GB1586411A

GB1586411A - Azo dyestuffs

Info

Publication number: GB1586411A
Application number: GB19218/78A
Authority: GB
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1977-05-27
Filing date: 1978-05-12
Publication date: 1981-03-18
Also published as: FR2392085A1; DE2724079A1; BE867525A; IT7823809A0; IT1096235B; JPS53147725A

Description

(54) AZO DYESTUFFS (71) We, BAYER AKTIENGESELLSCHAFT, a body corporate organised under the laws of the Federal Republic of Germany of Leverkusen, Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The invention relates to azo dyestuffs which, in the form of the free acid, correspond to the formula

in which R1 and R2 denote alkyl which is optionally substituted by halogen, hydroxyl, alkoxy, acyloxy, cyano, alkoxycarbonyl, dialkylamino or aryl, or allyl or together including the nitrogen atom, denote a monocyclic or bicyclic ring system.

R, denotes hydrogen, halogen, aryl, alkoxy, alkylmercapto, arylmercapto, alkyl amino, dialkylamino, arylamino, acylamino, acylalkylamino, alkylamino carbonylamino or arylaminocarbonylamino, R4 denotes hydrogen, C1-C4-alkyl, cyclohexyl or phenyl, which phenyl radical is optionally substituted by halogen, C1-C4-alkyl or C1-C4-alkoxy, R,; denotes hydrogen or C1-'C4-alkyl and n denotes 1 or 2.

.and their preparation and use for dyeing natural and synthetic fibre materials. As used herein the term "alkyl" excludes cycloalkyl radicals.

Suitable halogen is, in particular, fluorine, chlorine and bromine, preferably chlorine.

Suitable alkyl R1 and R2; in the alkyl and dialkylamino groups; in the alkyl mercapto radical; and in the alkylacylamino and alkylaminocarbonylamino groups is straight-chain or branched alkyl with 1 to 15 C atoms.

Suitable alkoxy contains 1 to 15 C atoms.

Suitable aryl R,, as a substituent of the alkyl radicals R1 and R2 and as arylmercapto, arylamino or arylaminocarbonylamino is, for example, phenyl which is optionally monosubstituted to trisubstituted by C1-C4-alkyl, C1-C4-alkoxy or chlorine.

Suitable acyl in the acyloxy and acylamino groups is, in particular, formyl Ci-Cs alkylcarbonyl which is optionally monosubstituted by chlorine, bromine, C1-C4- alkoxy, phenyl or methylphenyl, C2-C4-alkenylcarbonyl which is optionally monosubstituted by bromine, C1-C4-alkoxycarbonyl, phenoxycarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl which is optionally substituted by C1-C4-alkyl, aminocarbonyl which is optionally monosubstituted or disubstituted by C1-C4-alkyl or optionally monosubstituted by cyclohexyl, C1-C4-alkylcyclohexyl, phenyl, C1-C4-alkylphenyl, chlorophenyl, bromophenyl or trifluoromethylphenyl, benzoyl which is optionally substituted by C1-C4 -alkyl, C1-C4-alkoxy, hydroxyl, C1-C.1 -alkylcarbonyloxy, chlorine, bromine, nitro or trifluoromethyl, naphthylcarbonyl, thenoyl, furoyl, pyridoyl, C1-C., -alkylsulphonyl, benzenesulphonyl which is optionally substituted by fluorine, chlorine, bromine, trifluoromethyl, C1-C4-alkyl, C1-C4-alkoxy, nitro or C1-C4alkylcarbonylamino, naphthylsulphonyl, cyclohexylsuphonyl or C1-C4-dialkylaminosulphonyl.

Suitable rings which R1 and R2, together with the nitrogen atom, form are, for example, monocyclic and bicyclic ring systems with 5 to 10 ring members which optionally contain, in addition to the nitrogen, a further hetero-atom from the series comprising nitrogen, oxygen and sulphur, and which are optionally substituted by C1-C.,-alkyl or C1-C4-hydroxyalkyl, for example piperidine, morpholine, piperazine, pyrrolidine, 2 - methylpiperidine, thiomorpholine, thiomorpholine dioxide, 4 - hydroxyethylpiperazine, indoline, tetrahydroquinoline, hexahydroazepine, 3,3,6 - trimethylhexahydroazepine and 1,3,3 - trimethyl - 6 - azabicyclo - [3.2.1] - octane.

Dyestuffs in which R, and R, denotes hydrogen and the sulphonic acid group is in the 6-position of the naphthalene ring are preferred.

Dyestuffs of the formula (I) in which the total number of the C atoms of the alkyl, alkoxy, alkylamino, alkylmercapto, acylamino, alkylamino, carbonylamino, alkyl or cyclic radicals, as appropriate, of R1, R2 and R, is between 4 and 20 are also preferred.

