DE1951022A1 - Dyes, their manufacture and use - Google Patents

Description

DR. BERG DIPL.-ING. STAPF

PATENTANWÄLTE MÜNCHEN 2. HILBLESTRASSE

Dr. Berg Dipl.-Ing. Stapf, 6 MOnchen 2, HHblestraBa 20 .

Lawyers' A & te 1Ö 81 $ Be / Sch

Our sign date

ÄOKt

Ugine Kuhlmann, Paris / France

"Dyes, their manufacture and use ¹¹

The present invention has dyes in general Formula on the subject

009816/1340

(«11) * 5 U 20 Il T # tajK« mm.i PATfNTCUU! ΜβηΑ «ι Unkt loywlidi · Vmlnibank MPneh« n 453100 rOffcdMdu ΜΟικΜη 453

Ε «

0 R. (f , C-CH ₂ I.
ft ΛΤΪ
V / ·· - UOa O ₂ H ₄ ^ r ^ M. 0

where R is a hydrogen atom, an alkyl or alkyl-O-alkyl group is, wherein the alkyl groups contain from 1 to 4 carbon atoms, E ,, a hydrogen atom or a Is methyl group, Eo-- an alkyl group with 1 to 4 carbon atoms, a cycloalkyl, aryl, aralkyl or succinimidoethyl group is, ΐ is a hydrogen or halogen atom, an alkoxy, nitro, cyano, amino group and X is a is monovalent anion or its equivalent.

The stated in the explanation of Y amino group can be a simple amino group or a heterocycle by a alkyl, cycloalkyl, aryl radicals substituted amino group, or part of, these radicals being optionally nonionic substituents such as halogen atoms, alkyl, alkoxy, acyl , Acylamino, dialkylamino or alkyl (aryl) amino groups can carry.

The anion has no coloring properties . It will be

00981671340

^ 5

ORIGINAL INSPECTEO

preferably selected from anions. those soluble in water Deliver courtship of dyes. Examples are GhIor and Bromine ions, sulfate, phosphate, acetate, formate, oxalate, Chlorzincate.

The dyes of the formula (i) dye fibers made from acrylonitrile polymers and copolymers in blue and green Color shades with good fastness properties and good stability against artificial light. Among the dyes are the dyes of the formula below with regard to their affinity for the specified fibers particularly advantageous: '■

. R.

Y ¹

-OH ₂

"(II)

where "i? ^ a hydrogen atom or a methyl group, R ¹ 'exn hydrogen atom or an alkyl group with .1 to # carbon atoms, K" an alkyl radical with -1 to' ^ carbon atoms, ß'p an alkyl group with 1 to 4 carbon atoms, a cycloalkyl, aralkyl or aryl group, Y 'a V / water

BAP ORlGtNAL

material or halogen atom or an alkoxy,! nitro, cyano- or Arylaminοgruppe and X is a monovalent anion or Is equivalent.

The dyes of the formula I which ^{contain two 2 ', 5 l} -ϊjioxop; / rrolidinylethyl groups can be prepared, for example, by using a li (β-succinimidoethyl) aniline of the general formula

^V O-_OH _A

(XU)

~ OIL

in which the radicals R and & * have the same meanings as above, condensed with a benzaldehyde and the leuco derivative thus obtained is oxidized.

• The dyes of the formula II can be obtained by that one is an aminobenzophenone of the general formula

with an aromatic amine of the formula

• in the presence of a condensing agent such as phosphorus oxychloride condensed.

The dyes of the formulas I and II in which Y and Y are ¹ .substituted amino groups can also be prepared by using a halogenated dye of the formula

halogen

, Halogen

react with a primary or secondary amin.

In the French patent specification 95 ^ 752 the possibility is described, textile articles made of YinjrjLohlorid * and

■■ '• Ulw,

00011 S / 1i40 BAD ORlGINAi.

-6-

Acrylonitrile copolymers using dyes of the tri-phenylroethane series to color. In any case, the dyeings obtained with the known dyes lack this Type lightfastness.

Me following examples in which the specified parts are by weight, unless otherwise stated, illustrate the invention without limiting it.

example 1

a) Production of the Leuke derivative.

52 parts of N-ithyl-H- (β-succinyliminoethyl) -m-toluidine, 50 parts of isopropyl alcohol, 3 parts of urea and 10.6 parts of benzaldehyde are introduced into a device equipped with a condenser, coolant, thermometer and measuring container. It is then fed gradually, without the temperature 5Q ⁰ Cüberschreitet, 8.3 VoloTeile concentrated sulfuric acid. The mixture is then heated to 85 ° C. for 10 hours with stirring. The cooled mixture is poured into 1000 parts of water and the liquor is neutralized with a sodium hydroxide solution. The insoluble Leucoder.ivat is isolated by filtration, washed with water over the filter and dried in a drying oven. Trookehgewioht 61 parts.

