DE2514096A1 - Azo compounds difficult to dissolve in water, their production and use - Google Patents

Description

2514098

OZ- PATENT - GMBH LöiTacn

Case 150-3602

Azo compounds that are sparingly soluble in water, their production and use

It has been found that the compounds of the formula I

0OR

N =

(D,

R,

509843/08

Case 150-3602

where ΕΚ,

R,

Halogen or cyan,

alkyl or optionally carrying hydroxy, alkoxy or phenyl as substituents up to three halogen atoms, methyl or alkoxy groups as substituents load-bearing phenyl,

Hydrogen, chlorine, bromine, cyano, methyl, alkoxy, formylamino or a group of the formula -NH-R_-R _O ,

Hydrogen, chlorine, bromine, methyl or alkoxy, alkyl, which optionally has a substituent from the series chlorine, bromine, hydroxy, alkoxy, phenyl, phenoxy, cyano, formyloxy, alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy, Alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, Benzoyloxy or phenylaminocarbonyloxy, or alkenyl, hydrogen or one of the meanings of R-, -CO-, -CO-O- or -SO- and

Phenyl, or alkyl, which has a substituent from the group consisting of chlorine, bromine, hydroxy, alkoxy, Can carry phenyl, phenoxy or cyano, mean

where in R- and R "each alkyl, OH, alkoxy or Carries phenoxy, contains at least two carbon atoms, if attached to an oxygen or sulfur atom, and the alkyl, alkoxy and alkenyl radicals if not otherwise determined, contain 1, 2, 3 or 4 carbon atoms, excellent for dyeing or printing Fibers or threads or materials made from them made of fully or semi-synthetic, hydrophobic, high molecular weight organic substances.

509843 / Q8Q3

- 3 - Case 150-3602

25H096

Alkyl, in particular as R ", can be straight-chain or branched be. Halogen means fluorine and / preferably chlorine or bromine.

Chlorine or bromine is preferred as R _1. Preferred groups R_ are methyl, ethyl, hydroxyethyl, methoxyethyl, ethoxyethyl, propyl, n- or iso-butyl _# phenyl, chloro or bromophenyl, are particularly preferably methyl, ethyl, hydroxyethyl, and methoxyethyl.

R is preferably hydrogen, methyl, cyano, acetylamino, propionylamino, chloropropionylamino and Methoxy- or ethoxycarbonylamino, especially hydrogen, methyl or cyano. R. is preferably hydrogen, methoxy or ethoxy.

When R ₅ is C ₂ _ ₄ alkyl, which may even be substituted by cyano, alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy, phenyl, phenoxy or alkoxy, benzyl and allyl, and particularly ethyl beta-cyanoethyl, beta-Alkylcarbonyloxyäthyl, benzyl and .beta. -Phenylethyl preferred.

R, is preferably hydrogen or one of the groups mentioned above under R, but not both substituents contain a benzene nucleus at the same time.

Preferred among the new compounds of the formula I are those in which

R ₁ chlorine or bromine,

R_ alkyl with 1-4 carbon atoms, hydroxyethyl, alkoxyethyl, phenyl, chloro- or bromophenyl,

509843/0803

- 4 - Case 150-3602

25U096

R hydrogen, methyl or cyano,

R. hydrogen or alkoxy,

R_ optionally cyano, alkylcarbonyloxy, alkoxycarbonyl, Alkoxycarbonyloxy, phenyl, phenoxy or alkoxy as substituents C ". -Alkyl, Benzyl or allyl and

R ,. Hydrogen or optionally cyano, alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy or alkoxy as a substituent-bearing C ₂ _ ₄ ~ alkyl,

mean, where all alkyl and alkoxy radicals, unless otherwise specified, contain 1 or 2 carbon atoms.

The process for the preparation of the new compounds is characterized in that an amine is used Formula II-

COOR ₂

diazotized and the diazonium compound obtained with an amine of the formula III

R ₄

TSC (III)

Y \

^R 6 "3

clutch.

