Патент USA US2133439код для вставки
Patented Oct. 18, 1938 ’ 2,133,439 PATENT OFFICE MONOAZO DYESYTUFFS Richard Fleischhauer, Frankfort-on-the-Mainr Fechenheim, Germany, assignor to General _ Aniline Works, Inc., New York, N. Y., a cor poration of Delaware ' No Drawing}, Applicationseptember so, 1936, Serial No. 103,363. In Germany October 2, 1 " y " 1935 7' r ' lolaims. This invention relates to valuable new monoazo (o1. 260'—163) The new dyestuffs are particularly useful for dyestuffs, more particularly to those of the gen dyeing animal ?bers. eral formula: from the analogous dyestuffs notcontaining the . following Y-om acyl and benzene series, Z stands fora member se-. lected from the group consisting of hydrogen and —-SO3H, ‘andR meansthe radicle of a coupling ,. _ _ _ Thenew dye'stuifs are obtained bycombi'ning the diazo compounds of aromatic amines of the general formula: .. acyl wherein X and ,Y stand for members selected from the group consisting’ of ‘hydrogen and vmethyl acyl stands for an acyl radical and the aliphatic component. group: 1 2 151 '-'X~—OH, ’ NHz ‘ ' . 7' . ' v . in their ‘diazo-component partly by clear more yellowish shades and partly by an increased level 10. ling power. v Example 1 19.2 parts of 1-(N-acetyl-isopropylamino)-4 aminobenzene are diazotized in the usual manner and the diazo solution obtained is allowed to run into a solution of 32- parts-V of '2-.naphthol-6;8- disulfonic acid containing an excess of'sodium The dyestuff thus obtained of the‘ 20 H30 ‘ I’ | Z , carbonate. formula: ' ore-N acyl Y-CH: They are distinguished _ \ H30 . , ‘OH-N‘ /' I N=N 1 00 1 (wherein X, Y and Z have the above signification)v son; | HO CH3 with a coupling: component. ‘ The diazo components employed for the inanu?’ facture ofgthef dyestuffs of this inventionp'have, not hitherto been‘ described. They maybeqbj tained for example , by , acting 1 with ‘ ;1f-chloro:"l-v 30" nitrobenzene 'or 1-chloro-4-nitrobenzenef27sul fonic acid on' the corresponding aliphatic‘ amines, _ is isolated and dried. It forms a bright orange colored powder, soluble in water, dyeing wool and silk bright yellowish orange shades of good fast ness to washing and light and of good levelling power. _ so? ' if necessary splitting ‘off the sulfonic group, acylat¢ By employing instead of the 2-naphthol-6.8 ing the amino group and reducing th'ejf’nitro“ disulfonic acid other naphthol-mono-or-disulfonic group. Thus, for example, i- (N-acetyl-isopropyl acids such as per example 1-naphth0l-4-sulfonic 35-1 amino) ~4-aminobenzene may be‘ prepared ‘by acid, 1-naphthol-3-sulfonic acid, 2-naphthol-6 heating 1-chloro-4-nitrobenzene—2-sulfonic acid‘ with an excess of isopropylamine in the presence of an aqueous solution of sodium carbonate in an autoclave to about 130° C. for about 30 hours. 40 The resulting 1-isopropylamin0—4—nitr0benzene 2‘-sulfonic acid is then treated with dilute'sul 'furic acid in an autoclave at'about 1359C. for‘ about" 20 hours so 'as to split 011’ the sulfuric acid group. ‘The yield thereof, which is about 85% 45 of‘ the theoretical} is subsequently iacylated' by heating with’ acetic anhydri'de in the presence of sulfonic acid, -1-naphthol-3.?edisulfonic acid or’ 1,-naphthol-3.8-disulfonic acid dyestuifs are ob-v tamed-which yield similar orange to yellowish red‘ shades of likewise good levelling power. Example 2 25.4 parts of 1-(N-benzoyl-isopropylamino)-4 aminobenzene are diazotized in- the usual manner and the diazo solution obtained is allowed to run into a solution of 37 parts of 1-acetylamino-8 45 naphthol-3.6-disulfonic acid containing an excess When the combinationis a small amount of concentratedsulfuric acid,v of sodium carbonate. whereby 1-_(N-acetyl-isopropyl-amino)-4-nitro benzene is formed with a very goodyield. Finally 50 the nitro group of this compound is reduced in ~ the usual manner by ‘means ofv iron: and "acetic acid and‘ v1-(N-acetyl-isopropyl-amino) —4-amino~ benzene is obtained with a yield of about 75%. It crystallizes from benzine' in colorless crystals 55 ,‘of 117° C. melting point. In an analogous manner, l-(N-acetylisec-butyL amino) ~4-aminobenzene, 1- (N-benzoyl-isopropyl amino) —4-aminobenzene, 1- (N-benzoyl-s'ec-butyl amino) -4-nitrobenzene, and the like, may also be .jprepared. ' , complete the'dyestuifformed of the formula: en rlm- o o 0 H3, Ha C / 50" I 55 is-separated and dried. ~ ‘It is adark' red powder, , soluble in water, . dyeingwwool and silkpbright bluish. 