[1]Patented June 20, 1939 29163@073 UNITED STATES PATENT OFFICE 2,163,073 AZO DYESTUFFS INSOLUBLE IN WATER AND F]IBER DYED-, THEIREWITH Erwin Thonia, Frankfort-on-the-Main-Hochst, and WiIhelni Seldenfaden, Offenbach on-theMalm, Germany, assignors to General Aniline Works, Inc., New Yorkj N. Y., a corporation of Delaware No Drawing. Application March 23, 1937, Serial No. 132,632. In Germany April 2, 1936 10 Claims. (Cl. 260-188) The present invention relates to azo-d@estuffs lene radical of the pata-aminoazo-compound insoluble in water and to fiber dyed therewith, directly or through. an oxygen bridge and/or more particularly it relates to dyestuff8 of the through a hydrocarbon bridge or through a nifollowing general formula: Itrogen bridge containing as a substituent at the (2) third bond a hydrocarbon radical; the dyestuff 5 @5 OH components must not contain any group which R-N=N-RI-N=N-R2 lends solubility, for instance a sulfonic acid or x cb-NH-R3 carboxylic acid group. The dyestuffs may be (3) made in substance, on a fiber or on a subs a !,9 wherein the azo-groups stand . in paraposition adapted for the production of lakes. 10 to each other, R, Ri and M stand for radicals of The Paraaminoazo-compounds of the benthe benzene or naphthalene series, R2,stands for zene or naphthalene series used as diazo-coma, radical of the naphthalene series and X for a ponents may contain substituents of the followmember of the group consisting of @CO.alkyl, ing kind:- 15 -CO.C6H5, -CH--CH.CO.C6H5, -O.CI-12.CO.al- @CO.alkYl, -CO.C6H5, -CH=C CO. 6H5, 15 kyll -O.CH2.CO.C6H5, -0. C.alkyl, -0. c.coH5, 0 2( -COO.alkyl, -COO.C6H5, -CH2.COO.alkYl, -CH=CH.COO.alkyl, C]12-CE2 -0 O.N C H2, - CH2--CH2 20 -CH2.CO.N(alkyl) 2 --O-CI12.CO,.N(aakvi) 2, -CH--CH.CO.N(alkyl) 2, c 0. alkyl COH C O.alkyl 30 -N \ , -N \ I -N \ I alkyl-- alkyl CH2.CBH5 alkyl -N C 0. C 6115 35 -SO2.alkyl, -SO2.C6I-I5, -SO2.CH2.C$1151 -CH2.SO2.alkyl, -CH2.SO2.C6H5,, -SO2.0.C6H5, -O.SO2C6H5, -CH2.SO2.N (alkyl) 2, alkyl alkyl 40 -N and @-N S02.alkyl S02.coTT5 We have found that valuable water-insoluble azo-dyestuffs are obtainable by coupling an aryl45 ide bf an ortho-hydroxyarylcarboxylic acid or be ta-ketbearboxylic acid with a diazo-compound of a para-aminoazo-compound of the benzene or naphthalene series which contains as a substituent at least one group containing the radi-, ,@o cal: -Co- or - S02- which on the one hand i,- connected with a hydrobarbon radical directly or through an oxygen bridge or through a nitrogen b-ridge having as a substituent at the third bond a hydrocaxbon. radical; and on the other 5-0 hand is connected with the beilzene or naphtha--O@CH2.CO.alkyl, -O.CH2.CO.C6H5, -O.C.alkyl, -O.C.C6H5, -COO.alkyl, -COO.C6H5, -CH2.COO.alkyl, 20 -CH=CH.COO.alkyl, CH2-CH2 -C O.N CH2, CH2-CH2 -CH2.CO.N(alkyl)2, -0-CH2.CO.N(alkyl)2, 25 -CH=CH.CO.N(alkyl)2, CO.alkyl COH C 0. alkyl alkyl -N -N -N \ CH2.C6H5' -N CO.CaHs1 30 alkyl alkyl -SO2.alkyl, -SO2.C6115, ---SO2.CH2.C6H5, -CH2.SO2.alkyl, -CH2.SO2.C6H5, -SO2.0.C6H5, -O.SO2.C6H5, -CH2,SO2.N(alkyl)21 alkyl alkyl 35 -N and -N S02.,,ilkyl S02.CGHS The diazonium compounds, for example the diazonium chlorides and the zinc-chloride double 40 salts of these chlorides are in part easily soluble so that in making the dyestuffs in substance nG large dilu'Lion is necessary@ and in producing the dyestuff on the fiber in printin a terial concentrated printing pastes are obtainable. In 45 producing the dyestuff on Yarn there may be added to the diazo-salt solution a salt, as is the :case with the diazotized amines of the benzene series. Furthermore, in the case of the diazoniuhi compounds of the aforesaid kind, there is 50 freqtiently to be noticed the @ propetty, important for the making of the dyestuffs, that the rnineral acid diaz6-salt solutions are-little sensitive to the addition of buff er agents, as for example @ sodium acetate. This very favorable 55 0 0
[2]property makes it possible, after the production of the dyestuff, to wash out easily non-coupled portions of diazonium salt. Many combinations do not bleed yellow in the washing sample and 6 thus do not show a defect which is frequelitly to be observed in the combinations from diazotized 4-aminoazo-compounds which are freqliently used in practice. Other combinations are of high fastness to light. 