DE2254017A1 - HYDRO-INSOLUBLE AZO DYES AND PROCESS FOR THEIR PRODUCTION - Google Patents

Description

D the remainder of an optionally substituted aromatic or heteroaromatic diazo component free of ionogenic groups,

X is a hydrogen atom or an optionally substituted alkoxy group,

Y is a hydrogen atom, an optionally branched and / or substituted alkyl, an optionally substituted alkenyl, an optionally substituted cycloalkyl, an optionally substituted phenyl, a hetaryl, an optionally substituted alkoxy, an optionally

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substituted phenoxy group or the radical —NTI-it

H
where R is an alkyl, alkenyl or cycloalkyl group or an aralkyl or aryl group and

1 2
R and R are hydrogen or an alkyl group and

R is an optionally branched and / or substituted one

Alkyl group

1 2
mean. The radicals R and R can be identical or different

be.

All aromatic groups free of ionogenic groups come as radicals D or heteroaromatic diazo components into consideration. For example, D means a phenyl, naphthyl, thiazolyl, benzthiazolyl, Benzisothiazolyl or triazolyl radical, which is represented by a or more, for example two or three, substituents may be substituted. D is preferably a phenyl radical. The radical D, preferably the phenyl radical, can be substituted, for example, by one or more of the following radicals be, with multiple substitution the substituents can be the same or different:

Alkyl with 1 to h carbon atoms, in particular methyl or ethyl; Alkoxy having 1 to 4 carbon atoms, in particular methoxy and ethoxy; Nitro; Cyan; Alkylsulfonyl with 1 to k carbon atoms, in particular methylsulfonyl or ethylsulfonyl; Alkylthio with i to k carbon atoms; Chlorine; Bromine; Phenylazo. For a multiple substitution of the remainder D come in particular

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the radicals chlorine, bromine, cyano, nitro, alkyl, alkylsulfonyl into consideration.

An alkoxy group standing for X and Y can, for example, have 1 to C atoms, preferably 1 to k C atoms and can, for example, be replaced by a hydroxyl group, an alkoxy group with 1 to k C atoms, in particular with 1 or 2 C atoms, or an optionally substituted phenoxy group may be substituted. The last-mentioned phenoxy group can in particular be replaced by alkyl radicals, e.g. Methyl or ethyl radicals «, in the case of a substituted alkoxy group standing for X and Y, the substitution takes place · preferably in the eno position of the alkoxy radical,

An alkyl group representing Y normally has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. One for The alkenyl group in Y normally has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms. The one for Y standing alkyl or alkenyl groups can, for example be substituted by a halogen, in particular a chlorine atom, a hydroxyl group, an alkoxy group with 1 to 4 carbon atoms, an optionally substituted phenoxy or an optionally substituted one Phenyl group.

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Hetaryl radicals for Y can be, for example: pyridyl, thiazolyl, benzthiazolyl, iniidazolyl, benz imidazolyl, thienyl, furyl or pyrrolyl radicals. A phenoxy group standing for Y can, for example, by an alkoxy radical, in particular by methoxy or Ethoxy substituted.

The chain length of the alkyl groups in the radicals R and

ο
R is usually 1 to 3 carbon atoms. The chain length

■ z
the alkyl group in the radical R ^ is usually

1 to 5 carbon atoms.

üie for R ^ standing alkyl group can for example by a halogen, in particular a chlorine atom, an alkoxy, alkoxy-alkoxy, phenoxy, phenoxy-alkoxy or phenyl group be substituted, the chain length of the

Alkoxy groups is preferably 2 carbon atoms,

u
The alkyl radicals for R normally have 1 to 6 carbon atoms, preferably 1 to k carbon atoms. The alkenyl radicals represented by R preferably have from 2 to 6 carbon atoms, preferably 2 to h carbon atoms.

The cycloalkyl groups for Y and R have, for example, 3 to 8 carbon atoms, the cyclohexyl radical is preferred.

409820/0988

• ζ h
The phenyl group is preferred as the aryl group for Y, R "^ and \ i and the phenethyl, in particular the benzyl group, is preferred as the aralkyl group for the group Ii * one or more halogen atoms, in particular chlorine or bromine atoms, cyano groups, alkyl groups, preferably with 1 to 3 carbon atoms, and alkoxy groups, especially methoxy or ethoxy groups.

