DE1619602B - Anthraquinone dyes and their use for coloring or printing synthetic fiber materials - Google Patents

Description

The invention relates to anthraquinone dyes in which one of the two Z _{2 is} a hydrogen atom and

the other Z _{2 is} a halogen atom or a group of the formula '. ; .. X ·: '

formula

O NH

C ₂ H ₄ -Y

C ₂ H ₄ -CN

O OH

and R 'has the meaning given in claim 2. .

From the Belgian patent 634 633 an (I) anthraquinone dye of the following structure is known

in which R stands for a hydrogen atom, a low molecular weight alkyl group, a low molecular weight alkoxy group, a phenyl radical, a cyclohexyl radical or a halogen atom; Y denotes a cyano group or a R [CO group in which R _{1 is} a hydroxyl group, a primary amino group, an optionally substituted low molecular weight alkylamino group, an optionally substituted low molecular weight alkoxy group, a cyclohexylamino group, a morpholinyl group or a cyclohexyloxy group, each of the two Z a Hydrogen atom or one Z is a hydrogen atom and the other Z is a halogen atom or a group of the formula

-ο- / S

C ₂ H ₄ -Y
R.

and Y represents a group other than the cyano group if both Z are hydrogen atoms.

The substituted low molecular weight alkylamino group and the substituted low molecular weight alkoxy group has 1 to 4 carbon atoms.

A preferred anyraquinone dye according to the invention has the formula

O NH

40

C ₂ H ₄ -CO R ₁ (II)

O OH

45

in which each of the two Z is a hydrogen atom or one Z _{1 is} a hydrogen atom and the other is Z, a halogen atom or a group of the formula

C ₂ H ₄ -COR ₁

means, R 'stands for a hydrogen atom, a low molecular weight alkyl group, a low molecular weight alkoxy group or a halogen atom and R _{1 has} the meaning given in claim 1.

Another preferred anthraquinone dye according to the invention has the formula

Z ₂ O NH ₂

-C ₂ H ₄ -CN (III)
R '

C ₁ H ₄ CN

OH

Other comparable dyes are known from the French patent specification 1352 732, namely the dyes C

NH,

35

COOCH.,

COOC ₄ H ₀

O OH

There are dyes in the staining tables laid out compared according to the invention with the said dyes. The dyes of the invention give each a reddish color with good fastness to light, washing and sublimation. You can see the improved Color strength in the. Dyes according to the invention and, above all, the high degree of extract and the color depth achieved. The superior own, Shafts of the dyes according to the invention result from these color tables.

The invention also relates to the use of such anthraquinone dyes for dyeing or printing of synthetic fiber materials, especially polyester, polyacrylonitrile, polyamide, cellulose ester and polymer fibers.

The 'anthraquinone dyes according to the formula can be produced by various processes:

1, The special anthraquinone dyes of the formula III can be obtained by reacting an anthraquinone compound the formula

ZO NH ₂

O OH

- X

(IV)

O OH

3 4

in which one of the two Z is a hydrogen atom, a halogen atom or a sulfonic acid group, with

while the other Z is a halogen atom and X is a β- (4-hydroxyphenyl) propionitrile of the formula

HO-

-C ₂ H ₄ CN

(V)

in the presence of an alkali salt become a weak one. If the reaction is conducted at 100 to 160 ° C by acid, such as carbonate, bicarbonate or acetate, in such the essential part of the obtained dry state has produced at 100 to 250 ⁰ C io dye has the formula

X 'O NH

C ₂ H ₄ CN

(VI)

O OH

in which X 'denotes a halogen atom. If the reaction is ^{carried out at 160 to 250 °} C., the dye obtained has the formula

O NH,

NCH ₄ C ₂

C ₂ H ₄ CN

(VII)

or a mixture of this dyestuff is formed with the anthraquinone dyestuffs of the formula III being the dyestuff of the above-mentioned formula VI. The implemented. A reaction temperature of 100 to conversion can result in an inert solvent, such as 160 ⁰ C, dyes which correspond to the starting anthra-chlorobenzene, or in an excess of the reactant quinone compounds and the formula
tion component of the phenol type are carried out, as shown in formula V. O NH ₂

2. The anthraquinone dyes of the formula II can be prepared by the following process.

a) An anthraquinone compound of the formula

O NH,

(VIII)

40

45

C ₂ H ₄ COR ₁ (X)

or

O OH

X 'O NH

OH

in which both Z is a hydrogen atom or one Z is 50 Hydrogen atom and the other Z is a halogen atom and X has the same meaning as in formula IV has, is with a phenolic compound of the formula IX

O — C VC ₂ H ₄ COR ₁ (X ')

O OH

HO

C ₂ H ₄ COR ₁

(IX)

under the same meanings as in the

55 have.

