DE2260558A1 - DISAZOPIGMENTS AND METHOD FOR MANUFACTURING THEREOF - Google Patents

Description

CIBA-GEIGYAG, CH-4002 Basel

Case 3- 7906 _{Dr γ} zumstom ssn. - Dr. Έ. Asaman

¹ ' Dr.R. Ko9n! G3b.jrgsr - Dip !. P! y :: ·. f :. ii ^ iz

Germany ρ _o tVnVOVwYiV β

8 MOnch ·!) 2, Brüuhuu $; ticißa 4 / III

Disazo pigments and processes for their manufacture.

It has been found that new valuable disazo pigments of the formula

309825/1056

Ν-R ₁ R ₁ -N

B. ■■■■ »■ · ■■: .-- : ■■■■ .-. U ^ αΜ -ά :. ' NN _τ

I OH HO I ^f

COM-

wherein R, a 2-nitro-5-chlorophenyl or 1-nitronaphty1, -2-radical, R2 is a naphthalene residue in which the azo, hydroxy and -CO group are in 1,2,3-position and R ^ is a phenylene or. Naphthylene radical is obtained when a) a carboxylic acid halide of the formula

NR ₁
» ^X

T OH ' ^Π

COHaI

condensed with an arylenediamine in a molar ratio of 2: 1, or

b) a diazo or diazoamino compound of an amine the formula

H ₂ NR ₁ III

with a 2,3-hydroxynaphthoic acid arylide of the formula

OHH O

/ ^R 2 IV

CONII - R NHOC

309 8 25/1056

BATH ORIGINAL

in a molar ratio of 2; 1.

Since the dyes according to the invention are Pigments are water-solubilizing groups, especially acidic water-solubilizing groups, such as sulfonic acid or carboxylic acid groups, of course excluded.

Of particular interest are disazo pigments of the formula .. ■ '; - ·' - '·. . "" · '·· "''■''·;·"^{> v}

wherein Ri is a 1,4-phenylene or 1,5-naphthylene radical and Z is a hydrogen or halogen atom, a lower alkoxy group, i.e. those having 1 to 4 carbon atoms, a nitro or cyano group, or disazo pigments of the formula

VI

09825/1056

wherein Z and R have the meaning given. [

In the formulas given, R preferably represents a radical of the formula

YII

wherein X and Y are hydrogen or halogen atoms, cyano groups, lower alkyl, alkoxy, alkylsulfonyl or alkoxycarbonyl groups, i.e. those with 1 to 4 carbon atoms. The azo dye carboxylic acids, which according to the invention Acid halides to be used are based on, obtained by coupling the corresponding amine with a 2,3-hydroxynaphthoic acid, especially one of the formula

VIII

OÜH

where Z has the meaning given.

The azo dye carboxylic acids obtained in this way are with Agents that are capable of converting carboxylic acids into their halides, E.g. the chlorides * or bromides, transferring, so in particular with phosphorus halides such as phosphorus pentachloride

309825/1056

BATH ORIGINAL

or pentabromide or phosphorus trichloride, preferably thionyl chloride and the Phosphoroxyhalogeni-.

The treatment with such acid-halogenating agents is expediently carried out in inert organic solvents such as dimethylformamide, chlorobenzenes, for example mono- or dichlorobenzene, toluene, xylene or nitrobenzene,

in the case of the last 5 with the addition of di-

• · ■ ν * '' ¹ ViV. : '. ν methylformamide. > ·. -. ■ · ''';"-·' · ■

In making the. Carboxylic acid halides, it is generally expedient to first dry the azo compounds prepared in an aqueous medium or to free them azeotropically from water by boiling in an organic solvent. Azeotropic drying can, if desired, be carried out immediately before the treatment with the acid-halogenating agents
will. .

According to the present process, the monocarboxylic acid halides obtainable in this way are condensed with arylenediamines, preferably with phenylenediamines or 1,5-diaminonaphthalenes in a molar ratio of 2.1. One preferably uses
1,4-diaminobenzenes of the formula - ...

309325/1056

wherein X and Y are hydrogen or halogen atoms, lower alkyl, Alkoxy or methylsulfonyl groups mean.

