DE2329781A1 - NEW AZOPIGMENTS AND METHODS FOR THEIR PRODUCTION - Google Patents

Description

FARBWERKE HOECHST AG. formerly Master Lucius & Brüning

SUBMITTED

File number:

HOE 73 / F 159

Date: June 7th 1973

Dr.OT / Eh

New azo pigments and processes for their production

The present invention relates to new azo pigments of the general formula (1)

COCH,
N = N-CH-CONH-

(D

where η is the numbers 1 or 2 and A is an optionally substituted one The remainder, in the case of N = I, preferably benzene or naphthalene lin- or benzimidazolone series, in the case of n = 2 preferably represents the benzene or diphenyl series.

The invention also relates to a method for production of the above-mentioned dyes, in which one diazotized amino-benzoxazinediones of the general formula (2)

(2)

4Q988WU16

rait coupling components of the general formula (3)

CIUCOCIUCONH

where η and Λ have the meaning described above, couples. Of the used-Lon Amino-benzoxazin-dionone is 6-Amino-1,3-benzoxazin-2,4-dione described in French patent 1,368, the as yet unknown 7-amino-1,3-benzoxazine-2,4-dione can by methods known per se, for example by catalytic hydrogenation from the corresponding nitro compound (C. Wagner and D. Singer, Pharm. Zentralhalle 103, 791 (1964)) getting produced.

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

Suitable coupling components are N-acetoacetylaminonaphthalene; N-acetoacetylanilines of the formula

COCH ₂ CON Η-

^R 3

wherein R _{1 is} hydrogen, chlorine, bromine, alkyl with 1-4 carbon atoms, preferably .Methyl and ethyl, alkoxy with 1-4 carbon atoms, preferably methoxy and ethoxy, acetyl or acetylamino, R "and R ^ hydrogen, Is chlorine, bromine, alkyl with 1-4 carbon atoms, preferably methyl or ethyl or alkoxy with 1-4 carbon atoms, preferably methoxy or ethoxy; Benz imidazo] ones, which can be substituted in the 6- and 7-positions by chlorine or bromine, and bis-acetoacetylaminobenzenes and -benzidino, which can contain one or two chlorine or bromine, methyl or methoxy groups as substituents in the phenyl rings.

409884 / U16 - 2 a -

Examples of such coupling components are;

N-acetoacetylaniline

l-acetoacetylamino-miphthnlin N-Acctoacety] -2-clilor-aniline N-acetoacetyl-A-chloiwriilin N-acetoacetyl ~ 2.4-dichloro-aniline S-acetoacetylnmino-oniscl 4-acetoacetylamino-iiniEol 4-acetoacetylftmino-phcnotol K-acetoacetyl-2.5-diuctiioxy-aui] in

K-Acctoacctyl-4-chloro-2.5- (limetho3:. Y-aniline N-acetoacetyl-S-clilor ^ i-diniethoxy-aniline 2-Acetofccetylamino-toluene-4-toluene Acetoacetylauino 4-Acctoacetylaaino-1.3-xylene 4- Acctoacetylanino-acctylöiainobenzol 2-Acctoacetylnmino-5-chloro-toluene 2-Acetoacetyl] aiaiEO-5-acetylanisole 2 Acotoacetylamino ~ 5-acctyloreiuo-4-chloro-toluene N-acuacetyl-3-amino-3-amino-acetylamino-4-bromane Acetoacetylamino-4-methyl-anisole N-acetoacetyl-2 _t 5-dimethoxy-4-bromaniline N-acetoacetyl ^ .S-diethoxy ^ -chloraniline N-acetoacetyl-4,5-dimethoxy-2-chloroaniline N-acetoacetyl-2 , 5-dichloroaniline N-acetoacetyl-2,4-diethoxyaniline N-acetoacetyl ^ -ethylaniline N-acetoacetyl-2,4,6-trimethylaniline 3-acetoacetyl-4-bromo-6-methylanisole 2-acetoacetylamino-5-bromanisole 2- Acetoacetylamino-4-methylanisole 2-acetoacetylamino-5-methyl-6-bromophenetol δ-acetoacetylamino-benzimidazolone

