DE1927313A1 - Process for the preparation of anthraquinone dyes - Google Patents

Description

Imperial Chemical Industries Limited, London, S.V.1.,

You priority registration in the UK from 30 * 5-68

is used

The invention relates to anthraquinone compounds which are used for Coloring of textiles or as intermediate products in the Production of dyes are suitable.

According to the invention, anthraquinone compounds are Formula:

R ^{2 R}

1 p

created, with H and R each being a hydrogen atom or an optionally substituted hydrocarbon »or heterocyclic a radical or H and R with one another and with the carbon atom a 5- or 6-membered ring form, and the Hinge A and B may contain substituents.

As examples of the possibly represented by R ^ and R ²

Hydrocarbon radicals can be sub »

, inb © 8ond®re Hi @ d®r © lkyl *, Qfelohexyl «uad especially mention Phenylradlkaia. As certain examples , the following should be mentioned; - lower alkyl -

0 09848/1730 JI ² "

. ßAD O

such as methyl, ethyl, n-propyl and n-butyl, phenyl-lower alkyl like Bexusyl and p-Phenylethyl, CarhoniederalkosyaUgrl like Carboathoxymethyl, Ifydroxyniederalkyl like ß- ^ ydr oxyäthyl, Lower alkoxy lower alkyl such as ß ^ Hethoayäthyl, Phenyl and substituted phenyl such as chlorophenyl, XoXyI, tfitrophenyl, Hethoxyphenyl and sulfophenyl.

As examples of the optionally substituted heterocyclic radicals represented by E and ΈΓ , the following can be mentioned ι optionally substituted 5- and 6-membered heterocyclic radicals which contain oxygen, sulfur and preferably nitrogen atoms as heteroatoms, some examples of which are Iyridine- 2-yl, yridin-4-yl and furan-2-yl.

As examples of the 5- and 6-membered Hiagsyeteme, the can be formed by B and B ^ tusamwn, can «an Mention Cyolopentyl- and Qyclohezylring ^ ystoBd.

For the purposes of the invention, the terms "lower alkyl" and "lower alkoxy" mean alkyl or alkoxy radicals having 1 to 4 carbon atoms. ^:

As examples of the substituents which possibly may be included in the binge "A and B Lake Anthraehinonkerne" let the following mention _9: Chloro, bromo * HITRO, Cy®no, Aaino "IlederalkylaBino like !! ethylamino, acylamino

B # nsoyliiKinö ₉ 'Nstlianeulfonylesaino and ^ mino, anilino and substituted® Berl ^ ate thereof wi #

009846/1730 "^.

BATH ORIGINAL

Triaethylanilino, sulfoanilino and carbosgranilino, lower alkyl like methyl, lower alcohol like methoxy and xthoiy, sulfic acid, Sulfonamido and substituted derivatives thereof such as sulfo-H-methylamido and sulfo-RtN-diethylamido, carboxylic acid, mercapto, ftlederalkylmercapto such as Methy! mercapto, Fhenylmereapto and Benzthiazol-2-ylthio. Preferably there is one Substituent in the anthraquinone nucleus attached to ring B in para position to the -HH group of the heterocyclic ring.

According to a further feature of the invention is a method proposed for the production of the anthraquinone compounds according to the invention, which consists in the fact that an anthraquinone compound the forael:

Formula I.

wherein the rings A and B may contain substituents in Reaction with an aldehyde or ketone of the formula:

\ c - o

B ² '

is brought, where R and R ^ have the above meanings.

The inventive method can be implemented in a sweckaissig that the Beaktlon participants in one sauraa medium, e.g. sulfur »or acetic acid, or in Water or a water-miscible organic liquid that contains an acid such as acetic or hydrochloric acid to a temperature between 25 ° C. and. 4® »boiling point of the acidic

0 0 9 8 4 6/1730 * - 4 -

Medium lying temperature are heated. The thus obtained Product can be isolated in a known manner. If desired, an excess of the aldehyde or ketone can be used as Reaction medium can be used, the necessary acidity by the addition of an acid such as vinegar or Sulfuric acid or an acid generator such as thionyl chloride is achieved.

As examples of the aldehydes and ketones used in the invention Processes that can be used can mention the following: formaldehyde (also in the form of paraformaldehyde), Acetaldehyde, propionaldehyde, n-butyraldehyde, acetone, acrolein, Chloral (also in the form of its hydrates), benzaldehyde, acetophenone, 2-acetylpyridine, aldol (ß ~ Qfdro ^ ~ n ~ proplonaldehyde), Xthylacetoacetate, acetoacetanilide, cyclohexanone, furfural and white isobutyl ketone.

