CH683183A5 - Disperse azo dyes. - Google Patents

Description

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CH 683 183 A5

description

The invention relates to the disperse dyes of the formula I.

R

'L

d-n = n r.

CD,

'3

wherein

Ri phenoxycarbonyl-Ci-3-alkyl, where the phenyl nucleus up to two substituents from the group halogen, alkyl and alkoxy or a substituent from the group trifluoromethyl, hydroxy, nitro, formyl, cyano, rhodan, Ci-4-A! Kylcarbonyl, Ci-2-alkylcarbonyloxy, aminocarbonyl, Ci-3-alkoxycarbonyl, C1-2-AI-koxy-C2-3-alkoxycarbonyl, Ci_4-acylamino or phenyl,

R2 alkyl, alkenyl, haloalkenyl, alkynyl, cyanoalkyl, benzyl, phenylethyl, phenylpropyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkylcarbonyloxyalkyl or alkoxycarbonyloxyalkyl, or with R4 and the atoms in between, a heterocyclic six-membered ring optionally carrying up to 3 methyl groups, or, if D is 2,4-dinitrophenyl or 2,4-di-nitrophenyl or a heterocyclic radical which is further substituted in the 5- or 6-position, also hydrogen

R3 is hydrogen, halogen, hydroxyl or Ci_4-alkyl, or, if D is 2-cyano-4-nitrophenyl or phenyl bearing three substituents or a heterocyclic radical, also formylamino, Ci-3-alkylcarbonylamino, C2-3-alkenylcarbonylamino, Ci-2-alkoxy-Ci-3-alkylcarbonylamino, Ci-4-Àlkoxycarbonylamino or Ci-3-alkylsulfonylamino,

R4 is hydrogen, halogen, Ci-3-alkoxy or Ci-3-alkoxy-C2-3-alkoxy or with R2 a six-membered ring as described there, and

D is a diazo component of the triazolyl, pyrazolyl, cyano-Ci-2-alkylimidazolyl, 4-chlorothiazolyl-2-, isot-hiazolyl-5-, benzisothiazolyl-3-, 1,3,4-thiadiazolyl-5-, 4th -Chlorthienyl-2 series, a 3-phenyl-1,2,4-thia-diazolyl-5- or 5-nitrothiazolyl-2 radical, a phenyl radical carrying up to three substituents but free of sulfonyl groups or a radical of the formula da cyan, alkoxycarbonyl, aminocarbonyl, mono- or dialkylaminocarbonyl or alkylcarbonyl, b is hydrogen, alkyl, phenyl or alkylcarbonyl,

c cyan, formyl, alkoxycarbonyl, mono- or dialkylaminocarbonyl, aminosulfonyl, mono- or dialkylaminosulfonyl or alkylcarbonyl,

d hydrogen, methyl, halogen or nitro,

e is hydrogen, halogen, methoxy, cyano or nitro, and f is hydrogen, methyl or phenyl, where the alkyl groups mentioned can carry one or two substituents customary in disperse dyes, all the alkyl, alkenyl, alkynyl and alkoxy groups mentioned, unless otherwise indicated, preferably to 6, which contain alkyl groups in particular 1 or 2 carbon atoms and halogen (also shark) is preferably chlorine or bromine, in particular chlorine.

Common substituents for disperse dyes are e.g. in German laid-open specification 2120 089, published French patent application 2 008 404 and English patent specification 1 359 741.

The preferred Ci-3-alkylene intermediate (for phenoxycarbonylalkyl in R-i) corresponds to one of the following formulas:

e in which

-ch2ch2-, -ch2ch2ch2-, -CH2CH-

ch3

or -CHCH2-

2nd

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CH 683 183 A5

especially -CH2CH2-, and has no substituents. Compared to the closest comparable, well-known disperse dyes, these dyes are characterized above all by their excellent thermal behavior (household linen M & S C4A 60 ° C).

Preferred diazo components D- of the dyes of the formula I correspond to the formulas

° Xk ■

wherein R5 is hydrogen, methyl, chlorine, bromine, cyan or nitro, preferably cyan or nitro,

Rë chlorine, bromine, methyl, nitro or phenylazo, preferably nitro,

R7 is hydrogen, chlorine, bromine, cyan or Ci-2-alkoxycarbonyl, preferably hydrogen, chlorine, bromine or cyan,

R8 formyl, cyan or a group of the formula -CH = C (CN) Rn,

R9 is alkoxycarbonyl, nitro or cyan, preferably cyan and R11 is cyan or alkoxycarbonyl.

