GB2026012A

GB2026012A - Azo Dyestuffs

Info

Publication number: GB2026012A
Application number: GB7922922A
Authority: GB
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1978-07-08
Filing date: 1979-07-02
Publication date: 1980-01-30
Also published as: BE877532A; CH648718GA3; BR7904291A; DE2830154A1; DE2830154C2; JPS5512188A; ES482243A1; IT7924175A0; FR2430441A1; GB2026012B

Abstract

Azo dyestuffs of the formula <IMAGE> wherein D denotes the radical of a benzene- type diazo component, X denotes acyl, Z denotes hydrogen, alkyl, halogen or -COO alkyl, A denotes alkylene, R denotes hydrogen, alkyl, cycloalkyl or aryl and n denotes the numbers 2 to 8, when mixed with emulsifiers give dyestuff preparations which under dyeing conditions are in a liquid or dissolved form. As a result of this, the use of additional dispersing agents, protective colloids, levelling agents and carriers can be dispensed with when dyeing polyester fibres. The dyes are prepared by diazotisation of DNH2 and coupling.

Description

SPECIFICATION Azo dyestuffs The invention relates to azo dyestuffs of the formula

wherein D denotes the radical of a benzene-type diazo component, X denotes acyl, Z denotes hydrogen, alkyl, halogen or -COO alkyl, A denotes alkylene, R denotes hydrogen, alkyl, cycloalkyl or aryl and n denotes the numbers 2 to 8, it being possible for the said alkyl, cycloalkyl, aryl and alkylene radicals to be substituted by non-ionic radicals customary in dyestuff chemistry or by COOT.

Suitable radicals D are those of the formula

wherein X1-X4 independently of one another denote hydrogen, halogen, CN, NO2, V, SO2V, CO2V, CON(W)2, SO2N(W)2, OV or CF3, in which V represents alkyl and W represents hydrogen or alkyl.

Suitable acyl radicals X are COT, SO2Q, CON(W)2, SO2N(W)2 and COOV, in which V and W have the abovementioned meaning, 0 represents alkyl, cycloalkyl or aryl and T represents Qor H.

Suitable alkyl radicals, mentioned in any context, preferably have 1 to 4 C atoms and can, for example, be substituted by halogen, CN, OH, C1-C4-alkoxy, CO2CH3, CO2C2H5- or phenyl.

Suitable cycloalkyl radical are cyclopentyl and cyclohexyl radicals, which, for example, can be substituted by 1 to 3 C1-C4-alkyl radicals or halogen atoms.

Suitable aryl radicals are phenyl radicals, which, for example, can be substituted by 1-3 C1-C4-alkyl or C,-C4-alkoxy radicals or halogen atoms.

Suitable alkylene radicals have 2 to 6 atoms in the chain and can, for example, be substituted by halogen, C1-C4-alkyl, C1-C4-alkoxy or OH.

Preferred dyestuffs have the formula

wherein R1 denotes hydrogen, Cl, Br or CN, R2 and R3 independently of one another denote H, Cl, Br, NO2, CN, methyl, CF3 or C1-C2-alkylsulphonyl, R4 denotes hydrogen or Cl, R5 denotes hydrogen, methyl, ethyl, methoxymethyl, ethoxymethyl or hydroxymethyl, R6 denotes hydrogen, Cl, Br. methyl or ethyl and R7 denotes C1 -C4-alkyl, chloroethyl, cyanoethyl, C1 -C4-alkoxycarbonylethyl, phenyl or C1 -C4- alkylcarbonyl and m denotes the numbers 2 to 5 and preferably 3 to 4, with the proviso that R2 and R3 do not at the same time represent NO2.

Preferably, m represents the number 2 if R7 denotes hydrogen.

Dyestuffs of the formula II wherein R2 and R3 independently of one another denote hydrogen, Cl, Br, CN or NO2, but do not at the same time denote NO2, R5 denotes methyl, ethyl, methoxymethyl or ethoxymethyl, R6 denotes methyl or Cl, R7 denotes methyl or ethyl and m, R1 and R4 have the indicated meaning, are very particularly preferred.

The new dyestuffs are obtained, for example, by coupling diazotised amines of the formula D-NH2 (Ill) with compounds of the formula

in which formulae n, D, A, X, Z and R have the abovementioned meaning.

The coupling components of the formula IV have not previoulsy been described in the literature. They can, however, be prepared by methods which are in themselves known, for example by reacting anilines of the formula

with compounds of the formula M-(A-O),-R (Vl) wherein M represents halogen (especially Cl),

or CH3SO2.

