DE2533947A1 - METAL-CONTAINING DISAZOMETHINE COMPOUNDS, METHOD FOR THEIR MANUFACTURING AND THEIR USE AS A COLORANT - Google Patents

Description

HOECHST AKTIENGESELLSCHAFT

File number:

HOE 75 / F 190

Date: July 29, 1975

Dr. ST / Rt

Metal-containing disazomethine compounds, process for their Manufacture and their use as colorants

The present invention relates to metal-containing disazomethine compounds, Process for their preparation and their use as colorants.

The new compounds have the general formulas (Ia.) , (Ib) and (Ic)

= CH

(Ia)

CH = N-R-N = CH

(Ib)

09907 / 0Ö96

χ-

(Ic),

wherein R is a single bond, a straight-chain or branched one Alkylene radical formed by heteroatoms, a divalent group or an isocyclic or heterocyclic ring can be interrupted, a cycloalkylene radical, an arylene radical or a heterocyclic radical, Z one for metal complex formation capable group, X a carboxylic acid, carboxylic acid ester, optionally substituted carboxamide or carboxylic acid hydrazide group and M is a divalent metal atom.

In particular, the invention relates to those compounds of the abovementioned formulas (Ia) to (Ic) in which the radicals X have the same meaning in the same molecule and the respective radicals R and Z represent the same groups.

Of these, particular preference is given to those compounds of the formulas (Ia) to (Ic) in which R is a single bond, a Alkylene radical with 2 to 8 carbon atoms, which can be interrupted by a phenylene or cyclohexylene radical, a cyclohexylene radical, a phenylene radical, which is formed by chlorine atoms, methyl, methoxy, ethoxy, nitro, trifluoromethyl, carboxylic acid-iCj-C) -

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alkyl ester, carboxamide, carboxylic acid phenylamide, acetylamino, benzoylamino, sulfonic acid, sulfonic acid (Cj-C _) alkylamide and / or sulfonic acid phenylamide groups, or denotes a naphthylene, quinoline, benzimidazolone radical or, M for a copper, cobalt, nickel, zinc or manganese atom and Z for a -0-, -COO- or a lower alkoxy, e.g. methoxy or ethoxy group, or an optionally substituted by lower alkyl or aryl radicals ( Phenyl radicals) substituted amino group, for example the -N (phenyl) radical, or a carboxylic acid (C ₁ -Cj.) - alkyl ester, for example the carboxylic acid ethyl ester radical, or for the carbonate group or an optionally substituted by lower alkyl or aryl groups (phenyl groups) substituted sulfonic acid arid radical.

The preparation of the compounds according to the invention can be carried out in the Way done that one mole of one or more amines of the formula (II)

H ₂ N - R - NH ₂ (II)

wherein R has the meaning given above, with 2 mol of one or more compounds of the formula (III)

(III)

in which X has the abovementioned meaning, condensed and the disazomethine compounds obtained simultaneously or in metallized in a subsequent reaction.

The condensation of the diamines of the formula (II) with compounds of the formula (III.) Can be carried out either in water or in an organic Solvents such as an aliphatic alcohol, an aliphatic carboxylic acid, dimethylformamide, xylene, chlorobenzene, o-dichlorobenzene, nitrobenzene or glycol ethers carried out will. It is generally done quickly and quantitatively at

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a temperature of 50 - 100 ° C * It can be useful if necessary be, in a solvent or in a mixture of solvents at a higher temperature, for example at I50 C or higher, to work and a simultaneous azeotropic Perform distillation of the water released by the condensation!

To produce the metal complex compounds, one can proceed as follows: that the above-described condensation of the amine of the formula (II) with compounds of the formula (III) with addition metal donor performs or the isolated metal-free dye in water or an organic solvent or a solvent mixture, for example one of the abovementioned solvents, if appropriate with more precise compliance pH conditions and defined temperatures, then treated with a metal donor.

In general, the metallization is carried out in accordance with customary, analogous methods Process carried out, so at temperatures between 60 and 120 ° C and at a pH between 3 and 9, preferably 3,5 and 6; in the preparation of the compounds of the formula (Ic), however, a pH value above 7, preferably from 7 to 9, must be used incorporated v / earth.

To silence the free diamines of the formula (II) can also their salts, for example, the hydrochlorides or sulfates _s, optionally in the presence of acid-binding agents such as alkali or alkaline earth metal carbonates or hydroxides are reacted with the compounds of the formula (III) for reaction.