Another preferred diazo component D- is 5-nitrothiazolyl-2-,

Particularly preferred diazo components are 2-cyano-4-nitrophenyl, 2,4-dinitro-6-bromo or 2,4-dinitro-6-chlorophenyl.

Preferred substituents Ri correspond to the formula

-CH CH -C00— / ~~ V-R 2 2 »

* 12 * 12

wherein the two R12 are independently hydrogen, fluorine, methyl, Ci-2-alkoxycarbonyl, methoxy or ethoxy,

R13 is hydrogen, fluorine, chlorine, bromine, methyl, Ci-2-alkoxycarbonyl, methoxy, ethoxy or phenyl and R14 is hydrogen, methyl, methoxy or ethoxy.

R2 preferably denotes methyl, ethyl, allyl, 2-methylallyl, chlorallyl, propynyl or Ci-2-alkylcarbonyloxyethyl, Ci-2-alkoxycarbonyloxyethyl, in particular methyl.

R3 is preferably hydrogen, methyl or Ci-2-alkylcarbonylamino,

R4 is preferably hydrogen, methoxy or ethoxy.

The new compounds of the formula I are prepared by coupling a diazotized amine of the formula II

D-NH2 (II)

R,

at).

The amines of formula II are known, some of those of formula III are also known. All of them can be easily prepared according to methods familiar to the person skilled in the art.

The processing of the new compounds of formula I into dyeing preparations is carried out in a generally known manner, e.g. by grinding in the presence of dispersants and / or fillers. With the preparations which may have been dried in vacuo, by atomization or in a fluidized bed granulator, it is possible, after adding more or less water, to dye, pad or print in a so-called long or short liquor.

The dyes are excellently absorbed from aqueous suspensions on textile material made from fully synthetic or semi-synthetic, hydrophobic, high-molecular organic substances. They are particularly suitable for dyeing or printing textile material from linear, aromatic polyesters, as well as from cellulose-2 1/2 acetate and cellulose triacetate.

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CH 683 183 A5

One dyes or prints according to known, e.g. the methods described in French Patent No. 1,445,371.

The dyeings obtained have good general fastness properties; In addition to the good thermal migration fastness, the light fastness, heat setting, sublimation and pleating fastness as well as the excellent wet fastness properties, especially after permanent press finishing are to be emphasized.

In the following examples, parts are parts by weight and percentages are percentages by weight. The temperatures are given in degrees Celsius.

example 1

16.3 parts of 2-amino-5-nitrobenzonitrile are stirred in 100 parts of cold sulfuric acid (93%) and 32 parts of nitrosylsulfuric acid (40%) are added at 0 to 5 ° within 30 minutes. The mixture is stirred for a further 3 to 4 hours at 0 to 5 ° and then the resulting diazonium salt solution is poured into a mixture of 26.9 parts of 2'-methylphenyl ester of 3- (N-ethyl-N-phenylamino) propionate and 100 parts of glacial acetic acid , 2 parts of amidosulfonic acid, 200 parts of water and 500 parts of ice. The precipitated dye is filtered off, washed acid-free with water and dried in vacuo at 60 °. The dye obtained corresponds to the formula and dyes polyester fiber material in ruby shades with excellent fastness properties.

Xmax. = 532 nm Example 2

The procedure is as described in Example 1, but the 26.9 parts of 3- (N-methyl-N-pheny! Ami-no) -propionic acid 2'-methylphenyl ester are replaced by 29.9 parts of 3- (N-ethyl-N -phenylamino) -propionic acid 2'-methoxyphenyl ester. The resulting dye corresponds to the formula

«.,

\ = / XCH2CH2-C0-0-

it dyes polyester fiber material in bluish ruby-red tones with excellent fastness properties and is excellently suited for modern rapid dyeing processes such as the ®Foron-RD process.

Xmax. = 535 nm

Example 3

20.7 parts of 1-amino-2,6-dichloro-4-nitrobenzene are stirred in 100 parts of sulfuric acid (93%) and 32 parts of nitrosylsulfuric acid (40%) are added at 30 ° in the course of an hour. The mixture is stirred for a further 2-3 hours at 30-32 ° and the resulting diazonium salt solution is then added dropwise, with stirring, to a mixture of 28.5 parts of 4'-methoxyphenyl 3- (N-methyl-N-phenylamino) propionate and 50 parts of glacial acetic acid , 20 parts water, 300 parts ice and 0.5 parts amidosulfonic acid. The coupling mixture is then slowly diluted with 500 parts of water. The precipitated dye is filtered off, washed acid-free with water and dried in vacuo at 60 °. The dye obtained corresponds to the formula

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Cl

CH 683 183 A5

/ Œ3

°? N ~~ \ y— N "N - \ y — Nv

X = / XŒ2Œ2-C0-0- ^ J> -0CH3,

it dyes polyester fiber material in yellow-brown tones with excellent fastness properties and is ideally suited for modern rapid dyeing processes such as the ®Foron-RD process.

