4 1,868,612, of some fi-irtlier iryl,,imides pre,,),irecl the preseiit process: '@l,lelt in,, Arylamide prol),,ired filom: Recrystallize(I fr(,in: PCiTit:' 3-liydroxyd iplienylamino- acetic "leici 196, carb Oxyli(! acid+p-toluidine +(.anisi(lilic, 13ciizeno 123- 125' 3.hydro.xy-2'-metliyldil)llenvlaniine-carl,oxylic acid ,o + aD!Iino y I c n 174' + P-ilitro,qnilino Cl)lorol)ejizene I S2' +#-naplitliylamine Clilorol)Lnz(,iio 3-hy(iroxy-3'-inc,tlii,ldiplienyl+ amine-c,irboxylic aci(i ariilino C'Iilorobenzon (, +Pnitro,iniline Clil(,robeizeiic@ 218- +,6-naplit,113-1,imine ('Iilorobeiizeiie, anj ine-c,,irboxylic aci(i + aniline (',Iilorobon7,cn o, + m-aminopheiiol -\-Ylollo + -iniinoplenol p, Xylono, 1-1 !,5' +pnitro,,inilino Clilorobenz(,no 201-' 3-hyclroxN--2'-cliIorodiplienyl+,Illiine-carboxylic, icid an iline Clalo.@ol)enzpn(, 17C,-I-, i . m , 20 + -aminopbonol fr,,)-.Ti i(s l(@C,-167 c,iustic s,)(1@i-@.ioltition, +p-,,iniinopliciiol I)o. o-I +o-anisidine +p-nitro,.iiiiiino Cliloro,)enzeiio 3-liydi-ox@--3'-eliloro(liplienylamiiie-c,,,rlioxylic .icid +aniline +oani,@idin(,, Do. IS7' 25 +pnitroaniline Clilorol)cnzcll" 21 @',' 20C@- 207' ainine-@,irl)o.ylic icid +aniline ,ici(I 222' +otolui,,,ine "IC4(" @ ol. +P-toliiidine +o-cl)loroanilino clll(,rol),,Tlzelle, 30 +P-cliloroaniliiici ('Iilorolielizeii(i +4-cliloro-2-aiiiinotoltioiie Xylono +5-cliloro-2-aiiiinotoluene Xylene +P-aminoplienol 'I froni its +o-anisidine Clilorol@pnzollo +5-chloro-2-,,iiniiio - inisolo @\vlcllG 7,", s I 1 7 +p:,,ni,,,il,,l in(" i 35 +, 'I, tidine Pyri(iiiie 16" -0. +2-chIoro-4- nitroanilin(., TI@ri(lin@ 21" +5-nit,ro-2-aminotaltic @@ylcn 21.,3-20 1. n0 +4-nitro-2-,,iniino-anisole C,-Iaci,,il acetic ,i(li(, @-3@)-2 10' +,6- naplithi'laiiiin(,, I)ielilorobeii.11(lilo 2:z7-@@39. I)ic,,Iilc,,robenzcno -- +1-,,imino,,intlira(luiiione ,)-2@13- +2-amino,,intliraquinono 2P, 9 ' Prec@ipit,,ited frOTn il., ,au,tic soci@i-.,@ollitic,,i 40 +1.5- dLiinino,,inthrtquiiiolle Tichlorol)oi)zoiie iT)oi-o @i3O' (h,ilf its molecular I)rop,,)rtion) +3-amiiio-carbazol, Diclil(,,robenz(,ilcl 210' 3 -hydi,ox@,-2'- nyl,,iiniiie-cari)oxvii,, ici(I +aniliiie +m-aniiiioi)liciinl e, 1, 45 + p-,i rii i n o 1) li (,, i iol II I r ol eTi le! I 0 l(iO, +p-nitroai.iline Clilor@l,@eii, cT,.c,, 3-hydroxy-4'-mot li o xy(i i T)li c - liylamiiie-c,-,rl)oxylic acicl + atiilijle C',IIOTobe;i,,@(,,T,.c, p-iiitro,,iiiiliiie Clilpml)CT,Zclle 60 + "IC'. + +aniliiio +1)-nit,rofiiiiliiie Cliloro.,eiize-@in S-Iiydroxy-@-' @5'-diiiietlivlr) G +acid aniline +#-naplitlivliiiiine 3-hydroxy-2'-ilietliyl-4'-elil oi,odiphenyl,iiiiiiie-e,,iri)oxylic acid +,,iniline +p-iiitroaT,,iline, fio +i3-naplitliN-I,.iiiit)e -h -cliloro3 ydroxv -ilictli@ I r)' diplionylaiiiiiie-carboxylic aci(i + ai)iline p-nitroaiiiliiie ('Iilorolo-liz,,ie 3-hydroxy-3'-iTictli3TI-l'-(!Iilorocl iphenyl,,ini i n e - c a r 1) o x @@ 1 i c c@5 "cid AIolting .