The anthraquinone compounds of the formula I can be prepared by reacting an optionally substituted 1-aminoanthraehinone-2-8ulfonic acid with formaldehyde and a reducing agent in an alkaline Medium according to the methods described and claimed in British Patent 1,152,244.

The following can be mentioned as specific examples of the anthraquinone compounds of the formula I: 1-Aaino = 2-hydro2ymethyl ~ anthraquinone, 1-amino => 2- »hydroatymethyl <= 4— (chloro-, -cyano-, -bromo-, -hydroxy-, "phenyl t'hio ~, -aeetyi & mino-, -anilino", -m «toluidine-, -raeßidin-, -chlorasillnc», -methocyanilino-

0098 ^ 6/1730 _c

- 7th

BATH

or -ρ- (ß-hydroxy ät hooqjr) anil inc) anthraehinone, 1-amino-2-hydroxymethy1-4- (p ~ toluenesulfonamido) anthraehinone, 1-amino-2-hydroxymethyl ~ 4 ~ (m-sulfoanilino) anthraquinone , 1, & · »Diamino 2,7-di (hydroxymethyl) anthraquinone, 1-Amino-2-> hydro3qmethyl * 5 * (chloro» or -sulfo) anthraehinone and 1-Ai & ino-2-hydroxy & ethyl « M-- ( benzthiazol-2 '-ylthio) anthraohinone.

According to a further feature of the invention is a modified one Process for the preparation of the anthraquinone compounds

according to the invention, for aenen R ** and R2 each a hydrogen represent atom, proposed that consists in that an optionally substituted i-Äainoanthraquinone ^ -sulfoic acid in reaction with at least two molecular fractions of formaldehyde in the presence of a reducing agent and is brought to an alkaline agent and after the formation of the 2-Bydro3Qrmethylverbindungen the reaction mixture is acidified to result in the formation of the heterocyclic ring

to effect.

This modified method can thereby be expediently implemented that the formaldehyde and the reducing agent, e.g. zinc dust or sodium hydrosulphite, become an aqueous one alkaline LÖBimg of the 1 »Aminoanthraquinones2» auif ο acidic are preferably added under an internal atmosphere, w © ^ on slide erasure at a temperature between 0 and 100 ° C temperature to form the 3srdro3gym®thy! compound wis? d. The mixture is then acidified with hydrochloric acid, for example and r © i? Bmg @ Ti @ ig @ b © i.2O to 100 ° C to form dee hetero—

0098A6 / 1730. _6th

- * '* BAD ORIGiNAU

cyclic ring stirred. The ao obtained connection will then isolated in a known manner.

While the anthrachlnone compounds according to the invention are completely stable in solid form, their stability in a liquid medium depends on the temperature, the pH value and the type of groups B and E and / or the type of substituents contained in the groups A and B. away. In general, the compounds in which B or B ^{2 represents} a hydrogen atom are relatively unstable even in a neutral aqueous medium at elevated temperatures, and these compounds easily convert back to the anthraquinone compounds of formula 1 by hydrolysis. In contrast, the compounds in which neither R nor ΈΓ represents a hydrogen atom are stable in a neutral aqueous medium. However, the stability falls as the pH of the aqueous medium decreases and the temperature increases, so that these compounds (in which neither B ¹ nor B ^{2 represents} a hydrogen atom) are not stable in a hot acidic medium.

The anthraquinome compounds according to the invention, the auxochromes Groups, etc. Ifydroay or optionally substituted amino groups, contain, see suitable as dyes for textiles. This © Compounds that essentially contain water-solubilizing groups » js.B. Sulpho groups, contain, are suitable as acid dyes for natural and synthetic polyamides, g.B «Voll · und Hfl on, with such dyes on dies® Saacfeilstoff @

Dipping into an aqueous dye bath, if necessary, also known

009848/1730 -? -

BATH ORIGINAL

Contains auxiliaries, e.g. asmonium sulphate and sodium sulphate, can be applied.

Those compounds with the nature of dyes, which, however, do not contain acidic water solubilizing groups contain, disperse dyes are suitable for synthetic textiles, e.g. cellulose acetate, cellulose triacetate, Polyamides, polyacrylonitrile and especially fabrics made from polyesters. Such dyes are in the form of watery ones Used dispersions, which are produced by grinding the dyes in water in the presence of a dispersing agent will. These dyes can be dipped onto the synthetic textile fabrics from aqueous dye baths or im Klotz «· or printing process with the dispersed dye containing padding liquids or printing pastes are applied in a manner known per se.

