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Home , Benzoyl group

Patented Apr. 11, 1933 1903,599.

UNITED STATES PATENT office

HUGO ANILINESCHWEITZER, WORKS, OF INC,LEVERKUSEN-WIESDORF, OF NEW YORK, N.Y., A GERMANY,CORPORATION AssIGNOR OF DELAWARE TO GENERAL ... -- MONOAZODYESTUFFs No. Drawing. Application filed January 2, 1931, Serial No. 506,309, and in Germany January 4, 1930. manufacture of pigments and for printing. The present invention relates to new mono Individual representatives of the new class aZodyestuffs, more particularly it relates to of dyestuffs are also suitable in dyeing cel dyestuffs of the probable general formula: lulose acetate silk. - OE By employing diazo compounds, contain 50 ing groups capable of forming metallic com - R-NaN. plexes, mordant dyeing azo dyestuffs are produced, which likewise possess very nota ble fastness properties. . . . . - / The aminonaphtholsulfonic-acid- lo 22 so 2 . . . . used as coupling components in my inven wherein R stands for the residue of an aro tion are prepared by treating the corre matic diazo-compound of the or sponding acyl-aminonaphtholsulfochlorides naphthalene series, a, and a stand for hy. described in British Specification 326226 15 drogen, , substituted alkyl, such as With ammonia or a suitable base, such as ani 80 methyl, ethyl, hydroxyethyl, for hydrophe line, dimethylamine, benzylamine, ethylben nyl, phenyl or benzyl, y stands for hydrogen, Zylamine and the like, and saponifying the an acyl, alkyl or ; such as an acyl-amino group in the usual manner. acetyl or benzoyl group, and “n” stands for The invention is illustrated by the fol 20 one of the numbers one and two, and where lowing examples, without being limited 65 in R and the naphthalene nucleus may be thereto: further substituted by the Eaample 1-17.3 parts by weight of ani group, an arylsulfone group, the carboxylic line-2-sulfonic-acid are diazotized in the acid group, the sulfoneamide group, halo customary manner. The diazo-compound is 25 gen, the nitro group, the alkyl group, the alk run into an alkaline sodium carbonate solu- to oxy group, the , a substituted tion of 53.9 parts by weight of 1-acetylami amino group, the components being selected no 8-hydroxynaphthalene-3,6-disulfodi-(N- in such a manner that at least one of them methylanilide.) When the coupling is com contains a sulfonic acid group. . . . . plete, the dyestuff of the following formula: 30 My new dyestuffs are prepared in the usual HOas OB NH.co.CH, 75. manner by coupling an aromatic diazo.com pound of the benzene or naphthalene series with an amino-hydroxy-naphthalene con taining one or two unsubstituted or substitut 80 35 ed sulfamino residues of a derivative or a substitution product thereof, the coupling be ing carried out either in an alkaline medium on the hydroxy side or in an acid medium on 40 theThe amino dyestuffs side. thus- obtained are : generally is salted out, filtered with suction and dried. 85 red to dark powders, dyeing wool clear red It dyes wool a clear red shade, which with to black shades fast to light, often of un stands even severe fulling, is very fast to usual fastness to washing and fulling and light, and it also possesses a pronounced ca of unobjectionable evenness. The new dye pacity for even dyeing...... 4 stuffs are likewise very suitable for the When the aniline-3-sulfonic acid is re- 90 2 1,903,599 placed by 4-amino-1-methylbenzene-3-sul in the customary manner and coupled with fonic acid a clear bluish red is produced of 34.2 parts by weight of 2-amino-8-hydroxy the same fastness properties. Similar dye naphthalene-6-sulfo-N-ethylanilide in alka stuffs are obtained by the use of diazotized line sodium bicarbonate solution. The dye acid.4-acetylamino - 1 -aminobenzene-2-sulfonic stuff of the following formula: 70 Eacample 2-17.3 parts by weight of ani No. OH - line-2-sulfonic acid are diazotized in the customary manner. The diazo solution is 10 then run into an alkaline sodium carbonate () -- NE solution of 46.9 parts by weight of 1-amino SO3. 75 8-hydroxynaphthalene-3,6-di(sulfanilide). Chs When the coupling is complete, the dyestuff 56NY having the following formula: 5 oH NH, 80 is worked up in the customary manner; it dyes wool brick red shades, fast to fulling 20 and light and of satisfactory evenness. Eaample, 5-17.3 parts by weight of ani line-2-sulfonic acid are diazotized in the cus tomary manner. The diazo compound is run 25 into a cold solution, (diluted with a little is salted out and worked up by the known water) of 37.9 parts by weight of the hydro 90 methods. It dyes wool a wine red shade, chloride of 2-amino-8-hydroxynaphthalene fast to fulling and of satisfactory evenness. 6-sulfo-N-ethylanilide in 150 parts by weight Eacample 3-18.9 parts by weight of 2 of glacial acetic acid. Coupling begins at aminophenol-4-sulfonic acid are diazotized once. The excess of mineral acid is then 30 in the customary manner. The diazo com neutralized by careful addition of neutral 95 pound is run into an alkaline solution of Sodium acetate solution in such a manner, 46.9 parts by weight of 1-amino-8-hydroxy that a faint reaction due to mineral acid per naphthalene-3,6-di(sulfanilide). When the sists. When the coupling is complete the 35 coupling is complete the dyestuff of the foll dyestuff of the following formula: lowing formula: . ; OH 100 {Y- X i..H.N- . . . . - . - SOH C.H.