Xmax. = 439 nm

Example 4

4.1 parts of 2-amino-4-chloro-5-formylthiazole are mixed in 50 parts of 85% phosphoric acid at -10 ° to -5 ° within 30 minutes with 8 parts of nitrosylsulfuric acid (40%). The mixture is stirred for a further 3 to 4 hours at -5 ° and the solution obtained is then poured with stirring into a mixture of 7.9 parts of 3- (N-ethyl-N-3'-methylphenylamino) propionic acid 3 "-methoxyphenyl ester, 50 Parts of glacial acetic acid, 20 parts of water and 250 parts of ice. Stirring for a further 30 minutes and then slowly diluting with 500 parts of ice water. The precipitated dye is filtered off, washed with water until acid-free and dried in vacuo. The dye obtained corresponds to the formula cixs> - »-O <CA w:" 3

OHC S XCH2CH2 "C0-0- ^ J>,

CH3 ~

it dyes polyester fibers in bluish-violet tones with excellent fastness properties and is ideal for modern rapid dyeing processes such as the ®Foron-RD process.

Max. = 586 nm

Example 5

14.5 parts of 2-amino-5-nitrothiazole are mixed in a mixture of 75 parts of sulfuric acid (93%), 85 parts of glacial acetic acid and 15 parts of propionic acid and then at 0-2 ° within 30 minutes with 32 parts of nitrosylsulfuric acid (40%) transferred. The mixture is stirred for a further 1 to 2 hours at 0-2 ° and then the resulting solution is slowly poured into a mixture of 28.5 parts of 3'-methoxyphenyl 3- (N-methyl-N-phenylamino) propionate, 50 parts, with stirring Glacial acetic acid, 20 parts water, 300 parts ice and 0.5 parts amidosulfonic acid. The coupling mixture is then slowly diluted with approx. 500 parts of water. The precipitated dye is filtered off, washed acid-free with water and dried in vacuo at 60 °. The dye obtained corresponds to the formula

/ r-N _ / ch3

o2NA> - «'- * —0 ~' \

2 XCH2CH2-C0-0

it dyes polyester fiber material in bluish-violet tones with excellent fastness properties and is ideal for modern rapid dyeing processes such as the ®Foron-RD process.

Xmax. = 584 nm Example 6

19.6 parts of 1-amino-2-methoxycarbonyl-4-nitrobenzene are dissolved at 60 ° in 70 parts of glacial acetic acid. The resulting solution is poured into a mixture of 150 parts of ice and 30 parts of hydrochloric acid (approx. 30%) with vigorous stirring. A solution of 7 parts of sodium nitrite in 100 parts of water is added dropwise to the resulting fine suspension at 0-5 ° within 1 hour and the mixture is then stirred at 0-5 ° for 3 hours. 0.5 part of amidosulfonic acid is added to the diazonium salt solution obtained, and the mixture is then added dropwise

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CH 683 183 A5

within 15-20 minutes, a solution of 28.5 parts of 3- (N-methyl-N-phenylamino) propionic acid 3'-methoxyphenyiester in 50 parts of glacial acetic acid. To complete the coupling, blunt with sodium acetate. The resulting dye is filtered off, washed with water and dried in vacuo at 60 °. It corresponds to the formula c0-0-ch

/ j ch, och

° 2n_C3 — n = n — O—

n r-C 3

"ch2ch2-c0-0- / vv and dyes polyester fiber material in scarlet shades with excellent fastness properties. The dye is ideally suited for modern rapid dyeing processes such as the ®Foron-RD process.

Xmax. - 493 nm

Table 1 below shows further dyes of the general formula Ib / "

° 2N - (~ \ - N = 2 • (ib)

\ = / \ = / ch2ch2-co-o-b specified, they are prepared in analogy to the information in Examples 1 or 2.

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CH 683 183 A5

Table 1

Example No.

R2

B

Nuance on PES

10th

11

12th

13

14

15

16

-c2h5 -ch3

do.

do. do. do. do. -C2H5 -ch3 do.

^ 3

ruby co-o-c2h5

- ^^ - C0-0-C3H7-n do.

cil do.