If an anthraquinone compound of the formula VIII, in which one of the two Z is a halogen atom, is used as the starting material for the reaction at 160 to 250 ^° C., a dye of the formula is used

NH,

R ₁ OCH ₄ C ₂

C ₂ H ₄ COR ₁

PCI)

O OH

or a mixture of this dye with a dye of the formula X '.

b) The anthraquinone dyes of the formula II can be obtained by reacting corresponding anthraquinone compounds the formula

NH

C ₂ H ₄ Y (XII)

IO

obtained, in which Y is a cyano, carboamoyl or carboxy group and both Z is a hydrogen atom or a Z is a hydrogen atom and the other Z is a halogen atom or a group of the formula

-O

C ₂ H ₄ Y

NH

C ₂ H ₄ COCl
R (XIII)

O OH

C ₂ H ₄ COCl

15th

20th

with a compound of the formula R OH, in which R is an optionally substituted low molecular weight alkyl group, in the presence of hydrogen halide, sulfuric acid, benzenesulfonic acid or naphthalenesulfonic acid at 50 to 200 ^° C.

c) The anthraquinone dyes of the formula II in which R ₁ is a hydroxyl or an amino group of the formula III can also be prepared by heating the dye with a mineral acid such as hydrochloric or sulfuric acid or an alkali metal hydroxide at 30 to 150 ⁰ C.

d) The anthraquinone dyes of the formula II, in which R _{1 is} an amino or a low molecular weight alkylamino group, can also be obtained by reacting corresponding anthraquinone compounds of the formula

35

40

45

in which both Z is a hydrogen atom or one Z is a hydrogen atom and the other Z is a halogen atom or a group of the formula

55

and the radical R has the same meaning as in formula I, with ammonia or primary or secondary alkylamines with heating in the presence of an organic base such as pyridine or dialkylaniline, getting produced.

The anthraquinone compounds to be used as starting material for the production of the new anthraquinone dyes of formula IV and VIII are, for. B.

l-amino ^ -halogen ^ -hydroxyanthraquinone,
l-amino-4-hydroxy-anthraquinone-2-sulfonic acid, l-amino-2,5-dihalo-4-hydroxyanthraquinone, l-amino-2,8-dihalo-4-hydroxyanthraquinone, l-amino-S-halogen ^ -hydroxyanthraquinone-

2-sulfonic acid and especially l-amino-2-bromo-4-hydroxyanthraquinone, l-amino-2-chloro-4-hydroxyanthraquinone, l-amino-4-hydroxyanthraquinone-2-sulfonic acid, l-amino-2,5-dichloro-4-hydroxyanthraquinone, l-amino-2,5-dibromo-4-hydroxyanthraquinone, l-amino ^ -bromo-S-chloM-hydroxyanthraquinone,

l-Amino-2,8-dibromo-4-hydroxyanthraquinone, l-Amino ^ -chlor-S-bromo ^ -hydroxyanthra-

chinone,
l-amino ^ -bromo-S-chloro ^ -hydroxyanthra-

chinone,
l-amino-S-chloro ^ -hydroxyanthraquinone-

2-sulfonic acid and
1-Amino-S-bromo ^ -hydroxyanthraquinone-2-sulfonic acid.

As starting materials for the production of the new disperse dyes of the anthraquinone series too using phenolic compounds of the formulas V and IX, which contain a substituted ethyl group, are z. B .:

/ 5- (4-Hydroxyphenyl) -propionitrile, /? - (4-Hydroxyphenyl) -propionic acid, /? - (4-Hydroxyphenyl) -propionamide, /? - (4-Hydroxyphenyl) -propionalkylamide, ß- (4-Hydroxyphenyl ) -propionaralkylamide, _| g. (4-Hydroxyphenyl) -propioncycloalkylamide, ß- (4-Hydroxyphenyl) -propiondialkylamide, ^ - (4-Hydroxyphenyl) -propionalkylester, / S- (4-Hydroxyphenyl) -propioncycloalkylester, /? - (4-Hydroxyphenyl) - propionary alkyl esters

and those compounds in which the benzene nucleus of the above compounds has a different substituent as a sulfonic acid or carboxyl group and which has a low molecular alkyl group, a low molecular alkoxy group, phenyl or cyclohexyl group or a halogen atom and especially

iÖ- (2-methyl-4-hydroxyphenyl) propionamide, / S-P-CyclohexyM-hydroxyphenyrj-propionamide, / S- (4-Hydroxyphenyl) -propionäthylamid, ß- (4-Hydroxyphenyl) -propiondimethylamid, (3- (2-chloro-4-hydroxyphenyl) -pjopionmethoxypropylamid,

/ 9- (4-Hydroxyphenyl) -propionphenäthylamid, ^ - (3-Methyl-4-hydroxyphenyl) -propioncyclohexylamide,

/? - (4-Hydroxyphenyl) propionmorpholide,:.

/? - (4-Hydroxyphenyl) -propionic acid methyl ester, / 3- (3-Methyl-4-hydroxyphenyl) -propionic acid-

butyl ester,
jS- (4-hydroxyphenyl) propionic acid hydroxy

ethyl ester,
/ 3- (3-chloro-4-hydroxyphenyl) propionic acid

phenoxypropyl ester,
/ 3- (2-methoxy-4-hydroxyphenyl) propionic acid

cyclohexyl ester,
/ J- (4-Hydroxyphenyl) -propionic acid benzyl ester

and
/ 9- (3-Phenyl-4-hydroxyphenyl) propionic acid ethyl ester

can be.

