CH617713A5 - Process for preparing dyes - Google Patents

Description

617 713

2nd

PATENT CLAIMS I. Process for the preparation of dye mixtures, characterized in that one by reacting x mol of a compound or a mixture of compounds of the formula coom

(I).

wherein

Rj and R2 each represent hydrogen, halogen, hydroxy, optionally substituted alkyl or alkyloxy and

M is hydrogen or an equivalent of a cation and (1-x) mol of a compound or a mixture of compounds of the formula pu i

12

• Dlfll

12

e; 2

(VI),

r; 8-n = n

^ p) -N = N

Ru

(S (VVi

(VII),

r

(II),

wherein

R3 is hydrogen, halogen, hydroxyl or optionally substituted alkyl or alkyloxy and

R4 is hydrogen, halogen, hydroxy or optionally substituted alkyl or alkyloxy,

where x is 0 to 1 and at least 0.5 mol of the compounds used contain a COOM group, with at least 0.6 mol of formaldehyde or the corresponding amount of a formaldehyde-releasing compound, a coupling component mixture obtainable under acidic conditions, diazo compounds of one or more amines D -NH2 couples, 40 wherein D is the remainder of any diazo component occurring in azo dyes, at least one of the amines used being D-NH2 of the formula

- »corresponds to

wherein

R'12 hydrogen, chlorine, methyl, methoxy, sulfo, carboxy, arylamino or acetylamino,

R "12 is hydrogen, chlorine, methyl or methoxy, R '", 2 methyl, methoxy, chlorine, sulfo, carboxy, arylamino or acetylamino,

R "" 12 methyl, methoxy or chlorine,

R '13 is a radical of the formula r8-n = n or

R "-N = N 18

(a '),

(s0 "m) j m-1

(b%

RÏ2

Rj -N = N

nh,

R "i3 is a radical of the formula e; 2

(ni),

RJ3 - »- N

k;

Re

M-

(a "),

(so m) J m-1

(iv),

Tjllll

12

R '] [3-N = N

nh "

0> ").

65

ntt 1

12

(V),

8 VT /

Rio

(c ").

R11

3rd

617 713

R18 ~ N = N

or

The invention is a further development of the invention of dyes or dye mixtures described in main patent 599 250 and relates to the use of special (d ") amines as diazo components in the preparation of the dyes

s fabrics and partly also the use of special coupling components.

The invention thus relates to a process for the preparation of dye mixtures which is characterized in that by reacting x mol of a compound or a mixture of compounds of the formula

Rig-N = N

ó m-i

(e "),

OH

1 ÇOOM

X.

(I),

R's hydrogen, methyl, methoxy or nitro, R'6 hydrogen, chlorine, methyl, methoxy, nitro or carboxy,

R'7 is hydrogen, chlorine, methyl, hydroxy, carboxy or sulfo,

R '«hydrogen, chlorine, methyl or nitro,

R'y hydrogen, chlorine, methyl, methoxy, nitro, sulfo or carboxy,

R'io hydrogen, chlorine, methyl, methoxy, hydroxy, carboxy or sulfo,

R 'j! Hydrogen, chlorine, methyl, methoxy, sulfo or carboxy,

m 1,2 or 3,

R ', 8 is a radical of the formula (a ") or (b"),

R "18 is a radical of the formula (c"),

wherein

Rj and R2 each represent hydrogen, halogen, hydroxy, optionally substituted alkyl or alkyloxy,

and

M is hydrogen or an equivalent of a cation and (1-x) mole of a compound or a mixture of compounds of the formula

n = n

(C),

(II),

.N

V

(d '),

H3C SÖ3M

or o2N

mo3s

(e ').

wherein

R3 is hydrogen, halogen, hydroxyl or optionally substituted alkyl or alkyloxy,

and

4 p

R4 is hydrogen, halogen, hydroxy or optionally substituted alkyl or alkyloxy,

where x is 0 to 1 and at least 0.5 mol of the compounds used contain a COOM group, with at least 0.6 mol of formaldehyde or the corresponding amount of a formaldehyde-releasing compound, a coupling component mixture obtainable under acidic conditions, diazo compounds of one or more Coupled amines D-NH2, wherein D is the residue of any diazo component occurring in azo dyes, at least one of the amines of the formula used

R'I9 is hydrogen or hydroxy and

M is hydrogen or an equivalent of a cation.