The dyes of the invention can be prepared by using a diazonium compound of an aromatic or heteroaromatic amine of the general formula II

D - NH ₂ II

that is free of ionogenic groups with a coupling component of the general formula III:

NII-CO-Y

CH ₂ -H ¹

III

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225A017

is coupled, where D, X, Y H, R and R ^ the already have given meaning.

The diazonium compounds are prepared from the amines of the general formula II in a manner known per se by diazotization. The diazotization is normally carried out in an aqueous medium or an inorganic or organic acid at temperatures from 0 to 10 ^° C. by the action of nitrous acid. As usual, sodium nitrite and an acid, such as sulfuric acid or nitrosylsosulfuric acid, are used to generate nitrous acid. The diazo solution obtained is combined with a solution of the coupling component at temperatures from 0 to 25 ° C., preferably from 0 to 10 ° C. For this purpose, the coupling component can be dissolved in a suitable solvent such as ethanol, dimethylforraamide, etc. Normally, however, the coupling component is dissolved in water acidified with sulfuric acid. In some cases it can be useful to buffer the pII value during the coupling, for example by adding sodium acetate. The coupling is complete after a few hours and the dye can be isolated by suction filtration and dried.

Diazotizable aromatic and heteroaromatic amines der Formula II are for example:

2-, 3- or 4-nitroaniline, 2-methyl-4-nitroaniline, 2-, 3- or 4-cyano-aniline, 2-chloro - ^ - nitroaniline, 2-bromo-4-nitroaniline _t

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2-Nitro-4-chloroaniline ₃ 2-Nitro-Wbromaniline, 2,4-Dinitro-aniline, 4-Nitro-2-cyaxi-aniline _s ^ -methyl- or ethylsulfonyl-aniline, 4-nitro-2-methylsulfonyl ~ aniline, 4-nitro-2,6-dichloroaniline, 4-nitro-2,6-dibromaniline, 2,4-dinitro-6-chloroaniline, 2,4-dinitro »6-br.omaniline, ^ -nitro ^ -cyane -e-bromoaniline, 2,4-dinitro-6-cyanoaniline, 4-nitro-2,6-dicyanoaniline, ⁱ t -nitro-2-cyano ^{-6-methylsulfonylaniline, 2, z-} i-dinitro-6-methyl - or butyl-sulfonyl-aniline, 2,4 ~ dinitro-6-methylthioather- or -6-τα, butylthioether aniline, 4-nitro ~ 2-raethylsulfonyl-6-bromaniline, 2,4-di ~ nitro-6- methoxyaniline, 4-NitΓO-2-cyano-6-ethoxy-aniline, 4-nitro-2-bromo-6-methoxyaniline, 5-nitro-2-aminothiazole, 2 ~ amino-4-methyl-5-nitrothiazole, 2-Aminobenz.thiazole, 6-NitΓO-2-arainobenzthiazole, 3-Araino-5-nitΓO-2.1-benzisothiazole, ^ -amino-S-nitro-y-chloro- or brora-2.1-benzisothiazole, 3-Alinino- 5-β-hydroxy-propyl-1,2,4-triazole, 4-aminoazobenzene, ^ '- nitro - ^ - aminoazobenzene, 2,3' -j) imethyl-4-aminoazobenzene.

Substituents X in coupling component III and thus

Also in the dyes I are, for example:

Hydrogen, the methoxy,

Ethoxy,

2-hydroxy-ethoxy,

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2-ethoxy-ethoxy-, 2-phenoxy-ethoxy-, 2- (2'- or V-methyl-phenoxy-ethoxy) -, η or iso-propoxy or the n-butoxy group

Substituents Y in coupling component III and thus

Also in the dyes I are, for example:

Hydrogen, the methyl,

Chloromethyl, methoxy-methyl, ethoxy-methyl, n-butoxy-methyl-, phenoxy-methyl-, 4-chloro- or 4-bromo-phenoxy-methyl-, Phenyl-methyl-, ethyl-,

2-hydroxyethyl, 2-methoxy-ethyl-, 2-ethoxy-ethy1-, 2-phenoxy-ethy1-, 2- (2> - or 4'-methoxyphenoxy) -ethyl-, n- or iso-propyl-, 3-hydroxy-n-propyl-, Iso-butyl,

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η-Penty1-, allyl-,

2-methyl-allyl, 2-phenyl _vin yl, cyclohexyl, methoxy, ethoxy, phenoxy,.

