DD210171A3 - PROCESS FOR THE PREPARATION OF AZO-PURPOSES FROM SUBSTITUTED 4-AMINO-1-ARYL-PYRAZOLENE - Google Patents

Abstract

By diazotization of 4-amino-1-aryl-pyrazoles which have acceptor groups in the 3- and 5-position and subsequent coupling of the intermediary diazonium salts to substituted anilines, 2-aminothiophenes and beta-naphthols, yellow to red disperse azo dyes having good light fastnesses are obtained synthesized, which are suitable for the dyeing of fully or semi-synthetic, hydrophobic fiber material.

Description

Title of the invention

A process for the preparation of azo dyes from substituted 4- A .Tnino-1-aryl-pyrazoles

Field of application of the invention

The invention relates to a process for the preparation of azo dyes which are suitable for dyeing or printing "fully or semisynthetic hydrophobic fiber material."

Characteristic: the known technical solutions

From the general chemical literature, three process routes for the preparation of pyrazolo-1-azo dyes are known, which differ fundamentally from each other,

1 · Cyclocondensation of arylazo-1,3-dicarbonyl compounds (compare ζ.Β- DOS 2 209 255 (BASS '), GA.80-49247b). Pyrazolone dyes are mainly used.

2. Azocoupling on pyrazoles with a necessary donor in the 3-position. Here, such dyes are also known, dio'.iii .5-position have an acceptor (see * B. B. Jap 'Pat., 81 123 484 ν,> ^Λ ), .GA 96, 36865 0982)) ~

Dyes with acceptors in 3- and 3 ^ - ^ '~ 5 ^ - ~ ^cL - ^C! · ---- - -

Pyrazolekernes are not displayed.

-HAML 1933 * 087446

3. Azo coupling with diazotized 4-aminopyrazoles (cf Z * 3, The Chemistry of Heterocyclic Compounds, Vol. 22, Sd, H. Weissberger, Interscience Publishers New York 1967, Yakugaki Zasshi $ ±, 17 0974), CA "81, 6354-3 0974 ·)).

In the specified in the literature, a few examples of Method 3 no information about the fastness properties are made, which suggests low light fastness. The azo dyes synthesized for comparison from 4-aminoantipyrine (see below) only have a light fastness of 2. However, the structures obtainable by method 3 are not accessible by methods 1 and 2 *

The derived from 4- ~ aminopyrazoles azo dyes differ in their structure from the dyes prepared according to 1 and 2 and thus possibly in the dyeing properties, because here the pyrazole can be coupled to numerous selectable components, which can be and 2 can not be introduced.

In addition, this method allows the preparation of azo dyes, which are acceptor-substituted in the 3- and 5-position in the pyrazole and which have not been described in the literature ..

It is known that in some applications, by introducing electron acceptors in an a posteriori to the aerosol group, improvements, e.g. B. with regard to the light fastness and the Bathochromiej can be achieved. This is especially indicated for benzene and thiophene dyes.

However, there are no universally valid rules for this. It is also not stated how these improvements in individual cases, s. 3, the pyrazole can be realized, in particular not, as one can represent pyrazole-4-azo dyes with two of the azo group adjacent electron acceptors.

With respect to the light chthe it en is commonly found, _fl that while a fundamental relationship between constitution and light chtiie it must exist, "but that is not yet in a position to a universal broad-based and based on theoretical knowledge for each type to derive (Chimia, Suppl. 1968, S, 78; see The chemistry of the synthetic dyes YIII, 1978).

Object of the invention

The aim of the invention is to prepare special azo dyes based on 3 '5-acceptor-substituted 4-aminopyrazoles in a simple manner and to exceed the lightfastness of the dyes previously prepared on the basis of 4-aminopyrazoles.

Explanation of the essence of the invention

The object of the invention is to make new azo dyes based on special ^ Araino-1-aryl-pyraz oils accessible by a simple method. According to the invention the object is achieved in that 4-aminopyrazoles of formula I,

R ² NH ₂

_No

R ¹ I

in the R a substituted or unsubstituted aryl

2 rest, R is a Hitril-, ALkosycarbonyl- or Garbamidogruppe and He is a üTitril-, alkozsycarbonyl or benzoyl group, diazotized under customary conditions and the resulting diazonium salts with compounds of the formulas II, III IV.

