CH638551A5 - MONOAZO DYES AND METHOD FOR THE PRODUCTION THEREOF. - Google Patents

Description

The invention is illustrated by the following examples. Unless otherwise stated, parts therein are parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

example 1

21.8 parts of 6-chloro-2,4-dinitroaniline are suspended in 110 parts of 88% sulfuric acid and diazotized at 20 ° by dropwise addition of 32 parts of 40% nitrosylsulfuric acid within 30 minutes. After 2 hours of stirring at room temperature, the clear diazo solution obtained is stirred at 0-5 ° in a solution of 31 parts of the coupling component of the formula

/ 0CH3%

/ »- NH-CHCH COCH

/ '= # J

NHCOCH2CH3 CH3

in 12 parts conc. Hydrochloric acid and 300 parts of water were added dropwise within 30 minutes.

The coupling is ended immediately. The precipitated dye is filtered off, washed neutral with warm water and dried.

The dye thus obtained, which is finely divided with suitable agents, such as sulfite waste liquor or dinaphthylmethane disulfonic acid, shows good build-up and leveling properties on polyethylene glycol terephthalate fibers and dyes these fibers in navy blue shades. The dyeings are sublimation and lightfast.

The coupling component mentioned is prepared by hydrogenation of the Schiff base, which by condensation of 4-propionylamino-2-aminoanisole with acetoacetic acid remethyl ester according to the following reaction scheme k

\

4th

/

/ 0CH3

^ • -NH2 + 0 = C-CH2 "C00CH3» 1

NHCOCH2CH3

CH.

/ 0ch3

^ • -N = C-CH2 ~ COOCH3

• = •

H,

NÉIC0CH2CH3CH3

Kat,

OCH.

/

-x - / «- NH-CH-CH2-COOCH3 1

PH

NHCOCH2CH3 3

5

638 551

was obtained.

In an analogous manner, from the corresponding diazo and coupling components, the dyes listed in the following table, the polyethylene glycol ter-

Dye phthalate fibers also in navy blue shades, except for Examples 29 to 33, or 35 and 36, which give purely blue or violet shades.

° 2n- (

x

/

N = N - * ^

or,

\

no,

/

nhcoy

—Nh-ch-ch -coor, i 2 r

table

No.

X

R

Ri r?

2nd

3rd

4th

5

6

7

8th

9

10th

11

12

13

14

15

16

17th

18th

19th

20th

21st

22

23

24th

25th

26

27th

28

-Cl do. do. do. do. -Br do. do. do. do. do. do. do. -Cl -Br -Cl do. do. -Br do. -Cl -Br do. -Cl do. -Br do.

-ch3

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

-ch2och3 do.

-ch2och2ch3

-ch3

do.

do.

do.

-ch2c1

-ch3

do.

-ch3

do.

do.

-ch2c5h5

-ch3

do.

do.

do.

do.

do.

-ch2ch3 do.

-ch (ch3) 2 do.

-ch2ch2och3

do.

do.

-ch3

do.

do.

do.

do.

do.

do.

do.

do.

do.

-ch3 do.

-ch2ch3

-ch3 -ch2ch3

do.

do.

-ch3

-ch2ch3

-ch2ch2ch3

-ch3

do.

do.

do.

do.

-ch2ch3

-ch3

do.

do.

-ch2ch3

-ch2ch2oc6h5

do.

-ch2ch2ococh3 do.

-ch3

do.

• - •

'CO *

-ch3

-ch2ch3

do.

do.

-ch3 do.

-ch2ch3

do.

-ch3

do.

do.

-ch2ch3

do.

do.

-ch3

-ch2ch3

-ch3 -ch2ch3

do.

-ch3

-ch3

do.

do.

-ch2ch3

-ch3 -och3

-ch,

29

-cn do.

do.

-ch3

do.

30th

do.

do.

-ch (ch3) 2

do.

do.

31

-cn

-ch3

-ch2ch2och3

-ch3

-ch3

32

do.

do.

-ch2ch3

-ch2ch3

-ch2ch3

33

do.

do.

do.

do.

-och2ch3

34

-Br

-ch3

-ch3

-ch2ch2c1

-ch3

35

-h do.

do.

-ch3

-ch2ch3

36

do.

do.

-ch (ch3) 2

do.

• ■ - •

do.

37

-Br do.

-ch3

ru 11 11 \

0

-ch3

38

-Br do.

do.

do.

-ch2ch3

39

-cl do.

do.

do.

do.

40

do.

do.

do.

• •

-ch2-Ì h i

V

do.

41

-Br do.

do.

-ch2c7h5

do.

638 551 6

Table (continued)

No.

X

R

R.

R2

Y

42

-Br

-ch3

-ch2ch2och3

-ch2c7h5

-ch, ch3

43

do.

do.

do.

do.