The compounds of the formula VI are known or are readily accessible by known processes (compare, for example, DT-OS (German Published Specification) 1,544,599, page 22), by, for example, reacting compounds of the formula R-OH with alkylene oxides, subjecting the oxalkylation products to fractional distillation, replacing the terminal OH groups in the particular fractions by the radical M (for example by reaction with SOCI2 or methanesulphonyl chloride) and if appropriate distilling the reaction products in order to remove decomposition products.

It is not absolutely necessary that the fractions are single compounds. On the contrary it is possible-frequently even advantageous-to use mixtures of the compounds VI for synthesising the coupling components IV. Of course, the degrees of oxalkylation of such mixtures must at least statistically correspond to the values n and m.

When reacting V with VI it is sometimes not possible to avoid the formation of about 1-25% of dialkylation products also.

Moreover, the products which are obtained from the reaction of V with VI occasionally also contain unconverted V, the presence of which generally does not interfere during the further processing to azo dyestuffs. If desired, however, these impurities can also be removed relatively simply by the use of conventional methods for separating primary and secondary amines.

The new dyestuffs of the formula I, and mixtures of these dyestuffs, are outstandingly suitable for dyeing and printing synthetic fibre materials, especially those made of aromatic polyesters and cellulose esters, on which they produce dyeings with good general fastness properties, in particular good fastness to sublimation, washing and light. Furthermore, the good uptake on highly stretched polyester fibres should be singled out.

It is particularly advantageous to employ the dyestuffs in the form of liquid or pulverulent preparations, which contain, in addition to the dyestuff, emulsifying polar-apolar compounds and optionally formulating agents and extenders (especially inorganic salts, such as NaCI and Na2SO4).

These preparations are distinguished by very high solubility in cold water.

In general, a molar ratio of dyestuff to emulsifier such as 1:0.1 to 1:4 has proved advantageous; a ratio of 1:1 to 1:3 is preferred and a not too large excess of emulsifier in general does no harm. In practice, however, a ratio of 1:2 will generally be fully adequate.

The preparation of the dye preparations is not tied to specific preconditions in respect of apparatus. Spray drying, roller drying or drying in Venuleth apparatuses are just as suitable as simple drying on a metal sheet, after combination of the components, in normal kettles, or the combination of adduct formation and drying in the abovementioned apparatuses. It is particularly advantageous to mix the filter presscake or the oily or pasty dyestuff in the form in which it is obtained immediately from the preparation, with the emulsifiers and optionally to convert the mixture in a known manner to the dry pulverulent form.Attention should be drawn to the fact that if the dyestuff/emulsifier mixture should be comminuted, no expensive fine comminuting devices, such as bead mills and vibratory mills, have to be employed, but that coarse grinding to average particle sizes which are not below 50 fis is completely adequate if the dyestuffs are not in any case obtained in a plastic form or-at slithtly elevated temperature-in liquid form.

A list of suitable emulsifiers can be taken from Table 1 in "Tenside Detergents", year 11, 1974, No. 4, page 186.

Preferred polar:apolar compounds have the general formula G-L (veil) wherein G represents an aliphatic hydrocarbon radical with at least 10 C atoms and L represents -SO2H, -O-SO3H or OPO3H2 or the corresponding salts.

Examples which may be mentioned are: fatty acid soaps, such as sodium laurate, sodium oleate, sodium linoleate, ammonium ricinoleate, oleic acid esters of sodium isethionate or sodium paimitate, sodium bis(2-ethylhexyl)-sulphonesuccinate, sodium N-methyl-N-oleyl taurate, ss-(tert.-octylphenoxy)-diethyl ether-P'-(Na sulphonate), sodium isododecylbenzenesulphonate, sodium dodecylsulphate, sodium N-oleylsulphanilate, dodecylphosphonic acid, sodium dodecylbenzimidazolesulphanant, alkyloxyaryl sulphates, alkylsulphaminoaryl compounds, dodecylphenol sulphate, dodecylbenzenesulphamic acid, dibutylnaphthol sulphate and dioctylnaphthol sulphate.

Cationic surface-active agents which may be mentioned are dodecylamine acetate, dodecylbenzyldimethylammonium chloride and heptadecyl-N-aminoethyl)-imidazoline acetate.

Under dyeing or printing conditions, the new dye preparations are in the liquid or dissolved form. As a result of this, the use of additional surface-active agents such as dispersing agents, protective colloids and levelling agents or of carriers can be dispensed with in most cases when dyeing and printing.

