DE1129643B - Process for the preparation of anthraquinone dyes - Google Patents

Description

It has been found that compounds of the general formula

A-HN-OC-R ₁ -CR ₂ -CO-NH-B

Cl

Cl

in which A and B represent radicals of viable anthraquinone compounds, of which at least one is a 1-anthraquinonyl radical which is unsubstituted in the 4-position but can optionally be otherwise substituted, and in which R ₁ and R _{2 are} 4 ', 4 "-diphenylene radicals, valuable Vat dyes are characterized by the good fastness properties of the dyeings produced therewith, in particular by good to very good fastness properties to light, chlorine, washing and soda boiling.

The new dyes are obtained by adding 1 mol of a dicarboxylic acid of the general formula to a process for the preparation
of anthraquinone dyes

Applicant:
JRGeigy AG, Basel (Switzerland)

Representative: Dr. F. Zumstein
and Dipl.-Chem. Dr. rer. nat. E. Assmann,
Patent Attorneys, Munich 2, Bräuhausstr. 4th

Claimed priority:
Switzerland of May 4, 1957 (No. 45 722)

Dr. Hans-Rudolf Schwander, Basel (Switzerland),
has been named as the inventor

HOOC-R ₁ -CR ₂ -COOH (II)

Cl

Cl

wherein R ₁ and R _{2 have} the meanings given above, expediently in the form of their reactive descendants, allowed to act on 2 moles of the same or 1 mole each of two different aminoanthracbinone compounds. According to the definition, at least 1 mole of a 1-aminoanthraquinone with a free 4-position must be used.

The compounds of the general formula II are most conveniently condensed with the aminoanthraquinone compounds in the form of their acid halides. The condensation is carried out under conditions such as are customary in the acylation of aminoanthraquinones with higher molecular weight carboxylic acid halides. According to the definition, 2 mol of the same or 1 mol of two different aminoanthraquinone compounds are used. In the first case, it is advantageous to work in a single stage. In the second case, more uniform products are obtained with a two-stage process. One heated z. B. the dicarboxylic acid halides with the aminoantraquinones in an anhydrous organic solvent, for example in dichlorobenzene, trichlorobenzene or nitrobenzene, and advantageously in the presence of an acid-binding agent. As the latter, z. B. alkali and alkaline earth carbonates or oxides or tertiary nitrogen bases, such as pyridine, picolines, lutidines, dialkylanilines or mixtures of such substances, are used. When using 2 moles of the same aminoanthraquinone compound, the reaction mixture is heated to higher temperatures, e.g. B. to 120 to 170 ^° C. If 1 mole of two different aminoanthraquinones are used, then one of the amino compounds is condensed, advantageously the more easily soluble one with the dicarboxylic acid halide at a slightly elevated temperature, e.g. B. 25 to 40 ⁰ C, to the monoamide and then combines the same at 120 to 17O ⁰ C with the other aminoanthrachmone compound.

Suitable dicarboxylic acids or their reactive derivatives are those for which the symbols R ₁ and R ₂ in the general formula II are optionally substituted, such as. B. halogenated, alkylated or alkoxylated 4,4'-diphenyl radicals.

For condensation with the functional derivatives of dicarboxylic acids of the general formula II aminoanthraquinones come in Beträcht, which for example, by halogen, ^nitro,: substituted hydroxy, alkoxy, alkylcarboxyl, alkyl, alkylsulfone, sulfonamide, alkylamino and acylamino and / or with heterocyclic rings, such as. B. oxazole, thiazole, imidazole, pyrazole, thiophene, pyridine, pyrimidine, pyrazine, pyridazine, thioxanthone, carbazole and acridone rings are condensed.

