DE1644382B - Process for the production of disazo dyes and for dyeing or printing plastic material or paper - Google Patents

Description

SO,

R ₁ -CO-CH-CO -NH-A

"5

- OH

-R,

OH N

wherein the phenyl nuclei A by fluorine, chlorine or bromine atoms, low molecular weight alkyl or Alkoxy groups, nitro, cyano, trifluoromethyl, methylsulfonyl, aminocarbonyl, low molecular weight Alkylaminocarbonyl, phenylaminocarbonyl, Aminosulfonyl, low molecular weight alkylaminosulfonyl. Phenylaminosulfonyl, low molecular weight alkoxycarbonyl, low molecular weight alkanoylamino and benzoylamino groups may be substituted.

R _{1 is} an optionally substituted, low molecular weight alkyl group, preferably a methyl group.

R _{2 is} an optionally substituted phenyl or naphthyl radical, such as the nuclei A.

R, a methyl, methoxycarbonyl. Ethoxycarbonyl, aminocarbonyl. Methylaminocarbonyl or Phynylaminocarbonylgruppc denotes.

ti adurchgeke η η ζ cich η c t. that one 1 mol ♦ ines tetrazoticrten diamine of the formula
SO,

H ₂ N-

> -nh,

(IV)

Shark shark

with 2 moles of a coupling component or 2 moles a mixture of coupling components of the formula

X ₁ H

wherein X, has the abovementioned meaning, converts.

45

50

5.s.

f.o

_: , '■; —N = NX,

Shark shark

where Hai is a chlorine or bromine atom, the two X ₁ independently of one another each represent a radical of the formula

25 R ₁ -CO-CH-CO-NH

Y-OH

I - m - μη - ι

NH-R,

or

OH

40

the phenyl nuclei by fluorine, chlorine or bromatonic. low molecular weight alkyl or alkoxy groups. Nitro, cyan. Trifluoromethyl, methylsulfonyl, aminocarbonyl, low molecular weight alkylaminocarbonyl, Phenylaminocarbonyl, aminosulfonyl, low molecular weight alkylaminosulfonyl, phenylaminosulfony I, low molecular weight alkoxycarbonyl, low molecular weight alkanoylamino and benzoylamino groups can be substituted

Rι an optionally substituted, low molecular weight Alkyl group. preferably a methyl group.

R _{2 is} an optionally substituted phenyl or naphthyl radical, like the nuclei A, and

R _{3 is} methyl, methoxycarbonyl. Ethoxycarbonyl, aminocarbonyl, methylaminocarbonyl or phenylaminocarbonyl groups,

which is characterized in that 1 mol of a tetrazotized diamine of the formula

SO ₂

II, N

-NH,

(IV)

Shark

Shark

i 644 382

• Λ

by 2 mill of a coupling component or 2 moles fine mixture win coupling components of the I. irmel

X ₁

uorin X _{1 has} the meaning given above.

"Low molecular weight" are alkyl or

Aiko-N groups referred to, the 1 to 4. preferably

Contains 1 or 2 carbon atoms.

To carry out the method according to the invention you can /. B. 1 mol of the tetrazo compound from 2.7-diamino-3.6-dichloro-diphenylsulfone (II) or from 2.7-dianuno-3.n-dibromo-diphenylsulfone (III) with

2 mol of a coupling component or a mixture to implement coupling components of the formula X ₁ H. The diamines used for tetrazotization have the formula

SO ₁

HA"-

/ - NH ₁

(IVi

Shark

Shark

The compounds (II) and (III) can be prepared by reacting 4,4'-diamino-3,3'-dichloro-1.1'-diphenyl or 4.4'-diamino-3.3'-dibromo-l.I'-diphenyl with sulfur trioxide in sulfuric acid. They can be prepared in a number of ways, e.g. with sodium nitrite in hydrochloric acid suspension or better with nitres', ! sulfuric acid, teirazotize. like this e.g. in "Basic Operations in FarHn Chemistry" by l · i e r ζ David and B 1 a n gey. 5th edition (1943), P. 249 and 236. is given.

The coupling reaction can take place in weakly acidic, neutral or alkaline aqueous solution, namely in a pH range between about 3.5 and 11.5. be performed. It is often cheap. Add pyridine. But you can also use organic solvents couple, e.g. B. in pyridine or dioxane or in mixtures of organic solvents.

