DE1444591A1 - Process for the preparation of new monoazo dyes - Google Patents

Description

CASSEUA FARBWERKE MAINRUR SHARE COMPANY fief. 2598 FRANKFURT OfAIN) -FECHENHEIM

File number: P Ik hh 591.1

Process for the preparation of new monoazo dyes .

It has been found that new valuable monoazo dyes of the general formula can be obtained

OH A ₂

(SO ₃ H) _n

where the phenyl nucleus of the diazo component has further substituents may contain

A _{1 is} hydrogen or the acylamino radical -.NXYZ,

R '

Ap denotes the aylamino radical -ii-X-ΐ-Ζ or another aliphatic

AR ¹
or aromatic acylamino radical,

η = 1 or 2,

X = '6O ₂ or GU,

Y is a saturated or unsaturated alkylene group with more as 1 carbon atom,

Z = SO ₂ , 30, 0 or S,

R = R ¹ or hydrogen and ·>

R ^{1 is} an alkyl, aryl, aralkyl, cycloalkyl or heterocyclic radical,

and which contain at least once the radical -N-X-Y-Z is obtained,

R R '

if one uses diazo compounds of aminobenzenes of the general formula which are optionally further substituted in the phenyl nucleus

809809/1049 / 2

Documents ca * 7 _s , _{Ah,; ?} IH. _r ..; - _:. ,,,, v, _change “. _v . _{4 9} -, "..

- 2 - Ref. 2598

2 with acyl-periaminonaphtholsulfonic acids from allrtrj common formula

Oh kr

couples, choosing the diazo and coupling components so that that the finished dyes at least once the radical -BT-X-Y-Z

RR ¹

contain, or that one on monoazo dyes instead of kcylamino radicals of the general formula -N-X-Y-Z free amino groups

RR ¹

aesitz, halides or anhydrides of organic acids, which len radical -X-Y-Z-R 'contain, allows to act, or that one monoizo dyes the general formula

OH NH ₂

(SO, H)

lit anhydrides. or halides more aliphatic or aromatic acylated arboxylic acids.

The new dyes are thus characterized in that they contain the -NXYZ radical once in the diazo component or in the RR ¹

coupling component or both included once. If the est -NXYZ is in the diazo component, then the acylamino-H · ¹

group of the coupling component also contain any aliphatic ier aromatic acyl radical; If the radical -XYZR ^{1 is} connected to the amino group of the periaminonaphtholsulfonic acids, then the diazo component need not carry any acylamino group. This means that the group -NXYZ can be used once or

809809 / tO49 * ^R '/ 3

Ref. 2598

can be present twice in the dye molecule.

The periaminonaphtholsulfonic acids used can

Be mono- and disulfonic acids, such as
1-amino-8-naphthol-4-sulfonic acid,

1- ti -8th- η _5- 1- , M -8th- η -6- " 1- It -8th- η -3,6-disulfonic acid 1- η -8th- η -4.6- " 1- π -8th- η -3.5-

The introduction of the residue -N-X-ϊ-Ζ in the periaminonaphtholsulfon-

RR ¹

acids or in the finished monoazo dyes with free amino groups takes place according to known methods by reaction with the carboxylic acid halides, Sulfohalides or carboxylic acid anhydrides in aqueous solution.

The new dyes can be used for coloring animal, vegetable and synthetic fibers are used; they are distinguished in particular by the fact that they are used to wash cellulose fibers can dye or print if you use the dyes as a solution or suspension in the presence of alkaline agents, in particular reacts with the fiber at a higher temperature or by dry heating.

After rinsing and soaking, vivid red to purple or blue colors are obtained.,

The dyes are characterized on the one hand by good resistance to alkali and on the other hand nonetheless by good fixability from what could not be foreseen.

Example ii

38.4 kg of 1-amino-3- (β-phenylsulfonylpropionylamino) -benzene-6-sulfonic acid are dissolved with the necessary amount of water and soda. For this purpose, it is about 7.0 kg of sodium nitrite and the mixture is at about 15 - 20 ° run in submitted excess dilute hydrochloric acid.

■ 80 980 9/1049 / ₄

Ref. 2598.

~ ⁴ * U44591

The diazo suspension obtained is combined in the presence of excess Sodium bicarbamate with an aqueous solution of the sodium salt of 56 kg of 1- (ß-phenylsulfonylpropionyl) -amino-8-naphthol-3,6-disulfonic acid. Once the coupling has ended, it becomes weak with acetic acid acidified and salted out with potassium chloride. The dye forms a red water-soluble powder after filtering and drying, that printed in the presence of soda and alginate thickening, after steaming, rinsing and soaps on bright blue-tinged red prints Cotton or regenerated cellulose supplies, which are very good wet and lightfast. Wool or silk become luminous from an acidic bath colored scarlet.

The diazo component used is 1-amino-4- (ß-phenylsulfonylpropionyl aminobenzene-2-sulfonic acid, a dye is obtained which is in full ruby tones.

