Патент USA US2134728код для вставки
Patented Nov. 1, 1938 ' 2,134,728 UNITED STATES PATENT OFFICE 2,134,728 AZO nms'rurrs Heinrich Morschel, Cologne-Deutz, and Otto Goll, Leverknsen I. G.-Werk, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation ,of Delaware ' No Drawing. Application July 28, isssgseriai No. 93,117. In Germany August 16, 1935 6 Claims. (C1. 8-46) The present invention relates to water insoluble sulfonic acid. Development is effected with 1 azo-dyestuffs and to a process of preparing same, liter of a diazo ‘solution produced in the known more particularly it relates to water insoluble azo dyestuffs which may be represented by the fol- - manner from 1.75 gs.‘ of 2-nitro-4-anisidine. After the dyeing has been soaped at the boil, an lowing general formula: olive grey issobtained. ' The dyestuff corresponds to the following for mula: ' . NO: 10 HIN N=N®OCH1 OH In the said formula X stands for a ‘member ‘selected from the group consisting‘ of hydrogen, alkyl and aryl, R’ and R',’ stand for radicals of N=’N OClIs diazotization components free from solubilizing 20 groups, and n stands for one of the numbers 1 r and (2. I Our new dyestuffs are obtainable by coupling suitable diazo compounds with 4-arylazo-1-am Example 2 Cotton is printed with a paste produced as 20 follows: ino-‘l-hydroxynaphthalene or their N-alkyl or N- E 25 aryl substitution products. 4 Amixture of In as much as in the aryl nucleus of the 4'-arylazo group a further 4-(2'- chloro) - benzene-azo-1-amino-7-hy suitable coupling position is present, by employ ing a correspondingly larger, quantity of diazo The'diazoamino compound from diazotized 4-chloro-2-anisidine and sarcosine___gs_.. 3 droxynaphthalene ________________ __gs__ compound trisazo dyestuffs and ‘so on can be 30 1.0 ' manufactured. I - l 4.5 An aqueous solution of caustic soda of 38° ' Bé _____________________________ __ccs.._ The new dyestuffs can be manufactured with 3 Glycolmonomethyl ether ___________ __ccs.._ I 5 particular success on the ?ber according to the method of producing ice colors as the compounds Neutral starch tragacanth paste _____ __gs_- 50 of the type ofv ll-arylazo-1-amlno-7-hyiiroxy is made up with water to 100 gs. After an inter 35 naphthalene possess a good affinity for the ?ber. The new dyestuffs yield in general powerful dark brown to black shades. 25 mediate drying, development is effected with acid‘ steam, and then the dyeing is soaped ‘at the boil. 35 . A black shade is obtained. The following examples illustrate the invention: Example 1 40 .Cotton ?ber is slop-padded with the following grounding solution: 3 parts by weight of 4(2' The dyestuff corresponds to the following for- ‘ mula : 0 OH: 40 inethoxy)-benzeneazo¢1-amino- 7 -hydroxynaph thalene are stirred into a mixture of 3 parts by weight of water, 6 parts by weight of alcohol and ' 1.5 parts by weight of an aqueoussolution of caus tic soda of 38° Bé., and the whole is made up to 1 - 'liter with a solution containing per liter 10 cos. of an aqueous solution of caustic soda of 38° Bé., .10 50 cos. of vpuri?ed sul?te cellulose ‘waste liquor and 1 g. of the sodium salt of polyisobutylnaphthalene 45 2,184,728 2. Example 3 When in the printing paste of Example 2 there is used the diazoamino compound from diazotized 4-chloro-2-toluldlne and sarcosine, a saturated dark brown is obtained. l'ghe dyestuff has the probable following for ' "fl‘he dyestuff corresponds to the following for m 100 gs. Cotton is printed vwith this paste. After drying the print is steamed for 5 minutes with steam-containing acetic acid. Then the mate rial is rinsed, soaped at the boil, again rinsed and dried. A deep black shade is obtained. m a: a: .10 OH 1 15 E . NO: 20 Cl '20 In the following table there are given further Example 4 2.5 gs. of the diazoamino compound, which combinations prepared in accordance with the present process and their shades on cotton: 25 25 Coupling component Diazo component Shade on cotton 4(1-methyl-5’ chlotophenylezo)-l-amino-7-hydroxynaph- .2-nitro-4-chlorauiiine ............................ _. Olive-brown. no 30. ' ' D0 '4’—nitro-4-nmino-2,5-dimethoxyazobenzene........ .- ____ _. - 3-chloraniline ............................ __ Blackish brown. .. 30 Greyish brown. ‘(T-mthoxy-iV-chlorophenylaw)-1-amino-7-hydroxynapb- 2,6-dichloroaniiine ............................... .. Brown-olive. Dn . __ 2-chloro-a-methoxy-4-ben1.oylamino-i-aminoben- ' 35 Blackish brown. zene. 4(2'-methoxy-5’-chloro-l-emino-7-hydroxy-uaphthslene..__ 4-nitro~2-amino-l-methylbenzene ................. __ Olive-brown. ‘(T-nitrophenylnao)-l-amino-7-hydroxy-naphthalene.. . ___ kchloro-2‘amino-1-methoxybenzene. Brownian black, Do ._ b-nitro-2-emino-l-methoxybenzene... Dc ‘ ______ __ _ Greenish black. 4-chloro-3-amino-1-triiiuoromethylbe Reddish hlack brown. 