II

III

OH 4

In the formulas II - IV "S. mean one

Methyl, ethyl, hydroxyethyl, Έτ a methyl, cyanoethyl, benzyl group, S is an aryl radical, R 'is an alkoxycarbonyl or ITitrilgruppe and R is hydrogen or a U-substituted sulfonamide. As a result of the reactions, the pyrazole-4-azobrene bonds of the formula Y are obtained.

N = N-K

and Έ?

in which R, R and R " ^{1 have} the abovementioned meaning and K stands for the coupling components (II substituted anilines, III 2-aminothiophenes, IVβ-naphthols) expressed by the formulas II, III and IV. The result is yellow to red azo disperse dyes having good to very good light fastness, the 4-i-pyrazoles required as starting materials are obtainable according to Mh * Chenu 108 (1977), 611. Lightfastnesses:

Polyester 7>

Embodiment 2

3 4

6:

Polyester 7> Polyester 7, Polyester'6,

Polyamide 7 Polyamide 4 Polyamide 3 Polyamide 7 Polyamide 6

For comparison, two azo dyes based on 4-aminopyrazole oils prepared according to the literature (Liebigs Ann. Chem. 293-56 (1887)):

- 2,3-Dimethyl-1-phenyl-4-azo-5 »- (2 ^! -Acetylamino-4'-phenylthiophene-3-carboxylic acid ethyl ester) -pyrazol-5-one: Lightfastness: Polyester 2

- 2,3-Dimethyl-1-phenyl-4-azo-1 ^f - (naphthyl-2 '-ol) -pyrazol-5-one Light fastness: Polyester 2

Embodiments Example 1

^T - (U, II-

diiaethylanilin)

10 mmol of 4- Amln n ~ 3 ~ r.ya: n ~ 1-phi = iriy1-pyraTini-R-ethyl ester are in 50 - 60 al conc. Dissolved hydrochloric acid, liachdem the solution was cooled to 5 ⁰ C, 12 mmol of sodium nitrate dissolved in 20 ml of water is added with stirring. After 5 min. The Üiazoniumsalzlösung is filtered and into a solution of 10 nnnol ΙΤ, Ν-dimethylaniline in 30 ml of ethanol, to which 2.5 g of sodium acetate are added. »ITach 2 hours, is filtered off from a small precipitate and the filtrate with vigorous stirring with 150 - 200 21I water added and the precipitated dye aspirated. Y. 59%, Schnip. 165-170 ⁰ C (ethanol).

Example 2

3-cyano-ethosycarbonyl-1-phenyl-pyrazole - ^ - azo-1 · '- (IT-cyano-1-yl-T-ethylaniline)

10 mmol of 4-imino-3-cyano-1-phenyl-pyrazo-5-carboxylic acid ethyl ester, as described for Example 1, diazotized and 10 mmol H-Cyanethy1-U-ethylaniline, dissolved with the addition of 2.5 g of sodium acetate in 30 ml of ethanol, coupled. In the event of any precipitation of the precipitate, the mixture is filtered off after 2 hours and 200 ml of water are added dropwise with vigorous stirring. The greasy precipitate is decanted off and the residue is dissolved in 25 ml of ethanol. 50-60 ml of ether are slowly added to this solution while vigorously rubbing in and the precipitate is filtered off with suction

from. Y. 4-8 % _} Schrop. 24-8 - 252 ⁰ G (ethanol), Example 3

acetylamino - 4 · ^f -phenyl-thiophene-3'-carboxylic acid ethyl ester)

As indicated for Example 1, 10 nnaol 4-amino-3-cyano-i-pheriyl-pyrazole ^ -carboxylic be diazotized. It sets the Biasoniumsalzlösting about 0.5 g of urea to j and coupling 10 nunol 2-Amino-4- ~ phenyl-thiophene-3-carboxylic acid ethyl ester, which was dissolved in 100 al ethanol. Uach 1 h .. ¹ slowly 200 ml of water are added ,, and the precipitate filtered off and getroclmet (Sehmp, 220-222 ⁰ G (acetonitrile)) .- The mixture is heated in 15 ml of this Sssigsäureanhydrid 10 min at the boil, iiach is cooling. rubbed and sucked off. Y. 4-5%, Sciuap. 191-193 ⁰ G (ethanol).

