DE2413230A1 - DISPERSE Azo Dyes - Google Patents

Description

PATENT LAWYERS
D R.- ING. H.FINCKE DI PL.-I NG. H. BOHR DIPL.-ING. S. STAEGER

Remote call: '2iiO 60 Talegrammet Claims MDnchen Postal checking account: Munich 27044.802

Bank details Bayer. Vereinsbank Munich, account 620404

23465 - Dr.K / hr

Folder No. CaSβ Dd.25967 Please state in the answer

8 MUNICH B ₁ MOIIorstrasse 31

19th March

IMPERIAL CHEMICAL INDUSTRIES LIMITED, London, Great Britain

"Disperse azo dyes"

Priority : March 19, 1973, UK No. 13112/73

The invention relates to disperse azo dyes that can be used for dyeing aromatic polyester textile materials.

According to the invention disperse azo dyes are proposed, which are free of sulfonic acid groups and the general formula

409839/0974

D-N =

A - O.C - (CHJ - COOH

have, wherein A is an alkylene radical with at least 2 Carbon atoms; R for an optionally substituted Aryl or cycloalkyl radical or a substituted one Alkyl radical; Y is hydrogen, alkyl or alkoxy; X stands for hydrogen, alkyl, alkoxy, chlorine or bromine stands; η is 2 or 3; and D stands for a phenyl radical which may contain substituents.

The substituents which can be present in the phenyl radical represented by D can, besides sulfonic acid groups, be any substituents which usually occur in diazo components of the benzene series. Examples of such substituents are chlorine, bromine, alkyl, especially lower alkyl, for example methyl, alkoxy, especially lower alkoxy, for example methoxy, alkylsulfonyl, especially lower alkylsulfonyl, and alkylcarbonyl, especially lower alkylcarbonyl, for example ethylsulfonyl and acetyl, nitro, thiocyano, cyano, trifluoromethyl, carbonamido and sulfonamido and N-alkyl, N-aryl and N, N-di (alkyl) derivatives thereof, especially N-lower alkyl and N, N-di (lower alkyl) derivatives thereof, alkoxycarbonyl, especially lower alkoxycarbonyl, for example methoxycarbonyl and A ' thoxycarbonyl, and hydroxy, alkoxy, especially lower alkoxy, hydroxyalkoxy, especially hydroxy lower alkoxy, and alkoxyalkoxy _T , especially lower alkoxy lower alkoxy derivatives thereof, for example ß-hydroxyethoxycarbonyl, ß-methoxyethoxycarbonyl, ß- (ß'-

409839/0974

Hydroxyethoxy) ethoxycarbonyl and B- (B ¹ -ethoxyethoxy) ethoxycarbonyl, azo groups such as phenylazo, nitrophenylazo and chlorophenylazo, acylamino groups such as acetylamino and benzoylamino, arylsulfonyl groups such as benzylsulfonyl, such as phenylsulfonyl and and aryloxycarbonyl groups, such as, for example, phenoxycarbonyl.

Throughout this specification the term "lower alkyl" means and "lower alkoxy" alkyl and alkoxy radicals with 1 to ^ carbon atoms.

The alkyl radicals represented by X and Y are preferably lower alkyl radicals, especially methyl. The alkoxy radicals represented by Y and X are preferably lower alkoxy radicals, in particular Methoxy and ethoxy radicals.

Examples of alkylene radicals represented by A are Ethylene, trimethylene, propylene, tetramethylene and hexamethylene.

Examples of radicals represented by R are phenyl, Tolyl, cyclohexyl, hydroxyalkyl, especially hydroxy-lower alkyl, such as ß-hydroxyethyl and ß- or γ-hydroxypropyl, Chlör-oalkyl, especially chloro-lower alkyl, such as e.g. ß-chloroethyl and ß- or γ-chloropropyl, bromoalkyl, in particular bromine-lower alkyl, such as ß-bromoethyl, arylsulfonylalkyl, especially arylsulfonyl-lower alkyl, such as ß-phenylsulfonylethyl, alkylsulfonylalkyl, in particular Lower alkylsulfonyl lower alkyl, such as ß-methylsulfonylethyl, Aralkyl, such as benzyl. And ß-phenylethyl, Arylcarbonyl lower alkyl, such as ß-benzoylethyl, alkylcarbonylalkyl, in particular lower alkylcarbonyl lower alkyl, such as ß-acetylethyl, acyloxyalkyl, especially acyloxy