209 580/365

1-Aminoanthraquinones, which in the 4-position have no Containing substituents are, for. B. the 1-aminoanthraquinone itself, also the l-amino-6-chloroanthraquinone, the l-amino-ö ^ -dichloranthraquinone, the l-amino-o-chloro-V-bromoanthraquinone, thel-aminoanthraquinone ^ -carboxylic acid ethyl ester, 1-aminoanthraquinone-6-sulfonic acid dimethylamide, 1,5-diaminoanthraquinone, 1-amino - 5 - acetylamino anthraquinone, l-amino-5-cinnamoylaminoanthraquinone, the l-amino-5-benzoylaminoanthraquinone, the 1-amino-S-benzoylamino-S-methoxyanthraquinone, l-Amino-5- (2'- or 4'-chlorobenzoylamino) -anthraquinone, l-Amina-5- (2 ', 4'-dichlorobenzoylamino) -anthraquinone, l-amino-5- (3'-chloro-4'-bromobenzoylamino) anthraquinone, 1-amino-5,8 - bis - (4 '- chlorobenzoylamino) - anthraquinone, the 1 - amino - 5 - (4' - methoxybenzoylamino) - anthraquinone, dasl-Amino-5- (3'-trifluoromethylbenzoylamino) -anthraquinone, the l-amino-5- (3'- or 4'-methylsulfonylbenzoylamino) -anthraquinone, the l-amino-5 - (/ J-pyridoylamino) -anthraquinone, the l-amino-5 - (/ 5-anthraquinonoylamino) -anthraquinone, the 1-amino-5,2 '- (6' - dimethylsuifamidnaphthyl) - aminoanthraquinone carbazole, the 4-amino-l, 9-anthrapyrimidine, the 5 - aminoanthraquinone - 2 ', 4' - dichloro - 2,1 (N): Γ, 2 '- (N) -benzolacridone and the aminobenzanthronylaminoanthraquinone acridine of the formula

== O derivatives of dicarboxylic acids which can be used according to the invention are aminoanthraquinones which are at most further substituted by halogen atoms and / or aroylamino groups. Of these, in turn, those in which the two anthraquinone radicals contain the amino group in the 1-position and whose 4-position is free are particularly valuable. A modification of the production process for the new dyes consists in replacing the compounds of the formula II with those of the general formula

HOOC-R ₁ -CR ₂ -COOH (III) Cl-C-Cl

Cl

to use. In this formula, R ₁ and R _{2 have} the same meanings as in general formula II. One works under similar conditions and here, too, the reactive derivatives of these acids are used with advantage. In the resulting trichloroethane compound, hydrogen chloride is then split off under conditions as set out in the modified production process described below.

This second modification of the manufacturing process according to the invention consists in the fact that there are two identical or different aroylamino compounds with introduction of the remainder

O HN

\
\ / \ /

H ₉ N

35

40 cl

Cl

Is used for condensation with the reactive derivatives of those which can be used according to the invention Dicarboxylic acids per 1 mole of two different aminoanthraquinones, so one can any substituted 1-aminoanthraquinone or a 2-aminoanthraquinone compound. Examples for such usable compounds are the following: l-amino-4-hydroxy- or -4-methoxyanthraquinone, 1-amino-4-phenylammoanthraquinone, 1-amino-4-chloroanthraquinone, 1-amino-4-benzoylaminoanthraquinone, 1 - Amino - 4 - (4 '- chlorobenzoyl amino) anthraquinone, 1-amino-4- (3', 4 '~ dichlorobenzoylamino) anthraquinone, l-Amino-4- (3'- or 4'-dimethylsulf amidbenzoylamino) -anthraquinone, 1-amino-4- (methylsulfonylbenzoylamino) -anthraquinone, 1,4-diamino - 2 - acetylanthraquinone, 1,4-diaminoanthrachi non-2-carboxylic acid anilide, 4-amino-1,2'-dianthrimide, 5-amino-1,9-anthrathiazole, 5-amino-1,9-pyrazolanthrone, 4-amino-l, 9-pyrimidanthrone, 5-amino-l, 9-pyrimidanthrone, 4-amino-1,9-anthrapyrimidone, 4-amino- (N) -methyl- 1,9-anthrapyridone, [1 ", 4" - diamino anthraquinonyl- (2 ")] - anthraquinone-2 '(N), 3 ': 4,5-thiazole, 4-ammoanthraquinone-2,1 (N) -benzacridone, 2-aminoanthraquinone and aminodibenzathrone.

Valuable dyes are mainly obtained when they are linked to one another for condensation with reactive ones. The aroylaminoanthraquinones used as starting materials in this modified production method must contain as aroyl group an optionally further substituted diphenyl-4-carboxylic acid residue which is condensable with chloral. These aroylaminoanthraquinones are linked by treatment with trichloroacetaldehyde or its derivatives, which react like this, and subsequent elimination of hydrogen chloride in the condensation product. The treatment with the aldehyde compound is advantageously carried out in concentrated sulfuric acid at room temperature. The resulting α, α-trichloroethane- β, β- bis-aryldicarboxamides are, after isolation, heated in nitrobenzene to split off hydrogen chloride in the presence of pyridine or another tertiary nitrogen base. The cleavage can also be brought about by heating in pyridine, advantageously in the presence of a little concentrated sodium hydroxide solution. As mentioned above, the treatment with trichloroacetaldehyde is subjected to 2 moles of the same or 1 mole each of two different aroylaminoanthraquinone compounds. Here, too, it is a condition that at least 1 mole is a 1-aroylaminoanthraquinone which has no substituent in the 4-position. In this modified production process, the starting products are in particular the diphenyl-4-carboxamide derivatives.

linge of the 1-amino and 1-amino groups listed above 2-Aminoanthraquinone compounds into consideration.