@r@,Iimido prol),,irocl froili: Ileer37stallized from: point: A,-@i iil@ne Clilorobenzeie 202' Clilorobonzone 135, -2171 ,i(lille Clilorobenzone 215 70 +p,-iiit,ro,@ili"liiie Dielilorobenzon() 213-214' 3-liy(iroxy-3'-cliloro-4'-iiietiiylclil)li@iivliiiiiii(,,-carboxylic @iel(i +Zl!lilillo CIilorol)eiizene 176' +@l-cliloro-2-,,iiiiilio-toluelic Xyloilo ]so, +,')-c!l i I or o-2-,imi ilo' , olu eii e Xylono 199, @-1, -ii i' ,r oa nil i n e, C,ilorobeiizeiie 255' li ylainiiie Cliloroi)enzene 24,@,' 7 6 3-li @@(i ro@@y -3' - iii(@tliyl -,I' - iii e - ilio:@y-,Ili-I)II,-Ilylzlll-,ill("-CarI)Io@,,.rli(, ,I . ei(I '!III, 'ilorobeii7,elic 187' -Z, I-- -, Dic@ )-iiitroz,,iiiliiie Clilorob@,nzeno 24+1-2,1,rl Clilorol)eiizeiie 188, lic-c,,Irl)ox@@lic "lei(i so -218' Xylono 217 -243' Dielilorobenzeno 182' Dielilorobenzone 242 il@rl@i,,iiiiif,,-czirL)o-Nylic ,icid -1-i'llilil]O Dielilorol)ciizene 188, -@ I' D i c' i I or ol) on z e n c 258-259' 85 I)OXylic @l(!i(t Ciilorobeiazone 280' l@. I-r(,cess Avliieh coiiii)rises condensila,- iii go Ii',, of aii acid coi-id(-,nsiii(,- a-eiit aii ai@A--I-,,,iniiio-I)heiiol-carboxylic acicl. of tl)e i)i:ob.,,ble (-eiiei-al foriiiula: zn coori 95 X 0 H i,@icaiis li),-(:Iro(ycii or aii ac)TI-groLip f@or a radicil of the bel-izeiie -T 'lilies AATIli il)lc,, bAti.-e,atiii,,- the corloo SI ch is odt@iiii, n ar3,'aiii'no-plieilol NA,'th cai-bojiic i,espoidiiio aci(I tdi,,,tiita(yeously thc,, earboxi-"c ,,cict 't-,Iius ])rodticed, 'witli an arylI @ tn i-iii ic of the o'eneral formul,, 105 clil LI ii li'., aroiiatic rad'eal of the diplieii),I,, iitplitlialeiie or al'itliras@ @lll(,, )t tllo, iii,iliber I or 2. 2. '-@'i@ocess coiiiprises coiidensint in 110 "I .1! Ll"c I)rl@ISLIICO O-L ail ,tcicl coiideiisiiiol a(rent t, tn ai-ill@,,iiiiij)o-plie@iol-carbo--,@),-Ile acid of the a: Y- -,\T- -cooii 15 x OH )@rliero-i@ii iilc,@ii-is I)vclrogen or aii - acyl-o-roiip ,iid Y s'L-.,,jlds for all@yl-alkox,),-ar.),Ioxy or li,.ilo,eii, wlilch is ol)tain,,ible b,), ti-eatiii(- the -@,- 20 iicliii (y ai@ATlaiii'iio-I)heiiol witli carcorrespo I bojiie acicl a-@id aellatlii,, advaiit:t(yeot,,sl.)- 'Llic t@ c@,,,i-boxviie acid tlius pi,oduced. i@,itli aii @ii-yl"Ill-iiiie of the oeiicral foriiiiila: 325 :P,@@ iiie-@iiis ,tiiv ti-oiaiatic radical ofiitplitlialene oi, ,iii)t 'u-I)e --ii,,iiiber I or 2. 3. Process Y,-Iilcli coiiii,)i@ises col-ideiising iii

1,868,6i2 the presence of an acid condensing agent a aryleimino-phenolcarboxylic acids corre4' - chloro - phenylamino-phenol - carboxylic s-D6ndin to the probable -eneral foriiiula: 9 acid of the probable general formula: Cl-<:D-N COOH C O-NH R2 < : : @ - n OH -wherein X means hydr,ogen or an acyl-group, wherein X meins hydrogen or an acyl- R@ aiy aromatic radical of the be,.izene, d'lgroup, which is obtainable by treating the plieiiyl naplithalene or anthraquinone series 10 and n the number 1 or 2, which are obtainable 7 correspondina ar3TIainino-phenol with carbonic acid and acylating advantageously the by treatin(y the correspoiiding 3-(4'-chlorocarboxylic acid thus producecl, witll-i an arylPlien3TIaiiirno)-phejiol witl-i carbonic acid, acyl,4ti llo, advaiitageotisly the carboxylic amine of the general formula: t, acids thtis prodiieed aiid condensino- with a in 15 (H,N),@R, corres ponding arylamine, whicli coiiipounds C-0 -,vl-iereiD R. iiieaiis any aromatic radical of are ainorplious or crystallized si-lbstances, ha viii g a def inite iiie ltin g. poi nt, di the bei-izeiie, clipl-ieiiyl, iiaphtlialene or aiiy ti-iraqii.iiio.,ie sci.