DE1814519B2 - Process for the production of azo pigments - Google Patents

Description

H, N

where Z = H or

- SO ₁ - N

CH ₁ -CH ₁ -CN

and X = H. - CH _{1 - CH 2} - CN. Alkyl with 1 to 5 carbon atoms.

- CH ₁ - CH ₁

or -*:'

is. with the acid chloride of 2,3-oxynaphthoic acid, 2,3-oxycarbazole carboxylic acid, coumarin-3-carboxylic acid, a phenylpyrazolonecarboxylic acid or with acetoacetic ester or diketene is condensed and the condensation product thus obtained with a diazonium compound from aniline or naphthylamine. also with a maximum of three identical or different ones the following subscribers

Cl. Br. —CN. -SCN. -NO ₁ . -CH ₁ . - OCH ,. - CONH ₁ . - NHCÖCHj.

CF ₁

-CO

-SO ₂ C ₂ H ₅

CH ₂ -CH ₁ -CN

- SO., H. - COOH. - COOCH.,. -OH groups possibly still present iöslichmachende with salt solutions containing as cations Ba + ^+, Ca ^++, Cu ⁺ Ni ⁺ Mn ⁺⁺ or Al ^{++ +} are laked at temperatures between 40 and 95 ° C optionally with the addition of anionic surfactants or nichlioniseher .

> - NH, The invention relates to a method of production of azo pigments, which are excellent for paints and plastics as well as for dyeing viscose dope and suitable for printing inks

It is known to have alkyl substituted sulfonamide groups to be incorporated into dyes (see Swiss patent specification 395 387 and Austrian patent specification "MO 488) In the German Auslegeschrift 1 242 774 and in the Swiss patent specification 413 16R Lsi mentions the possibility, among other things, of groups of the species

- SO ₂ - N (Cr I ₂ CH ₂ CN ₁ ¹ I ₂

to use. According to Swiss Patent 394 438, similar non-alkyl substitutes are known Groups in the diazo component. According to the German Auslegeschrift 1 153 476, diazo components from a compound of the formula

(AIkVIkN-SO ₂ -QH ₄ -N = N-QH ₄ NH ₂

which is also substituted s; in can, but the Alkyl groups are not substituted, obtained.

Finally, the most recent French patents 1 50.5 707 and I 505 708 are still available imagine that the dyes show a similar structure

All of these patents deal with disperse dyes.

The aim and object of the invention was now to create azo pigments on a similar basis, the better one Have fastnesses than those previously known.

It has now been found that valuable Azopiemente can be obtained obtained when compounds of the general formula

CH ₁ -CH ₇ -CN

may be substituted, where Y = H. Cl, —CH ₃ , _{—OCH 3} or —NO ₂ and X has the meaning given. is coupled and any solubilizing groups present in the molecule of the dye are laked with salts of polyvalent metals.

2. The method according to claim I, characterized in that the coupling in weakly alkaline to weakly acidic medium at temperatures from 0 to 70 C and in the presence of aiiionic or non-ionic surfactants is carried out.

3. The method according to claim 1, characterized in that given in the dye molecule —y

or

NH, -

SO, - N

SO, - -N

CH ₂ - CH ₂ CN

X X

Yh, cn, cn

I 814

u ο hei X ■ - H,
5 carbon atoms,

CU, -Cl Ij-CN, alkyl with! his

-CH ₁ -CII ₁

or

is, with acid chlorides of 2,3-oxynaphthoic acid, ^ -Oxycarbazolecarboxylic acid.Curnarin -Vcarboxylic acid, a Phenylpyrazokmearbonsaure or with Acetcssigester or condensed diketene and the condensation products thus obtained with diazonium components starting from aniline or naphthylamine, also with a maximum of three identical or different of the following substituents

Cl. Br. -CN, -SCN, -NO ₁ , -CH ₃ . -CF ₁ . - OCH. ,, -CONH ₂ , -NHCOCH ₃ .

-CO — ίζ

-ο-

CW- - CH, - CN

SO, C ₂ M ₃

SO,

SO,!!. -COG !!. - COOCH,

OH.