4-ethoxy-phenoxy-, ethylamino-, Allylamino, cyclohexylamino and the phenylamino group, further

2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2,3 or 4-pyridyl residues.

1 substituents R and R are for example:

Hydrogen, the methyl, ethyl, or n-Propy1 group.

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225Λ0 1 7

Substituents Ii are, for example, the methyl,

Phenyl-methyl-, ethyl-,

2-chloroethyl-, 2-methoxy-ethy1-, 2-ethoxy-ethy1-, 2- (2'-ethoxy-ethoxy) -ethy1-, 2-phenoxy-ethyl-, 2- (2'-phenoxy-ethoxy) -äthy1-, 2-Pheny1-ethy1-, n- or, iso-propyl-, n-, iso- or tert-butyl or the iso-pentyl group.

The preparation of a group of dyes according to the invention can also take place in that the dyes of the formula IV, likewise according to the invention

^m ' ^C0 - ^Y CH ₂ -R ¹

CH ₂ RN = N- ^ ^ S-NH-CC 00R · ⁵

IV shark. ^Λ

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1 2
wherein Z and Z are identical or different substituents from the group consisting of Cl, Br, NO ₂ , CN, -SO ₂ -R ⁵ , Oll · ⁵ and Hal. denote a halogen atom, in particular chlorine or bromine

1 2 " ¹ I.
and X, Y, R, R, R have the meanings given above

and R ^ denotes an alkyl group with 1 to 6 carbon atoms, according to the information in "DOS i 80yS, LJ _f 1 809 921, Brit.Pa 825 by nucleophilic exchange reaction

with N0 "in

N = N

NH-COO-R "

CII ₂ -R '

with CN I.
i in NH-CO-Y IVn = Z ¹ " X CN

NH-C-COO-R ³

^CH 2 ~ ^R

VI

NH-CO-Y

N = Nf 7-NH-C-COO-R ³

SO _p -R

CH ₂ -R '

VII, and

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with H- ⁵ S "in

VIII

be convicted.

The exchange reactions are carried out in an inert organic solvent, preferably a dipolar aprotic solvent such as, for example, N-methylpyrrolidone, dimethylformamide or dimethyl sulfoxide. The reaction temperatures are normally between 20 and 150 ° C. The nucleophilic agent (NOg ", CN ~, R ^ SO ₂ "", and R- ⁵ S") is in the form of an alkali or alkaline earth compound (eg NaNOp, NaSOpR, NaCN), but preferably as a copper (i) compound or introduced into the reaction in the presence of another copper (I) compound, such as, for example, CuCl, CuBr, CuJ or CUpO.

For the preparation of the dyes according to the invention The coupling components required can be produced by known processes.

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r- 13 -

For example, the coupling components III can be obtained by that first an aniline derivative of the formula IX in glacial acetic acid as a solvent with a ketone of the general formula X. and KCN is implemented.

This creates the nitriles of the general formula XI (see: v. Walter and Hübner, J.pr.Chem. £ 2 »123) NH-CO-Y

₊ C ₌ . O ₊ KCN ¹ "2nd

NH-CO-Y

/ ^CH 2 ^-R NH-C-CN

+ CH, -C00K

XI

The nitriles of the formula XI are in the presence of mineral acids, preferably in the presence of hydrogen chloride or Reacted hydrogen bromide with alcohols of the general formula R-OH and deliver according to the following reaction scheme

NH-CO-Y

NH-

CH ₂ -R ^J

• 6-CN c CH _n -R '