The process for dyeing synthetic fibers such as polyester, cellulose ester, polyamide fibers or other textile materials made of synthetic polymers using the new dyes, is to mix one or more kinds of the disperse dyes of the formula I and the dye or to disperse the dyes in an aqueous medium in a conventional manner, using a dye bath or a printing paste for bath coloring or for printing the textiles is produced.

When Badfärben a dyeing bath of a dispersion of an anthraquinone dye of the formula I is prepared, corresponding to a desired color tone, and dyeing is carried out at 80 to 13O ⁰ C, depending on the properties of the dyed fabric 60 to 120 minutes, is carried out whereupon a conventional soaps.

In the preparation of the dye bath or the printing paste, a dispersant such as a Condensate of naphthalenesulfonic acid and formaldehyde, a condensate of cresol, hydroxynaphthalenesulfonic acid and formaldehyde or a condensate of a low molecular weight alcohol and naphthalenesulfonic acid be used. As dyeing auxiliaries, z. B. phenylphenol, chlorobenzene, Hydroxybenzoic acid ester, benzene dicarboxylic acid ester or phenylmethylcarbihol may be present.

The new dyes dye synthetic fibers such as polyester, cellulose ester and polyamide fibers, Polyacrylonitrile textile materials and other textile materials made from synthetic polymers in red or bluish-red shades with great light, sublimation and wash fastness. The new dyes especially dye polyester fibers in red or bluish-red shades with excellent results Fastness to light and sublimation.

The fiber materials dyed with the new dyes are particularly excellent in their nature Fastness to sublimation compared to known dyes of the formula

Furthermore, the new dyes give the fiber materials reddish to red-blue tones in one wide range, while the known dyes only produce reddish tones.

In the following examples, parts are understood to mean “parts by weight”.

example 1

A mixture of 156 parts of ^ -hydroxyphenyl) propionamide, 145 parts of nitrobenzene and 26.1 parts of potassium carbonate was ^{heated to 130 °} C. for 2 hours with stirring. To this, 100 parts of 1-amino-2-bromo-4-hydroxyanthraquinone were added and the mixture was heated to 155 ° C. for 25 hours with stirring. After the reaction, the resulting solution was cooled, and 3.7 parts of acetic acid was added thereto to neutralize the excess potassium carbonate. The solution was freed from the nitrobenzene by steam distillation. The resulting precipitate was filtered off, washed with methanol and then with water and dried, 115 parts of 1-amino-2- (4'-carbamoylethylphenoxy) -4-hydroxyanthraquinone being obtained.

Were instead of the l-amino ^ -bromo ^ -hydroxyanthraquinone 1 - Amino - 2 - chloro - 4 - hydroxyanthraquinone and the sodium salt of l-amino-4-hydroxyanthraquinone-2-sulfonic acid used, the same results were obtained.

The obtained product was recrystallized from chlorobenzene and the purified product had a melting point of 243 to 244 ° C and a maximum absorption wavelength of 516 and 552 πΐμ.

A dispersion of the dyes dyed synthetic fibers, such as polyester fibers, under pressure at 120 ^° C. in a brilliant red shade with great lightfastness and sublimation fastness.

O NH

Example 2

(CH ₂ ) ^ ₃ CN

OH

While z. B. the sublimation fastness of the color shades by means of the above-mentioned known Dyestuffs in the fiber materials are about 4 ° or less, with a noticeable discoloration taking place, the sublimation fastness of the new dyes is about 5 °, with essentially no staining takes place. .

For condensation of the anthraquinone compounds listed in column A with those in column B of the The phenolic compounds listed below in Table I were followed by the same procedure as in Example 1, whereby 2-substituted phenoxyanthraquinone dyes were obtained.

These dyes dyed synthetic fibers in a red to bluish-red hue with good results Fastness to light and sublimation.

The melting points and the maximum absorption wavelength of the dyes are in column C. and D, while the tints produced on the synthetic fibers by means of the dyes are listed in column E.

Table I.

