DE1544459A1 - Process for the production of disazo pigments - Google Patents

Description

15U459

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND) Case 5623 / E

Germany

Process for the production of disazo pigments.

It has been found that valuable disazo dye pigments can be obtained the formula

COCH COCH-.

1 ³ I.

(1) AHNOCB-N = N-CH-COHN-R-NHCO-CH-N = N-B-CONHa

obtained when a) a dihalide of a dicarboxylic acid of the formula

COCH COCH,

(2) HOOC-B-N = N-CHCONH-R-NHCO-Ch-N = N-B-COOH

condensed with an aminobenzene in a molar ratio of 1: 2, or b) the diazo compound of an amine of the formula

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15U459

(3) AHNOC-B-NH ₂

with a diacetoacetyl-arylenediamine of the formula

(4) H, C -COCH ^ -COHN-R-

Coupling in a molar ratio of 2: 1, given in deo Formula A is a benzene residue, B is a benzene residue, which is a carboxylic acid ester group in the ο-position to the azo group has, and R is an arylene radical, in particular a phenylene or diphenylene radical, preferably a radical of

Formula _vv

i2 Ϊ2

or
^Y l

mean, wherein X, a hydrogen or halogen atom, a Alkyl or alkoxy group, Y, a hydrogen or halogen atom, an alkyl or alkoxy or trifluorinethyl group and Yp is a hydrogen or halogen atom, an alkyl or Mean alkoxy group.

Since the dyes according to the invention pigments are water-solubilizing groups, in particular acidic, water-solubilizing groups, such as Sulphonic acid or carboxylic acid groups, of course excluded.

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The dicarboxylic acid of the formula (2) is conveniently obtained by coupling the diazo compound Monocarboxylic acid of the formula

. (5) 'HOCC-B-NH ₀

where B has the meaning given, with a compound of formula (4) in a molar ratio of 2: 1. The connection of the Formula (4) is obtained in a simple manner by the action of diketene or acetoacetic ester on aromatic diamines, such as

1,4-diaminobenzene, 1,3-Diaminobenzolj 1, 3-diamino-4-methylbenzene, 1, 3-diamino-4-methoxybenzene, 1,3-diamino-4-chlorobenzene, 1,4-diamino-2-chlorobenzene , l 4-diamino-2-bromobenzene, l-diamino-2 _J 4, _{<5-dichlorobenzene,} LJ4-diamino-2-methylbenzene, 1,4-diamino-2,5-dimethylbenzene, 1, 4-diamino- 2-methoxybenzene, 1,4-diamino-2,5-dimethoxybenzene, l, 4-diamino-2 _J 5-diäthoxybenzol,

1,3-diamino-2,6-dimethylbenzene, 4,4'-di aminodiphenyl,

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15U459

3,3'-dichloro-4,4'-diaminodiphenyl,

3,3'-dimethyl-4,4'-diaminodiphenyl, 3,3'-dimethoxy-4,4 ¹ -diaminodiphenyl, 3,3 ', 5,5'-tetrachloro-4,4'-diaminodiphenyl, 3,3 '-Dichloro-5,5'-dimethyl-4, 4'-diaminodiphenyl, 2,8-Diaminoehrysen,

4,11-diaminofluoranthene,

2,6- or 1,5-diaminonaphthalenes.

The amino to be used as diazo components carboxylic acids preferably correspond to the formula

COOR ₁

(6)

OOH,

wherein R _{1 is} a lower alkyl radical. Examples are:

2-amino-4-carboxy-benzoic acid methyl ester, 2-amino-4-carboxy-benzoic acid ethyl ester, 2-amino-4-carboxy-benzoic acid propyl ester, 2-amino-4-carboxy-benzoic acid isopropyl ester, 2-Amino-4-carboxy-benzoic acid butyl ester.

The azodicarboxylic acids of the formula (2) are treated with agents that are capable of converting carboxylic acids into their To convert halides, e.g. the bromides or chlorides, for example with phosphorus halides, e.g. phosphorus trichloride, pentachloride or oxychloride, but in particular

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BATH

Thionyl chloride. Treatment with such acid-containing agents is best in inert organic solvents, such as chlorobenzenes, e.g. mono- or dichlorobenzene, toluene, xylene, benzene or nitrobenzene. at Using thionyl chloride as an acid-chlorinating agent, it proves to be advantageous in the presence of dialkyl formamides, especially dimethylformamide to work.

