GB2031930A

GB2031930A - Monoazo dyestuffs

Info

Publication number: GB2031930A
Application number: GB7931104A
Authority: GB
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1978-09-12
Filing date: 1979-09-07
Publication date: 1980-04-30
Also published as: GB2031929A; FR2436167B1; GB2031929B; GB2031930B; IT7925581A0; JPS5538896A; FR2436167A1; FR2436165B1; JPS5538895A; JPS5538894A; IT7925579A0; DE2839562A1; FR2436165A1

Abstract

Dyestuffs of the formula <IMAGE> wherein B is a direct bond or a bridge member linked to an aromatic carbocyclic carbon atom in D, R is H or C1-C4 alkyl, R1 and R2 are hydrogen or optionally substituted alkyl or cycloalkyl, or (R1 + R2) form a ring with the N atom and optionally a further hetero atom, n is 1 - 6, D is a diazo component of the benzene or naphthalene series K is a coupling component of the naphthalene, pyridone, pyrazolone or acetoacetic acid arylide series, both D and K being free from reactive groups, and their use for dyeing and printing materials containing hydroxyl groups or amide groups, such as textile fibres, filaments and fabrics of wool, silk or synthetic polyamide or polyurethane fibres, and for dyeing and printing natural or regenerated cellulose in dyeings and prints which are fast to washing.

Description

1

GB 2 031 930 A

1

SPECIFICATION Monoazo dyestuffs

5 The present invention relates to monoazo dyestuffs of the formula o—cu °

c> N*N XT n

? CI)

10 N-R

15

wherein

B = a direct bond or a bridge member,

R = hydrogen or CrC4-alkyl,

20 R, and R2 = hydrogen, optionally substituted alkyl orcycloalkyl, or

Ri and R2 form a ring with the nitrogen atom,

optionally including a further hetero-atom,

n = an integer from 1 to 6,

25 D = the radical of a diazo component of the benzene series or naphthalene series and K = the radical of a coupling component of the naphthalene, pyridone, pyrazolone or acetoacetic acid arylide series, both D and K being free from reac-30 tive groups.

The bridge member B is linked to an aromatic-carbo-cyclic C atom of K.

The radicals D and K can carry the substituents customary for azo dyestuffs, for example: halogen atoms, such as fluorine, chlorine or bromine, CrC4-alkyl, CrC4-alkoxy or carboxyl, amino, hydroxyl, nitro, sulphonamide or acetylamino groups.

35 B is preferably a direct bond.

Examples of suitable optionally substituted alkyl radicals R, and R2 are: methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, n-pentyl, n-hexyl, p-hydroxy-ethyl, p-methoxyethyl, p-ethoxyethyl, carboxymethyl, p-sulphoethyl, phenylmethyl, p-phenylethyl and cyclohexyl.

Preferred alkyl radicals Ri and R2 are C1-C4-alkyl radicals. The following are examples of cyclic radicals of 40 the formula

-N :

^R2

Examples of coupling components

50

OH

I

H-K (||)

55 are:

(a) pyridones: 1-ethyl-3-carbamoyl-4-methyl-6-hydroxy-pyrid-2-one, 1-methyl-3-carbamoyl-4-methyl-6-hydroxy-pyrid-2-one, 1-methyl-3-sulphomethyl-4-methyl-6-hydroxy-pyrid-2-one and 1-ethyl-3-sulphomethyl-4-methyl-6-hydroxy-pyrid-2-one.

(b) Pyrazolones: 1-(2'-, 3'- or4'-sulpho-phenyl)-3-methyl-pyrazol-5-one, 1-{2'-chloro-4'-or-5'-sulpho-60 phenyl)-3-methyl-pyrazol-5-one, 1-(2'-methyl-4'-sulpho-phenyl)-3-methyl-pyrazol-5-one, 1-(2'-methyl-4'-