Beispiel'Λ

3-cyano-5-ethoxy-arbonyl-1-phenyl-pyrazole-4-azo-4'- (IT-benzyl-H-methyl-aniline)

Is diazotized, as indicated for Example 1, 10 nrniol ^ -AEdjao-S-cyan-i-phenyl-pyrazole ^ -carbonsaureethylester and coupled to 10 nnaol IT-benzyl-IT-aethylaniline, which under Susatz of 2.5 g of sodium acetate are dissolved in 20 ml of ethanol, liach 2 hrs. Is diluted with 200 al water and the aqueous phase separated from the oily. The resulting oil is heated with 15-20% ethanol and the precipitated after cooling precipitate. Y. 4-8 %, mp 133-136 ⁰ G (ethanol).

7 Example 5

3-Cyano-5-e-thosycarbonylo-1-phenyl-pyrazole-4-azo-4 '- (IT-cyanoethyl-H-acylgxyethyl aniline)

Sine after. Example 1 prepared diazonium salt solution of 10 mmol ^ -Aiäino ^ -cyan-i-phenyl-pyrazole ^ -caxbonsäure etiiylester is in a mixture of 10 mmol! T-cyanoethyl-H-hydrosqrethyl aniline ,. 30 ml of ethanol and 2.5 g of sodium acetate stirred. Each 2 hrs diluted with 200 ml of water and the precipitated greasy Produlct separates .. This is heated with 10 ml of acetic anhydride for 10 min. Sum boiling. To Srkalten add 30 ml of ethanol and after 30 min »with vigorous rubbing with 100 ml of water. It is filtered off with suction and washed with water. 59%> mp. 120 - 125 ⁰ C (methanol).

Example 6

3, 5-bis-eth.O2ycarbonyl-1-plienyl-pyraaol - 4 - azo - 5 '- (2 ^r acetylaiai "no - ^' - phenyl - thiophen-3 '-carboxylic acid ethyl ester)

As indicated for Example 1, 10 nanol of 4-amino-1'-phenyl-pyrazole-3-bis-5-carboxylic acid ethyl ester are diazotised. The excess uritol is destroyed with urea and the diazonium salt solution is dissolved in a solution of 10 zamol After stirring for 1 hour, the mixture is diluted with 150 ml of water and the precipitated viscous mass is separated off. This is heated to boiling with 20 ml of acetic anhydride for 5-7 min. Subject the cooling is triturated with a mixture of 60 ml of water and 20 ml of ethanol, the reaction product and the precipitate is filtered off with suction. Y. 67%, mp. 159 - 163 ⁰ C (methanol).

3 Example 7

-5 ^f -

(2'-acetylamino - ^ - ^! -Phenyl-thiophene-3'-carboxylic acid ethyl ester)

10 mmol ^ Aaino-S-carbamido-i-phenyl-pyrazole ^ -carboxylic acid ethyl ester, as described for Example 1, diazotized. The excess liitrit is destroyed with urea. Coupling is 10 millimoles of 2-amino-4 ~ phenyl-j thiophene-3-carboxylic acid ethyl ester, which was dissolved in 100 ml of ethanol, and adds * 100 ml of water is added after 1 hour. The precipitated viscous mass is separated and heated to boiling with 10 ml of acetic anhydride for 10 min. After cooling, 50 liters of water are added and after prolonged standing, san separates the plastic reaction product. This is triturated with ether, filtered off with suction and washed with ether. Out*). 56 %, mp 225-230 ⁰ G (ethanol).

Example 8

5-benz oyl-3 -e thozyc arb onyl-1-phenyl-pyraz ol-4 ~ az 0-5 '(2'-acetylariino-4- ^{T -phenyl-thiophen-3?} -Carboxylic acid ethyl ester)

10 nanol of 4-AmJJio-5-benzoyl-1-phenyl-pyrazole-3-carboxylic acid ethyl ester is diazotized as indicated for Example 1, the excess nitrite is destroyed with urea and coupled. to 10 mmol 2-lIaino-4-phenyl-thiophene-3-carboxylic acid ethyl ester, dissolved in 100 ml of ethanol. Tray 1 hr. Are added to the reaction mixture 200 ial water. The separated precipitate is heated to boiling point in 15 si of acetic anhydride for 10 min. After cooling, 50 - 60 ml of water are added and after prolonged standing and vigorous rubbing the precipitate is sucked off. Y. 85%, mp 224 -. 228 ⁰ C (acetonitrile). ·