A09839 / 097A

lower alkyl, such as ζ.Β- * · ß- (acyloxy) ethyl, and in particular Lower alkylcarbonyloxy lower alkyl, such as ß-acetoxyethyl, and arylcarbonyloxy lower alkyl, such as ß-benzoyloxyethyl, Alkoxyalkyl, especially lower alkoxy lower alkyl, such as B- (methoxy- or ethoxy-) ethyl and -γ-methoxypropyl, Aryloxy lower alkyl, such as ß-phenoxyethyl, alkoxycarbonylalkyl, in particular lower alkoxycarbonyl-lower alkyl, such as ß-methoxycarbonylethyl and ß-ethoxycarbonylethyl, Aryloxycarbonyl lower alkyl, such as ß-phenoxy-

carbonylethyl. and NOC-alkyl, especially NOC-

S Η

Lower alkyl, where R ^ and R each independently represent hydrogen or alkyl, such as, for example, ß- (Carbo-N, N-dimethylamido) ethyl and ß- (Carboanilido) ethyl.

According to the invention, a method for Proposed preparation of the azo dyes according to the invention, which is carried out by adding an amine to the Formula D-NE ^ diazotized and the diazo component obtained with a coupling component of the formula

- OC - (CH ₂ ) _n - COOH O.

couples, the amine and the coupling component being free of sulfonic acid groups and A, D, R, X, Y and η as above have given meanings.

The method according to the invention can expediently be carried out in this way be that you can make a solution or suspension of the amine in an aqueous solution of a strong sodium nitrite

409839/0974

inorganic acid is added, or that the amine to a Solution of nitrosylsulfuric acid is added, whereupon the resulting solution or suspension of the diazo component to a solution of the coupling component in water, which is an acid and / or a water-soluble organic liquid contains, adds. If necessary, the pH of the mixture can be adjusted to facilitate coupling. The azo dye formed is then isolated in the usual manner.

Specific examples of the amines mentioned are aniline, 2-, 3- or 4- (methyl, methoxy, chloro-, bromo-, nitro, cyano-, sulfonamido, carbonamido, carbomethoxy or Methylsulfonyl-) aniline, 3- or 4-aminophenylacetic acid, 3- or 4-aminophenoxyacetic acid, 2- or 3-nitrο-4-aminophenylacetic acid, 2,4-dinitroaniline, 2,4-dinitro-6- (chloro-, bromo, cyano or nitro) aniline, 2- (chloro, bromo, nitro, cyano, methyl or methoxy) - 4-nitroaniline, 4-aminoazobenzene, 4-Amino-4 '- (methyl-, nitro- or chloro-) - azobenzene, 2,6-di- (chloro-, bromo- or cyano-) - 4-nitroaniline, 2,4,6-tri- (chloro-, bromo-, cyano- or nitro) -aniline, 2,4-dicyanoaniline and 2- (sulfamoyl, carbamoyl, Methoxycarbonyl- or methylsulfonyl-) - 4-nitroaniline.

The mentioned coupling components themselves can thereby be obtained

be that you can get a compound of the formula

with succinic acid or glutaric acid or the corresponding anhydrides esterified, where A, R, Y and X have the meanings given above and where an excess of the acid

409839/0974

is used to prevent the formation of the corresponding diesters.

Specific examples of the coupling components mentioned are N- (β-cyanoethyl, β-hydroxyethyl, β-phenoxyethyl, β-ethylsulfonylethyl, β-benzoyloxyethyl, T'-chloro-β-hydroxypropyl, β-carbamoylethyl, β -Ethylcarbonyläthyl-, ß- (ß'-Methoxyäthoxycarbonyl) ethyl-, ß-Acetoxyäthyl-, ß-Methoxycarbonyläthyl- or Y-methoxypropyl -) - N- / ß- (ß'-carboxyäthylcarbonyloxy) äthyl7anilin, N- (ß-Cyanoethyl) - or ß-hydroxyethyl) -Έ- / β- (γ '-carboxypropylcarbonyloxy) ethyl7-m-toluidine, N- / ß- (ß'-carboxyethylcarbonyloxy) ethyl7diphenylamine, H- (ß-acetoxyethyl or benzyl -) - N - / ^ B- (ß '-carboxyäthylcarbonyloxy) äthyl7-2,5-dimethoxyaniline, N-Cß-Cyanoäthyl) ^ - / ^ - ^ ¹ -carboxypropylcarbonyloxy) äthyl7anilin or -m-toluidine and the N- (ß-cyanoethyl ) -N- / ß- (ß'-carboxyäthylcarbonyloxy) äthyl7 -derivate of m-toluidine, m-chloroaniline, m-bromoaniline, m-anisidine, o-toluidine, o-anisidine, 2-methoxy-5-methylaniline and 2 , 5-dimethylaniline.

