DE1769503C - Process for the production of water-insoluble aminoazo dyes - Google Patents

Description

The invention relates to a process for the preparation of water-insoluble p-aminoazo dyes of the general types Formula I.

in which D is the remainder of an amine of the thiadiazole or benzisothiazole series, R is a hydrogen atom or a methyl, ethyl. Methoxy or ethoxy group, R ₂ a hydrogen or chlorine atom or a methyl, ethyl, methoxy, ethoxy, acetylamino or propionylamino group, R ₃ a radical of the formula

O O

ii i!

-C _n H _1n -OC-CH ₁ -C-CH,

20th

Rj. A residue of the formula

-C _1n H ₂₁₁₁ -OC-CH ₂ -C-CH ₃
or the formula

Have meanings using the acetoacetic acid radicals of the formula

-C-CH ₁ -COCH ₃

Il ο

acylated donating compounds.

Amines or diazo components, from which the remainder D is derived, si..d for example:

2-Amino-5-phenyl-thiodiazoI-l, 3,4, 2-Amino-5-ethyI-thiodiazole-l, 3,4,

2-Amino-5- (4'-chlorophenyI) -thiodr.zol-l, 3,4,

2-amino-4-methylmercapto-thiodiazole-1.3,5.

S-Amino-benzisothiazole-i, 1,

S-Amino-S-nitro-benzisothiazoI ^, 1 or S-Amino-S-nitro-T-bromo-benzisothiazole-ljl.

In front. R ₃ different radicals R ₄ are z. B. methyl. Ethyl, n- or i-propyl, n- or i-butyl, / i-hydroxyethyl. , i-cyanoethyl. / i'-methoxyethyl, p'-ethoxyethyl. ■ -hydroxypropyl or -methoxypropyl.

Aniline derivatives of the general formula III

«The numbers 2. 3 or 4. in the numbers 1. 2, 3 or 4 and X is a hydrogen atom or a hydroxy, cyano. Methoxy or ethoxy group means which is characterized in that one

a) Diazo compounds of amines of the general formula II

D-NH ₂

with coupling components
Formula III

II
the general

R,

⁷ "'

R,

in

-N

in which R ₁ , R ₂ , R ₃ and R _{4 have} the meanings given and which are contained in the dyes of the formula I as coupling components are, for example

45

where the radicals D and R to R ₄ mentioned in formulas II and III are identical to those in formula I, or that one
b) Compounds of the general formula IV

R,

C _n H _2n OH

IV

R,

in D, R ₁ and R ₂ the N-fAcetoacct-fi-oxyäthylJ-N-methyi-aniline, N-bis- (acetoacet - // - oxyäthyl) -aniline, N- (acetoacet- "i -oxybutyl) -N-ethyl-aniline, N- (acetoacet - // - oxyethyl) -N- / y-cyanoethyl-aniline, N- (acetoacet- / i-oxyüthyI) -N - // - oxyethyl-aniline.

N- (Acetoacet - // - o. \ Yäthyl) -N - /? - methoxyethylaniline,

N- (Acetoacct- / i-oxyethyl) -N-ethyl-m-toluidine, N- (Acetoacet- / f-oxyäthyl) -N-ethyl-m-methoxy-

aniline.
2-methyl-5-ethoxy-N- (acctoacet- / i-oxyethyl) -

N-ethyl-aniline or
N- (Acetoacet - ^ - oxyäthyl) -N - /; - oxyäthylm-acetylamino-aniline.

Diazo components derived from ßenzisothiazclen- (2, l) are preferred.

Particularly valuable dyes correspond to the general formula V.

50

, OCOCH ₂ COCH ₃

in which Z is a hydrogen, chlorine or bromine atom or a nitro, methylsulfonyl, carbomethoxy or carboethoxy group, Y is a hydrogen or bromine atom and n 'is the number 2 or 3 and where R ₁ , R ₂ and R _{4 are} the have given meanings.

The acetoacetic acid donating compounds are z. B. alkyl acetoacetate, preferably the Methyl or ethyl esters or especially diketene.

The new dyes are particularly suitable in ic finely divided form, for dyeing and / or printing fully and semi-synthetic fibers such as polyesters, Polyamides, polyurethanes, polyvinyl chloride and especially cellulose esters and ethene.

