DE2329781C2 - Benzoxazinedione azo pigments, process for their preparation and their use as colorants - Google Patents

Description

Ri

Rj

represents in which

Ri is hydrogen, chlorine, bromine, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, acetyl or Is acetylamino,

R _{2 is} hydrogen, chlorine, bromine, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms and Rj is hydrogen, chlorine, bromine, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms Atoms means or

A in the case that η stands for the number 2, denotes the benzene radical which can be substituted by one or two chlorine or bromine atoms, methyl or methoxy groups, or the diphenyl radical which is in the rhenyling can be substituted by one or two chlorine or bromo, methyl or methoxy groups.

2. Process for the preparation of the compounds according to claim 1, characterized in that one is a diazotized amino-benzoxazine of the general formula

NH ₂

with a coupling component of the general formula [CHjCOCH ₂ CONH-] "[A]

wc / in η and A have the meanings described in claim 1, coupling.

3. Use of the compounds according to claim 1 for dyeing or printing paints, paint formers, solutions and products made from acetyl cellulose, natural resins or synthetic resins, polystyrene, Polyolefins, polyacrylic compounds, polyvinyl compounds, polyesters, rubber, casein or silicone resins, as well as paper or textile fibers made from cellulose, cellulose ethers, cellulose esters, polyamides or polyurethanes.

Azo compounds are known from Examples 10 and 14 of German Offenlegungsschrift 2208302, from the acetoacetyl (l-N-methyl-benzimidazol-2-one-5-amide) as a coupling component and from the 6-amino-quinazolone- (4) or the 7-amino-phenmorpholone- (3) are built up as a diazo component. These However, pigments do not have satisfactory lightfastness.

With the present invention, new azo compounds have now been found, one of which is opposite These azo compounds of DE-OS 22 08 302 constitutionally comparable compounds have a significantly better lightfastness. These new azo compounds correspond to the general formula (1)

CO-CH ₃ N = N-CH-CO-NH

(D

in softer

η stands for the number 1 or 2 and

If η is the number 1, A denotes the 5-benzimidazolone radical, which can be substituted in the 6- and 7-positions by chlorine or bromine, or the naphthalene radical or a benzene radical of the general formula

10

20th

Hydrogen, chlorine, bromine, alkyl with 1 to 4 carbon atoms, preferably methyl and ethyl, alkoxy with 1 up to 4 carbon atoms, preferably methoxy and ethoxy, acetyl or acetylamino,

Hydrogen, chlorine, bromine, alkyl with 1 to 4 carbon atoms, preferably methyl and ethyl, or alkoxy with 1 to 4 carbon atoms, preferably methoxy and ethoxy, and

Hydrogen, chlorine, bromine, alkyl with 1 to 4 carbon atoms, preferably methyl and ethyl, or alkoxy with 1 to 4 carbon atoms, preferably methoxy and ethoxy, or

A in the case that η stands for the number 2, denotes the benzene radical which can be substituted by one or two chlorine or bromine atoms, methyl or methoxy groups, or denotes the diphenyl radical which is represented in the phenyl rings E by one or two <: i chlorine or bromine atoms, methyl or methoxy groups can be substituted.

The present invention further relates to a process for the preparation of these compounds of the general Formula (1), in which a diazotized amino-benzoxazinedione of the general formula (2)

30th

NH ₂

with a coupling component of the general formula (3) CO-CH ₃

CH ₂ -CO -NH-] - A

(2)

(3)

in which A and η have the meanings given above, couples.

The 6-amino-1,3-benzoxazine-2,4-dione is known from French patent 13 68739; that still 7-Amino-1,3-benzoxazine-2,4-dione not described can be prepared by methods known per se, for example by catalytic hydrogenation from the corresponding nitro compound (see C. Wagner and D. Singer, Pharm. Zentralhalle, 103, 791 (1964)).

The compounds used according to the invention as coupling components of the general formula (3) are largely described in the literature and can be prepared by known methods, for example by reacting the corresponding aromatic mono- or diamine with diketene or methyl acetoacetate.

