CH631197A5 - Dispersion dyes of the monoazo series - Google Patents

Description

The invention relates to monoazo disperse dyes which are suitable for dyeing synthetic textile materials.

According to the invention, monoazo dispersion dyes are proposed which are free from sulfonic acid groups and have the formula:

X

35

OHC *

N = N-

45

50

55

60

corresponds where W is hydrogen, lower alkyl or lower alkoxy, V is hydrogen, lower alkyl, lower alkoxy, chlorine, bromine or acylamino, Z3 is hydrogen or optionally substituted alkyl and Z4 is hydrogen, optionally substituted alkyl or aryl or cycloalkyl stands.

8. Dyes according to claim 7, characterized in that the acylamino group represented by V has that in which

X represents nitro, cyano, optionally substituted phenyl, -COOR, -CONHR1, -COR1 or S02R2,

Y represents hydrogen, optionally substituted alkyl or phenyl,

R represents hydrogen or optionally substituted alkyl, cycloalkyl or phenyl,

R1 represents hydrogen or optionally substituted alkyl or phenyl,

R2 represents optionally substituted alkyl or phenyl or optionally substituted amino and

E stands for the rest of a coupling component.

Throughout the description, the terms “lower alkyl” and “lower alkoxy” refer to alkyl and alkoxy radicals, each having 1 to 4 carbon atoms.

Examples of substituted phenyl radicals R, R1, R2, X and

Y are lower alkylphenyl radicals such as tolyl and xylyl, lower alkoxyphenyl radicals such as anisyl, halogenophenyl radicals such as chlorophenyl and bromophenyl, lower alkoxycarbonylphenyl radicals such as methoxycarbonylphenyl and ethoxycarbonylphenyl, and nitrophenyl radicals. It is preferred that when R, R1, R2, X and Y are phenyl radicals, they are unsubstituted phenyl radicals.

Examples of optionally substituted alkyl radicals R, R1, R2 and

Y are alkyl radicals with 1 to 18 carbon atoms, which can be substituted, for example, by halogeno, cyano, hydroxy, carboxyl or lower alkoxy. However, it is preferred that the alkyl radicals R, R1, R2 and Y are optionally substituted lower alkyl radicals. Examples of such unsubstituted radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-

3rd

631197

Butyl and isobutyl. Examples of substituted lower alkyl radicals R and R1 are hydroxy-lower alkyl radicals, such as β-hydroxyethyl, α-methyl-β-hydroxyethyl, β- or γ-methoxyethyl, β-ethoxyethyl and α-methoxypropyl, lower alkoxycarbonyl-lower alkyl radicals, such as β -Athoxycarbonyl ether, carboxy-lower alkyl radicals, such as ß-carboxymethyl, cyano-deralkyl radicals, such as ß-cyanoethyl, halogeno-lower alkyl radicals, such as ß-chloro- and ß-bromoethyl, and phenyl-lower alkyl-radicals, such as benzyl and ß-phenylethyl. Unsubstituted lower alkyl radicals are particularly preferred. Examples of cycloalkyl radicals R are cyclopentyl and cyclohexyl.

Specific examples of the radicals -COR1 and -S02R2 represented by X are acetyl, propionyl, benzoyl, methylsulfonyl, ethylsulfonyl, phenylsulfonyl and p-tolylsulfonyl. Examples of the -CONHR1 radicals represented by X are carbamoyl, N-methylcarbamoyl, N-ethyl-carbamoyl and N-phenylcarbamoyl, and examples of the -COOR radicals represented by X are carboxy, methoxycarbonyl, ethoxycarbonyl , n-Butoxycarbonyl, ß-Hydroxyäthoxycarbonyl, ß-Methoxyäthoxycarbonyl, ß- (ß'-Methoxyäthoxy) äthoxycarbonyl, phenoxycarbonyl and cyclohexyloxycarbonyl. However, it is preferred that X represents nitro, cyano or lower alkoxycarbonyl.