R ^ -OH

HCl, 20 "C

NH-CO-Y

NH-

XII

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R ⁵ -OH

HCl

225-017

CH ₂ -R ^J NH-C-COOH-

CH ^ -R *

XIII

first the salts of the corresponding imidic acid esters XII and in a second step, which is carried out between 20 ° and the boiling point of the alcohol used Π -OH, the esters of the general formula XIII. This generally results in saponification of the compounds in the compounds X | existing group —NH-CO-Y to an NII ₂ group. By reacting the ester XIII with acylating agents that introduce the acyl radical -CO-Y, such as carboxylic anhydrides 0 (COY) ₂ , carboxylic acid halides HaICOY, chloroformic acid esters (if Y is an alkoxy or phenoxy group), the desired esters III are obtained

won:
NH _n

NH-CO-Y

NH-C-COOH

H ₂ -R '

Acylation

middle

CH, - B ^ JiH-C-COOR-

CH ₂ -R '

XIII

III

To prepare the coupling components III, the α-halocarboxylic acid halides XIV (in particular the cfc-bromocarbon-

Hal - C - CO - Shark
¹ 2
^C V ^R

+ HO-R-

Shark.

C COOR-

CH ₀ -R ²

XIV

XV

XVI

acid bromides) with the corresponding alcohols XV to the 4-halogen

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-JHf-

React esters XVI and then condense them with aniline derivatives XVII to form the coupling components III.

NII-CO-Y NII-CO-Y

Γ ² .

NH-C-COOR-

I 2 ^CH 2 " ^R

XVII

+ Hal-C-COOIl ^ CII ₂ -R ²

XVI

Preferred dyes according to the invention are those in which in general formula I.

XYR ¹ and R '

a 2.4-dinitro-6-chloro- or -6-bromo-phenyl-

or a 2-cyano-4-nitro-6-bromophenyl radical,

Hydrogen, a methoxy or ethoxy group,

a methyl radical,

hydrogen

an ethyl, normal butyl, secondary butyl,

iso-butyl, 2-methoxy-ethyl, 2-ethoxy-ethyl,

2- (2'-kethoxy-ethoxy) -ethyl or a

2- (2'-jlthoxy-ethoxy) -ethyl group

mean.

The azo dyes according to the invention are used individually or as a mixture various dyes according to the invention or mixed with other disperse dyes, excellent for dyeing and printing on hydrophobic synthetic materials,

Possible hydrophobic synthetic materials are: cellulose-2 1/2 acetate, cellulose triacetate, polyamides and

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especially polyester materials such as polyethylene glycol terephthalate. These materials can be in the form of sheet-like or thread-like structures and can be processed into yarns or woven or knitted fabrics, for example. Using the customary dyeing and printing processes, they then give strong orange, red, violet and blue dyeings and prints with very good fastness properties, in particular very good fastness to light and sublimation. Dyeing of the fiber goods mentioned with the dyes of the invention is advantageously carried out from an aqueous suspension, optionally in the presence of carriers between 80 to 140 ⁰ C, and by the so-called thermofixing process at about 180 to 23O ⁰ C. The printing of the materials mentioned can be carried out so that the printed with the new dyes product is optionally treated in the presence of a carrier at temperatures between 80 to 23O ⁰ C.

The dyes of the invention are also suitable for Bulk dyeing of the hydrophobic materials listed above.

The invention is explained in more detail by the following examples, where the temperature specification details are given in percent by weight:

explained, with the temperature ^{data in 0} C and percent

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example 1

a) A mixture of 16.7 parts by weight of nitrosylsulfuric acid 42 foig and 35 parts by weight of concentrated sulfuric acid is cooled to 0 to 5 °. Then be under good Stirring 8.6 parts by weight of 2-chloro-4-nitroaniline entered and then stirred for one hour at 0 to lo °. The mixture is then poured onto ice, and the aqueous 0.5 parts by weight of sulfamic acid are added to the diazo solution to remove excess nitrous acid. The diazo solution is then run in at 0 ° to 10 ° in a solution of 13.2 parts by weight of «C- (3-acetylaminophenyl) -amino-isobutyric acid ethyl ester in 200 parts by weight of 5% sulfuric acid. The coupling is very ' quickly and ends in 1 to 2 hours. The resulting dye is filtered off with suction, washed neutral with water and dried.

The cC- (3-acetylaminophenyl) -amino-isobutyric acid ethyl ester required as a coupling component can be made as follows:

200 parts by weight of glacial acetic acid, 93 parts by weight of acetylm-phenylenediamine hydrochloride and small parts by weight of sodium acetate are stirred for one hour at 20 to 25 °. Then 58 parts by weight of acetone are added and this mixture is added at 20 to 25 ° in the course of k hours

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⁴⁹ ' 225A017

a solution of 50 parts by weight of potassium cyanide in 75 parts by weight of water were added dropwise.