N "H-,

can be substituted, where "
Is OCH, or -NO ₁ and

= H.

ie

Cl. -CH ,.

specified

Has meaning, coupling. The resulting product

If no solubilizing groups are present in the molecule, it is precipitated with dilute acid in the presence of anionic or nonionic surfactants. It represents the desired azo pigment. If there are still solubilizing groups in the molecule, the product has to be separated off by salts and then laked to pigment by treatment with salt solutions of polyvalent metals. The following cations are suitable for lamination: Ba ⁺ \ Ca ^{T +} , Cu ^{+ +} , Ni ^{T +} , Mn ^{+ +} , Al ^{+ + +} and others, which can be present as nitrates, chlorides, acetates, etc. The laking leads to be: temperatures between 40 and 95 ° C, especially at 70 ⁰ C, in a weakly basic, neutral or weakly acidic range. Anionischc or nonionic surfactants should also be used. B. for the diazo component of a compound of the formula

NH,

-NH,

go out, where Y has the meaning given. A bisdiazotized compound is formed by diazotization, which is best obtained with condensation products of acetoacetic acid or phenylpyrazolone-jirboxylic acid clutch.

The coupling of the diazonium salt with the condensation product mentioned is weak in the alkaline to weakly acidic medium at temperatures from 0 to 7OC, advantageously at 30 to 50 C, and carried out in the presence of anionic or nonionic surfactants.

A whole series of pigments can be produced in this way, in the simplest case one of the following pigments formula

HO CO --NH - <

/ Vn-ν - ^ S

SO ₁ -N

CH ₁ - CH ₁ - CN

CH ₁ - CH, - CN

for which unsubstituted aniline and 2,3-oxynaphthoic acid chloride form the starting materials.

The diazo component used is, for example:

Aniline. 2-anisidine. Cresidin, 4-chlorocresidin. Anlliranilic Acid Methyller. 2,4-dichloroaniline. 2.5 dichloroaniline. 2-chloroaniline. 3-chloroaniline. 4-chloroaniline. 4-chloro-2-anisidine. 4-chloro-3-aminotoliol.

3 - chloro-2-aminotoluene. 4-chloro-2-aminotoiuol 5-chloro-2-aminotoluene. 6 -Chlor-2-aminotoiuol.

4 - chlorine - 2.5 - dirnelhoxyaniline. ί - Trilluormelhyl-2 - chloroaniline, 3.5 - ßistrilluormeihylaniline. 5 - trifluoromethyl - 2 - ethyl sulfonic aniline. 4-aminoben / ophenon. 4 - acelaniinoaniline. 2.6 - dichloro - 4 - nitr; tniline. 4- Rhodananiline. 4-rhodane - 3 -chioraniline. 3-aminohene / .onitrile. 3-aminobene / amide. 4-Aminohen / ol-NN-bis-. " ^1- cyanilhyl-sulfonamide. 3-Aminobcii / .ol-NN-bis-2-cyanoethyl-sulfonamide. 2-Aniinobenzene-NN-bis-2-cyanoethyl-sulfonamide, 4- Aminobenzene-N-2-cyanoethyl-sulfonamide, 3-aminobenzoi-N-2-cyanoethyl-sulfonamide.2-aminobenzene-N-2-cyanoethyl-sulfonamide, 3-aminobenzene - N, N - ethyl- (2-cyanoethyl) - sulfonamide, 1-naphthylamine, 2-naphthylamine, 2-naphthylamine-1-sulfonic acid, 2-chloro-5-aminotoluene-4-sulfonic acid.

Naphthalene sulfonic acids added in small amounts to stabilize labile diazonium salts do not interfere with the coupling.

Those producible by the process according to the invention Azo pigments are ideal for incorporating into paints and plastics, especially into Polyvinyl chloride. They can also be used for dyeing viscose pulp and for printing inks. They color very well oil, solvent and lightfast, pure yellow, orange, red, purple and brown Nuances of high color strength and brilliance. Geücn-

I 814

The azo pigments according to the invention, for example, as zinc white blend in linseed oil or in soft PVC or as heavy spar blend used in the Lcim / water system, are markedly larger than the next comparable azopium ducks of German patent specification 908 050 and USA patent specification 2 252 844 Colorability from. The good oil and soft fastness properties of the dyes according to the invention should also be particularly emphasized. So shows z. B. the dye 2,5-dimethoxy-4-chloranüin - ♦ 4-acetoacetylaminobenzene-N, N-bis-jp'-cyanothyl) sulfonamide compared to the dye 4-ethoxy-3 known from German patent 9Γ »8 050 -aminobenzene-N, N-bis- (n-propyl) -snlfonamid - * Acetoacetylamino - 2,5 - dimethoxy- tj 4-chlorobenzene a 2 ', Λ level better oil resistance and ^{1 1} Z ₂ levels better plasticizer fastness. The following examples should serve as an explanation:

Example 1 * °

155.3 parts of 2.3 - oxynaphthoic acid - 4 - NN - bi. - (2-cyanoithyl) sulfanilide are made into a paste with 26 parts of sodium hydroxide solution (D = 1.32) and, after heating, diluted with 200 parts of water. N..in filtered and:> 73 parts of hydrochloric acid (O = 1.09) are added dropwise at 45'C with stirring. A solution of 63 parts of diazotized! 2.5-Dimethoxy-4-ehloraniiin to. The mixture is stirred for a further 15 minutes, heated to 85 ° C. and filtered off with suction. After drying, a blue-black powder is obtained which, when incorporated into Pohvin dichloride films, results in a true-to-migration, strong blue-tinged violet coloration.

Example 2

50 parts of chlorobenzene. 2.5 parts of thionyl chloride and 0.5 part of dimethylformamide are heated to 70.degree. 6.3 parts of 2,3-oxynaphthoic acid are now added and the mixture is heated to 100 ° C. for 20 minutes. The excess thionyl chloride is driven off in vacuo, 2 parts of dry pyridine are added and a solution of 9.2 parts of 3-aminobenzene-NN-bis- (2-cyanoethyl) sulfamide in 25 parts of chlorobenzene and 1 part of dimethylformamide. The mixture is heated for 1 hour and filtered off with suction at 30 to 40 ^J C. It is washed with chlorine benzene, then with a little dioxane and finally with water, and 2,3-oxynaphthoic acid-4-NN-bis- (2-cyanoethy]) sulfanilide is obtained as a yellowish powder.

Example 3

34 files of 4-chlorocresidine are mixed with 38 parts of ice cream. This solution drips 5 times with stirring; 80 parts of hydrochloric acid [D = 1.16) and 500 parts of water. Now 400 parts of ice are added, diazotized with 56 parts of 4 n-nitrite solution. The mixture is stirred for 30 minutes and filtered. 63 parts of 4-acetoaeetyl-N, N-bis- (2-cyanäthylisulfamidanilid are dissolved in 2000 parts of water and 100 parts of 2 η-sodium hydroxide solution by heating. 100 parts of 2 n-acetic acid are added dropwise at 50 ° C. while stirring The resulting suspension runs the above diazo solution within 15 minutes at 50 ° C. A yellow powder is obtained which colors polyvinyl chloride a bright greenish yellow. These colorations are very fast to light and migration.

Example 4

92.5 parts of 4-aminobenzene-N, N-bis (2-cyanoethyl) sulfainide are suspended in 250 parts of water and 91 parts of hydrochloric acid (D = 1.16). After 30 minutes it is cooled with ice to +5 to 7 "C and diazotized within 40 minutes with 167 parts of 2N sodium nitrite solution. which you run under the surface leaves. The mixture is then stirred for 30 minutes. You can now use the clutch. as in the example! I stated, perform.

Example 5

6.1 parts of o-dianisidine are diazotized as usual in 160 parts of water in 62.5 parts of 2η-hydrochloric acid. The solution of the resulting bisdiazotized product runs under the surface of the following coupling solution at -MO ⁰ C. 18.0 parts of 4-acctoacetyl-NN-bis- (2-c ;, anälhyO-sulfamidanilide are dissolved in 200 parts of water and 30 parts of 2 n -Natronlauge dissolved by heating. After cooling to IO C 33 parts of 2 drops η-acetic acid with stirring. wherein the coupling component precipitated as white suspension. After the coupling is heated for 10 minutes to 90 ^c C. filtered off and washed neutral. for Finally, it is dried. Yield: 22.8 parts. Stains rubber in a reddish yellow with fast migration.

Example 6

4.35 parts of diazotized 2-nitroaniline-4-sulfonic acid are coupled to the coupling suspension Example 3. After the coupling has ended, 10 parts are added Salt and sucks. The filter cake is boiled in 330 parts of water with 3 parts of emulsifier and varnished with 36 parts of 10% barium chloride solution at 70 ° C. within 20 minutes. After 30 minutes vacuum, wash, dry. 10 parts of a loose yellow powder are obtained. It stains polyvinyl chloride pure yellow.