The diamines of the formula (II) which can be used as starting compounds are, for example, hydrazine, aliphatic diamines with a straight-chain or branched alkylene radical with 2 to 8 carbon atoms, which is replaced by heteroatoms such as oxygen, sulfur or Nitrogen atoms, a divalent group or an isocyclic one, for example a cycloalkylene or a phenylene rest, can be interrupted, cycloaliphatic diamines, such as cyclopentylene or cyclohexylene diamines, aromatic diamines Benzene, naphthalene or anthraquinone series as well as those that follow the general formulas

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correspond, where D is a single bond, an oxygen or sulfur atom, an NH-, -N (alkyl 1-4) -, -CH ₂ -, -CH = CH-, -CO-, -CONH-, - NHCONH-, -CONH-CO-NH-, -SO-, -SO ₀ -, -SO ₀ NH- or -N = N-

• Ct Cl

Group and E is an oxygen or sulfur atom, an -NH-, -N (alkyl 1-4) -, -CH-, -CO-, -CH = CH-, -CONH-, -NHCONH-, -SO _,

" in *

-SO ₀ NH- or -N = N- group, the aromatic radicals optionally replaced by halogen, such as chlorine, bromine, nitro, lower alkyl, cyano, trifluoromethyl and hydroxy, amino, lower alkylamino or Arylamino (phenylamino), lower alkoxy, carboxy, carboxylic acid (C. -C) ester or hydrazide groups or hydroxamic acid groups, sulfonic acid ester or optionally substituted sulfonic acid amide groups and acylamino groups of aliphatic lower carboxylic acids or aromatic carboxylic acids, such as acetyl , Propioni'yl- or benzoylamino groups, can be substituted, furthermore heterocyclic diamines, for example diaminopyridines. Of these, diamines with carbonamide groups, in particular cyclic carbonamide groups, such as, in particular, diamines of the general formula, are preferred

^(N Vn

(CO)

in which R _{0 is} hydrogen, a lower alkyl or phenyl radical and m and η each can be the number 1 or 2, the sum of m and η being 3 or 4 and the group of the formula

[(NR ₀ ) (CO) J, in which -NR ₀ - and -CO- are arbitrarily attached to each other- et η m · * et

are arranged, together with two o-position carbon atoms of the ring system B, a five- or six-membered heterocyclic ring forms; furthermore diamines of the formula (IJ) are particularly preferred, in the o-position to one of the amino groups by a capable of metal complex formation ligands Z are substituted, where Z is a hydroxy, lower alkoxy, carboxyl or an optionally by lower alkyl or aryl radicals (phenyl

- 6 709807/0896

radicals) substituted Aiiiiir.; group and a carboxylic acid (C, -C _) - ester, Carboxamides or a sulfonic acid amide radical optionally substituted by lower alkyl or aryl groups (phenyl groups) means.

The metals M are, for example, chromium, manganese or iron, preferably however, zinc and cobalt and, in particular, copper and nickel, can be considered.

The aldehydes of the formula (III) used as starting compounds are easily accessible connections. For their preparation, for example, compounds of the formula (IV)

(IV)

in which X has the meaning given above, in lower aliphatic Carboxylic acids reacted with hexamethylenetetramine.

The new compounds, which are advantageously suitable as pigments, are suitable, in particular after conditioning that is customary with pigment dyes, for example for coloring plastic compounds, which are understood to mean solvent-free, solvent-containing, plasticizer-free and plasticizer-containing compounds made of plastics or synthetic resins, and also suitable for pigmenting paints on oily or aqueous basis and verschiedenster paints type, for spin dyeing of viscose and cellulose acetate, or for pigmenting of polyethylene, polystyrene, polyvinylchloride, rubber and synthetic leather.

They can also be used in printing inks for the graphic industry, for pulp dyeing, for the coating of textiles or pigment printing can be used. The colorations obtained are

outstanding

Immigration, light, weather and solvent fast, show excellent Heat resistance and are characterized by high color strength, good transparency and often surprisingly pure shades the end.

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The following examples serve to illustrate the invention. The parts specified therein are standard parts *

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Example 1;

21.6 parts of l-formyl-2-hydroxy-6-naphthoic acid are added Stir to 3.0 parts of 1,2-diaminoethane dissolved in 250 parts Ethanol and 10 parts of glacial acetic acid, and heated to boiling for 3 hours. After cooling, the yellow compound is filtered off with suction and washed well with ethanol. The moist product is then added to 150 parts of dimethylformamide with 9.0 parts of nickel diacetate added and heated to 120 ° C for 4 hours. The yellow pigment obtained in this way is filtered off while hot, well only with hot Water and then washed with ethanol. After drying, 30.2 parts of the yellow pigment of the formula are obtained

CH = N - CH ₂ - N «ρ CH

HOOC COOH

Ni calc. 11.4% found: 11.3%

the polyvinyl chloride dyes a clear yellow with excellent fastness properties.

