Патент USA US2128256код для вставки
Patented Aug. 30, 1938 ,. 2,128,256; PATENT OFFICE ' UNITED STATES 2,128,256 AZO DYESTUFFS Hans Krzikalla and Hanns Ufer, Ludwigshafen on-the-Rhine, Bernd Eistert, Mannheim, and Gustav Klaproth, Ludwigshafen-on-the Rhine, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware‘ No Drawing. Original application December 18, .1935, Serial No. 55,040. Divided and this appli cation July 16, 1936, Serial No. 90,944. In Ger many December 22, 1934 '7 Claims. (01. 260-200) The present invention relates to the produc with dimethylamine and subsequent reduction of tion of new azo dyestuffs. This application has been divided out from our copending application the nitro group. By the reaction of > meta-nitro-omega-chlor Ser. No. 55,040, ?led December ‘18, 1935. acetophenone with ethylamine and subsequent We have found that new valuable azo dyestuffs are obtained if the coupling components and the reduction of the nitro group, an amine is ob 5 tained having the formula: diazo compounds employed in the preparation of the new dyestuffs are so chosen that the molecule of the dyestu? contains at least one sulphonic acid group and at least one basic group of the 10 CIHI general formula N H: From 1-brom-2-(dlethylamino)—ethane and para-acetamino—thiophenol, a. sulphide is ob 15 in which R1 and R2 may be identical or different 15 tained having the formula: and may be hydrogen or alkyh‘ cycloalkyl, hy droxyalkyl or aralkyl radicles or members of a saturated ring system and X is an aliphatic 20 radicle combined with an aromatic nucleus’ of.’ the dyestu? molecule either directly or by‘ means of a non-basic bridge.v As non-basic bridges may be mentioned for example —-O—-, -S—-, —CO-, —SO2—--, —O—CO—, --NH—CO--, —SO2—NH-— 25 and -CO—NH--. Dyestuffs of the said kind may also be pre pared by introducing at least one basic group of the said general formula ‘into ‘a ,dyestu?-‘which does not yet contain such a basic group combined 3 O in the manner described above. Thus for example a diazotizable amine having the formula:v 35 " ‘ HmOom-pm-mom). may be prepared by converting para-nitrophenyl ethyl alcohol by means of thionyl chloride into omoo-rvn-O-s-(omh-mcm.» 20 which may be saponi?ed as such to'form the amine or may ?rst be oxidized to form the sulphone having the formula: omoo-NHOs-onronrmolnm g \ - 25 30 and then saponi?ed. The amines prepared according to the above methods or by other known methods and having external basic. groups are capable of diazotiza 35 tion in the same way as ordinary aromatic amines and yield azo dyestuffs of the said kind by cou pling with compounds‘ which are capable of para - nitro - omega - chlorethyl - benzene, reacting the latter with dimethylamine and reducing the 40 nitro group in the resulting amine. coupling. ‘ ‘ Coupling ‘components having external basic 40 groups are obtained for example by reacting An amine having the formula: 2—amino-8-hydroxynaphthalene-6-sulphonic acid with chloracetyl chloride or a chlorpropionic acid chloride and treating the resulting 2-(chlor 45 OH: NH: is obtainable for example by the reaction of meta nitroaniline with .chloracetyl chloride, treatment 50 of the resulting chloracetyl-meta—nitro-anilide acylamino) - 8 - hydroxynaphthalene - 6 - sulphonic acid with piperidine, dimethylamine or other nitrogen bases which have at least one reactive» hydrogen atom. By reacting 2-acetoxy-3-naph thoio acid‘ chloride with N-diethyl-ethylene 45 2f _ 2,128,256 _. diamine and then splitting off the acetyl group, a naphthol is obtained having the formula: aminoacetyl) -amino-8-hydroxynaphthalene-3,6 - disulphonic acid, yellower dyestu?s are in general obtained. Example 2 208 parts of p-amino-omega-diethylamino CO-—NH—GHz—CHr-N(C:Ha)i Further suitable