In the following, a number of other dyes are listed that with the same coupling component, but different diazo components received:

Diazo component shade

Aniline scarlet

3-chloroaniline scarlet red

4- ". Red

2-toluidine bluish red

3- "'red

4- "- bluish red m-xylidine red

p- "ruby

6-chloro-2-toluidine red

5- "-2-" * ruby red 1-amino-2-methoxy-5-methylbenzene purple 2-aminobenzoic acid red

2-aminobenzenesulphonic acid "

809809/1049

Diazo component

-Amino-4-benzoylamino-2,5-dimethoxybenzene

«-4-acryloylaminobenzene I- ⁿ ^ -acryloylamino ^ -methoxybenzene-toluidine-4-sulfonic acid

-3-chloroaniline-6-sulfonic acid

Chloro-5-toluidine-4-sulfonic acid

»-4-« -5- » Sulfo-2-aminobenzoic acid

«_2-" (Cu connection)

Hitro-4-aulfo-2-aminophenol (Cu compound) Chlor-6- "-2- ^w (Gu compound)

Ref. 2598

hue

blue red-violet violet red bluish red red scarlet red red red red bluish red

M Il

violet violet

4,6-Dinitro-6-sulfo-2-aminophenol (Cu compound) dark purple

Example 2;

24.2 kg of 1-amino-4- (ß-methylsulfonylpropionyl) -arainobenzene are dissolved with dilute hydrochloric acid while cooling with ice and diazotized by adding an aqueous solution of 6.9 kg of sodium nitrite. The diazo solution is allowed to run into an aqueous solution of the sodium salt of 44 kg of 1-benzoylamino-8-naphthol-3,6-disulfonic acid containing excess sodium carbonate. After the dye has formed, it is warmed up and " salted out with 10" potassium chloride. After filtering and drying, the dyestuff forms a dark red, water-soluble powder and, after the printing and spraying process in the presence of soda, gives lively, full red-violet shades of very good wet fastness and good etchability on cotton.

8098.09 / 1049

Ref. 2598

The above; The dye described can also be found in the Prepare way that the diazo solution mentioned in paragraph 1 in the presence of sodium carbonate with a solution of the sodium salt of l-amino-e-oxynaphthalene-.}, 6-disulfonic acid combined and acylated the aminoazo dye thus obtained in the presence of sodium bicarbonate with benzotrichloride.

The corresponding dye from 1-amino-4- (ß-ethylsulfonylpropionyl) -amino-benzene has similar properties and also leads to vivid red-violet tones.

If the acylperiamino-naphtholsulfonic acids mentioned below are used as coupling components, the following are obtained named shades

1-acetylamino-8-naphthol-6-sulfonic acid
1- · "-8-" -4- "
1- "-8-" -5- "
1-ßenzoylamino-8-naphthol-4,6-disulfonic acid 1- "-8-" -3,5- "
! - (Benzenesulfonamido) -8-naphthol-3,6-disulfonic acid 1_ (4'_Chlor-2 ', S'-dimethylbenzenesulfonamido) -8-

naphthol-3> 6-disulfonic acid

ruby red red-violet

It

ruby red red violet r.uby
red-violet

809809/1049

- 7 - ^{Ref 2} 598

Example 3 *

25.6 leg 1-amino-3- (ß-ethylsulfonylpropionyl) -amino-benzene become diazotized in the process listed in Example 2. The diazo solution is with an aqueous solution of the sodium salt of 44 kg of 1-benzoylamino-8-naphthol-3,6-disulfonic acid combined in the presence of excess sodium bicarbonate. After separating, filtering and drying gives a dark red water-soluble powder. When printing in the presence of soda, after steaming, one obtains Rinse and soap full, vivid bluish red prints with very good lightfastness and good lightfastness and etchability.

If the same diazo compound is combined with a solution of 1- (ß-phenylsulfonylpropionyl) -amino-8-naphthol-3,6-disulfonic acid, in this way a dye is obtained which gives particularly full blue-tinged red hues.

In the following there are some other colors that can be obtained with the diazo and coupling components listed below:

Diazo component, coupling component, color shade

i-Benzoylamino-8-naphthol-blausti-3, "6-disulfonic acid chig red

NH.CO.OH ₂ .CH ₂ .

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Diazo component Coupling component

Ref. 2598

hue

SO, H

./ i-chloroacetylamino-8-naphthol-3,6-disulfonic acid

bluish red

i-Methoxyacetylamino-8-naphthol-3 »6-disulfonic acid

1- (o-chlorophenoxyacetylI-amino-e-naphthol ^ > 6-disulfonic acid

i-Äcetylainino-8-naphthol- red. 4,6-disulfonic acid

NH.CO.GH ₂ .CH ₂ . ι

Red

1-acetylamino-8-naphthol 3 , 6-disulfonic acid

ruby

NH,

. 3O ₂ . CH ₂ . CH ₂ . ο 1-Benzoylamino-S-naphthol- red-violet 3,6-disulfonic acid

Ή. CO. CH ₂ . CH ₂

809809/1049

Eef. 259β - 9 -

Diaz o component, coupling component, color shade

Cl

JLma t-acetylamino-S-naphthol- red

f ^ j ^ Z 3f6-disulfonic acid

BH.CO ^ CH ₂ .CH ₂ .