-ies and 9@ th.-I iiviiiber 1 or 2. soluble in orgaiiie solnients, easily solu in 4. As new coiiipounds the arylaiiiides of alkalies, distingiiish ed by a great afiinity to 20 arylan-lino-phonol-carboxylic acicls corre- tl-ie vegetable fiber. S5 sponding to the probable general formula: c 7. As new coiiipounds the arylaiiiides of hlorophenylaiiiiii6- phenolcarboxylic acids corriespond iiig to the p robable general f orRr--N- >-CO-NEE R2 iiiula: 2,5 x n 00 OH 0 NTI@ 0 ()-NH R2 whereiii I", meaiis a, radical of tl-ie beiizene series, R@ any aromatic radical of the beiizene oil a di@henyl, iiaplithalene or anthraquinone wlierein R, iiieans any aromatic radical of 5 i'D series, X me,,ins hydrogen or tn acyl-group tiie bei-izene, dipheiayl, i-iaphtlialene or aiithraand n the ntimb(@r 1 or 2 ivhich are obtainquinoiie series and qi the number I or 2 which able by trea'tiiig the corresponding aryl- are obtainable b37 trea,tina the corresponding aiuino-phenols with carbonic acid, acylatino,- 3- (i'- chloro-phenylamlil,o) -pheiiol -",ith car-5 advantageously the carboxylic acids thus pro- bonic acid and conde@nsing with a correspond10, duced and condensing ivitli a corresponclino, iiig aryl-anaine, wliieh coinpouiids are amoraryl,,imine, which coinpouiids are a@morphoi@s phous or crystallized substances, havina a or crystallized substances, liaviiig a defiiiite definit e iiieltiiig poiiit, 'ifficultly soluble in meltin- point difficulty soluble in organic orgaiiie solveiits, easily soluble in alkalies, solvents, easily soluble in alkalies, distindistinguished by a gre:it affiiiity to the vege40 guished by a great affinity to th'e vegetable table fiber. 105 fiber. 8. As n6w coiilp6unds the arylainides of 5. As new ecmpounds the arylamides of chloro-phenyl-amino-phenol--carbOX3TIic aeids arylamino-phenol-carboxylic acids correcorresponding to the probable general forsponding to the probable gei-ieral f ormula: mula: iio y- N- CONH R2 ciNH- CON 0 <:@)- I <::> OH n <:@>H wherein Z iiiea-i-is hydrogen, alkyl, alkoxy or i 5 wherein X meins liydrogeii or an acyl-group, Y means alli:yl, all@oxy, aryloxy or ha looen, chlorine, which are obtainable by treatiiig the RI@ any aromatic radical of the benzene, correspondin(y 3- (4'-chloro-pheiiyl,,tmino) - di- . n phenyll naphthalene or Itnthraqtilnone series phenol in@ith carbonic acid and condensin, and n tlile niimber 1 or 2, which are obtainable with an arylainine of the probable general by treatino, the corresponding ai-ylamiiio- formula: 120 henols with carbonic acid, acylating advantpageol'Isl y the carboxylic acids tlius produced H2N-<::>-NO2 and condensing with a corresponding arylamine, which coi-iipounds are ainorphous or crystallized substances, having a, definite wherein Z h,,is the above significatioii, wliieh 125 n-ielting point, difficulty soluble in oroanic con-ipounds are aiiiorphous or crystallized solvents, easily soluble in alkalies, ccistin- substances, havii-ig a definite iiieltii-i- poiiit, guished by a great affinity to the vegetable difficultly soluble iii organic solvents, easily fiber. solubl e in alkalies, distinguished by a great 0 6. As new compounds the arylamides of affinity to the vegetable fiber.