The rest of coupling component E may be the rest of any of a number of coupling components that couple with diazo compounds, such as e.g. the remainder of a coupling component of the acylacetarylamide, pyrazolone, aminopyrazole, phenol, naphthol, 2,6-diaminopyridine or 2,6-dihydroxypyridine series. In particular, E is the residue of a coupling component of the aromatic series which couple due to the presence of an optionally substituted amino group, e.g. the rest of a coupling component of the l-naphthylamine series, and especially the rest of a coupling component of the aniline series, which couples in the p-position to an optionally substituted amino group.

The rest of the coupling component E preferably has the formula:

in particular lower alkyl, or optionally substituted aryl or cycloalkyl.

Examples of optionally substituted lower alkyl radicals Z3 and Z4 are hydroxy-lower alkyl radicals, such as β-hydroxyethyl, 5-methyl-β-hydroxyethyl, β- or γ-hydroxypropyl and ô-hydroxybutyl, lower alkoxy-lower alkyl radicals, such as β- (methoxy- or ethoxy) ethyl and y-methoxypropyl, cyano-lower alkyl radicals, such as ß-cyanoethyl, phenyl-lower alkyl radicals, such as benzyl and ß-phenylethyl, acyloxy-lower alkylra-io radicals, such as ß-acetoxyethyl and l-acetoxy-2-propyl, carboxy-lower alkyl radicals, such as ß-carboxyethyl -Carboxybutyl, lower alkoxycarbonyl-lower alkyl radicals, such as ß-meth-oxycarbonylethyl, hydroxy-lower alkoxy-lower alkyl radicals, such as ß- (ß'-hydroxy-ethoxy) ethyl, lower alkoxy-lower alkoxy-15 lower alkyl radicals, such as (ß- (ß'-methoxy-ethoxy) lower alkyl, lower carbon such as ß- (ß'-methoxyethoxycarbonyl) ethyl, acyloxy-lower alkyl radicals, in particular lower alkylcarbonyloxy-lower alkyl radicals, such as ß-acetoxyethyl and ò-acetoxybutyl, chloroniederal-20 alkyl radicals, such as y- Chloropropyl, and lower alkoxycarbonyloxy lower alkyl radicals, such as β-ethoxycarbonyloxyethyl.

According to the invention, a process for the preparation of the azo dyes defined above is also proposed, which is carried out by using an amine of the formula:

30th

ohc

_nh "

35

wherein Z1 and Z2 each independently represent hydrogen or an optionally substituted hydrocarbon radical, in particular an optionally substituted lower alkyl radical, and the benzene ring B may contain additional substituents or form part of an optionally further substituted naphthalene or quinoline ring.

E represents in particular a radical of the formula:

45

50

is where W is hydrogen, lower alkyl or lower alkoxy, V is hydrogen, lower alkyl, lower alkoxy, chlorine, bromine or acylamino, especially an acylamino group of the formula -NHCOT2 or -NHS02T3 (where T2 = hydrogen, alkyl, especially lower alkyl, aryl, amino or aminoalkyl, T3 = optionally substituted lower alkyl or aryl), Z3 stands for hydrogen or optionally substituted alkyl, in particular lower alkyl, and Z4 stands for hydrogen or optionally substituted alkyl,

diazotized and the resulting diazo compound couples with a coupling component of the formula E-H, where E, X and Y have the meanings given above and the amine and the coupling component are free from sulfonic acid groups.

The process according to the invention can expediently be carried out by adding sodium nitrite to a solution or dispersion of the amine in a strong inorganic acid or in an aqueous solution thereof or by stirring the amine with nitrosylsulfuric acid, whereupon the resulting solution or dispersion of the diazo component is added to a Add solution of the coupling component in water or in a mixture of water and a water-miscible organic liquid, adjust the pH of the mixture to facilitate the coupling reaction if necessary and finally isolate the resulting dye by conventional methods.