It is particularly advantageous to add mixtures of dyes which can be prepared according to the invention use. Such mixtures are obtained, for. B .. if you d '> Diazo compounds of amines of the formula

D - NH ₂

with a mixture of coupling components of the formula III implemented by incomplete Acylation of starting components of the general formula VI

C _n H _2n OH

H _2m X

VI

was prepared, or when dyestuffs of the formula IV are incompletely acylated. As to be acylated Compounds are preferably used in which X is a hydroxyl group.

With the dyes or dye mixtures which can be prepared according to the invention, scarlet-red ones are obtained to blue dyeings that have excellent light and wet fastness properties and are very resistant to Smoke gases are.

In the following examples, parts and percentages are based on weight.

Example I.

45

In a mixture of 15 parts by weight of nitrosylsulfuric acid (12.7 dinitrogen trioxide), 15 parts by weight sulfuric acid. 50 parts of glacial acetic acid and 50 parts Propionic acid is 7.3 parts of 3-methylmercapto-5-aminothiodiazole-l, 2.4 entered, then stirred for 4 hours and the diazo solution then allowed to run into a coupling solution which consists of 14.0 parts N-acetoacet-zi'-oxyethyl-N-ethyl-m-toluidine, 10 parts Hydrochloric acid (10 mol / l), 100 parts of water and 50 parts of ice and, after dissolving, more 600 parts of ice has been prepared.

After the diazo solution has been run in, the mixture is blunted by adding 100 parts of sodium hydroxide solution (10 mol / l) to a pH of 5 to 6. The dye formed precipitates in crystalline form after stirring overnight out; it is filtered off with suction, washed neutral and dried at 50 ° C. under reduced pressure Acetate silk is used to obtain bright scarlet colorations.

B e i s ρ i e 1 2

12 parts of i-carbomethoxyethylmercapto-S-aminothiodiazole-1,2,4 are at 10 to 15 ° C in a mixture of 30 parts by weight of sulfuric acid, 50 parts Propionic acid and 50 parts of glacial acetic acid entered. 15 parts by weight of nitrosyl sulfuric acid are slowly allowed in (12.7% dinitrogen trioxide) and then gives the thus prepared diazo solution after 4 hours Stir in a coupling solution, which can be obtained by dissolving 14.5 parts of N-acetoacet-zi-oxyethyl-N- / i-cyanoethyl-aniline in 25 parts of hydrochloric acid (10 mol / l) and 100 parts of water, followed by addition obtained from 700 parts of ice and 200 parts of ice water. After the diazo solution has been added, the mixture is blunted with 120 parts of sodium hydroxide solution (10 mol / l), stirred overnight and the dye isolated as usual. 20 parts of a powder which has a bright scarlet color on acetate silk are obtained.

Example 3

In a mixture of 50 parts of phosphoric acid. 15 parts by weight of sulfuric acid and 15 parts by weight Nitrosylsulfuric acid (12.7% dinitrogen trioxide) becomes 9 parts of 2- amino -5-phenyl-thiodiazole-1.3.4 registered. After stirring for 4 hours, the diazo solution prepared in this way is added to a coupling solution, by dissolving 13.5 parts of N-acetoacet -,) '- oxyäthyl-N-ethyl-aniline in 10 parts Hydrochloric acid (10 mol / l), 100 parts of water and 50 parts of ice and subsequent addition of 600 parts Ice was obtained.

When the addition of the diazo solution is complete, it is diluted with a further 250 parts of ice water and blunted by adding 140 parts of sodium hydroxide solution (10 mol / l) to pH 5 to 6. After stirring overnight The precipitated dye is suctioned off, washed neutral with water and dried at 50.degree under reduced pressure. 15 parts of an acetate silk powder which has a brilliant scarlet coloration are obtained.

Example 4

10 parts of 3-amino-5-nitro-benzisothiazole are IOC in 100 parts by weight of 85% sulfuric acid dissolved and by slowly adding 15 parts by weight of nitrosylsulfuric acid (12.7% dinitrogen trioxide) diazotized.

The diazo solution prepared in this way is then allowed to flow into a coupling solution after stirring for 4 hours, that by dissolving 14.5 parts of the coupling components prepared as described below in 6 parts of hydrochloric acid (10 mol / l) and 50 parts of ice water and subsequent addition of 400 parts of ice was obtained.