coupling components are for 10 ties are obtained. By employing 1- (dimethyl phenetol are diazotized in the presence of 350 examplejthe‘pyrazolone's'prepared from the above parts of concentrated hydrochloric acid and 1000 parts, of water with 69 parts of sodium nitrite. amines by the usual methods, and also the aceto 10 acetyl or benzoyl-acetyl and 2-hydroxy-3-naphe. These‘ The diazo solution thus obtained is added to an ifaqiieous solution, containing such an amount of thoyl compounds of the said amines. coupling components may be coupled with ‘any. ~ sodium hydroxide to neutralize the hydrochloric desired diazotized aromatic‘amines toyield dye-Z acid; of 213 parts of the sodium salt of 1-amino naphthaléne-7—sulphonic acid. The mono-azo If the coupling component employed contains \dyestu? thus prepared is salted out, separated, an amine group, the mono azo dyestuff prepared @dissolved" agai‘n'under the addition of acid and‘ may be diazotized and the diazo-v-compound' be, dia'zoti‘zed- with?sodium nitrite. The diazo solu coupled with any desired coupling component. tion thus'obtained is added to an aqueous solu 20 Disazo dyestuffs are thus obtained with excellent tion, containing such an amount of sodium acetate 15 stuffs of the said kind. " i . ' properties as regards levellingrpower. and fastness. " to-n'eutralize the'acid,'of 289 parts of the sodium The introduction of the external basicradicle, salt offl:l-phenylaminonaphthalene-8-sulphonic of the general formula ;_,facid. disazo dyestuff is thus obtained which ' /Rl 25 fxrl‘i c I Bl‘ > . ' v _ V V _ . in‘ which X stands ,for an ialiphatic radicle into aminoazo or hydroxyazodyestu?'s is e?ected in 30 a similar manner. . ’ dyes wool beautiful blue shades of good fastness to ' washing ‘and ~fulling. Instead of para-aminoromega-diethylamino T - phenetol ‘other amines" containing externalfbasic gl'qllpsmay beemployed. As amines of this kind there may vbe mentioned ‘iraminobenzyl-di methyl - amine, 3 - amino - 4 -. methylphenyl - l - . The azo dyestu?s obtainable according-to this invention and having‘external basic groups are distinguished by an excellent levelling power and for the most part by good to very good fastness omega -_(dimeth_ylamino'ethyl) -_ sulphone, 3,-, ami compounds. ‘ Instead of ‘ lv-ramino-naphthalene?e tain groups which are capable of being exchanged by metals, they may be converted in substance sulphonic acid or a mixture of these two acids. When the dyestuffs con or on the ?bre into their complex metal com 30 n'o 5f!- methoxyphenyl e omega -(_dimethylamino ethyl) -sulphone_ _ or the correspondingr'rdieethyl sulphonic acid there may also. be employedas :the ?rst coupling component l-aminonaphthaleneg? 35 to washing and fulling. 25 35 Instead of 1 - phenylamino - naphthalene -8- sul phonic acid there may be employed as the second '40 how the said “invention may b'e'fjcarried? out ‘in coupling component,’ the LOP-methylphenyl) aminonaphthalene-8Jsulphonic acid. practice but the invention‘is ‘not restricted "to these examples. The parts are by weight. diazo componentqalready contains a‘ sulphonic " ,The following. examples/will ‘furtheyillustrete _ _ _ acid; group;v 1-_-amino'-naphthalene maybe ~eme ployed'as thel?rst coupling component in this Examplél 107 parts of para-toluidine are diazotiz'ed in the usual manner and the diazo solution is stirred into 50 a vsolution, rendered ‘alkaline with sodium carbon-v ate, of 340' parts of 2-(dimethyl-amino-acetyl)A amino -8- hydroxynaphthalenee?