-7-

b) Oxidation ⁵ on the Leu c or i vats.

The obtained leuco derivative is dissolved in 150 parts of methyl alcohol, 20 parts of water and 40 parts of concentrated hydrochloric acid. This cooled to +5 ⁰ C solution is added over 30 minutes keeping the temperature between +5 and +10 ⁰ O Q keeping j 60 parts of 50 / öiges lead dioxide is added and stirred for one hour at the same temperature. Then, a solution of $ 0 parts of crystalline sodium sulphate in 200 parts water to ₀ after I5 minutes of stirring, the insoluble lead sulphate separates you from by filtration and washed over the PiIter with I3OO parts water. The dye is precipitated in the filtrate in the form of zinc chloride, with 300 parts of sodium chloride and then 20 parts by volume of 50% zinc chloride solution being added one after the other. The mixture is stirred for a further hour, the dye is isolated by filtration and washed over the filter with 50 parts of 20% sodium chloride solution. The dye, dried with air in a heating oven, weighs 87 parts. It dyes acrylonitrile polymer or mixed polymer fibers in very lightfast, vivid green-yellow shades.

Example 2

if the benzaldehyde in Example 1 is replaced by an equivalent amount of 5- ^ itrobenzaldehyde, a greenish-yellow color is obtained Dye with similar properties.

009816/1340 _{BAD 0R) QINAL}

Example 3 .

If the benzaldehyde in Example 1 is replaced by an equivalent amount of A-- chlorobenzaldehyde, the dye of the formula is obtained

v '

N? -CE ₃

oi - <^ Vc

-CH

ZnCl,

He dyes acrylonitrile polymer or Hi s clip ο lyra er i sat fibers in green-yellow tint with very good clarity properties"

Example 4

Han solves 40. parts of the dye of Example 5 in 25 'i'eilen water with a' was acidified hawks concentrated hydrochloric acid solution is added uieser 14! Parts xj-toluidine, then heated at 80 ⁰ G, until the The presence of the initially green dye can no longer be detected by paper chromatography. The mixture is then poured into 3000 parts of warm water which has been acidified with 30 parts of acetic acid. The solution is refined by filtering it under heat. 100 parts of sodium chloride are added to the deselected filtrate, and the resulting

-9-

The dye precipitated by filtration, washed over the filter with a 5% sodium chloride solution and dried at 60 G in a drying cabinet. It dyes acrylonitrile or polymeric fibers in blue, very lively shades that are stable to artificial light and generally color-fast.

The following table summarizes further examples in a more analogous manner Dyes together that were prepared in Example 4, but where p-toluidine was replaced by those given in the second column Amine XH was replaced.

example

Amin YH

Color shades of the polyacrylic fibers

5 6 7 8

p-anisidine

aniline

N-ethylaniline

p-phentidine

ρ-toluidine

m-chloroaniline

Morpholine

Otj-haphthylaroin

4-acetylarainoaniline

4- Am in ο diphenyl

3,5-Tue

blue blue blue blue blue blue-red blue-green blue blue-green blue violet-blue

00981671340

BATH ORIGINAL

-1Q-

Example 16 ■ "\ ■

In Example 1, the 52 parts of H-ethyl-M- (ßsuccinyliminoethyl) -m-toluidine are replaced by 56 parts of ri- (ß-14ethoxyethyl) -N- (ß-succinyliminoethyl) -in-toluidine and the 10.6 parts of benzaldehyde by 14.1 parts of p-chlorobenzaldehyde and if the procedure described there is followed, the dye of the formula is obtained

CH,

C ₂ H ₄ OCH ₃

.C ₂ H ₄ OCH ₃

«/ Λ

- CH ₂

It dyes acrylonitrile or hischpolymerisatfibres in a green-yellow lightfast shade.

Example 17

Leaving 41 parts of the dye of Example 16 with 14 parts If p-toluidine react under the conditions described in Example 4, a dye is obtained which dyes acrylonitrile polymer or mixed polymer fibers in lightfast, vivid blue shades.

-11-

009810/1340

Example 18

Do you continue in example 1? p-Töluidin by an equivalent amount of p-anisidine, a dye is obtained with the same staining conditions.

Example 19 ^;

Mix 4-5 parts of 4-dimethylaminobenzophenone with 52 parts

len H-ethyl-W- (2-succinimidoethyl) -m ~ toluidine and 50 parts Phosphorus oxychloride, then heated the whole thing for several hours at 100 ° C. Add 1000 parts to the still warm mixture warm water too. The solution obtained is allowed to cool, and 100 parts of sodium chloride and 150 parts by volume of 50% solution are added Zinc chloride solution too. The dye separates in resinous form, is isolated and in new 2000 parts boiling Dissolved water, which is acidified with 50 parts of glacial acetic acid became. The liquor obtained is purified by filtering it under heat. The dye becomes in the filtrate by adding precipitated from 50 parts by volume of a 50% zinc chloride solution, then isolated by filtration and finally washed over the filter with a 20% sodium chloride solution and dried. It has the following formula:

^BA0

009816/134

Il

I '■>

ZiiC

l »

The dye dyes acrylonitrile or mixed polymer fibers in green-yellow tint with good general Authenticity properties, in particular towards Light.