The following diamines are examples:

1,4-diaminobenzene

1,4-diamino-2-chlorobenzene
1,4-diamino-2-bromobenzene
1,4-diaraino-2,5-dichlorobenzene
1,4-diamino-2-methylbenzene

1,4-diamino-2,5-dimethylbenzene ''"*.?.;'\''1,4-diamino-2-methoxybenzene
1,4-diamino-2,5-dimethoxybenzene "1,4-diamino-2,5-diethoxybenzene

1,4-diaminobenzene-2,5-dicarboxylic acid dimethyl ester '2-cyano-1,4-phenylenediamine

2-trifluoromethyl-1,4-phenylenediamine
2-chloro-5-methyl-1,4-phenylenediamine
2-chloro-5-methoxy-1,4-phenylenediamine
2-methyl-5-methoxy-1,4-phenylenediamine, 2-methylsulfonyl-1,4-phenylenediamine
1,3-diaminobenzene
2-methyl-1,3-diaminobenzene
4,6-dichloro-1,3-diaminobenzene
1,5-diaminonaphthalene

The condensation between the carboxylic acid halides of the type mentioned and the amines is expedient in carried out in an anhydrous medium. Under this condition, it generally takes place surprisingly easily at temperatures those in the boiling range of normal ^ organic solvents such as toluene, monochlorobenzene, dichlorobenzene, trichlorobenzene,.

309S25 / 1056

Nitrobenzene and the like. To accelerate the reaction, it is generally advisable to use an acid-binding agent such as anhydrous sodium acetate or pyridine. The dyes obtained are partly crystalline and partly amorphous and are mostly obtained in very good yield and in a pure state. It is advisable to first remove the acid chlorides obtained from the carboxylic acids. However, the acid chlorides can be dispensed with in some len Fäl- without damage to a separation and condensation take place immediately subsequent to the preparation of carboxylic acid chlorides. .

According to embodiment b) of the method according to the invention the new dyes are obtained by using a diazo or diazoamino compound of an amine of the formula

wherein R, which has the meaning mentioned at the beginning, with a 2,3-hydroxynaphthoic acid arylide the formula

OHH O

CONHR ₃ MCO

H ₂ XI

couples in a molar ratio of 2: 1.

30982B / TÖ66

The 2,3-hydroxynaphthoic acid arylides required for this purpose are from a method known per se 2,3-hydroxynaphtoic acid optionally substituted in the 6-position and an arylenediamine in an anhydrous medium, such as toluene, xylene, chlorobenzene, etc. under the influence of a condensing agent, can be produced like phosphorus trichloride. The coupling takes place advantageously through gradual

would give the aqueous-alkaline solution of the coupling component to the acidic solution of the diazonium salt instead of the to the solution the amount of alkali metal hydroxide to be used in the coupling component is expediently dimensioned in such a way that it serves to neutralize the mineral acid liberated from the diazonium salt during the coupling sufficient. The coupling is expediently carried out at a p "value of 4 to 6. The p "value becomes advantageous adjusted by adding a buffer. The salts, in particular the alkali salts of formic acid and phosphoric acid, are used as buffers or in particular acetic acid. The alkaline solution of the coupling component expediently contains a Wetting, dispersing or emulsifying agents, for example an aralkyl sulfonate such as dodecylbenzenesulfonate or the sodium salt of 1, l'-naphthyl methanesulfonic acid, polycondensation products of alkylene oxides, such as the action product of ethylene oxide on p-tert-octylphenol, also alkyl esters of sulforicinoleates, for example n-butyl sulforicin oleate. The dispersion of the coupling component can also be advantageous protective colloids, for example

309825/1056

wise methyl cellulose, or smaller amounts of inert ones, in water poorly soluble or insoluble organic solvents contain, for example, optionally halogenated or "nitrated aromatic hydrocarbons, such as benzene, toluene, Xylene, chlorobenzene, dichlorobenzenes or nitrobenzene ^ as well as aliphatic halogenated hydrocarbons such as carbon tetrachloride or trichlorethylene, also miscible with water organic solvents such as acetone, ethylene, glycol monomethyl ether, Methy läthy Ike ton, methanol, ethanol, isopropanol or dimethylformamide.