Examples of such coupling components are: N-acetoacetylaniline

l-acetoacetylamino-naphthalene

N-acetoacetyl-2-chloro-aniline

N-acetoacetyl-4-chloro-aniline

N-acetoacctyI-2.4-dichloro-aniline

40

45

50

55

60

65

23 29 78 ϊ

2-acetoacetylamino-anisole

4-acetoacetylamino-aniscI

4-acetoacetylaminophenetol

N-acetoacetyl ^ .S-dimethoxy-aniline
N-acetoacetyl ^^ - dimethoxy-aniline

N-acetoacetyl-'t-chloro ^ .S-dimethoxy-aiiilin

N-Acetoacetyl-S-chloro ^^ - dimethoxy-aniline

2-acetoacetylamino-toluene

4-acetoacetylamino toluene
4-acetoacetylamino-1,3-xylene

4-acetoacetylamino-acetylaminobenzene

2-acetoacetylamino-5-chloro-toluene

2-AcetoacetyIamino-5-acetylanisoI

2-acetoacetylamino-5-acetyIamino-4-chloro-toluene
N-acetoacetylamino-4-bromaniline

2-acetoacetylamino-3-chloro-toluene

2-acetoacetylamino-4-methyl-anisole

N-acetoacetyl ^ .S-dimethoxy ^ -bromaniline

N-acetoacetyl ^ .S-diethoxy - ^ - chloraniline
N-acetoacetyM.S-dimethoxy ^ -chloraniline

N-acetoacetyl ^ .S-dichloroaniline

N-acetoacetyI-2.4-diethoxyaniline

N-acetoacetyM-ethylaniline

N-acetoacetyl ^ Ao-trimethylaniline
S-acetoacetyM-bromo-o-methyl anisole

2-acetoacetylamino-5-bromanisole

2-acetoacetylamino-4-methyl anisole

2-acetoacetylamino-5-methyl-6-bromophenetol

S-acetoacetylamino-benzimidazolone
S-acetoacetylamino-o-chloro-benzimidazoIon

S-acetoacetylamino-T-chlorobenzimidazolone

l ^ -Bis-acetoacetylamino ^ -bromobenzenes

1,4-bis-acetoacetylamino-benzene

1,4-bis-acetoacetylamino-2-chloro-benzene
1 ^ -Bis-acetoacetylamino ^ .S-dichloro-benzene

2.5-bis-aceioacetylamino-ioiuoi

2,5-bis-acetoacetylamino-1,4-xylene

2.5-bis-acetoacetylamino-anisole

l ^ -Bis-acetoacetylamino ^ .S-dimethoxy-benzene
2.5-bis-acetoacetylamino-4-methoxy-toluene

N.N'-bis-acetoacetyl-SJ'-dichlorobenzidine

N.N'-bis-acetoacetyl ^^ '- dichloro-berizidine

N.N'-bis-acetoacetyl-J.S'-dimethoxy-benzidine

N.N'-bis-acetoacetyl-S.S'-dimethyl-benzidine

The azo pigments according to the invention are produced by processes known per se, for example by coupling the diazotized aminobenzoxazinediones with the coupling components in aqueous Medium, advantageously in the presence of a nonionic, anionic or cationic dispersant or in the presence of an organic solvent. The coupling reaction can also take place in organic Solvents are carried out.

The diazonium salts of aminobenzoxazinediones are not very soluble in water. The diazotization can therefore advantageously also be carried out in a suitable organic medium, such as, for example in glacial acetic acid, alcohols, formamide, dimethylformairide or dimethyl sulfoxide. The solution thus obtained of the diazonium salt can then be combined with the azo component.

It is often expedient to use the azo pigments obtained in this way to achieve full color strength and some to subject particularly favorable crystal structure to an aftertreatment. For example, one heats to this Purpose the wet or dried and ground pigments in pyridine, or dimethylformamide other organic solvents such as dimethyl sulfoxide, alcohol, chlorobenzene, dichlorobenzene, glacial acetic acid, Quinoline, GIy kol or nitrobenzene for some time under reflux or at higher temperatures under pressure. In

In some cases, the conversion into a particularly favorable crystal structure also succeeds by heating Water for boiling or at higher temperatures under pressure, optionally with the addition of dispersants and, if necessary, with the addition of organic solvents, for example of the type mentioned above. The new azo pigments are completely insoluble in water and are suitable for the production of colored lacquers, Lacquer formers, solutions and products made of acetyl cellulose, natural Ha'zen or synthetic resins, such as polymerization or condensation resins, such as amino or phenoplasts, as well as made of polystyrene, Polyolefins, such as polyethylene or polypropylene, polyacrylic compounds, polyvinyl compounds, such as polyvinyl chloride or polyvinyl acetate, polyesters, rubber, casein or silicone resins.