O-s

-o ch3

do.

do. do. do. do. do. do. do.

c00c2h5

7

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CH 683 183 A5

Table 1

Example No.

R2

B

Nuance on PES

17 -C2H5

18 -CH3

19 -C2H5

20 -CH2CH20C00CH3

21 -CH2 CH2 OCOOC4 H9-n

22 -CH3

23 -C2H5

24 -CH3

25 do.

26 -C2H5

27 th.

28 -CH3

29 do.

30 do.

31 -C2H5

SCN

do.

^!

CH,

<r \

OCH,

do.

0C2H5 ok

-O

r \

r \

Br

CH,

Y / \

ruby do. do. red

GOCH,

-0-a

- ^^ - NHC0CH3 do do.

ruby do.

do.

do.

do.

do.

do.

do. do.

8th

No

32

33

34

35

36

37

38

39

40

41

42

43

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46

47

CH 683 183 A5

R2

Nuance on PES

-c2h5

-ch3

-ch3

-c2h5

-ch3

do. -ch3 do. -c2h5

-ch3

do. do. do.

-Q

CF3 do.

-Q

0C0CH, do.

■ P

OCH

c00ch3

——COOCH3

——COOC2H5

-ch2ch2ocooch3

-ch3 do.

ruby do. do. do. do. do.

do.

do.

do.

do. do.

do.

do.

red ruby do.

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CH 683 183 A5

Table 1

Example R2 R5 nuance

No. on PES

48 -CH3

49 -C2H5

50 -CH3

51 do.

52 do.

53 do.

The dyes listed in Table 2 below correspond to the formula Ic rubin do.

do.

do.

do.

do.

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CH 683 183 A5

Table 2

E.g. DK R2 R3 R4 B nuance

No polyester

NO '

54 02N - / ^ y— -CH2C = CH -NHCOCH3 -OCH3 2-methoxy-navy blue

\ j phenyl

55 do. -CH2CH = CHC1 do. do. do. do. C00CH3

56 -CH2CH3 H H do. Scarlet fever

57 do. H H do. violet

H H 3-methoxy do.

phenyl

-NHCOCH3 H 2-methoxy- reddish phenyl violet do. H do. do.

H H 2-methoxy tan phenyl

H H 3-methoxy do.

phenyl

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CH 683 183 A5

Table 2

Ex. DK R2 R3 R «B nuance

No. Polyester nc- ^ N

63 {[_ 7- C4H9-n -CH3 H 3-methoxy-red f phenyl

CH2CN

64 do. -C3H7 do. H 2-methoxy-do.

phenyl no2

65 02N- ^ 3- -CH2C = CH -NHCOCH3 -0C2H40CH3 3-methyl-navy blue phenyl

66 do. -C2H5 -NHCHO do. 3-methoxy-do.

phenyl

67 -CH3 -CH3 H do. bluish ° 2 violet

68 02N - (/ -C2H5 do. H do. Reddish blue

SCN

69 do. CH3 do. H 3-methyl-do.

phenyl

H C CN

70 3 ß ^ -C2H5 do. H 2-methyl-red phenyl

71 do. do. do. H 2-methoxycar- do.

bonylphenyl

CH, CN

.CN

72 »\ do. do. H —CgHj do ”

CH2CH2CN

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CH 683 183 A5

Table 2

E.g. DK R2 R3 R4 B nuance

No polyester

73

^ V_CN ~ ^ 2H5

T

74 do.

C6H5

-ch3

-ch2ch2ococh3 H

-ch3 H 3-methoxy-phenyl do. H 2-methoxy

phenyl

H H 4-acetyl

phenyl

H H do.

H do.

-nhcoch3 -och3 -C6H5

bluish red do.

yellow-brown do.

do.

navy blue do.

-C2H5

do.

do.

do.

do.

do.

—CH2ch-ch2

do.

do.

do.

do.

do.

-ch2ch »chci do.

do.

do.

do.

do.

r- /

do.

N02

do.

do.

3-methoxy-phenyl do.

- do •

do.

do.

do.

do.

S

do.

îr

-C2H5

-nhcoc2h5

do.

2-methoxy

do.

phenyl

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CH 683 183 A5

Table 2

E.g. DK R2 R3 R4 B nuance

No polyester

/ N ° 2

85 02N-V V- -C2H5 -NHCOCH3 -OC2H5 2-methoxy- marine-

\ gr phenyl blue

86 do. -CH3 do. do. 3-methyl-do.

phenyl

87 do. -CH2CH2OCOCH3 do. do. do. do.