The mixture is then stirred at 20 to 25 ° for 20 hours.

The crystallized • C- (3-acetylaminophenyl) -aminoisobutyric acid nitrile is suctioned off and washed neutral with water.

21.7 parts by weight of <* - (3-acetylaminophenyl) -amino-isobutyric acid-nitrile are suspended in 200 parts by weight of ethanol. While stirring at 20 to 25 °, in dfe Suspension a rapid stream of dry hydrochloric acid gas is passed until the mixture is saturated with hydrochloric acid is. Then the supply of hydrochloric acid is throttled and stirring is continued for 48 hours at 20 to 25 °.

After the time has elapsed, the o6- (3-acetylaminophenyl) -aininoisobutyric acid nitrile can no longer be detected by chromatography. The supply of hydrochloric acid is now interrupted and the mixture is refluxed for a further 8 hours. The reaction mixture is then heated to 40 to 50 in vacuo, the volatile constituents distilling off. The distillation residue is stirred with 30 parts by weight Acet ^a nhydrid at 20 to 25 ° 16 hours. The acetylation mixture is then poured into 200 parts by weight of water and stirred for 3 to 4 hours at 20 to 30 °.

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The organic phase consists mainly of oC- (3-acetyl-aminophenyl) -amino-isobutyrate-ethyl ester. It is separated and can be used in this form directly for the coupling. The product can also be duroh Purified distillation in a high vacuum.

b) 1.0 part by weight of the finely dispersed material thus obtained Dye of the formula

NII-CO-CIL

3. ^OJ1 3

NH-C-COOC,

\
CH ^

are stirred into 2000 parts by weight of water. The pH is adjusted to 5 to 6 with acetic acid, and k parts by weight of ammonium sulfate and 2 parts by weight of a commercially available dispersant based on a naphthalenesulfonic acid-formaldehyde condensate are added.

100 parts by weight of a polyester fabric based on polyethylene glycol terephthalate are added to the dye liquor thus obtained and colors 1 1/2 hours at 120 to 130 °. After rinsing, more reductive Post-treatment with a 0.2% alkaline sodium

it
dithior solution for 15 minutes with 60 to 70 _{tons of} rinsing and drying, a strong orange dyeing with very good flatness properties, in particular very good lightfastness, is obtained.

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Example 2

a) 8.6 parts by weight of 2-chloro-4-nitroaniline are like in Example 1 a described diazotized.

The diazonium compound is coupled with a solution of 14.7 parts by weight "<.- (3-acetylamino-6-methoxy-phenyl) amino-isobutyric acid ethyl ester in 300 parts by weight of 5 'coward sulfuric acid. The coupling is complete after 1 to 2 hours. The resulting dye is filtered off with suction, washed neutral with water and dried. The »c- (3-acetylainino-6-methoxy-phenyl) -ainino-isobutyric acid ethyl ester required as coupling component is obtained by reacting isobutyric acid with bromine and red phosphorus to form oC-bromo-isobutter acid bromide, adding this intermediate product to ethanol, purification of the resulting oC-bromo-isobutyric acid ethyl ester by vacuum distillation and condensation with 4-acetylamino-2-amino-anisole in the presence of an acid-binding agent.

b) 30 parts by weight of the obtained according to Example 2a Dye of the formula

1 NH-CO-CH, CH, \ I.

N = Ν- ^ Λ-ΝΗ COOC ₀ H-

ι * - j

CH, OCH, >

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- 2Θ--

be in a fine distribution of a printing paste that
45 parts by weight of locust bean gum, 6 parts by weight
share 3-nitro-benzene-sulphate sodium and 3
Parts by weight of citric acid to 1000 parts by weight,
contains, incorporated. With this printing paste, after printing, drying and fixing in the heat-setting frame for 45 seconds at 215 °, rinsing and finishing, as in the example, are obtained on a polyester fabric
1 b, paragraph 2, a bluish red
Printing with very good fastness properties. When printing triacetate fabric, if it is used in the form of the above printing paste and the printed fabric is steamed, rinsed, soaped, rinsed again and dried for 10 minutes at 1.5 atmospheres, the dye gives a very good red print coloristic
Properties.