The new pigments are also suitable for pigment printing on substrates, especially textile fiber materials.

rials or other sheet-like structures, such as paper.

The pigments can also be used for other purposes, e.g. B. in finely divided form for dyeing Rayon made of viscose or cellulose ethers or esters, polyamides, polyurethanes, polyglycol terephthalates or polyacrylonitrile can be used in the spinning pulp or for dyeing paper. In the mentioned In media, the new pigments have good light, weather and migration fastness properties. They are also heat resistant, strong in color and in many cases show pure hues. Against the influence of chemicals, especially They are resistant to solvents, diluted acids and alkalis.

The temperature data in the following examples relate to degrees Celsius.

example 1

17.8 g (0.1 mol) of 7-amino-1,3-benzoxazine-2,4-dione, 60 ml of glacial acetic acid and 27.8 ml of 31% strength hydrochloric acid are used Stirred for 1 hour and diazotized at 0 ° with 20 ml of 5 η sodium nitrite solution.

The mixture is stirred for 30 minutes, diluted with ice water, stirred for a further 90 minutes and clarified.

24 g (0.103 mol) of 5-acetoacetylamino-benzimidazolone are dissolved in 121 ml of 2 η sodium hydroxide solution and 200 ml of water dissolved and the solution clarified. 25.2 ml of glacial acetic acid, 50.4 ml of 2 η sodium hydroxide solution and 1 g of one are placed in the dome Submitted mixture of Sinarolsulfamido-acetic acid-sodium and Sinarol. By adding ice you set the Temperature to Ί0 "and iäBi zuirepfen the solution of the coupling component.

The diazonium salt solution then runs in slowly.

After the coupling has ended, the mixture is heated to 90 ° by passing in steam and this temperature is maintained for 20 minutes long, sucks off the pigment, washes it with water and dries at 65 °. The dry pigment is ground and heated to 100 ° with 800 ml of dimethylformamide and 200 ml of water for 30 minutes, the color of the pigment changing from orange-red to yellow, suctioned off at 60 °, washed, dried and ground.

The pigment of the formula thus obtained

COCH ₃

N = N-CH-CONH

NH

NH

has excellent solvent fastness, when incorporated in polyvinyl chloride, in a lacquer, results in a Printing ink or a spinning mass, pure, strongly colored, yellow dyeings with very good migration and lightfastness.

In the above example, instead of 5-acetoacetylamino-benzimidazolone, the equivalent amount is used 5-Acetoacetylamino-7-chlorobenzimidazolone, a yellow pigment is also obtained, which when incorporated z. B. in polyvinyl chloride has similarly good fastness properties.

Example 2

8.9 g of 7-amino-1,3-benzoxazine-2,4-dione are diazotized as in Example 1.

8.7 g (0.252 mol) of 1,4-bis-acetoacetylamino-2,5-dichlorobenzene are dissolved in 200 ml of water and 17 ml of 33% strength Sodium hydroxide solution dissolved, diluted with 300 ml of water and 1000 ml of isopropanol, then mixed with 15 ml of glacial acetic acid. The clarified diazonium salt solution is then allowed to run slowly at 20 ° to the coupling component, and the mixture is stirred 1 hour and then heated under reflux for a further 1 hour. The pigment is suctioned off with water washed, dried, ground and a further 2 hours with 350 parts by volume of dimethylformamide at 100 ° heated. It is again filtered off with suction, washed with methanol and water, dried and ground. The thus obtained Pigment of the formula

NHCOCH -COCHj

Il N

20th

30th

40 45 50 55 60 65

when incorporated into polyvinyl chloride, lacquer, printing ink or spinning material gives a greenish tinge yellow colorations with very good heat resistance and very good light and migration fastness.

