DE2236800A1 - PIGMENT DYES OF THE 2,4-DIHYDROXYCHINOLINE SERIES - Google Patents

Description

Our reference: O.Z. 29 311 E / lG 6700 Ludwigshafen, July 26, 1972

Pigment dyes of the 2,4-dihydroxyquinoline series

The present invention relates to new pigment dyes of the 2,4-dihydroxyquinoline series of the formula I.

OH / CH ^ CH ^ C = N-N = A = N-N = C

<Vn

in the

R. for a hydrogen atom, a halogen atom or a nitro

group,

η for the numbers 1 or 2 and
A for the remainder of a difunctional aldehyde or ketone

stand.

Possible halogen atoms for R are, in particular, chlorine and bromine. Compounds are particularly preferred as pigments of formula I in which R 1 is hydrogen.

Bifunctional aldehydes and ketones for the group A come aliphatic and aromatic dioxo compounds, e.g. glyoxal, diacetyl, isophthalaldehyde, terephthalaldehyde, dichloroterep ^ thalaldehyde, Dimethoxyterephthalaldehyde, naphthalene-1,4-dialdehyde, Naphthalene-2,6-dialdehyde, diphenyldialdehyde, benzil, dimethoxybenzil, Cyclohexanedione-1,2,2,5-dibenzoyl-hydroquinone-dimethyl ether or 2,4-dibenzoyl-1,5-dimethoxybenzene into consideration. Glyoxal, terephthalaldehyde, 2,5-dimethoxyterephthalaldehyde are particularly preferred, 2,5-dichloroterephthalaldehyde, Isophthalene dialdehyde, naphthalene-1,4-dialdehyde, naphthalene-2,6-dialdehyde, Diacetyl and Behzil.

The dyes of the formula II are of particular technical interest

401/72 - 2 -

309886/1038

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PH 73 Y 3 QH

C = N-N = A = N-N = C

(II),

in which A stands for a glyoxal radical or a terephthalaldehyde radical.

The new pigment dyes can be produced, for example, by that hydrazones of the formula III

CH-

< ^R l> n

C = N-NH

in which R. and η have the meaning given, is reacted with dialdehydes or diketones of the general formula O = A = CfIn in a manner known per se. The reaction is expediently carried out in an organic solvent, in which case, for example, ethanol, propanol, isobutanol, glycol monomethyl ether, ethylene glycol, glacial acetic acid or mixtures thereof are particularly suitable. It is particularly advantageous to work in the temperature range from 70 to 130 ^{° C. for the reaction.}

In a particularly preferred embodiment, the pigment dyes according to the invention can be obtained by first preparing the hydrazones of the formula III in the solvent from the corresponding 3-acetyl-2,4-dihydroxyquinolines by reaction with hydrazine hydrate at temperatures of 40 to 70 ° C. and then preparing them , this is reacted, without intermediate isolation of the hydrazones at temperatures from 70 to 130 ⁰ C, preferably from 100 to 12O ⁰ C, with the dialdehydes or diketones. Particularly suitable starting compounds of the formula III are 3-acetyl-2,4-dihydroxyquinoline, 6,8-dichloro-3-acetyl-2,4-dihydroxyquinoline and 6-nitro-3-acetyl-2,4-dihydroxyquinoline.

The new pigment dyes are very good Color strength, high brilliance and excellent solvent + or their acetylene or ketals

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BATH ORIGINAL

-3- ο.ζ. ——G ₀₀

. They are green in color, tinged yellow to reddish yellow. They can be used for all purposes of pigment technology, preferably for coloring plastics, such as polyolefins, polystyrene, polyvinyl chloride, polyamides ^ polycarbonates, polyesters, polyacrylonitrile, polyacrylates and methacrylates, aminoplasts and phenoplasts, furthermore for coloring dispersions and printing inks, which are characterized by high color strength, glaze and good spreadability, In particular, the new pigment dyes are also suitable as paint dyes.

Those specified in the following working examples Parts and percentages are based on weight.

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BATH ORIGINAL

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example 1

21.7 parts of the hydrazones of 5-acetyl-2,4-dioxychinolinii are in Slurried 200 parts of ethylene glycol. 6 parts are left at 40 ° C a 40 ^ igen, aqueous glyoxal solution and rflh £ t the Including mixing at 115 for 2 hours, suction is carried out at room temperature off and washes with ethylene glycol and ethanol.

After drying at room temperature, 22.4 parts of a yellow one are obtained Pigments of the formula

Oh? ^H 3? ^H 3 OH

C »N-N = CH-CH« H-li »C

with a melting point of 340 ° C.

example

40.6 parts of 3-acetyl-2.4-dioxychinolin and 10.0 parts Hydrazinliydrat are stirred in 400 parts of ethylene glycol at 40 Ws 1/2 hour 50 ⁰ C. Then 12 parts of a 40% aqueous glyoxal solution are added dropwise and the mixture is stirred at 115 ° C. for 2 hours. It is weighed at room temperature, washed with ethylene glycol and ethanol and dried at room temperature. 46.6 parts of the yellow pigment indicated in Example 1 are obtained.