Example 1 1 7.3 g of 2-chloro-4-nitroaniline are introduced in the form of a paste into 42 ml of water and 42 ml of 30% strength hydrochloric acid and the mixture is stirred overnight. 7.1 g of sodium nitrite in the form of a 30% strength aqueous solution are then allowed to run in dropwise at 0 to 5" C in the course of about 2 hours, with the addition of ice. The resulting mixture is then stirred for a further 3 hours and then clarified with 0.1 g of active charcoal and the slight excess of nitrite is destroyed with aminosulphonic acid. A solution of 32 g of the coupling component of the formula

in 100 g of glacial acetic acid is added to the diazonium salt solution thus obtained, whilst stirring. The mixture is then buffered to about pH 6 with dilute sodium hydroxide solution, with the addition of ice, and the dyestuff thus obtained is filtered off and washed salt-free with 1 ,000 ml of water. When mixed well to a paste with the samw amount by weight of dodecyl/myristyl sulphate, the dyestuff dissolves readily in an aqueous dyebath. Polyester fibres are dyed under HT conditions (1 30 C) in a red shade with good fastness properties.

If the procedure followed is as indicated in Example 1, but the starting materials listed in the table which follows are used, similarly good dyestuffs are obtained which on polyester fibres give the colour shade indicated in the table.

No. Diazo component Coupling component Colour shade

Icl ? 2i 2 2 N8( 284 )5 3 blue g lI}iCOClIa cH3 3 orSc2w4 )5C2Bs 1;COE C1 :m1C2H40)4O2R5 violet EEC 4gS Br FEr 5 O?NjH2 CzHIO) gCBJ CET aacoca,oa ca, Q 02≈ 2 t (C2 h )7 O violet I-' (O2N2O)7 ON cl EIR(C2H40)7 CH2 O violet ON. SHCOCH3 C1 8 2 fffi\NR(O2H4o )2H red C1 NI{COO c2E 9 n(C2B10)2H s NHCOCE20a21I 5 10 NH(O4E8o)2c2H4o CR3 I NHCOOR3 Br 11 > E(c2S4 36 t3 EECOCb No.Diazo component Coupling component Colour shade

FH 12 2 NH2 V NH(C2H40)4C2H4Cl red Cl NHCOCH3 3 n H3 13 n Ç3 (C2H4 )4C2H4Cl n NHCOCH) FH, 14 02N t NH2 O NH(C2z40)6C2E5 n /NEICONH2 ~~CHs 15 n -E(C2H4o)3CH3 n BECOOCH3 C1 16 2 $f\ClN(02H4o)3cH3 n NHCONHCH3 17 02N- t NH2 9 NH(C2E4 )2Cz3 violet so2N(CH3)2 NECOCH3 IS H2NCONH2 " red CN CH3 19 02N- f#NH(C2H40)4C4H9 SO2CH3 NIlCOCH3 20 02N- X NH2 9 NH(C2H40)5H 'V Cl NHCOH CH 21 no X }gn2 Çg5 ( 2 4 ) 3 3 n CN NHCOCH3 No. Diazo component Coupling component Colour shade

C1 CH3 22 > E2 f N3(C2H4o)3CH3 scarlet CN NHCOCH3 23 NC-NH2 ,' V' C1 24 NO- 2 V, NC N 25 C1p-NH2 " ! cl ON 26 Cl tV ON 1 H3 27 NOOI\NH2 '\NHCO2H40)3OH3 scarlet C 21ECOCa 3 Fw --11 28 OH3- O (C2H4Q)C2H4CooCE3 red ON NHCOCR3 cl 29 CH3BO2qNH2 1(O2H4o)3H orange NHO nCH3 0 2R5 c( -'^2 ''NH(O2H40)4OE3 :Br ECOCH3 No. Diazo component Coupling component Colour shade

CH C2i5 31 / NCO- -- NH(C 2H40)qCIj red OH3 NHC OCH3 32 02N- t H2 violet N Cl 33 02N- ss NE2 Cl ON H3 34 02N-NH2 NH(C2R40)3H blue N02 NHCOCH3 000C2H400H3 35 02ff- t NH2 ss H(C2E4o)4CE3 red Cl NECOCH3 C1 36 " (C2H4 )4C % red SHECGCE3 F 37 O2NH2 9 H2 t NH(C2H40)3CH3 red : :OCH3 C1 38 o2N X NH2 !C=H,D) 3CH3 red l NHCOCh -, No. Diazo component Coupling component Colour shade