Particularly preferred dyestuffs are those which, in the form of the free acid, correspond to the formula

wherein R@ and R7 denote alkyl with 1 to 15 C atoms which is optionally substituted by cyano, hydroxy, C1-C12-alkoxy, C1-C4-alkylcarbonyloxy, benzoyloxy, chlorine, di-C1-C4-alkylamino, C1-C4-alkoxycarbonyl or phenyl- or, together with the nitrogen atom, denote piperidinyl, morpholinyl, piperazinyl or optionally methyl-substituted hexahydroazepinyl, Ra denotes hydrogen, C1-C4-alkoxy, C1-C4-alkylaminocarbonylamino, phenyl aminocarbonylamino, C1-C4-alkylcarbonylamino or benzoylamino, it being possible for phenyl to be substituted by chlorine, Cl~C4-alkyl or C1-C4- alkoxy, and n denotes 1 or 2, the substituents R8 being in the 4-position and 5-position relative to the azo bridge and the sum of the C atoms of the alkyl, alkoxy, alkylaminocarbonylamino, alkylcarbonylamino and cyclic groups, as appropriate, of R6, R7 and R8 being 4 to 20.

Dyestuffs of the formula (II) wherein Ra denotes hydrogen and RG and RT have the meaning indicated are particularly preferred.

The new dyestuffs are obtained by a process in which amines of the formula

wherein R1, R2, R, and n have the meaning already given, are diazotised in a known manner and the diazotisation products are coupled, in an acid medium, with coupling components of the formula

wherein R, and R5 have the meaning already indicated, but preferably with v-acid in an aqueous or aqueous-organic medium.

The diazo components of the formula (III) are obtained by known processes by reacting sulphonic acid chlorides of the formula

wherein R3 and n have the abovementioned meaning, with amines of the formula

wherein R1 and R2 have the abovementioned meaning, in the presence of acid-binding agents, and subsequently reducing the nitro group.

The new dyestuffs of the formula (I) are suitable for dyeing and printing natural and synthetic fibre materials, in particular fibre materials containing nitrogen atoms, such as wool and polyamide fibres, polyamide fibres being understood, in particular, as those consisting of synthetic polyamides, such as e-caprolactam or condensation products of adipic acid and hexamethylenediamine.

The dyestuffs are already absorbed well onto polyamide fibres from a neutral to weakly acid.dyebath and give red dyeings of very good levelness and with very good fastness to light and wet processing.

Example 1.

3.7 g of 2 - amino - N,N - diisopropylbenzenesulphonic acid amide are triturated in 20 g of half-concentrated hydrochloric acid, the mixture is discharged onto 20 g of ice and the amide is diazotised with 10 g (10% strength solution nitrite solution.

The clear diazonium salt solution is poured into a suspension of y-acid in water and the pH value is increased by adding 10% strength sodium hydroxide solution, until coupling starts. After the coupling has ended, the dyestuff is filtered off, washed and dried. This gives 6.9 g of a black-red powder which dyes polyamide materials bluishtinged red with very good fastness properties. Wool is dyed red by the same dyestuff, also with very good fastness properties. The dyestuff has, in the form of the free acid, the formula

In the Tables which follow, further dyestuffs are indicated which are obtained after coupling the diazo components listed with γ-acid.

TABLE 1 Diazo component of the formula

Example R1 R2 Colour shade on polyamide Wool 2 methyl ss-cyanoethyl bluish-tinged red red 3 methyl n-butyl " " " " 4 methyl iso-butyl " " " " 5 methyl sec-butyl " " " " 6 methyl n-propyl " " " " 7 methyl iso-propyl " " " " 8 ethyl n-propyl " " " " 9 ethyl n-butyl " " " " 10 n-propyl n-propyl " " " " 11 iso-butyl iso-butyl " " " " 12 allyl allyl " " " " 13 2-hydroxypropyl 2-hydroxypropyl " " " " 14 2-methoxyethyl 2-methoxyethyl " " " " 15 2-cyanoethyl 2-cyanoethyl " " " " TABLE 1 (Continued) Example R1 R2 Colour shade on polyamide Wool 16 n-propyl sec-butyl bluish-tinged red red 17 n-butyl n-butyl " " " " 18 sec-butyl sec-butyl red scarlet 19 2-ethylhexyl 2-ethylhexyl bluish-tinged red red 20 2-acetoxypropyl 2-acetoxypropyl " " " " 21 2-benzoyloxypropyl 2-benzoyloxypropyl " " " " 22 2-chloroethyl n-butyl " " " " 23 2-chloroethyl n-octyl " " " " 24 methyl n-dodecyl " " " " 25 n-butyl 2-(N,N-dibutylamino)-ethyl " " " " 26 methyl 2-dodecyloxyethyl " " " " 27 ethyl 5-cyanopentyl " " " " 28 methyl 5-carboethoxypentyl " " " " 29 ethyl 2-phenethyl " " " " 30 n-butyl benzyl " " " " 31 benzyl benzyl " " " " 32 2-phenethyl 2-phenethyl " " " " TABLE 2 Diazo component of the formula