The following ■ dragonfly summarizes some of the preceding analogous examples together, with äie dyes when used other benzopnenones were made.

at
game "Benzopnenone Color of the Faro-
stοffs on acrylic
fiber η 20th 4-diethylamino-benzophenone green yellow 21 4- diethylamino-2-meth, ylbenzo-
phenone green yellow 22nd 4 — JJiniethyiaujino-4 '-chlor-
benzophenone leDnaft green 23 4-DiethylaTflino-2-nieth _l ) 'l-4-
c hl oiibeu z-bpIren'o n vivid green-yellow 009816/1340 BATH ORIGINAL

- ■ 13 -

- Example 24

han heated a mixture of 22 parts of the dye from Example 22, 15 '!' Rush p-anisidine, 60! 'Rush water and 0.5 parts of concentrated hydrochloric acid at 85 ° G for 5 hours.

The reaction mixture is then poured into 1000 parts of warm water poured, which was acidified with 50 parts of acetic acid «. Han adds 100 parts of sodium chloride. The dye precipitates, is isolated by cold filtration, over the filter with a 3 ^ igen- sodium chloride solution filtered and dried at 60 0. He dyes acrylic fibers in a colourfast way lively blue tint.

The table below summarizes analogous examples, for example 24 together, the dyes having been prepared by replacing p-anisidine with other aromatic Replaced amines.

uei- used Atnin color shade

play acrylic fiber !!

25 p-toluidine bright blue

26 aniline blue

_ÄL -14-

009 * 16/13 * 0.

Claims (1)

Patent claims: 1. Dyes of the general formula: O- R. t, ?, 0 - ^V O ₂ H ₄ -N 0 - «I. * Ό -OH ₂ wherein H is a hydrogen atom, an alkyl or alkyl-O-alkyl group the alkyl groups are 1 to 4 carbon atoms have, R. * a hydrogen atom or a methyl group Rp is an alkyl group with 1 to 4 carbon atoms, Cycloalkyl, aryl, aralkyl or buccinimidoethyl group is, Y is a hydrogen or halogen atom, an alkoxy, nitro, cyano, amino group and X. is a monovalent anion or its equivalent. 2. Dyes according to claim 1, characterized in that ^ "' that Υ. is a simple amino group or an amino group, those substituted by alkyl, cycloalkyl or aryl radicals "^ or which forms part of a heberocyclic king. 009816/1340 -15- ι. Dyes according to claim 1 of the general formula: OH ₉ CH ₂ € · (II) wherein R ^ is a hydrogen atom or a group h ethyl, H ¹ is a hydrogen atom or a ^ lkylgruppe having 1 to 4 carbon atoms, R "is an alkyl radical having 1 to 4 carbon atoms, H'p a Älkylgruppe having 1 to 4 carbon atoms, cycloalkyl , alkyl or ryl group, I ^{1 is} a hydrogen or halogen atom or an alkoxy, ivitro, cyano or arylamino group and X is a monovalent anion or its valent. . Process for the preparation of dyes according to claim wherein Hp is an ouccinimidoethjlgruppe, characterized in that that one is an N- (li-juccinimidoethyl) aniline the Foymel:. BATH ORIGINAL -16- 0 0 981 §7-1-340 r where H and & * have the same meanings as in claim i, condensed with a benzaldehyde and the so " ³ -r holding leuco derivative oxidized. I «Vorfsnren inr the production of dyes according to ^" l \ spiUQh 3 daduroh * that nian is an aminobenzo- I phenone of the general formula; rb finö « aioniatisclien Ainin der Fornael 0-0H ₂ conaenöiert in the presence of a condensing agent. 6. Process for the production of dye =; - offer, according to An ^ Ϊ . i * ί K , ' 009816/1340 BATH ORIGINAL Claim 2, wherein I is a substituted amino group or one Forms part of a heterocyclic ring, characterized in that a "halogenated dye of the formula Halogen* -CH ₂ - CH ₂ with a primary or secondary amine. 7. Procedure for. Coloring - of, fibers on the basis of Polymers or copolymers of acrylonitrile characterized in that -. That one.,. the fibers "with a. Dye according to any one of claims 1 to 3 treated. 8. Fibers based on polymers * or copolymers of acrylonitrile, provided they have been colored by a method according to claim 7. . -J -. Ϊ́. ti '. 9. Compounds according to claim 1, 2 or 3 ORIEiNAL INSPECTED 009816/1340