CH ₅

i-Benzoylamino-8-naphthol ruby 3 »6-disulfonic acid

m CO »CHo · CHr> · SOp · CH

1- (ß> phenylsulfonylpro-

pionyl) amino-8-naphthol 3t6-disulfonic acid

HH. CO. CH ₂ . CH ₂ .

MH _?

"red-violet

NH. CO. CH ₂ . CH ₂ . S0 ₂ - / ~ \

bluish red

CH ₂ . CH ₂ . SO ₂ -C ₂ H ₅

SH. CO. CH ₂ . CH ₂ . SO ₂ . 0Η ₂ - / ~ Λ

809809/1049

Ref. 2598

Diazo component Coupling component color

CH -CH 2 ~

NH.CO.CH ₂ .CH ₂ .SO ₂ .CH. 1- (ß-Phenylsulfo- bluusti- <L 2 \ nylpropionyl) -amino- chy red

Oil,

CH ₀ -CH,

. CO. CH ₂ . CH ₂ . S- / N 8-naphthol-3,6-di-8μ1ίonic acid

l-benzoylamino-8- bluish tint naphthol-3 * 6-disulfone red acid

NH.

NH

.00.CH ₂ -CH ₂ -SZ ^{- NO}

HO ^ S

NH,

^r xx

. CO. CH = CH.

! I

NH,

. CO. CH = CH

. 0-Z N

H,

N CH

CH,

CO.CH ₂ .CH ₂ .SO ₂ .C ₂ H ₅

NH,

.CH ₀ .CH ₀ .SO ₀ .CH ^{2 2} ruby

l- (ß-chloropropionylamino) -8-naphthol- >, 6-disulfonic acid

'^ 09809/1049

Diazo component

Ref. 2598

Coupling component . hue

00.CH ₂ -CH ₂ -SO ₂ -CH,

CO.CH ₂ .CH ₂ .SO ₂

l-acetylamino-8- bluish naphthol-.?* 6-disul- red fonic acid

l-Benzoylamino-8-ruby naphthol-3 * 6-disulfonic acid

Example 4

15 kg of l-amino-4-acetyl-aminobenzene are diazotized in the usual way. The diazo solution is combined with an aqueous solution of J2 sodaalkalischen kg l-amino-8-naphthol-j5 * 6-disulfonic acid. The dye solution obtained is adjusted to a concentration of 5 % of the latter with solid sodium hydroxide and then heated to 95-100 ° for 1 hour. After neutralization with hydrochloric acid, the monoazo dye formed is deposited with rock salt, filtered off and redissolved in water. This solution is stirred in the presence of excess sodium bicarbonate with an excess of β-phenyl-sulfonyl-propionic acid chloride at 10-20 ° until no more diazotizable amino groups can be detected. The monoazo dye thus obtained is salted out with potassium chloride and filtered off. After drying, it forms a dark red, water-soluble powder and, after printing and steaming on cotton in the presence of soda, produces lively, full, ruby-red tones with very good wet fastness.

809809 / 10Λ9

Claims (1)

- 12 - Kef. 2598 Claim Process for the preparation of new monoazo dyes of the general formula OH A ₂ where the phenyl nucleus of the diazo component has further substituents may contain A _{1 is} hydrogen or the acylamino radical -Ii-XYZ, ρ pt Α «the acylamino radical -H-X-Y-Z or another aliphatic RR ^r or aromatic acylamino radical,
η = Γ or 2,
X = SO ₂ or CO,
Y is a saturated or unsaturated alkylene group with more than 1 G atom, Z = SO ₂ , 30, 0 or i3,
R-JR ¹ or hydrogen and
R ' ^{f is} an alkyl, aryl, aralkyl, cycloalkyl or heterocyclic Rest mean
and which contain the remainder -NXYZ at least once, thereby R R ' characterized in that diazo compounds of "given in the phenyl nucleus" if further substituted aminobenzenes of the general formula. 809809/1049 . · Fief. 2598 - 1 ₃ - ** with acyl periaminonaphtholsulfonic acids der general formula OH A (SO ₃ H) _n coupling, wherein one so selects the diazo and coupling components that the finished dyes at least once the radical -NXYZ RR ¹ contain, or that one on monoazo dyes which instead of acylamino radicals of the general formula -NXYZ free amino groups RR ¹ own, halides or anhydrides of organic acids which contain the radical -ZYZR ', allowed to act, or that one monoazo dyes of the general formula OH R · 1 < ^S0 3 ^H) n with anhydrides or halides more aliphatic or aromatic Acylated carboxylic acids. 809809/1049