-och3

44

-cl do.

-ch2ch3

do.

-Ohuch,

45

-Br do.

-ch3

-ch, ch, ch3

-ch3

46

-cl do.

do.

-ch2ch (ch,) o do.

47

do.

do.

do.

-ch (ch3),

do.

48

do.

do.

do.

-ch2ch2ch2ch3

do.

49

-Br do.

do.

do.

do.

do.

• - •

/ \

50

do.

do.

"\ h / -ch3 • - •

do.

ch.

/ 3rd

51

do.

do.

do.

H \

do.

\ /

* ~ \

3rd

Dyeing instruction

1 part of the dye obtained according to Example 1 is wet-ground with 2 parts of a 50% aqueous solution of the sodium salt of dinaphthylmethane disulfonic acid 30 and dried.

This dye preparation is stirred with 40 parts of a 10% aqueous solution of the sodium salt of N-butyl-n-heptadecylbenzimidazole disulfonic acid and 4 parts of a 40% acetic acid solution are added. A dye bath of 4000 parts is prepared from this by diluting 35 with water.

One enters this bath at 50 ° with 100 parts of a cleaned polyester fiber material, raises the temperature to 120 to 130 ° within half an hour and dyes for 40 hours in a closed vessel at this temperature. It is then rinsed. A level, strong navy blue coloration of excellent light and good sublimation fastness is obtained.

Printing instruction

25 parts of the dye according to Example 1, which had been finely ground beforehand, are mixed, 550 parts of 8% aqueous thickening from modified locust bean gum, 50 parts of a 10% solution of the sodium salt of m-nitro-benzenesulfonic acid, 10 parts of a mixture of potassium oleate and pine oil and make up to 1000 parts with water.

With the help of a high-speed stirrer, the mixture is stirred until the dye has completely dispersed and then polyethylene glycol terephthalate fabric is printed with this paste. After printing, the fabric is dried and steamed at 11/2 atm for 20 minutes, rinsed with cold water for 10 minutes, soaped twice hot with the addition of a little hydrosulfite, rinsed cold and dried. You get a real navy blue print.

C.

Claims (4)