-sulphonic acid, having the formula" ~ ~ .If._the> amineused for-the preparationot-the “ ‘ ‘ case“ ~- - ' ‘Whatwe claim is:—-: " V e ' -' " ' , 45 ' 1:1. Azo' dyestu?s corresponding to the general formulae" .7 " r‘ T 50 - wherein' Ar stan'dsfor an aromatic radical; the group,,.. H018 60'. red'shades of good fastnesstqwashing; - - - ~ pounds dyestuffshaving a good levellingpower and good fastness to washing. are obtained, giving the following color shades: ' V m 1-;aminonaphthalene._--2- sulphonic ‘ , —N/ 5 i stands for 5. basic‘radical'selected from the group consisting of —-NH2, primary and secondary alkyl, . hyd'rox'y'alkyl, v _ aralkyl and cycloalkyl amino groups and the radicals of hydrogenated hetero cyclic ‘nitrogen compounds includingthe N atom, _, sulphanilic acid__'_'_;_____1_"_'__-___. Red.: Aminoazobenzene sulphonic acid;; Bordeaux red. l:.-cmethylj-3-‘ amino .-'6-'chlorben~-g_,, 70 ' and;the"mixtures ;worked up in the usual .manner. The dyestuif obtained dyes wool uniformcarmine By starting from-thefollowing diazotized come 65 . V c cid—~.—.———-+?-;--:-~-_f?-f-r-f'ff' ~Blue-red' ' If, instead of "the ‘2-'(dimethylaminoacetyl) amino *8- hydroxynaphthalene '-6I- sulphonic ‘acid the’ic’orresponding v3,6-disulp‘honic acid be em-v 75 ployed, dyestuffs ‘of similar 'shades'and proper X stands for achain containing carbon atoms, which is free from; a basic action, and, _B stands for the radicle of an aromatic ‘a'zo compound,v ‘and in which at least one of the radicles marked Ar and B contains a sulphonic acid'gro‘up. 2. A20 dyestuifs corresponding to the general 70 V formula '_ iB——'N=N—Ar--X—N .Y : ' ‘ \ . Br. 3 2,128,256 which is free from a basic action, and, B stands for a radicle corresponding to the general formula wherein Ar stands for an aromatic radical, the group “gag -—N \ Rl/ Ra stands for a basic radical selected from the group in which at least one of the naphthalene nuclei I and 11 contains at least one sulphonic acid group 10 and in which R3 stands for hydrogen or a radicle of the benzene series. 5. The azo dyestuff corresponding to the formula consisting of —-NI-I2, primary and secondary alkyl, hydroxyalkyl, aralkyl and cycloalkyl amino groups and the radicals of hydrogenated heterocyclic nitrogen compounds including the N atom, X stands for a chain containing carbon atoms, which is free from a basic action, and, B stands 15 CaHs 15 N=NOO CHzCHiN/\ CzHs 20 S 0:11 6. Azo dyestu?s corresponding to the general for a radicle corresponding to the general formula: HRN formula R1 OH 25 11035; wherein Ar stands for an aromatic radical, the group ‘S0311 in which the nucleus marked A contains at least 30 one substituent of the class consisting of halogen atoms and nitro groups. 3. The azo dyestu?f corresponding to the formula i R1 30 —-N R: stands for a basic radical selected from the‘group 35 GEN o Hm 1 olN— OH | N=N o CaHn \ ¢ S-CHaCHzN /N=N C 2H5 40 40 1103s \SO3H 4. A20 dyestuffs corresponding to the general formula /R1 B—N=N--AI—X—N 45 R2 wherein Ar stands for an aromatic radical, the groups and the radicals of hydrogenated hetero 45 cyclic nitrogen compounds including the N atom, X stands for a chain containing carbon atoms, which is free from a basic action, and, B stands for the radicle of a condensation product of 1 molecular proportion of phosgene with 2 molecu 50 lar proportions of an amino-hydroxynaphthalene group 50 —N \ R2 stands for a basic radical selected from the group 55 consisting of —NH2, primary and secondary alkyl, hydroxyalkyl, aralkyl and cycloalkyl amino consisting of -—NI-I2, primary and secondary alkyl, sulphonic acid and in which Y stands for a radicle of the benzene series. 7. The azo dyestuif corresponding to the 55 formula CH 0 011 0H 0 s-cmonm /N=N 60 if 11101? HO:S 0,135 \ % 03H! \SOzH H 11 hydroxyalkyl, aralkyl and cycloalkyl amino groups and the radicals of hydrogenated hetero cyclic nitrogen compounds including the N atom, X stands for a chain containing carbon atoms, HANS KRZIKALLA. HANNS UFER. I BERN'D EISTERT. GUSTAV KLAPRO'I'H.