These amines can themselves be obtained by conventional methods, for example by Vilsmeier formation of 2-acetylaminothiophene and subsequent nitration (the nitro group enters the 3-position) and hydrolysis, where 2-amino-3-nitrothiophene-5 aldehyde is obtained. In some cases, the Vilsmeier reaction conditions can be used to make other desired modifications to the 2-aminothiophene-5-aldehyde structure. For example, if 2-acetylamino-3-aminocarbonylthiophene is heated with phosphorus oxychloride in dimethylformamide, then the 5-aldehyde group is introduced, but in addition the aminocarbonyl group is also dehydrated to form the cyano group and the acetylamino group is converted to the easily hydrolyzable dimethylformamidino group.

The amines mentioned can also be obtained from the corresponding 65 5-methyl, 5-chloromethyl or 5-hydroxymethyl compounds by oxidation, the amino group being protected beforehand if necessary.

Specific examples of these amines are 2-amino-3-nitro

631197

4-methylthiophene-5-aldehyde, 2-amino-3- (methoxycarbonyl-, -ethoxycarbonyl-, -acetyl-, -benzoyl-, -methylsulfonyl- or -N-methylcarbamoyl) thiophene-5-aldehyde and preferably 2-amino- 3-nitrothiophene-5-aldehyde or 2-amino-3-cyano-thiophene-5-aldehyde.

Examples of these coupling components are acylacet-arylamides, such as acetoacetanilide and acetoacet-2,5-dimethoxy-anilide; Aminopyrazoles such as l-phenyl-3-methyl-5-aminopyrazole; Pyrazolones, such as 1,3-dimethyl-5-pyrazolone and in particular l-phenyl-3- (methyl-, -carbonamido- or -carbometh-oxy) -5-pyrazolones, in which the phenyl radical may be, for example, methyl, methoxy, ethoxy , Chlorine, bromine, nitro, sulfonamido or acetylamino is substituted; 2,6-dihydroxypyridines such as 3-cyano-4-methyl-2,6-dihydroxypyridine and l-ethyl-3-cyano-4-methyl-6-hydroxypyrid-2-one; 2,6-diamino-pyridines such as 3-cyano-4-methyl-2,6-di (N-2-methoxyethylamino) pyridine; Phenols such as o-cresol, resorcinol and 3-acetylaminophenol; Naphthols, such as β-naphthol; and in particular arylamines of the naphthylamine series, such as 1-naphthylamine, and very particularly of the aniline series, such as 2,5-dimethoxyaniline, N, N-diethylaniline, N, N-di (β-hydroxyethyl) -m-toluidine, N, N-di ( ß-cyanoethyl) aniline, N-ethyl-N- (ß-ethoxyethyl) aniline, N, N-di (ß-carbomethoxyethyl) -m-toluidine, 2-methoxy-5-methyl-N- (ß-acetoxy -a-methylethyl) -aniline, N- [ß- (ß'-meth-oxyethoxycarbonil) ethyl] aniline, N, N-di- (ß-acetoxyethyl) -m-toluidine, N-ethyl-N- (ß- cyanoethyl) aniline, N-ethyl-N- (ö-acet-oxybutyl) aniline, N-ethyl-N-benzyl-m-toluidine and N, N-di-ethyl-m-acetamidoaniline.

The azo dyes according to the invention are suitable for dyeing synthetic textile materials, in particular those made from secondary cellulose acetate and cellulose triacetate, polyamide, such as polyhexamethylene adipamide, and especially aromatic polyesters, such as polyethylene terephthalate. Such materials are in the form of threads, fibers or woven or knitted materials.

The azo dyes mentioned can be applied to synthetic textile materials by methods which are usually used to apply disperse dyes to such textile materials. Thus, the dyes can be applied in the form of aqueous dispersions by padding, dyeing or printing processes, using the conditions and other additives which are customary in carrying out such processes. Alternatively, the dyes can be applied to synthetic textile materials by solvent dyeing processes, for example by applying a solution or dispersion of the dye in perchloroethylene, which may contain a small amount of water, to the textile material, preferably at an elevated temperature.