SON 40 105

is salted out, converted into its sodium salt 45 and dried. It dyes wool a clear red shade, 110 is salted out and worked up in the known fast to fulling and light and of very satis manner. It dyes wool a reddish violet shade, factoryDyestuffs evenness. of similar properties...... are. obtained. . which, on after-chroming, is converted into by replacing the aniline-2-sulfonic acid by 50 a fast greenish blue. - other aromatic amino-sulfonic- or carboxylic When the 2-aminophenol-4-sulfonic acid acids, for example, by chloro-aniline-sulfonic is replaced by other o-aminophenolsulfonic acids or by 4-acetylamino-1-aminobenzene theacids, 1-amino-8-hydroxynaphthalene-3,6-di such as chloro- or nitro-derivatives or Sulfonic acids; furthermore the substitution (sulfanilide) by the corresponding N-methyl for the 2-amino-8-hydroxynaphthalene-6-sul or N-ethylanilide, dyestuffs of similar prop fo-N-ethylanilide of other 2-amino-8-hy. 2 G erties are produced. droxynaphthalene-6-sulfonic acid , as Instead of the sulfamides of the amino 2-methylamino-8-hydroxynaphthalene-6-sul hydroxy-naphthalenes indicated in the above fonic-N-methylanilide yields dyestuffs of the 60 same fastness properties. . . . examples other sulfamides of other amino Easample 6. 25.3 parts by weight of ani 2s naphthols,amino-8-hydroxynaphthalene-4,6-disulfo-di such as for example, 1-acetyl line-2.5-di-sulfonic acid are diazotized in the (N-methylanilide) can likewise be used. customary manner. The diazo compound is Eacample, 4-21.8 parts by weight of 3. added to a solution, diluted with water, of nitro-1-aniline-6-sulfonic acid are diazotized 2-amino-8-hydroxynaphthalene-6-sulfo-N-37.9 parts by weight of the hydrochloride or 80 1903,599 3 methylanilide in 200 parts by weight of gla anilide by the corresponding N-ethyl- or N cial acetic acid and the coupling and work hydroxy-ethyl compound or by 2-phenylam ing up of the dyestuff is carried out as de ino-8-hydroxynaphthalene-6-sulfonic anilide scribed in Example 5. The dyestuff having similar dyestuffs are produced. When the the following formula: , - 2-amino-4-hydroxy-3-carboxy-diphenyl 70 -4-sulfonicdroxy-3-carboxy-2-amino-5-acetylamin acid is replaced by 4'-h i. SO3 phenylsulfone and the 2-amino-8-hydroxy naphthalene-6-sulfo-N-methylanilide by the 2-amino-8-hydroxynaphthalene-6-sulfo-(4- s 0 hydroxy-3-carboxy anilide) a bordeaux shade results, which on after-chroming be comes somewhat yellower and very fast. The used as diazo components in this example are derived from the salicyclic. 80 .5 sulfones described in British Specifications Nos. 245765 and 245865. Eacample 8-22.3 parts by weight of 4 dyes wool a red shade of satisfactory fast chloro-2-amino-phenol-6-sulfonic acid are di ness to fulling and light, combined with satis azotized in the known manner with 6.9 parts 85 20 factory evenness. . by weight of sodium nitrite in the presence When the anine-2,5-disulfonic acid is re of excess hydrochloric acid. The diazo solu placed by aniline-2,4-disulfonic acid a red is tion is run into an alkaline sodium carbonate likewise produced; replacement by 3-nitrani solution of 314 parts by weight of 2-amino 90. line-4,6-disulfonicsimilar satisfactory acid properties. yields a ruby shade. . . of 5-hydroxynaphthalene-7-sulfanilide. When Eacample 7-37.3 parts by weight of 2 the coupling is complete, the dye-stuff of the amino - 4'-hydroxy-3-carboxydiphenylsul following formula: fone-4-sulfonic acid are dissolved in 400 95 partsAfter ofthe wateraddition by ofmeans 6.9 parts of a bylittle weight alkali. of - soNH-O sodium nitrite the solution is run at about HO- ...... 