After adding the diazo solution, the mixture is diluted with 250 parts of ice water and, by adding 225 parts of sodium hydroxide solution (10 mol / l) have a pH of 5 to 6. Obtained after the usual work-up 23 parts of a dye which dyes acetate silk and polyester fabric pure blue.

Manufacture of the coupling component

90.5 parts of N-di-p-oxyäthylanilin are mixed with 70 parts of methyl acetoacetate, and first to 12O ⁰ C and then slowly heated to 160 ° C. The total heating time is 6 hours. 18 parts of methanol are slowly distilled over. It is then cooled to 8O ⁰ C and removed to bei'10 15.Torr a small amount (about 1 part) of unreacted methyl acetoacetate.

This gives 132 parts of a light-colored oil which, in addition to N - (acetoacet - β - oxyäthyl) - N - β - oxyäthyl-

aniline as main product also contains small amounts of contains the corresponding diester and the starting product. The molecular weight from coupling with Nitrosamine cheats 270,

In the same way, the following coupling components were also made from the corresponding starting compounds prepares the N- (acetoacet- / i-oxyäthyl) -N - /; - oxyäthyl-m-toluidine as the main product or the N- (Acetoacet - // - oxyüthyl) -N - // - oxyäihylm-aceiamino-aniline and which are listed below under the name of the main product

are ,, .- au ι · u

Analogous to that described in Examples 1 to 4 The procedure also gives those in the table below using diazo and coupling components characterized dyes:

Diazo component coupling component

Shade on acetate silk

3-Amino-5-nitro-7-bromobenzisothiazole-2, l 3-Amino-5-nitro-7-bromobenzisothiazo! -2, l 3-Amino-5-nitro-7-bromobenzisothiazole-2.1. 3-Amino-5-nitro-7-bromobenzis ..lhiazole-2.1 3-Amino-5-nitro-7-chromobenzisothiazole-2.l 3-Amino-5-nitro-7-bromobenzisolhia / o] -2.! 3 -. \ Min (v5-nitro-7-brumben / .iso! Hiazol-2, i 3-Anlino-5-nitro-7-broInbcnzisothiazol-2. ' 3-Amino-5-nitro-7-bromobenzisothiazole-2.1

3-methylmercapto-5-amino-lhiodiazole-3-methylmercapto-S-amino-thiodiazole-3-methylmcrcapio-S-amiiio-liiodiazole -. '■ Methylmercapto-S-ammothiodiazole-3-Mclh \ lmercapt.o-5-amino -lhiodiazol-3-Mcthylmcrcίlpto-5-amino-tl ^ iodiazol-3-Mcthylmcrcapto-S-amino-thiodiazol-3-Methvlmercapto-S-amino-thiodiazol-

.2.4 .2.4 .2.4, 2.4 .2.4 .2.4 .2.4, 2.4

J-Carbomcthoxyäthylniercaplo-S-amino-

thiodiazole-1,2.4
3-Carhomethylethylmcrcapto-5-aminothiodiazole-1.2.4

3-Carbomcthoxyäthylmcrcaplo-S-amino-

thiodiazole-1,2,4
3-Carbomcthoxyäthylmcrcapto-S-amino-

thiodiazole-1,2,4
Ji-Ca rbomethoxyäthylmcrcapto-5-amino-

thiodiazole-1,2.4
3-Carbomethoxyäthyiinereapto-S-aminothiodiazole-1,2,4

3-Carbomcthoxyäthylmercapto-S-amino-

thiodiazole-1,2,4 S-carbomethoxyethylmercapto-S-amino thiodiazole-1.2,4

2-Amino-5-phenyl-thiodiazole-1,3,4 2-Amirio-5-phenyl-thiodiazole-1,3,4 2-Amino-5-phenyl-thiodiazole-1,3,4 2-Amino-5-phenyl-thiodiazole-1,3,4