10 The new dyestuffs are of very various tints. Thus, by using arylides of beta-ketocarboxylic acids, there are obtained on the fiber orangeyellow, orange-red, orange-brown, scarlet, bluishred, bordeaux-red and brown-red tints which in ],5 part cannot be obtained with the already known para-amir@oazo-cor.lpounds. With the arylides of ortho - hydroxy - carbazole@ - carboxyhe acids tl-,ere may be obtained for exarnple, currant tints of high fastness to light. Further, fine black tints a-re obtained which in pa-rt are essentially faster to light than the dyeings obtainable from 'k-nowiipara-aminoazo-compounds. Byusin g2,3hydroxynaphthoic acidarylides, there are obtp,i-@ied, for example bordeaux, currant, garnet, 25 iiavy blue and greenish-blue, blue-black, blaekviolet and deep grey tints which in many cases a,-,,e distiriguished by a hi-h fastness to light and good fastness to washin,@ and chlorine. The co-:or tints are Profoundly dependent, apart .@i 0 from the kind of coupling component, on the kind of the aforesai-d substituents and on the position ivhich they have in the para-aminoazo body of the benzene or naphthalene series. Further, the pre@-eiice of other substituents such as alkyl-, 3,5 alkoxy- or nitrogroups and halogen is of importance. The following examples serve to illustrate the inventioii, but they are not intended to limit it thereto: 40 1. 50 grams of cotton Yarn aTe treated with I liter of an alkaline grounding solution which cont,@lins 2.5 grams of the arylide of the followi,ig constitution: H 45 OH CHs C O.NEC- <:D -OCIIS ,,5 (lo The grounded yarn is developed in a solution coiitaining per liter 4 grams of 2,5- dimethoxy2'-N-phenyl-sulfonyl - rnethyl-aniinoazobe nzene4-diazoniumchloride, 0.8 gram of glacial acetic acid and 15 grams of sodiuin sulfate. After soaping in a bath containing per liter 3 grains of soap and I gram of sodium carbonate, there is obtained a black of very good fastness to light. if the grounded cotton is developed with a diazo-solutioii from 3.6 grams of 2,5- dimethoxy2'-carboxyl,@'c acid - diethylamide-4-aminoazoben-, zene,,there is also obtained a black of very good f@-stness to light. . If for developing the dyestuff there is used a di@-zo-solution from 4-grams of 2,5-21- trimethoxy-5'-carboxylic acid-diethylamide - 4 - aminoazobe,izene made by diazotizing the base in 4 cc. 7() of hydroch'@oric acid of 30 per cent. strength and water by means of 0.7 gram of sodiiim nitrite and makin,9 up the solution to I li-ter by addition of 40 grams of sodium chloride, 4 grams of sodium acetate and 0.7 gram of sodium bicarbonate, there 7,:') i-s b'otained a biack fast to light. 2,163,073 If the diazo-compound from 4-amino-2-methoxy-5-meth yl-4'-carboxylic aciddiethyl-amideazobenzene or from 4 - amino - 2 - methoxy - 5 methyl-21-carboxylic acid-diethvlamide-azobenzene is used there is also obtained a valuable r) black. By using as coupling component an arylide of the following constitution: H 10 OR 15 CO.NH-<::@:>OCH3 there are obtained valuable black tints with the 20 diazo-compounds from: 4-amino-2,5-dimethoxy41 - N - methylphenylsulfonylarninoazobenzene, 4- amino-3- methoxy - 3' - carboxylic acid - diethylamide-azobenzene, or 4-amino-2,5-dimethoxy-2'- phenylsulfonylrnethyl-azobenzene. 25 2. 50 grams of cotton yarn are treated in one liter of an alkaline grounding solution which contains 1.8 grams of 1-(2'-hydroxy-3'-carbazole - carbonylanlino) - 4 - chlorobenzene. T h e grounded yarri is developed with a solution of 4 grams of the zinc-chloride double salt of 2,5- dimethoxy- 3' - @cetylazobenzene - 4 - diazoniumchloride, @O@6 gr,.tm of glacial acetic acid and 20 grams of sodiurn sulfate per liter. After soaping with 3 grams of soap and I gram of sodium carbonate per liter, there is obtained a violetbrown fast to light. If the development is conducted with a diazosolution from 3.6 grams of 2,5-dimethoxy-2'-carboxylic acid-diethylamide-4-aminoazobenzene, a 40 violet of good fastness to light is obtained. By using the 2-methyl - 5 - methoxy - 4' - carboxylic acid-diethylamide-4-aminoazobenzene as the diazo-component, a currant tint is obta@ned. With the diazo-compounds from 4-amino-2,5-dimeth- 45 oxy-2'-carboxylic acid-diethylamide - azobenz6ne or from 4 - aniino - 2,5 - diethoxy -41- phenylsulfonylmethyl-azobenzene there are obtained covered violet tints, 3. A rnercerised calico is grounded with a pad- 50 ding solution which contains per liter 15 grams of 4,4'-di-(aceto-acetylamino)-3,31-dimethyldiphenyl. It is then printed with a diazo solution from 18 grams of 2,5-dimethoxy-2,5'-bis-(carboxylic:, acid-diethylamide) -4-aminoazobenzene, 55 14 cc. of hydrochloric a,cid of 30 per cent. strength, 3 @rams of @ s6dium nitrite and 6 grams of sodium acetate, th6 *hole having been made up to 500 cc. and then made up to I liter by addition of a, thickening agent. After drying, the 60 material is handled in a solution of 10 grams of sodium carbonate per liter at 90' C., rinsed, soaped at the boil and rinsed. There is obtained a scarlet-r6d. When one uses as diazo-component 4-amino- 65 2,5-dimethoxy-4'-acetylazobenzene, there is obtained a medium red; with 4-aniino-2,5-dimethoxy-3',4'-bis-(carboxylic acid-ethylester)- azobenzeiie, there is also obtained a middle red; W"th 4-amino-2,5-diethoXY72'-carboxylii,, acidethyl6st6,i-4,-nitro-a7obenzene, there is obtained a dark red-brown; with 4-amino-2,5-dimethoxy2'-methylsulfonyl-4'-nitro-azbbenzene, there is obtained a reddish black-brown. 4. Bleached cotton piece goods @Lre grbunded 75