A. O
Il NH ₂ -Br HO - / ^ B. C. D.
ταμ 'E A.
ι ι
O T
OH C. )> - C ₂ H ₄ COOH over 285 515
550 Brilliant red
(Acetate)

009585/362

continuation

10

A. O
Il Jl T
O O NH ₂ -Br -Br HO B. C.
⁰ C D.
in," E. K) O
Ij Λ τ-
Y V T
O Y T
O T
OH ^ "AC ₂ H ₄ CONH ₂ 268
273 525
561 Bluish red
(Acetate) τ
Cl O
Il T
O NH ₂ A-Br
Y -Cl HO O
Il T
OH CH ₃ C.
V Y NH ₂ - \ V- C ₂ H ₄ CONH ₂ 233.4 to 234.4 513
550 Brilliant red
(Polyester) T
O -Br HO O
Il OH V Y NH ₂ - \ / - C ₂ H ₄ CO OH over 285 526
562 Bluish red
(Polyester) Cl T
O rV
Ύ HO Cl OH I.
V the same NH ₂ - ^< (~ ^ \ - C ₂ H ₄ CONH ₂ 271.5 to 274.5 525
558 Bluish red
(Polyester) the same V HO the same OH Cl / ^
ν the same -Br ~ \ / ~ C ₂ H ₄ C ONH ₂ 258 to 260 516
551 Brilliant red
(Polyester) HO V HO CH ₃ T
Cl HO - \ / - C ₂ H ₄ CONH ₂ 215 to 218 514
549 Brilliant red
(Polyester) HO - ^ "^^ C ₂ H ₄ C ONHC ₄ H ₉ 226.3 to 229.3 526
560 Brilliant red
(Acetate) NH ₂ ^^ ~ V- C ₂ H ₄ CONH - ^ hS 261.4 to 263.4 526
561 Brilliant red
(Polyester) V HO - \ / - C ₂ H ₄ CONHC ₃ H ₆
~ OCH ₃ 216.5 to 218.5 524
560 Brilliant red
(Polyamides ( DH ^ / "VC ₂ H ₄ CN 219 to 223 524
560 Bluish red
(Polyester)

continuation

A. - Cl O
Il NH ₂ B. C.
⁰ C D.
τημ E. Y \
χ / Λ-Br A,
. T T
OH HO - <ζ ~. VC ₂ H ₄ CN 216 to 219 525
560 Bluish red
(Polyester) Il
O NH ₂ O
A. VsO ₃ Na
T OH HO - \ ~ \ - C ₂ H ₄ CONHCH ₃ 233 to 235 520
555 Brilliant red
(Polyester) Y
O NH ₂ O
Il \ -Br
Nf. Cv I.
OH HO - ^ "VqH ^ ONHCH ^^ NB, 220
decomposed 522
560 Bluish red
(Polyester) Y
O the same HO - ^{H <} \ ~~ VC ₂ H ₄ CONHCH ₂ - <(~ \ 239 to 241 524
560 Brilliant red
(Polyester) the same HO ^ / "VC ₂ H ₄ CONHCH ₂ CH ₂ OH 247
decomposed 525
561 Brilliant red
(Polyester) C ₂ H ₄ OH the same HO - / V _{- C 2} H ₄ CON
"" ^ C ₂ H ₄ OH 182 to 184 526
561 Brilliant red
(Polyester) O Av_a \ A / HO- -f VC ₂ H ₄ CON O 152 to 154 523
554 Brilliant red
(Polyester] OH Il
O

B e i s ρ i e 1 3

A mixture of 196 parts of /? - (3-methyl-4-hydroxyphenyl) -propionic acid ethyl ester, 300 parts of nitrobenzene and 26 parts of potassium carbonate was ^{heated to 130 °} C. for 2 hours with stirring. Then 100 parts of 1-amino-2-bromo-4-hydroxyanthraquinone was added to the mixture. The temperature of the mixture was then elevated to about 14O ⁰ C and the reaction was carried out for 25 hours under stirring. After the completion of the reaction, the reaction mixture was cooled, and 3.7 parts of acetic acid was added thereto to neutralize the excess potassium carbonate. The nitrobenzene was then driven off by steam distillation. The resulting precipitate was washed with methanol and then with water and dried, 120 parts of the dark red-colored 1-amino-2- (2'-methyl-4'-ethoxycarbonylethylphenoxy) -4-hydroxyanthraquinone being obtained. .

The product was recrystallized from chlorobenzene. The purified material had a melting point from 115 to 116 ° C and a maximum absorption wavelength from 515 and 552 ηΐμ. '

The suspension of the dye thus obtained, containing a dispersant, dyed synthetic fibers such as modified polyester fibers at about 125 ° C. under pressure in a brilliant red of great lightfastness and sublimation fastness, ¹

Example4

The condensation of the anthraquinone compounds listed in column A with those in column B of the Phenolic compounds listed in the tables were carried out as in Example 3, with 2-substituted Phenoxyanthraquinone dyes were obtained.

13 14

These dyes dyed polyester fibers in red to bluish-red shades with good light and color Fastness to sublimation.

The melting point and the maximum absorption

The wavelength of these dyes are in columns C and D and the hues that the dyes are based on Polyester fibers produced, compiled in column E.