The new dyes are conveniently treated by mechanical treatment, e.g. B. with the help of mills Or roller mills, optionally together with dispersants, e.g. B. condensation products Naphthalenesulfonic acids and formaldehyde, processed into pigment doughs. These can be as such can be used, but they can also be used e.g. B. (lurch / dust, dry and the powder obtained grind. The new compounds are excellent pigments. They are in the most common solutions practically insoluble. They are suitable e.g. B. to liirbcn of paper in bulk and possibly dissolved masses on the basis of Natiir-Cxler Synthetic resins. Plastics or rubber lowic for printing on textiles and paper. the The finishes obtained are extremely lightfast and have good to very good washing properties. Chlorine bleach. Hypochlorite bleaching, tinting. Blind vat. Hydrosulfite. Pcroxydblcich-, dry cleaning? .-. Friction. Migration, Overcoating and solvents and are characterized by good transparency and heat resistance out.

The closest comparable from the U.S. patent 2,879,266 known dyes are those according to the invention Superior to dyes in terms of lightfastness.

The parts mentioned in the following examples parts by weight and percentages mean percentages by weight. The temperatures are in ι elsius degrees specified.

example 1

In a nitrosylsulfuric acid made from 100 parts of concentrated sulfuric acid and 14 parts of sodium nitrite are at 0 to 5 31.5 parts of 2,7-diamino-3,6-dichloro-diphenylsulfone registered. After about 3 hours, 550 parts of ice are poured out. A small excess of nitrite is made with sulfamic acid removed and the solution filtered.

The clear, slightly yellow solution obtained in this way are combined with a fine, acetic acid suspension of 41.4 parts of l-acetoacetylamino-2-methoxybenzene at 10 to 15 ", the pH being between 3.5 and

ίο 4.5 is held. After the coupling has ended, the mixture is ^{heated to 90 L} , filtered and washed free of salt. The pigment obtained dyes polyvinyl chloride in greenish yellow shades with good lightfastness and migrationfastness.

Used instead of 1-acetoacetylamino-2-methoxy-benzene the equimolecular amount

l-acetoacetylamino-2-ethoxy-benzene,
l-acetoacetylamino-4-methoxy-benzene,
l-acetoacetyiamino-4-ethoxy-benzene,
- ¹⁰ l-acetoacetylamino-l-methoxy-S-ethyl-benzene.

l-acetoacetylamino-2,5-diethoxy-benzene,
l-acetoacetylamino-2-methyl-benzene.
l-acetoacetylamino-2,4-dimethyl-benzene or
1-acetoacetylamino-benzene

or the equimolecular amount of a mixture of two of the coupling components mentioned, yellow pigment dyes are also obtained which, for. B. overall for coloring polyvinyl chloride in the mass λο is shown.

Example 2

54.3 parts of 1-acetoacetylamino ^ .S-dimethoxy-4-chlorobenzene are dissolved in 1000 parts of water and 22 parts of 30% sodium hydroxide solution. The filtered The solution is mixed with a mixture of 13 parts of glacial acetic acid and 100 parts of water while stirring vigorously and then 60 parts of crystallized sodium acetate dissolved in 100 parts of water are added. For this A tetrazo solution prepared as described in Example 1 is examined. By adding 15% sodium hydroxide solution, the pH is kept at 4.8 to 5.2. The coupling temperature is 20. After coupling has ended, the mixture is heated to 90, filtered and washed.

0.1 part of the disazo dye thus obtained is with 0.2 parts of a high molecular weight polyester plasticizer, e.g. B. Paraplex 53 (Rohm and Haas, Philadelphia). on a color scrubbing machine rubbed and mixed with 100 parts plasticized polyvinyl chloride mass. The colored one The mass is on the rolling mill at about 150 to 160 ° for 10 minutes with friction gelatinized and the film peeled off with synchronism or weak friction. A lightfast and excellent migration-fast orange coloration.

You get just as good results. if you have the I -acetoacetylamino-2,5-dimethoxy-4-chlorobenzene by the iiquimolecular amount

I-Acetoacety lamino-4-chloro-henzene.

1-Acetoacetylamino-2-metho \ y-4-chloro-halide.

1-acetoacetylamino-3-chloro-4-methyl-henzene.

l-acetoacetylamino-2-methyl-3-chloro-ben / ol.

l-acetoacetylamino-2-methyl-6-chloro-henzene.