According to the invention, there is also an alternative method proposed for the preparation of the azo dyes according to the invention, which is carried out in that one an azo compound of the formula

A-OH

D-N-

W ί \

X '. i ^fi

with succinic or glutaric acid or the corresponding anhydrides esterified, where D, A, R, X and Y have the meanings given above.

409839/0974

The alternative method of the present invention can expediently carried out by the fact that the A-zo connection with an excess of the dibasic acid in the presence of a catalyst such as sulfuric acid in a water-immiscible solvent, the reaction preferably taking place at the boiling point of the reaction medium is carried out and wherein the water formed in the reaction is removed by distillation.

The azo compounds mentioned can even be obtained by diazotizing an amine of the formula D-RHg and the resulting diazo compound with a coupling component the formula

couples, where A, R, X, Y and D have the meanings given above.

A preferred class of the dyes according to the invention includes the dyes in which D is a radical of the formula

stands, where U is hydrogen, lower alkyl, lower alkoxy, Is chlorine, bromine, cyano or lower alkoxycarbonyl and V is hydrogen, chlorine, bromine, ritro or cyano.

409839/0974

The dyes according to the invention are suitable for dyeing aromatic polyester textile materials. The dyes can be prepared by conventional aqueous dyeing, padding or printing processes can be applied using the dyes in a finely divided form. This can be achieved thereby be, that one grinds the dyes in an aqueous medium in the presence of dispersants. Alternatively The dyes can be used in the form of water-soluble alkali metal, ammonium or amine salts for the preparation of the aqueous dye baths, printing pastes or padding liquids can be used. JAn acid ** such as acetic acid, before or after using the dye baths, pastes or liquids mentioned on the aromatic polyester textile material be applied. The dyes according to the invention give yellow on aromatic polyester textile materials to navy blue shades with excellent fastness to light, wet treatments and dry heat treatments .

The invention is illustrated in more detail by the following examples, in which the parts and percentages are by weight are expressed.

example 1

A solution of 10.1 parts of 2-bromo-6-chloro-4-nitroaniline in 160 parts of hot acetic acid, the mixture is cooled to 40 ° C. and 32 parts of a concentrated aqueous hydrochloric acid are used is added and the mixture is cooled to 5 ° C. Then it will be a solution of 2.92 parts of sodium nitrate in 20 parts of v / water at 5 to 10 ° C was added, whereupon the mixture was further Is stirred for 15 minutes at the same temperature. Excess nitrous acid is then destroyed by the addition of sulfamic acid. The obtained solution of the diazo compound is then a solution of 11.6 parts of N- (B-cyanoethyl) -N- / ß- (ß'-carboxyäthylcarbonyloxy) äthyl7anilin

409839/0974

added in a mixture of 200 parts of water, 200 parts of ice and 200 parts of acetone. Sodium acetate is then added until the mixture is no longer acidic to congo red. After stirring for 2 hours at 5 to 10 ^° C., the precipitated dye is filtered off, washed with water and dried.

A solution of the dye in an aqueous solution of sodium carbonate is acidified, and an aromatic PoIyestertextilmaterial is dyed at 130 ⁰ C under überatmosphärischom pressure in the thus obtained dyebath. The red dyeing obtained has excellent fastness properties after rinsing in an aqueous sodium carbonate solution and then in water / water.

The same dye is obtained if a mixture of 2.1 parts of the azo compound is obtained by coupling diazotized 2-bromo-4 ~ nitro-6-chloroaniline with N- (ß-cyanoethyl) -N- (ß-hydroxyethyl) aniline is obtained, 0.5 part of succinic anhydride, 10 parts of toluene and 0.1 part of pyridine are stirred at 90 ^° C. for 12 hours. The mixture is then ^{cooled to 20 °} C., and the precipitated dye is filtered off, washed with ethanol and dried.

In the following table are further examples of the invention Dyes prepared as above are indicated, the symbols being those in the corresponding Columns of the table have the meanings given. The last column of the table indicates the shades that are obtained when the dyes are applied to aromatic polyester fabrics.