88 do. do. do. -OCH3 2-methoxycar- do.

bonylphenyl

89 do. -CH2C * CH -NHCOC2H5 do. 4-acetyl-do.

phenyl

90 do. -C2Hs -NHC0CH «CH2 do. 4-methyl-do.

/ N02 phenyl

91 02N- / ~ V- -CH2C = CH -NHCOCH3 -OC2H5 3-methyl- do.

M Πphenyl

Cl T, N

92 [I \\ do. do. do. do. do.

0HC

93 do. -C2H5 do. do. do. do.

94 do. -CH3 do. do. 3-methoxy-do.

phenyl

95 do. -C2H5 do. -OCH3 2-methoxy- do.

phenyl

96 do. —CH2CHsCHCl do. —OC2H5 do. do.

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CH 683 183 A5

Table 2

Example DK No.

Rs

R4 B

Nuance on

polyester

97

98

Cl

99 do.

-CH2C = CH -NHCOCH3 -OC2H5 2-methoxycar- marine-

bonylphenyl blue

-CH3 H H 2-fluorophenyl tan do.

H H 4-methoxy do.

carbonylphenyl

100

-C2H5 -CH3

103 do.

H

do. H

104 do. -CHj

H do.

reddish blue

H do. yellow-brown

H 2-methoxy-do.

phenyl H 4-methoxy-do.

phenyl H 3-methoxy-do.

phenyl

105 do.

106 02N

107 do.

Cl do. B

do. H

do. H

H 2-methoxy-do.

phenyl

H 4-methoxy-do. phenyl

H 3-methoxy-do.

phenyl

15

5

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CH 683 183 A5

Table 2

Example DK No.

R2 R3 R4 B

Nuance on

polyester

«/ V - <

108 "CHS

109 02N do.

110 02N

do.

H H 4-methoxy

phenyl

H

H

H do.

H do.

Ili 02N- / ^ ch2c = ch

Br

112 do. -C2H5

113o2n 114 do.

-c2h5

do.

cl y a c00c2hc

115 xy

NC

-NHCOCH3 -OC2H5 3-methoxy-

phenyl do. do. 2-methoxy

phenyl

H H do.

-CH3 H -CjH5

do. H 3-methoxy

phenyl yellow-brown do.

do.

navy blue do.

reddish blue violet

116 do. -C2Hs do. H -C6H5

do.

117 H5C6

.CN -n = n-Osdo.

H

H do.

navy blue

16

5

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40

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55

CH 683 183 A5

Table 2

E.g. DK R2 R3 R4 B nuance

No. Polyester s CN

118 H5Cfi-N = N- ^ gX ^ -CH3 - <"^ 3 ® 3-methyl-navy blue

, phenyl nc—

119 ^ | H H 4-chloro-do.

02nhTVn = n

\ = / -I

CH2CH20CH3 phenyl

120 do. do. H H 2-methoxy do.

phenyl hçc, —- n- n h '

121 3 0 // \\ -C2H5 H H do. red

122 do. -CH3 H H -C6H5 do.

S5C6 ~ J— $ ~ ° N

123 g V-CD, H H 2-methoxy-red

SS '

phenyl

124 do. do. -CH3 H -CgHs do. H3C h COOC2H5

125 -C2H5 H H do. red

126 do. -CH2CH-CH2 H H 2-methyl- do.

ci cn p1 "^ 1

127 —C2H5 -NHCOCHs H 3-methoxy-blue n phenyl n-oc2h5

CN

128 r = C do. do. H -C6H5 red h * c-Q-

129 do. ^ do. -NHCOCH2OCH3 h 2-methoxy- do.

phenyl

17th

5

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30th

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40

45

50

55

CH 683 183 A5

Table 2

Example DK No.

Rb

B nuance

polyester

130

.cn do.

HsC ~ V ^

cn.

131 do.

-CHCH2CH3

132 cl- £ v "CHs cn

133 rr® -CH3

o2N ^ s> ~

134 do. -CH2C = CH

135 do.

136 02N

-C2HS

^ -CH2CH20H 137 ° 2N -C2H5

-NHS02CH3 h 2-methoxy-4- do.

methylphenyl do do.

H 2-fluoro-phenyl

-NHCOOCH3 H 3-trifluoro- do.

methylphenyl -NHCOCH3 -OCH3 -C6H5 navy blue do. -0CH2CH3 2-methoxy- do.

phenyl do. -0CH3 -C6H5 do.