Table II

⁰ C

ταμ

O NH,

HO

C ₂ H ₄ COOCH ₃

0 OH

0 NH,

HO

C ₂ H ₄ COOC ₂ H ₅

Cl O OH O NH ₂

HO

^ -C ₂ H ₄ COOCH ₂ - ^ ^

O OH

the same

O NH,

HO - <f VC ₂ H ₄ COOC ₂ H ₅

O OH

CH ₃

the same

C ₂ H ₄ COOCH ₃

O NH,

HO

^ -C ₂ H ₄ COOCH

CH ₃

CH ₃

O OH

the same

the same
the same

3 ^ -C ₂ H ₄ COO-ZhN

C ₂ H ₄ COOC ₂ H ₄ OH

HO

C ₂ H ₄ COOC ₂ H ₄ OCH ₃ to 145

515 550

Brilliant red

to 151.5

525 560

Bluish red

to 106

154.5 to 155.5

to 134

516 550

516 550

515 550

Brilliant red

Brilliant red

Brilliant red

to 151

to 114

515

552

516 550

Brilliant red

Brilliant red

136.5 to 138.5

to 118
up to 160

516 551

514 548

518 548

Brilliant red brilliant red brilliant red

continuation

A. O NH ₂ Br - HO- B. ■ ^ ~ y- C ₂ H ₄ CO I.
f ~ \ C ΤΤΓ ^ ΤΤ O ^ ₃ C.
⁰ C 123 D.
m μ E. 111
. \ λ / / HO- UV ^ JtIv ^ JtI ₂ U 104 I.
0
the same OH ■ ^ \ - C ₂ H ₄ COOC ₂ H ₄ OC ₂ H ₅ 122 to 518
552 Brilliant red ■ ζ ^) - C ₂ H ₄ COOCH ₂ CH ₂ O 1 \ / 101 to 517 Brilliant red HO- ¹ CH ₂ CH ₂ OH 144 549 the same CH ₃ O
Il NH ₂ -egg HO- - \ ~ \ - QH ₄ C 0 OCHCH ₂ 0- / ~~ S 142 to 130 516
548 Brilliant red \
Y (II
Χ / γ I.
OH ^ XC ₂ H ₄ COOCH ₂ CH ₂ Cn 127 to 517
551 Brilliant red Il
O NH ₂ -Br HO- 135 o ^r
II. \
\ / OH \\ - C ₂ H ₄ C 0 OCH ₂ CH ₂ NH ₂ 134 to 516
552 Brilliant red HO- 121 Λ HO- CH ₃ 104 ^v Ϊ.
O - <f ~ \ - C ₂ H ₄ CO OCHCH ₂ OCH ₃ 119 to 517
549 Brilliant red HO- - <\ ~~ V- C ₂ H ₄ COOC ₂ H ₄ - ^ yy 103 to 162 514
548 Brilliant red the same Cl the same NH ₂ -SO ₃ K HO- - \ ~~ V- C ₂ H ₄ COOC ₂ H ₅ 160 to 150 516
548 Brilliant red CH ₃ the same I.
OH V ^ SC ₂ H ₄ COOC ₂ H ₅ 148 to 516
551 Brilliant red O
Il HO- 131 Cu CH ₃ 1
O 129 to 516
550 Brilliant red the same

Example 5

A mixture of 1500 parts of ethanol, 300 parts of concentrated sulfuric acid and 100 parts of 1-amino-2 - (4 '- carbamoyläthylphenoxy) - 4 - hydroxyanthraquinone was heated 15 hours with stirring at 78 to 81 ⁰ C. After the reaction had ended, the reaction mixture was cooled and the resulting precipitate was filtered off and washed with water, 107 parts of the red 1-amino-2- (4'-ethoxycarbonylethylphenoxy) -4-hydroxyanthraquinone being obtained.

This product was suspended in ethanol and the purified product had a melting point of 132 to 133 ° C and a maximum absorption wavelength of 515 and 550 ηΐμ in an acetone solution.

A dispersion of the dyes thus obtained colored synthetic fibers such as polyester fibers at about

12O ⁰ C under pressure in brilliant red shades with high light and sublimation.

Example 6

The reaction of the anthraquinone compounds listed in column A with the in column B of table III Listed alcohols were carried out as in Example 5, with corresponding 2-substituted Phenoxyanthraquinone dyes were obtained.

These dyes dyed polyester fibers in red to bluish-red shades with great light and color Fastness to sublimation.

The melting points, the maximum absorption wavelength in an acetone solution of the dyes and the hues of polyester fibers dyed by means of the dyes are in columns C, D and E. compiled in Table III.

Table III

0
Ν NH ₂ NH ₂ NH ₂ 0- A. CH ₃ C ₂ H ₄ CONH ₂ H ₃ C B. C.
° C D.
m / i E. V Y V ir
Y \ = / H ₃ C C. Il
O OH ( I.
OH \ = / CHOH 112 to 114 516
550 Brilliant red the same DH NH ₂ C. O
Il the same (j O- C ₂ H ₄ CONH ₂ 154.5 to 155.5 516
550 Brilliant red V O
Il ( CH ₃ C ₂ H L. !
0 f I
V )H ₅ OH 115 to 116 515
552 Brilliant red Il
O O O- C ₂ H ₄ CONH ₂ 136.5 to 138.5 516
551 Brilliant red Λ Cl
I. C ₂ H C. Il
0 ₅ OH 160 to 162 516
548 Brilliant red O- C ₂ H ₄ CONH ₂ C. the same 148 to 150 516
551 Brilliant red

continuation

A. O NH ₂ B. C.
⁰ C D.
m / i E. Cl O OH the same. ■ ■ · ^: 150 to 151.5 525
560 Bluish red 0 OH ^ / γη-ox ^ VC ₂ H ₄ C ONH ₂ C ₂ H ₄ OH 0 OH ό 103 to 104 514
548 Brilliant red the same the same HIGH ₂ CH ₂ OH 117.5 to 118.5 514
548 Brilliant red the same C ₂ H ₅ OCH ₂ CH ₂ OH 122 to 123 518
552 Brilliant advice the same HOC ₂ H ₄ OC ₂ H ₄ OH 101 to 104 517
549 Brilliant red the same CH ₃ OCH ₂ CHOH
CH ₃ 129 to 131 516
550 Brilliant red H ₃ C ^ ~ \ - OCH ₂ CHOH
CH ₃ 129 to 131 516
550 Brilliant red

Example 7

A mixture of 2000 parts of ß-methoxyethanol, 50 parts of benzenesulfonic acid and 100 parts of 1-amino-2 - (4 '- carboxyethylphenoxy) - 4 - hydroxyanthraquinone was heated with stirring for 5 hours, the water formed during the reaction being drawn off would.