Example 3

a) 13.1 parts by weight of 2,4-dinitro-6-bromo-aniline are diazotized as described in Example 1a, paragraph 1 and coupled with 17.6 parts by weight of ethyl c- (3-Y-hydroxybutyrylamino-6-ethoxyphenyl) -amino-isobutyric acid. The clutch ends quickly. The resulting
The dye is filtered off with suction, washed neutral with water and dried.

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225 ^ 017

The coupling component required for the preparation of this dye can be obtained by. implementation of 2-nitro-4-amino-pheuetol with γ-butyrolactone to the 2-nitro- "4-y-hydroxybutyrylamino-phenetol, reduction the nitro group to the amino group and condensation of the intermediate product obtained with o ^ -Brora-isobutyric acid ethyl ester as already described in example 2, b) a fabric made of polyethylene glycol terephthalate is padded on the padder at 30 ° with a liquor, the 30 parts by weight of the brought in fine distribution Dye of the formula

NH-CO-CH ₀ -CH ₀ -Ch ₀ -OH

₀ ά d

nH-C-COOC ₀ H

Br L, "~" 3

l _{t contains} 0 parts by weight of polyacrylamide with a K value of 120 and 0.5 parts by weight of a polyglycol ether of oleyl alcohol and 968.5 parts by weight of water. After drying, it is fixed in the heat-setting frame for 60 seconds at 210 °. After subsequent rinsing and finishing, as described in Example 1b, Paragraph 2, a violet dyeing with very good fastness properties is obtained.

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According to the examples given were synthesized more dyes of the formula I, the polyester materials also with very good fastness properties in orange ₉ red, purple and blue
Coloring or printing nuances and which are given in the following table:

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2-cyano-4-nitrophenyl

-CH- -H -H

" ^H

2,4-dinitrophenyl

O CD OO 00

2,4-Dinitro-6-chlorophenyl

Cl ° 2 ^N \ / -N = N

2-chloro-4-n i tropheny1

-CB,

2-cyano-4-ni tropheny1 2.4-dinitro-6-ohlorphenyl 5- (beta-hydroxypropyl) -i, 2 _f% triazolyl (3)

Λ "Ί 2

X R IT R

2-cyano-4-nitrophenyl -CH- -OCH ₃ -H - ° 2 ^Η 5 " ^Π

2,4-dinitro-6-ohlorpheny3

ο he οο

2, Al-Diiiitro-O-bromophenyl

2-cyano-4-tlitro-6-bromophylene-nyl

5-nitro-thiazoly1- (2)

2,4-Dinitro-6-chlorophenyl -C ₁ Jh (η)

2,4-Dinotro-6-Iromo-phenyl ro

NJ)

cn

2-cyano-4-nio-6-bromopheny1

• »J

ΪΓ

R-

a- cyano-4-nitrophenyl -CH- -OCH. -H -C ₂ H ₄ OCH ₃ -H

2,4-dinitro-6-chloropheny1

W tf

2,4-Dinitro-6-bromophenyl 2-cyano- k- nitro-6-bromophenyl 2,4-dinitro-6-chlorophenyl

tf Il

-C ₂ II ₅

If if

-C ₃ H ₇ (n) ".

-C ₂ H ₅

cn ο ■ ο

-CH ₃ ■ ".« -C ₂ H ₄ OCH ₃ "

2-cyano-4-nitro-6-bromophenyl -CH

Benzthiazolyl- (2)

C ₃ H ₇ (U) "

"-C ₂ II ₄ OCII ₃

»-C

5-nitro-thia _z olyl- (2) C ₂ II ₄ OCH ₃

2,4-dinitro-6-bromophenyl

R ^J

2-cyano-4-nitro-6-bromophenyl

-CII ₀ CH ₂ CH ₀ OH -II

-C ₂ H ₅

-H

2,4-dinitro-6-oblophenyl

-CH ₀ OCH ₃

O CD 00 OO

2-cyan — 4 — η i trο — 6 -Bromophenyl

2 ^ -Dinitro-G-chloro- _m _ _m wj _H = CH _o phenyl 2

4-nitrophenyl

-H -OCH ₂ CH ₂ OH -CII,

CH- -CH ₅

2-methyl 1-4-n-i trophenyl

C ₂ H ₅ -H

-H

2 — Broil — 4 — η i t ro— phenyl

4-cyanophenyl

-CH

-CH ₂ -OC ₄ H in)

-OC

2 = 5

-H

-C.