1-acetoacety lamino-2,4-dimethoxy-5-chloro

benzene,
l-acetoacetylaminoO-methuxy ^ -chlor-

5-methylben.7ol.
! -Acetoaeetylamino ^ -methuxy ^^ - diehlor-

benzene.
I-acetoacety lamino-2,5-dimethoxy-4-fliior-

benzene.
l-acetoacetylamino ^^ - dimethoxy ^ -cyan-

benzene,
1-acetoacety lamino-2,5-dimethoxy-4-nitro-

benzene,
l-AcetoacetylaminoO-methoxy ^ -acetylamino-

benzene,

l-acetoacetylamino-2.4.5-dichlorobenzene,
l-acetoacetylamino-2,6-dibromo-4-nitro-benzo!
or
! -Acetoacetylamino ^ J-dimethyl ^ .o-dichloro-

benzene

replaced.

The 2,7-diamino-3,6-dichloro-diphenyl- >> ulfone used can be obtained as follows: ! 2 'parts of 4,4'-diamino-3,3'-dichlorodiphenyl are dissolved in 250 parts of 40% oleum for 2 hours SO warmed. After it has cooled down, it is poured onto 3000 parts of ice. filtered and gulp down the residue in water. This suspension is neutralized with sodium hydroxide solution and then heated to 100. It is filtered hot and dried.

Example 3

1 , 31.5 parts of 2.7-diamino-3.6-dichlorodiohenyl sulfone are etrazotized according to the information in the Beisnie! 1 and combined the filtered and buffered tetrazo solution with a solution of 41.4 parts of '-Aceioacetylamino-2-methoxy-ben / ..) l in Pyridir ·. so you get a greenish yellow after filtering and washing salt-free. strong pigment of recorded migration and Liehlechthciter :.

1 part of the pigment obtained in this way is na:! Part of tricresyl phosphate rubbed on the paint grater. 1 part of the ground pigment paste is mixed with 4 parts of ethyl cellulose N 14 (HerciilcM and a solvent mixture of 50 i'eiien methyl isobtityl ketone, 40 parts of ethyl acetate and W) parts of n-butyl alcohol and then diluted to scratch viscosity. The Äthvlcellulosclack is aiii aluminum sheet or chrome cardboard, sprayed on.

The I-acetoacetylaniino-2-methoxy-bcn / oi can Replace with the following compounds in equimolecular amounts with equally good results; ■■ ground '

1-acetoacetylamino-3-triluomethylbenzene.
I -acetoacety lamijio-4-methyl-sulfonyl-benzene.
l-aceloacetylamino-2-methoxy-5-tn (luormeinyl-

benzene,
I -Acetoacetylamino ^ - chior-5-trifluoronciethyl-

bcnzol,

1 -

benzene,

-Acetoaceiylamm. ^ Vvbis-lirifluormetrnh-

benzene.
-Acetoacety lamino-2.5-dimetho \ y-4-mL.ih \ l-

sulfonvl-henzol.

-Acetoacetylamino-4-ben / oylammo-hen / .H.
-Acetoacety lamino-4-acetylamino-ben / i) i.
-Acetoacetylamino-2.5-dimethoxy-4-heii / o \ l-

amino-benzene.
-Acetoacetvlamino-2.5-diethoxy-4-ben / (ivl-

amino-benzene,
-AcetoacetylaminoO-methyl ^ -acetylammu-

5-methoxy-benzene.
-Acetoacetylamino ^ -methoxyo-chloro-

4-acetylamino-benzul.
-Acetoacetylaminü-benzül-4-carboxylic acid-

amide,
-Acetoacety lamino-berii. '.) L-4-carboxylic acid-

methyl ester.
-Acetoacety lamino-benzene-4-carboxylic acid-

ethyl ester.
-Acetoacety lamino-2-methoxy-benzene-

5-carboxylic acid phenylamide.
• Aceioacctylamino ^ .S-dimethoxy-benzene-.

4-sulfonic acid amide.
-Acetoacetylamino-2,5-dimethoxy-benzene-

4-sulfonic acid phenylamide.