6 1,8681612 9. As a. iiew coiiipolind the para-nitroanilide of 4'-cliloro-3-I)ydi-ox3,-diphei iylaiiiiiie-carboxylic acid of tlio probable fori,nul,t: Cl-<D>-NH-<@: >Col\lrf-<::>-NO2 I Ofi obtaiiiable by treitiii(y the coi@i@espoiidiii(y 3- 10 (4'-cliloro-pf@eliyl-aiiilllo)-plleiaol Nvi'L-li carboiaic aci@i aiid coiicleiisiiig iiitli 4-iiltro-ailiIiii.e, i-vhich coiiipound is ,i ci,vstallized silbstance, liai,iii(y its iiieltill,- poiiit at 229", diflicultly soluble in orgaiiie sola,elits. easily soluble iii alkalies, distiiigt,,ished by a great @iffinity to the i,-e(,Yotable fiber. 10. As t iieii, coiiapound. the para-chloro,inilide -cliloi of 4' -o-,' )-li), clrox.1, - dipheiiylaiiiiiie-carboxvllc acid of @i-ie p, obable for20 mult,: 01-<:::>,Nn-<:::>-c O-NH-<::>-Gl Oli 2i iiieltin(y AA,heii recrystallized froji-i clilorobeii@:1 zeiie at 188-190', di@Yicultlv soliible iii or-,inic solven'Ls. easily soliible iii all@:alles, distiiigtiislied by a (yreat affiility to the veetable fiber. 11. As a iieiv coiiipouiaci, the ortho-aiiisiclidc,, of - 4'chloro-"- Iii,cli-ox3--dipliel-il,laiiiiiiecarboxylic acid of the probable foria@iila: OCH3 85 Cl-<:D-NH--<D>- C O-NH-<::> OH meltii-ig i-@heii recrystallized froii-i clilorobei-izeiie at 142', diffictiltl.), sol-Lible ii) oi-gaiiie sol,@o veiits, easily soluble iii ,tll@,- ,Ii-es, distiii(Itiislied by a -i,eat affij-iiti, to the i-egetable fiber. III testilliolly lvliei-eof I iie affix our sign,,ttures. LEOPOLD L,@-SKiV OSKIVR I-il@LLEpt. 53 Go

Patented July 26, 1932 lt868,612 UNITED STATES PATENT OFFICE LEOPOLD LASKA AND OSKAR HALLER, OF OF.VEN33ACH-OK-THEMAIN, GER.XANY, ASSIGNORS TO GF-,NERAL ANILINE WORKS, INC., OF NEIV YO--RK, N. Y., A CORPORATION OF DELAWARE ARYLAMIDES OF 3-HYDROXY-PHENYL-ARYL-AMINE-CARBOXYLIC ACIDS AND PROCESS OF MAKING SAME No Drawing. Application filed February 20, 1930, Serial No. 430,130, and in Germany February 27, 1929. The preseiit inveiition relates to new arylaiiiides of 3- hydroxy-phenylarylamine carboxylic acids which correspond probably to the general formula,: RI-N- @C O-NH R2 OH and to ,t process of malkin- saine. The process being the object of the present i invention coinprises condensing in the presensing a ei-it aii arylence of an acid cond amino-phenol-carboxylic acid of the probible general formula: 2@D Ri-N- cooli , < x :@>- I 0 H wherein X tnd R, haie the above significatioii which isobtainable by treatiug the cor2 5 responding arylamiilo-phenol witli carbonic acid under pressure (see U. S. application Serial No. 407,274, filed November 14,1929) and acylating advantageously the @earboxylic acid thus prodticed, with an arvlalnine o-f,the general formula:' (H@N),, R., wherein n and R. have the above signification 'wheretoadiluentmaybe,,Ldmixed., As ,tr3,lamino-phe nol-carboxylic ,teids stiitable for this process mty be named, for instance, 3-phenylomino-phenol-carboxylic aci.d aiid its halogen-, all@yl-, alkoxv- or aryloxyI deriiatives having these groups ELtt@,,tched to the phenylamino radical, wliieh coi-npou-.qds ,q.re described in U. S. application Serial No. 407,274, filed November 14, 1929. Appropriate aryl,,tmines are, for instance, aniline, its substitiition products coiitaiiiing h,,tlogen-, alkyl-, alkoxy- or nitro-groups or simultaneously several of these groups, furthermore amino - phenols, ainino - cresols, a,inino-na-phthols, ainino-anthraquinones, dialliino-naphthalenes, diamino-diaryls. 