DE1927310C3 - Process for the preparation of anthraquinone dyes - Google Patents

Description

CH ₂ ZR

wherein X is a hydroxy or amino group, R is a hydroxy, alkoxy, mercapto or alkyl mercapto group represents, Z represents an optionally substituted phenylene or naphthylene radical and the rings A and B are optionally substituted, characterized in that an anthraquinone compound of the form!

CH, OH

ίο

Reacts in the presence of an acid catalyst with a compound of the formula HZR.

2. Modification of the method according to claim 1, characterized in that there is an anthraquinone compound the formula

C ^- H ₂ Y

O X

t, s

^: A II! IB

Il O

with a compound of the formula HZR, where A, B, R. X and Z are those in claim 1 have given meanings and Y represents a chlorine or bromine atom.

3. Modification of the process according to claim I for the preparation of the anthraquinone dyes where R represents an alkoxy or alkyl mercapto group, characterized in that the corresponding dyes in which R represents a hydroxyl or mercapto group, with a Reacts alkylating agent

The invention concerns! Anthraquinone dyes, the are suitable for dyeing textiles, especially synthetic textiles,

created, wherein X represents a hydroxy or amino group, R a hydroxy, alkoxy, mercapto or Represents alkyl mercapto group, Z represents an optionally substituted phenylene or naphthylene radical and rings A and B are optionally substituted.

The alkoxy groups represented by R are preferably lower alkoxy groups such as methoxy. Ethoxy, n-propoxy and n-butoxy radicals. The alkyl mercapto groups represented by R are preferably lower alkyl mercapto groups. such as B. methyl and ethyl mercapto radicals.

For the purposes of the invention, the terms lower alkyl and lower alkoxy denote alkyl and alkoxy radicals with 1 to 4 carbon atoms.

As examples of any further substituents present in the phenylene or naphthylene radical Z. one can use lower alkyl radicals such as methyl radicals. Chlorine atoms. Mention lower alkoxy groups such as methoxy groups and hydroxyl groups.

As examples of the substituents. those on the rings A and B can be present, one can be chlorine, bromine, cyano. Lower alkyl, e.g. B. methyl. Hydroxy, lower alkoxy, such as Methoxy, amino, lower alkylamino. such as B. methylamino, acylamino, such as. B. acetylamino and benzoylamino, anilino and substituted derivatives thereof, such as. B. chloroanilino. Bromanilino. Lower alkoxyanilino. how /. B. anisidino, lower alkylanilir.o. such as B. Toluidino and 2,4,6-Trimeihylcinilino, Sulfoanilino and carboxyanilino. Sulfonic acid c. Sulfonaniido and N-substituted derivatives thereof such as /. B. sulfo-N-methylamido and sulfo-N.N-diethylamido. Mercapto, lower alkyl mcrcapio. such as Mention, for example, methyl mercapto, and phenyl mercapto.

The inventive method for preparing the anthraquinone is that one Anthraquinone compound of the formula:

O X

(II, Oi!

formula 1

in the presence of an acid catalyst with a compound of the formula HZR.
This method according to the invention can

bo expediently thereby that the reaction participants in an organic solvent, which may be an excess of the compound of the formula HZR, in the presence of an Acid Kalalysalon such. B. sulfuric acid, the reaction being carried out at a temperature lying between 20 ° C. and the boiling point of the reaction medium . B. aluminum chloride or zinc chloride, as acid catalyst

tciren can be used. The dyes obtained can then be isolated in a manner known per se, e.g. durcl. ' Distilling off the organic solvents in Presence of steam or by adding a liquid, e.g. B. methanol, which is a solvent for the is organic solvent and in which the dye is insoluble, so that the dye is then filtered off can be.

Examples of the compounds of the formula HZR that can be used are phenol, anisole, phenetol, thiophenol, o-cresol, p-cresol, o-chlorophenol, 4-methoxyphenol, o-, m- or p-dimethoxybenzene, Mention thioanisole, hydroquinone, resorcinol, 2- or 4-methoxyphenol, 2- or 4-ethoxyphenol and / \ - or /? - naphthol.

In this reaction, the methylene group attached to the anthraquinone nucleus is attached to the phenylene or Naphthylene radical Z in pars position to the group R bound. If the para position is occupied by a substituent, the methylene group is attached to the radical Z in ortho position zai group R bonded. Contains the Compound of the formula riZR two groups, such as. B. Hydroxyl and methoxy groups. each influencing the attachment position of the methylene group but then a mixture of products can be obtained.