S-acetoacetylamino-e-chloro-benzimidazolone

ö-Acetoacetylamino-T-chlorobenziraidazolon

40988A / HI 6 - 3 -

1. -l-Bie-acetoacetylamino - ^ - brorobenzenes

1,4-bis-aeetoacetylamino-benzene

1. ^ - Bis-acetoacetylainino ^ -chlor-benzene

1 .'t-bis-acetoacetylainino ^. 5-dichlorobenzene

2.5-bis-acetoacetylamino-toluene

2.5-bis-acetoacetylamino-1.4-xylene

2.5-bis-acetoacetylamino-anisole

l'i-Bi8-acetoacetylamino-2,5-dimethoxy-benzene 2.5-bis-acetoacetylamino- ^/ t-methoxy-toluene

N.N'-bis-acetoacetyl-3.3'-dichloro-benzidine N.N'-Bi8-acetoatetyl-2.2'-dichlorobenzidine NN ¹ -Bis-acetoacetyl-3 · 3'-dimethoxy-benzidine NN ¹ -Bis-acetoacetyl-3.3'-dimethyl-benzidine

The production of the azo-pigments according to the invention takes place according to the principle known processes, for example by coupling the diazotized aminobenzoxazinediones with the coupling components in an aqueous medium, advantageously in the presence of a nonionic, anionic or cationic agent Dispersant or in the presence of an organic solvent. The coupling reaction can also be carried out in organic solvents will.

The diazonium salts of the aminobenzoxazinediones are not large in water Solubility. The diazotization can therefore advantageously also be carried out in a suitable organic medium, such as, for example in glacial acetic acid, alcohols, formamide, dimethylformamide or dimethyl sulfo xide. The solution of the Diazonimsalzee obtained bo can then with the azo component be united.

It is often useful to use the pigments obtained in this way to achieve the to subject full color strength and a particularly favorable crystal structure to an after-treatment. For example, heating is used for this purpose die.feuchten or dried and ground pigments in pyridine, dimethylformamide or other organic solvents such as methyl sulfoxide, Alcohol, chlorobenzene, dichlorobenzene, glacial acetic acid, quinoline, glycol or nitrobenzene under reflux for some time or at higher temperatures under pressure. In some cases the conversion into a particularly favorable one succeeds Crystal structure also by heating with water for boiling or to higher temperatures under pressure, optionally with the addition of dispersants and optionally with the addition of organic solvents, for example of the type mentioned above.

409884/1416 ' ^k '

The new A / .opiguient «· are completely water-insoluble and are suitable for the production of colored lacquers, lacquer formers, solutions and Products made from Acctylccllulo.se, natural resins or synthetic resins, such as Polymerization or condensation resins, such as amino or Phenoplasts, as well as 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, in particular textile fiber materials or other sheet-like materials Forms such as paper.

The pigments can also be used for other purposes, e.g. finely divided Form for dyeing rayon or cellulose ethers rayon or esters, polyamides, polyurethanes, Poiyglykolterephthalaten or Polyacrylonitrile used in spinning pulp or for dyeing paper will. In the media mentioned, the new pigments show good light, Weather and migration fastness. They are also heat resistant, strong in color and in many cases show pure hues. Against the influence of chemicals, especially solvents, diluted acids and alkalis are they persistent.

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

409884 / U16

example 1 ^w

17.8 g (0.1 mol) 7-Λπιίϋο-1.3-ΙίΘ]) ζοχαζΐη-2.4-άΐοιι, 6θ ml glacial acetic acid and 27.8 ml 31% hydrochloric acid are stirred for 1 hour and stirred at 0 ° with 20 ml 5N sodium nitrite solution diazotized.

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

24 g (0.103 mol) of 5-acetoacetylamino-benziinidazolone are dissolved in 121 ml Dissolved 2N sodium hydroxide solution and 200 ml of water and the solution was clarified. 25.2 ml of glacial acetic acid, 50.4 inl of 2N sodium hydroxide solution and 1 g are added to the dome a mixture of Sinaroleulfamido-easigsauren-Sodium and Sinarol submitted. By adding ice, the temperature is set to 10 ° and left add dropwise the solution of the coupling component.

The diazonium salt solution then runs in slowly.

After the coupling has ended is heated by introducing steam at 90 °, this temperature häjtt 20 minutes, the pigment is filtered off with suction, washed with water and dried at 65 ^0th The dry pigment is ground and heated with 800 ml of dimethylformamide and 200 ml of water at 100 ° 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

has excellent solvent fastness, when incorporated in polyvinyl chloride, in a varnish, a printing ink or a spinning mass , it produces pure, strong, yellow colorations with very good migration and light fastness

If, in the above example, instead of 5-acetoacetylamino-benzimidazolone, the equivalent amount of S-acetoacetylamino ^ -chloro-benzimidazolone is used, it also has a yellow pigment that has similarly good fastness properties when incorporated into polyvinyl chloride, for example.