sulpho-phenyl)-3-carboxy-pyrazol-5-one, 1-p-carboxy-ethyl-3-carboxy-pyrazol-5-one, 1M4',8'-disulpho-naphth-2-yl)-3-methyl-pyrazol-5-one, 1-(5',7'-disulpho-naphth-2-yl)-3-methyl-pyrazol-5-one, 1-(2'-chloro-5'-sulpho-phenyl)-3-methyl-5-amino-pyrazole, 1-(2'-chloro-4'-sulpho-phenyl)-3-methyl-5-amino-pyrazole, 1-(3'-or4'-sulpho-phenyl)-3-methyl-5-amino-pyrazole, 1-carboxy-methyl-3-methyl-pyrazol-5-one, 1-P-65 carboxyethyl-3-methyl-pyrazol-5-one, 1-p-carboxyethyl-3-methyl-5-amino-pyrazole and 1-(4'-sulpho-

5

10

15

20

25

30

35

40

45

50

55

60

65

2

GB 2 031 930 A

2

phenyi)-3-carboxy-pyrazol-5-one.

(c) Acetoacetic acid arylides: 1-acetoacetylamino-2-methoxy-4-acetylamino-5-sulpho-benzene, 1-acetoacetylamino-2,5-dimethoxy-4-sulpho-benzene and 1-acetoacetylamino-2-methoxy-4-sulpho-5-methyl-benzene.

5 (d) Naphthols: 1-hydroxy-5-sulpho-naphtha(ene, 1-hydroxy-3,6-disulpho-naphthalene, 1-hydroxy-3,7- 5 disuipho-naphthalene, 1-hydroxy-3,8-disulpho-naphthalene, 1-hydroxy-4,6-disulpho-naphthalene, 1-hydroxy-4,7-disulpho-naphthalene, 1-hydroxy-4,8-disulpho-naphthalene, 1-hydroxy-3,5-disulpho-naphthalene, 2-hydroxy-3,6-disulpho-naphthalene and 2-hydroxy-5,7-disulpho-naphthalene.

(e) Aminonaphthols: 1-amino-2,4-disulpho-8-hydroxy-naphthalene, 1-amino-4,6-disulpho-8-hydroxy-

10 naphthalene, 2-phenyl-amino-6-sulpho-8-hydroxy-naphthalene, 2-amino-3,6-disulpho-8-hydroxy- 10

naphthalene and 2-amino-1,6-disulpho-5-hydroxy-naphthalene.

(f) Acylaminonaphthols: 1-hydroxy-8-benzoylamino-3,6-disulpho-naphthalene, 1-hydroxy-8-benzoyl-amino-3,5-disulphonaphthalene, 1-hydroxy-8-ureido-3,6-disulphonaphthalene, 1-hydroxy-8-ureido-3,5-disulpho-naphthalene, 1-hydroxy-8-acetylamino-3,5-disulpho-naphthalene, 1-hydroxy-8-acetylamino-3,6-

15 disuipho-naphthalene and 1-hydroxy-6-methylamino-3-sulpho-naphthalene. 15

The following compounds are examples of the diaminophenols and diaminonaphthols

OH

!

0 - NHg

20 n-R (Ilt) 20

1

H

on which the dyestuffs of the formula (I) are based:

25 4-nitro-6-aminophenol-2-sulphonic acid (nitro group reduced), 6-amino-4-acetylaminophenol-2-sulphonic 25 acid (acetylamino group saponified), 4-nitro-6-aminophenol-3-sulphonic acid (nitro group reduced), 6-nitro-2-aminophenol-4-sulphonic acid (nitro group reduced), 4-N-methylamino-methyl-2-aminophenol, 2-amino-1-hydroxy-4-nitrobenzene (nitro group reduced), 2-amino-1-hydroxy-5-nitrobenzene (nitro group reduced), 1-amino-2-hydroxy-6-nitro-naphthalene-4-sulphonicacid (nitro group reduced), 2-amino-1-30 hydroxy-6-nitro-naphthalene-4,8-disulphonic acid (nitro group reduced) and 2-amino-1-hydroxy-6- 30

acety!amino-naphthalene-4,8-disulphonic acid (acetylamino group saponified).