The anthraquinone compounds of the formula I can be generated by an optionally substituted 1- (hydroxy or amino) anthraquinone-2-sulfonic acid treated with formaldehyde in the presence of an alkali and a reducing agent.

As certain B '' play for the anthraquinone compounds of formula I one can mention the following:

1 - (hydroxy or amino) 2-hydroxymethylanthraquinone,

I - (hydroxy or amino) - 2-hydroxymethyl-4- (anilino-, methylanilino-, methoxyanilino-,
2.4.6- trimethylanilino-.chloranilino-,
phenylthio-, benzthiazol-2'-ylthio-, chloro-,
bromo- or hydroxy-) anlhraquinone and

1-Amino-2-hydroxymethyl-5- (chloro- or sulfo -) - anthraquinone.

According to a further feature of the invention proposed a second process for the preparation of the anthraquinone dyes according to the invention, the consists in that an anthraquinone compound of the formula:

O X

Ϊ Ui

CHA '

Formula Il

is brought into reaction with a compound of the formula HZR, where A. B. R. X and Z are the o. Have meanings and Y represents a chlorine or bromine atom.

This method according to the invention can expediently; Big; be realized in that the response time Always mixed with each other and with an organic liquid, optionally an excess the compound of the formula HZR, optionally in the presence of an acid-binding agent Agent, which can be the sodium salt of the compound of the formula HZR, be heated. The so obtained Dyes can be isolated in a manner known per se, e.g. B. by adding a liquid, e.g. B. Water, through which the dye is excreted from the solution in grams of the organic liquid.

The anthraquinone compounds of the formula II can be obtained by treating the corresponding compounds of the formula I can be produced with a chlorinating or bromination agent.

ίο The anthraquinone dyes according to the invention where R represents a hydroxy or mercapto group, can be converted into the corresponding alkylated or acylated Derivatives thereof are converted by reacting with an alkylating agent, e.g. B. dimethyl sulfate, or an acylating agent, e.g. B. acetic anhydria, acetyl chloride, Benzoyle chloride or methanesulfonyl chloride. treated under the known conditions for alkylation or acylation reactions.

A preferred class of anthraquinone dyes according to the invention consists of the dyes which contain no acidic, water-solubilizing groups and the formula:

CiWZ ¹ R

O X

have, where X and R have the o. a. Have meanings 'Z' represents an optionally substituted phenylene radical and T represents a hydrogen atom or a substituent

Γ) th represents. X preferably represents an amino group and R represents a hydroxy or alkoxy group. The substituents represented by T are preferably hydroxy. Phenylthio-. Benzthia / .ol-2'-y! Ihio-, p-toluenesulfonamido- and especially optionally substituted

4 (i anilino substituents.

The anthraquinone dyes according to the invention which contain sulfo groups are suitable as acid dyes for dyeing wool. Silk and synthetic polyamide fabrics from an aqueous dye bath.

4'j also conventional dyeing auxiliaries, e.g. B. formic acid. Acetic acid. Sulfuric acid. Sodium sulfate or ammonium sulfate. The so obtained Dyeings have excellent fastness in the samples, which is usually the case with such textile fabrics

^r , d are performed.

The anthraquinone dyes according to the invention which do not contain any acidic, water-solubilizing groups, are suitable for dyeing synthetic textiles, e.g. B. Cellulose Acetate and Cellulose Triacetate

^r > 5 tat textiles, polyamide textiles, z. B. fabrics made of polyhexamelhyleneadipamide, polyacrylonitrile fabrics and preferably aromatic polyester fabrics, e.g. B. Textiles made from polyethylene terephthalate. Such fabrics can take the form of threads, yarns. Have woven or knitted fabrics.

If desired, the textile fabrics mentioned can be combined with other types of textile fabrics, τ. Β. forming a

"■ Mixture of polyester textile fabrics and CeIIuIoSe-

or woolen fabrics, be mixed up,

Such fabrics can be expediently with the water-insoluble anthraquinone dyes according to the Invention dyeing that the textile fabric is immersed in a dye bath that consists of an aqueous

Dispersion of one or more of the dyes and preferably a nonionic, cationic and / or anionic surfactant contains, whereupon the dyebath is heated to a suitable temperature for an appropriate time. in the In the case of cellulose acetate secondary fabrics, the dyeing process is preferably carried out at one point between 60% and 85 ° C lying temperature carried out; in cellulose triacetate or potyamid fabrics the dyeing is preferably carried out at a temperature between 95 and 100 ° C .; with aromatic Polyesler fabrics can be dyeing either at a temperature between 90 and 100 ° C Temperature preferably in the presence of a carrier, e.g. diphenyl or o-hydroxydiphenyl. carried out or at a temperature between! 20 and 130 ° C temperature below atmospheric pressure.

