DE922728C - Process for the production of new cobalt-containing azo dyes - Google Patents

Description

Process for the production of new cobalt-containing azo dyes It has been found that valuable, new cobalt-containing azo dyes are obtained if one uses monoazo, dyes which are free from sulfonic acid and cairboxyl groups and the general formula where Y is an amino or an oxy group, Ri is a benzene radical bonded to the azo group in o-position to the oxy group, Re - Y is the radical of an azo component bonded to the azo group adjacent to the group Y and X is a Aryl radical means one of the substituents of the formula contains, in which Z1 and Z2 are each r hydrogen atom or an aliphatic radical containing at most 6 carbon atoms, allows cobalt-donating agents to act.

The above-mentioned formulas en, t- serving as starting materials in the present process spitting monoazo color monkey bind to tell knows. Sire can be obtained (by coupling one in Nachhamstellumg to an amino or oxy- group-coupling azo component--, i that of sulfone- sour and carboxy greens fireli is, with from Sulphonic acid and cacboxyl groups look forward to Amines of the formula Dmazoiver connections available, where the be @ den- Use of the various symbols R1: and X are sufficient the formula (i) already explained results. The benzoil radical R1 of these amines .kann to the Amsino group in 2-position, to the oxy group in i position and to the - S 02 N HX group in 4-oider, tied in 5-seat pitch; he can do more Suhstituenten not s! B. a Halogen atom or a nitro group. Of the Aryl radical X can, for. B. a naphthalene or preferred w! eiioe, e, in benzoil residue, be "deir a Suilfonsäuireamild- group, -z. B. a Siulfonnäurialkylamid- or one Swlfonsäureoxyalkylairniidgruppe, but preferably one of the formula - S 02 N H2 and given as far as subscribers are concerned, such as an alkyl group (e.g. mebhyl), a chlorine atom and the like holds. Such compounds of the formula (2) can be sp; ielisweüise from Arniinen of the formula XN H2, womin X, which has the meaning given above, and i-chloro-2-nitrobenzene-4-sullfo @ rnsäurechloiriid produced tolilt weiriden, liindem you, the resulting i-Qhlloir-2-nitroibenzoil-4-s, sulfonic acid anvi @ de with Al- potash or ezidialkali hydroxides correspond to ides converts the i-Oxyve; rbiinidunaolen and in these last berries. -the office group -in a known way in a Amino group wbeu leads. Instead of i-chlorine 2-nii, broibenzene-4-isulphonic acid #chlomld can also be used z. B. front i, 2-Benzoxazoilon-5-isalföinsäur, echlorlid awsigehen, after which, the condensation with the Amines, the formula X-NH2 to the corresponding .den i, 2-Benzoxazolon-5-sullfonsäuireami, the only nor. the saponification of the oxazolone ring is necessary is to also lead to compounds of the formula (2) to hired. All amines of the formula (2) are: 2-Amiino @ -i-oxybienzoQ-4- # s, üllfo, näur-N-i'-napihbhyl- amiüd-q .'- isiulfonsä, ureiamßiid, 2-Amli; no- i-oxy-6-chloir- benzene - 4 - sulphonic acid epihenylamide - 3'- sulphonic acid amide, 2-amino-i-oxy-6-niibrobenzene-4-.s, nilfonic acid Phenyl: am.iid -4'- sulfonic acid amide, 2 -amino - i - oxy- : benzene-4- o, der -5-su! lfonsänx: repihenyl: am.iid-3'-sulfone- . Acid methylamide, 2-am! ino- i -oxybienzoil-4- or - 5 -isulfonsänrephenyliamdd - 3 '-isnnilfons äuire - ß - oxy- ethyl amide, 2-amino-i-oxyb, enzod-4- or -5-suafo @ n- sä @ urephenyliawi, d-4 '- isopiopyl- or -n-butylamiiid, 2-Amimo-i-oxybenzoil-4- or -5-.s@ulfonsäurephemyl- iam @ ild-3'-sulfonsäuireid @ mebhyl; ami @ d and in particular 2-Amiino-i @ axybenzol-4- or -5-siuIfo: nisäurephenyl- axnild-2'-, -3'- order '-4' -, sulfonsämTeamiiid. As azo components come for the production in the original process as starting materials serving monoazo fibers amdno or preferred because Oxyverbiindunigen, im. Consider "those of sulfone acid and carboxyl groups are free and those in Needless to say, to an amino or Oxy group can connect. All amino hindrances Examples of this office are: two naphthylamines, such as ß-Napihthydiamdn, 2-Amnnonuphbhalhn-6-s @ uilfK) nsäwre- amiid, older i amlinonaphthalliin-4-sulfoic acid amn (d, to mention. Among these oxy compounds there are probably aromatic oxy compounds such as Tauich compounds biinidiungi & l to understand, idlie iii your coupling ability owe a ketomebhylene group. This last terem can be the ketomethylene group in either an open chain oider in an ihetero, cyclic Ring included. As Oxyveriblindungen; of the specified kind are Mentioned: , a) p-substituted oxybenzenes, such as 4-mebhyl-, 3, 4-Diimebhyl-, 4-Teribiäriamyl- oider 4-Acetylamiino- i-oxybenzene, 4-methyl-2, acety4-amli: no-i-oxybenzene; Dioxybenzolle, such as resorcinol, Oxyniapihthaliine, such as 2 - Oxynapihbhal! Iin, 2, 6 -Dioxynaphbhaliin, 2 - Oxy- 6 - b @ rom - or - 6 - mebh @ oxynapihthallii @ n, i - Oxy- 4-mebhylnapbibhabin, 2-Oxyn, aph @ hallin-6-sulfone- acid amiide, i-Oxy-5-chilioirniaphthalmn, i-Oxy-5, 8-di- chdoirnaphbhadin, also i-acylamiino-7-o # xYznaphbha- line, such as i -acetylamino-, i n-butyrylamino-, i-Garbomebhoxy- or i-Carboäbhoxyamiino-7-oxy- niapihbhalin adeir i-benzoyl, amino-7-oxyniapihthaliin. b) pyrazolones, 'WI-- 3-iMebhyl- or 3-phenyl- 5-pyrazolone, i n-butyl-3-methyl-5-pyrazolone, i-phenyl-3-mebhyl-5-pyriazollon, 1- (2 '-, 3 "- or 4 '- Ghlo, r) -phenyl - 3 - methyl - 5 -pyrazodün, 5-Pyr- azolone-3-carboxylic acid amild, 5-pyrazolone-3-carbon , acid - N-methyl-, -ethyl-, disopropyl-, iseikundybutyl-, t, -rbiobutyl- or -n-biutyilami! d, S-Pyrazoilon-3-: car- bonsäuire-N-2'-, -3'- or -4'-chlorop'henyl amide, 5-Pyrazolön-3-carboxylic acid-N-phenyl- or -tolyl- amiiid, iP $ enyl-5-pyrazolon-3-carb, o @ nsäureami @ d, Barbiburic acids, such as the B-airbilturic acid itself, di- oxychinoliine, like, the 2,4-dioxyquinoline, acyl acyl acetic acid , acid ester oider, am @ iide, such as Aceteiss-igsäureamiid, Acetesis, iigsäure-N-mebhyl-, Jn-buityl- or -phenyl- : amiid, Aoetes! s: iigsäure-N, d @ imebhyl: amii.d, Ace: tesisiig- acid-N-2'-, -3'- or -4'-chlorophenylamide, benzoyl- ies, s! igsäuireiamiid, Benzoylessligsäurep @ henylami-d. Diie Di @ azofiiernunig, the amines ider Foirmel (i) can in a bad way with the help of sodium nitrite and S. salty be made. The coupling of the so mentioned D, @ azo blinding with Iden- ten azo components can also be used in the usual Way to be done. After the completion of the implementation process, the Dyes from the coupling gennisah easily through Filter off separately as they are in general are little wasiserlösilicih. Indesisen are they as Alkali @ terhindungen in water still -sufficiently soluble- Lich to get out of dye baths that do not have added acid need to be able to be colored. According to the present method, content complex connections arise that point to i or 2 monoazo color, hydrogen molecules in the atom of cobalt hold When using o, o'-D; ioxymonoazo- farbhs.tofen old are the Kob # old- complex compounds, which are based on 2 monoazo color s, substance molecules in the atom of cobalt contain, especially valuable. To obtain