When preparing the carboxylic acid halides, it is usually expedient to use them in an aqueous medium prepared azo compounds to dry first or azeotropically by boiling in an organic solvent .. of Free water. This azeotropic drying can, if desired, be carried out immediately before the treatment with acid-halogenating agents Funds are made.

The so. available dicarboxylic acid halides with aminobenzenes, especially those of the formula

Z
implemented. * where X, Y and Z are hydrogen or halogen atoms,

Alkyl, alkoxy, phenoxy, trifluoromethyl, carbalkoxy or Mean cyano groups. Examples are:

Aniline,

2-, 3- or 4-chloroaniline,

2, 5-dichloroaniline,

2,4,5-trichloroaniline, -

BATH

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2,4,6-trichloroaniline, 4-bromoaniline,

2-, 3- or 4-methylaniline, 2-, 3- or 4-methoxyaniline, 2-methyl-3-chloroaniline, 2-methyl-4-chloroaniline, 2-methyl-5-chloroaniline, 3-trifluoromethylaniline, 2-chloro-5-trifluoromethylaniline, 3,5-di- (trifluoromethyl) -aniline, 2-aminobenzoic acid methyl ester, 2-aminobenzoic acid ethyl ester, 4-amino benzoic acid methyl ester, 3-amino-4-chlorobenzoic acid ethyl ester, 3-amino-4-methoxybenzoic acid methyl ester, 4-cyananiline.

BATH

00S815 / 0694

The condensation between the carboxylic acid halides of the type mentioned at the outset and the amines are expediently carried out in an anhydrous medium. On this condition it is generally surprisingly easy even at temperatures that are in the boiling range of normal organic solvents, such as toluene, monochlorobenzene, dichlorobenzene, trichlorobenzene and nitrobenzene. To speed up the Implementation, 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 in very good yield and preserved in a pure state. It is advisable to first remove the acid chlorides obtained from the carboxylic acids. In some cases, however, it is possible to dispense with the separation of the acid chlorides without damage and the condensation takes place immediately, subsequent to the preparation of the carboxylic acid chlorides. ■

According to embodiment b) of the invention Process is the diazo compound of an amine of the formula (3) with a diacetoacetylarylenediamine of the formula (4) coupled in a molar ratio of 2: 1. Diazo compounds of amines of the formula are preferably used

COOR,

CONHA

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wherein A and R have the meaning given.

The coupling takes place preferably in Sühwachraaurem Medium instead of, expediently in the presence of customary, coupling-promoting agents. As a means of promoting the clutch dispersants may be mentioned in particular, for example aralkyl sulfonates, such as dodecylbenzenesulfonate or 1,1'-dinaphthylmethane-2,2'-disulfonic acid or polycondensation products of alkylene oxides. The dispersion of the coupling component can also be advantageous protective colloids, for example methyl cellulose or smaller amounts of inert, in Water containing sparingly soluble or insoluble organic solvents, 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, for example, hydrocarbon tetrachloride or trichlorethylene, furthermore water-miscible organic solvents such as acetone, methyl ethyl ketone, methanol, ethanol or isopropanol.

The coupling can also advantageously be carried out in such a way that an acidic solution of the diazonium salt is continuously combined with an alkaline solution of the coupling component in a mixing nozzle, the components being coupled immediately Quantities are present in the mixing nozzle, it proves to be advantageous to use a small excess of the

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- 9 - to use naphthols. The easiest way to do this is through control

of the p "value of the liquid in the mixing nozzle. Also is η

in the mixing nozzle for a strong swirling of the two Solutions to provide. The resulting dye dispersion is the The mixing nozzle is continuously withdrawn and the dye is separated off by filtration.

The new dyes represent valuable yellow up

orange pigments, which can be used for a wide variety of pigment applications, e.g. in finely divided form for dyeing rayon and viscose or cellulose ethers and esters or of superpolyamides or super-polyurethanes or polyesters in the spinning mass, as well as for the production of colored lacquers or lacquer formers, solutions and products made from acetyl cellulose, nitrocellulose, natural resins or synthetic resins such as polymerization resins or condensation resins, e.g. aminoplasts, alkyd resins, phenoplasts, polyolefins such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, rubber, casein, silicone and silicone resins. They can also be used to advantage in the production of colored pencils, cosmetic preparations or laminating plates *

Compared to the closest comparable dyes of the

German patent specification 1 150 165 (Case 3782) , the dyes according to the invention are characterized by better lightfast

unity and compared to those in Belgian patent specification 626. analog monoazo dyes described by a better one Light and migration fastness and color strength.