In a corresponding manner, azo pigments can be made from the components of the following list Be won:

Azo pigments can be obtained in a corresponding manner from the components in the following list

will:

Diiizoticrungskompiincnlc

2-anisidine

Anthranilic acid methyl ester
2,5-dichloroaniliii

K tippluniiskonipnncntc condensed

11 ml:

2,3-oxynaphthocic acid

the same
the same

4-aminobenzene-NN-bis-2-cyanoethylsulfamide
the same
the same

NlKMKC

Blue red

Red
Blue rustic red

k; γ |>! ι: μ_'Λ. in | ' -11 -. - r 11L Ι ι.ink :, -: r I

\ ΙΙ, ΠΙ ¹

4- ('liloramlm

RoI

the same 2-c \ anath> lsiiir, imid Blue red . ^ς - <I ¹ lor- 1-; mi i (liη desui dosg! Hoido 4- (hint "2-aniMdin the same the same ruby krcMdin the same the same violet I-naphthylamiii the same the same Red 3-C'hk) r-2 "t () luidine the same the same Blue red 4-chloro-2-toluidine the same the same Blue red 5-Cb! Or-2-to] uidine the same the same Red fi-chloro-2-toliiidin desel. the same Scarlet fever 2,6-l) ichlorauilin the same the same Blue red 2.4-dichloroiline the same the same ruby 4- (chlorocresidin the same the same Scarlet fever 5-trifluoromethyl-2 - '; lilonniline the same dtsgl. ruby 4 aminodiphenyl ethers the same the same Bordo I X-chloronaphthylamine the same the same Reddish blue J - (. 'Chloro-2,5-dimcihoxyaniline the same the same Scarlet fever 4-aminobenzene the same the same orange 3.5-bis-trifluoromethylaniline the same the same orange > -Trifluoromethyl-2-ethysulfone \ l- the same aniline dcsgi. RoI 2-chlorane "in desiil the same (ielbsticliigroi 3 (chloraniline the same 4-Aminobcn / ol-N.N-bis-2-cvan- the same Blaus'icliigrol ethyl sulfamide 2.3-Oxycarbazilcarbon- the same 5-f'hlor-2-iiihiidin s.'iure the same Red-brown the same Brown 2,4-dichloroaniline Cu ma rin-3-carhon - .; i u rc dL, gl. Reddish yellow 4-chloro-2-loluidine the same the same Reddish yellow 6-chloro-2-toluidine the same the same Griinstigge 2.5 dichloroaniline 2.3-Ox vna ph t hoes au re the same violet 2.6-Diehlor-4-nilraniline the same the same violet 2-cyano-4-nitroaniline 4-aminoben / .o! -N.N-bi> - desul. 2-cyanoethylsulfamide orange 2.5-i) chloroaniline 3-aminobenzene-N.N-bis- the same 2-cyanoithyl sulfamide Bordo 4 - ('hlor-2.i'-dirnetho \ yanilin the same the same Sharia. ! i 4-chloro-2-toluidine the same the same Scarlet fever 2,4-dichloroaniline the same the same Yellowish tinge 5-trifluoronic thv! -2-chloroaniline the same orange the same Red 4-aminobin7ophynone 3-aminobenzene-N.N-bis- the same 2-cyanoethylsulfamide Bluish red 2-anisidine the same the same Scarlet fever 4-aminoben / ol-N.N-bis-2-cyan- the same ethylsulfonamide the same orange 4-aminobenzene-N.N-bis-2-cyano- 2-aminobenzene-N.N-bis- ethyl sulfonamide the same 2-cyanoethylsulfamide Roistichig- 2.5 dichloroaniline the same orange the same Violet ' 4-chloro-2.f-dimelho \ yaniline the same desg !. Red 4-chloro-2-toluidine desel. the same Scarlet fever 2,4-dichloroaniline the same

continuation

10

5-Trilluoi "meth \ l-2-chli> i \ inilin

'^ Aminobcn / .ophenon 2-anisidine
4-rliodananiline
4-Rhodan-2-toluidine J2,5-dichloroaniline

