DE1808017B2 - WATER-INSOLUBLE MONOAZO COMPOUNDS, PROCESS FOR THEIR MANUFACTURING AND THEIR USE AS PIGMENTS - Google Patents

Description

CH ₃ CO-CH ₂ -CO-NH

where * and R _{1 are} those in the pronouncement Ϊ ^
deutune have ^ r1c * Jj? pelt.
. 6. Use of Verbiaäungera according to An spoke 1 jäsä ^ Öenie.

7. Use / the connection according to An spoke 1 about pigmenting plastics, Rubber, natural or synthetic resins, textile fiber materials. ÖrucWarben. Color lacquers or dispersion paints.

The present invention relates to new, valuable ones water-insoluble monoazo compounds of the general formula

χ COCH ₃ ^H

_ N-CO

CO-NH

wherein X is a hydrogen, chlorine or bromine atom or a methoxy group, Y and Z hydrogen-chlorine or bromine atoms, nitro, methoxy, ethoxy-butoxy groups, optionally with chlorine atoms:

or phenoxy groups substituted by methyl groups, methyl, trifluoromethyl, cyano, lower carbon acid alkyl ester, carboxamide, lower carboxylic acid monoalkylamide groups, optionally in Phe nyl radical by methyl, methoxy or trifluoromethyl-I

groups or chlorine atoms substituted carboxylic acid] phenylamide groups, acetamino, sulfonic acid amide lower Sulfonic acid monoalkylamide or in the phenyl radical optionally by methyl or methoxy] groups or chlorine atoms substituted sulfonic acid

phenylamide groups, R an alkyl group having 1 to] 6 carbon atoms and R ₁ a hydrogen, chlorine | or a bromine atom or a methyl or methoxy group, a process for their preparation, in which one diazotized amines of the general form

NH,

in which X, Y and Z have the above-mentioned Be meanings, with azo components of the general my formula

wherein X, Y and Z have the meanings given in claim 1, with azo components of general forms!

N-CO

CH ₃ CO-CH ₂ -CO-NH

in which R and R _{1 have} the abovementioned meanings, couples, and the use of these compounds as pigments.
The have particularly advantageous properties

18 38 017

jeaigen monoazo connections of the above fence! <1 ί, in which Y is a group of the formula R ₂ HNOC-, R ₃ HNO ₂ S- or R ₄ OOC-, in which R ₁ and R _{3 are} a water atom, a lower alky3 group or optionally as indicated above substituted phenyl radical and R ₄ «ine Biedere ücygpp

Draw the compounds according to the invention opposite to those from DT-AS 12 81606 and US-PS 31 «9« 42 known structural words Connections due to significantly improved lightfastness the end.

Suitable amines of the above formula { 2) for the preparation of the compounds according to the invention are, for example, specifically chlorine-sulins such as 2-Chk> raniline, 2,4-dichloroaniline, 2 ^ -dichloraniline, 2-chloro-5-diethylaniline, 2-chloro-4-: inethoxyanflin, 4-chloro-2-trifluoromethylaniline, nitro-aniline, such as 2-nitro-anilm, 2-nitro-4-chior-aniline, 2-nitro-4-niethykniline, 2-nitro-4-acetylamtnoaniline, further aminobenzoic acid esters, such as 2 - aminobenzoic acid methyl ester. 2 - aminobenzoic acid butyl ester, 1 - aminofcenzene - 2,5 - dicarboxylic acid dimethyl ester, 1 - aminobenzene - 3,5 - dicarboxylic acid dimethyl ester, 4 - aminobenzoic acid methyl ester, further aminobenzoic acid amides. -alkylamides or -arylamides. such as, for example, 4-aminobenzoic acid amide, 4-chloro-3-aminobenzoic acid amide, 4,6-dichloro-3-aminobenzoic acid amide, 3-amino-4-methoxybenzoic acid phenylamide. 3-Amino-4-methyl-benzoic acid methylamide, 3-amino-4-carbomethoxybenzoic acid - (2 ', 5' - dichloro) -phenylamide, finally - \ minobenzenesulfonic acid amides, -alkylamides or -arylamides, such as, for example, 3-amino-4-methoxy - benzenesulfonic acid butylamide. 3 - Amino - 4 - methylbenzenesulphonic acid methylamide and S-amino ^ -chlorobenzenesulphonic acid-isopropylamide, 2,5-dimethox> -4-aminobenzene-sulphonic acid methylamide and 2,5-dimethoxy-4-aminober.zene-sulphonic acid-phenylamide.