Example R0 Colour shade on polyamide Wool 33 pyrrolidin-1-yl bluish-tinged red red 34 piperidin-1-yl " " " " 35 2-methylpiperidin-1-yl " " " " 36 morpholin-1-yl " " " " 37 thiomorpholin-1-yl " " " " 38 4,4-dioxothiomorpholin-1-yl " " " " 39 piperazin-1-yl " " " " 40 4-(2-tydroxyethyl)-piperazin-1-yl " " " " 41 2-methyl-indolin-1-yl " " " " 42 1,2,3,4-tetrahydroquinolin-1-yl " " " " 43 azepin-1-yl " " " " 44 3,3,6-trimethylazepin-1-yl " " " " 45 1,2,3-trimethyl-2-azabicyclo-[3,2,1]-oct-6-yl TABLE 3 Example Diazo component Colour shade on polyamide Wool 46 2-(N,N-di-n-butylaminosulphonyl)-5- biuish-tinged red bluish-tinged red chloroaniline 47 2-(N,N-di-n-butylaminosulphonyl)-4- ruby " " " chloroaniline 48 2-(N,N-di-n-butylaminosulphonyl)-4,6- " " " " dichloroaniline 49 2-(N,N-di-n-butylaminosulphonyl)-5- bluish-ringed red " " " methylaniline 50 2-(N,N-di-n-butylaminosulphonyl)-4- " " " " " " methylaniline 51 2-(N,N-di-n-butylaminosulphonyl)-4- " " " " " " ethylaniline 52 2-(N,N-di-n-butylaminosulphonyl)-4- ruby " " " bromoaniline 53 2-(N,N-di-n-butylaminosulphonyl)-4- " " " " methyl-5-chloroaniline 54 2-(N,N-di-n-butylaminosulphonyl)-3- " " " " chloro-6-methylaniline 55 2-(N,N-di-n-butylaminosnlphonyl)-4- " " " " methoxyaniline 56 2-(N,N-di-n-butylaminosulphonyl)-4- " " " " ethoxyaniline 57 2-(N,N-di-n-butylaminosulphonyl)-4- " " " " butoxyaniline TABLE 3 (Continued) Example Diazo component Colour shade on polyamide Wool 58 2-(N,N-di-n-propylaminosulphonyl)-4- ruby bluish-tinged red butoxyaniline 59 2-(N,N-di-n-propylaminosulphonyl)-4- " " " " benzoylaminoaniline 60 2-(N,N-di-n-propylaminosulphonyl)-4- " " " " (4-chlorobenzoylamino)-aniline 61 2-(N,N-di-n-propylaminosulphonyl)-4- " " " " (N-acetyl-N-ethylamino)-aniline 62 2-(N,N-di-n-propylaminosulphonyl)-4- " " " " benzoylamino-5-methoxyaniline 63 2-(N,N-di-n-propylaminosulphonyl)-4- " " " " butylaminocarbonylaminoaniline 64 2-(N,N-di-n-propylaminosulphonyl)-4- " " " " phenylaminocarbonylaminoaniline 65 2-(N,N-di-n-propylaminosulphonyl)-4- " " " " (3',4'-dichlorobenzenesulphonamido) aniline 66 2-(N,N-di-n-butylaminosulphonyl)-4 " " " " (4-tolyacetylamino)-aniline 67 2-(N,N-di-n-propylaminosulphonyl)-4- " " " " amino-6-methoxyaniline 68 2-(N,N-di-iso-octylaminosulphonyl)-4- " " " " aminoaniline TABLE 3 (Continued) Example Diazo component Colour shade on polyamide Wool 69 2-(N,N-di-iso-butylaminosulphonyl)-5- ruby bluish-tinged red ethoxyaniline 70 2-(N,N-di-iso-butylaminosulphonyl)-5- " " " " phenylaminocarbonyloxyaniline 71 2-(N,N-dimethylaminosulphonyl)-4- " " " " pentadecylcarbonylaminoaniline 72 2-(N,N-dimethylaminosulphonyl)-4- " " " " (N,N-di-n-butylamino)-anilione 73 2-(N,N-diethylaminosulphonyl)-4- bluish-tinged red " " " (4-chlorophenylmercapto)-aniline 74 2-(N,N-diethylaminosulphonyl)-4- ruby " " " phenylaminoaniline 75 2-(N-n-butyl-N-methylaminosulphonyl)-4- " " " " (4-acetylaminophenhyl)-aniline Example 76 0.1 g of the dyestuff obtained according to Example 1 is dissolved hot in 100 g of water. 5 ml of ammonium acetate solution are added and the mixture is diluted to 500 g with cold water. 10 g of polyamide textile material are introduced into this dyebath, the bath is heated to the boil in the course of 20 minutes, 4 g lf 10% strength acetic acid are added and the mixture is kept at the boiling point for 1 hour. Thereafter, the dyed polyamide material is removed form the dyebath, rinsed with hot water and dried at 70 to 80 C. This gives a polyamide fabric dyed bluish-tinged red.