409884/1416

Hot game 2

8 »y ß 7-amino-1,3-l» enzoxozin-2,4-dione are vie in Example 1 diazoticrt.

8.7 g (0.252 mol) 1.4-H.ifi-acetoacety] ac.ino-2.5-dichloro-benzene in 200 ml of water and 17 ml of 33% sodium hydroxide solution yellow, with 300 ml of water and 1000 ml of isopropanol diluted, then mixed with 15 ml of glacial acetic acid. The clarified diazonium sulphate solution is then slowly added at 20 ° The coupling component is run in, the mixture is subsequently stirred for 1 hour and then refluxed for a further 1 hour. The pigment is sucked off, washed with water, dried, ground and another 2 hours with 350 parts by volume of dimethylformamide heated to 100 °. It will be again Sucked off, washed with methanol and water, dried and ground. The pigment of the formula obtained in this way

Cl

When incorporated in polyvinyl chloride, in a varnish, a printing ink or a spinning dope, it produces very good greenish yellow colorations Heat resistance and very good light and migration fastness. ...

Example 3

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

The diazonium salt solution is slowly added dropwise to this suspension, whereby the simultaneous addition of dilute sodium hydroxide solution

40988 W HI 6

Maintains pH at 4.5-5. Noel) when the coupling is complete, the heat is applied Reaction mixture at 90 ° for 30 minutes, sucks off the dye and bites washes with water. The moist press cake is with glacial acetic acid for 1.5 hours boiled, drained, washed with water, dried and ground. By thermal aftertreatment in 25 / vi i; eiii aqueous dimethylformamide the color strength can be further improved. The obtained dye of the formula

COCH ₃

OClI ₃

when incorporated in polyvinyl chloride, in a varnish, results in a printing ink or pure, yellow dyeings with good lightfastness and migration fastness.

Is used in the above example instead of N-acetoacety] -2,4-dimethoxyenilindic equivalent amount of 2-acetoacetyl-ü-chloro-anisole is obtained a greenish yellow pigment with similarly good properties.

Example 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 S-acetoacetylamino-benziinidazolone are dissolved and clarified in 17 ml of 33% sodium hydroxide solution and 500 ml of ipopropanol. Is then adjusted with about 13 ml of glacial acetic acid to pH 5.5, can löeung slowly run the diazonium salt and heated after completion of the clutch in the heating bath 30 minutes 70-80 °. The dye is filtered off with suction, washed with water, dried and ground. After a short thermal aftertreatment at 100 ° with a dimethylformamide / 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,

When incorporated in polyvinyl chloride, in a varnish, a printing ink or a spinning mass, it produces greenish-tinged yellow colorations of excellent lightfastness and migration fastness.

409884 / U16

Bjt; \ j *) yi «J 5

8 »9 £ 6 ~ Ajniiio-1.3-benzoxazine-2. ⁱ J-dioii are diazotized as in Example 3. 8 | 7 β (0.0252 mol) 1,4-bis-acetoacety 1 amino-2,5-dichlorobenzene are dissolved in 200 ml of water and 17 ml of 33% sodium hydroxide solution, clarified, diluted with 280 ml of water and 500 ml of Ieopropanol and with 15 ml of glacial acetic acid partially precipitated again. Then the Diazoni urasalzlösung is slowly added dropwise, stirred for 2 hours and boiled for 1 hour under lllickfluss, sucked off, washed the press cake with water, made this again with 500 ml of glacial acetic acid and then refluxed for 1 hour. It is filtered off with suction, washed with water, dried and ground. By treating the dye with dimethylformamide for 1 hour at 120 °, the opacity can be further improved.
The dye of the formula thus obtained

Cl

H ₃ CCOCT-COMI- / OV NlI-COCIl-COCIL,

N /. N

I! Cl H

N N

When incorporated in polyvinyl chloride, in a varnish, a printing ink or in a spinning mass, it gives greenish yellow colorations of very good lightfastness and migration fastness.

The following table contains a number of further process-wise usable components, as well as the color tones of the graphic prints of the pigments produced therefrom in substance.