The coupling can also advantageously be carried out in such a way that an acidic solution of the diazonium salt is obtained continuously combined with an alkaline solution of the coupling component in a mixing nozzle, the components being coupled immediately. It is important to ensure that Diazo component and coupling component in equimolecular amounts are present in the Mischdlise, with a lower excess of coupling component proves advantageous. The easiest way to do this is to check the pu value of the Liquid in the mixing nozzle causes. Also is in the mixer nozzle for a strong vortex of the two solutions care for. The resulting dye dispersion is continuously withdrawn from the mixing nozzle and the dye is separated off by filtration *

The coupling can also be carried out in such a way that a diazoamino compound of the amine of the formula

309825 / 10Si

- if -

NH ₂ , XII

where R ^ has the meaning mentioned at the beginning »together with the Coupling component in an organic solvent, if appropriate heated in an aqueous organic solvent, preferably in the presence of an acid.

The aryldiazoamino compounds to be used according to the process are obtained according to a known process by condensation of an aryldiazonium salt with a primary or, preferably, with a secondary amine. A wide variety of amines, for example aliphatic amines, such as methylamine, ethylamine, ethanolamine, propylamine, butylamine, hexylamine and especially dimethylamine, diethylamine, diethanolamine, methylethanolamine, dipropyldmin or dibutylamine, aminoacetic acid, methylaminoacetic acid, are suitable for this purpose. Butylaminoacetic acid, aminoethanesulphonic acid, methylaminoethanesulphonic acid, guanylethanesulphonic acid, jS-aminoethylsulphuric _{acid, t} alicyclic amines such as cyclohexylamine, "N-methylcyclohexylamine, dicyclohexylamine, aromatic amines, aromatic amines, 2-aromatic amines, 2-aromatic amines, such as 4-atninobenzoic acid, 2-aromatic amines, sulfo-benzoic acid (4-amino-benzoic acid, 4-sulfo-amines, sulfo-amines, such as 4-atninobenzoic acid, sulfo-benzoic acid (4-amino) sulfoic acid (4-sulfo-benzoic acid) -succinobenzoic acid, guanylethanesulfonic acid, jS-aminoethylsulfonic acid, guanidine, 4-N-methylaminobenzoic acid, 4-ethylaminobenzoic acid, l-aminonaphthalene-4-sulfonic acid, 1-aminonaphthalene-2,4-disulfonic acid, heterocyclic amines such as piperidine, morpholine, pyrrolidine, dihydroindole and finally sodium cyanamide or dicyandiamide.

303325/1055

As a rule, the diazoamino compounds obtained are sparingly soluble in cold water and can optionally separated from the reaction medium in crystallized form after salting out. In many cases, the press cake can be moist can be used for further implementation. In individual cases it may prove to be useful to use the diazoamino compounds before the implementation to dewater by vacuum drying or after slurrying the moist press cake in a solvent to remove the water by azeotropic distillation. ·

- The coupling of the diazoamino compound with the naphthol takes place in an organic solvent, for example chlorobenzene, o-dichlorobenzene, nitrobenzene, pyridine, ethylene glycol, Ethylene glycol monomethyl or monoethyl ether, dimethylformamide, formic acid or acetic acid; Using of solvents that are miscible with water, it is not necessary to use the diazoamino compounds in anhydrous form. It can, for example, the watery-moist Nutschkuchen be used. The cleavage of the diazoamino compound preceding the coupling takes place in an acidic medium. Used one neutral solvent, then the addition of an acid, For example, hydrogen chloride, sulfuric acid, formic acid or acetic acid are required.

The coupling is expediently carried out in the warm, preferably at temperatures between 80 and 180 ^° C. and generally proceeds very quickly and completely.

309825/1056

2250558

Finally, the coupling can also be carried out in such a way that the amine to be diazotized with the coupling component suspended in an organic solvent in a molar ratio of 2: 1 and with a dietetic agent, in particular treated with an ester of nitrous acid, such as methyl, ethyl, butyl, amyl or octyl nitrite.