One can also proceed so that the aqueous dispersion of the anthraquinone dye mentioned the textile material broken open after a block or printing process! is, according to which the textile fabric depending on the type Temperatures up to 230 ° C heated or treated with steam. In such procedures, the aqueous dispersion of the anthraquinone dye, preferably a thickener, such as. B. tragacanth. Gum arabic or sodium alginate.

At the end of the dyeing process, the dyed fabric is preferably rinsed with water or briefly treated with soapy water before drying finally. With aromatic polyester textile the dyed fabric preferably undergoes treatment with an alkaline aqueous sodium hydrosuiritol solution subjected before being treated with soapy water to remove loosely tied dye from the Remove the surface of the fabric.

The anthraquinone dyes of the invention have excellent affinity and buildability with respect to synthetic fabrics. especially aromatic polyester fabrics. so that deep color can be obtained Tönunge ^n. The resulting colorations have excellent resistance to light. Wet treatments and especially dry heat treatments, such as those described e.g. B. be carried out at high temperatures during pleating.

If desired, the dyes according to the invention can be used when applied to the synthetic Textiles in connection with other dispjrsen Dyes, such as those used for. B. UK patents

8 06271.835i, 19. 840903, 847 175, 85239b.

8 52 493. 8 59 899. 8 65 328. 8 72 204. 8 94 012.
<·> 08 656. 9 09 843. 9 10 306, 9 13 856. 9 19 424.

9 44 513. 9 44 722. 9 53 887, 9 59 816. 9 60 235,
9 61 412, 9 76 218, 9 93 162 and 9 98 858

are used.

He ^r indungsgemäßen anthraquinone in which the radical represented by 7.R is a 1.4-Dihydroxyphenylradikal. are also suitable as color developers in color transfer processes in color photography, as described, for example, in British Patent 8 04 97! are described and claimed,

The invention is explained in more detail below with reference to exemplary embodiments, purely by way of example. all quantities being based on weight.

Example I.

A mixture of 2 parts of 1-amino-2-chloroimethylanthraquinone and 20 parts of phenol is stirred at 70 ° C. for 2 hours. Then 40 parts of water are added and the dye precipitated therewith is filtered off and washed with a 10% aqueous methanol solution. The solid is dissolved in 200 parts of a 10% strength aqueous sodium hydroxide solution at 90 ^° C., the solution is filtered and the filtrate

in is acidified with aqueous hydrochloric acid. The eliminated 1-Amino-2- (4'-hydroxybenzyl) anthraquinone is then filtered off, washed with water and dried.

With an aqueous dispersion of the thus obtained

Ii dye can be used in luminescent polyester fabrics Orange shades of excellent fastness can be dyed.

Instead of 2 parts 1-amino-2-chloromethylanthraquinone can be a corresponding amount of

1 • Amino ^ -chloromethyl-S-chloranthraquinone.
l-amino-2-chloromethyl-4-ilinoanthraquinone
or
l-amino-2-chloromethyl-4- (p-toluidino) -

anthraquinone
"'can be used, where

1-amino-2- (4'-hydroxybenzyl) -

5-chloranthrac! Iinon or
1-Amino-2- (4'-hydroxybenzyl) -4- (anilino or

p-toluidinojanthraquinone

obtained with which polyester fabrics in yellow, blue or blue shades are more excellent Authenticity can be colored.

"Example 2

A mixture of 2 parts of 1-hydroxy-2-chloromethyl anthraquinone. 40 parts of phenol and 20 parts of sodium phenate are ^{heated to 110 °} C. for 2 hours. the

4 »mixture is then cooled and poured into water, whereupon the precipitated l-hydroxy-2- (4'-hydroxybenzyl) anthraquinone filtered off, washed with a methanol / water mixture and dried will.

4Ί mil of a dispersion of this product in water can use polyester fabrics in yellow shades can be dyed with excellent fastness.

Example 3

A mixture of 2 parts of 1-amino-2-hydroxymeihylanihrachine Dn. 20 parts of phenol and 0.25 parts of 98% sulfuric acid are heated for 2 hours at 70.degree touched. The mixture is cooled and put into a

r, I: 3-methanol / water mixture poured in, whereupon the excreted l-amino-2- (4'-hydroxybenzyl) anthraquinone filtered off, washed with water and gcirocknet is.