R ^J

R-

2-nitro-4-chlorophenyl -II -II - ^C 2 ^U 5

-II

4-nitro-2-bromo-6-methoxypheny1

-CH,

-II -II

-H

4-nitro-2-cyano-6-ethoxyphenyl

4-methylsulfony! Phenyl .OC ₂ H ₄ OC ₆ II ₅ ··

-H

-H

-CH ₀ CH ₀ Cl

-H

-H

O IO OO

4-nitro-2,6-dichlorophenyl

Cl -O-n-C-H- -H

-C ₂ II ₅

-H

-n.Butylsulfonylphenyl -CII, -H -H -CH ₂ CH ₂ OC ₆ H ₅

-H

4-nitro-2 _> , .6-dibromo- CH ₂ CH ₂ OH phenyl

4-Nitro-2,6-dicyano phenyl

-CH, -OC ₂ H ₅ -H

-OCH ₃ -H

-C ₂ II ₅

-C ₂ H ₅

-H

-H

R ^J

OO ΙΌ O

4-Ni tro-2-cyan-6 -methylsulfonylphenyl

^ -Nitro-2-methyl-

sulfonyl-6-bromo

phenyl

^ t-Me thy 1-5-n it rothiazolyl- (2)

6-nitro-benz-thiazolyl- (2)

5-nitro-2.1-benzisothiazolyl- (3)

-cn.

-CH ₂ CH ₂ OCH ₃

-CH,

-OCH ₃ -II

-H

(n)

-OC ₂ H ₅

C ₂ H ₅

-H

5-nitro-7-bromo-2,1-benzisothiazolyl- ^ 3)

η Ο

225-017

(Γ

VO

O O CM

CM

in

GM

Ü CM

■ ^

CM

m in
m a W. ο VO CM O CM 8th j * r | a CM in Jt] O W. O O I. P. it I I. W. w ⁰¹ ο ο I. ι

• Η P

CM ρ.

»Η

• Ρ
■ rt
P.

0 H

Λ P

O Φ

1 xi cm ft

• Ρ ^ ₁ • ^ H • Η P. • Η P. φ P. P. I. Λ I. φ • 4 * Λ I. I. Cu P. ρ B. α «3 ο ρ ». ^ ₁ j ^ O Yes ι I.

CM ft

CM I

409820/0988

R-

2-cyano- k- nitro-6-bromophenyl

-CH = CH _r

OC ₂ II ₅

C ₂ H ₅

-H

2-chloro-4-nitrophenyl -CH = CHC ₆ H ₅

-H

2,4-dinitro-6-chlorophenyl

2-cyano-4-nitrophenyl

-OH.

-OC ₂ H ₅ It 2-cyan - ^ - η i tropheny1 -OC ₆ H ₅ -H ti -O ^ VoCH ₃ η 2.4-Dinitro-6-ehlor-
phenyl -NHC ₂ H ₅ -OC ₂ H ₅ 2-cyan-4-ni tr0-6-
bromophenyl -NH- (h \ η

-H

R ^J

R-

2-Cyah-4-nitro-6-bromophenyl

I I

-OC ₂ H ₅ -H -C ₂ H ₄ OC ₂ H ₄ OCH ₃

ι ι

-C ₂ H ₄ OCH ₃

O CD OO KJ O

O (O OO OO

The indication (η) means "normal"; for example -CH ₇ (η) means: "normal-propyl"; correspondingly means, for example, -C ₄ H "(iso):" iso-butyl ".

example k

12.2 parts by weight of the dye:

j- ^ CO-C ₃ H ₇ ( _n )
0 ₂ ^N "\ 7" ^N = ^N "\

Till ,, Br OC _n IU ■>

become yellow in 80 parts by weight of dimethylformamide, 2 Parts by weight of copper (I) cyanide are then added and heated to 85 for 8 hours with stirring.