Claims

WHAT WE CLAIM IS:

1.4. A natural or synthetic fibre material when dyed or printed by the process of claims 12 or 13.

1. An azo dyestuff which, in the form of the free acid, corresponds to the general formula

in which Rl and R2 independently denote an alkyl group which is optionally substituted by halogen, hydroxyl, alkoxy, acyloxy, cyano, alkoxycarbonyl, dialkylamino or aryl, or an allyl group or together, including the nitrogen atom, denote a monocyclic or bicyclic ring system, R., denotes a hydrogen or halogen atom or an aryl, alkoxy, alkylmercapto, aryl mercapto, alkylamino, dialkylamino, arylamino, acylamino, acylalkylamino, alkylaminocarbonylamino or arylaminocarbonylamino group, Rt denotes a hydrogen atom or a Cl to C4 alkyl, or cyclohexyl group or a phenyl radical, which phenyl radical is optionally substituted by halogen, Cl to C4.

alkyl or C1 to C4 alkoxy, Rs denotes a hydrogen atom or a Cl to C4 alkyl group and n denotes 1 or

2.

2. An azo dyestuff according to claim 1, in which R4 and R5 denote hydrogen atoms and the sulphonic acid group is in the 6-position of the naphthalene ring.

3. An azo dyestuff according to claim 1 or 2, in which the total number of carbon atoms of the alkyl, alkoxy, alkylamino, alkylmercapto, acylamino, alkylamino, carbon.

amino, alkyl or cyclic radicals, as appropriate, of Rl, R2 and R3 is between 4 and 20.

4. An azo dyestuff according to claim 1 which the form of the free acid, corresponds to the general formula

m which R0 and R7 independently denote an alkyl group with 1 to 15 carbon atoms which is optionally substituted by cyano, hydroxyl, Cl to C12 alkoxy, (Cl to C4 alkyl)-carbonyloxy, benzoyloxy, chlorine, di-Cl to C4 alkylamino, (C1 to C4 alkoxy)-carbonyl or phenyl. or, together with the nitrogen atom, denote a piperidinyl, morpholinyl, piperazinyl or optionally methyl-substituted hexa hydroacepinyl ring, R8 denotes a hydrogen atom or a C1 to C4 alkoxy, (C1 to C4 alkylamino) carbonylamino, phenyl- aminocarbonylamino, (C1 to C4 alkyl)-carbonylamino or benzoylamino group, it being possible for phenyl to be substituted by chlorine, C1 to C4 alkyl or C1 to C4 alkoxy, and n is 1 or 2, the substituents Ra being in the 4-position and 5-position relative to the azo bridge and the sum carbon atoms of the alkyl, alkoxy, alkylamino carbonylamino, alkylcarbonylamino and cyclic groups, as appropriate, of R6, R7 and Ra being 4 to 20.

5. An azo dyestuff according to claim 4, in which Ra denotes a hydrogen atom.

6. An azo dyestuff according to claim 1, as hereinbefore specifically identified.

7. A process for the production of an azo dyestuff as claimed in Claim 1, in which an amine of the general formula

in which Rl, R2, R, and n have the same meanings as in claim 1, is diazotised and the diazotisation product is coupled, in an acid medium, with a coupling component of the general formula

in which R4 and R1 have the same meanings as in claim 1, in an aqueous or aqueousorganic medium.

8. A process according to claim 7, in which the coupling component of formula (IV) is y-acid.

9. A process according to claim 7 or 8, in which the amine of formula (III) has been produced by reacting a sulphonic acid chloride of the general formula

in which R3 and n have the same meanings as in claim 1, an amine of the general formula

in which R1 and R2 have the same meanings as in claim 1, in the presence of an acidbinding agent, and subsequently reducing the nitro group.

10. A process according to claim 7, when carried out substantially as described in any one of Examples 1 to 75.

11. An azo dyestuff as claimed in claim 1, when produced by the process of any of claims 7 to 10.

12. A process for dyeing or printing a natural or synthetic fibre material comprising treating the material with an azo dyestuff as claimed in any of claims 1 to 6 and 11.

13. A process according to claim 12, when carried out substantially as described in Example 76.