves or in admixture with the compound of the formula II is 1:99 to 99:1.

15. A mixture of anthraquinone compounds according to any of claims 10-14.

wherein each anthraquinone is one of those identified herein.

16. A process for dyeing or printing textile materials, with anthraquinone dyestuffs, in which there is used as dyestuff a mixture according to any of claims 8 or 10.

17. A process according to claim 16 in which polyester materials are dyed.

18. The textile material, dyed and printed with a mixture of anthraquinone compounds according to claim 8 or 10.

19. Textile material dyed by the process of claim 16.

20. Polyester textile dyed by the process of claim 17.