If the azo dyes according to the invention are applied to synthetic textile materials, they result in dyeings whose color ranges from yellow to green and which have excellent fastness to light and wet and dry treatments. The dye obtained remains by the dye bath conditions, e.g. pH, largely unaffected. The dyes mentioned also have excellent structural properties on synthetic textile materials, in particular those made from aromatic polyesters, so that deep colors can be easily obtained. In this regard, these dyes are corresponding known dyes that have an acetyl group (instead of the aldehyde group) in the

5-position of the thiophene nucleus included, superior. Alternatively, the dyes can be used for the coloring of synthetic polymers in bulk, which are then to be converted into fibers or threads. The dyes can also be applied to synthetic textile materials by a transfer printing process, which is optionally carried out under reduced pressure or under wet or moist conditions.

The invention is illustrated by the following examples, in which the parts and percentages are expressed in weight.

5 Example 1

1.72 parts of 2-amino-3-nitrothiophene-5-aldehyde become a solution of nitrosylsulfuric acid (which is obtained by dissolving 0.75 part of sodium nitrite in 24.5 parts of sulfuric acid at 70 ° C., cooling and diluting with 30 parts of acetic acid and 5 parts of propionic acid has been obtained), the temperature being kept at -5 to 0 ° C. by external cooling. The temperature of the mixture is raised to 0 ° C and stirring is continued for 45 min. The resulting solution of the diazo compound is then mixed with 15 3.5 parts of N, N-di (β-acetoxyethyl) -m-toluidine, 1 part of sulfamic acid, 20 parts of a 1% aqueous sulfuric acid and 500 parts of ice / Water is added and the pH of the mixture is then raised to 4 by the addition of sodium acetate. The mixture is stirred for a further hour and the precipitated dye is filtered off, washed with water and dried.

If the dye is dispersed in an aqueous medium, it dyes textile materials made from aromatic polyesters in bluish violet shades.

25 The 2-amino-3-nitrothio-phen-5-aldehyde used in the example above was itself obtained as follows:

180 parts of a nitration mixture obtained by mixing 66.3 parts of nitric acid (sG 1.50), 120 parts of 20% oleum and 713 parts of sulfuric acid, 30 slowly became a solution of 33.8 parts of 2-acetylamino Thiophene-5-aldehyde (prepared according to the instructions of the Journal of American Chemical Society, 1953, Vol. 75, p. 989) was added in 310 parts of sulfuric acid, the temperature of the mixture being kept between -10 and -5 ° C Was 35. The mixture was then stirred for a further 5 minutes and poured into an ice / water mixture containing 5 parts of sulfamic acid. The precipitated 2-acetylamino-3-nitrothiophene-5-aldehyde was then filtered off, washed with water and dried. The N-acetyl group was then removed 40 by stirring the solid in a 4% aqueous solution of sodium hydroxide at 40-50 ° C and filtering off the resulting 2-amino-3-nitrothiophene-5-aldehyde.

45 Examples 2 and 3

The following table relates to further dyes according to the invention, which are obtained by adding the 3.5 parts of N, N-di (β-acetoxyethyI) -m-toluidine from Example 1 by equivalent amounts of the -50 in the second column of the following table guided coupling components are replaced. The hues obtained with these dyes are given in the third column of the table.

55

60

Example coupling component

hue

3-acetylamino-N, N-diethyl greenish blue aniline

3-methyl-N, N-diethylaniline blue

Example 4

2-Acetylamino-3-aminocarbonylthiophene, mp 220-222 ° C., was prepared by 2-amino-3-aminocarbonylthiophene (prepared according to Bull. Soc. Chim. France, 1974, p.

65 2869) was treated with acetic anhydride. 36.8 parts of the acetylamino compound was added to 280 parts of dimethylformamide and 55.6 parts of phosphorus oxychloride were added dropwise to the mixture. The temperature was

5

631197

kept below 60 ° C by external cooling. The mixture to a previously prepared mixture of 14 parts dimen-

The mixture was then stirred at 60 ° C. for 75 min, cooled and poured into ethylformamide and 5.5 parts of phosphorus oxychloride at about an ice / water mixture. 10 ° C added. There was a slow exothermic reaction