# -Chlor-2,5-dimethoxyaniline 4-chloro-2-toluidine
2,4-dichloroaniline
j5-trifluoromethyl-2-chloroaniline

4-aminobenzophenone t-anisidine

i-aminobenzoi-N.N-bis-cyano-

ethyl sulfamide
JI-Aminobenzene-NN-bis-2-cyanoethyl-sulfonamide

VAminobenzene-N.N-bis-2-cyanoethyl-sulfonamide

i-AminobenzoI-N, N-bis-2-cyanoethyl-sulfonamide

i-aminobenzene-N, N-bis (2-cyanoethyl) sulfonamide

2-aminobenzene-N, N-bis (2-cyanoethyl) sulfamide
the same

the same

the same

Coupling component condensing and:

2,3-Oxyniiphthocsiiire

like. like. like. like.

like. like. like. like.

like. like. like.

the same

like. like. like.

like. like. like.

the same

2-Aminobcn / ol-N.N-Ws- ■ (ielboraiige j 2-cyiinälhylsulfamid i

like. like. like. like.

N-2-cyanoethylsulfonamide

dcsgl. like. like. like.

like. like. like.

4-aminobenzene-N, N-bis-2-cyanoethylsulfonamide

3-AmJnObCnZoI-N ₁ N-Ws-2-cyanoethylsulfone-

amide
2-aminobenzene-N, N-Ws-2-cyanoethylsulfonamide

4-aminobenzene-N -? - cyanoethylsulfone-

amide
3-aminobenzene-NN-bis-

2-cyanoethylsulfamide 2-AmJnObCnZo] -N ₁ N-Ws-

2-cyanoethylsulfamide 4-aminobenzene-N-2-cyanoethylsulfone- amide

4-aminobenzene-N, N-bis-2-cyanoethylsulfamide

Scarlet Bdtxlo

Bluish red Bor do ruby

Bordo

Red

Scarlet fever

Gel bsi i ίμ-oranne

Ruby scarlet

Reddish

Scarlet scarlet red

Red

Scarlet fever

Braunsiic! ',!. · - ;!

Red

2-chloro-4-sulfo-5-amip.oi (iltiol 4-chlorocresidine

nponcn.e Kiippiiinüskomponcnlc otoltiol the same. Ba Nium. phosic acid 2,3-oxynaph- 4-aminobenzene- Mn Bln> stichi> - ■ ' thoic acid N.N-bis- 4-acetacetylaminobenzene-NN-bis-
2-cyanoethylsulfamide Biaustichigrol ^! (2-cyanälhyD- sulfamide Ba VIn Bluish red - Bluish tint Green tint

continuation

! "> l.IΛl! I! Π U -ki'ΠΙ pt MlCt 1 ', C 4-Acetaeetylaminoben / ol-N.N-bis- Ba Nn.iiKV 4-chloro-2,5-diinctho \ yaniline 2-cyanoethylsulfiimide Approx Greenish yellow dcsgl. Cu 2-cold> r-4-nitroaniline desr! Greenish yellow 4 - ('hli> r-2-nitr; nilin the same Ciriinstichy yellow 3-nitro-4-toluidine dcsgl. Greenish yellow 2-nitroaniline-4-sulfosene dcsgl. - yellow the same dcsgl. yellow the same the same Green yellow o-dianisidine 3-acetoacctylamiiiobenzo! -N.N-bis- yellow 4-chlorocresidine 2-cyanoethylsulfamide Greenish the same Ba yellow 4-chloro-2,5-dimethyl oxyaniline the same Approx Greenish
yellow
Greenish 2-chloro-4-nitroaniline Cu yellow the same yellow 3-nitro-4-toluidine the same yellow 4-chloro-2-nilraniline dcsgl. yellow 2-nitroaniline-4-sulfosiune dcsgl. yellow the same dcsgl. Green yellow the same dcsgl. - ■ Greenish o-dianisidine - ■ yellow 4-acetoacetylaminobenzene yellow 4-chlorocresidine N- (2-cyanoethyl) sulfamide Ba the same Approx yellow 4-chloro-2,5-dimethoxyaniline the same Cu yellow 2-chloro-4-nitroaniline the same - yellow 4-chloro-2-nitroaniline the same Rotstichiggclb 3-nitro-4-toluidine the same Rotstichiggclb 2-nitrarsiline-4-sulfos; iurc the same Reddish yellow the same the same yellow the same the same Reddish yellow o-dianisidine

Claims (1)

Claims 1. A method for the production of azo pigments, characterized in that a Compound of the general formula CH ₂ - CH ₂ - CN SO ₁ -N