Example 3

8.9 g (0.05 mol) of 6-amino-1,3-benzoxazine-2,4-dione, 40 ml of water and 40 ml of 5 η hydrochloric acid are left overnight stirred and diazotized at 0 ° with 10 ml of 5 η sodium nitrite, diluted with water to 200 ml and clarified. 11.9 g (0.05 mol) N-acetoacetyl-2,4-dimethoxyaniline are dissolved in 200 ml of water and 7.5 ml of 33% sodium hydroxide solution, clarified and reprecipitated in the presence of 2.75 g resin soap (50%) at 10 ° with 5.1 ml glacial acetic acid.

The diszonium salt solution is slowly added dropwise to this suspension, with simultaneous The addition of dilute sodium hydroxide solution keeps the pH value at 4.5-5. After the coupling has ended, the heating is carried out Reaction mixture at 90 ° for 30 minutes, the dyestuff is filtered off with suction while hot and washed with water. The damp press cake is boiled with glacial acetic acid for 1.5 hours, filtered off with suction, washed with water, dried and ground. By Thermal aftertreatment in 25% aqueous dimethylformamide can further improve the color strength will.

The obtained dye of the formula

COCH ₃

"Χ, -χΧΧ N = N-CH-CONH - <()> - OCH ₃ ΐ

OCH ₃ I.

When incorporated into polyvinyl chloride, lacquer, printing ink or spinning material, it produces pure, yellow colorations of good light and migration fastness.

In the above example, instead of N-acetoacetyl-2,4-dimethoxyaniline, the equivalent amount is used 2-acetoacetyl-5-chloro-anisole, a greenish yellow pigment with similarly good properties is obtained.

B e i s ρ i e 1 4

8.9 g of 6-amino-1,3-benzoxazine-2,4-dione are diazotized as in Example 3. 12.2 g (0.0525 mol) of 5-acetoacetylamino-benzimidazolone are dissolved and clarified in 17 ml of 33% strength sodium hydroxide solution and 500 ml of isopropanol. Then the pH is adjusted to 5.5 with approx. 13 ml of glacial acetic acid, the diazonium salt solution is allowed to run in slowly and heated after \

Complete coupling in the heating bath for 30 minutes at 70-80 °. The dye is filtered off with suction, washed with water, dried and ground. After a brief thermal aftertreatment at 100 ° with a dimethylformamide / glacial acetic acid / water mixture (2/1/1), it is again filtered off with suction, washed with water and dried.
The dye of the formula thus obtained

° COCH ₃ '

y \ ^NH

-N = N- CH- CONH- fryf

NH

when incorporated into polyvinyl chloride, lacquer, printing ink or spinning material gives a greenish tinge yellow colorations with excellent light and migration fastness.

Example 5

8.9 g of 6-amino-1,3-benzoxazine-2,4-dione are diazotized as in Example 3. 8.7 g (0.0252 mole) 1,4-bis-acetoacetylamino-2,5-dichlorobenzene are dissolved in 200 ml of water and 17 ml of 33% sodium hydroxide solution, clarified with 280 ml of water and 500 ml of isopropanol and partially reprecipitated with 15 ml of glacial acetic acid. Then one lets slowly add dropwise the diazonium salt solution, stir for 2 hours and reflux for 1 hour, suck hot, wash the press cake with water, paste it again with 500 ml of glacial acetic acid and then boil 1 hour under reflux. It is filtered off with suction, washed with water, dried and ground. By Treatment of the dye with dimethylformamide for 1 hour at 120 ° can further improve the opacity will.

The dye of the formula thus obtained

when incorporated into polyvinyl chloride, varnish, printing ink or spinning mass gives a greenish tinge yellow colorations with very good light and migration fastness. 20th

The following table contains a number of further components that can be used in the process, as well the color tones of the graphic prints of the pigments made from them in substance.