The compounds used as azo components can be prepared by known processes, for example by reacting 2,4-dinitrochlorobemzenes with an area of the formula R-NH ₂ , in which R has the meaning given above, to give the corresponding 2,4-dinitraniline, whose partial reduction, for example with sulfhydrate liquor, to the corresponding 4-nitro-o-phenylenediamine, reaction with urea or phosgene to give the corresponding nitrobenzimidazolone, reduction to the corresponding aminobenziniidazolone and addition of diketene to the corresponding 5-acetoacetyI-aminobenzimidazoion according to the following scheme, where R _{1 is} the above mentioned meaning has:

C = O

CH ₃ COCH ₂ CONH

C = O

H N-C = O

NO

O ₂ N

Examples of suitable amines R — NH ₂ are methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine or isobutylamine.

Examples of suitable azo components of the formula (3) mentioned are:

l-methyl-5- {acetoacetylamino) -benzimidazolone, 1-ethyl-S-iacetoacetylaminoJ-benzimidazolone, 1 -n- Pr & pyl-S-iacetoacetylaminoJ-benzimidazolone,

1 -iso- propyl-S-iacetoacetylaminoJ-benzimidazolone,
l-iso-butyl-S-iacetoacetylamino ^ benrimidazolon,

1-η-Butyl- S-iacetoacetylaminoJ-benzimidazolone, !, o-Dimethyl-S-iacetoacetylaminoJ-benzimidazolone,

l-Methyü-ö-chloro-o-iacetoacetylaminoJ-benzimidazolon,

1-methyl-7-bromo-5- (acetoacetylamino) benzimidazolone,

l-methyli-V-chloro-S-iacetoacetylaminoJ-benzimidazolone,

1-methyl-o-methoxy-S-i.acetoaceiylaminoJ-benzimidazolone.

The preparation of the diazonium compounds he follows in a known manner. In some cases you are Diazonium salts are sparingly soluble in an aqueous medium and separate out. They can be isolated and al; Bring moist paste to the coupling. However, you can also organize the diazotization in a suitable see medium perform, for example in glacial acetic acid, alcohol, dioxane, tetrahydrofuran, formamide Dimethylformamide or dimethyl sulfoxide, and the se Combine the resulting solution of the diazonium compound with the azo component.

The dyes can be used in bulk or on a] substrate, e.g. B. barite produce.

The preparation in substance takes place according to methods known per se, for example by association of the diazonium compounds with the azo components in an aqueous medium, advantageously in Presence of an anionic, cationic or nonionic dispersant or in the presence an organic solvent.

The dyes thus obtained are often hard Korn and then have to undergo an aftertreatment to achieve full color strength and optimal fastness properties be subjected. For example, the dried and ground or heated moist dyes in pyridine, dimethylformamide or other organic solvents such as dimethyl sulfoxide, Alcohol or chlorobenzene under reflux or at higher temperatures for some time negative pressure. In some cases the transfer succeeds into a grain-soft form by heating with water under pressure, if necessary under Addition of dispersants.

The dyes obtainable by the present process are water-insoluble pigments. They are suitable for the production of colored paints. Lacquer formers, solutions and products made from acetyl cellulose, natural resins or synthetic resins such as polymerization or condensation resins such as Aminoplasts or phenoplasts, as well as from polystyrene, polyolefins, such as polyethylene or polypropylene. Polyacrylic compounds. Polyvinyl compounds, for example polyvinyl chloride or polyvinyl acetate, polyesters, rubber. Casein or silicone resins.