60 2 2,133,439 red shades of good levelling power and good fast ness to fulling, light, seawater and perspiration. Dyestu?s of similar shades and fastn'ess proper ties are obtained by replacing the said diazo com ponent by the corresponding amounts of l-(N acetyl-isopropylamino) -4-aminobenzene, - l-(N acetyl-isopropylamino) -3-aminobenzene, ' 1'-(N< methoxyacetyl~isopropyl-amino) <- 4L a min 0 ben - ll) 20 The dyestu?! formed by employing 2-benzoyl amino-5-naphthol-7-sulfonic acid as coupling component represents a yellowish red powder, soluble in water, dyeing wool and silk bright I orange shades of similar fastness properties. Example 6 ' 26.8 parts ‘of ~1- (N-benzoyl-sec-butylamino) -4 zene, l- (N-acetyl-isopropylamino) -4-aminoben - aminobenzene are diazotized in the usual manner zene-2-sulfonic acid or of analogous amines which and the “diazo ‘solution obtained is allowed to run 10 at’ about 10-15“ C. into a solution of 29 parts of may contain any other acyl radicle. 2-acetylamino-8-naphthol-6-sulfonic acid con By combining 1-(N-acetyl-isopropylamino) -4 aminobenzene-2-sulfonic acid with 2-amino'-8 ‘ taining an excess of sodium acetate or sodium bi naphthol-G-sulfonic acid in a medium containing carbonate. When the combination is complete a mineral acid a dyestuif is obtained which dyes - ‘the dyestu? formed of the formula: 15 OH wool bright red shades of good levelling power and excellent fastness to light. 1110.052 1 Example 3 19.2 parts of 1-(N-acetyl-isopropylamino) -4 /o H-lTI-C>—N=N H10 -NH—C o 0' H1 CO aminobenzene are diazotized in the usual manner and the diazo solution obtained is combined with 37 parts of l-acetylamino-8-naphthol-4.6-disul fonio acid. The dyestuff formed of the formula: 25 ‘CHa on ‘lrlH-COCHa \ /CH—III CH: N=N' CO 30 ing, light and perspiration. > HOSS | SOsH It is a dark 'red'powder, soluble in water, dyeing wool and silk brightred shades of good levelling power and fast to light. Example 4 35 19.2 parts of 1-(N-acetyléisopropylamino) -4 aminobenzene are diazotized in the'usual manner and the diazo solution obtained is combined with 26 parts of 1‘-(2'echloro-5'-sulfopheny1) ~3-meth 40., y1-5-pyrazolone. I Dyestuifs of similar properties are‘ obtained by ‘ CH3 is isolated and dried. is'isolated ‘and dried. It is a red powder‘, soluble 25 in water, dyeing wool and silk bright red shades of good levelling power and good fastness to full The dyestuff ’ formed of the employing other diazo components such as for‘ ex ample aminobenzene or 1-(N-p-toluenesulfo-isopropyl amino) Aéaminobenzene. There may be used as coupling ‘components de rivatives of 2-amino-8-naphthol-6-sulfonic acid, l-amino-S-naphthol-G-‘sulfonic acid, 1-amino-5 naphthol-‘l-sulfonicacid or 2-ar'nino-5-naphthol '7-sulfonic acid containing other a‘cyl radicles such as for example the methoxyacetyl, chloroacetyl, carbethoxya'cetyl, benzoyl, ' hexa-hydro-benzoyl. and phenoxyacetyl radicle and derivativeslthere'of substituted in the benzene nucleus. Furthermore, the. acylamino-naphthalene-sulfonic acids "em ployed as coupling components may contain in their acyl'ated amine group aliphatic, hydroaro-v 45 80 1 - (N - benzenesulfo - sec - butylamino) "- 4 - matic or aromatic radicles, by which the shades 40 45 and. properties of the 'dyestu?s'obtained are I changed. I'claim: lfThe monoazo'dyestu?s' of the general form 50 ula: is when" dry a lemon-yellow" powder,-soluble in water, dyeing wool and silk bright‘ greenish yellow x-om shades of very good levelling power and fastto Y— CH a 55 washing and light. Example 5 20.6 parts of 1-(N-acetyl-sec-butylamino) -4 aminobenzene are diazotized in the usual manner and the diazo solution obtained is allowed to run 60 into a solution of 36 parts of l-benzdylamino-S naphthol-‘l-sulfonic acid containing an excess of sodium acetate. When the combination iscom plete the dyestuff formed of the formula: 65 acyl l 2 65 wherein ‘X and Y stand for 'members selected from the groupv consisting of hydrogen and methyl; acyl stands for‘ an acyl radicle of the-ali phatic 'and'benzene'seriesi Z stands-for a'member selected ‘from the group consisting of hydrogen 60 and —SOxH, and R means- the radicle of a cou pling component,vwhich dyestuffs yield on ?bers, especially wool‘ and-silk,- clear‘ yellow to yellowish red shades of good fastness properties'and’ of very good levelling-power. - ~2. The-monoazo dyestu? of the formula: you lTIH-COKJH: 70 is isolated and dried. It is a brick-red powder, soluble in water, dyeing wool and silkbright yel lowish red shades of‘ very good levelling‘ power = and. good fastness especially .to light. 50 65 3 2,133,439 which dyestu? represents a dark red powder, soluble in water, dyeing wool and silk bright bluish red shades of good levelling power and good fastness to fulling, light, seawater and per 5 spiration. 3. The monoazo dyestu? of the formula: HIC 10 H10 \ /CH—I?'00 N=N—?-—(|Z|LCH2 110.0 N \ / CHI OH 10 NH-CO N 01 15 greenish yellow shades of very good levelling power and fast to washing and light. v4. The monoazo dyestu? of the formula: Hogs which dyestuff represents a lemon-yellow powder, soluble in water, dyeing wool and silk bright which dyestu?‘ represents a brick-red powder, soluble in water, dyeing wool and silk bright yel lowish red shades of very good levelling power and good fastness especially to light. RICHARD FLEISCHHAUER.