The new dyes are valuable pigments which can be used in finely divided form for pigmenting high molecular weight organic material, for example cellulose ethers and esters, such as ethyl cellulose, nitrocellulose, cellulose acetate, cellulose butyrate, super polyamides or super polyurethanes or polyesters, natural resins or synthetic resins such as Polymerization resins or condensation resins, for example aminoplasts, especially urea and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters, rubber, casein, silicone and silicone resins, individually or in mixtures. Z It does not matter whether the high molecular weight compounds mentioned are in the form of plastic masses, melts or in the form of spinning solutions, varnishes, paints or printing inks. Depending on the intended use, it proves to be advantageous to use the new pigments as toners or in the form of preparations.

' ⁿ ? 5/1056

228.0559

In the following examples, unless otherwise stated, parts are parts by weight and percentages Weight percentages, and temperatures are in degrees Celsius specified. ··

3Q982S / 1Q58

22SQ558

example 1

18.6 parts of the diazotized by coupling! l-nitro-S-chloro-l-ainino-benzene with 2,3-hydroxynaphthoic acid The dye obtained are in 50 parts by volume of chlorobenzene with 7.2 parts by volume of thionyl chloride for 20 minutes to ■■■■■ 135 ° heated. The dye goes into solution, Mari leaves cool and isolate the precipitated, crystalline dyestuff * carboxylic acid chloride by filtration, dried is obtained 17 parts of the chloride.

2.34 parts of this chloride are in 150 parts by volume len o-dichlorobenzene with 0.475 parts of 1,5-diamino-naphthalene heated to 135 ° for 12 hours. The pigment formed is then filtered off while hot, with hot o-dichlorobenzene, then washed with dimethylformamide, methanol and water. After drying there are 2.4 parts of the pigment! the formula

before. The pigment colors polyvinyl chloride in yellow-brown. Tpn vpn, very good migration uncj

309825/1056

K? ⁵ C ^f \ i ^r

2200558

■ Examples 2 to 10

The following table contains further examples of pigments obtained using that in Example 1 Dye carboxylic acid chloride with those listed in column I. Diamines, as indicated in Example 1 ,, im, Molver- ·, ratio 2: 1 condensed, and column II is in polyvinyl chloride received nuances of ..

at
game
No. ■ I II 2 1,4-diamino benzene reddish. Brown 3 2-chloro-1,4-diamino-benzene Brown 4th 2,5-dichloro-1,4-diamino-benzene Brown orange 5 2-methylsulfonyl-1,4-diamino-benzene Red 6th 2,5-diethoxy-1,4-diamino-benzene Yellow-brown 7th 2-methoxy-1,4-diamino-benzene Yellow-brown ¹ 8 2-methyl-5-chloro-1,4-diamino-benzene Brown 9 2,5-dimethyl-1,4-diamino-benzene Brown 10 1,4-diamino-benzene-2,5-dicarboxylic acid
dimethyl ester - ■ 'Red-brown 11 2-methyl-1,4-diamino-benzene, Brown 12th 2,5-dimethoxy-1,4-diamino-benzene Yellow-brown 13th 2-methyl-5-methoxy-1,4-diaminobenzol Yellow brown '

3 0 9 8 2 5/105 6
BAO ORIQINAt

'"" 2200558

Example 14

19.5 parts of that obtained by coupling diazotized 1-nitro-2-amino-naphthalene with 2,3-hydroxynaphtoic acid Chlorobenzene will share the dye in 150 volumes

7.2 parts by volume of thionyl chloride at 135 ° for 30 minutes, warmed up. The dye goes into solution. It is allowed to cool and the carboxylic acid chloride which has precipitated out in crystalline form is separated off by filtration. When dried, 18.3 parts of the chloride are obtained.