The following table are further examples of the

mi anthraquinone dyes according to the invention to cntnch men. where they each by implementation of the anlhrachinonverbin given in the 2nd column of the table = dung with the Phcnolverbindurig according to the 3rd column as in Example 3. In the 4th column of the The table shows the composition of the dye, indicated, while the 5 column shows the shade that is used when dyeing polyester-Tcxlil · with the respective dye.

7th 1927310
8th Composition of the dye Color at Anhraquinone compound Phcnol- clayey game connection l-amino-2- (4'-hydroxybenzyl) ^ blue 4th I-amino-2-hydroxymethy! -4-anilino- phenol 4-anilinoanthraquinone anthraquinone i-amino-2- (4'-hydroxybenzyl) - Red 5 i-amino ^ 2-hydroxymethyl-4- {p-loluene- phenol 4- (p-toluenesuironamido) anthraquinone sulfonamido) anthraquinone l-amino-2- {4'-hydroxybenzyl) - Red 6th l ^ Amino-24iydroxymethyl-4- {benzthi- phenol 4- (bcnzthiazoI-2 "-yllhio) anthrachinoh azoI-2'-ylthio) anthraquinone l-amino-2- {4'-hydroxybenzyl) - Red 7th l-amino ^ -hydroxymelhyl ^ hydroxy- phenol 4-hydroxyanthraquinone anthranhinon l-amino-2- {4'-hydroxybenzyl) - Red 8th l-amino ^ -hydroxymethyl ^ phcnyl- phenol 4-phcnylthioanlhraquinone thioanthraquinone l-amino-2- (4'-hydroxybenzyl) - BIaU 9 l-amino-2-hydroxydmethyl-4- (p- phenol 4- {p-anisidino) anthraquinone anisidino) anthraquinone l-amino-2- (4'-hydroxybenzyl) blue 10 l-amino-2-hydroxymethyl-4- (p-chloro- phenol 4- {p-chiofaniiinojanihrachinon anilinojanlhraquinone !, S-dihydroxy ^ S-diamino- blue 11th 1,5-dihydroxy-4,8-diamino phenol 2- (4'-hydroxyphynyl) -6- (4 "-hydroxy- 2- (4'-hydroxyphenyl) -6-hydroxymethyl- benzyl) anthraquinone anlhraquinone l-Amino-2- {4'-ethoxybenzyl) - orange 12th 1-amino ^ -hydroxymethyl anthraquinone Phenetol anlhraquinone i-Amino-2- (4'-methoxybenzyl) -
anthraquinone orange 13th 1-amino ^ -hydroxymethylanthraquinone Anisole l-Am;> io-2- {4'-methoxybenzyl} - blue 14th l-amino-2-hydroxymethyl-4-anilino- Anisole 4-anilinoanthraquinone anthraquinone l-amino-2- (4'-mercaptobenzyI) - blue 15th l-amino ^ -hydroxymethyl ^ anilino- Thio 4-aniinoanthracinone anthraquinone phenol I-amino-2- (2'-hydroxy-5'-methyl- orange 16 l-amino-2-hydroxymethylanthraquinone p-K. resol

benzyl) anthraquinone

Example 17

A mixture of 2 parts of 1-amino-2-hydroxymethylanthraquinone, 25 parts of o-cresol and 1 part of aluminum chloride is ^{stirred at 100 °} C. for 15 minutes. The mixture is cooled and poured into 15 parts of methanol, whereupon the precipitated solid is filtered off. This solid is dissolved in a hot mixture of 50 parts of methanol and 10 parts of an 8% aqueous sodium hydroxide solution and the solution is filtered. The filtrate is acidified with acetic acid, and the precipitated I-amino-2- (3'-methyl-4'-hydroxybenzyl) anhraquinone is filtered off, washed with methanol and dried

With an aqueous dispersion of this dye, polyester fabrics in bright orange shades can be produced can be dyed with excellent fastness.

If the first part of aluminum chloride is replaced by 1 part of zinc chloride, the same dye is obtained.