Diazo component

Coupling component color

6-amino-1.3
6-amino-1.3
6-amino-1.3
6-amino-1.3
6-amino-1.3
6-amino-1.3
6-amino-1.3
6-amino-1.3
6-Arnino-1.3
6-amino-1.3
6-amino-1.3
6-amino-1 J
6-amino-1.3
6-amino-1.3
6-amino-1.3
6-amino-1.3
o-amino-O
6-amino-1.3
o-amino-O
6-amino-1.3
6-amino-1 J
6-amino-1 J
6-amino-1.3
7-amino-1.3
T-amino-U
7-amino-1.3
T-amino-U

benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine benzoxazine

2.4-dione 2.4-dione 2.4-dione 2.4-dione 2.4-dione 2.4-dione 2.4-dione 2.4-dione 2.4-d! Ön 2.4-dion 2.4-dion ^ -dion ^ .4-dion 2.4-dion 2.4-dion 2.4-dion ^^ - dion 2.4-dion ^^ - dion 2.4-dion ^ -dion ^^ -dion 2.4-dion 2.4-dion ^^ dion 2.4-dion ^^ dion

7-amino-1,3-benzoxazine-2,4-dione 7-Amino-l J-benzoxazine ^^ - dione 7-Amino-U-benzoxazine-2,4-dione 7-Amino-1,3-benzoxazine-2,4-dione 7-amino-1,3-benzoxazine-2,4-dione

N-acetoacetylaniline yellow

l-acetoacetylamino-naphthalene yellow

N-acetoacetyl ^ -chloro-aniline greenish yellow

N-AcetoacetyW-chloro-aniline greenish yellow

N-Acetoacetyl ^^ - dichloro-aniline greenish-yellow

2-acetoacetylamino-anisole yellow

4-acetoacetylamino-anisole yellow

2-acetoacetylamino-toluene yellow

4-acetoacetylarnino-toluo! yellow

4-acetoacetylamino-1.3-xy lol yellow

N-AcetoacetyM-chloro ^ .S-dimethoxy-aniline yellow

2-Acetoacetylamino-5-chloro-toluene yellow 2-Acetoacetylamino-5-acetylamino-4-chloro-toluene yellow

S-Acetoacetylamino ^ -chloro-benzimidazolone yellow

l / t-bis-acetoacetylamino-benzoI yellow

1 ^ -Bis-acetoacetylamino ^ -chlorobenzene yellow

2.5-bis-acetoacetylamino-toluene yellow

2.5-bis-acetoacetylamino-1,4-xylene reddish yellow

2.5-bis-acetoacetylamino-anisole reddish yellow

2.5-bis-acetoacetylamino-4-methoxy-toluene reddish tinge

N.N'-Bis-acetoacetyl ^ J'-dimethyl-benzidine yellow

N.N'-Bisacetoacetyl ^ J'-dichlorobenzidine yellow

N.N'-bis-acetoacetyl-SJ'-dimethoxy-benzidine yellow

2-acetoacetylamino-anisoI yellow

4-acetoacetylamino-anisole yellow

2-acetoacetylamino-toluene yellow

4-acetoacetylamino-toluene yellow

N-acetoacetyl-2,4-dimethoxy-aniline yellow

N-acetoacetyl ^ .S-dimethoxy-aniline yellow

2-acetoacetyl-5-chloro-anisole greenish yellow

N-Acetoacetyl ^ ciiior-J ^ -dimethoxy-aniline yellow

1.4-Bii-acetoacetyIainino-benzene yellow

1.4-bis-acetoacetylamino-2-chloro-benzene yellow

continuation

Diazo component, coupling component, color shade

7-Amino-1,3-benzoxazine-2,4-dione l ^ -Bis-acetoacetylamino-anisole reddish-tinged-yellow

7-Amino-1,3-henzoxazin-2,4-dione 1 ^ -Bis-acetoacelylamino-anisole ^ .S-dimethoxy- reddish yellow

benzene

7-Amino-1.3-benzoxazine-2.4-dione 2.5-bis-acetoacetylamino-1.4-xyloI reddish yellow

Claims (1)

Patent claims: 1. Azo compounds of the general formula CO-CH ₃ N = N-CH-CO-NH stands for the number 1 or 2 and in the event that η is the number 1, the 5-benzimidazolone radical, which is in the 6- and 7-position by chlorine or Can be substituted bromine, or denotes the naphthalene radical or a benzene radical of the general formula