5 09843/0803

- 5 - Case 150-3602

25U096

The diazotization and coupling are carried out according to general methods, some of which have been known for over 100 years. In general, the coupling in an acid, optionally a buffered medium, for example in the pH range under 5 is, and under cooling, for example carried out at temperatures below 20 ° C, preferably between -5 ° and + 5 ⁰ C. Alkali metal salts of low molecular weight alkanoic acids, for example acetic acid or propionic acid, in particular sodium acetate, are preferably used as buffer substances.

The processing of the new compounds of the formula I into coloring preparations takes place in a generally known manner, e.g. by grinding in the presence of dispersants and / or fillers. With the possibly in a vacuum or by After adding more or less water, you can atomize dried preparations for a long time or short liquor dyeing, padding or printing.

The dyes pull out of aqueous suspension excellently on textile material made of fully synthetic or semi-synthetic, hydrophobic, high-molecular organic substances. They are particularly suitable for Dyeing or printing of textile material made of linear, aromatic polyesters, as well as cellulose-2 1/2 acetate, Cellulose triacetate and synthetic polyamides.

Coloring or printing is carried out according to known methods, for example that described in French patent specification No. 1.445.371 Procedure.

The dyeings obtained have good all-round fastness properties; to be emphasized are the lightfastness, the thermosetting, Fastness to sublimation and pleating.

50984 3/0803

Case 150-3602

In the following examples, parts are parts by weight and percentages are percentages by weight. The temperatures are given in degrees Celsius.

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Case 150-3602

25H096

example 1

18.5 parts of methyl 2-amino-4-chloro-benzoate are stirred in a mixture of 30 parts of concentrated hydrochloric acid and 120 parts of water and brought to 0 ° chilled.

At this temperature one slowly adds, while stirring, a solution of 8 parts of sodium nitrite in 20 parts of water and stirred for 2 hours. Then the Excess sodium nitrite destroyed with aminosulfonic acid. A solution of 25 parts of 3- (N-ß-cyanoethyl-N-benzyl) toluidine is added to the clear-filtered diazonium salt solution while cooling with ice slowly pour in 200 parts of glacial acetic acid. The dye is formed immediately and precipitates in crystalline form. He will after filtered briefly stirring, washed acid-free with water and dried.

The dye conforms to the formula

CH ₂ CH ₂ CN
^CH 2 ^C 6 ^H 5

and dyes polyester material in golden yellow tones with very good fastness properties.

509843/0803

Case 150-3602 25UG96

In the following table are further dyes of the Formula I indicated, which are prepared analogously to the procedure of the 1st example and polyester fiber material dye in the specified nuances, the fastness properties are very good.

509843/0803

I.
U a O O in O O O O O O in te CJ O O O in CN O O Cl J-W i U <o TJ TJ te TJ Tl TJ TJ TJ TJ te CN CN I. TJ TJ TJ 53 te TJ 53 rQ
H CN Ά ω VO te VO U ie U 0) 53 4-1 π)
/ rt S_i π Cn CJ from ir CJ 251 U CN AC O U OM I. CJ I. I. 53 Previous year
O CN O) -PM CJ 53 U CN 53 O CQd I. 53 CJ (d tHi O O O I. PHg CN U CN S3 O in te 53 CM 53 CJ Cl O ■ Λ V VO CN
te te I. "I.
53 cn CJ U
1 O C. CN 53 in 53 I. O O te CJ CJ 53 CJ • O • O • in TJ '8th • a O CN
O
O CN O CJ te O O O te O ■ 8 O O O in
53 te TJ I. CN TJ CN TJ CN TJ TJ O Cl CN CJ O te U te CN 53 CJ CN CN O I. O 53 O
O te te CN CN U U VO CJ CJ d te te CN 53 PS I. CN TJ CJ O 53 53 te I. I. CJ U te I. ¹ te 6th 53 TJ O te Cl TJ d O 53 Ϊ3 O
ΓΜ TJ TJ O O O
CN 6th d VN
53 O O cn
te O d TJ CN
O te TJ O TJ U TJ TJ O TJ Tt cn ο TJ CN I. in 53 CN te CO
te H ! 3 te U • Λ O in O I. Ul
te ¹ pi I. CN O O 6th TJ te TJ TJ • Η ! U te te te te O te Cl 53 te U H O « O TJ . "* O ■ Η d te TJ VO cn
te 8th Cl
53 H te CJ te U te te 53 O I. te I. oT P * O O te CJ
■ 8th cn
T * O O O O O I.
a CN
53 O M4
CJ T » TJ TJ TJ TJ CJ
/ Nl TJ ι O IN
53 TJ CJ
I. 05 O O O O O O O TJ TJ TJ TJ TJ 1-4 TJ TJ U H CJ in VO t- » CO CN 1" H CN iH H 05 ά · CQ O CQ 2