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WC

154U59

- ίο -

In the examples below, the parts mean, unless otherwise stated, parts by weight, the Percentages by weight and temperatures are given in degrees Celsius.

^BAb

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- li -

Example 1"

73.3 parts of the dye from 2 moles of diazotized 2-amina-terephthalic acid-1-methyl ester and 1 mole of 2-chloro-S-methyl-1 ^ -bis-acetoacetylaminobenzene the formula

COOH? ^H 3. CH, COOCH,

A j A-NH-CO-CH-N = N-,

M-N = N-CH-CO-HN-M »

H-N = N-A

COOCH ₃ Cl CH, COOH

are stirred in 1000 parts of ο-dichlorobenzene with 5 parts of dimethylformamide and heated to 75 to 100 °. At this temperature can be in 15 minutes 32.8 parts of thionyl chloride flow to and stirred for 2 hours at 100 to 110 °. The end of the reaction can be recognized by the fact that the development of hydrochloric acid has ceased and that a sample shows uniformly yellow needles under the microscope. It is now allowed to cool to kO ° and suction filtered, washed with 600 parts of cold ο-dichlorobenzene and then with 200 parts of benzene. After drying at 50 in vacuo, 1k parts of the color acid chloride are obtained as a yellow crystal powder. It is very sparingly soluble in organic solvents. It can be recrystallized in small amounts from hot nitrobenzene. At temperatures above 270 ° it decomposes without melting.

7i7 ^ parts of the acid chloride obtained above in 150 parts of ο-dichlorobenzene with 0.2 parts of thionyl chloride stirred and heated to 90 to 95 °. Then you give one Solution of 3 * 3 parts of 2,5-dichloroaniline in 50 parts

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BAD ORIQtNAt

o-Dichlorobenzene is added and the mixture is then heated for 12 hours l40 to 145 °. Then the pigment formed is sucked hot off, washes with hot o-dichlorobenzene until the filtrate is colorless. Then it is displaced with cold methanol Dichlorobenzene and then wash thoroughly with hot water. After drying at 25 to 100 °, one obtains a fluffy soft powder that is practically insoluble in common solvents and in polyvinyl chloride Rolled in lively, greenish yellow tones with excellent migration and lightfastness results. ' The Pigsient corresponds to the formula

COOCH, CH,

-N = N-CH-CO-HN-A, _{ri r} , _{C1 V co} Li -NH-CO-CH-N = N- i I

-NHOC CH ^ Cl COOCH,

In the table below, further disazo dyes are described, which are obtained when one after the method described in paragraph 1 2 mol of the diazo compound of the aminocarboxylic acid mentioned in column I. 1 mol of the bisacetoacetyl compound of the diamine mentioned in column II couples the disazo dye dicarboxylic acid obtained converted into the acid chloride and condensed with 2 mol of the amine mentioned in column III. Column IV called the hue of a polyvinyl chloride film colored with the pigment obtained.

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154Α459

ι
I.
Diazo base II
Bisacetoaeetylver-
binding of diamine III
Condensation
base IV
Nuance O ₁
in PVC. yellow χ 2-amino-4-carboxy ^
benzoic acid methyl
ester para-phenylenediamine aniline greenish
yellow yellow 2 η Il reddish
yellow 3 It 2-chloro-p-phenylene-
diamine 2-methyl
aniline It yellow
~ * COPY
! AL 4th dd It 2-methyl
5-chiorani
lin η 5 ti It 2,5 dichloro
aniline very greeni
chig yellow -6 dd dd 3-trifluoro
methylanlline η 7th It Il 2-chloro-5-
trifluorine
methylanilln I green:
yellow 8th ti 2,5-dichloro-p-
phenylenediamine 2-methylani-
lin It 9 ' It ti. 2-methyl-3-
chloraniline It It dd 2-methyl-5-
chloraniline η 11 Il η 3-trifluoro
methylaniline dd 12th ti It 2-chloro-5-tri-
fluoromethyl
aniline If 13th Il 2-methyl-5-chloro
p-phenylenediamine 2,4,5-trichloro
aniline 14th Il It aniline 15th η « 2-methyl
aniline 16 « H 2-methoxy
aniline ti
0 09815/01 2,5-dimethoxy
4-chloroaniline
ί k
BAD QPJ.Q ^