H

-Cl

H

H

do.

do.

do.

bluish ruby

139 02n.

no2

140 02N £} - _C2H5

141 do. \ (ji do. Cl

-c

142 02N - ^^ _ -CH3 Cl

-NHCOCH3 H 2-methoxy- reddish phenyl violet do.

-OCH3 do.

navy blue do. do. do. blue

-NHC0CH2CH3 -OC2H5 -C6H5 do.

H

H 4-ethoxy tan phenyl

18th

5

10th

15

20th

25th

30th

35

40

45

50

55

60

CH 683 183 A5

Table 2

Example DK No.

r2

r3

r4

Nuance on

polyester

143

1 // ^ CN

144 do.

145 02N- / ~ \ _

Eq

146 do.

147 do.

do. -ch3

-ch3

do. do.

-CH,

h h

148

02N

/ ° j ch2ch2ococh3 -nhcoch3

149

do.

'Br no.

do.

do.

\ C1 N0,

h 2-hethoxy- bluish tint-

phenyl violet h 2-fluoro violet phenyl

-ch3 3-nitro-yellow-brown phenyl h 4-fluorophenyl h 2-fluorophenyl -OCH3 2-methoxy-phenyl -ocb2ch3 —cçhs

15002N- / ~ V- "CH2 CHz 0C00CH3 do * - ° ch3

2-methylphenyl

/ 2nd

15102N / ~ V ~ CB2 lHCHa -NHC0CH £ H3

\ == / ococh3

Br do. 3-methoxy-phenyl do.

do. navy blue do.

do.

do.

The dyes in Table 3 below are prepared analogously to the information in Examples 1 to 6 and correspond to the formula Id

R4

(Id),

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55

Table 3

CH 683 183 A5

Example D No.

R3

r3

R4 Bx

TT

152 02 -CH3

/ C1

153 OjN- ^ V- do.

^ C1

154 do. do.

CN

Alkylene shade on

PES

155 02N

156 do.

157 do.

158 do.

do.

do.

do.

do.

Cl / CN 159 -C2H5

CHO

H H

H H

H H

H H

H H

H H

H -CH2CH2CH2- ruby

H

H H 3-0CH3

do. do.

2-OCH3

3-CH3

do. yellow-brown do. do.

do. ruby

—CH — CH2— do.

CH3

-CH2CH- do.

I.

CH3

-CH2CH2CH2CH2- do.

-CH3 H 2 -OCH3

do.

blue

160 do.

do.

161

C1X5- do-

(à

do. H 3 —OCH3 —CH2CH2CH2— do.

do. H do. do. bluish purple

162 do.

163 02N

164 do.

do. -NHC0CH3 -OCH3 do.

N0 "

Br

—CH2C = CH do. —0C2Hs do «

-CH2CH = CHC1 do.-0CH3 do.

do. blue do. do.

blue do.

20th

5

10th

15

20th

25th

30th

35

40

45

50

55

CH 683 183 A5

Table 3

E.g

. D

R2

r3

r4

Bi alkylene

Nuance on

No.

PES

165

02N- ^

nhcoch3

—Oc2h5

4-och3

ch2ch2-

blue

166

do.

-ch2c = ch do.

do.

do.

do.

do.

167

do.

do.

do.

-och3

4-c00c2h5

do.

do.

168

do.

do.

n0 "

do.

do.

4-c00ch3

do.

do.

169 02N- / ~

do.

do.

do.

do.

do.

170

Cl —jF

ux i cn —c2hs -ch3

H

3-CH3

do.

reddish blue ohc ^ s.

A

171

do.

do.

do.

H

2-0ch3

do.

do.

172

do.

-ch3

H

H

3,4-di-CH3

do.

violet

173

do.

-c2h5

-ch3

H

3-0CH3

do.

reddish blue

174

do.

-ch3

do.

-och3

2-CH3

do.

blue

175

Clj.— K

[do.

H

H

3-0CH3

do.

violet ohc ^ S-

176 do.

-C2H5

-ch3

H

2-0CH3

do.

do.

177

do.

H

-nhcoch3

-0CH3

3-CH3

do.

do.

178

do.

-ch2 =

CH do.

do.

do.

do.

blue

179

do.

do.

do.

—Oc2h5

4-0CH3

do.

do.

180

do.

-c2h5

-ch3

H

3-CH3

do.

violet

181

do. -

-ch2c = ch -

nhcoch3 -

0CH3

4-0CH3

do.

blue

182

do.

do.

do.

do.

4-0C2H5

do.

do.

Analogous to the information in the previous examples 1

to 6 also the dyes c following Table 4 are prepared.