2- (N, N-DimethyIformamidino) -3-cyano-5-formylthiophene instead, so that the temperature rose to approximately 35 ° C. After 2

slowly crystallized from the aqueous mixture and the mixture was poured into ice and water for 5 hours. Yellow kri

de collected and from a 20: 10: 1 propanol / methyl cello stall of 2- (N, N-dimethylformamidino) -3-cyano-4-methyl-5-

solve / water mixture recrystallized, whereby orange needles, formylthiophene slowly precipitated out and were filtered off. These

Mp 192-193 ° C, were obtained. Compound was obtained by the procedure described in Example 4

20 parts of this compound were hydrolyzed with 100 parts of methylrene, giving 2-amino-3-cyano-4-methyl-5-formyl-cellosolve and 100 parts of cold 2N sodium hydroxide solution 1 (> thiophene. The latter compound was diazo-mixed and the mixture was heated for 5 min at 60 ° C. The solution obtained with N, N-diethyl-m-aminoacetanilide after the previous solution was filtered and coupled with 120 parts of 2N hydrochloric acid from Example 4, the precipitated 2-amino-3-cyano-5-formyl-, the textile material made from aromatic polyesters in thiophene was filtered off. The IR spectrum of the compound turned bright blue-violet shades when Nujol muH) had peaks at 3390.3295.3150.2210.1695 15 conventional exhaustion staining procedures, and 1650.

15.2 parts of 2-amino-3-cyano-5-formylthiophene were used in Examples 6 to 18

a temperature below 0 ° C to a mixture of 220 The following table relates to other inventive

Parts of acetic acid, 40 parts of propionic acid and 160 parts of a dye, the column headings X, Y, V, W, Z1 and

Solution of nitrosylsulphuric acid in sulfuric acid (the 13 parts 20 Z2 refer to the following formula. In the last column le nitrosylsulphuric acid contained) added. According to one and a half of the table, the shades that are obtained are given

hour stirring at 0 ° C., the above mixture was applied when an aqueous dispersion of the respective dye was applied to a mixture of 2000 parts of ice and water, 100 parts of 2 textile material made of an aromatic polyester n-sulfuric acid, 20.6 parts of N, N- Diethyl-m-aminoacetanilide is.

and 50 parts of 1 M sulfamic acid. The pH was adjusted to 3-4 by the addition of sodium acetate, and the precipitated dye was filtered off after the mixture had been stirred for 30 minutes.

When the dye was applied from an aqueous dispersion to a textile material made from an aromatic polyester, reddish-blue shades with good fastness properties were obtained.

Example 5

3.6 parts of 2-acetylamino-3-cyano-4-methylthiophene were 35

30th

Example x

y v

w z1

z2

hue

6

no2

h ch3

h c2h4cooch3

c2h4cooch3

blue

7

do.

do.

do.

och3

do.

do.

do.

8th

do.

do.

do.

do.

c2h4cooc2h4och3

h do.

9

do.

do.

NHCOCH3

h h

h do.

10th

do.

do.

do.

och3

c, h4cooch3

c2h4cooch3

greenish blue

11

do.

do.

do.

h c2h4cn

C2H5

do.

12

cn do.

ch3

h c2h4cooch3

q, h4cc> och3

violet

13

do.

do.

nhcoch3

och3

c2h5

c2h5

blue

14

do.

do.

h h

c2h5

c6h5ch2

violet

15

do.

do.

NHCOCH3

h c2h5

ch2ch (ch3) 2

blue

16

do.

ch3

ch3

h c2h4cooc2h5

c2h4cooc2h5

violet

17th

cooqhj h

do.

h c2h4cooch3

c2h4cooch3

bluish red

18th

do.

do.

h h

c2h4cn c2h5

red

19th

cn h

ch3

h c2h5

c2h4cooch3

violet

20th

do.

c6h5

ch3

h qhs c2h4oh do.

21st

do.

m-ClC6H4

H

H

C2H5

c2h4nhcoch3

do.

22

do.

H

och3

H

C2Hs c2h5

blue

23

do.

H

NHCOCHj

H

H

ch2ch (ch3) 2

do.