II. The dye mixtures prepared by the process according to claim I.

III. Use of the dye mixtures according to claim II for dyeing non-textile substrates which can be dyed with anionic dyes.

p "

12

Ri3 "N = N

NH,

(HI),

RÌ2

617 713

4th

r'3-n = n

RÏ3-u = N

rj

(so m)

3 m-1

(IV),

(a "),

R7

(v),

fso_m). 3 m-1

(b ").

R-

r; 8-n = r-

or

N = N

p11 '

12

r "" 12

r'e-n = n

(C "),

Rii

(d "),

■ n = n

* 12

-i ^) - J {SOnM) «or

J m-1

(vii),

r'8-n = N

corresponds to what

R'12 hydrogen, chlorine, methyl, methoxy, sulfo, carboxy, arylamino or acetylamino,

R "l2 hydrogen, chlorine, methyl or methoxy,«

r "', 2 methyl, methoxy, chlorine, sulfo, carboxy, arylamino or acetylamino,

R "" 12 methyl, methoxy or chlorine,

R 'I t is a radical of the formula fso m) n 3 m-1

(e "),

R'5 is hydrogen, methyl, methoxy or nitro,

R'6 hydrogen, chlorine, methyl, methoxy, nitro or carboxy,

rl ^ g — n = n-

or r "0 n = n-

lo

R'7 is hydrogen, chlorine, methyl, hydroxy, carboxy or sulfo,

R'ij hydrogen, chlorine, methyl or nitro, 511 R'9 hydrogen, chlorine, methyl, methoxy, nitro, sulfo or carboxy,

R'io hydrogen, chlorine, methyl, methoxy, hydroxy, carboxy or sulfo,

R'u is hydrogen, chlorine, methyl, methoxy, sulfo or carb- (a '), 55 oxy,

m 1,2 or 3,

R'lg is a radical of the formula (a ") or (b"),

R "18 is a radical of the formula (c"),

* so, m), 3 m-1

(b ')>

(c ').

R "13 is a radical of the formula

R «2

5

617 713

H3C S'03M

or

° 2

mo3e

W).

(»').

M is hydrogen or an equivalent of a cation.

If the radicals R '| 2 and R "i2 in the above formulas are both not hydrogen, the azo groups or azo group and amino group bonded to the same benzene nucleus are preferably para-to one another; the two radicals R'12 and R" i2, and R "'| 2 and R" "12 are then preferably para to one another. Arylamino preferably stands for

R9

8 N "~

r

Rio

R ',,, hydrogen or hydroxy and

Preferred dye intermediate mixtures are those wherein x is 0.8 to 1.

Preferred amines of the formula (I) correspond to the formula

° 2

(I ').

or

Preferred amines of the formula (II) correspond to the formulas so3m

(I "),

'so m

(II '),

617 713

° 2

(II "),

scyi and

O.

in

so3m

The diazotization of the amines of the formulas (III) to (VIII) and the coupling to the corresponding dye intermediate mixtures were carried out e.g. as described in the main patent. Salicylic acid is preferably used as the compound of the formula (I) and resorcinol is used as the compound of the formula (II) and 1-4 mol of diazo compound are advantageously used per 4 mol of salicylic acid.

The dyes obtained can be used for dyeing textile or non-textile substrates as described in the main patent and have good dyeing properties, particularly on leather.

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

example 1

276 parts of salicylic acid, 100 parts of 20% sodium hydroxide solution and 42 parts of raraformaldehyde are stirred at 98 ° for 10 hours. The resulting viscous melt, which no longer has an odor of formaldehyde, is mixed with 550 parts of 40% sodium hydroxide solution and made up to 1000 parts with water.

(II '"),

S03M

Example 2

276 parts of salicylic acid, 130 parts of 30% sodium hydroxide solution and 51 parts of paraformaldehyde are stirred for 10 hours at 98 °. The resulting viscous melt, which no longer has an odor of formaldehyde, is mixed with 500 parts of 40% sodium hydroxide solution and made up to 1000 parts with water.

Î5 Example 3

138 parts of salicylic acid, 75 parts of 10% sodium hydroxide solution and 24 parts of paraformaldehyde are boiled under reflux for 2 hours and then, within 1 hour, 22 parts of resorcinol dissolved in 20 parts of water are added dropwise at the boiling point.