such i: 2 complexes, recommends e! s in general, on 2 1Iol one of the general my formula (i) corresponding azo dye or to a mixture of about i mol each of two different azo dyes, of which at least corresponds to one of the general formula (i), a containing about 1 gram-atom, the remaining amount of a delivering 1VI: i @ ttelis to use and or the me- tallins.ierung in weakly acidic to alkaline Funds to carry out. As a cobalt-reducing agent there are complex cobalt wares aliphatic shear oxycarboxylic acids or D: icarboansäu, ren and simple salts of your divalent cobalt, like Kob, al-tsiu, lfat, Kob.aIfia! Cetat or Kohb, old formate, ge if necessary, cobalt hydroxide can also be considered. the Conversion of the dyes into the complex ones Cobalt prevention takes place with advantage in the Heat, open or under pressure, e.g. B. at boiling temperature! of the reaction mixture, if necessary in the presence of suitable additives, e.g. B. at wesenhet of salts of organic acids, of Bases, organic solvents or others the complex investment promoting means. The lIetallnsierung just explained can z. B. a uniform dye with the formula (i) be thrown. But it is possible and in many ways Cases vore! I! Lhh-aft, z. B. also to achieve different color tones, a mixture of two different different such azo dyes or a Gambian, consisting of an azo dye of the formula (i) and another: from sulfonic acid, and carboxyl groups freineu o, o'-D.ioxymonoazofarb, sto @ ff, dev- to metallize speaking. The cobalt complex compounds obtainable in this way Contain 2 Mo @ no; azo, dye molecules -an i atom Koibailt tied complex, and aas must at least one of the general monoazo suture molecules Correspond to formula (i). Are particularly valuable the Kob, alltlcomplexverbiintd @ ungen of this kind, the two comprising the bleached composition Contain monoazo dyes of the formula (i). The new cobalt complex compounds are in Water and in chemically weakly acidic, aqueous Medium soluble, and more soluble than that to hers Raw materials used in manufacture. You own for dyeing various fabrics, such as plastic different masses, resins, waxes, lacquers and the like, but preferably for ferry and printing tieiris, cheT materials such as silk, leather and ins- special wool, as well as for dyeing and print synthetic fabrics made from super polyamides and super-polyurethanes. They are especially suitable for dyeing from weakly alkaline, neutral or weakly acidic, e.g. B. Acetic acid bath. the The colorations obtainable in this way are characterized by a good equilibrium, quality, good wet fastness properties ten and very good the end. Compared to the USA patent specification 2 024 864 described Chromkoanplexverbin! Du.n- gene show those manufactured according to the process Cobalt complex compounds prefer to be loose To dye wool evenly - n. Compared to the colorations, d-ie with then according to USA.-Paitentschrift 2 499 133 and the German Patent specification 445 888 produced chromium complex verlyindungen are generated, are characterized by according to the procedure; produced. cobalt-containing Colorings obtained by better colorings Lightfastness -off. In the following examples, the mean Parts, unless otherwise stated, parts by weight and the percentages percentages by weight. Example i 34.3 Te'i'le 2-Arnihno-i-oxybenzod-4-su, lfo @ nisäure- phenylamide-3'-su-lfo, asärureamhi! d are used in Zoo Part- len i n hydrochloric acid at q. & dissolved. By adding ice is cooled to 0 ° and at 0 to 1o ° with 25 parts 4 n-Natrüumniiitrii! Tlöisunhg