The nucleophilic exchange of the bromine in the diazo component by the cyano group can be easily followed by thin-layer chromatography on silica gel plates. After the reaction has ended, the dye is precipitated by adding water or methanol to the reaction mixture and isolated in a known manner.
The resulting dye has the formula NO ₂ NH-CO-C ₃ H _{7 (n)} CH ₃

N = N - (/> -NTI - C - COOC ₂ H ₅ OC ₂ H ₅ ^CH 3

It colors materials in pure blue tones with very good coloristic properties.

409820/0988

725-07

Will the dye

PTT "

NO ₀ Niirociu V 3

reacted analogously with one of the nucleophilic reagents listed in column I of the table below, the dyes of column III are obtained, which also dye or print polyesters in blue tones. . If the dye Table No. k is oxidized at 20 to n “0 in glacial acetic acid or with peracetic acid, then dye No. 5 is obtained

409820/0988

CD CC OO NJ O

No,

1.

5.

Nucleophilic reagent

CuCN

Zn (SO ₂ CH ₃ ) ₂

NaHO / Cu

CuSCj dye

NH-CO-CH, CH ₃

NH-C-COOC ₂ H-CII

SO ₂ -CH ₃

.NH-C-COOC ₂ II ₅
OC ₂ H ₅ CH ₃

NH-CO-CH.

CH

= N

NO.

.NH-C-COOC ₂ H ₅

CH

NH-CO-CH

3 CH,

^ "" 3 NH-C-COOC,

CH,

NO

NH-CO-CH

rsj cn

Claims (1)

Claims 1. Water-insoluble azo dyes of the general formula I: D-N = N wherein
D. -CO-Y ^H 2 " ^R - COO-R ^J H ₂ -R ² γό η ionogenic groups. the remainder of a V-free, if applicable substituted aromatic or heteroaromatic diazo component, one hydrogen atom or one optionally substituted alkoxy group one hydrogen atom, one optionally branched and / or substituted alkyl, an optionally substituted alkenyl, an optionally substituted cycloalkyl, an optionally substituted Phenyl, one hetaryl, one given. if substituted alkoxy, one optionally substituted phenoxy group or the radical -NH-R, where R is an Alley 1-, Alkenyl or cycloalkyl group or an aralkyl or aryl group and 09820/0988 1 2 R and R are hydrogen or an alkyl group and an optionally branched and / or substituted alkyl group mean. 2. Water-insoluble azo dyes according to Claim I _1, characterized in that D a 2.4v dinitro-6-chloro- or 6-brora-phenyl- or a 2-cyano ^/ t-nitro-6-broic- henyl radical, X is hydrogen, a methoxy or ethoxy group, Y is a methyl radical, i 2 R and Il hydrogen and R ^ an ethyl, normal butyl, secondary butyl, iso-butyl, 2-methoxy-ethyl, 2-ethoxy-ethyl, 2- (2'-liothoxy-ethoxy) -ethyl or a 2- (2'-etho ^ y-ethoxy) -ethyl group mean. 3. Process for the preparation of dyes of claims 1 and 2, characterized in that a diazonium compound an aromatic or heteroaromatic amine of the general formula II D- NlI ₂ II which is free of ionogenic groups, with a coupling component of the general formula III: 40y820 / 0988 2 2 5 Λ 017 NH-CO-Y _E i ¹ 3
NH-CG 00R- ⁵ III is coupled. k. Process for the preparation of dyes of claims 1 and 2, characterized in that dyes of the general formula IV NH-CO-Y ^C ^ 2 ^R N = N - {/ VnH-C-COOR ⁵ IV Hal. 1 2
wherein Z and Z are identical or different substituents from the series Cl, Br, NO ₀ , CN, SO ₀ R, OR, where R ^ is an alkyl group with 1 to 6 carbon atoms and Hai. mean a halogen atom, the halogen atom Hal is nucleophilically exchanged for NO ₀ , CN, R ^ S or R SO ₀ . 5. A method for dyeing and printing synthetic hydrophobic materials, characterized in that a dye according to claim 1 or 2 is used for this purpose. 409820/0988 ^? 25Λ01 7 6. Dyed by the method of claim 5 or printed synthetic, hydrophobic materials. 409820/0988