Preferred dyestuffs correspond to the formulae and

Civ)

so3h

So3«

3

GB 2 031 930 A

3

The dyestuffs (I) can be obtained by various processes: 1) Dyestuffs of the formula

10 P N P

are reacted with amines of the formula

/R-,

15 HI\T 15

\r2 (VII)

wherein

20 Ri and R2 have the meaning indicated above, hydrofluoric acid being split off. This condensation reaction 20 is preferably carried out in aqueous solution or suspension, at low temperatures and at a weakly acid, neutral to weakly alkaline pH value. The hydrogen fluoride liberated during the condensation reaction is advantageously continuously neutralised by adding aqueous alkali metal hydroxides, carbonates or bicarbonates. The neutralisation can also advantageously be effected with a second equivalent of amine 25 (VII), in particular with ammonia. 25

2) Dyestuffs of the formula

°~lYv^

"\c

NyN

p

(VIII)

35 35

are treated with agents which donate copper. Examples of agents which donate copper which can be used are salts which contain copper as a cation, such as, for example, copper sulphate or copper acetate.

The dyestuffs are coppered by methods which are known per se, for example at room temperature and in a neutral to weakly acid range.

40 3) Dyestuffs of the formula 40

JjS — N ** N —

6-rvV<Rl

45 R N M Ra ^ 45

y

F

are subjected to the oxidative coppering process, the hydroxyl group necessary for complex formation only 50 being introduced into the radical D, in the o-position relative to the azo bridge, during the coppering reaction 50 by the simultaneous action of an oxidising agent. (Angew. Chem. 70,232 (1958)).

4) Dyestuffs of the formula

55

60

O — CU -O (SO3v0n ("D —NeN-Kj^ 55

^ — B-N-H (X.)

are reacted with difluoroaminotriazines of the formula

60

✓ Ri N / '

'rr

NyN

F

x Re C*z~)

4 GB 2 031 930 A

4

hydrofluoric acid being split off. This condensation reaction is preferably carried out in aqueous solution or suspension, at low temperature and at a weakly acid, neutral to weakly alkaline pH value. The hydrogen fluoride liberated during the condensation reaction is advantageously continuously neutralised by adding aqueous alkali metal hydroxides, carbonates or bicarbonates.

5 The following are examples of amines (VII): ammonia, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, t-butylamine, n-pentylamine, n-hexylamine, cyclohexyla-mine, dimethylamine, diethyiamine, di-n-propylamine, di-iso-propylamine, methylethylamine, ethanola-mine, diethanolamine, p-methoxyethylamine, p-ethoxyethylamine, aminoacetic acid, N-methylaminoacetic acid, taurine, N-methyltaurine, benzylamine, p-phenylethylamine, N-methylbenzylamine, pyrrolidine, piper-10 idine and morpholine.

The following compounds may be mentioned as examples of difluorotriazine compounds (XI): 2,4-difluoro-6-amino-1,3,5-triazine,2,4-difluoro-6-methylamino-1,3,5-triazine, 2,4-difluoro-6-dimethylamino-1,3,5-triazine, 2,4-difluoro-6-n-propylamino-1,3,5-triazine, 2,4-difluoro-6-n-propylamino-1,3,5-triazine, 2,4-difluoro-6-ethylamino-1,3,5-triazine, 2,4-difluoro-6-diethylamino-1,3,5-triazine, 2,4-difluoro-6-n-butylamino-15 1,3,5-triazine, 2,4-difluoro-6-cyclohexylamino-1,3,5-triazine and 2,4-difluoro-6-morpholino-1,3,5-triazine.

The new dyestuffs are suitable for dyeing and printing materials containing hydroxyl groups or amide groups, such as textile fibres, filaments and fabrics of wool, silk or synthetic polyamide or polyurethane fibres, and for dyeing and printing natural or regenerated cellulose in dyeings and prints which are fast to washing, the treatment of cellulose materials appropriately being carried out by the processes disclosed for 20 reactive dyestuffs, in the presence of acid-binding agents and if appropriate by the action of heat.

"Hie formulae indicated for the dyestuffs are those of the corresponding free acids. The dyestuffs were generally isolated and used for dyeing in the form of alkali metal salts, in particular the Na salts.