The vat dyes obtainable according to the invention can be used for cleaning with low-boiling solvents, such as alcohol or glacial acetic acid. They can further be recrystallized from high boiling points Solvents, such as nitrobenzene, chloronaphthalene or quinoline, or by changing the vat getting cleaned. They present valuable vat dyes, which are used for dyeing and printing various fibers, especially those containing cellulose, such as cotton, linen, rayon and rayon regenerated cellulose, can be used. The dyes show in the form of their leuco compounds good to very good drawability compared to cellulose-containing materials. The strongly colored Dyeings and prints are very pure and, as already emphasized, have good to very good fastness properties on. The vat dyes obtainable according to the invention are distinguished in particular by the valuable Property of being able to use cotton from the warm to hot vat, d. H. at temperatures of 50 to 80 ° C. They are therefore known as "hot dyers" for modern continuous dyeing processes particularly useful. Various anthraquinone dyes obtainable according to the invention, In particular, the more highly condensed derivatives are also valuable pigment dyes. Finally you can the present dyes also in a manner known per se in leuco preparations, in particular Sulfuric acid ester salts, converted and by the methods customary for this class of dyes Dyeing and printing can be used.

Compared to the vat dye known from US Pat. No. 1911714, obtained by reaction of diphenyl-4,4'-dicarboxylic acid dichloride with 1-aminoanthraquinone, according to the invention, consists of α, α-dichloro / S, / 3-bis [4 "-carboxydiphenylyl-4 '] - ethylene and 1-aminoanthraquinone has better chlorine fastness and is more suitable as a hot dye. In comparison with the pigment known from French patent specification 885 754, obtained by reacting maleic anhydride with 1,5-diaminoanthraquinone, the similar, according to the invention from "," - dichloro - ^, ^ - bis- [4 "-carboxydiphenylyl-4 '] - ethylene and 1,5-diaminoanthraquinone

ίο obtained dye has a greater color strength, and its polyvinyl chloride color is more transparent.

The following examples serve to illustrate the invention. Unless otherwise noted is, the parts are understood as parts by weight. They are related to parts by volume as grams are to Cubic centimeter.

example 1

A mixture of 48.8 parts «, a-dichloro / 5, / 3-bis- [4" -carboxydiphenyl-4 '] - ethylene, 200 parts of nitrobenzene, 200 parts of thionyl chloride and 5 parts of pyridine is so long at 80 to 120 ^° C. until everything has dissolved and the formation of the acid chloride has ended, the excess thionyl chloride is then removed by distillation, finally in vacuo 600 parts of nitrobenzene and 8 parts of pyridine were added and the mixture was stirred ^{at 35 ° C. overnight.}

Thereupon 15 minutes, heated to 110 ⁰ C for and then a solution of 34.2 parts of 1-amino-5-benzoylaminoanthraquinone added in 700 parts of nitrobenzene. The mixture is stirred for 4 hours at 120 ° C. It is filtered warm and the precipitated dye is washed first with nitrobenzene and then with alcohol. The color of the constitution obtained in the form of red-yellow crystals

O NH-CO

> —CO — HNO

O NH-CO-:

dyes cotton from a hot vat in pure, yellow shades with good fastness properties.

One uses 1-amino-5-benzoylaminoanthraquinone instead of 34.2 parts 37.6 parts of 1-amino-5- (o-, m- or p-chlorobenzoyl) -aminoanthraquinone, 44.9 parts of l-amino-5- (3'- or 4'-sulfonic acid-dimethylamidbenzoyl) -aminoanthraquinone, 36 parts of 1-amino-5- (o-fluorobenzoyl) -aminoanthraquinone, 37.2 parts of 1-amino-5- (p-methoxybenzoyl) -aminoanthraquinone or 41 parts of l-ammo-5- (m-trifluoro-methylbenzoyl) -aminoanthraquinone, this gives dyes with similar properties. Dyes are also obtained with good fastness properties if, in these examples, instead of 22.3 parts, 1-aminoanthraquinone 29.1 parts of 1-amino-6,7-dichloroanthraquinone are used.