[3]163,073 on a foularci in a solutfon which contains per hot sodium 6arbonate solution (containing 2 liter grams of anhydrous sodium carbongte per liter) I - (2',3' - hydroxynaphthoylamino) - ben- and soaped at boiling temperature. There is obzene --------------------------- gran-is-- 15 tained a deep black of ver)r good fastness to light. 5 Caustic soda solution of 34' B6 -------- cc-- 22.5 The dyestuff correspoiids with the following for- 5 TurkeY-red oil ----------------------- CC-- 15 rnula: 0OH3 10 M02-- <c:@N=N- N=N 10 I O H C OO-C2H5 @(C"IHI,@@ 15 15 and dried. On the goods thus grounded there is 5. Also on cellulose esters and -ethers there printed a paste which contains rnay be obtained valuable dye'mgs with a series of para-amino-azo-conipounds of the composi20 2,5 - dimethoxy - 41 - riitro - azobenzene- tion indicated above, if the operation is con- 20 2' - carboxylic acid - ethylester - 4 - di- ducted as described in German Patent No. 637,31 . 'D-ius, acetate silk yarn may be impregnated, for azonium-chioride -------------- grams-- 20 instance, with 4-amino-2,5-dimethoxy-4'-NAcetic acid of 50 pi@r cent strength --- do---- 50 acetyl-methylamino-azobenzene and 1-(21,31-hy25 Water ---------------------------- do ---- 430 droxynaphthoylamino)-benzene in the presence 25 Starch tragacanth thickening ------ do ---- 500 of guanidine and the dyeing may be de@eloped by treatment with an acidified sodium nitrite bath. There is obtained a dark blue. GramsL- 1000 The following table illusltlrates a number of 30 further azodyestuffs obtainable according to the 30 After drying the material is passed through a present invention: Diazo colliponelat Coupling comp onent Shade 35 3t; 1-(2', 3'-hydroxyn,,Aphthoylamino) 4-ami]20-2-carboxylic acid-diettiyl,,iiLide-41- methoxyazobeiazene ------- -benzene--. --------- ------------------- Bordeaux. 4-amizlo-2-carboxy]40 aciddietbylaniide-2'-nietliyi-4'-methoxyazo- -2, 5-dimethoxybenzene -------------- Do. be Cne. 4-a,,nino-2-N-phenylsulfonyl-metb,.k-lamine-5- inethoxy-41-nitroazo- -2-inethyl-4- inethoxyl)enzoi3e ---------- Very deep currant. benzene. 40 4-aniino-3-metboxy-3'-carboxylic acid diethyl,)inide-azobenzene--. ---- ---- ----- do --------------------------------- Garnet. 1?0- --------------- ----------------- -2, 4-din,,ethoxy-B-clilorobenzene ------- Do. 40 i -i carboxylic ,cid diethyIRmide,,.zo- -2, 5-dimethoxy -4-chlorobenzone ------- Currant. 4-.amino y beiazene. 4-amiuo-2-methoxy-5-methyl-21-carboxylic acid-dietliylamideazo-Dapbth,,ilene ------------------------ - Dark blue. beiazenp. 4-omino-2-Tnethoxy-5-methy]-S'-carbo,x@lic acid-d;ethyl -2. 4-dirnethoxy-5-cblorobenzene ------ - Curraiat. benzene. 45 4-arnino-2-methoxy-5-meth7l-4'-carbox@,lic teid-dieth@,lainide-s7o- -2, 5-dimethoxy-4-chlorobeilzei2e ------- Dark currint. 45 benzene. Do ------------------------------------------- ------------------ -2, 4- dimethoxybeiazone ---------------- Currant. Do -------------------- ----------------------------- -2, 4-diiiaethoxyB-chIGrobenzene ------- Do. 4-amino-2, 5-dimethoxy-21-@jif@fWic;@j@zene ------------------- ----- --------- do---- --- -------------------- Dull currant. Deep currant. 4 amino-2, 5-dimethoxy-31-acetyl-azobenzere ------------------------ -4- metboxii 3ne -------------------- 4-amino-2, 5-dimethoxy-4'-acetyl-azobenzene ------------------------ -2, 5- dii:aethoxybenzeiae ---------------- Reddish dull blue. 4-amino-2, 5-diinothoxy-41-acetyl-21- mothoxy-azobenz(3ne ------------- -2- methy]4-chlorobenzene ------------- Do. 50 4-,.imino-2, 5-diTnethoxy-41-benzoyl-azobenzene -- -2, 4- dimetho)cy-6-chlorobenzene ------- Blue-black. 50 4-amino-2,.5-diimethoxy-21-carboxylic acid -4- chlorobenzene ------------ ----------- Very reddish dull blue. 4-amino-2, 5-diinothoxy-41-carboxylic acid-ethylesterazobenzene ----- -2-metbylbenzene ---- --- ------------- Difl] blue. 4-auiino-2,5-dimethoxy-21-carboxylic - acid-diethylamide-azobenzeDe-- -4-chlorobenzone ---------------------- Blue-blaclc. Do ------------------------------------------- ------------------- -2, 4-dimethoxy-5- chlorobenzene ------- Reddish dark blue. 4-araino-2,.5-diTnethoxy-31-carboxylic acid-diethylaraide-azobenzenc-- - 4-methoxybenzeiie -------------------- Very reddish dark blue. 4-amino-2,5-@liniethoxy-41-carboxylic acid-diothyh-irnide-azobenzene-- -2,4-dimethoxy-5-chlorobenzene -------- Reddish blue-black. 