638 551 2 PATENT CLAIMS 1. Monoazo dyes of the general formula I / x / 0Ri ° 2n ~ # \) -n = N- <) .- NH-CH-CH2-COOR2 (I) • = • • = • | Nfî-COY R in which X is hydrogen, chlorine, bromine or cyan, R is isopropyl or methoxyethyl and Y is methyl or ethyl optionally substituted alkyl radicals with 1 to 4 carbon atoms. Substance atoms, R! an optionally with lower alkoxy, aryl 4. monoazo dyes according to Claims 1 to 3, oxy or aryl substituted alkyl radical with 1 to 4 carbons- 15 in which R2 is optionally with aryloxy, acyloxy, aryl Substance atoms or an optionally substituted phenyl or a hetero ring substituted alkyl radical with 1 to 4 rest, R2 means optionally by hydroxy, acyloxy, carbon atoms or cyclohexyl. der-alkylsulfonyloxy, aryl, halogen, aryloxy or a 5. monoazo dye according to claim 1, wherein R2 is one Hetero-substituted alkyl radical having 1 to 4 carbon-unsubstituted alkyl radical having 1 or 2 carbon atoms, atoms or an optionally substituted cycloalkyl-20 6. monoazo dyes according to claims 1 to 5, rest and Y are lower alkyl or lower alkoxy. wherein X is chlorine or bromine, R and R, methyl, Y methyl or Ethyl and R2 methyl, ethyl, propyl, isopropyl, phenoxy ^ 2 Nfî-COY R in which X is hydrogen, chlorine, bromine or cyano, R is an optionally substituted alkyl radical with 1 to 4 carbon atoms, Rj is optionally with lower alkoxy, Aryloxy or aryl substituted alkyl radical having 1 to 4 carbon atoms or an optionally substituted phenyl radical, R2 one optionally substituted by hydroxy, acyloxy, 638 551 lower alkylsulfonyloxy, aryl, halogen, aryloxy or a hetero ring-substituted alkyl radical having 1 to 4 carbon atoms or an optionally substituted cycloalkyl radical and Y are lower alkyl or lower alkoxy, and a process for their preparation. ° 2N- < / / X -NH, (II) ^ 0. The terms lower alkyl and lower alkoxy refer to alkyl or alkoxy radicals with in particular 1 to 4, preferably with 1 to 2 carbon atoms, such as methyl, ethyl, methoxy or ethoxy. R, R] and R2 in the meaning of an alkyl group having 1 to 4 carbon atoms can be the same or different, unbranched or branched. It is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl. These alkyl radicals can be substituted, e.g. in the case of R by halogen, such as bromine or especially chlorine, lower alkoxy, especially methoxy, ethoxy or propoxy or aryloxy, especially phenoxy, in the case of R, by lower alkoxy, especially methoxy or ethoxy, aryloxy, especially phenoxy or aryl, especially Phenyl and in the case of R2 by hydroxy, acyloxy, in particular acetyloxy, or a lower alkylsulfonyloxy group, in particular methylsulfonyloxy, aryl, in particular phenyl or methylphenyl, a hetero ring, in particular an oxygen-containing hetero ring, such as, for example Furfuryl or tetrahydro-furfuryl. For R, methyl, ethyl, methoxy-methyl, ethoxymethyl or chloromethyl may be mentioned, for R, methyl, ethyl, propyl, isopropyl, methoxyethyl, phenoxyethyl, benzyl and phenethyl and for R2 methyl, ethyl, propyl, isopropyl, phenoxyethyl, Acetyloxyethyl, chloroethyl, benzyl, furfuryl, tetrahydrofurfuryl or cyclohexyl. R, in the meaning of a substituted phenyl group can e.g. Tolyl, xylyl or chlorophenyl. An optionally substituted cycloalkyl radical for R2 is in particular a cycloalkyl radical with 5 to 7 carbon atoms, such as e.g. the methylcyclohexyl and especially the cyclohexyl radical in question. X is preferably chlorine or bromine. R is preferably unsubstituted alkyl having 1 to 4 carbon atoms, in particular methyl. R is preferably isopropyl, ethyl or methoxyethyl and especially methyl. R2 is preferably an alkyl radical with 1 to 4 carbon atoms or cyclohexyl optionally substituted with aryloxy, acyloxy, aryl or a hetero ring, in particular methyl, ethyl, propyl, isopropyl, phenoxyethyl, acetyloxyethyl, chloroethyl, benzyl, furfuryl, tetrahydroxyfurfuryl or cyclohexyl; above all, R2 is the unsubstituted methyl or ethyl radical. Y is preferably methyl or ethyl. In preferred monoazo dyes of the formula I, X is chlorine or bromine, R is methyl, methoxymethyl or ethoxymethyl, R, methyl, ethyl, isopropyl or methoxyethyl, Y is methyl or ethyl and R2 is an alkyl radical with 1 which is optionally substituted by aryloxy, acyloxy, aryl or a hetero ring up to 4 carbon atoms or cyclohexyl, and especially methyl or ethyl. Monoazo dyes of the formula I are particularly preferred, wherein X is chlorine or bromine, R and R, methyl, Y is methyl or ethyl, R2 is methyl, ethyl, propyl, isopropyl, phenoxyethyl, acetyloxyethyl, chloroethyl, benzyl, furfuryl, tetrahydrofurfuryl or cyclohexyl. The dyes of the formula (I) are obtained if di-azo components of amines of the general formula II with coupling components of the general formula III 10th / ° R1% • N ^ «- NH - CH - CH2 - COOR (III) 15 • = • 1 Nfî- COY r in which formulas (II) and (III) X, R, Rb R2 and Y have the meaning given under formula I, couples in the p-position to the 2o amino group. The diazo components of the formula II are known; the coupling components of formula III are new and can be obtained by processes known per se; e.g. by condensation of a ketone of the formula 25th OC-CH2-COOR2 I. R 30 with an amine of the formula / 0R1 35 \ > -nh2 Nfî- COY wherein R, Rb R2 and Y have the meaning given under formula I and subsequent reduction of the condensation product. The diazotization of the diazo components mentioned can be carried out in a customary manner, preferably with the aid of a solution of nitrosylsulfuric acid in concentrated sulfuric acid. "The clutch can also be used in a manner known per se, e.g. be carried out in neutral or advantageously acidic aqueous solution or suspension by adding the resulting solution or dispersion of the diazo compound to a solution of the coupling component in water which contains such an acid and / or a water-miscible organic solvent. After coupling, the dyes formed can easily be removed from the coupling mixture, e.g. by filtration, since they are practically insoluble in water. An alternative method for producing the dyes according to the invention is e.g. one in which the corresponding dye of the formula I, in which -COY is a hydrogen atom, is treated with an acylating agent. Examples of acylating agents are acetic anhydride, acetyl chloride or propionyl chloride. This alternative process is conveniently carried out by reacting the reactants in the presence of a base, e.g. Pyridine. 