509843/0803

Case 150-3602

E.g.
NO. "1 ^E 2 ^R 3 ^R 4 ^R 5 ^R 6 Nuance on
Polyester fiber
material· 17th Cl -CH ₃ -NHCOOCH ₂ Ch ₂ OCH, ^H - ^C 2 ^H 5 -CH ₂ CH ₂ OCOCH ₃ yellow 18th CN do. -CH H do. do. Red 19th do. " ^C 6 ^H 5 do. H do. do. do. 20th do. do. Cl H do. do. do. 21 do. -CH ₃ H H do. -CH ₂ CH ₂ CN yellow ⁰¹ 22
ο Br H H do. do. do. cd 23
OO do. - <g> -ci H H -CH ₂ CH ₂ Cl -CH ₂ CH ₂ Cl do. DO ²⁵ do.
Cl -CH ₂ CH ₂ OCH 3)
CN H
H -CH ₂ CH ₃
-CH ₂ CH ₂ CN -CH ₂ CH ₂ COOCH ₃
-CH ₀ C ^ H ₁ .
2 6 5 do. *
red "^ ι οο 26 do. do. -OCH ₃ H -CH ₂ CH ₂ OCOCH ₃ do. yellow * ω 27 do. do. Br H do. do. do. 28 Br -CH ₃ -NHCOCH ₃ H -CH ₂ CH ₂ CN -CH ₂ CH ₂ -O-COCH ₃ do. 29 Cl - ^C 2 ^H 5 do. H do. -C ₂ H ₅ reddish
. yellow 30th do. HC ₃ H ₇ do. H do. -CH ₂ CH ₂ OCOCH ₃ yellow 31
32 do.
do. -CH ₃
do. do.
H -OC ₂ H ₅
H -CH ₂ CH ₂ -O-COCH ₃ do.
-CH ₂ CH ₂ COOCH ₃ Red
yellow Q- 33 do. do. -CH ₃ H -C ₂ H ₅ -C ₂ H ₅ reddish = "*
yellow ⁴ ^ 34 do. -CH ₂ CH ₂ OCH 3 ^H. H do. -CH _o CH _o -0-C0NHC ^ H _c
Δ Δ OO yellow CD
CD

Case 150-3602

Ssp. ο.

R.

R.

Nuance on

Polyester fiber material

cn
cz>
co

O OO O CO

35 36 37 38

39 40 41

42 43 44

45 46 47 48 49 50 51

52

Cl do. Br Cl

Cl

do.

do.

do. do.

do.

Br

Cl

do.

Br

Cl

do.

do. do.

-CH ₀ CH ₀ OOQ -CH.

do.

do. do.

do.

-CH

do. do. do. do. do. do.

do.

-NHCOCH ₂ CH ₂ Cl -NHCOCH ₃ do.