4o 4 parts of paraformaldehyde are then added and the mixture is boiled under reflux for 5 hours. The condensation product is mixed with 80 parts of 30% sodium hydroxide solution and, for further reaction with water, made up to 500 parts.

45

Example 4

54.3 parts of the aminomonoazo dye of the formula prepared in the customary manner

° 2

E ° 3H

are suspended in 350 parts of 3% hydrochloric acid and 7 parts of sodium nitrite in the form of a 25% aqueous solution are added dropwise at 5 °. After the end of the diazotization, 22.3 parts of l-aminonaphthalene-6-sulfonic acid, dissolved in 140 parts of 3% sodium hydroxide solution, are added, the pH of the

The suspension was adjusted to 5.5 by adding 30% sodium hydroxide solution and, after the coupling had ended, the amino disazo dye was salted out by addition of sodium chloride and suction filtered. The paste is then suspended in 350 parts of 3% hydrochloric acid and at 5 ° with 7 parts of sodium

7

617 713

nitrite, in the form of a 25% aqueous solution. After the end of the diazotization, the diazo suspension is run into an initial charge of 100 parts of the condensate solution prepared according to Example 1, at 5 ° and at pH 13, the pH 13 being maintained by adding sodium hydroxide. Then a further diazo suspension, prepared as usual by diazotizing 31.9 parts of 4-amino-4'-nitro-diphenylamino-2 'sulfonic acid, is allowed to run in at 5 ° and pH 13.

The resulting dye is isolated by adding sodium chloride and hydrochloric acid. It is dried, a brown powder, which dyes leather in level brown tones.

A dye with similar good properties is obtained if, instead of the condensation product prepared according to Example 1, 100 parts of the condensate solution prepared according to Example 2 are used and the procedure is otherwise the same as above.

Likewise, a dye with similar good properties but with a redder shade is obtained if, instead of the condensation product prepared according to Example 1, 100 parts of the condensate solution prepared according to Example 3 are used.

The following table shows the composition of dyes according to the invention and the color of the dyeing on leather. They can be produced analogously to the information in example m 4.

Mean:

n! Number of moles of the 1st diazo component! s n2 number of moles of salicylic acid used to prepare the condensation product n3 number of moles of the second diazo component.

table

Example nj 1. Diazo component no.

nh - @ - n = n-0-n = n - @ - nh.

i rorS03H

no,

<c> so3h

<o>

S ° 3H

n2 condensation product produced

2 Example 1

2. Diazo component nuance of

Coloring on

Leather brown

6 1

do.

2 Example 3

do.

7 1

do.

o-n

V- \

2 Example 1 1 nh — l * qj so3h do.

i _ ^ ~ so_h i N = N- ^ 3 H2 '0CH •

ch "3

do.

2 Example 3 1

02n nh — so h.

^ - # ° 3H d ° -

och3

ch3

9 1

do.

2 Example 1 1 H N - @ - N = N - @ - SO H do.

2 3

10 1

do.

2 Example 3 1

do.

617 713

8th

Example No.

11

ti, 1st diazo component

! hn - @ - n = n- © -n = n - @ - nh.

sö3h p

s ° 3h

<p> s / o3h n2 condensation product produced as in

2 Example 1

2. Diazo component

Nuance of

Coloring on

Leather brown

12 1 do. 2 Example 3 1 do.

13 1 do. 2 Example 1 1 H N - ^^ - C — do.

2 \ J

S0 "H

14 1

15 1

hn-®-n = n - @ - n * n - @ - nh.

, —V 2 2 Example 3

IS s ° 3H P P

^ j so h so h no2

HN- © -N = N - @ - N = N- © -NH2

SO H 2 Example 1

do.

do.

do.

COT 3

so3h

16 1

do.

2 Example 3

do.

Example iij 1. Diazo component no.

so "h ch.

o n - ^^ nh-®-n = n - @ - n = n- £ $ -nf

17th

<o>

SO ^ H

F NH2

NH

ûf® ° 2

Io3h

18th

do.

19th

do.

20th

do.

21st

do.

22 1 * do.

23 1 do.

n2 condensation product manufactured as in

2 Example 1

2 Example 3

2 Example 1

2 Example 3

2 Example 1

2 Example 3

2 Example 1

24 1

do.

2 Example 3

2. Diazo component h î5-§-c = n # ch3

Xs SO "H

SO ^ H

H2N - €> -NH - ^> - N02

do.

h 2 n. - © -n = n - @ - s o ^ h do.

och3

S ° 3H

h-N - @ - N = N- @

Nuance of

Coloring on

Leather brown do.

do.

do.

do.

do.

do.

och3 s03h n - ^ - n = n- ^

do.