309886/1038

BAD ORfGINAi

O.Z. 29

Example 3

21.7 parts of the hydrazone of 3-acetyl-2,4-dioxyquinoline and 9.2 parts Naphthalene-2,6-dialdehyde in 300 parts of glycol monomethyl ether Boiled under reflux for 3 hours. It is filtered off with suction, washed with glycol monomethyl ether and water and dried at 60 ° C. 29 parts are obtained of a yellow pigment with the formula

0H? ^H 5

C = U-N = CH

? ^H 30H

CH = N-IT = C

HO-fr

with a melting point of> 3 ^ 0 C.

Example 4

In Example 3, 9.2 parts of naphthalene-2,6-dialdehyde are replaced by 6.7 parts of terephthalaldehyde and the procedure described in Example 3, 27.4 parts of a yellow pigment of the formula are obtained in this way

with a melting point of 36O C.

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O.Z. 29

223680U

Example 5

Proceed as described in Example 2 and replace 12 parts of one 40 ^ igen aqueous glyoxal solution with 13.4 parts of terephthalaldehyde, 48.7 parts of the yellow pigment described in Example 4 are obtained in this way.

Example 6

Proceed as described in Example 4 and replace 9.2 parts Naphthalene-2,6-dialdehyde with 9.7 parts of 2,5-dimethoxyterephthalaldehyde, 29 * 4 parts of a reddish-tinged yellow pigment are obtained the formula

CH

CNN = CH J /

if ^ OH

CH

OCH,

with a melting point> 360 C.

Example 7

26.2 parts of the hydrazone of 6-nitro-3-acetyl-2,4-dioxyquinoline and 9.7 parts of 2,5-dimethoxy-terephthalaldehyde are refluxed in 500 parts of glycol monomethyl ether for 3 hours. Hach off with suction, wash with glycol monomethyl ether and Vasser and dried at 60 ⁰ C is obtained 33.2 parts of a reddish yellow pigment

309886/1038

the formula

O.Z. 29

C = NN = CH -J /

CH

OCH,

Example 8

Tex drive as described in example 7 and replace 9f7 parts 2.5-dimethoxy-terephthalaldehyde by 6.7 parts of terephthalaldehyde, 15.7 parts of a reddish-tinged yellow pigment of the formula are obtained in this way

C = N-N-CH

Example 9

If 9.2 parts of naphthalene «2,6-dialdehyde are replaced in Example 3 by 10.4 parts of 2.5-Mchloroterephthalaldehyde and proceeds as in the example J, 23.1 parts of a reddish yellow are obtained Pigments of the formula

Cl

CE, If »CH -Jf C = N-N = ^ 0H Cl
■ OH I.

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O.Z. 29 311

Example 10

21.7 parts of the hydrazone of 3-acetyl-2,4-dioxyquinoline and 4t3 parts Diacetyl are refluxed for 3 hours in 300 parts of i-butanol. It is filtered off with suction, washed with i-butanol, methanol and water and dried at 60. 22.4 parts of a greenish yellow are obtained Pigments of the formula

Oh? ^H 3? ^H 3
C = NN = C -

Example 11

Proceeding as indicated in Example 10 and replacing 4t3 parts of diacetyl with 21.0 parts of benzil and 300 parts of i-butanol with 400 parts of glycol monomethyl ether, 18.4 parts of a greenish tinge are obtained yellow pigment of the formula

Example 12

In Example 1, 21.7 parts of the hydrazone of 3-acetyl-2,4-dioxyquinoline are replaced by 28.6 parts of the hydrazone of 6.8-dichloro-3-acetyl-2.4-dioxyquinoline and proceed as indicated in example 1,

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θ. ζ. 29

30.3 parts of a yellow pigment of the formula are obtained in this way

C = U-IT = CH-

Example 15

20 parts of the pigment obtained according to Example 1 or 2 are with 80 parts of book or offset varnish rubbed in the usual way on the three-roller mill. The printing ink made in this way gives prints of excellent quality when processed in letterpress and offset printing HTardeness, brilliance and glaze, when using the in the other examples given pigments are obtained with printing inks corresponding properties.

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Claims (4)

Claims, 1. Pigment dyes of the 2,4-dihydroxyquinoline series of the formula OH CH, CH ι t 3, ¹ ^ = NN = A = NN = C QIT X ""> S ~ J 1 in the R represents a hydrogen atom, a halogen atom or a Nitro group, η for the numbers 1 or 2 and
A for the remainder of a difunctional aldehyde or ketone stand. 2. Pigment dyes according to claim 1, characterized in that R is hydrogen and A is a glyoxal radical or a terephthalaldehyde radical. 3. Process for the preparation of pigment dyes according to Claim 1, characterized in that hydrazones of the formula in which R. and η have the meaning given, with dialdehydes or diketones in a manner known per se all the more; nt. 4. Use of pigment dyes according to claim 1 for coloring plastics and paints and for their manufacture of printing inks. Badische Anilin- & Soda-Fabrik AG 30 9 8 86/1038