diirazoti.ert. The received yellow-colored Ds, azo! su @ spe: nsi @ on is with, t sodium carbonate neutralized and then with a lot more about 5 ° cooled solution of 14.8 parts of 2-oxy- nap! hthalrin in 100 waists of water, 4.2 parts of Na- trium hydroxide and 5 parts of sodium carbonate agree. After the coupling is complete, the 9b- different dye filtered off, with 2% sodium chlorine, solution .washed and dried. The color Solder the fabric in a dilute sodium carbonate solution mhi @ t purple and in concentrated sulfuric acid with pure blue-red color. 4.98 parts of the dye thus obtained Slurried in 100 parts of water, with 8 vol- Partly 2 n-sodium hydroxide solution added, to 80 ° heated and divided with iiobal: tsu: lfa.t solution with a cobalt fig content of 2.950 / 0 . To brief heating, to 85 to 90 ° the complex education ended. You neutralize with thinner ter acetic acid and sodium chloride addition is the Kobal.tkomplexver@bihndung of the dye fully constantly secluded. The .abfiltrie arte and dried nete coloring matter, is a dark brown ice powder, dias in hot water and dilute sodium carbonate solution with burgundy, in concentrated Sulfuric acid with a pure blue-red color dissolves and Wool from neutral or weakly acidic bath in Bordeaux-red, very good wash and light: ahten Tones colors. In the following table, other similarly higher adjustable Kobelt complex connections are given. In column III! The color tone is the one with the cobalt complex compound of the corresponding, in Column I and II specified components receive dyestuff on wool or fibers from Supher-- polyami: indicated the coloration obtained. "III I II Cobalt complex Diazo component Azo component compound OH N H2 0 CH3-CO-CH2-CI-HN yellow I. SO2NH- @; S02NH2 0 C1 1I likewise. CH, -CO-CH2-C-HN @@ yellow CH, I. CN yellow brown the same. y N CH, -CO C H3 the same. i NN yellow-brown CH, -CO / Y) Cl O 1I C-NH - (, H2-CH, -CH, -CH3 also I brown orange CN jNH CH, -CO also 0 H blue acoustic big Br - @ \ @ bordeaux NH-CO- CH, - CH, -CH3 desgI. Purple gray 7 HO I II III Diazo component azo component cobalt complex link OH O -NH2 C-HN - @ \ -C1 8 CN 1 brown orange S02NH - @ - SO, NH2 jNH CH, -co OH O -NH2 him O Brownish red u #N O = S-HN > I \ NH CH, -co S 02N H2 OH / \\ - N H2 io y barbituric acid yellow brown S02NH @ l S 02N H2 ii same as 2,4-Dioxyquinoline Orange Brown i2 the same. ß-naphthylamine gray OH 02N 1-NH2 13 @ same gray-green S02NH \ D S02NH2 I II III Diazo component azo component cobalt complex link OH i \ -NH2 . 1q. = -Acetylamino-7-oxynaplithalin violet gray S02-NH- -S02NH2 OH NH2 S 02 N H2 the same - SO2-NH 0 OH NH-CO-OCH3 16 NH2 S 02NH, HO S02- NH_CD The here to be used alis Dnaza component 2-Amino-i-oxyben20l-q.-sulfonic acid-N-phenylamdd- 3'-su! Ifonsäureanvi, d can be made by applying one i-Chdor-2-iniibrobenzol-4 @ sulfonisäurechlori! d mrit i - aminobenzene - 3 - sulfonic acid amiide converts that Chlorine atom of the resulting i-chloro-2-nitrabenzo! L- q. sulfb @ näur-N-phenylamid-3'-su; lfo @ nsäuxe @ am @ ids by means of alkali or E-nd @ alkali hydroxides replaced by the oxy group and finally the nitro group In a known way to the amino group reduced. Dias 2-amino-i-oxybenzene - $ - sulfonic acid-N-phe- ny! lamdide-3'-sulfone, acid-amiide can be obtained, by main i, 2-benzoxazalone - $ - sulfone, säurechlo @ ri-d with i-aminobenzo, l-3-su1fo @ nsäureaanid and the oxazolone ring of the resulting i, 2-benzoxa- zodon- $ -s! u! lfonsäure-N-phenylarniiid-3'-suilfo # n, acid- am # iid @ s z. B. with alkali