NHCOOCH ₂ CH ₂ OCh ₃ -NHCOCH -NHSO ₂ CH ₃

-CN -CH ₃ -NHCOC-H-

D D

-CH ₃ -NHCOCH

-NHCOC-H ₁ . 6th

-NHCHO -NHCOCH ₂ CH ₂ Cl

-CH,

do.

H H H H

H H H

H H H

-OH. do. do.

-C ₂ H ₅ do.

-C ₂ H ₅

do.

- ^C 2 ^H 5

- ^CH 2 ^C 6 ^H 5 -CH ₂ CH ₂ COOC ₂ H ₅

-CH ₂ CH = CH ₂ -CH ₀ CH ₀ CH-

A JL Ki O

-CH ₀ CH ₀ -O-CONHC ₀ H-

- ^C 2 ^H 5
-CH ₂ CH ₂ -O-COCH ₃

-C ₂ H ₅

-CH ₂ CH ₂ -O-COCH ₃
do.

do.
-CH ₂ CH ₂ COOC ₂ H ₅

" ^C 2 ^H 5

-CH _CH _o OCONHC, H _c AA ob

-CH ₂ CH ₂ OCOCH ₃

-CH ₂ CH ₀ OCHO -CH ₂ CH ₂ OCH ₃

OCOCH.

-CH ₂ CH

-CH ₂ CH ₂ OCOCH
H
H

-CH _o CH _o 0C, H_
Z. A ο .b

-CH.CH_OCH0
Δ A

yellow do. do.

reddish yellow

yellow do.

reddish yellow

yellow *

do. - ^

reddish yellow ^

yellow do. do.

yellowish red
do.

do. yellow

reddish yellow

CD CD cn

25H096

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APPLICATION EXAMPLE A

7 parts of the dye prepared according to Example 1 are mixed with 4 parts of dinaphthylmethandisulfonsaurem Sodium, 4 parts of sodium cetyl sulfate and 5 parts of anhydrous sodium sulfate in a ball mill for 48 hours ground to a fine powder.

1 part of the dye preparation obtained in this way is made into a paste with a little water and the suspension obtained through a Sieve added to a dyebath containing 2 parts of sodium lauryl sulfate in 4000 parts of water. The liquor ratio is 1:40.

100 parts of cleaned polyester fabric are then added to the bath at 40-50 °, and 20 parts of a chlorinated benzene are added emulsified in water, slowly heats the bath to 100 ° and stains for 1-2 hours at 95-100 °.

The yellow colored fabric is washed, soaped, washed again and dried. The level, strong coloring has excellent light, sublimation and heat setting fast.

APPLICATION EXAMPLE B

30 parts of the dye prepared according to Example 1, 40 parts of sodium dxnaphthylmethanedisulfonic acid, 50 parts of sodium cetyl sulfate and 50 parts of anhydrous sodium sulfate are ground to a fine powder in a ball mill.

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25U096

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100 parts of purified water are added to 4 parts of the dye preparation obtained in 1000 parts of water at 40 ° -50 ° Polyester fiber material and slowly heats up. It is dyed for about 60 minutes under pressure at 130 ° and after rinsing, soaping, rinsing and drying, a yellow dyeing with the same fastness properties as that Coloring of example A.

APPLICATION EXAMPLE C

2O parts of the dye prepared according to Example 1, 550 parts of sulfite cellulose liquor powder and 800 parts of water are ground in a ball mill until the size of the dye particles is less than 1 u.

The colloidal solution obtained is mixed with 25 parts of diethylene glycol monobutyl ether and 40O parts of 6% strength Carboxymethyl cellulose mixed. This printing paste is very suitable for Vigoureux printing on polyester sliver. The printing takes place with the help of two rollers (coverage 78%), whereupon without intermediate drying at 120 ° is dampened. Yellow prints with good fastness properties are obtained.