21

5

10th

15

20th

25th

30th

35

40

45

50

55

CH 683 183 A5

Table 4

ch

) ~ YCIÌ3

D-N = N- ^ y.N ^ CH3

): h2ch2coo-b

Ex. D R3 B Nuance on PES

No.

no2

02n / 1

183 02N- ^ y- -CH3 3-methox- blue

\ phenyl

Br

184 do. -NHCOCH3 2-methoxy- do.

phenyl

185 do. do. -C6H5 do.

Cl-r-N

186 do. do. do.

> P

CHO

187 do. do. 2-methoxycar- do.

bonylphenyl

188 do. -CH3 2-methoxy- do.

phenyl cl ~ nrCN

189 (* ° * ^ ° * ^ ° "

cho ss'

190 do. -NHC0CH = CH2 4-fluoro- do.

phenyl

22

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

CH 683 183 A5

Example 199

16.3 parts of 2-amino-5-nitrobenzonitrile are stirred in 100 parts of cold sulfuric acid (93%) and 32 parts of nitrosylsulfuric acid (40%) are added at 0-5 ° within 30 minutes. The mixture is stirred for a further 3 to 4 hours at 0-5 ° and then the resulting solution is poured with stirring to a mixture of 13.5 parts of 3- (N-methyl-N-phenylamino) propionic acid 2'-methylphenyiester, 13.5 Parts of 4- (N-methyl-N-phenyla-mino) propionic acid, 4'-methylphenyl ester, 100 parts of glacial acetic acid, 2 parts of amidosulfonic acid, 200 parts of water and 500 parts of ice. The coupling mixture is blunted with sodium acetate. The precipitated dye mixture is filtered off, washed with water and dried in vacuo at 60 °. The mixture obtained consists of the following two dyes

/ = T / = \

"_R (W1 _ / = \ <w" 532ra,)

-CH2CH2-C0-Q— ^

and ^ 3

CN

M / = \ / "CH3

° 2N ~ ^ ~ / ~ N \ CH2cH2-co-o - ^ - ch3 (\ n »x. = 531nm)

It dyes polyester fiber material in ruby red shades with excellent fastness properties and is ideally suited for modern rapid dyeing processes such as the ®Foron-RD process.

Example 200

The procedure is as described in Example 3, but the 13.5 parts of 3- (N-methyl-N-phenylamino-no) -propionic acid 2'-methylphenyl ester are replaced by 13.5 parts of 3- (N-methyl-N-phenylamino) ) -propionic acid 3'-methylphenyl ester. The resulting mixture consists of the following two dyes

CN

/ _ / ch3

02 N- ^ ~ ^ - N = N- ^ ~ ^ -N

\ alca2-C0-0-6 A (> w. = 531nra)

CN rw

/ ch3 2

n v

and 0; N- (J-N.N-Q-N

nCH2CH2-C0-0- ^. ^ -CH3 (Xn, x. = 531 nm)

It dyes polyester fiber material in ruby red shades with excellent fastness properties and is ideally suited for modern rapid dyeing processes such as the ®Foron-RD process.

COLOR EXAMPLE

20 parts of the dye according to Example 1 are wet-ground in the form of the moist press cake with 80 parts of a commercially available dispersant based on lignisulfonates and atomized to a powder. 3.0 parts of this dyeing preparation are introduced into 2000 parts of demineralized water at 70 °, which contains 40 parts of ammonium sulfate. The pH of the dyebath is adjusted to 5 with 85% formic acid. 100 parts of cleaned polyester fiber fabric are added to this dyebath, the apparatus is closed, heated to 130 ° in the course of 20 minutes and dyed at this temperature for a further 40 minutes. After cooling, the polyester fiber fabric is made

23

5

10th

15

20th

25th

30th

35

40

45

50

55

CH 683 183 A5

taken from the dyebath, rinsed, soaped and reductively cleaned in the usual way with sodium hydrosulfite. This gives a clear, brilliant ruby-red color with very good fastness to thermal migration, washing, rubbing, light and sublimation.