The dyes of the invention have excellent properties Affinity for textiles that come in different shades of color which have excellent fastness to the samples normally used for such fabrics carried out «earth.

The invention is illustrated below with the aid of exemplary embodiments purely for example explained in more detail, with all quantitative data being based on weight. For the nomenclature of the compounds in these examples the following numbering is used:

00 98 4 6 / Η 73 0

ORIGINAL

example 1

There are 2 parts of paraformaldehyde to a solution of 5 parts i-Juaino-2-hydroxymethylanthraquinone in 250 parts of 96 # iger Sulfuric acid is added and the mixture is stirred at 50 ° C. for 2 hours. The mixture is then poured into Eiswaasor, and the precipitated 1,2 ~ dihydro ^ ~ H ~ anthra (i, 2 ~ d) => (1,3) "Oxazine-7» i2 »dione is filtered off and washed with water and dried. The yield is 4.85 parts. To When crystallized from ethanol, the product has a melting point of 174-175 ° C.

1,2-Dihydro-4-H-6 ~ bromoanthra- (1,2-d) (1,3) -oatazin-7,12-dione is made in a similar way if the 1 ~ amino ~ 2 « hydroxymethylanthraquinone is replaced by an equivalent amount of i-amino-2-hydroxyBrethyl ^ -bromoanthraquinone.

Example 2

There are 200 parts of a 37 # solution of formaldehyde was added to a solution of 30 parts of sodium hydroxide and 73 * 5 parts of the Hatriunealzes of 1 -aminoanthraquinone-2 <1 ° eulfofiäure in 500 parts of water at 20 ⁰ C was added. Then, 50 parts Matriuehydrosulfit are added, and the mixture is stirred for 1 hour at 70 ⁰ C. The mixture is made with a

009846/1 ^l 730 ~ ⁹ ~

BATH ORIGINAL

concentrated aqueous hydrochloric acid solution acidified and stirred at 70 ⁰ C for minutes. The precipitated 1,2 ~ dihydro ~ 4-H ~ anthra- (1,2 ~ d) i1,5 | o: xazin ~ 7 »12 ~ dione is then filtered off, washed with water and dried. The yield is 50 parts.

Example 5

A mixture of 3 parts of 1-amino-2-hydro: K ^ ethyl <= ^ anilinoanthraehinone, 1 part acrolein and 20 parts acetic acid is stirred for 2 hours at 105-110 ° C. The mixture is cooled and 15 parts of water are added, whereupon the precipitated 1,2- »dihydr o - ^ - He-anilino-S-yinylanthra · =» ί 1,2d) - (i _t 5) ~ oxazine ~ ?, 12-dlon is filtered off and dried.

The table below are more examples of that Anthraquinone compounds according to the invention can be found. These have the formulas

and are produced as in Example 3, with 1 part acrolein replaced in each case by the aldehyde indicated in the 2nd column of the table and the indicated reaction conditions can be applied. The respective meaning of R is in the

given in the last column.

-10-

009846/1730 bad original

Chloral hydrate - 10 - 105-110 1927313 Aldol 105-110 R. E.g. aldehyde Paraformaldehyde Reaction
time «temp.
Min. ° 0 100 Trichloromethyl 4th acetaldehyde 90 75-80 ß-Hydroaty-n-propyl 5 Benzaldehyde 120 100 hydrogen 6th n-butyraldehyde 5 100-105 methyl 7th Benzaldehyde-o "
sulfonic acid 30th 105-110 Phenyl 8th Example 11 60 n-propyl 9 60 o ~ sulfophenyl 10 120

A mixture of 1.65 parts of 1-aaino-2-hydroxymethyl-4 ~ anilinoanthraquinone, 50 ropes of acetone and 1.2 parts of thionyl chloride is refluxed for 1 hour. The mixture is then poured into water, and the excreted Product is filtered off, washed with water and dried. The product is 1,2-Mbydro ~ 4 ~ H ^ anil: Uio ~ 2,2-dimethylanthra « (1,2-d) (1 * 3) -oxasin-7,12 ~ dione of the formula:

I.
CH ₂

wherein Z is anilino.

By using the appropriate amounts τοη 1-Ατι1ηο-2 « hydroxyaethy 1-4- (bensthiazöl = 2 ~ yithio-, -thiophenyl «or -p-toluoleulfonamido) anthraquinone instead of τοη the 1.65 parts

0 098 IS A173 0

- 11 -

BATH ORIGINAL

the anthraquinone compound used in this example get nan the corresponding compounds of the above formula, in which Σ

-S-C I) j, phenyl thio bew. P ~ toluenesulfonamido means.