39 OZN--NH,N(C2H40)qCZHq COOCH3 red Cl NHCOCH3 Cl 40 02N 9 2 A Nutc2H4o)4cH3 orange 3/ p NW (CZMD) 4CH3 orange 41 02N'H2 re ruby CN 3r CH3 42 O2NNH2 NX(C2H40)4C H3 blue N NHcOCH3

Claims

1. An azo dyestuff of the general formula

in which D denotes the radical of a benzene ring-containing diazo component, X denotes an acyl group, Z denotes a hydrogen atom, an alkyl group, a halogen atom or a -COO alkyl group, A denotes an alkylene radical, R denotes a hydrogen atom, an alkyl, cycloalkyl or aryl group and n is 2, 3, 4, 5, 6, 7, or 8, the above-mentioned alkyl, cycloalkyl, aryl and alkylene radicals being optionally substituted by one or more non-ionic radicals or by COOH.

2. An azo dyestuff according to Claim 1, in which D denotes a radical of the general formula

in which X1 to X4 independently of one another denote a hydrogen or halogen atom or a CN, NO2, V, SO2V, CO2V, CON(W)2, SO2N(W)2, OV or CF3 radical, in which V denotes an alkyl group and W denotes a hydrogen atom or an alkyl group.

3. An azo dyestuff according to Claim 1 or 2, in which X denotes a COT, SO2Q, CON(W)2, SO2N(W)2 and COOV radical in which V and W have the same meanings as in Claim 2, Cl denotes an alkyl, cycloalkyl or aryl radical and T has any of those meanings given for radical Q or denotes a hydrogen atom.

4. An azo dyestuff according to Claim 1 of the general formula

in which R, denotes a hydrogen, chlorine or bromine atom or a cyano group, R2 and R3 independently of each other denote a hydrogen, chlorine or bromine atom or a nitro, cyano, methyl, trifluoromethyl or C, or C2 alkylsulphonyl group, R4 denotes a hydrogen or chlorine atom, R5 denotes a hydrogen atom or a methyl, ethyl, methoxymethyl, ethoxymethyl or hydroxymethyl group, R6 denotes a hydrogen, chlorine or bromine atom or a methyl or ethyl group and R7 denotes a C, to C4 alkyl, chloroethyl, cyanoethyl, (C1 to C4 alkoxy)-carbonylethyl, phenyl or (C, to C4 alkyl)-carbonyl group, and m is 2, 3, 4 or 5, with the proviso that R2 and R3 do not at the same time denote nitro groups.

5. An azo dyestuff according to Claim 4 in which m is 3 or 4.

6. An azo dyestuff according to Claim 4 in which R7 denotes a hydrogen atom and m is 2.

7. An azo dyestuff according to Claim 4, in which R2 and R3 independently of each other denote a hydrogen, chlorine or bromine atom or a cyano or nitro group but do not at the same time denote nitro groups, R5 denotes a methyl, ethyl, methoxymethyl or ethoxymethyl group, R6 denotes a methyl group or a chlorine atom, R7 denotes a methyl or ethyl group and m, R, and R4 have the same meanings as in Claim 4.

8. An azo dyestuff according to Claim 1, substantially as hereinbefore specifically mentioned.

9. A process for the production of an azo dyestuff as claimed in Claim 1, in which an aniline of the genreal formula D-NH2 (Ill) in which D has the same meaning as in Claim 1, is diazotised and coupled with a compound of the general formula

in which A, X, Z, R and n have the same meanings as in Claim 1.

10. A process for the production of an azo dyestuff as claimed in Claim 1, when carried out substantially as described in any one of the Examples.

11. An azo dyestuff according to Claim 1 when produced by the process of Claim 9 or 1 0.

1 2. A mixture of dyestuffs containing at least 2 individual dyestuffs of the formula (I) as claimed in Claim 1, the said dyestuffs differing from one another in respect of the index n.

1 3. A process for dyeing or printing a synthetic fibre material, comprising treating the material with a dyestuff as claimed in any of Claims 1 to 8 or with a mixture as claimed in Claim 12.

14. A process according to Claim 1 3 in which the synthetic fibre material is an aromatic polyester or a cellulose ester.

1 5. A synthetic fibre material when dyed or printed by the process of Claims 1 3 or 14.

16. A dyestuff preparation comprising a dyestuff as claimed in any of Claims 1 to 8 or a mixture as claimed in Claim 13, together with an emulsifying polar-apolar compound.