Example 2; _.

21.6 parts of l-formyl ^ -hydroxy-e-naphthoic acid, 3.0 parts of diaminoethane and 9-0 parts of nickel diacetate are heated to boiling in 300 parts of ethanol for 5 hours. The yellow compound is filtered off hot and washed well with hot water and ethanol. The product is then heated in 150 parts of dimethylformamide for 1 hour at 120 ^° C., filtered off while hot and washed thoroughly with hot water and ethanol. After drying, 31.0 parts of a yellow pigment which is identical to that obtained in Example 1 are obtained.

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Using an analogous procedure, the following are described Table 1 listed nickel complex compounds of the following formula with R and X the meaning given in Table 1;

CH = N-R-N = GH

Table 1:

example R. X nuance
in PVC 3 -OH ₂ CH ₂ - -COOCH,
O yellow 4th -CH ₂ CH ₂ - -GOOCH ₀ CH ₀ Ch ₀ CH,
ddd O yellow 5 -CH ₂ CH ₂ - -CONH ₂ yellow 6th -GH ₂ CH ₂ - -CONHCH, yellow 7th -CH ₂ CH ₂ - -CONHCH ₀ CH ₀ CH ₀ Ch,
ddd 5 yellow 8th -CH ₂ CH ₂ - -CON (C ₄ H ₉ ) ₂ yellow 9 -CH ₂ CH ₂ - -CONHCH ₂ CH ₂ N (GH,) ₂ yellow 10 —CHpGHp- -CONH - (Ty yellow-green 11 -CH ₂ CH ₂ - -CONHNH - \ S yellow-green 12th -CCH ₂ V -COOH yellow-green 13th - (CH ₂ ) - -COOK yellow-green

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- ίο

example

jNiiance in PVC

- (CH ₀ ) _X NH (CH ₀ ), -

-COOH

yellow-green

CH

-COOH

yellow-green

- (CH ₂ ) ₆ -

-COOCH,

yellow-green

Example 17?

To 12.2 parts of 3.3'-dimethoxy- ^. V-diaminodiphenyl in 200 parts of ethanol and 10 parts of glacial acetic acid, 22.9 parts of ^{1-5 I} ormyl-2-hydroxy "-6-naphthoic acid methylamide are added with stirring and then heated to reflux for M hours The red compound is filtered off with suction, washed well with ethanol and then again introduced into 300 parts of ethanol. 21.0 parts of copper acetate are then added and the mixture is heated to boiling for 6 hours. The yellow pigment is filtered off while hot and washed well with hot water and ethanol drying gives 34.6 parts of the dye of the formula.

= CH

H ₂ CNHOC 3-

Cu calc. 16.7 % found . 16.9%

CONHCH,

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The pigment obtained in this way colors polyvinyl chloride. in -iiiem opaque GsIb 'of very good fastness properties. In an analogous process, those in the following are obtained Table 2 listed copper complex compounds of the following Form1

-N = CH

with X and Z as defined in Table 2:

Table 2: example

nuance
in PVC

18th -COOH 19th -COOCH 20th -CONH ₂ 21 -COOH 22nd -COOCH 25th ^ ^- ν / V »/ ΟΧΙλ Example 24-

-ο-

-0-

-COO-

-COO-

-COO-

-COO-

yellow-brown yellow-brown yellow-brown yellow-brown yellow-brown yellow-brown

3 parts of 1,2-diaminobenzene are dissolved in 170 parts of ethanol and 10 parts of glacial acetic acid. To this end, 21.6 parts of l-formyl-2-hydroxy-6-naphthoic acid are introduced with stirring and the mixture is then heated to the boil for 3 hours.

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The gelte bis-azomethine is filtered off while hot, washed with ethanol and then added moist to 200 parts of dimethylformamide. The mixture is then heated to 100 ^° C. and 9.0 parts of nickel diacetate are added. After heating for 3 hours, the red pigment is filtered off and washed well with hot water and ethanol. After drying, 33.4 parts of the pigment of the formula are obtained

HOOG

Ni calc. 10.5% found. 10.3%

The pigment colors polyvinyl chloride in a brownish red with excellent resistance to bleeding.

Example 25

2.8 parts of 1,2-diaminobenzene and 11.3 parts of l-formyl ~ 2-hydroxy-6-naphthoic acid are heated for 1 hour at 120 ⁰ G in 100 parts of dimethylformamide. Then 4.5 parts of nickel diacetate are added and the mixture is ^{heated to 120 °} C. for a further 3 hours. The red compound is filtered off hot and washed well with hot water and ethanol. After drying, 14.2 parts of a red pigment which is identical to that prepared according to Example 24 are obtained.