The dyes of these examples were obtained by diazotization of the corresponding amine of the formula D-NIL ·) and

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Coupling with the corresponding coupling component of the formula

A - O. C

²ⁿ

COOH

> —N

or by reacting an azo compound of the formula

, —Ν

A-OH

with succinic acid or glutaric acid or the corresponding anhydrides, procedures similar to those described in Example 1 were used.

409839 / 097Λ

Ex. D. X Y R. A. η hue I. I. 2 2-cyano ~ 4-nitrophenyl methyl water
material β-cyanoethyl Ethylene 2 Ruby red -Λ
I. 3 2-ChIOrO- ² I-nitrophenyl ti Il It * Il 2 Red * ■ » Il Il Il ß- (ß'-cyano-
ethoxy) ethyl Il ι 2 ti O
to 5 Il Il methyl β-cyanoethyl ti 2 Il 00
co 6th 2-cyano-4,6-dinitrophenyl Il water
material ß-methoxyethyl It 3 violet H-"
ro O
• «-a
*> - 7th
8th It
2-methoxy-4-nitrophenyl Il
ti Methoxy
water
material ß-methoxy
carbonylethyl
ß-methoxyethyl It
It 3
2 reddish
marine
blue
Red 4132! 9 Il bromine It ß-chloroethyl Trimethylene 2 It O 10 4-chlorophenyl methyl ti ß-methoxyethyl Ethylene 2 yellow 11 2-bromo-A-, 6-dinotrophenyl Il ft Il Trimethylene 2 Ruby red 12th 4-phenylazophenyl It Il η dd 2 Sharlac
Red 13th 2-chloro-4-nitro-6-bromo
phenyl water
material It β-cyanoethyl Ethylene 2 yellow
Brown

Ex. D. X Y · R. A. η hue 14- 2-chloro-4-nitrophenyl chlorine water
material Benzyl Ethylene 2 Red 15th Il water
material Il Phenyl II- 2 bluish
Red 16 2-cyano-4-nitrophenyl methyl Il m-tolyl Tetramethylene 2 violet O 17th 2-methyl 1-4-nitrophenyl chlorine η Cyclohexyl Ethylene 2 Red 9839i 18th 2-bromo-4,6-dinitrophenyl Methoxy Me thoxy ß-carbamoylethyl 2 reddish
marine
blue ο
«Ο 19th 2-cyano-4-nitrophenyl methyl water
material ß-carboxyethyl Tetramethylene ² Ruby red - «J 20th 2-methoxycarbonyl-4-
nitrophenyl water
material Il β-cyanoethyl ^ -Methyl-
ethylene 2 Sharlac
Red 21 2-chloro-4-cyanophenyl ■ 1 Il It
S. ß-methyl
ethylene 3 orange 22nd 2-chloro-4-, 6-dinitrophenyl Il Il ß- (ß'-methoxy-
ethoxy) ethyl Ethylene 2 bluish
Red 23 Il methyl Il ß-phenoxyethyl ti 2 Ruby red 24 2-bromo-4-nitrophenyl Il H γ-methoxypropyl Il 2 Red 25th 2,4-, 6-trichlorophenyl π ti ß-acetylethyl Hexamethylene 2 orange

Claims (1)

PATENT CLAIMS : 1. Disperse azo dyes that are free from sulfonic acid groups are and the formula Λ - OC - (CH-J _n - COOH have, where A is an alkylene radical with at least 2 Carbon atoms; 'R is an optionally substituted aryl or cycloalkyl radical or a substituted one Alkyl radical; Y is hydrogen, alkyl or alkoxy '; X stands for hydrogen, alkyl, alkoxy, chlorine or Bromine; η is 2 or 3; and D for a phenyl radical stands, which optionally contains substituents. 2. Process for the preparation of the azo dyes according to claim 1, characterized in that an amine is used Formula D-NHp diazotized and the resulting diazo compound with a coupling component of the formula Λ - OC - (CHj_ - COOH couples, wherein the amine and the coupling component are free of sulfonic acid groups and A, D, R, X, Y and η in claim 1 have given meanings. J. Process for the preparation of the azo dyes according to 409839/0974 Claim. 1, characterized in that one is an azo compound the formula D-N A-OH with succinic or glutaric acid or the corresponding anhydrides esterified, where D, A, R, X and "* Y have the meanings given in claim 1. 4. Use of the dyes according to claim. 1 for coloring of aromatic polyester textile materials, said textile materials being mixed with an aqueous dispersion of the azo dye treated. 409839/0974