The previously unknown dicarboxylic acid of formula II

HOOC-;

can be prepared, for example, by adding 297.5 parts of diphenyl-4-carboxylic acid to a Ge OD at 20 ° C

Cl

mix of 3000 parts of 96% sulfuric acid and 110 parts of chloral enters. The mixture is stirred for 24 hours

20 ° C, pour on ice, suck off the precipitate and wash it with water. The intermediate product obtained the composition III

HOOC

COOH

is boiled under reflux for 5 hours to split off hydrogen chloride in 2.5% sodium hydroxide solution, and then is leavened. Recrystallized from nitrobenzene, the acid II is obtained in fine needles with a melting point of 343 ° C.

Example 2

To a solution of 22.3 parts of 1-aminoanthraquinone in 250 parts of o-dichlorobenzene at 120 ⁰ C, a solution of 26.2 parts of the acid chloride of compound & ot ,, - dichloro -beta, '-bis ß - [4 "- carboxydiphenyl

yl-4 '] - is ethylene in 30 parts of dichlorobenzene, followed by stirring the mixture at 120 ⁰ C, until the formed dye. The deposited dye is filtered off with suction while cold and washed first with dichlorobenzene, then with alcohol. The obtained color

substance of the constitution

O NH-CO

X_co—

HN O

Ii ο

dyes cotton from a hot vat a real greenish yellow.

The same dye is also obtained if one

80.6 parts of 1 - (4'-phenylbenzoylamino) - anthraquinone at 2O ⁰ C in a mixture of 1000 parts of 98 ^o / cent sulfuric acid and 14.6 parts of chloral enters and stirred for 6 hours at this temperature. Discharge on ice gives the product of the composition

O NH-CO

α _G1 α

as a yellow precipitate, which is filtered off and washed well. One carries the product in a mixture of 2000 parts of pyridine and 20 parts of potassium hydroxide and the solution is refluxed for 5 hours, with with elimination of hydrogen chloride, the dye of the above constitution is formed.

As described in Example 1, dyes of similar properties with asymmetrical structure can be be obtained by, for example, 52.4 parts of diacid chloride of £ x, a-dichloro-jS, / 3-bis [4 "-carboxydiphenylyl-4 '] - ethylene in the first stage at 35 ° C. in nitrobenzene on one side with 22.3 parts of 1-aminoanthraquinone and then at 120 ° C with 29.1 parts of 1-amino-6,7-dichloroanthraquinone converts to the dye. Is used instead of 29.1 parts of l-amino-6,7-dichloroanthraquinone in the second stage 25.7 parts of 1-amino-4-chloro- or 1-amino-S-chloroanthraquinone or 22.3 parts of 2-amino-anthraquinone, dyes are also obtained, the cotton from the vat yellow to dye. ■ -

Example 3

To a mixture of 58.2 parts of l-amino-6,7-dichloroanthraquinone and 500 parts of trichlorobenzene at 120 ⁰ C, a solution of 52.4 parts of a diacid chloride, "- dichloro - /, /? - bis- [ 4 "-carboxydiphenylyl-4 '] -ethylene is added in 50 parts of trichlorobenzene and the mixture is stirred at 120 ° C. until the dye has formed. The dye which has separated out is filtered cold

and washed with trichlorobenzene, then with alcohol. He corresponds to the formula

O NH-

-C- N-CO-HNO

C Cl Cl

, —Cl

pt

and dyes cotton from a hot vat in a real reddish yellow.

Is used instead of 58.2 parts of 1-amino-6,7-dichloroanthraquinone 51.4 parts of l-amino-6- or 7-chloroanthraquinone are obtained with a dye similar properties.

For the preparation of the diacid chloride of α, α-dichloro, / 3-bis [4 "-carboxydiphenylyl-4 '] - ethylene heated a mixture of 200 parts of this compound in

O NH- CO- <

700 parts of thionyl chloride and 5 parts of pyridine under reflux until a clear solution has formed. That Excess thionyl chloride is finally distilled off in vacuo, the acid chloride remaining behind. the end Recrystallized ligroin, it is obtained in fine needles with a melting point of 135 ° C.

The same dye is also obtained by boiling 1 part of the product for 10 hours constitution

COHN O

with 28 parts of nitrobenzene and 2 parts of pyridine. The above intermediate is obtained by reaction of 58.2 parts of 1-amino-6,7-dichloroanthraquinone with 56 parts of the diacid chloride of ",", "- trichloro-, S, | 3-bis- [4" -carboxydiphenylyl-4'I-ethane in 600 parts of o-dichlorobenzene at 120 ° C.