55 4-amino-2,5-dimethoxy-31-carboxylic acid-N-irothY!@qDilide-azobeTi- - 2,5-diimethoxy-d-chlorobenzene ------- Very reddish bliie. 55 zone ' 4-41nino-2,5-dii:ae'@hoxy-21,51-bis-(carboxylic acid-diethyla3ride)-,,izo- - benzene ------------------------------ Reddish 1)1(ie. beDZene. 4-,.irnino-2,5-dir nethoxy-21-carboxylic - acid-pir)eridide-41-nitro-azoben - -------- - do --------------------------------- Greenish dull blue. zene. Do ------------------------------------------- ------------------- -2- methvlbenzene --------------------- Black. PO- --------------- -------------------------- -3-methyl4-methoxy-t)enzpnc ---------- Do. 60 60 --------- -@- methyl-4-methoxy-benzene ---------- Darl@ blue. Do ------------------------------------------------------- -2,5-dimethoxy4-chlorobenzene -------- Do. 4-aiuino-2,5-diTr.etboxy-31-othylsul,'on,vl-61-met' @,oxy-,tzobenzeile ------ - naphthalei2e -------------------------- Blue-black. 4-amino-2,5-dii-t)etbox3,-21-phenylsulfonyl-pzobenzone ---------------- - benzene ---------------------------- Deep blue. 4-aniinc-2,5-di,,iiethrxy-,',I-sulfoiiie @@cid-phenylester-azobenzeiie -- --- -------- do --------------------------------- Black-vi--Iet. 4-F.miiao-2,6-dime,tboxy-31-sulfoni(, acid-di etliyl-,.,,iT)ide-@izobenzene ----- - 2,4-dimethoxv-5-chlorobeiizene -------- Do. 4-amiiio-2 5-dimethoxy-31-sulfoiiie acid diethylamide-6'- methoxy- -2-methyl-4-chlorobenzene ------------- Dull blue. 65 4_ azoben;@ne. 65 amino-2, 5-dimethoxy-21-N-ethyl sulfonyl-raethylanaineazoberLzoi2e - --------- do ------- - ----- Black-violet. i Blue 4-amino-2, 5-dimethoxy-21- N-phenylsulfGnyl-methylaraineazobon- -2, 4-diraothoxy- -------- -blacl,. zel@e. - 4-arnino 2, 5-dimethoxy-31-Npheiaylsulfonylmethyl,,tmine-,,izoben- - bei2zeiae ------------------------------ Very reddish - iark bitie. zei@e. 4-amino-2, 5-dimetho-xy-21-Npheilylsulfonyl-methylamilae-51-meth -2, 5-dimethoxy-4-chlorobenzene ------ Dark blue. oxy-azo-benzene. 70 4-amino-2, 5-dimethoxy-3 1-N-phenyl-sulfoi2ylmethylamine-41-meth- - 4-chlorobenzene ----------------------- Blue-black. 70 oxy-azobenzone. 4-amino_2, 5-diiiaethoxy-31-Nphenyl-sulfonylmethylamine-G'-meth2, 4-diraethoxy-5-chlorobeiazene -------- Do. ox@,-az_obenzene. 4-amino 2, 5-dimethoxy-41-N -phenylsulfonylmethylamine-31-meth- - 2-raethyl-4-chlorobenzene ------------- Do. oxy-azobeiazene. 2-(21,31-hydroxynaphthoylamino)- I-ainino-2, 5-dimetboxy-41-N-ph eiaylsulfonyl-methylarGine-azoben.- - naphtbalene-@ -------I-------------- -I,Black. 75 zene, 75
[4]4 2,163,073 Diazo component Coupling component Sbade 2-(21,31- hydroxynaphthoyl amino)- iniiao-2, 5-diniethoxy-41-pben,-Isulfonyl-iretllyl-azobenzene -------- -naphthalene --------------------------- -blq 5 4-a 1-(21,31- hydroxynaphtboylamino) Blue . ck. 5 Do -------------------------------------------- ------------------ -2, 4-dimetboxy-5-clilorob ei3zene ------- Dark blue. Do -------------------------------------------- ------------------ -2, 5-dimethoxy-4-chloro benzene ------- Violet. 4 - a m i n o - 2 , 5 - d i m e t h o x y - 3 1 - p h e n y l s u l f o n y l - o x y - a z o b e i i z e n e - - - - - - - - - - - - - - - - - - - - d o - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - R e d d i s h d a r k b l u e . D o - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 2 - T n e t h o x y b e i L z e n e - - - - - - - - - - - - - - - - - - - - D o . 4 - a m i n o - 2 , 5 - d i m e t h o x y - 4 1 - a c e t y l - o x y - a z o b e i i z e n e - - - - - - - - - - - - - - - - - - - - - 2 , 5 - d i m e t h o x y - l - c h l o r o b e r i z e n e - - - - - - - D o . 4 - a m i n o - l - ( o r t h o - c a r b o x y l i c a c i d d i e t h y l a m i d e - p h e i 2 y l a z o ) - n a p h t b a - - 2 - i i a e t h y l b e n z o n e - - - - - - - - - - - - - - - - - - - - - - D a r k b l u e . I 0 10 lene. 4-amino-l-(meta-carboxylic acid-die thylamide-phenylazo)-naphtha- -3- nitrobenzeiae ------------------------ Very reddish dark blue. lene. 4-amiiao-l-(para-carboxylic acid-diethylainidephenylazo)-naphtha- -2,5-dimethoxy-4-chloroberizene ------- Do. lene. 4-amiiao-2-methoxy-5-inethyl-31-sulfonic acidphenylester-azobenzene-- -2,4-dimetboxy-5-eblorobenzene ------- Currant. 4-amiiao-2-iiaethN@1-6-methoxy-21-benzoyl-41-niti:o-azobenzene ---------- -2,4- diTrethoxy-benzene --------------- ReddLsh blue-black. 