Claims (6)

Claims 1. The disperse dyes of the general formula I ) -N = N - / "X— \ / N \ (I) ' / Rl 3rd wherein Ri phenoxycarbonyl-Ci-6-aikyi, the phenyl nucleus having up to two substituents from the group halogen, alkyl and alkoxy or one substituent from the group trifluoromethyl, hydroxy, nitro, formyl, cyano, rhodan, Ci_4-alkyicarbonyl, Ci-2- Alkylcarbonyloxy, aminocarbonyl, Ci-3-alkoxycarbonyl, C1-2-AI-koxy-C2-3-aikoxycarbonyl, Ci-4-AcyIamino or phenyl, R2 alkyl, alkenyl, haiogenalkenyl, alkynyl, cyanoalkyl, benzyl, phenylethyl, phenylpropyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkylcarbonyloxyalkyi or alkoxycarbonyioxyalkyl, or with R4 and the atoms in between, a heterocyclic six-membered ring which optionally has up to 3 methyl groups, or, if D is 2,4-dinitrophenyl or 2,4-di-nitrophenyl or a heterocyclic radical which is further substituted in the 5- or 6-position, also hydrogen R3 is hydrogen, halogen, hydroxyl or Ci-4-alkyl, or, if D is 2-cyano-4-nitrophenyl or three substituents or phenyl or a heterocyclic radical, also formylamino, Ci-3-alkyicarbonyla-mino, C2-3- Alkenylcarbonylamino, Ci_2-alkoxy-Ci-3-alkylcarbonylamino, Ci-4-alkoxycarbonylamino or Ci-3-alkylsulfonylamino, R4 is hydrogen, halogen, Ci-3-alkoxy or Ci-3-alkoxy-C2-3-alkoxy or with R2 a six-membered ring as described there and D is a diazo component of triazolyl, pyrazolyl, cyano-Ci-2-alkylimidazolyl, 4-chlorothiazolyl-2-, isot-hiazolyi-5-, benzisothiazolyl-3-, 1,3,4-thiadiazolyl-5-, 4th -Chlorthienyl-2 series, a 3-phenyl-1,2,4-thia-diazoiyl-5- or 5-nitrothiazolyl-2 radical, a phenyl radical carrying up to three substituents but free from sulfonyl groups or a rest of the formula CQOAlkyl or NC——> wherein a is cyan, alkoxycarbonyl, aminocarbonyl, mono- or dialkylaminocarbonyl or alkylcarbonyl, b is hydrogen, alkyl, phenyl or alkylcarbonyl, c cyan, pormyl, alkoxycarbonyl, mono- or dialkylaminocarbonyl, aminosulfonyi, mono- or dialkylaminosulfonyl or alkylcarbonyl, d hydrogen, methyl, halogen or nitro, e hydrogen, halogen, methoxy, cyan or nitro, f is hydrogen, methyl or phenyl, where the alkyl, alkenyl and alkynyl groups mentioned can contain up to 6 carbon atoms and the alkyl groups can carry one or two substituents customary in disperse dyes. 2. The disperse dyes of the general formula I, according to claim 1, wherein the diazo component D is a radical of the formula 24th 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 CH 683 183 A5 R, Cl » 7 wherein R5 is hydrogen, methyl, chlorine, bromine, cyan or nitro, preferably cyan or nitro, R6 chlorine, bromine, methyl, nitro or phenylazo, preferably nitro, R7 is hydrogen, chlorine, bromine, cyan or Ci-2-alkoxycarbonyl, preferably hydrogen, chlorine, bromine or cyan Rß formyl, cyan or a group of the formula -CH = C (CN) Rn, R9 is alkoxycarbonyl, nitro or cyan, preferably cyan and R11 is cyan or alkoxycarbonyl, or 5-nitrothiazolyl-2. 3. The dispersion dyes of the general formula I, according to claim 1 or 2, wherein D is 2-cyano-4-nitrophenyl, 2,4-dinitro-6-chlorophenyl or 2,4-dinitro-6-bromophenyl. 4. The disperse dyes of the general formula I, according to one of the preceding claims, wherein Ri corresponds to the formula. in which the two R12 independently of one another are hydrogen, fluorine, chlorine, methyl, methoxy, ethoxy or Ci_2-alkoxycarbonyl, R13 is hydrogen, fluorine, chlorine, bromine, methyl, methoxy, ethoxy, Ci-2-alkoxycarbonyl or phenyl and R14 is hydrogen, methyl, methoxy or ethoxy. 5. The disperse dyes of the general formula I, according to one of the preceding claims, wherein R2 methyl, ethyl, allyl, 2-methylallyl, chlorallyl, propynyl or Ci-2-alkylcarbonyloxyethyl, Ci-2-alkoxycarbonyloxyethyl, especially methyl, R3 is hydrogen, methyl or Ci-2-alkylcarbonylamino and R4 is hydrogen, hethoxy or ethoxy. 6. A process for the preparation of the dyes of the formula I according to claim 1, characterized in that a diazotized amine of the formula II D-NH2 (II) with an amine of formula III '3 (iii) couples. 25th