Example nt 1. Diazo component n2 condensate

jsjr, tion product manufactured as in

. So "h ', ch3

2nd

25 1 0oir ^ -NH- © -N «N- © -K = N - ^ - NH2 Example 1

/ rVS?! ?? »

.oj> nh 3 "

so, h CoT * '° 2

26! s03h do. 2 Example 3

27 i do. 2 Example 1

28 1 do. Example 3

29 1 do. 2 Example 1

30 1 do. 2 Example 3

31 1 do. 2 Example 1

32 1 do. 2 Example 3

33 i do. 2 Example 1

n3 2nd diazo component shade s *

the -1

Coloring J *

on W

Leather brown no

2nd

do.

h2n- <§> - nh - <q>

so3h do.

do. do.

do.

H2N- © -C = N-0-CH3 do.

^ s'so h do.

do.

ch "och, \ o \ i

1 h2n- <c) -n = n <q>

do.

nh

è- ™ 2

so3h so3h do.

do.

so h

1 K2N - <^ - C = C - ^> - N02 do.

ho3s h h

Example ni 1. Diazo component n2 condensate

No ion product manufactured as in

. so h 'ch3

1 02N - ^ - NH-®-N = N - ^ - N = N - ^ - NH.

34 1 u2 ^ J.sxa2 2 Example 3

\ Q> NH

s03h (^ fn02

so3h so3h och3

35 1 b ^ - ^ ~ nh- ^ q) ~ n = n "© ~ îî = n" ^ 'kh2 2 ex. 11

'z p so k

36 1 I do. 2 Example 3

37: 1 1 °. 2 BelspidI

38 1 do. 2 Example 3

39 1 do. 2 Example 1

40 1 do. 2 Example 3

41 1, do.

42 1 do.

2 Example 1 - Example 3

2. Diazo component nuance of

Coloring on

Leather so3H

2 ^ ~ <^ C C-b N02 brown ho3s h h do.

do.

S ° 3K

H2N - @ - NH - ^ - N0 dodo.

do.

H2N-®-N = N - @ - SQ'H do.

do.

do.

H2N-p-N = N-q do.

oh so h and y

do.

do.

1. Diazo component n2 condensation product produced as in

S .- <^ - NH-®-N = N - @ - N = N- <g> -NU1 2 Example 1

PP

S00h so h do. Example 3

do. 2 Example 1

do. 2 Example 3

do. 2 Example 1

do. 2 Example 3

n02 och,

(S - <§) -nh- <q> -n = n- <g) -n = n - ^ - nh, 2 examples

<o>

so3h do. 2 Example 3

n3 2nd diazo component nuance of

Coloring ÏÎ

on w

leather

- 2 r Ns0 H brown

OCH. 3rd

do.

so -h \ 3

1 H2N - <g> -NH - @ - N02 do.

io

1 do. do.

do.

do.

Example rij 1. Diazo component n2 condensate

No ion product manufactured as in

NO 2 CCI "s

51 1 H03S 2 Example 1

so3H

52 1 do. 2 Example 3

53 1 do. 2 Example 1

54 1 do. 2 Example 3

55 1 do. 2 Example 1

56 1 do. 2 Example 3

57 1 d ° - 2 Example 1

58 1 do. 2 Example 3

2. Diazo component nuance of

Coloring on

leather

2N- <0) -N = N- <0> -S OH brown do.

do.

ï - N -4çfr-N = N- © -N = N- © - SO

(â>

S03H

do.

do.

do.

H2N brown

S03H

do.

do.

Example 1. Diazo component n2 condensate

No ion product manufactured as in

59

SO, H OCH, CH,

3 / o / 3

1 02N - ^) ~ NH-XQ> -N = N - ^ - N = N- <P ^ -NH2 2 Example 1

NH

SO H

60 1 do. 2 Example 3

61 1 do. 2 example!

62 1 - do. 2 Example 3

63 1 Na "C- © -N = N - @ - N = N- <S) -NK) 2 Example 1

'H., C' i S © B *

3 SO H / r

3 S03H S03H

64 1 do. 2 Example 3

65 1 MO S - @ - N = N- © -N = N - @ - N = N - @ - NF2 Example 1

SO3H so3H

66 1 do. 2 Example 3

2. Diazo component nuance of

Coloring on

leather

K2N - <0> -NK-p-N02 brown S ° 3h

- do.