4(2'-chlorophenyluo)-1-am1no-7-hydroxynaphthalene....-- 3-chioreniline .............. .._---.Do - i-chloro-z-amino-l-methoxybenzen Do I _. .... ._ Greenisb black brown. Bluish dark brown. l-amino’nnthraquinone ....... _- Dark brown. 4(2'-methoxyphenylar.o)-l-emino-7-hydroxynaphthalene_ _ . 2’ ,3-dirnethyl-4-aminoazoben1-en Brownish olive. . 2.5-dichloraniline_..__ Do. 40 4(?itro-?-methyipbenylazo~1-amino-7-hydroxynephtha- Itchlorauiline ______ ._ 40 Dark brown. e. . 4(7-methoxyphenylazo)~1amin0-7-hydr0xynaphthalene .. B-amino-l-chiom-l-tri?uormethylbenzene ......... _. Bleckish brown. “?itro-f-methylphenylaw-l-amino-7-hydroxynephths- 5-cliloro-2-nmino‘l-methylbenzcne _______________ __ e. D0 4(1-nitm-4'-metboxyphenylaz0)-1-emino-7-hydroxynsph- 4-chloro-2-amino-1-metl1ylbenzene ............... __' .45 2(2’-nitn>4'-methoxypbenylam)~1-amino-7-hydroxynaph 4(1-nino-4'-methoxyphenyluo)-1-amino-7-hydmxynaph timiene. Y thalene. . . 4(7'-hydxoxynaphthyl-(l’) ~ezo) - l -emlno- 7 -hydroxynaph thabne. __ 50 D0 ..... __ 4(2' - nltmphenylazo) - 1 - methylamino - 7 - hydroxynapli thulene. J Do Do. Greenish black brown; 5-chloro-2-amino-1-metl1ylbenzeue..; ............ ._ Blackish brown. 5-nitro-2-emino-1-methylbenzene ................. _ . Olive dark brown. 4-chloro-2-amino-1-methoxybenzen _ _ _ hy?oxynaphthalene. henylsso)-1-etbylamino-Whydroxynaphthaleue. 4(1-nitrop euyluo)-l-etbylamino-7-hgdmgnnphthalene. ?il-lnitrophenylam)-1-phenylamino- -lzy roxynaphtlma > hydmxymphtlnlene. 60 D0 , D0“ Greeuisli black. ine ____________________ .- ‘ - .___ _. Greenisb black. ' 4-nitmniline__._-‘_ _______________________________ __ Olive. 6-11itm-i-amino'l-methoxybenzene _____________ __‘._ Greenish blackish brown. _ 2,5-dichloraniline__ ___________ __. ________________ __ 4-nitrsniline -.. ' is obtainable from diaz'otized 4,4'-dia.mino-3,3' dimethcxydiphenyl and sarcosine (=1/200 mol) , and 3.1 gs. or 4(2'-nitrophenylazo)~1-amino-7 hydroxynaphthalene (=1/200 mol) are stirred into a paste with the aid of a small quantity of water and dissolved by adding 3.0 com. of caustic soda solution of 38'’ B6. and 5.0 ccm. of glycol The so lution is added to a neutral starch tragacanth paste while stirring and ?lled up with waterto 70 monoethylether while slowly heating. Brown. Dark olive brown. 2,5-dichlor'aniline_ ........................ ., ____ _- Olive brown. . 4(4' - nitropheuylaso) - 1 - (4" - methoxyphenylamino) - 7 - 50 . Blackish brown. 5-chloro-2_-amino-l-methylbenzene ............... __ 0. Do Black. l-chlom-2-amino-l-methoxybenzene 4(3' 55 Do. Yellowish dark brown. 4-nitzo~l-amino-benzene __________________ ._ 5-chl0ro-2'emino-i-methylbenzone__ ' ' 4(2' - methoxy - 5 - chlorophenylew) - 1 - methylemino - 7 - Do. 5-nitm-2-emino-l-methoxybenwne ............... __ 2-aminodiphenyl-sulione _______ __ . Do. 4-chl0ro-2-amino-1-metl1oxybcnzene .............. __ We claim: \ ' . Blackish brown. Ycllowlsh dark brown. , 1. Water insoluble azodyestu?s of the general formula: 65 H x l I 70 2,134,728 wherein X stands for a member selected from the group consisting of hydrogen, alkyl and aryl, R’ and R" stand for di?erent radicals of di 3 amines and amino azo compounds with a com pound of the general formula: azotization components free from solubilizing H \N groups, and n stands for one of the numbers 1 . x/ and 2, yielding when produced on the vegetable ?ber in general brown to dark shades. 2. A water insoluble azodyestuif of the for mula ; on R'-—-N=N NH, N02 | the group consisting of hydrogen, alkyl and aryl, R’ stands for the radical of a diazotization com-' —OH OCH: 15 ] wherein X stands for a member selected from ponent free from solubilizing agroups, yielding when produced on the ?ber in general brown to dark brown to black shades. 6. The process for the manufacture of water ‘insoluble azodyestu?’s which comprises combin .20 ing on the ?ber a diazo compound free from - solubilizing groups derived from an amine select ed from the group consisting oi.’ monamines, di amines and amino azo compounds with a com pound of the general formula: 25 - H \N x/ yielding when produced on the vegetable ?ber 30 OH ‘ deep black shades. 3. Fibers dyed with a dyestu? as claimed in Claim 1, al ; I 4. Fibers dyed“ with a dyestu? as claimed in claim 2. R’—N=‘N ‘ i 5. The process,‘ for themanufacture of water 35 insoluble azodyestuifs which comprises combin ing on the ?ber a diazo compound free from solubilizing groups derived from an amine select ed from the group consisting of monamines, di' wherein‘ X stands for a member selected from the group consisting of hydrogen, alkyl and "aryl, R’ stands for a radical of the benzene series free from solubilizing groups, yielding when produced on the ?ber in general brown to dark brown to black shades. HEINRICH MORSCHEI... O'I'I'O GOLL.