Example 12

A mixture of 5 parts of 1-amino-2-hydroxymethyl-4- (ptoluidlno) anthraehinone, 100 parts of acetone and 0.9 Tollen 98% sulfuric acid is refluxed for 2 hours. The mixture is cooled and the precipitated solid is filtered off, washed with water and dried. The yield of 1,2-dihydro-4 ^ H-2,2 ~ diiaethyl-6 ~ (p-toluidino) - anthra- {1 _t 2 ~ dMi _f 3) -oxaBin-7,12 "dione is *, 5 parts.

The table below shows other examples of the anthraquinone compounds to be found according to the invention. These have the formula:

and are produced by interlacing the anthraquinone compounds given in the 2nd column of the table with the ketone according to the 3rd column as in Example 12 under the given reaction conditions. The respective meanings τοη R *, H * and are indicated accordingly. _ΛΟ

0098 ^ 8/1730

BATH ORIGINAL

Ββρί . Anthraohlnonrexbiadunc !•volume Heaktion -
selt -teap. Sdp. methyl methyl Leobutyl Β? "Ι k 19273 13th i-Amino-2-hydrowBethyl - * - acetone 1 h 20 ⁰ C
20 ⁰ C
Sdp.
Sdp. Penta-
methylene
Methyl -CH ₂ COO-
Methyl methyl
Methyl FhenjL Anilino V
I. 1*
15th
16
17th
I. ■ to XJ wmitfritTiMT? * F iy *** Cyclo
hexanone
Xthylaeet-
aeetat
acetone
Aoeto 2 h
2 h
2 h
10 am Sdp.
95-10O ⁰ C Tetra
Ethylene
Methyl -CH ₂ COOXt
Methyl n-propyl 19th
20th dto.
dto.
i-amino-a-hydroxymethyl-A-
(ρ — β thoa ^ ranl 1 ino) anthrechi non Oyclo-
pentanone
Ethyl acetate
acetate 10 am
18 h
3 h 100 ° C methyl Anilino 8600 21 (binithiaiol ^^ Tthio) - propyl
ketone
Leobutyl
ketone 90 am p-methosy «
anilino
Benxthiazc
2 ^f -ylthio σ>
u>
ο -. dto.
dto. dto.
dto.
Anilino dto. ■ Jf.
D.
O
33
δ
I.
Γ " -

Hit aqueous dispersions of the dyes according to the examples 12 to 16, 20 and 21 can use polyester fabrics in bright green-blue shades of excellent fastness can be dyed while they are munching with the dyes Examples 17 to 19 can also be dyed in bright red shades of excellent fastness.

Example 22

A mixture of 1 part of 1-amino-2-hydro3 3rmethyl £ - ^ - anilinoanthraquinone, 10 (dents furfural and 0.5 parts of 98% sulfuric acid is heated to 100 ⁰ C 5 Hinuten organic mixture is then heated to 20 °. C cooled and poured into methanol. The precipitated 1,2-dihydro- * - H-6-anilino-2-furfurylanthra- (1,2-d) { 1,3) -oxazine-7,12-dione is filtered off, washed with methanol and dried.

0098 46/1730 '- 1 * -

SAD ORJGINAL

Claims (2)

Claims ΛJ Anthraquinone compounds of the formula: characterized in that R ¹ and R ² each represent a W hydrogen atom or an optionally substituted hydrocarbon or heterocyclic radical or R and B ² together with the carbon atom form a 5- or 6-membered ring system, and that the rings A and B have substituents may contain. 2. Process for the preparation of the anthraquinone compounds according to claim 1, characterized in that an anthraquinone compound of the formula: in reaction with an aldehyde or ketone of the formula: is brought, where A, B, R ¹ and IBr have the meanings given in claim 1. 009846/1730 - 15 - BATH ORIGINAL 3 · Process for the preparation of the anthraquinone compounds according to Claim 1, in which R and R each have a hydrogen atom represent, characterized in that an optionally substituted i-Aainoanthraquinone-2-sulfoic acid with at least two molecular fractions of formaldehyde in the presence of a reducing agent and an alkaline agent but reaction is brought, whereupon the reaction mixture after Formation of the 2-lfcrdrosymethyl compound is acidified to to cause the formation of the heterocyclic ring. MVNTi 0 0 9 8 4 6/17 3 0 BATH ORIGINAL