H.Kdo.

do. do.

do.

do.

do.

do.

Example rij 1. Diazo component n2 condensate

No ion product manufactured as in

67 1

0_N- <Q> -CK = CH-O-N = N- <C) -N = N- © -NH_ Example:

2 \ / fa J

sooh s0_ h © (q> j 3 //

so h so k

68 1

do.

2 Example 3

69

71

so tall.

3/3

1 ^ -N = N - ^ - N = N- © -N = N - @ - NH, 2

P

(c)

s03h s03h

70 1

do.

so3h och 3

p so3h

72 1

73 1

do.

example 1

2 Example 3

1 02N - <^ - NH- <Q) -N = N-O-N = N - ^ - NI ^ 2 Example 1

F * CH.

/ och,

0 2 N - ^ - CK = CH- <g> -N = N- © -N = N- <g) -KK ^

2 Example 3 3 Example 1

74 1

so h so h p '

so3H

do.

Example 3

2. Diazo component nuance of

Coloring on

Leather do.

do.

do.

do.

do.

SÒH N - @ - NH- <O> -N0,

do.

do.

do.

1. Diazo component n2 condensation product produced as in

SO rl CCH,

\ / 3

© -N = N- © -N = N- <g> -N = N- <gv-NH2 2 Example 1

SO "K SO" M

3 '

do. 2 Example 3

do. 2 Example 1

do. 2 Example 3

, 0- ^ © -NH - @ - N = N- © -N = N - <^ - NH., 2 Example 1

i 2 \ (c) H 2

no p / y

SO, H SO, H

do.

2 Example 3

f ^ N, * C - ^ - N = N - @ - N «N- € ^ -Na 2

<g> @

example 1

i v. j i> - ^; - \ /.

H „C ■

i03 "h SO 3 h s03h do. 2 Example 3

n3 2.Diazo component shade 2

the ^

1

Coloring on

leather

s03h

H N- <Ü) -NH - ^ - NO brown do.

do.

OVER SOM

\ —J / 3

H2N- © -N = N-g)

do.

do.

do.

S 0oH

H2N- <g) -NH- <Ç> -N02 do.

do.

do.

do.

do.

1

do.

do.

1. Diazo component ^ condensate_

tion product manufactured as in

N ^ / CH3

"R> ^ J ^ C ^ -N = N- <g) -N = N- <5) -NK12 Example 1

3 ioi • :: h p *

érso2 SO3K

d ° - SO ^ H 2 Example 3

£ 03H OCÇ

02N "^ © ~ NH ~ © -N = N - <^ - N == N -! G> -NH, | 2 Example 1

P '

. so3H

d ° - 2 Example 3

do. 2 Example 1

2 Example 3

'SO3H H3CO / 0CH

& 2K- © -NH- (g> -M = N - ^) - N-N- <g.-KH 2 Example 1

d ° '2 Example 3

d0- 2 Example 1

do.

Example 3

2. Diazo component nuance of

Coloring on

leather

SO*

NO, brown do. do.

do. do.

do. do.

3 '

H N - ^ 5} -N = N- ^

0CKo SO K

do.

do.

do. do.

do. do.

H2N- © -NH- <§> -NO, d „. BoJ 2

do.

do.

Example iij 1. Diazo component n, condensate

No ion product manufactured as in

XN ° 2 "0CH2 Oca

98

99

93 1 ho_ S ^ - ^ H- ^ ~ N = N- <Q) -N = N- <b> -nh 2 Example 1

94 1 do. 2 Example 3

95 1 do. 2 Example 1

96 1 do. 2 Example 3 gy j do. 2 Example 1

do. 2 Example 3

do. 2 Example 1

100 1 do. 2 Example 3

The dyes of Examples 4 to 100 above can be used as in Dyeing Examples A-D of the main patent and give level leather dyeing with good fastness properties.

C.

2. Diazo component nuance of

Coloring on

leather

H, N- © -NH-p-N ° 2 baun H07S

do. do.

H2N ~ © ~ nh- © -S03H do.

no2

do. do.

NH-jQ> -S03H

pj "^ no do.

Z /

CH3

do. do.

0ch3 so3h

H2N- ^ Q> -N = N- ^ do.

do.

do.