Example 1

25 60 g of the dyestuff which is obtainable by coppering 2-hydroxy-3-sulpho-5-amino-benzene <1 azo 2> 1-hydroxy-5,7-disulpho-8-amino-naphthalene are stirred in 1 litre of ice-water. 13.5 g of trifuorotriazine are added dropwise in the course of 15 minutes, the pH value being kept between 3.5 and 4.5 by simultaneously adding 20 % strength sodium carbonate solution. When the condensation reaction has ended, 12 % strength ammonia solution is added until the pH value is 8.5-9. The temperature is allowed to rise to 5-10°Cand the 30 pH value is kept at 8.5 - 9 until the second fluorine atom has been replaced by ammonia. After salting out, filtering off, drying and grinding the product, a blue dyestuff powder which readily dissolves in water giving a blue-coloured solution is obtained.

The dyestuff corresponds to the formula

Clear reddish-tinged blue dyeings are obtained on cotton by one of the dyeing processes customary for 45 reactive dyestuffs.

If methylamine, dimethylamine, ethylamine, N-methylethylamine, diethyiamine, iso-propylamine, n-butylamine, N-methylethanolamine, ethanolamine, diethanolamine, sulphuric acid mono-(2-aminoethyl) ester, cyclohexylamine, aminoacetic acid, taurine, N-methyltaurine, benzylamine or morpholine is used in this example instead of ammonia, dyestuffs with similar dyeing properties result.

50 The aminoazo dyestuff used as the starting material in this example is obtained by diazotising

1-amino-2-hydroxy-3-sulpho-5-acetylamino-benzene, coupling the diazotisation product with Chicago acid SS, saponifying the acetylamino group and then coppering the product. The saponification and coppering can be carried out in the reverse sequence.

If the procedure followed is as according to the statements of this example, but compounds which are 55 obtainable by diazotising the diazo components listed in column 1, coupling the diazotisation product with the azo components given in column 2, saponifying the acetylamino group and then coppering the product are used instead of the copper complex dyestuff used in this example and ammonia, methylamine, dimethylamine, ethylamine, diethyiamine, iso-propylamine, n-butylamine, N-methylethylamine, ethanolamine, diethanolamine, sulphuric acid mono-(2-amino-ethyl) ester, cyclohexylamine, aminoacetic acid, 60 taurine, N-methyltaurine, benzylamine or morpholine is used as the amine for replacing the second fluorine atom, further valuable dyestuffs which dye cotton in the shade indicated likewise result.

5

10

15

20

25

30

35

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55

60

5

GB 2 031 930 A

5

Example Diazo component

3

4

10 5

1 -Am i no-2-hydroxy-3-acetyl-amino-5-sulpho-benzene 1-Amino-2-hydroxy-3-sulpho-5-acetylamino-benzene

Azo component

1 -Hyd roxy-8-a mi no-5,7 -disuipho-naphthalene 1-Hydroxy-4,8-disulpho-benzene

1-(2',5'-Disulphophenyl)-3-methyl-pyrazol-5-one 1-Hydroxy-3,6-disulpho-naphthalene

Colour shade on cotton reddish-tinged blue ruby yellow-

brown claret

Example 6

65 g of the copper complex dyestuff obtained from 2-hydroxy-4-sulpho-6-amino-naphthalene <1 azo 2> 15 1-hydroxy-5,7-disulpho-8-amino-naphthalene are stirred in 1 litre of ice-water. 13.5 g of trifluorotriazine are added dropwise in the course of 15 minutes, the pH value being kept between 3.5 and 4.5 by simultaneously adding 20 % strength sodium carbonate solution. When the condensation reaction has ended, 12 % strength ammonia solution is added until the pH value is 8.5 -9. The temperature is allowed to rise to 5-10° and the pH value is kept at 8.5 - 9 until the second fluorine atom has been replaced by ammonia. After salting out, 20 filtering off, drying and grinding the product, a blue dyestuff powder which readily dissolves in water giving a blue-coloured solution is obtained.