After the completion of the reaction, the mixture was cooled to a temperature below 10 ° C., whereupon 500 parts of methanol were added thereto. The precipitate formed was filtered off, washed with methanol and further washed with water to give 90 parts of a red product consisting of 1-amino-2- [4 '- (/? - methoxyethoxy) -carbonylethylphenoxy] -4-hydroxyanthraquinone. This product was recrystallized from chlorobenzene, was with a final product having a melting point of 159 to 16O ⁰ C and a maximum absorption wavelength at 518 and 548 receive πΐμ.

A dispersion of the dye thus obtained colored synthetic fibers such as polyester fibers at about 100 ° C under atmospheric pressure in the presence of a carrier in brilliant red tones with great light and fastness to sublimation.

Examples

The anthraquinone compounds listed in column A were compared with those in column B of table IV Listed alcohols reacted as in Example 7, with 2-substituted phenoxyanthraquinone dyes were obtained.

These dyes dyed polyester fibers in brilliant red shades of great light and sublimation. authenticity.

The melting points and the maximum absorption wavelength of the dyes in methanol are in Columns C and D of Table IV compiled, while those on polyester fibers by means of the dyes tints produced are listed in column E.

Table IV

NH ₂ NH ₂ A. B. C ₂ H ₅ OH CH ₃ 132 C.
⁰ C 133 D.
ταμ E. O
I. «Ν «Ν / "" V-OCH ₂ CHOH I.
OH T
OH O until 515
550 Brilliant red I.
O CH ₃ OH 142 144 the same O
T 150 until 151 516
549 Brilliant red CH ₃ ti
O O until 515
552 Brilliant red -C ₂ H ₄ COOH -C ₂ H ₄ COOH

B e i s ρ i e 1 9

A mixture of 3000 parts of ethanol, 500 parts of concentrated sulfuric acid and 100 parts of 1-amino-2 - (4 '- cyanoethylphenoxy) - 4-hydroxy - 5 - chloro-anthraquinone was stirred for 10 hours at 78 to 80 ° C heated. After the completion of the reaction, the reaction mixture was cooled and the precipitate was cooled filtered off, washed with water and dried, 100 parts of a red, from 1-amino-2 - (4 '- ethoxycarbonylethylphenoxy) - 4 - hydroxy-5-chloroanthraquinone existing dye.

This product was suspended in ethanol with stirring and the purified product had a Melting point of 150 to 151.5 ° C and a maximum absorption wavelength in an acetone solution 525 and 560 πΐμ.

A dispersion of the dyes thus obtained colored synthetic materials at about 80 ° C. under normal pressure Fibers such as cellulose acetate in bluish-red tones with great lightfastness and sublimation fastness.

Example 10

The anthraquinone compounds listed in column A were compared with those in column B of the table V listed alcohols reacted, with 2-substituted phenoxyanthraquinone dyes obtained became.

The dyes dyed polyester fibers in brilliant red shades with good lightfastness and sublimation fastness.

The melting point and the maximum absorption wavelength in an acetone solution of the dyes are in columns C and D and the tints produced on polyester fibers by means of the dyes in column E.

Table V

A. NH ₂ - C ₂ H ₄ CN B. C. D. E. ⁰ C ταμ O
Il OH CC CH ₃ OH 143 to 145 515
550 Brilliant red Il
O the same / h \ -OH 154.5 to 155.5 516
551 Brilliant red

Example 11

A mixture of 2000 parts of ethanol, 35 parts of 3-naphthalenesulfonic acid and 100 parts of 1-amino-2 ^: (2'-methyl -4-carbamoylethylphenoxy) -4-hydroxyanthraquinone was heated at 75 to 79 ° C. for 15 hours with stirring. After the completion of the reaction, the reacted mixture was cooled. The resulting precipitate was filtered off, washed with methanol, further washed with water and dried to give 100 parts of a red product consisting of 1-amino-2- (2'-methyl-4'-ethoxy-carbonylethylphenoxy) -4-hydroxyanthraquinone became. This product was suspended in ethanol with stirring, and the purified product had a melting point of 115 to 116 ° C. and a maximum absorption wavelength in an acetone solution at 515 and 552 πΐμ.