Example 9

cyane methyl-M-ethyl aniline)

A Diazaniuiasalzlösung prepared from 10 mmol ^ - carboxylic acid ethyl ester, which, as described in Example 1, was prepared, is stirred into a mixture of 10 mmol IT-cyanoethyl-iT-ethylaniline, 30 al ethanol and 3 g ITatriunacetat. Tray 2 hours is diluted with 250 ml of water while vigorously rubbing and, after standing, the dye is removed by suction. Y. 78%, Sch & p. 66-74- ⁰ C (high product).

Example 10

benzyl-IT-never-methyl-aniline)

10 ml of 4-ariiino-5-benzoyl-1-phenyl-pyrazole-3-carboxylic acid ethyl ester, as indicated for Example 1, diazotized and 10 nuaol U-benzyl-lT-methylaniline, with the addition of 4 g of sodium in 40 ml of ethanol, are dissolved, coupled · With vigorous rubbing 2 ml 250 ml of water are added and the precipitate is filtered off with suction. Y. 83%, mp 58-62 ⁰ G (crude product).

Example 11

5-Bey £ oyl-3-etho: £ fevt-Butyloxycarbonyl 1-phenyl-pyrazol-4-azo-1 '- (naphth-2'-ol)

10 amol-f-amino-benzoyl-i-phenyl-pyrazole ethylcarboxylate diazotized aane as indicated for Example 1, coupling with 10 mmole of β-ilaphthol under ice-cooling.

which were dissolved in 100 ml of 20% sodium hydroxide solution. Bach 30 min. Diluted with 100 ml of water and acidified with dil. Hydrochloric acid. The precipitate is filtered off with suction and washed with water. Y. 87 %, Sehm. 175 - 177 ⁰ O (ethanol).

Example 12

5 ~ benzoyl-3-carbamoyl-1-phenyl-pyrasol-4-azo-i '- (naphth-2-ol *)

10 amol ^ -

are as described for Example 1, diazotized and as indicated for Example 11, coupled to 10 nniol ß-naphthol and worked up, Ausb. 52 % _t Sciun.pl 278-281 ⁰ C (tetrahydrofuran).

Example 13

3,5-bis-ethoxy ^ "carbonyl-1-phenyl-pyrazole-4-azo-i" - (naphth-2- ^J- ol)

According to Example 1, 10 rnsol 4-amino-1-phenyl-pyrasol-3j5 ~ qis-carboxylic acid ethyl ester are diazotized and, as indicated for Example 11, coupled to 10 ranol ß-naphthol. Y. 42 %, mp 146-147 ⁰ G (dimethylformamide).

Example 14

3 ^ -bis-ethosycarbonyl-i-phenyl-pyrazole - ^ - azo-S ^! - (2'-acetylamino-4 ^T -phenyl-thiophen-3 -carbonitrile ^f)

10 Imaol 4-amino-1-phenyl-pyrazole-3,5-bis-carboxylic acid ethyl ester, as indicated for Example 1, diazotized. The excess nitrite is destroyed with urea and the diazonium salt solution is coupled to 10 μmol of 2-amino-4-phenylthiophene-3-carbonitrile dissolved in 100 μl of ethanol. To

1 hr. Diluted with 200 ml of water and separates the plastic dye. This is dissolved in 15 ml of acetic anhydride for 5 min, for. Boil boiling. On cooling, add 50 ml of water, allow to stand overnight and separate the seeping precipitate. This is dissolved in 30 ml of ethanol with heating. By dropwise addition of a little water and rubbing the dye is precipitated. A.usb. 59% »Schnip. 153-156 ⁰ C (ethanol).