The dyestuff corresponds to the formula

25

30

SO3H

10

15

20

25

30

Clear blue dyeings are obtained on cotton by one of the dyeing processes customary for reactive dyestuffs.

If methylamine, dimethylamine, ethylamine, N-methylethylamine, diethyiamine, iso-propylamine, n-35 butylamine, N-methylethanolamine, ethanolamine, diethanolamine, sulphuric acid mono-(2-aminoethyl) ester, cyclohexylamine, aminoacetic acid, taurine, N-methyltaurine, benzylamine or morpholine is used in this example instead of ammonia, dyestuffs with similar dyeing properties result.

The aminoazo dyestuff used as the starting material in this example is obtained by coupling 1-diazo-2-hydroxy-4-sulpho-6-nitro-naphthalene with 1-hydroxy-8-amino-5,7-disulpho-naphthalene, reduc-40 ing the nitro group and then coppering the product.

If the procedure followed is as according to the statements of this example, but compounds which are obtainable by coupling the diazo compounds listed in column 1 with the coupling components given in column 2, reducing the nitro group and then coppering the product are used instead of the copper complex dyestuff used in this example and ammonia, methylamine, dimethylamine, ethylamine, diethyiamine, 45 iso-propylamine, n-butylamine, N-methylethylamine, ethanolamine, diethanolamine, sulphuric acid mono-(2-aminoethyl) ester, cyclohexylamine, aminoacetic acid, taurine, N-methyltaurine, benzylamine or morpholine is used as the amine for replacing the second fluorine atom, further valuable dyestuffs which dye cotton in the shade indicated likewise result.

6 GB 2 031 930 A

6

Example Diazo component

Coupling component

Colour shade on cotton

57

10

15

10

1 -Diazo-2-hyd roxy-4-sulpho-6-nitro-naphthalene

1 -Hyd roxy-4,8-d isu I pho-naphthalene

1-Hydroxy-8-benzoylamino-3,6-disulpho-naphthalene

1-Hydroxy-3,6-disulpho-naphthalene

1-(2',5'-Disulphophenyl)-3-methyl-pyrazol-5-one violet bluish- tinged violet violet yellow- brown

10

15

11

20

1-Ethyl-3-sulphomethyl-4-methy/-6-hydroxy-pyrid-2-

one

20

Example 12

25 71 g of the copper complex obtained from 1-hydroxy-4,8-disulpho-6-amino-naphthalene <2 azo 2> 1-hydroxy-4,8-disulpho-naphthalene are stirred in 1 1 of ice-water. 13.5 g of trifluorotriazine are added dropwise in the course of 15 minutes, the pH being kept between 3.5 and 4.5 by simultaneously adding 10% strength sodium carbonate solution. When the condensation reaction has ended, 12 % strength ammonia solution is added dropwise until the pH is 9. The temperature is then allowed to rise to 10°C and the pH is

30 kept at 9 with further ammonia solution until the second fluorine atom has been replaced by ammonia. After salting out, filtering off, drying and grinding the product, a blue dyestuff powder which dissolves in water giving a blue-violet coloured solution results.

The dyestuff corresponds to the formula

35

40

25

30

35

40

The dyestuff can also be isolated by evaporating the reaction mixture or by spray-drying instead of by salting out.

45 If methylamine, dimethylamine, ethylamine, N-methylethylamine, diethyiamine, iso-propylamine, n- 45

butylamine, N-methylethanolamine, ethanolamine, diethanolamine, sulphuric acid mono-(2-aminoethyl)

ester, cyclohexylamine, aminoacetic acid, taurine, N-methyltaurine, benzylamine or morpholine is used in this example instead of ammonia, dyestuffs with similar dyeing properties result.

The aminoazo dyestuff used as the starting material in this example can be obtained by diazotising 50 2-amino-4,8-disulpho-6-nitro-naphthalene, coupling the diazotisation product to 1-hydroxy-4,8-disulpho- 50 naphthalene, reducing the nitro group with sodium sulphide, acetylating the amino group, subjecting the productto oxidative coppering and saponifying the acetylamino group.