The dyes according to the invention are also suitable for pigment printing on a substrate, in particular on textile fibers as well as on other sheet-like Forms, such as on paper. They can also be used for other purposes, z. B. in finely divided form for dyeing rayon rayon or cellulose ethers or esters. Polyamides or polyurethanes can be used in the spinning pulp or for dyeing paper.

Due to their favorable rheological properties, the dyes can be easily processed in the media mentioned. They then show good light-. Weather and migration fastness properties on you are still heat-resistant, strongly colored and in many cases show pure, brilliant shades. Against the influence of chemicals, e.g. B. of solvents, they are resistant, especially to acidic and alkaline effects. Example 1 ^{like this}

20.9 parts by weight of 5-amino-isophthalic acid dimethyl ester are stirred with 80 Voliumteüen 5N hydrochloric acid for about an hour and then with 300 parts by volume of water diluted. It is diazotized at 10 C with 20 parts by volume of 5N sodium nitrite solution, clears with kieselguhr and removes any excess nitrous acid with a little sulfamic acid.

This diazo solution is allowed to form an acetic acid suspension at about 20 ° C. with thorough stirring Azokomponcntc flow in the following way was produced:

25.5 parts by weight of 1-methyl-5-acetoacetylaminobenzimidazolone are stirred with 200 parts by volume of water at room temperature and by adding dissolved by 60 parts by volume of 5 η sodium hydroxide solution. This solution is clarified with activated charcoal and the clarified Dissolve in the course of about 30 minutes with stirring in a solution of 300 parts by volume of water, 41 parts by volume Glacial acetic acid and 80 parts by volume of 5N sodium hydroxide solution added dropwise at room temperature.

The coupling is terminated immediately. The coupling mixture is brought to the boil, filtered off with suction, washed thoroughly with water and rot-kneaded at 60.degree. C. The yellow pigment obtained is powdered and heated to 130.degree. C. in 450 parts by volume of dimethylformamide for 4 hours. It is then filtered off with suction, the dimethylformamide is washed out with methanol and the dye is dried. A yellow pigment with a soft grain, good color strength and a refnem shade is obtained. When incorporated into polyvinyl chloride, a varnish, a printing ink or a dispersion paint, yellow colorations of high lightfastness, perfect overcoating fastness and heat resistance and very good bleeding resistance in polyvinyl chloride are obtained.

Instead of dimethylformamide, the same amounts by weight of pyridine or glacial acetic acid can be used. In this case, the mixture is refluxed for 4 hours.

Is used in the above example instead of 1-methyl-5-acetoacetylamino-benzimidazolone the equivalent amounts of I-methyl-o-chloro-S-acetoacetylamino-benzimidazolone, 1 - methyl-7-chloro-5-acetoacetylaminobenzimidazolone, 1 - methyl - 7 - bromo - 5 - acetoacetylamino - benzimidazolone, 1 - methyl - 6 - methoxy - 5-acetoacciylaiiiino-benzimidazolone or 1,6-dimethyl-5-acetoacetylaminobenzimidazolone, yellow pigments with good fastness properties are likewise obtained in this way.

The processing in polyvinyl chloride takes place, for example, according to the following process: 1b, 5 parts by weight a plasticizer mixture consisting of equal parts of dioctyl phthalate and dibutyl phthalate. are mixed with 0.05 part by weight of dye and 0.25 part by weight of titanium dioxide. Then will 33.5 parts by weight of polyvinyl chloride were added. The mixture is on a two roll mill for 10 minutes rolled with friction, whereby the skin that forms is continuously cut up with a spatula and is rolled up. One of the rollers is set to a temperature of 40 C, the other on one Maintained temperature of 140 C. The mixture is then peeled off as a fur and 5 minutes at 160 C pressed between two polished metal plates.

Example 2

24.6 parts by weight of 1-amino-Z.S-dimethoxybenzene-4-sulfonic acid methylamide are mixed with 50 parts by volume of water and 45 parts by volume of 5N hydrochloric acid Stirred for several hours, the hydrochloride of the amine used being formed. Thereafter is diluted with UK) parts by volume of water, at 15 Γ diazotized with 20 parts by volume of 5N sodium nitrite solution, a possible excess of nitrous acid eliminated by adding a little sulfamic acid and finally clarified with kieselguhr.

