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3,030,352 ,. 1C@ Patented Apr. 17, 1962 1 2 3,030,352 of the sequestering agent tetrasod-ium salt of ethylene diamine~tetra~acetic acid. This partial demetallisation may also be elfected by simply mixing the sequestering NEW CUPRIFEROUS TRISAZO DYESTUFFS AND A PROCESS FOR THEIR PREPARATION agent with the isolated and dried dicupric compound or Marcel Jirou, Sotteville-les-Rouen, and Vasili Urne, by addition of the same agent of the dyebath. Rotten, France, assignors to Compagnie Francaise des 5 The cupriferous complexes containing one to two Matieres Color-antes, Paris, France, a company of France atoms of metal per molecule of trisazo compound are especially well suited for dyeing vegetable ?bres in shades No Drawing. Filed Apr. 16, 1959, Ser. No. 806,760 fastto light and to Washing. 9 Claims. (Cl. 260—145) 10 The following examples, in which the parts indicated are parts by weight, illustrate the present invention with The present invention relates to the copper complexes out restricting it. of the trisazo dyestuffs of the general formula: I SOaH SOzH in which R represents the residue of an acylaminohy droxynaphthalene-sulphonic acid coupled in the ortho po sition to the hydroxyl group. Example 1 109.4 parts of the trisazo dyestu? of the formula OOH: OH I 0 5H! SOaH These complexes can be prepared by dealkylating met allisation of the dyestutfs of the general formula as the sodium salt are dissolved in 2400 parts of water at ‘90° C. This solution is treated with 10 parts of O-alkyl in which R has the same signi?cance as above, by means sodium bicarbonate. A solution of 30 parts of crystal of compounds of divalent copper. The O-alkyl group is line copper sulphate in 150 parts of water to which 56.5 converted into an hydroxyl group by hydrolysis and the- 45 parts of 20% by volume ammonia have been added, is COPPBI‘ becomes attached to the hydroxyl groups in the slowly added. The mixture is heated for 10 hours at OI‘thO-OIthO' POsition t0 the 320 linkage1 90-92“ C. and the metallised dyestuif is precipitated by When represents a radical of the formula the addition of sodium chloride, ?ltered and dried. This dyestu? only contains one atom of metal in its molecule. Hots” NH'acyl 50 It dyes cellulosic ?bres a bluish green shade. Example 2 (‘)H The dyestu?' employed in Example I is replaced by the excess copper which may possibly be present in the 55 the same weight of the trisazo compound of the formula: 00m 011 metallisation medium is ?xed in its turn. For example, 65 The procedure of Example llis followed, but 50 parts cupriferous compounds containing two atoms of copper ' of copper sulphate are _used instead of _30 parts. A per molecule of dyestuff may be obtained and the solucupric compound 1s obtained which contains two atoms bility of the latter is not thereby reduced. These 2:1 of metal in Its molecule and whlch dyes cellulosic ?bres complexes can be used for the preparation of complexes greenlsh blue. Example 3 _ containing only one atom of copper per molecule of 70 To the reaction mixture resulting from the metall1sa— trisazo dyestuff, and for this result it is su?icient to tion described in Example 2 is added a concentrated solu treat the dicupric compounds at 80° C. with a solution aoeaaee 4% tion of the tetrasodium salt of ethylenediamine-tetra acetic acid in such quantity that its concentration in the mixture is equal to 1%. After 30 minutes’ agitation at 80—85"v C., the dyestu? is isolated by the addition of hydroxy-azo grouping resulting from the hydrolysis of the o-methoxyo’-hydroXy-azo-grouping. 2. Cupriferous derivatives of trisazo dyestu?s of the general formula: SOgH' sodium chloride. The copper complex obtained only in which R representsa member selectedfrom the group consisting of the‘ acetylamino-l-hydroXy-monosulpho-2 contains one atom of metalper molecule of azo dyestutf. It dyes cellulosic ?bres a shade which is a little vbluer 15 naphthyl, methoxy - carbonylamino-l-hydroxy - monosul than that given by the dicupric compound. pho-Z-napht-hyl, ethoxycarbonylamino-l-hydroxy - mono sulpho-Z-naphthyl and benzoylamino-l-hydroXy-monosul Example 4 pho-2~naphthyl groups, which derivatives contain one to The copper complex of the trisazo dyestu?