15 Do -------------------------------------- ------------------------ -61-broi:ao -2,4-dimethoxyberLzene ------ Reddish black. 1.5 4-amino-2-methyl-5-methoxy-21-nitro-41-carboxylic acid-ethylester- -2- methylbenzene ---------------------- Currant black. azobenzene. Do ----------------------------------------------- --------------- -2-methoxybenzene -------------------- Do. Do ----------------------------------------------- --------------- -4-chlorobeiazene ---------- ------------- Do. 4-an2ino-2-methyl-5-methoxy-4'-N-acetyl-mothylamino-azobenzene-- -2, 4-dimethoxy-5-chlorobenzene ------- Bordeaux. 4-amino-2-metbyl-5-methoxy-21-methyl-sulfonyl-41-ni tro-azobenzene-- -2- methyl-4-methoxybenzene ----------- Black-blue. Do ----------------------------------------------- --------------- -6'-bromo-2, 4- dimethoxy-berizene ----- Blue-black. 20 4-amino-2-methyl-5-inethoxy-21-nitro-41-methylsulfonyl-azo-beDzene-- - benzene ------------------------------- Currant. 4-amino-2-metbyl-5-methoxy-31-sulfonic acid-phenyl-ester-azoben- -2, 5-dimethoxy-4-chlorobenzene ------- Deep currant. zene. 4-amino-2-methyl-5-ethoxy-11-benzoyl-41-nitro-azoborkzene ------------ 2- methyl4-methoxy-benzeiae ----------- Black. Do---- -6'-br(?ino-2, 4-dimethoxy-benzene ----- Reddish black. 4-amiiio-2-ii@@C@il-@ -et-h-o-x-y---2-1-- -m-e-t-h-y-1--s-u-1-f-o-n-y-l- -4-1--n-i-t-r-o- - a-z-o-b-e-n- -ze- -n-e ---- ---- ---- do ---------- ----------------------- Black. 4-amino-2-inethoxy-5-iLethyl-41-N-n;ethyl-,,,cetyl, @Ll,ino-azo@,enzeiie @ - 2,5- cliiLethoxy-4-ch".Orobenzene -------- Currant. ,2Z; 4'aiuino-2,5-dimetlioxy-21-benzoyl-41-nitro-azobenzene ---------------- -2- inethoxybenzene -------------------- Black. 5 4-amino-2,5-diinethoxy-41-beiizoyl-ethyleTiyl-,,izobenzone ------------- -bedzene ------------------------------ Currint. 4-amino-2,5-diiuethoxy-21,,'.I-dicarbox@,lic Pei(I ethylester-azobcnzone- -2,5- dimethoxy-4-chlorobenzene -------- Reddisli violet. 4-1,imino-2,5-dimetboxy-31-carboxylic aci d-etliyl-ester-ethylenyl-azo- -2- mothylbenzone --------------------- Reddisli dark blue. benzene. Do ----------------------------------------------------------- -2,5-diinethoxy-4- chlorobCDZene -------- Do. 4-ainino-2,5-dimethoxy-41-carboxylic acid ethyl-ester-etbylenyl-2zo- -4- chlorobenzene ----------------------- Black-violet. benzei2e. 30 4-aTnino-2,5-diniethoxy-21-carboxylic a cil-methyl-ester-41-iiitro-@.@zo- - benzene ------------------------------ Blue-black. benzene. Do ------------------------------------------------------ ------ -2-methylbenzene --------------------- Reddish blue-bl,,ick. 00 ------------------------------------------------------ -------- -4-chlorobenzene ----------------------- Blueblack. 4-amino-2,5-dimethoxy-21-ciirboxylic acid -ethylester-4'-nitro-,,izoben - --------- do --------------------------------- Neutral black. zene. 4-amino-2,5-diinethoxy-21-carboxylic acidcthylester-51-nitro-tizobela- - benzene -- --------------------------- Currant. ene. Do ---------- --- -2, 4-dimethoxy-5- chlorobenzene ------- Do. 3 4-amino-2, -benzene ------------------------------ Reddish blue-black. zene. Do ----------------------------------------------- --------------- -2-methylbenzeiae --- ------------------ Do. Do ----------------------------------------------- --------------- -2-inethoxybenzene - ------------------- Do. Do ----------------------------------------------- --------------- -4-chlorobei2zene ---- ------------------- Do. 4-ainino-2, 5-dimethoxy-4Lcarboxylic a cid-dimethylamide-azobenzene- -2, 5-dimethoxy-4-chlorobenzene ------- Violetish dark blue. 40 4-araino-2, 5-dimethoxy-31-carboxylic acid-dimethylamide-azobenzene- -2- methylbenzene ---------------------- Dark blue-grey. 40 4-amii2o-2i 5-dimethoxy-21-carboxylic acid diethylamide-ethylenyl- - naphthalene -------------------------- Dark blue. azobenzene. 4-amino-2, 5-dimethoxy-31-carboxylic acid-diethylamide-ethylenyl- - benzene ------------------------------ Do. azobenzene. Do ------------------------------------------------------------- -2-methylbenzene ---------- ----------- Do. 4-amino,2, 5-dimethoxy-4@-carboxylic aciddiethylamide-ethylenyl- - benzoiae ------------------------------ Navy blue. 45 azobenzene. 45 4-aiiaino-2, 5-dimethoxy-41-carboxylic aciddiethylamide-methyl- -2, 5- dimethoxy-4-chlorobenzene -------- Violet. azobenzene. 4-aTnino-2, 5-dimetlioxy-41-carboxylic acid pipel idide, azobenzone ----- --------- do ---------------- ---------------- Black-blue. 4-,,iniino-2, 5-dimethoxy-31-benzoyl-oxy-azobenzene ------------------- -2, 5- dimetbox3,-benzene --------------- Currant. 