3.65 parts of this chloride are in 150 parts by volume of o-dichlorobenzene with 0.485 parts of 1,4-diaminobenzene and

1.3 parts by volume of triethylamine heated to 135 ° for 12 hours. The pigment formed is then filtered off while hot, with hot o-dichlorobenzene, then with dimethylformamide, Washed methanol and water. After drying, there are 3.5 parts of the pigment of the formula

309825/1056

OCHK

-M-OC

before * Bas Pigment colors polyvinyl chloride in a red violet hair dryer very good migration and light fastness,

Examples -15 Ms 19

Is used instead of 1,4-Diaminobenzoi the Compounds mentioned below in column I and the procedure otherwise as indicated in Example 14 are obtained Pigments with the nuance mentioned in column II »

example
No. I. Bordeaux
Bordeaux
Bordeaux
Bordeaux
Bordeaux 15th
16
17th
18th
19th 2-methoxy-1,4-diaminobenzene
2,5-bimethyl-1,4-diaminobenzene
2 methyl ~ 5-methoxy-1,4-diaminobenzene
2-chloro-5-methoxy-1,4-diaminobenzene
1,5-diamino-naphthalene

3D932B / 1ÖB6

22-058

Example 20

65 parts of stabilized polyvinyl chloride, 35 parts of dioctyl phthalate and 0.2 part of that obtained in Example 1 Dyestuff are stirred together and then reciprocated on a two-roll calender for 7 minutes at 140 ° »· rolls. A yellow-brown colored film of very good fastness to light and migration is obtained.

JÜ9B25 / 1056

Claims (1)

Patent claims Disazo pigments of the formula N
I OH COMH- R ₁ -N . Il -HD .I -NHOC wherein R _{1 is} a 2-nitro-5-chlorophenyl or 1-nitronaphthyl-2 radical, R _{2 is} a naphthalene radical in which the azo, hydroxy and -CO groups are in the 1,2,3-position and R ₃ denote a phenylene or naphthylene radical. Disazo pigments according to claim 1 of the formula | o ₂ . κ O η I CO — NH- in which R 1 denotes a 1,4-phenylene or 1,5-naphthylene radical and Z denotes a hydrogen or halogen atom, a lower alkoxy, nitro or cymene group * 3 0 Q :; ■> 5/1 0 SS BADORlGINAi Disazo pigments according to claim 1 of the formula NO, ¹ H. CO-NH NO, ■ N I! N HO NH-CO wherein Z and R have the meaning given in claim 2. 4. Disazo pigments according to claims 2 and 3, wherein R # is a radical of the formula means, in which X and Y are hydrogen or halogen atoms, cyano groups, lower alkyl, alkoxy, alkylsulfonyl or alkoxycarbonyl groups mean. 5. Process for the preparation of disazo pigments of the formula 309825 /. 1.056 BATHROOM OFFLFGINAL 22QP558 —Ir If · ■■ "■■ N I OH HQ I R / ^X COlH Rv KHOO wherein R, an S-Mtrd-S-chlorophenyl or 1-nitroaphthyl-2 radical * R2 is a naphthalene radical in which the azo, hydroxy and -CO groups are in the 1,2,3-position and R ^ denote a phenylene or raphthylene radical, characterized in that a) a carboxylic acid halide of the formula . j OH COHaI condensed with an arylenediamine in a molar ratio of 2: 1, or. · ■ "-". b) a diazo or mazoariino compound of an amine the formula Vt Vl Ό TTT MoJM-tfc}. JLJLi- with a 2,3-hydroxynaphthoic acid arylide of the formula GH HO / ^R 2 CONII-— iL · —-NHÖG 3 0 9.82 5/105 8 couples in a molar ratio of 2: 1. 6 «The method according to claim 5, characterized in that that one of a carboxylic acid chloride of the formula COCl starts in which Z is a hydrogen or halogen atom »a lower alkoxy, nitro or cyano group. - 7. The method according to claim 5, characterized in that one of a carboxylic acid chloride of the formula OH COCl proceeds, where Z is the indicated in claim 6? Bedcmtunf, hdt * 309825/1056 . - 23 - 8. The method according to claims 5 to 7, characterized that a phenylene or 1,5-naphthylenediamine is used as the arylenediamine. 9. The method according to claim 8, characterized in that that a phenylenediamine of the formula is used as arylenediamine used, in which X and Y are hydrogen or halogen atoms, cyano groups, lower alkyl, alkoxy, alkylsulfonyl or alkoxycarbonyl groups mean. 10. A method for pigmenting high molecular weight organic material, characterized by the use of the dyes according to claims 1 to 4.. ·. 11. The pigmented material obtained according to claim 10. 3 0 9 8 2 5/1056
BAO ORIGINAL