509843/0803

Claims (12)

Claims ^R 2 optionally hydroxy, alkoxy or phenyl as substituent-bearing alkyl or optionally up to three halogen atoms, methyl or alkoxy groups as substituent-bearing phenyl, R is hydrogen, chlorine, bromine, cyano, methyl, alkoxy, formylamino or a group of the formula -NH-R_-R _O , / O R. hydrogen, chlorine, bromine, methyl or alkoxy, R ₅ alkyl, which optionally bears a substituent from the group consisting of chlorine, bromine, hydroxy, alkoxy, phenyl, phenoxy, cyano, formyloxy, alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, benzoyloxy or phenyl, 509843/0803 25H096 - 15 - Case 150-3602 R_ hydrogen or one of the meanings b from R_,
R_ -CO-, -CO-O- or -SO ₃ - and R ₀ phenyl, or alkyl, which has a substitute ducks from the range of chlorine, bromine, hydroxy, Can carry alkoxy, phenyl, phenoxy or cyano, mean each alkyl bearing OH, alkoxy or phenoxy containing at least two carbon atoms, when attached to an oxygen or sulfur atom, and the alkyl, alkoxy and alkenyl radicals Contain 1, 2, 3 or 4 carbon atoms. 2. Azo compounds according to claim 1, in which R. is chlorine or bromine. 3. Azo compounds according to claim 1, wherein R _{7 is} methyl, ethyl, hydroxyethyl, methoxy ethyl, ethoxyethyl, propyl, butyl, phenyl, Means chloro- or bromophenyl. 4. azo compounds according to claim 1, wherein R is hydrogen, methyl, cyano, acetylamino, propionylamino, chloropropionylamino or Means methoxy or ethoxycarbonylamino. 5. azo compounds according to claim 1, where R. is hydrogen, methoxy or ethoxy. 6. Azo compounds according to claim 1, wherein R ₅ C ₂ _ ₄ -alkyl, substituted once by cyano, alkyl carbonyloxy, alkoxycarbonyl, alkoxycarbonyl- oxy, phenyl, phenoxy or alkoxy can be substituted, benzyl or allyl. 509843/0803 25U096 Case 150-3602 7. azo compounds according to claim 1, wherein Hydrogen, C _3-4 -alkyl, which can be substituted once by cyano, alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy, phenyl, phenoxy or alkoxy, is benzyl or allyl, but only one of the substituents R ₁ - and R- may contain a benzene nucleus . 8. Azo compounds of the formula I according to claim 1, wherein R _{1 is} chlorine or bromine, R ₂ alkyl with 1-4 carbon atoms, hydroxyethyl, alkoxyethyl, phenyl, chloro- or bromophenyl, R_ hydrogen, methyl or cyano, R ₄ hydrogen or alkoxy, R optionally cyano, alkylcarbonyloxy, Alkoxycarbonyl, alkoxycarbonyloxy, phenyl, phenoxy or alkoxy as a substituent-bearing C ₂ _ ₄ ~ alkyl, benzyl or allyl and
R ,, hydrogen or optionally cyano, _{C 3-4} alkyl bearing alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy or alkoxy as substituents mean, where all alkyl and alkoxy radicals, unless otherwise specified, 1 or 2 carbon atoms contain. 509843/0803 25H096 - 17 - Case 150-3602 9. Process for the preparation of the azo compounds of the formula I according to claim 1, characterized in that that an amine of the formula II COOR ₂ (II) diazotized and the diazonium compound obtained with an amine of the formula III (III) clutch. 10. Use of the azo compounds according to claim 1 as disperse dyes for dyeing or printing of fibers or threads or materials made from them made of fully or semi-synthetic, hydrophobic, high molecular weight organic substances. 11. Process for dyeing or printing fibers or threads or materials made therefrom from fully or semi-synthetic, hydrophobic, high molecular weight organic substances with dyes of the formula I. 509843/0803 25H096 Case 150-3602 12. The dyed or printed according to claim 11 Materials. SANDOZ - PATE .'-. T- GMBH 3700 / HW / HSc 509843/0803