2-(21, 31- hydroxynaphthoyl aniino)- 4-amino-2, 5-diinethoxy-41-benzoyl-oxy-azobenzene ------------------ - naphthalene -------------------------- Reddish dark blue. 50 1-(2', 31-hydroxynaphthoylamino)- 50 4-a.Tnin,)-2,5-dimethoxy-21-methylsulfonyl-met'iyl-azobenzene -------- -2, 5- dimethoxybenzene ---------------- Blile-black. 4-amino-2, 5-diiucthoxy-41-inethyl-sulf onylmethyl-,izobenzene ------- -2, 5- diinethoxy-4-chlorobenzene ------- Currant. .4-amino-2@ 5-diiiiethoxy-31-otbylsi7lfonyl niethyl-azobeiizene ---------- -2, 5- dimethoxybenzene ---------------- Do. 4-amiiio-2, 5-dimethoxy-21-methylsulfony l-41-Ilitro-azobenzene ------- - benzene ------------------------------ Neutral black. Do -------------------------------------------------- ------------- -2-methylbenzene ---------------------- Greenish black. I)o ------------------------------------------------------ ------ -4-chlorobenzeiie ------------------------ Neutral black. 55 Do ------------------------------------- - ---------------- -2-iriethyl-4-niethoxy-benzene ---------- Greenish black. 55 Do ------- ------------------------------------------------------- -2, 6-diniothoxy-4-chlorobenzene ------- Blue-black. 4-aiiaino-2, 5-dimethoxy-21-i3itro-41-inet hylsulfonyl-azobenzone ------- benzene ------------------------------ Black ' Do ----------------------------------------------- --------------- -2-ulethylbenzene ---------- ----------- DO. Do ----------------------------------------------- --------------- -2-niethoxybenzene -------- ------------ Do. 4-amii2o-2, 5-diiiiethoxy-2'-nitro-41-meth yl-sulfonyl-azobenzeue ------- -4- chlorobenzene ----------------------- Do. 4-amino-2, .5-dinaethoxy-31-sulfonic acid-phenyl-ester-61-methyl- -2, 5- diinethoxy-4-chlorobenzene ------- Blue-black. azobenzene. 60 4.amino-2, 5-dimethoxy-3'-sulfonic acid-phenyl-ester-41- methyl - --------- do --------------------------------- Deep currant. 60 azobei3zone. 4-amino-2, 5-dimethoxy-21-pliei2ylsultony l-oxy-azobeiazene ----------- -2, 4-dimethoxy-5-chlorobenzene ------- Blue-black. Do ------------------- ------------------ ------------------------ -2, 5-dimethoxy-4- chlorobenzene ------- Do. 4-amino-2, 5-dimethoxy-41-phenylsulfon yl-oxy-azobenzene ----------- -2, 4-dimethoxy-5-chlorobenzene ------- Do. 4-amino-2, 5-dietl)oxy-21-benzoyl-41-nitro-azobenzeiie ----------------- -2-mel;byl4-methoxy-benzene ---------- Black. 4-amino-2, 5-diethoxy-3'-carboxylic acid-ethylester-51-nitro-azo- benzene - ------------------------------ Reddish black. 65 benzene. 65 4-amino-2, 5-diethoxy-21-carboxylic acid-ethylester-41-nitro-azo - --------- do ------------- -------------------- Neltral black@ benzene. Do ------------------------------------------------------ -------- -2-metbylbei3zene --------------------- Do. Tio ------------------------------------------------------ --------- -4-eblorobenzeiie ----------------------- Reddisb black. 4-amino-2, 5-diethoxy-21-raetbylstilfonyl41-nitro-azobenzene --------- -benzene ---------------------------- - Neutral black. Do -------------------------------------------------------------- -4-chlorobenzene -------------------- --- Do. 4-amino-2, 5-dietboxy-2'nitro-4- methyl-stilfonyl-azobenzene ---------- - benzene ------------------------------ Black. 70 Do -------------------------------------- ------------------------ -4-chlorobenzeno --------- -------------- Do. 70 4-amino-l-(para-carboxylic acid-d imethylamide-phenylazo)-naph- -2-methyl4-chlorobenzene ------------- Black-grey. thalene. 4-amiiio-l-(orthocarboxylic Lcid-N-niet hylinilide-pheiiylazo)-nap@l- 2, 5- dimethoxy-benzene ---------------- Reddish blue-black. thglene. Do ----------------------------------------------- --------------- -2, 5-dimethoxy4@chlorobenzene ------- Do. 4-ainino-l-(parL-carboxylic acid-N-inet hylanilide-phenylaz(,)-ncipb- -2- metbyl-4-chlorobenzone ------------- Deep grey-blue. 75 thaie-ue,
[5]2,163,073 Diazo component Coupling cpmponeut Shade 1- (2',31-hydroxynaphthoylamino)- 4-amino-l-(ortho-carboxylic acid diethyl-amide-methyl-oxyphenyl-benzeine ------------------------------ Grey-black. azo)-naphthalene. Do ----------------------------------------------- ----------------- -2, 4-,Iimethoxy-5- chlorobenzene ------- Blue-black. 4-amino-l-(meta-carboxylic a cid-dietbylamide-methyloxy-phenyI- - benzene ------------------------------ Do. azo)-naphthalene. 4-amino-l-(,iiet,,,i-earboxylic aci d-diethylainidp-methyl-oxy-phenyl- -4- r.,,ethoxybenzene. -------------------- Do. azo)-naphtbalene. 4-amino-l-(Pai,.,i-earboxylicaci(I-diethylamide-met hyl-oxyphenylazo)- --9- methyl-4-cbloro-benzeue ------------ Do, ' plithaleiae. 10 4-anm@ino-l-(Dari-e@,,rboxylic,,icid-piperididephenylazo)-naphttialeile-- ---..