Example 4

40.4 parts of 2,7-diamino-3,6-dibromo-diphenylsulfone are suspended in 55 parts of 30% strength hydrochloric acid and 4 (H) parts of water. By adding 13.8 parts of sodium nitrite as a normal aqueous solution; is diazotized. The filtered tetrazo solution is combined with a solution of 40.8 parts of l -! ^ - methox> * - nhenyl-3-methyl-5-pyrazolone in 2000 parts of water and 3000 parts of 30% sodium hydroxide solution Temperature held at 10. After the coupling has ended, the mixture is made acidic in the Congo, heated to 80 to 90 ', filtered and washed free of salt. The dried \ '\ s \ ment dyes PVC in strong red tones

In the same way one can ζ. Β with Iniüi.-mu.T Pyra / olon domes:

! -Plienyi-3-niethyl-: 5-para._ .ilci.
l-13'-chlorophynyl-3-methyl-5-pyrazolo! "_;
! - (3'-cyan) -pi; er.>! .Vrncthyl-f-pyrazoior ..
1- (2'-Mclhyl) -phynyl-3-mcthy! -5-pyrazoioi :.
! - (2'-Methoxy) -phynyl-3-methyi ~ 5-pyra / oio!,.
^: - (4'-methyl) -phenyl-3-methyl-5-pyi "azoioii.
l-Phcnyl-5-pyrazolone-3-carboxylic acid ethylsia; l-Phcnyl-5-pyrazolone-3-carboxylic acid

methyl ester.

! -Phcnyl-5-pyrazoloIl-3-carboxylic; iure-amide.
! -Plienyl-S-pyrazolone-S-carboxylic acid-

dimethylamide.

-PhcHyl-S-pyrazolon-i-carboxylic acid-ethylamide. l-phenyl-5-pyrazolone-3-carboxylic acid

plicnyia.riid.

Example 5

31.5 parts of 2,7-diamino-3,6-dichloro-diphynylsulfone are tetrazotized according to the information in Example 1. The tetrazo solution is filtered and treated with a solution of 71.5 parts of 2-Hvdroxv-nanhth: lin-l-rnrhnn-

acid - (2.4 '- dimclhoxy ■ 5 - chlori - plujii \ lamul in K) (M) parts of water. 5 (K) I rush to combine methyl alcohol and 50 parts of less sodium hydroxide solution at 10 !. The pH value is maintained at ILS by simultaneous addition of 600 parts of 30% sodium hydroxide solution. After coupling has ended, the precipitated dye is separated off and washed neutral.

In a corresponding way you can use /. B. couple with the following 2 - hydroxynaphthalene - 3 - carboxamides:

2-hydroxy-naphuialin-1-carboxylic acid

phenylamicl.
2-hydroxy-naplithalin-3-earbonsäiire-

(2'-methoxy) -phen \ lamiil.
2-Hvdro \ v-naphthalene-3-carboxylic acid

(2'.5'-dimethoxy) -pheinlamid.
2-1 lydro \ y-naphthalene-3-carboxylic acid

! .V-nitro) -phen \ lamid.

11 \ dro \\ -naphihalin -.'- cai bonsäure-

lT-nitro-phenylamide.
2-hydroxy-naphlhalin-3-carboxylic acid

(2'.4'-dimeth> li-phen ;, lamid. 2-1 lulroxy-naphlhalin-3-carboxylic acid

(2 '-met In I) - ph a I a mid. 2-11 yd roxy-na ph I ha I in-3-car bonsäu! ΤΙ 4'-chi or! -Phenyl a mid. . 2-Myilmxy-ii <iphthalin-3-e; irr) onsiuire-

(2'.5-dimethoxy-4'-chloro) -phen \ lamii 2-Hydroxy-naphthalene-3-carboxylic acid (2'-methyl-4'-methoxy) -phenylamide. 1 hydroxy-iiiiphthalene-Vcarboxylic acid

(2'-ethoxy) -phcny1amide, 2-hydroxy-naphtha Ii ii-.Vcarhonsii u re

(4'-methoxy) phenylamil. 2-1 hydroxy-naphthalene- 3-carboxylic acid

(2'-methyl-4'-elil (ir) -phenylamici. 2-1 hydroxy-naplithalin-3-carboxylic acid | 2'-methoxy-5-chi or) -ph en via mill.

Claims (2)

Patent claims: ! Process for the preparation of disazo dyes of the formula SO, 2. A process for dyeing or printing synthetic material or paper, characterized in that one or more of the disazo dyes of the formula I are incorporated or applied to them. X ₁ -N = N- ".-N = NX ₁ Shark shark ^(I) wherein Hai is a chlorine or bromine atom, the two X ₁ independently of one another each have a radical of the formula The invention relates to a process for the preparation of disazo dyes of the formula