Example 4

A mixture of 22.3 parts of 1-aminoanthraquinone, 52.4 parts of diacid chloride des <x, «- dichloro-ß, / 3-bis-

O NH-CO

and dyes cotton from a hot vat in yellow tones. If, instead of 6-aminopyrimidanthrone, 23.5 parts of 8-aminopyrimidanthrone are used a dye that dyes in reddish tones. The symmetrical one also shows similar properties Dye obtained by reacting 47 parts of 8-aminopyrimidanthrone with 52.4 parts of diacid chloride of α, α-dichloro - / ?, | 3-bis- [4 "- carboxydiphenylyl-4 '] - ethylene obtained in nitrobenzene at 130 ° C.

[4 "-carboxydiphenylyl-4 '] - ethylene, 8 parts of pyridine and 600 parts of nitrobenzene are ^{stirred first for 12 hours at 35 ° C. and then for 15 minutes at HO 0} C. A solution of 23.5 parts of 6- Aminopyrimidanthrone in 200 parts of nitrobenzene is added and the mixture is stirred until the formation of the dye has ended at 120 ° to 130 ° C. After cooling, the dye which has separated out is filtered off with suction and washed with nitrobenzene and alcohol

—CO — HN O

anthraquinone acridine of the formula

O HN

-O

60

Example 5

A mixture of 22.3 parts of 1-aminoanthraquinone, 52.4 parts of diacid chloride of the oc, «- dichloro - ^, / S-bis- [4" -carboxydiphenylyl-4 '] - ethylene, 8 parts of pyridine and 600 parts of nitrobenzene is stirred for 12 hours at 35 ° C and then for 15 minutes at HO ⁰ C. then 46.4 parts of the carrying one Aminobenzanthronylamino-H ₂ NO

and stirred at 160 to 17O ⁰ C continued until the termination of dye formation. The excreted color

209 580/365

substance is filtered off after cooling and with nitrobenzene and alcohol washed. With this dye on cotton, green ones can be obtained from a hot vat Dyeings that have good fastness properties. Is used in place of the aminobenzantronylamino-anthraquinone acridine 46.9 parts of the intermediate of the formula

SO ₂ -N

CH ₃

CH _a

ίο

H ₂ N

in this way a dye is obtained which really dyes cotton from a hot vat yellow-brown.

Example 6

A mixture of 17.1 parts of l-amino-5-benzoylaminoanthraquinone, 26.2 parts of diacid chloride of a, a-dichloro - ^, / 3-bis- [4 "-carboxydiphenylyl-4 '] - ethylene, 6 parts of pyridine and 400 parts of nitrobenzene was stirred for 20 hours at 35 ⁰ C and then 15 minutes at 12O ⁰ C. then are added 23 parts Aminodibenzanthron and stirred at 160 to 170 ° C until the completion of the dye formation. the precipitated dye is at 60 ° C Filtered off and washed with nitrobenzene and then with alcohol.This dye gives gray-blue dyeings on cotton from a hot vat.

If 12 parts of 5-amino-l, 9-pyrazolanthrone are used instead of aminodibenzanthrone, the result is a pigment dye which gives polyvinyl chloride a reddish-tinged yellow color.

Claims (1)

PATENT CLAIM: Process for the preparation of anthraquinone dyes the general formula A-HN-OC-R ₁ -CR ₂ -CO-NH-B (I) 12th in which A and B are radicals of viable anthraquinone compounds and R ₁ and R _{2 are} 4 ', 4 "-diphenylene radicals, characterized in that 1 mol of a compound of the general formula HOOC-R ₁ -CR ₂ -COOH (II) Il Cl Cl or HOOC-R ₁ -CR ₂ -COOH (III)
Cl-C-Cl
Cl in which R ₁ and R _{2 have} the meanings given above, advantageously in the form of their reactive derivatives with 2 mol of the same or different aminoanthraquinone compounds linked acid amide-like and optionally splitting off hydrogen chloride in the reaction product and choosing the components so that at least one of the anthraquinone radicals A and B is a 1-Anthraquinonyl radical, which is unsubstituted in the 4-position, but can optionally be otherwise substituted, or that 2 mol of the same or 1 mol of two different aroylaminoanthraquinone compounds which contain a condensable diphenyl-4'-carbonyl radical as the aroyl group and of which at least 1 mol of a 1-aroylaminoanthraquinone compound unsubstituted in the 4-position is condensed with trichloroacetaldehyde or with derivatives reacting like this and splits off hydrogen chloride in the reaction product. Cl Cl Considered publications:
French Patent No. 885,754;
U.S. Patent No. 1,111,714. When the application was announced, three coloring tables were laid out. © 203 580/365 5.62