The table below are more examples of the Anthraquinone dyes according to the invention can be found, whereby they are each made by reacting the in the 2. Column of the table indicated anthraquinone compound with the phenol compound according to the 3rd column as in Example 17 can be prepared. The 4th column of the table shows the composition of the dye in each case indicated, while the 5th column shows the shade used when dyeing polyester Te ^ tilstoffen is obtained with the respective dye.

example

Anthraquinone bond

Phenolic compound

Composition of the dye

Color tint

18 l-amino-l-hydroxymethylanthraquinone

19 l-amino-2-hydroxymethyl anthraquinone

l-Amino-2-hydroxyincibyi-4- (benzthiazol-2'-ylthio) -

anthraquinone

o-chlorophenol 4-methoxyphenol

o-tue-

methoxy

benzene

l-Amino-2- (3'-chloro-4'-hydroxybenzyl) anthraquinone

Mixture of l-amino-2- (2'-hydroxy-5'-methoxybenzyl) anthraquinone and l-amino-2- {2'-methoxy-5'-hydroxybenzyl) anthraquinone
1-Aniino-2- {3 ", 4" -diir.ethoxybenzy!) - 4- {benzth! azol-2'-ylthio) anthraquinone

orange

orange

909 613/54

continuation

ίο

At- anthraquinone compound
game

Phonolv connection

Composition of the dye

tint

21 l-amino-2-hydroxymethyl

4- {benzthiazol-2'-ylthio) anlhraquinone

22 l-Arriino ^ -hydroxymethyl ^ eniHnoanthraquinone

23 l-Amino ^ -hydroxymethyl ^ anilinoanlhraquinone

24 l-Amino ^ -hydroxymethyl- ^ anilinoanthraquinone

2-melhoxyphenol

melhoxybcnzol

4-chlorine

3-methyl-

phcnol

Thioanisole mixture of l-amino-2- {3 "-hydroxy- ^ '- melhoxybcnzylM-ibenzthiazoI-2'-ylthiö) anthfächinön and 1-amino-2 ^ (3 "-methoxy-4" -hydroxybenzyl) -4-benzlhiazoi-2'-ylthio) anthraquinone

l-Amino ^^ VI '^ dimethoxybenzyl) -4-anilinoanlhraquinone

I-Amino-2- {2'-hydroxy-4'-methyl-5'-chlorobenzyl) -4-anilinoanthraquinone

1-Amino-2- (4'-methylmercaptobenzyI) -4-anilinoanthraquinone

Red

blue

blue

blue

Example 25

I part of 1-amino-2- (4'-hydroxybenzyl) anthraquinone (prepared according to Example I) is dissolved in 200 parts of a 2.5% strength aqueous sodium hydroxide solution at 20 ^° C. Then 3 parts of dimethyl sulfate are added, and the mixture is heated ^{to 50 ° C. to complete the reaction.} The precipitated 1-amino-2- (4'-ynethoxybenzyl) anthraquinone is then filtered off, washed with water and dried.

Example 26

A mixture of 3 parts acetic anhydride, 1 part 1-amino-2- (4'-hydroxybenzyl) anthraquinone and 25 parts Pyridine is heated to 25 ° C. for 30 minutes while stirring. The mixture is then poured into water, and the precipitated l-amino-2- (4'-acetoxybenzyl) anthraquinone is filtered off, washed with water and dried.

With an aqueous dispersion of this dye, polyester fabrics in bright orange shades can be produced can be dyed with excellent fastness.

Example 27

A mixture of 2 parts of 1-amino-2-hydroxyniethyl-4-anilinoanthraquinone, 6 parts of hydroquinone and 10 parts of nitrobenzene is heated to 100 ° C. and 18 parts of aluminum chloride are added. The mixture is held for 30 minutes at 100 "C and then poured, after cooling \ n methanol. To the mixture formed is added so much water that the l-amino-2- (2 \ 5'-dihydroxybenzyl) -4-anilinoanthraquinone excreted. The solid is filtered off, washed with water and dried.

The product can be used to dye polyester textile fabrics in blue shades of excellent fastness ι- J5 will be.

If resorcinol is used instead of hydroquinone, l-amino-2- (2 ', 4'-dihydroxybenzyl) -4-anilinoanthraquinone is obtained.

Used instead of hydroquinone ^ -naphthol or a-naphthol used, l-amino-2- (2'-hydroxynaphth-r-ylmethyl) -4-aniIinoanthraquinone is obtained and 1-amino-2- (4'-hydroxynaphlh-1 '-ylmethyl) -4-anilinoanthraquinone.

Claims (1)

Piuent claims: U ₁ Process for the preparation of anthraquinone dyes of the formula According to the invention, anthraquinone dyes of the formula: CH ₁ ZR