20° C. with thorough stirring into an ex cess of dilute hydrochloric acid. The diazo Hos 8 H compound, which separates, is filtered with 100 suction, made into a paste... with a little wa - NEI. ter and added to a solution, diluted with wa ter, of 37.9 parts by weight of the hydrochlo is salted out and worked up in the known ride of 2-amino-8-hydroxynaphthalene-6- manner. It dyes Wool from an acid bath a sulfo-N-methylanilide in 100 parts by weight brick red shade, which on after-chroming, is 105 40 of glacial acetic acid. The working up of converted into a bluish black, very fast to fulling and of excellent fastness to light. the dyestuff of the following formula: Similar dyestuffs are obtained by replac ing the 4-chloro-2-aminophenol-6-sulfonic acid by other o-aminophenol- or o-amino 110 - l OE naphthol-sulfonic acids or by the correspond dooh ing carboxylic acids or by o-aminophenol Sulf-amides and similar compounds. When instead of the 2-amino-5-hydroxynaphtha Iis lene-7-sulfanilidemethylamide, cyclohexylamide, the corresponding benzylamide, amide, methylanilide or piperidide or other are used similar fast dyestuffs are pro duced, which are distinguished from the dye stuff of the example by possessing somewhat 120 which is quickly formed, is carried out in the bluer or redder shades. On coupling molec customary manner...... ular quantities of the diazo compound from The dyestuff dyes wool a beautiful bluish 2-aminophenol-4-sulfamide and 2-amino-5- - red shade, which on after-chroming becomes hydroxynaphthalene-7-sulfo-di-methylamide somewhat bluer and very fast. When the a monoa Zo, dyestuff- is obtained, the after 125 2-amino - 4'-hydroxy-3-carboxy-di-phenyl chromed dyeing of which on wool is likewise sulfone-4-sulfonicamino-2'-hydroxy-3-carboxy-5'-methyldi acid is replaced by 2 a veryEacample fast bluish 9-23.4 black. parts by weight of 6 phenylsulfone-4-sulfonic acid and the 2-ami nitro-2-aminophenol-4-sulfonic acid are di 5 no-8-hydroxynaphthalene-6-sulfo-N-methyl aZotized in the customary manner with 6.9 30 1,903,599 parts by weight of sodium nitrite in the pres ence of an excess of hydrochloric acid and are diazotized in the customary manner. ice. The diazo solution is then run into a The diazo compound is then run into a solu cold alkaline sodium carbonate solution of tion of 35.7 parts by weight of 2-amino-8- 31.4 parts by weight of 2-amino-8-hydroxy hydroxynaphthalene-6-sulfo-N-hydroxyeth naphthalene-6-sulfanilide. When the cou ylanilide in dilute hydrochloric acid and the 70 pling is complete, the dystuff having the fol coupling and working up of the dyestuff lowing formula: which corresponds to the following formula: 10 HOas ch, co-NH-(D-N- -- OH Hol EN /CHCH-OH -SON ls 80