ι
I. - 14 - II 154U59 III IV - ~ * 2-amino-4-carb
oxy benzoic acid -
methyl ester
It 2-methyl-5-chloro
p-phenylenediamine
ti 2-methyl-3-chloro
anilln
2-methyl-5-chloro
anllin greenish
yellow
neutral
yellow 17th
18th It Il 2-chloro-5-tri-
fluoroethyl
anllln η 19th It 2,5-dimethyl-p-
phenylenediamine 2,4-DIchlor-5-
trlfluoraethyl-
aniline η 20th It It 2-chloro-5-tri-
fluoromethyl
aniline greenish
yellow 21 ti - It 2,5-dieethyl
aniline neutral
yellow 22nd It It 2-methyl-5-chloro
aniline π 23 η It * 4-aeinobenzoe-
acid ethyl ester greenish
yellow 24 It It 3-A »ino-4-chloro-
benzoic acid ethyl
ester It 25th It " It 3-jtaino-4 -siethoxy-
henzoic acid ethyl
ester η 26th dd It 2-aeinobenzoic acid
ethyl ester greenish
yellow 27 It
S. 2-methoxy-5-
me thy1-ρ-phenylene-
diamln aniline reddish
yellow 28 It η I 2-Kethy1-5 ~ ehlor-
aniline It 29 009815 0694 _

BATHROOM GRK3INAL

I. II III IV 30th 2-amino-4-carb
oxy benzoic acid
methyl ester 2-methoxy-5-methyl-
p-phenylenediamine 2-chloro-5-trifluoro-
methylaniline neutral
QeIb 31 n 4,4'-diamino
diphenyl 2-methylanilline 32 Il 4,4'-diamino
3,3'-dimethyl
diphenyl 2,5-dichloroaniline green-
oh yellow 33 Il ti 2-chloro-5-trifluoro-
methylaniline η 3 * It H 3-trifluoromethyl
aniline η 35 Il 4,4'-diamino
3,3'-diohlor-
diphenyl aniline neutral
yellow 36 η It 2- «ethylaniline π 37 η It 2-methoxyaniline R. 38 ti
* 1,5 diamino
naphthalene 2-chloro -4 -methyl -
aniline rotsti
chig yellow 39 It η 2-chloro-5-tri-
fluoromethyl
aniline neutral
QeIb * 0 2-A * ine-4-o * rb-
oxy b «nce tellurium -
tthyleettr 2-chlorine pr
phenyltnttiaain 2- «ethyl-5-chler-
WiIlIn green1-
ohlg yellow

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BATH

154U59

2-amino-4-carboxy ethyl benzoate

2-Amino-4-carboxybenzoic acid butyl ester

2-Amino-4-carboxy benzoic acid isopropyl ester

2-Amino-4-carboxy benzoic acid methyl ester

II

2-chloro-phenylenediamine

2-trifluoro

methyl-p-

phenylenediamine

2,5-dichloro-1,4-phenylened i ami η

2-chloro-1,4-phenylenediamine

2-methyl-1,4-phenylenedlamine

2-ethyl-1,4-phenylenediamine

3-trifluoromethyl-1,4-phenylenediamine

4,6-dichloro-1,3-phenylenedianine

2,5-dimethoxy-1,4 phenylenediamine

phenylsndlaaln III

2-methyl-3-chloroaniline

2-chloro-5-trifluoromethylaniline

aniline

2-methylaniline

2-methyl-5-chloroaniline

2-methyl-3-chloroanillin

aniline

3-trifluoromethyl ■ aniline

2-methylanaline

2,4,5-trichloroaniline

aniline

IV

greenish yellow

2-methylaniline

2-chloro-5 - «« ethyl aniline

S / 0694

neutral yellow

greenish yellow

reddish yellow

DAD ORIGINAL

Copy

Example 2.