--- do -------------------------------------- Grey-blnk. 10 4-aniino-l-(@F,ra-N-acetyl-methylamino-phenylc,zo-) i2aphtlialene ---- - beiazen ------------------------------ :- 131,,ick-blue. Do ------- ------------------------------- ---------------- ----- -2-iiiethyi-4- eblorobenzone ------------- Gre3,-black-. Do ----------------------------------------------- ---------------- -2,4- dimc@thox,.y-5-ei,.IorobenzeTle ------- Deep currint. Do --------------------------------------- ---------------------- 5- diinethoxy-4-clilorobeiazene ------- Dark bl-ac. 4-amino-l-(ortho-methyi-siilfonylmethyl-phenylazo)-naphtl,.alene ---- .2- iiietbyl-4-nethoxy-Nnzene ---------- Dull violet. Do ----------------------------- ------------------------- ------ -2. 4-dimethox@,-,Ichlorobenzene ------- Dull bltie. 4'aujino-l-(ireta-sulfoiiic acid-pho nylester-phenylizo)-naphth:)Iene-- -2. 5- diirethoxybenzoiae ---------------- Darl- blue-,@rey. 15 4-amino-',-(PI-siilfonic acid pbenylest er-61-mothyl@-pl)eny',12',o)-urph- -2- Tucthyl-4-iiifth(,xv-bonzene ---------- Gr(,,y-blue. thale,,,e 4...ino-l-(ortho-pbenyl-sulfonyl-oxyphenylazo)-.u,,iphtlie.lene ------- -2,4- dipet]-ioxy-,9-cl@lor(,bcnzone ------- Vi(i@et-black. Do -------------------------------------------------- ---------- -2,5-diniethoxy-4- chl,,robe.,Az,,ne ------- Do. 4-aTnino-2, 5-dimetboxy-41-carboxylic acid-propylester-azobenzene --- - naphthalene -------------------------- Very dull reddish blue. 4-amino-2, 5-dimetboxy-21, 51-dicarboxylic acid-methyle,@,ter-azoben- - 2-metbylbenzone ---------------------- Bordeaux. zene. 20 4.amino-2, 5-diraethoxv-41-bromo-21-carboxylic acid-methylester-qzo- -4- methoxybenzeile --------------------- Currant. 20 beiazone. 4-amino-2-metbyl-5-methoxy-21-bromo-51-carboxylic acid-methyles- - 2-niethyl-4-chlorobonzon,e ------------- Bordeaux. ter-azobenzene. 4-amino-5-inethyl-2-inethoxy-21-broiiao-51-carboxylic acid-methylester - 2, 5-dimethoxy-4-chlorobenzene ------- Do. azobedzene. 4-amino-2-methyl-5-methoxy-4!-nitro-21-carboxylic acid mothylester- - 2-methylbenzene --------------------- Currant-black. 25 azobenzen 25 4_amino-2-methyl-5-inethoyy-51-nitro-21-carboxylic acidethylester- -4-metbOxybenzene ------ -------------- Bordeaux. azobenzene. 4-amino-2-iuethyl-5-metho.xy-31-N-acetyl-methylam ino.azobenzelae- -2- niethoxybenzene ------ -------------- Garnet-. 4-a.!no-2, 5-dimethoxy-31-N-acetyl-mothylamino-azobenzone ------- -2- methyl-4-chlorobenzene-- --------- Violet. 4-am@no-2-methyl-5-methoxy-41-N-acetylothylamino-azobenzene- - -- -3- nitrobenzene ------------------------- Cnrrant. 4-amino-2, 5-diinethoxy-N-acetylethylamino-azobenzene ------------ - iiaphthalene -------------------------- Greenish dull blue. 4-amiiio-2-methyl-5-methoxy-41-N-formylmethylainino-azobenzoi2e-- -3- nitrobenzene ------------------------ Currant. 30 4-amino-2, 5-dimethoxy-41-N-formylmethyl-amino-azobenzene ------ -n@iphtholene -------------------------- Navy blue. 4-amino-2, 5-dimethoxy-41-Npheiayl-acetyl-mothylamino-azobon- - benzene ------------------------------ Very deep dark blue. zene. . 0 4-am@n _2-ioethyl-5-motboxy-41-N-benzoyl-methylamino-azobenzene-3-nitrobenzene --------------------- Currant. - @ r a y @ 4_amino-@-methyl-5-methoxy-41-N-benzoyl-ethylamino-azobeiazene --- -2-methyl-4-chlorobenzei2e ------------- Very deep blue 4 amino-2, 5-diinethoxy-41-N-benzoyl-ethylamino-azobenzene -------- -2- methoxybenzene -------------------- Navy blije. 4_amino-2-methyl-5-methoxy-21-sulfonic acid diethylamidemethyl - --------- do --------- ------------------------ Bordeaux. azobenzen Do. 35 35 4_amino-2-meeihyl-5-niethoxy-41-sulfonic acid diethylamidemethyl -naptbalede --------------------------azobedzelie. 4-aiiaino-2, 5-dimethoxy-21-sulfonic acid-diethylamide-methyl-azo - -------- -- do -------------------------------- Dark blue. benzene. 4-amino-2, 5-dimethoxy-41-sulfonic acid-diethylamide-inethyl-azo- -2- methylbenzeiie --------------------- Navy blue. beiazene. 4-amino-l-(21, 51-dicarboxylic a cid-methylester-phenylazo)-naptha- -4- methoxybenzene -------------------- Dark blue. lenc,. 40 4-amino-l-(31-carboxylic acid-et hylester-naphthyl-21-azo)-iaaphtha-benzene ------------------------------ Blue-black. 1("De. 4-amino-l-(21-bromo-51-carboxylic acid iDethylester-phenylazo)- naph- -4-methoxybenzene --------------------- Violet-brown. thalene. 4-amino - 1 - (para-bromo-ortho-carboxylic acid methylester-phenyl-benzene ------------------------------ Bordeaiix. azo)-i3apthalene. 4-amiiao-l-(2,,')!-dicarboxylic ac id-diethylamide-phenylazo)-naphtha2-(21 31-hydroxynaphthoylamino) - naphNavy blue. 45 lene. ihaleiae' 4-aiiaino-l-(para-N-formyl-methylamino-phonylazo)-naphthalene ---- ----- do ------------------------------------ Blue-black. 