85 is salted out, pressed and dried. It dyes are carried out as indicated in Example 5. wool a navy blue, which on after-chroming The conversion of the dyestuff into a color is converted into a bluish black, very fast to lake or pigment is carried out by the known fulling and of excellent fastness to light. methods with or without the use of a sub stratum. - - By varying the diazo or coupling components When employed as a coating as size color 90 shadesas in Exampleare likewise 8, fastobtained. dyestuffs of similar a clear bluish red, fast to water and of very Eacample 10-24.8 parts by weight of 2 satisfactory fastness to light is obtained. The barium lake of the dyestuff is insoluble nitraniline-4-sulfonic acid are diazotized in in the organic solvents customarily used in the known manner with 6.9 parts by weight conjunction with pigment dyestuffs. 95 of sodium nitrite and excess hydrochloric Eacample 12-18.7 parts by weight of 2 acid. The diazo compound is run slowly into amino-1-methylbenzene-4-sulfonic acid are an ice-cold solution of 32.8 parts by weight diazotized in the customary manner. The 35 of 2-amiro-8-hydroxynaphthalene-6-sulfo-N- diazo compound is run into an alkaline sodi methylanilide, to which a little sodium bi um carbonate solution of 53.9 parts by weight 00 plingcarbonate is complete has been addedthe dyestuff and when having the couthe of 1-acetylamino-8-hydroxynaphthalene-3,6- following formula: disulfo-di- (N-methylanilide). When the 40 followingcoupling is formula: complete the dyestuff having the

SO3H OH NH. CO. Cls

. CH, 110 - / SON

5 is worked up in the customary manner. It dyes wool from an acid bath a reddish brown shade, fast to fulling and light and of satis factory evenness. Similar brown dyestuffs are obtained by is salted out, filtered with suction and dried. replacing the 2-nitraniline-4-sulfonic acid by From a neutral bath, for example, with the 5-nitro -2-amino-1-methoxybenzene -4-sul addition of sodium sulfate, it dyes acetate fonic acid or by using, instead of the 2 silk a pink shade, fast to washing. - amino -8-hydroxynaphthalene - 6 -sulfo - N Eacample 13-18.7 parts by weight of 1 2 methylanilide, the corresponding N-ethylan amino-4-methylbenzene-2-sulfonic acid are 5 ihide, N-hydroxyethylanilide or dimethyl diazotized in the usual manner. The diazo amide or the like. compound is introduced in an alkaline sodi Eacample 11-23 parts by weight of 1 um solution of 40 parts by weight of 2-acetyl amino-4-acetylaminobenzene-2-sulfonic acid amino-8-naphthol-6-sulfo-N-(hydroxyethyl 38 1908,599. 5 anilide). When the coupling is complete wherein R stands for the residue of an aro the dyestuff having the following formula: matic diazo-compound of the benzene or pH...... naphthalene series, a stands for alkyl, a . . . ! . . ; : stands for the benzene nucleus, y stands for 70 Hic-(D-N-N- N.C.O. CH hydrogen, an acyl, alkyl or phenyl group, “n” ... " ''' stands for one of the numbers one and two, HOS "..., : the components of the dyestuffs being selected in such a manner that at least one of them Ho-Ho-Hic Nos contains a sulfonic acid group and wherein 5 O thestituents nuclei selected may be furtherfrom the substituted group consisting by sub of the sulfonic acid group, an arylsulfone group, the group, the sul is salted out, filtered by suction, pressed and thefoneamide alkyl group, group, the halogen, alkoxy the group, nitro thegroup, hy. 5 dried. It dyes wool from an acid bath a droxy group, a substituted amino group, be red shade, fast to fulling and light and of ing generally red to black powders, dyeing satisfactory evenness...... wool clear red to black shades fast to light. A similar dyestuff of somewhat yellower 3. Monoazo dyestuffs of the probable gen shade is obtained on replacing the 2-acetyl 85 amino-8-naphthol-6-sulfo-N-(hydroxyethyl eral formula: - - - - . anilide by the 2-amino-5-naphthol-7-sulfo-N- hydroxyethylanilide. On replacing the 1-amino-4-methylben zene-2-sulfonic acid by the 1-naphthylamin 90 4-sulfonic acid a bluish red of similar prop erties is obtained. Yo-Y I claim: wherein R stands for the residue of an aroma 1. Monoazo dyestuffs of the probable gen tic diazo compound of the benzene or naph 95 eral formula: thalene series, a stands for alkyl, ae, stands OBI for the benzene nucleus, y stands for hydro gen, an acyl alkyl or phenyl group, n stands for one of the numbers one and two, the azo bridge standing in orthoposition to the 100 group NHy, the components of the dyestuffs being selected in such a manner that at least one of them contains a sulfonic acid group, wherein R stands for the residue of an aroma and wherein the nuclei may be further sub tic diazo-compound of the benzene or naph stituted by substituents selected from the 105 thalene series, a, and as stand for hydrogen, group consisting of the sulfonic acid group, alkyl, hydrophenyl, phenyl or benzyl, gy an arylsulfone group, the carboxylic acid stands for hydrogen, an acyl, alkyl or phenyl group, the sulfoneamide group, halogen, the group, “n” stands for one of the numbers nitro group, the alkyl group, the alkoxy one and two, the components of the dyestuffs group, the hydroxy group, a substituted ami 0 being selected in such a manner that at least no group, being generally red to black pow one of them contains a sulfonic acid group, ders, dyeing wool clear red to black shades and wherein the nuclei may be further sub fast to light. ... - stituted by substituents selected from the 4. Monoazo dyestuffs of the probable gen group consisting of the sulfonic acid group, eral formula: . . , 115 EC an arylsulfone group, the carboxylic acid group, the sulfoneamide group, halogen, the nitro group, the alkyl group, the alkoxy