2-Amino-5-phenyl-thiodiazole-1,3,4 2-Amino-S-phcnyl-thiodiazole-1,3,4 N- (acetoacet- / i-oxyäthy!) - N-ethyl-

aniline C)
N- (acetoacet- / l-oxyethyl) -N-cyanoethyl-

anihn ( ² >
N- (Acetoacet- / io. \ Yäihyl) -N-cyanoethyl-

m-toluidin '- ^)
N- (Acetoacet - /) '- oxyäthyl) -N-methoxy-

ethyl-aniliii (4)
K. N-Di-I Acctoa cct-p'-oxyethyl) -

r ..- toluidine (5)
N- (Aceloaccl- / i-oxypropyl) -N-cyanoethyl-

aniline (6)
N- (Accloacct - ^ - oxyälhyl) -N-bcnzyI-

m-toluidine O)
N- (Aceioacel - / -; - oxyethyl) -N-benzyl-

aniline (8)
N- (Aceloacel- / i-oxäthyl) -N-Äihyl-

m-loluidine (9)

Coupling component (I)

Clutch component (2)

Clutch component (4)

Clutch component (5)

Clutch component (6)

Clutch component (7)

Clutch component (8)

Clutch component (9)

Clutch component (1)

Coupling component
Coupling component
Coupling component
Coupling component
Coupling component
Coupling component
Coupling component

Coupling component
Coupling component
Coupling component
Coupling component
Coupling component
Coupling component
Coupling component

(3)
(4)
(5)
(6)
(7)
(H)

blue

violet

Violas

blue

blue

blue

blue

blue

blue

Red

Scarlet fever

Rol

Red

Scarlet fever

Red

Red

Red

Red

Red Red Red Red Red Red Ruby

orange

Red

Red

Red

orange

Red

Red

Claims (3)

71 769 5038 (9) shade on acetate silk diazo component, continuation (1) red 2-amino-5-phenyl-thiodiazole-1.3.4K coupling component (2) blue, VAmino-S-nitro-benzisothiiizole ^. Coupling component (3) violet ^ amino-5-nitro-benzisothiazole-2, l coupling component (4) blue3 * amino-5-nitro-benzisothiazole-2, l coupling component (5) blue3-amino-5-nitro-benzisothiazole-2.1K coupling component ( 6) BlueJ'Amino - ^ - nitro-benzisothiazole ^ J coupling component (7) Violet 3-Amino-5-nitro-benzisothiazole-2, l coupling component (8) Blue 3-arnino-5-nitro-benzisothiazole-2, l coupling component (9) Biau3- Amino-5-nitro-benzisothiazole-2, lK coupling component N- (acetoacet- / I-oxyethyl) -N- / i-oxyethyl blue3 * Amino-5-nitro-benzisothiazole-2, l coupling component-toluidine blue3-amino-5-nitro -benzisothiazol-2, lK coupling componentN- (Acetoacet - /? - oxyäthy1) -N - /? - oxyäthyl-greenish blueB-Amino-S-nitro-benzisothiazole-LI m-acetamino-aniline • Claims: 1. Process for the preparation of water-insoluble p-aminoazo dyes of the general formula (I) Rj DN = N- ^ V- _N (D R * in D the residue of an amine of the thiadiazole or benzisothiazole series. Ri is a hydrogen atom or a methyl. Ethyl-. Methoxy or ethoxy group. R _{2 is} a hydrogen or chlorine atom or a methyl. Ethyl-. Methoxy-. Ethoxy, acetylamino or propionylamino group. R _{3 is} a radical of the formula Il Il -CH ^ -OC-CH ₂ -C-CH ₃ R _{4 is} a radical of the formula - CH ^ -OC - CH ₂ -C-CH., or the formula ^ i_i "γ- η the numbers 2. 3 or 4. m the numbers 1. 2. 3 or 4 and X is a hydrogen atom or a hydroxy. Cyan. Methoxy or ethoxy group means, characterized in that one «ο a) Diazo compounds of amines of the general formula (II) D-NH ₂ (ID with coupling components of the general formula (III) / VR ₂ (IN THE) _{where the radicals D and R, to R 4} mentioned in the formulas (II) and (III) are identical to those in the formula (I), or that b) compounds of the general formula (IV) ^R. D-N = N C _n H ₂ "OH H ₂ "X in which D. R, and R _{2 have} the meanings given in formula (1 ), using the acetoacetic acid radicals of the formula - C-CH ₂ -COCH,
O acylated donating compounds. 2. Use of the dyes obtainable by the method according to claim 1 for dyeing of textile material made from cellulose esters or polyesters. 3. Use of mixtures of the dyes obtainable by the process according to Claim 1 for dyeing textile material made from cellulose esters or polyesters.