Claims

55 55

1. A monoazo dyestuff of the general formula

O Cu—O

? CD

N -R

A

N nN

P N N

7

GB 2 031 930 A

7

in which

B denotes a direct bond or a bridge member linked to an aromatic carbocyclic carbon atom of radical K,

R denotes a hydrogen atom or a Ct to C4 alkyl group,

5 R, and R2 independently denote a hydrogen atom or an optionally substituted alkyl or cycloalkyl group, or R-i and R2 form a ring with the nitrogen atom,

optionally including a further hetero-atom,

n is 1,2,3,4,5 or 6,

10 D denotes a radical of a diazo component of the benzene series or naphthalene series which is free from reactive groups and

K denotes a radical of a coupling component of the naphthalene, pyridone, pyrazolone or acetoacetic 15 acid arylide series which is free from reactive groups, with the proviso that D and K cannot simultaneously be components of the naphthalene series

2. A monoazo dyestuff according to claim 1 in which B denotes a direct bond. 2q

20 3. A monoazo dyestuff according to claim 1 of the general formula

25

25

JlJv"*

p M N

30

SRa 30

in which R-) and R2 have the same meanings as in claim 1. 4. A monoazo dyestuff according to claim 1 of the general formula

35

40

r- lil .

40

Nr£

in which R-i and R2 have the same meanings as in claim 1. 45 5. A monoazo dyestuff according to claim 1 of the general formula in which R, and R2 have the same meaning as in claim 1.

6. A monoazo dyestuff according to claim 1 as hereinbefore specifically identified.

7. A process for the production of a dyestuff as claimed in claim 1 in which a dyestuff of the general formula

GB 2 031 930 A

o cu_o t>5— M.N K ^

-B

r

(vfl

N —«

5 n\ 5

M,

P N P

in which B, R, n, K and D have the same meaning as in claim 1, is reacted with an amine of the general 10 formula 10

^Ri

HN (VII)

^R2

15 15

in which and R2 have the same meanings as claim 1, hydrofluoric acid being split off.

A process for the production of a dyestuff as claimed in claim 1, in which a dyestuff of the general formula 20 20

25 ly* Rs <vm) 25

F

in which B, R1( R2, R,/7, Kand D have the same meanings as in claim 1, is treated with an agent which donates

30 copper. 30

9. A process for the production of a dyestuff as claimed in claim 1, in which a dyestuff of the general formula r

I D — N <= M — K-rp "

35 i 35

B-N. ,nj ../r1

if"

N K1

Y

F

40 40

in which B, R-i, R2, R, n, K and D have the same meanings as in claim 1, is subjected to oxidative coppering, the hydroxyl group necessary for complex formation only being introduced into the radical D, in the o-position relative to the azo bridge, during the coppering reaction by the simultaneous action of an oxidising agent.

45 10. A process for the production of a dyestuff as claimed in claim 1, in which a dyestuff of the general 45 formula o_cu-o"l CSC.3U)n ■D-NtN - K-J

50 ^ B-n-H CX.) 50

I

R

in which B, R, n K and D have the same meanings as in claim 1, is reacted with a difluoroaminotriazine of the 55 general formula 55

- M /R1

60 >N 60

F

r r it sr2 (ix)

in which R-i and R2 have the same meanings as in claim 1, hydrofluoric acid being split off.

65 11. A process for the production of a dyestuff as claimed in claim 1 when carried out substantially as g5

9

GB 2 031 930 A 9

described in any one of the Examples.

12. A dyestuff as claimed in claim 1 which produced by the process of any of claims 7 to 11.

13. A process for dyeing or printing a material containing hydroxyl groups or amide groups comprising treating the material with a dyestuff as claimed in any of claims 1 to 6 and 12.

5 14. A material containing hydroxyl groups or amide groups when dyed or printed by the process of claim 5 13.

Printed for Her Majesty's Stationery Office, by Croydon Printing Company Limited, Croydon Surrey, 1980. Published by the Patent Office, 25 Southampton Buildings, London, WC2A 1AY, from which copies may be obtained.