This diazo solution is allowed to form an acetic acid suspension of 25.5% by weight at 20 ° C. with thorough stirring parts of 1-methyl-S-acetoacetylamino-benzimidazolone, manufactured according to Example 1. After the coupling is complete, the dye is suctioned off, washed and dried. The ground dye is with 600 parts by volume of glacial acetic acid for 3 hours heated under reflux, then suctioned off.

washed first with methanol, then with water and dried. A yellow pigment is obtained which, incorporated into polyvinyl chloride, a varnish, a printing ink or a dispersion paint, reddish-tinged Yellow colorations of high lightfastness, perfect fastness to overcoating and very good fastness to bleaching in polyvinyl chloride. If you work the pigment into an oil-in-water emulsion or a water-in-oil emulsion one, then one obtains printing pastes with which one textile fabric, for example made of cotton or polyester fibers, in yellow shades with good lightfastness and good fastness to dry cleaning Can dye.

Example 3

17.1 parts by weight of 1-amino ^ -chlorobenzene-S-carboxamide are dissolved with 50 parts by volume of 5N hydrochloric acid and 175 parts by volume of water and hot diazotized after addition of ice at 5 with 20 parts by volume of 5N sodium nitrite solution. The diazo solution is clarified and with a suspension prepared according to Example 1 of 25.5 parts by weight 1 - methyl - 3 - acetoacetylamino - benzimidazolone coupled. When the coupling is complete, the dye is vacuumed, washed and dried. The ground dye becomes glacial acetic acid with 600 parts by volume ? Heated under reflux for hours, then filtered off with suction, first with methanol, then with water washed and dried.

A yellow pigment is obtained which, in polyvinyl chloride, is a. Lacquer, a printing ink or a dispersion paint incorporated, gives reddish-tinged yellow colorations of high lightfastness, perfect fastness to overcoating and very good fastness to bleeding in polyvinyl chloride. If you work the pigment into an oil-in-water emulsion or a water-in-oi-Err.uisio "■ -s ^>. E ^r - *" ^ y-nwti_i] i «.ü.vkf« 3tCi ;, m: i der.tr. textile fabrics, for example made of cotton or polyester fibers, can be dyed in yellow shades with good light fastness and good dry-clean fastness properties.

If, in the above example, instead of 25.5 parts by weight of 1-methyl-S-acetoacetylamino-benzimidazolone, the equivalent amount of 1-ethyl-5-acetoacetylamine-hen7imidazolone or 1-isopropyl-5-acetoacetylamino-benzimidazolone or l-lsobutyioace-5-acelain benzirr.idazolon, ^c <"> yellow pigments with similarly good properties are also obtained.

According to Examples 1 to 3, the diazo and diazo compounds listed in the table below can be used Use azo components. The hue of the pigments produced in this way in the graphic Pressure is given in the right column:

Diazo component A / otuimponcmc

2,5-dichloranine, 1-methyl-5-aceto-yellow

acetyJamino-benzimidairolone

4-chloro-2-nitroaniiine like. orange

4-methyl-2-nitroaniline de * .gi. Red

clear yellow diazo component

2,5-dichloro-4-nitroaniline

2-methoxy-5-acetylaminoaniline

5-methyl-2-chloroaniline

2-trifluoromethyl

,. aniline

4-chloro-2-trifluoromethylaniline
2-amino-5-chlorobenzonitrile

2-aminobenzoic acid methyl ester
4-chloro-2-aminobenzoic acid methyl
ester

4-Bromo-2-aminobenzoic acid methyl

CStCr

5-chloro-2-aminobenzoic acid methyl
ester

3-chloro-4-aminobenzoic acid remeth yl ester

2.4-dichloro-5-aminobenzoic acid methyl

£ SI_f? R _._

5-nitro-2-amino

bcii / oesäuremethyl-

ester

Methyl 4-trifluoromethyl-2-aminobenzoate
1-aminobenzcl-

4-acetylamino-2-nitroaniline

reddish yellow dimethyl ester

1-Amjnobenzol-

2-carboxylic acid methyl

ester-5-carbon ^ ureamide

1-aminobenzene-2-carboxylic acid ethy! -
ester-5-carboxylic acid

amide

1-aminobenzene-2-carboxylic acid so
butyl ester-5-carboxylic acid camide

1-aminobenzo! -
Methyl 2-carboxylate-5-carboxamide

(> s l-Amino-ben7ol-2-carboxylic acid methylsler-5-carbiHisaurcmcth \ lamid

A / ncomponentc the same.