Example 15

3, 5-dic7an-1- (p-tol7l) -p7ra2ol-4-azo-4 '- (! JyN-dimettiylaniline)

5 mmol of 4-amino-1- (p-tol7l) -p7razole-3,5-icar'bonitril are dissolved in a mixture of 35 ml of glacial acetic acid and 5 ml of conc. Sulfuric acid dissolved. This solution is added dropwise at 10 C under ^G stretchers to 2.5 ml Hitrosylschwefelsäure (from 5i5iehüo1 sodium nitrate prepares). After 1-2 hours, the mixture is stirred at 10 ⁰ G in a solution of 5 mmol N, JST-dimethylaniline in 5 ml of glacial acetic acid, added 1.0 g of sodium acetate and after 20 min. With 10% sodium hydroxide while cooling to pH 3 - 4 · one. After 2 hours, it is diluted with water and filtered with suction. Y. 57 % · The melting point is 108-115 ⁰ Cj cLa as an admixture of 3-carbamo7l-5-C7an-1- (p-tol7l) -p7razol-4-azo-4- '- (N, l ^: T-dimethsilaniline) contained in the partially hydrolysed starting material.

Example 16

3, 5-dic7an-1 - (p-tolyl) -p7 -rasol-4-azo-4 '- (IT-cyanoethyl-IT-ethyl-aniline)

5 mmol of 4-amino-1- (p-tol7l) -p7razol-3,5- ^< -a-carbonitrile, as indicated in Example 15, diazotized and coupled to 5 mmol ITrOyanethyl-IT-ethyl-aniline, Ausb. 63 %, Schinp. 98-104 ⁰ G. The admixture is 3-carbamo7l-5-C7an-1- (p-tol7l) -

pyrazole-4-azo-4 '- (IT-cyanethj ^ l-F-ethyl-aniline), which arises from partially hydrolyzed Aussangsprodukt.

Example 17

3, ^5-I> icyan-1-CSS-naphthyl) pyrazole - 4 - A3o - 4- ^I - (lT, H "- diethylaniline)

5 mmol of 4-AnLiJiO-1- (β-naphthyl) -pyrazole-3,5-bicarbonitrile are diazotized as described in Example 15 and coupled to 5Nanol U, IT-dimethylaniline, yielding 79% of melt 163 192 ⁰ C, As admixture 3-carbamoyl is ~ 5-cyan-1 - (B-naphthyl) -4-azo-4 '- (ίΓ, ΙΤ-dimethylaziilin) formed from partially hydrolyzed starting material.

Example 18

3,5-Bicyan-1 - (ß ~ naphthyl) pyr az ol-4 -az ^T 0- (ET-cyane thyl-IT-ethyl aniline)

5 mmol. 4-Amino-1- (β-naphthyl) -pyrasol-3,5-dicarbonitrile are diazotized and reacted as indicated in Example 15. ϊί-cyanoethyl-iT etiiylaniline coupled. Y. 70%, melting range 140-158 ⁰ G. The admixture is 3-carbamoyl-5-cyano-1 - (ß-naphthyl) -4-azo-4 ^! - (IT-cyanoethyl-lT-ethyl-aniline) consisting of partially hydrolyzed Ausgangsp. is formed.

Claims (3)

1. A process for the preparation of azo dyes from substituted 4-amino-1-aryl-pyrazoles, characterized in that 4-aminopyrazoles of the formula I, where H is an unsubstituted or substituted Anyl radical, R is a nitrile of nitrile, alkoxycarbonyl or carb amido group and S- ^{5 represents} a mtril, alkoxycarbonyl or benzoyl group, diazotized under customary conditions and the diazonium salts obtained in solution with the compounds of the formulas II, III, IV, ^ = ⁷ VS NH ₂ 4 · where R is a methyl, ethyl or hydroxyethyl group, Έ? a methyl, cyanoethyl or benzyl group, R an aryl radical, R 'an alkoxycarbonyl or ITitrilgruppe and R a; A hydrogen atom or a U-substituted; .. sulfonamido group means to be reacted (coupled), whereby Azofarbstoffe of the general formula V R ² N = NK R ¹ 12 3 arise in which R, E and Ir have the abovementioned meaning and K stands for the reproduced with the formulas II, III, 17 coupling components. 2. The method according to item 1, characterized in that products of the general Forme1 Y, which are formed with 2-aminothiophenes of the formula III, are then converted with acetic anhydride in the JT-acetyl derivatives. 3. The method according to item 1, characterized in that products of the general formula V, which are formed with E-ethyl-H-hydrozyethyl-aniline of formula II, then with sacetic anhydride in the Q-acetyl derivatives are transferred.