Diazo component

Clutch component

hue

6-amino-1,3-benzoxazine-2,4-dione

N-acetoacetylaniline

1-acetoacetylaminonaphthalene

N-acetoacetyl-2-chloroaniline

N-acetoacetyl-4-chloroaniline

yellow

Grünetichifgel

409884/1416

Diazo component

6-amino-1,3-benzoxaziii-2,4-dione

Kupp) .ungeJ < ütnponciitc

Γη ratοη

N-Acetorutyl-2. k di chi or-un.i iin

2-Ac et oat ο tylaniinnuii i sol

'i-Acetoacf.-tylaininoani Sol

2-acetoacetylaiiiinotoluene

4-acetoacetylaminotoluene

Ί-acetoaceiylamino-1,3-xylene

N-acetoacetyl-4-chloro-2.5-dimethüxy-aniliu

2-acetoacetylamino-5-chloro-toluene

2-acetoacetylamino-5-acetylauiino-4-chloi toluene

5-acetoacetylamino-7-chloro benzimidazolone

1,4-bis-acetoacetylarainobenzene

l. ^ - bis-acetoacetylaraino-2-chloro-benzene

2.5-bis-acetoacetylaminotoluene

2,3-bis-acetoacetylamino-1,4-xylene

2.5-bite-acetoacetylaminoeniaol

green »tit-li;. ^ - yellow

yellow

yellow

reddish yellow

N 2.5-Bi8-acetoacetylamino-
4-methoxy-toluene reddish N N.N'-bis-acetoacetyl "
3.3'-diniethylbenzidine yellow H N.N'-bisacetoacetyl-
2.2'-dichloro-benzidia yellow N NN ¹ -Bis-acetoacetyl-
3.3 ^l -dimetbojcy-ben7.idin yellow 7-aaino-1,3-benzoxazine-
2.4-dione 2-acetoacetylamino
anieol yellow 4-acetoacetylamino
aniaol H

- 10 -

409884 / U16

Diazo component, coupling component, color shade

-1. 3 "-beil / oxazin-2-Act (om e lylaüiim, - l.üluol yellow

2.4-dione

¹¹ 4-acetoacetylamino-toluene "

¹¹ N-aceloacetyl-2.4 "dimethoxy- ^|:

aniline

"N-acetoacetyl-2.5-dyne) ethoxy-"

oni1in

"2-Acctoacetyl-5-chloi-anisole green-tinged-R

"N-Acetoace tyl- '* - rlilor- yellow

2.5-diiuethoxy-aniliri

"1,4-Bi.s-bcetoacctylainino-"

benzene

¹¹ 1.4-Bifi-acetouceiylamino- "

2-chloro-benzene

"1.4-Uis-acetoacctylamino-rotstich.'R-ßelb

anisol

"1.4-Uis ~ iicctoncety]« 'imino- ""

anisole-2.5-dimethoxy-lienzol

"2.5-BiB-acctoaceiylaraino-" "

1,4-xylene

- 11 -

409884 / U16

Claims (3)

where η the numbers 1 or 2 and Λ ei non if necessary ·· subsii tuici Ι. ', υ RcbI, in the case of · \ <»n n-1 preferably the benzene, naphthalene or Densiraidazolnihe, in the case of u-' .l vnr?; i. ^ sviiic of UenzaJ.- odoi "Dijshonylrciliü dai stoll 1. 2. Process for Ilerfctel J ung tlor undm · l) beonepj nrli! .En pigments, dadiu'ch. characterized in that one diazotierto / uaino-bcnjcixa / ine of the general formula ILN with coupling elements of general distance 1 cn * j cocii, COMH— Λ], vorin Λ has the meaning described according to claim 1, couples. 3. Paints, paint formers, solutions and products made from acetyl cellulose, natural resins or synthetic resins, l'ols'styrene, polyolefins, polyacrylic compounds, Polyvinyl compounds, polyesters, rubber, caseiti or silicone resins, also paper or textile fibers made of cellulose, Cellulose ethers, cellulose esters, Pciyainideu or Polyurethanrn, printed with the dyes mentioned iu Aaspriicli 1 en gcfärbi oiler have been. k. \ ^r use of the dyes mentioned in claim 1 for dyeing or printing Lat-ken, Lacl.bi 1 duei'ii, solutions and products from Acctyl ccllulo.se-, natural resins or synthetic resins, polystyrene, Polj ^r - -IU- A09884 / Ί 4 1 6 6AD CRiGSNAL ο lc · Ti uen, lVlya «:. vyl connection on, poly vinyl connections, polyesters, Guiii'ii, casein or SiI iron resins, also Pi'pitr o'lrr Textile fibers from cellulose, CclluJ.oseüthern, Cellulosces to η, Polyamides od-jr l'olyure tliancii. COPY BAD ORiGINAL 409884/1416