the same

the same
the same
the same
the same
the same
the same

the same
the same
the same
the same
the same
the same
the same
the same

the same

the same

1-Isobutyl-5-acetnacelylamino-benzmrida7olone

l-Methyi-5-acetate aceiyianiinc.bcn?- imida7olon

l-'iirblon

reddish yellow

stichiiies yellow yellow

yellow yellow yellow yellow yellow

yellow yellow yellow uelb

Red-

stichigei yellow yellow

yellow gcib

yellow yellow yellow yellow fiO9 585 /

continuation

Diii / okimiponcmc

10

A / nkvinpoiKUlc

Diazo component Azo component fluoromethylphenylamide desgL Cure 5 4-chloro-3-amino- the same 4-meth} 1-3-ataino- benzoic acid ethylamide benzoic acid iso- 4-chloro-3-amino- the same I-aminobenzene the same propylamide yellow benzoic acid 2-carboxylic acid methyl 2'-methyl-3'-chloro- ester-5-carboxylic acid IO phenylamide 2 ', 5'-dichlorophenyl 4-methyl-3-amino- the same amide benzoic acid-2'-chloro- i-amino-benzene- the same yellow 5'-trifluoromethyl- 2-carboxylic acid methyl phenylamide ester-5-carboxylic acid 15th 4-chloro-3-amino- the same 3'-trifluoromethyl- benzoic acid phenylamide 20th n-butylamide
1-aminobenzene
3,5-dicarboxylic acid l-methyl-6-bromo
5-acetoacetyl- 4-methyl-3-amino
benzoic acid remeth y 1-
ester the same yellow diamid aminobenzimide 4-methoxy-3-amino the same yellow 1-aminobenzene l-ethyl-5-aceto- benzoic acid methyl
ester 25th 3.5-dicarboxylic acid
diamid
1-aminobenzene acetylaminobenz-
imidazolone
1-n-propyl 4-chloro-3-amino-
benzoic acid methyl
ester the same yellow 3,5-dicarboxylic acid 5-acetoacetyl-
aminübciiZiniirf-
azolone 4-aminobenzoic
acid amide the same yellow 30th 1-aminobenzene 1-methyl 4-Mcthy! -3-amino- the same yellow 3,5-dicarboxylic acid 6-methoxy- benzoic acid methyl di-monomethyiamide acetoacetylamino ΗΓΠ1Π benzimidazolone 4-methoxy-3-amino the same yellow 4-methoxy l-methyl-5-aceto- benzoic acid reamide 35 3-aminobenzoic acid acetylaminobenz- 4-ethoxy-3-amino- the same yellow 2'-methoxy-5'-chior- imidazolone bef57oesäurearnjd phsr.y! a ~; d d-n-Riiinw-i-aminn. ee! b 4-chloro-3-a.Tiino- the same benzoin amide benzenesulfonic acid 4-MethyS-3-amino- l-methyl-6-chloro yellow ^4th amide benzoic acid amide 5-acetoacety! - 4-amino-2,5-di- the same aminobenzimide methoxybenzene azolone sulfonic acid amide 4,6-dichloro-3-amino- 1-isopropyl- yellow 45 4-amino-2,5-di- l-methyl-6-chloro benzoic acid amide 6-chloro-5-aceto- tni> tVinY from 7 / 1I- acetylaminobenz- sulfonic acid amide benzimidazolone imidazolone 4-amino-2,5-di- 1,6-dimethyl 2-Afriiiiü-2'.4'-ui- i-methyl give methoxybenzoi- 5-acetoacetyl- Chlorine diphenyl ether 5-acetoacetyl- 50 suHbic acid amide aminobenz 4-carboxamide aminobenzimide imidazolone azolone 4-amino-24-di- l-methyl-6-meiü- 2-amino-4'-methyl- desgL yellow methoxybenzoi oxy-5-aceto- iuphenyl ether sulfonic acid methyl acetylaminobenz- 4-carboxamide 55 amide imidazolone 2-amino-4'-chloro- the same yellow 4-amino-2,5-di- 1-n-propyl öiphenyJäuicr- meihoxybenzo! - 5-acetoacety! - 4-carboxylic acid sulfonic acid methyl aminobenzimide methylamide Art amide azolone 4-ChloT-i-amino- the same yellow DO 4-amino-2,5-di- 1 -n-butyl-5-aceto- benzoic acid-2 ', 5-di- niethoxvbenzc! - acei "lair.inobenz- chlorphenylamide sulfonic acid methyl imidazolone 4-methoxy-3-amino desgL yellow amide benzoic acid-3'-tri- 65 4-atnino-5-meth- 1 -Methyl-5-aceto- öxy-2-methyibenzoi- aceiyiaminobenz- give sulfonic acid ethyl imidazolone amide