A dispersion of the dye thus obtained dyed synthetic fibers, such as the commercially available modified polyester fibers, ^{under normal pressure at about 80 ° C. in brilliant red shades of great lightfastness and sublimation fastness.}

Example 12
1 part of the dye of the formula

NH

C ₂ H ₄ CONH ₂

O OH

was in 3000 parts 2 parts of a condensate of naphthalenesulfonic acid and formaldehyde and 4 parts Dispersed water containing sulfuric acid ester of a higher alcohol. 100 parts of polyester fibers were immersed in the dyebath thus obtained and treated at 130 ° C. for 60 minutes. After this treatment the fiber was washed with water and in 3000 parts of sulfuric acid ester of a higher molecular weight Alcohol-containing water at 90 ° C 20 Mi-

IO grooves soaped. The material dyed in this way showed brilliant red tints of great lightfastness and sublimation fastness.

The dried material had a lightfastness of 6 to 7 ° and a sublimation fastness of 5 ° using a tester at 185 ° C for 30 seconds was established.

Example 13
1 part of the dye of the formula

NH

C ₂ H ₄ CN

Cl O OH

20 was dispersed in 300 parts of 2 parts of a condensate of hydroxynaphthalenesulfonic acid, cresol and formaldehyde and 2 parts of a condensate of naphthalenesulfonic acid and formaldehyde-containing water. 5 parts of o-phenylphenol were added to the dyebath prepared in this way, whereupon 100 parts of polyester fibers were treated in the dyebath at 100 ° C. for 90 minutes. After the treatment, the fiber was soaped in 3000 parts of water containing 4 parts of the above condensate. The dyed material had a bluish-red tint of great lightfastness and sublimation fastness. The dyed material had a lightfastness of 7 ° and a fastness to sublimation of 5 °, which was determined by means of a tester at 185 ° C. for 30 seconds.

B ei s ρ i e1 14

Using the dyes listed in Column A of Table VI, polyester fibers were made into treated in the same way as in Example 12 or 13. The materials dyed in this way had the in Column B listed light fastness determined by means of a fade-O-meter and one listed in column C. Fastness to sublimation (tester: 180 ° C, 30 seconds).

Table VI

O NH ₂

O OH

C ₂ H ₄ COOCH ₃ 6 to 7 ^C

C ₂ H ₄ CONH ₂ 6 to 7 ^C

009 585/302

0
Il NH ₂ -Ο— ■ Continuation A. B. C. \ I Ι γ V / SC ₂ H ₄ COOC ₂ H ₅ 6 to 7 ° 5 ° Γχ Il
ο OH 0 NH ₂ -Ο— ' ) Y \ V- C ₂ H ₄ COOC ₂ H ₅ 6 to 7 ° ' 4 to 5 ° Yx Il
0 OH 0 NH ₂ -0- Cl \ γ ν ^ ~ \ - C ₂ H ₄ COOCH ₂ - ^ f ^ / 6 to 7 ° 5 ° (X Il
O τ
OH N = / N / O
Il NH ₂ -Ο— K rV V \ ~ V- C ₂ H ₄ CONH - ^ H / 6 ° 5 ° / γ Il
O I.
OH ~ "" " \ / \ O
Il NH ₂ -Ο— K «Ν ν \ / - C ₂ H ₄ COOC ₂ H ₄ OCH ₃ . 6 to 7 ° 4 to 5 ° I Il Il
O ι
OH O
Il NH ₂ -ο- K ir CH ₃ γ. V ν ^^ - C ₂ H ₄ COOC ₂ H ₅ 6 to 7 ° 4 to 5 ° Oc O τ
OH O
H NH ₂ -ο- K γ V <^^ - C ₂ H ₄ COo - ^ hS 6 to 7 ° 4 to 5 ° (X Il
O ί
OH N = / N ^ = / O
\\ NH ₂ -ο- K Λ- γ ν ^ "^ QH.COOQ ^ ^^ 6 to 7 ° 5 ° Oc Il
O < DH

Example 15
1 part of a dye of the formula

Example 16
1 part of the dye of the formula

Cl O NB

C ₂ H ₄ CONH ₂

O OH

IO

O NH,

O OH

0- ^ yC ₂ H ₄ COOH

was 3 parts of a condensate of naphthalenesulfonic acid and formaldehyde and 5 parts in 3000 parts Dispersed water containing Marseille soap. 100 parts of cellulose acetate were added to the dyebath obtained in this way immersed and treated at 80 ° C for 60 minutes.

After the treatment, the cellulose acetate was washed with water and soaped in 3000 parts of water containing 5 parts of Marseille soap. The dyed material showed a bluish-red tint of great lightfastness and sublimation fastness. The light fastness was 7 °, and the sublimation fastness 5 ⁰ ^ l 20 ° C, 5 hours).

was dispersed in 3000 parts of 3 parts of a condensate of naphthalenesulfonic acid and formaldehyde and 4 parts of a sulfuric acid ester of a higher molecular weight alcohol-containing water. 100 parts of cellulose acetate were immersed in the dye bath obtained in this way and ^{treated at 80 °} C. for 60 minutes. After this treatment, the cellulose acetate was soaped off in 3000 parts of water containing 4 parts of the abovementioned condensate. The dyed material showed brilliant red shades of great lightfastness and sublimation fastness.