- of the .720 two atoms of copper per molecule of dyestuif, one of them ‘forming a coordination complex withpthe o:o’-di formula: OOH; I solar OH NHOOGH3 ‘ , SOaH is prepared according to the directions in Example 1. SOQH hydroxy-azo grouping resulting from the hydrolysis of the o-methoxy-o'-hydroXy-azo-grouping. The dyestu? obtained only contains one atom of copper '30 3. The cupriferouscomplex of the trisazo dyestu? of in the molecule and dyes cellulosie ?bres green. the formula: 803E We claim: 1. Cupriferous derivatives of trisazo dyestu?s of the general formula: in which an atom of divalent pcoppervis attached to the dyestuif by the o.o'-methoxy group. OCH; N=NTR . I I , $0311 in which R represents a member selected from the group consisting of ,the acetylamiuo-1-hydroxy;monosulpho-2¢ 4. The cupriferous complex‘ of the trisazo dyestuff of the formula: OCHa naphthyl, methoxy - carbonylamino-l-hydroxy - monosul pho-2-naphthyl, ethoxycarbonylamino-l-hydroxy - mono sulpho-Z-naphthyl and benzoylamino-l-hydroxy-monosul OH in which‘ at atom of divalent copper is attached to the dyestu? by the o.o'-methoxy group. 5. The cupriferous complex of the trisazo dyestu? of - pho-2~naphthy1 groups, which derivatives contain one to 65 the general formula: OOHa | 0H NHCOCHB i sop: S0311 803E in which an atom of divalent copperis attached ‘to the two atoms of copper per’ molecule of dyestui‘f, one of them forming a coordination complex with the o:o'-di- 75 dyestuif by the o.o’-methoxy group. W 3,030,352 5 6 6. Cupriferous derivatives of the trisazo dyestuif of the formula: 8. A process for the preparation of a cupriferous com plex containing 1 atom of copper per molecule of dye (lm?a SIOQH OH H038 NH 60 (lluHg 303E containing two atoms of copper. 7. A process for the preparation of a cupriferous com- stuii which comprises effecting a dealkylating coppering of a dyestulf of the general formula: 0 —0 Ha plex containing 1 atom of copper per molecule which comprises eifecting a dealkylating coppering of a dye stu? of the general formula: OH 0311 R’ represents a member selected from the group con sisting of the acetylamino, methoXy-carbonylamino, eth oxy-carbonylamino and benzoylamino groups in the pres~ SOBH in which R represents a member selected from the group ence of excess copper, and then e?ecting a demetallisa consisting of the acetylamino-l-hydfoXy-monoslllphoa- tion of the dicupric derivative by treating said compound naphthyl’ methoxy ' carbonylammojl'hydmxy 'monosul‘ with a heated solution of the tetrasodium salt of ethyl phO-Z-naphthyl, ethoxycarbonylanf‘lm"l'hydroxy ' mono‘ 35 ene-diamine-tetra-acetic acid in an alkaline medium. sulpho-Z-naphthyl and benzoylamino-l-hydroxymonosul- pho-2-naphthyl groups by reacting said dyestut‘r‘ in aheated alkaline medium with a compound of divalent copper 9 A 1 . d . in the ratio of 1 atom of copper Pel- molecule of dyestuff. 40 enediamine tetra-acetic acid. References Cited in the ?le of this patent UNITED STATES PATENTS 1,901,393 2,381,599 2,779,756 2,794,798 2,834,773 1933 1945 1957 1957 Bissell ______________ __ Dec. 24, 1957 Scalera ______________ .__ May 13, 1958 955,715 Germany ____________ .__ Ian. 10, 1957 2,817,656 1 . 8 . h. h h d " _ PFOCeZSS as 6 mm?’ m cfnm, “1 w m t e 6' metallisatron 111 an alkaline medium 1s effected by means of an aqueous solution of the tetrasodium salt of ethyl Glietenberg __________ __ Mar. 14, Krebser et a1__________ .._ Aug. 7, Riat ______________ __,__ Jan. 29, Durig _______________ __ June 4, FOREIGN PATENTS OTHER REFERENCES Taylor, A.: “Organic Chelating Agents as Aids to In~ dustry,” Chemistry and Industry, No. 41, Oct. 20, 1956, pages 1131-1135.