yellow yellow

- - - 11th 18th 08017 12th continuation 4-amino-2,5-di-
methoxybenzene
sulfonic acid ethylamide - Diazo component Azo components lc Diazo component 4-amino-2,5-di- Carbon fiber methoxybenzene 4-amino-2,5-di- the same sulfonic acid isopropyl Azo component c yellow ⁵ methoxybenzene
sulfonic acid-2 ', 5'-di-
methoxy-4'-chloro-
• 1 * y amide .. - yellow phenylannd 4-amino-2,5-di- the same 4-amino-2,5-di-
IO the same menhoxybenzene the same methoxy benzene suH'onic acid-n-butyl- sulfonic acid-2 "-methyl- amide yellow phenylamide 4-amino-2,5-di- 4-methyl-3-amino the same methoxybenzene the same , ₅ benzenesulfonic acid acid rephenylamide methylamide yellow 4-methoxy-3-amino the same benzenesulfonic acid the same methylainid

yellow valid

Claims (5)

PateAbSpeccae: V \ l. MejK> azovCTbindOTgen of the general formula wherein X is hydrogen, chlorine or bromine or a methoxy group, Y and Z / -hydrogen, Chlorine or bromine atoms, nitro, wethoxy, ethoxy. Butoxy groups, phenoxy groups optionally substituted by ChloT atoms or methyl groups, Methyl, trifluoromethyl, cyano, lower carboxylic acid alkyl ester, carboxamide. lower carboxylic acid monoalkylamide groups. optionally in the phenyl radical by methyl, methoxy or trifluoromethyl groups or chlorine atoms substituted carboxylic acid phenylamide groups, Acetamino-, sulfonic acid amides lower SnI-fonsäure-monoalkylamid- or sulfonic acid phenylamide groups optionally substituted in the phenyl radical by methyl or methoxy groups or chlorine atoms. R is an alkyl group with 1 to 6 carbon atoms and R, a hydrogen, chlorine or bromine atom or a methyl or methoxy group. 2. Compounds according to claim 1, wherein the group Y in the general formula is a group of the formula R ₃ HNQ ₂ B-, in which R _{3 is} a hydrogen atom. a lower alkyl group or the optionally substituted phenyl radical as indicated in claim 1. 3. Compounds according to claim 1, wherein the group Y in the general formula is a group of the formula R ₃ HNO ₂ S-, in which R _{3 is} a hydrogen atom, e ^: ne lower alkyl group or the optionally substituted phenyl radical as indicated in claim 1 . 4. Monoazo compounds according to claim 1, wherein the group Y in the general formula is a group of the formula R ₄ OOC— in which R _{4 is} a lower alkyl group. 5. Process for the preparation of the compounds according to claim 1, characterized in that one diazotized amines of the general formula