The light fastness was 6 °, and the sublimation fastness 5 ° (120 ⁰ C, 5 hours).

B ice ρ i el 17

Using the cellulose acetate dyed in this way in column A of Table VII 35 had the dyes listed in column B, cellulose acetate was treated with the same lightfastness and in the manner listed in column C as in Example 15 or 16. The fastness to sublimation (120 ⁰ C, 5 hours.)

Table VII

O
Il NH ₂ -o- < A. B. C. Λ
γ V Ci
V / Il
0 ι
OH * ^r ~ \ - QH ₄ C ONH ₂ 6 to 7 ° 5 ° ι
Cl 0
Il NH ₂ -o- < Λ V Q Il
0
0
Il I.
OH
NH ₂ -o- < ^^^ C ₂ H ₄ CONHC ₄ H ₉ 5 ° 4 to 5 ° Br J ¹ J- Il
0 OH ⁷ ^^ QH ^ OOQHs 6 to 7 ° 5 °

continuation

0
Il NH ₂ A. - C ₂ H ₄ CONH ^ \ Η / B. C. V 5 ° 5 ° Λ / Il
O OH

Example 18 1 part of the dye of formula

NH

C ₂ H ₄ CONHC ₃ H ₅ OCH ₃

O OH

3 parts of a condensate of naphthalenesulfonic acid and formaldehyde and 2 parts of the sodium salt of water containing alkylbenzenesulfonic acid were dispersed in 3000 parts. 100 parts of polyamide fiber were immersed in the dyebath obtained in this way and treated in this at 100 ° C. for 90 minutes. After the treatment, the fiber was soaped in 3000 parts of water containing 4 parts of the above condensate. The dyed material showed a brilliant red tint with great light fastness and sublimation {\ fastness.

The light fastness was 5 to 6 ° and the sublimation fastness 5 ° (150 ° C, 120 seconds).

B e i s ρ i e 1 19 1 part of a mixture of the formulas consisting of the dyes (1) and (2) in a ratio of 1: 1:

NH

CH ₄ COOCH,

(1)

Cl O OH O NH,

H ₃ COOCH ₄ C ₂

C ₂ H ₄ COOCH ₃

(2)

0 OH

was in 3000 parts 2 parts of a condensate of naphthalenesulfonic acid and formaldehyde and 2 parts of the sodium salt of alkylbenzenesulfonic acid containing water. 100 parts of polyester ether fibers were immersed in the dyebath obtained in this way and treated in this at 100 ° C. for 120 minutes.

After the treatment, the fiber became 3000 parts containing 4 parts of the above condensate Soaped in water. The dyed material showed a bluish red tint of great light and lightness Fastness to sublimation. The light fastness was 6 to 7 ° and the sublimation fastness 5 ° (test device: 185 ° C, 30 seconds.)

Claims (6)

Patent claims: 1. Anthraquinone dyes of the formula NH, C ₂ H ₄ -Y OH in which R is a hydrogen atom, a low molecular weight alkyl group, a low molecular weight alkoxy group, a phenyl radical, a cyclohexyl radical or a halogen atom, Y is a cyano group or an R ₁ CO group, in which R _{1 is} a hydroxyl group, a primary amino group, an optionally substituted low molecular alkylamino group, an optionally substituted low molecular alkoxy group, a Cyclohexylamino group, a morpholinyl group or a cyclohexyloxy group is any of the both Z is a hydrogen atom or one Z is a hydrogen atom and the other Z is a halogen atom or a group of the formula -O —V and Y is a group other than the cyano group if both Z are hydrogen atoms. 2. Anthraquinone dyes according to Claim 1 of the formula CO · R ₁ IO R ' 20th O OH in which each of the two Z _{1 is} a hydrogen atom or one Z _{1 is} a hydrogen atom and the other Z _{1 is} a halogen atom or a group of the formula C ₂ H ₄ -COR ₁ means, R 'stands for a hydrogen atom, a low molecular weight alkyl group, a low molecular weight alkoxy group or a halogen atom and R _{1 has} the meaning given in claim 1. 3. Anthraquinone dyes according to claim 1 of the formula NH ₂ ° ~ ^< \ Ι><Γ ~ C ₂ H ₄ -CN 40 R '. Z ₂ O OH in which one of the two Z _{2 is} a hydrogen atom and the other Z _{2 is} a halogen atom or a group of the formula -C ₂ H ₄ -CN
R ' and R 'has the meaning given in claim 2. 4. Anthraquinone dyes according to Claim 1 and 2 of the formula O NH -CO-R ₂ O OH in which R _{2 is} a methoxy, ethoxy or cyclohexyloxy group and R _{3 is} a hydrogen atom, a chlorine atom or a methyl group. 5. anthraquinone dyes according to claim 1 and 3 of the formula Z, - O NH C ₂ H ₄ -CN Z ₃ O OH in which one of the two Z _{3 is} a hydrogen atom and the other Z _{3 is} a chlorine atom and R _{3 has} the meaning given in claim 4. 6. Use of the anthraquinone dyes claimed according to claims 1 to 5 for dyeing or printing on synthetic fiber materials. 009585/362