27jO parts of 2-amino-terephthalic acid-1-methylester-4-anilide are stirred in 150 parts of glacial acetic acid with 25 parts of 30% hydrochloric acid and cooled to 0 ° by adding 150 parts of ice ° by adding 25 parts of 4N sodium nitrite solution, stirred for 15 minutes at 0 to 2 and the solution filtered off from minor impurities. The Piltrat is adjusted to a volume of 600 parts and a temperature of 0 °. Excess nitrous acid is destroyed with sulfamic acid and then neutralized by adding about 30 parts of crystalline. Sodium acetate up to p _H. 4

At the same time, 19 parts of 3,25'-dimethyl-4,4'-bis _r acetoacetylamino-diphenyl are dissolved with 25 parts of 3O # strength sodium hydroxide solution in 500 parts of water, small amounts of impurities are filtered off and, after addition of 0.2 parts of the product of action 8 moles of ethylene oxide per mole of p-tert-octylphenol were added dropwise to the diazo solution with thorough stirring. After the dropwise addition, the temperature of the reaction mixture has risen to 20 ° and the diazo

connection --— has disappeared. One warms now within

one hour to 75 to 80 °, stirred for one hour at this temperature, filtered hot and washed thoroughly with hot water. After drying in vacuo at 95 ° to 100 °, 46 parts of the dyestuff of the following ^{design are obtained}

^C00CH 3 COOCH

A -N = N-CH-COHN - ^ "" ^ ~ <f% -NHCO-CH-N = N-Zw

Υί ° HOJ CH, Y ⁰ γ

NH0C CH, * ■> CH, CONH-

The NaOH drying pigment obtained is stirred with advantage in xylene or ο-dichlorobenzene for 1 to 2 hours at 100 to 130 ^0, where it merges into a single crystalline form. After filtering, washing with hot Xylpl resp. After drying, dichlorobenzene and methanol give a soft, loose pigment which, when rolled in, colors polyvinyl chloride films in strong, greenish yellow tones. The colorations are migration and lightfast.

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Example 5

65 parts of stabilized polyvinyl chloride, 35 parts of dioctyl phthalate and 0.2 parts of according to Example 1 obtained dye are used together stirred and then while on a two-roll calender Rolled back and forth at 14o for 7 minutes. A greenish yellow colored film of very good light- and migration authenticity

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Claims (6)

15U459 claims. 1. Process for the preparation of disazo dye pigments the formula COCH, COCH, AHNOC-B-N = N-CHCOHN-R-NHCO-CH-N = N-B-CONHa characterized in that a) a dihalide of a Dicarboxylic acid of the formula COCH, COCH, 1 ι HOOC-B-N = N-CH-CONH-R-NHCO-CH-N = N-B-C00H condensed with an aminobenzene in a molar ratio of 1: 2, or b) the diazo compound of an amine of the formula AHNOC-B-NH ₂
with a diacetoacetyl-arylenediamine of the formula ■ H C-CO-CH-COHN-R-NH-COCH-COCH, 3 2 2 3 in the molar ratio 2: 1, where in the given formulas A is a benzene radical, B is a benzene radical, which in o-position to the azo group has a carboxylic acid ester group, and R is an arylene radical. 2. The method according to claim 1, characterized in that one is an aminobenzene of the formula 009815/06 used, where X, Y and Z are hydrogen or halogen atoms, alkyl, alkoxy, phenoxy, trifluoromethyl, carbalkoxy or mean cyano groups. 3. The method according to claims 1 and 2, characterized in that that one of the chlorides of dicarboxylic acids of the formula JOOR ₁ COCH-. COCH, COOR ₁ 1 j 3 I 3 -N = N-Ch-CONH-R-NHCO-CH-N = N-. COOH COOH starts out, wherein R is a phenylene or diphenylene radical and R, represent an alkyl group. 4. The method according to claim 3 *, characterized in that that one starts from dicarboxylic acids of the formula given, in which R is a radical of the formula ^X l ^Y l means in which X, a hydrogen or halogen atom, an alkyl or alkoxy group, Y, a hydrogen or halogen atom, denote an alkyl, alkoxy or trifluoromethyl group. 5 · Method according to claim 3 »characterized thereby-" draws that one starts from dicarboxylic acids of the formula given, wherein R is a radical of the formula Y Y 72 72 ■ & ■ <£ ■ 8.AD OPSGHNAt 009815/0694 15U459 means wherein Yp is a hydrogen or halogen atom, a Denotes alkyl or alkoxy group. 6. The method according to claim 1, characterized in that that one of the diazo compound of an amine of the formula COOR ₁ CONH starts out, where R ,, X, Y and Z have the meaning given, 009815/0694