1-(21, 31- hv,droxynaphthoy lamino)- 4-amino-l-(para-N-acetyl-ethylainino-phenylazo)-naphthalene ------- -2- iiaeihvl-4-chlorobenzene ------------- Dull greenish blue. 4-amiiao-l-(para-N-benzoyl-methylamiiio-pheiayl@izo-) , naphthalone- - - beiazene ------------------------------ Deep grey-blue. 4-amino-l-(p,,tra-N-benzoyl-ethvlamino-phonylazo)-n apththalene---- -2- methyl-4-chlorobenzene -------------- Currant. 4-,,imino-l-(pari-sulfonic aciddiethylamide-mothyl-phenylazo)- naph ----------- do --------- ------------------------ Blueblacli. thilene. 50 4-aniino-l-(ortho-sulfonic acid-diethylamide-methyl-phenylazo) - --------- do --------- ------------------------ Very deep blue. - naphthalene. 4-amino-2, 5-dimethoxy-21-phenoxy-51-acetyl-azobenzone ------------- -2- methoxybe'lzene -------------------- Reddish black. 4-iirii2o-2-ine,thyl-5-methoxy-2'-nitro-41-benzoyl-azobenzene ---------- - benzene ------------------------------ Black. 4-an,ill()-2, 5-dimethoxy-21-nitro-41-benzoyl-azbbenzene --------------- -2- methoxybenzene -------------------- Reddish bl@tclz. 4-amiu6-2, 5-diethoxy-21-iaitro-41-benzoyl-azobenzene ----------------- -4- chlorobenzene ----------------------- Greenish black. 5 4-,,imino-2, 5-dhiietboxy-2'-cliloro-51-benzoyl-azobenzene -------------- - beiazene ------------------------------ Black. 55 4-amino-2, 5-dimethoxy-:"-phenoxy-51-carb6i@lic acid-othylester- -2- methoxybenzone -------------------- Reddish black. azobenzene. 4-amino-2, 5-dimethoxy-41-chloro-2'-carboxylic acid-methylester-azobedzene ------------------------------------------ I----------------- -benzene ------------- ------------- --- Black. 4-amii3o-2, 5-diethoxy-41-chloro-21-carboxylic acid-methylester-azobenzeiae ----------------------------------------- ------------------ -4-chlorobenzene -- --------------------- Do. 4-amirLo-2, 5-diiiaethoxy-31-chloro-5'-carboxylic acid-ethylester-azobenze3ae ----------------------------------------- ------------------ .-2- methoxybenzene -------------------- Do. 60 4-amino-2, 5-diethoxy-31-chloro-5'-carboxylic acid-ethylester-azobenzene ----------------------------------------- ------------------ -4-eblorobeiazene -- --------------------- Deep black. 4-amino-2, 5-dimethoxy-3'-chloro-4'-carboxylic acid-methylester-azobenzene ----------------------------------------- ------------------ -benzene ----------- ------------------- Blue-black. 4-amino-2, 5-dimetboxy-5'-cbloro-21-carboxylic acid metbylester-azo--------- Reddish blaclc. benzeiae ------------------------------------------ ----------------- --------- do ----------------- ------4-ami-o-2, 5-dimethoxy-4'-chloro-3'-carboxylic acid-etbylester-azoC. 15 ben,e,,--, ----------------------------------------------------- --------- do --------------------------------- Blue-black. 4-a.ill(I-2, uaethoxy-2'-chloro-5'-carboxylic acidethylester-azoil.i@zene ---------------------------------------- ------------------- -- ------- do --------------------------------- Black-blue. 4-amino-2, 5-dimethoxy-2'-chloro-5'-carboxylic acid-methylester-azo---------------------- -black. be,nzeiie ----------------------------------------- ------------------ --------- do ----- ------ Blue 4-,,i,mino-2, 5-dimethoxy-4'-chloro-2'-carboxylic acid-ethylester-azobenzene ----------------------------------------- ------------------ --------- do ------------- -------------------- Do. 7 0 4-amino-2, 5-dimethoxy-3'-nitro-5'-carboxylic acid-ethylester-azobenzel,e ------------------------------------------ ----------------- -2-methylbenzeiae ----------------- ---- Black. 4-amii2o-2, 5-dimethoxy-2'-phe noxy-51-carboxylic aciddiethylamideazobenzene ------------------------------------- ------------------ -benzene ------------ ------------------ Reddish black. 4-,,.mino-2, 5-dimetboxy-2',4'-bis-ethyl sulforiyl-azob6Dzene ------------ -2- methylbenzene --------------------- Neutral black. 4-amino-2,5-diethoxy-2'-ethylsulfonyl-5'-trifluoromethyl-azobenzoiae- - beiizene ------ ----------------------- Reddish black. 4-amino-2, 5-dimethoxy-4'-nitro-2'-sulfonic acid phenylester-azobendo --------------------------------- Do. zene. 7,5 75
[6]6 2,163,0 73 Since an object of the present invention is to provide dyestuffs of good fastness properties which dyestuffs are insoltible in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims do r-,ot contain any substituents which are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestuffs to alkalies. 10 Substituents of this kind are, for instance, the sulfonic acid and the carboxyli6 acid group. We