group, the hydroxy group, a substituted - - - amino group, being generally red to black 120 . ... powders, dyeing wool clear red to black N / shades fast to light. 3 : 2. Monoazo dyestuffs of the probable gen eral formula: wherein R stands for the residue of an aro OE matic diazo compound of the benzene ornaph thalene series, a stands for alkyl, as stands i25 60 / E. for the benzene nucleus, y stands for hydro R-N=N. N/y gen, an acyl, alkyl or phenyl group, “n” standsthe azo for bridge one standingof the numbers in ortho-position one and two, to Xo1, the hydroxy group of the naphthalene nu 130 6 1,903,599. cleus, the components of the dyestuffs being a brown, powder, dyeing wool from an acid selectedof them incontains such aa mannersulfonic that acid atgroup, least andone tobath fulling reddish-brown and light. shades of good fastness wherein the nuclei may be further substi- 8. The dyestuff of the following formula: 5 tuted by substituents selected from the group OCH . , OH 70 arylsulfoneconsisting ofgroup, the thesulfonic carboxylic acid acidgroup, group, an on K)--- - the sulfoneamide group, halogen, the nitro so group, the alkyl group, the , the O3. to hydroxy group, a substituted amino group, 75 being generally red to black powders, dyeing CHCH wool clear red to black shades fast to light. - Ho Yo 5. Monoazo dyestuffs of the probable gen 5 eral formula: - -

being in the form of its alkali metal saltsa brown powder, dyeing wool from an acid 20 bath reddish-brown shades of good fastness 85 wherein R stands for a benzene nucleus, cal to fulling and light. kyl” stands for an alkyl group from one to In testimony whereof, I affix my signature. two carbon atoms, “n” stands-for one of the HUGO. SCHWEITZER. numbers one and two, and wherein the nu- . . . . clei may be further substituted by substitu- ...... 90 ents selected from the group consisting of the - sulphonic acid group, an arylsulfone group, the carboxylic acid group, the sulfonamide group, halogen, the nitro group, the alkyl group, the alkoxy group, the hydroxy group, 95 a substituted amino group, the components being selected in such a manner that at least one of them contains a sulfonic acid group, being generally red to black powders, dyeing - - wool clear red to black shades fast to light. 100 6. The dyestuff of the following formula: OE . . . . - HC-K)-N-N- w -NH. Co-CH, - 40 105 Hoss / - -- : - - SO2N-CHCH-OH

45 - 10

being in the form of its alkali metal salts a so red powder dyeing wool from an acid bath w 5 red shades of good fastness to fulling and light. - 7. The dyestuff of the following formula: O

no-K)--No. Hsc Y

60 - . No . . . 25

"being in the form of its alkali metal salts 30