65 The new monoazo dyes are ideal for dyeing and printing hydrophobic materials from aqueous dispersions, especially synthetic textile materials, in any form, such as fibers, threads 638 551 2. Monoazo dyes according to claim 1, wherein X is chlorine ethyl, acetyloxyethyl, chloroethyl, benzyl, furfuryl, tetra or bromine. mean hydrofurfuryl or cyclohexyl. 3. Monoazo dyes according to claim 1, wherein R Me- 7. Process for the preparation of monoazo dyes of thyl, methoxymethyl or ethoxyethyl, R, methyl, ethyl, formula I. X / / I 02N ~ * \ N = N - * ^ ^ • -NH-CH-CH2-COOR2 (1) \ o2 Nti-COY R in which X is hydrogen, chlorine, bromine or cyano, R is an alkyl radical with 1 to 4 carbon atoms which is optionally substituted by a coupling component of the general formula III, R, is an alkyl radical which is optionally substituted by lower alkoxy, aryloxy or aryl and has 1 to 4 carbon / 1 fatomen or an optionally substituted phenyl radical, 40 R2 one optionally by hydroxy, acyloxy, meder-Al- • • -NH-CH-CH2 ~ COOR2 (III) kylsulfonyloxy, aryl, halogen, aryloxy or a hetero- • = • | ring substituted alkyl radical with 1 to 4 carbon atoms Nf} - C OY R or an optionally substituted cycloalkyl radical and Y Lower alkyl or lower alkoxy, characterized thereby 45 is characterized in that the diazo component of an amine of the all-in which formulas (II) and (III), X, R, Rh R2 and Y have the meaning of the formula II ter formula I given in the p-position Amino group couples. X / 02N- • ^ • -NH 2 (II) The invention relates to valuable new blue, ma- »Rine blue to violet monoazo dyes of the general ^ Formula I 50 ► = • NO. 55 / X OR 02n- <) -n = n -. (> -NH - CH - CH2 - COOR2 (i) • - • • = • I 4th and fabrics, for example of polyamides, but especially textiles or fibers made from aromatic polyesters, such as polyethylene glycol terephthalate or condensation products made from terephthalic acid and 1,4- (bis-hydroxymethyl) cyclo-hexane or cellulose triacetate. In particular, the monoazo dyes according to the invention have very good coloring and building properties on aromatic polyester textile materials, which makes it possible to obtain level, deep and reproducible color tones with uniformly defined monoazo dyes. io The navy blue dyeings and prints obtained on the materials mentioned with the preferred dyes in which X denotes chlorine or bromine are distinguished by a good evening color and color strength and by good general fastness properties, in particular good pH stability, good leveling ability good sublimation and high light fastness. The usual conditions and additives that are usually used when applying disperse dyes to synthetic textile materials are used. 20th The dyeing with the dyes of the formula I is carried out in detail in such a way that the material to be dyed, preferably at elevated temperature, e.g. at 40 ° C, in an aqueous dispersion of the dyes, optionally adding conventional auxiliaries, such as sulfite cellulose degradation products, 25 condensation products from higher alcohols with ethylene oxide, polyglycol ether of fatty acid amides or alkylphenols etc. and preferably adding acidic agents to the bath, for example with organic acids such as formic acid or acetic acid or inorganic acids 30 such as phosphoric acid. The bath is then heated to the optimal dyeing temperature, preferably and depending on the type of fiber materials to be dyed to a temperature between 70 to 140 ° C. Dyeing is carried out at this temperature until the desired depth of color is reached. After the bath has cooled, the dyed fiber material can be subjected to an aftertreatment, e.g. in the case of acetate fibers, an aftertreatment with soaps or, in the case of fibers from aromatic polyesters, a reductive aftertreatment with the addition of alkali. 40 When dyeing aromatic polyesters or triacat fibers at temperatures of 105 ° C., it is generally advantageous to use conventional carrier substances, such as mono-, di- or trichlorobenzene, benzoic acid, salicylic acid, o- and p-phenylphenol or benzyl alcohol. 45 To heat-fix the dye, the fouled fabric is expediently dried after drying, e.g. heated in a warm air stream to temperatures above 100 ° C, for example between 180-210 ° C. The printing is also carried out in a manner known per se by applying a printing paste to the materials which, in addition to the customary auxiliaries, contains the dye or dyes and then subjecting it to heat or heat treatment. Likewise good fastness properties are achieved in the application from organic solvents, in which the dye is applied to the substrate to be colored from a solvent in which it is dissolved or in the form of a fine dispersion. The most suitable solvents are chlorinated hydrocarbons (e.g. perchlorethylene), which can be used alone or as a dispersion together with water. Dyes, especially those that vaporize at least 60% in less than 60 seconds at atmospheric pressure between 150 to 220 ° C, can also be used in the transfer printing process, in which the dyes are removed from a temporary support, e.g. Paper can be transferred to the textile material. As a rule, brief heating (10 to 60 seconds) under atmospheric pressure or in vacuum, to 150 to 220 ° C is sufficient for this purpose. The closest comparable dyes are superior to the claimed dyes due to their better resistance to boiling when dyeing polyester materials.