631197

Example x

y v

w z1

z2

hue

24th

no2

H

NHCOCH3

h h

ch2ch (ch3) 2

greenish blue

25th

o-N02C6H4

h ch3

H

QH4OCOCH3

c2h4ococh3

red

26

coch3

H

ch3

H

do.

do.

violet

27th

conh2

h ch3

H

qhs n-C4H9

do.

28

so2ch3

H

NHCOCH3

H

c2h5

do.

do.

29

so2c6h5

H

ch3

H

c2h4cooch3

c2h4cooch3

red

30th

so2n (ch3) 2

H

H

ch3

h ch (ch3) ch2cooch3

do.

31

cn

H

NHCOCH3

OCH3

H

QH4CO O C2H40 CH3

greenish-

blue

Examples 32 38 th column of the coupling component given in the table

The following table relates to further examples according to the invention. The hue of the corresponding dyes obtained when the diazonium-containing dyestuff is obtained from an aqueous dispersion on a tex compound, which is obtained by diazotizing the tilmaterial from an aromatic polyester in the second column, fin table specified amine is obtained with that in the third in the fourth column of the table.

example

Amine

Coupling component

hue

32 2-amino-3-nitro-5-formylthiophene

N-phenylmorpholine purple

33

do.

1-phenyl-3-methyl-5-pyrazolone red

34 2-Amino-3-cyano-4-methyl-5-formylthiophene

Resorcin do.

35

do.

1-ethyl-3-cyano-4-me-

thyl-6-hydroxypyride

2-on do.

36

do.

N- (ß-hydroxyethyl) -l-naphthylamine blue

37 2-Amino-3-cyano-5- ß-naphthol formylthiophene red

38

do.

Acetoacetanilide orange

C.

Claims (9)

631197 PATENT CLAIMS 1. Monoazo series disperse dyes that are free from sulfonic acid groups and of the formula (I) OHC " N = N- correspond where X is nitro, cyano, optionally substituted phenyl, -COOR, -CONHR1, -COR1 or S02R2, Y is hydrogen, optionally substituted alkyl or phenyl, R is hydrogen or optionally substituted alkyl, cycloalkyl or phenyl, R1 represents hydrogen or optionally substituted alkyl or phenyl, R2 represents optionally substituted alkyl or phenyl or optionally substituted amino and E represents the remainder of a coupling component. 2. Dyes according to claim 1, characterized in that the phenyl radicals represented by R, R1, R2, X and Y are unsubstituted phenyl radicals. 3. Dyes according to claim 1 or 2, characterized in that the substituted or unsubstituted alkyl radicals represented by R, R1, R2 and Y are substituted or unsubstituted lower alkyl radicals, preferably unsubstituted lower alkyl radicals. 4. Dyes according to one of claims 1 to 3, characterized in that X represents nitro, cyano or Niederalkoxycar-bonyl. 5. Dyes according to one of claims 1 to 4, characterized in that the rest of the coupling component, which is represented by E, of the formula: N in which Z1 and Z2, which are the same or different, stand for hydrogen or an optionally substituted hydrocarbon radical and the benzene ring B may contain additional substituents or may be part of an optionally further substituted naphthalene or quinoline ring. 6. Dyes according to claim 5, characterized in that the optionally substituted hydrocarbon radicals, which are represented by Z1 and Z2, are optionally substituted lower alkyl radicals. 7. Dyes according to one of claims 1 to 4, characterized in that the rest of the coupling component, which is represented by E, of the formula: Formula corresponds to -NHCOT2 or -NHS02T3, in which T2 represents hydrogen, alkyl, aryl, amino or alkylamino and T3 represents optionally substituted lower alkyl or aryl. 9. Dyes according to claim 8, characterized in that the alkyl radical represented by T2 and the optionally substituted alkyl radicals represented by Z3 and Z4 are lower alkyl radicals or optionally substituted lower alkyl radicals. 10. A process for the preparation of the disperse dyes of the io monoazo series according to claim 1, characterized in that an amine of the formula: OHC diazotized and the resulting diazo compound couples with a coupling component of the formula E-H, the amine and the coupling component being free from sulfonic acid groups. 25th