metal hydroxides. splits. Example e 4.98 parts of the example i, first paragraph, hold dye and $, 76 parts of dye from di @ azoibated 2 anvino-i-oxybenzene- ¢ -sudfon- säu! re-2'-ch @ rorarü! li @ d - $ '- isnz! lfonsäuremebhy @ am, üd and i-Phenyl-3-methyl- $ pyrazolone are sold in Zoo Part Slurried water with 16 parts by volume 2 n-sodium hydroxide solution added, to 80 ° warms and with 22 parts of a Kob, altsu @ lfatläsung with a Kob! alib content of $ 2.9 per cent. To brief heating to 78 Mis 82 °. is> the complex education ended. Duirch Nafiniumchlo @ r! Id addition and by neutralizing them with dilute acetic acid the Kabalt complex connection is completely divorced. The filtered and dried paint fabric represents! a: To @ tbiraunes powder that is in Water with yellow-brown, concentrated sulfuric acid with red color dissolves and wool from weak alkaline, neutral or weakly acidic bath colors in roat-brown tones. In the following table, others are analogous preserved Kobalüm! iGchkampdex connections given which from dien im. Column I and II said monoazo colorants are obtained; she dye wool in the manner specified in column III Color titanium. I II III OH HO OH HO N = N -N = N- C -> Cl., Red-tinged z -J 1 '- Bordeaux , S02NH- y S02NH-I \ y 4.98 parts S02NH2 5.56 parts S02NH- CH " OHH O -N = N- # HN-- b of the 1st , bluish tint g parts of CO-CH, CH, CH3 Bordeaux 4.98 2 S02NH y 5.83 parts of S 02 N H2

Claims (1)

PATENT CLAIMS: i. Process for the production of new adhesive azo @ dyes, labeled diaduireh, that one. on monoazofairibsitoffe, that from .Sulfon, acid and carboxyl groups, are free and the general formal correspond, where Y is an Am @ ino: - adeir an Oxygr, group, R1 an on o-position to the oxy- group: benzoil residue bound to the azo group, pe, Re --Y the remainder of one in; Position adjacent to Group Y bound to the azo group azo component and X is an aryl radical which a substituent of the formula contains, where Z1 and Z2 each i hydrogen atom or a maximum of 6 carbon atoms holding ialip: hatiisehen remainder mean, or on Mixtures of such azo dyes cobalt lets acting agents act. 2. The method according to claim i, daduirch ge indicates that one koball donated; the means can act in such a way that koba4 @ active azo farbistaffe enitsitehen, dlie an 2 monoazo colors, toff- molecules i atom of cobalt in; complex bond contain. 3. The method according to claim i and 2, there- marked by the fact that one of. Suelfonsäu! Re- and carboxyl group-free monoazo, dyes, substances the general form used, where R2-OH is the remainder of an in Position adjacent to the oxy group on the azo group bound azo components and X one Benzoil radical means: the one sub-substituent of Formula -S02-NH-Cn_nH2n_i contains, where n is an integer with a value of at most 7 means. q .. method according to AnspTiuch i blew 3, thereby characterized in that one of sulfonic acid and Carboxyl group-free monoazo dyes deT # Formally used, where R.-OH is the remainder of an in Position adjacent to the oxy group on the azo group-bound azo component means which is free from sulfonic acid amide groups. 5. The method according to claim 2 büs 4, there- , durcab. gdlcemvzeit that the Meballisne- , rung tin @allkalliisiahem Mibbel, duirchführung. 6. The method according to claim 2 to 5, there- , characterized by the fact that mlan as a koballt from @ giving MiibMl simple salts of the bivalent used in cobalt. Referred publications: USA. Patent Specification No. 2 02. [86q., 2,499,133 ; German P.atzm; tschrift No. 445 888.