In a corresponding way, as described in the previous examples, the nickel complex compounds of the following formula listed in Table 3 below are obtained

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with the meanings given there for X and Y

example Table 5;

Nuance in FVG

26 27 28 29 30 31

32 33 '34

-COOCH,

-CONH ₂ -CONHCH,

H H H H

-CONHCH ₀ CH ₀ N '

-CONH

-CONHNH

-COOH

-COOH

-COOH

.CH-

CH,

H H NO.

Cl CH,

orange orange red red red

Red

orange orange red red red

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example X Y 2533947
nuance
in PYC 37 -COOH -NHCOCH-,
3 Red 38 -COOH -NHCO -ζ ~% Red 39 -COOH -COOH Red 40 -COOH -CONH ₂ Red 41 -COOH -CONH -fy ► red 42 -COOH -SO ₀ NH -f ^
d \ zz / > red 43 -CONH ₂ -NO ₂ Red 44 -CONHCh ₀ CH ₀ CH ₀ CH,
ddd Z> -COOH Red 45 -CONHCH ₀ CH ₀ CH ₀ Ch,
ddd O -COOCH ₃ Red 46
Example 47 -COOCH,
3 -COOCH,
3 Red

11.5 Tei3el-i ⁿ ormyl-2-hydroxy-6-naphthoesäuremeth7lester with stirring, to 1.5 parts of hydrazine hydrate (80% strength) are added in 150 parts of ethanol. The mixture is then heated to boiling for 3 hours. Then 3 parts of sodium acetate and 4.5 parts of nickel diacetate are added and the mixture is heated to the boil for a further 5 hours. The pH is always kept above 7 using dilute aqueous sodium hydroxide solution.

The yellow compound is then filtered off hot, washed well with hot water and ethanol. After drying, 14.3 is obtained Parts of a yellow pigment to which the formula Ic with R a single bond ^ M is Ni and X is -COOCH. comes to.

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A paint color pigmented with it shows good overcoating and lightfastness.

Example 48

11.5 parts of methyl l-5Ormyl-2-hydroxy-6-naphthoate are added to 1.5 parts of hydrazine hydrate (80%) in 150 parts of ethanol with stirring. The mixture is then heated to the boil for 3 hours and the yellow compound is filtered off while hot, it is washed well with ethanol and then wet into 100 parts of dimethylformamide. 5.0 parts of nickel diacetate and 30 parts of sodium acetate are then added at 100 ° C. and the mixture is stirred at this temperature for 5 hours. The yellow complex compound obtained in this way is ^{filtered off at 30-40 °} C. and washed thoroughly with hot water and ethanol. After drying, 9.8 parts of a yellow pigment which is identical to that obtained according to Example 47 are obtained. If the methyl l-5Ormyl-2-hydroxy-6-naphthoate in Example 47 is replaced by the aldehydes listed in Table 4, the corresponding nickel complex compounds of the general formula Ic with R and X with the meaning given in the table are obtained:

Table 4:

Example aldehyde R X. Nuance·

in the paint

CHO OH CONH ₂ yellow ⁴⁹ \ f H ₂ NC ^ CHO - OH COOH yellow 0
50 (jf HO-C ~ "^

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Claims (6)

HOE 75 / F I90 claims: 1. Metal-containing disazomethine compounds of the formulas -M _Z ZM 0. CH = N N = CH CH = N-R-N = CH and 709807/0896 HOE 75 / F! 'PO wviJn Il «a simple bond, a straight-chain or branched one Alkylene radical formed by heteroatoms, a divalent Group or an isocyclic or heterocyclic ring can be interrupted, a cycloalkylene radical, an arylene radical or a heterocyclic radical, Z a group capable of forming metal complexes and X a carboxylic acid, carboxylic acid ester, optionally substituted carboxamide or carboxylic acid mean ehydrazide group and M is a divalent metal atom. 2. Process for the preparation of metal-containing disazomethine compounds according to claim 1, characterized in that 1 mol of one or more diamines of the formula H ₂ N - R - NH ₂ wherein R has the meaning given in claim 1, with 2 moles of one or more compounds of the formula wherein X has the meaning given in 1), condenses and the disazomethine compound obtained at the same time or metallized in a subsequent reaction. 3. Use of the compounds mentioned and defined in claim 1 or of the compounds prepared according to claim 2 as colorants, 4. Use according to claim 3 as ^a pigment. 5. Use according to claim 3 for pigmenting printing pastes, high molecular weight plastic masses, varnishes, paints or spinning masses. 6. Use according to claim 3 for the production of printing inks.