50 In the case of using diamino-compounds one or two molectilar proportions of the earboxylic-acid inay be subjected to the action of the diamine. Those of the new arylamides are of a spe- 55 cial value which correspond to the propable wherein the beiizene nucleus signified by I contains halogen-, alkyl-, alkoxy- or aryloxygroups or seve:ral of these groups and the nucleus sionified by III may contain halogen, 65 alkyl-, @lkoxy- or nitro-groups or several of these groups. When the compounds obtained by this process contain an acyl-group (X of the ab6ve tormulao being acyl), this acyl-group may be 70 split ofr by an after-treatment with saponifyino, means. Yile new compoui-ids thus produced are distingiiish od by a great affinity to the vegetable fiber being manifold that of the correspond- 1'5 ina arNTI-amides of salicylic acid. For this r eason they represent valuable intermediates f oi- t,lie prodliction of d@estuffs. In order@to furtlier illustrate our invention the f ollowing exainples are given the parts 80 being by wei@,,Iit and all teiiiperatures in centi(,Yrade degrees ' but it is however to be understoo d, that our invention is liot limited to the particular products or reacting conditions mentioned therein:- 85 Examp7e 1 22.9 part,, 'of 3-liydroxv-diDlienvlaminecarboxy lic acid, obtainable accordin- to the example, of U. S. application @Serial No. 9( gen or aii acyl-group aiid n the number 11 or 2, general formilla: i -k) wherein R, n-ieans a rtdical of the benzene series@ R, any aromatic radical, X meaiis hydroN]][- II C O-NH60 on

1,S68,612 ,IO oj' -1@9.-29, ,ire lie,,itecl iii 300 parts of ide aiicl 300 part's of clilo,-o-belizene are treattolticiie to CO'. Tli,-rt@'Lo 9.'o 1),,irt-,s of e(I is (lescril)e(I iii the fore-oiilg exailiples. ,,re acided. At ')0-70' 6 ptrts of pliosi)ilor- The tlius obtaii-iocl corresl,)oncts ous trieliloride ai-e alloayed to ruii iii aiid pi-obal)ly to the foriliult: H-<@::>- c 0--l@IH-("\^ N H - oil @DC> O i l IL, Cl: )'st,,illizcs 'i@oii-i nitro-l,)enzeii(, iii i-ioarly coloi.@less siii,,ill -ic-,c,,OLles iiieltiiic, at 293o (lincori--,c'c.ed). E o , a 7 i ? , p l c 5 s o 26.4-. pai,ts of 3-Iii,cli-oxy-4-'-cliloro-d'l)heacid aild 11 parts of iiicti-aiiiiiioi)lieiiol are dissoli,- ed ,it 60-70' iii 300 1),-Li-ts of d'metli.),Iai-iilii-ie. Tlieii 6 pti,ts oil plio.,,,,plioriis trielilori(le ai-e acld,-,d at this teiiiper,,iture aiid tli,., iniss is iiiaiiita,ii-iod at 120' -i"or 8-10 liotii-s@ The reactioii procl-Liet is i.iiti-o(l@,icecl -whil(-, stirri.i-i(y ;iito Iii c@xcess ofdilute h@,cli@oclilorie ,ielcl. Tlie rcsidii-. is ivaslic(i froc@d fi-olii diiiiethylaiiiliiie, if distillatioij af'(-@r b ' @@ LI eill(I rendor,@d Avitli a socla solutiol-I The oT'L-iie pr(,,babi-@,., ClNu CONllon Oil ei,ystallizes froiii placii,l acetic acid a@,,, siliclthe ivliole is beated to boiliii,, foi- ,ibou'c, 3 lioi:,i.@s iiiiiii the eiolu@L:i.oii of liycli-o,,@hloi-le acid I-La- coise@,. Tli,- coiiclersatioi-i product is puriliocl 13-v cl@ssolAin,, it@ in t cliltite caiistic socl-,i lve :incl bv i,,i-ecipit@it'lii,,, Av-itli carl)oiiie ae I c3 - 11A T cli,ox -di-I)iieiiyl,,iiiiiiio-(@,,,rbox3,lic acicl ,iiill'lde o-L' 'L-,Ile pro',)able -i-'oi,iiitila: OTT represe-.its colorle--s (-,Iitteriiio- iieeclle-, iiieltin-- at lS6' (Ulicorre,tecl). ET ct, @ 77 (,' 2 ')2.9 I)arts of c,irbo@@i@l;e ,cid Avl,"-Ii 14.3 o-f 2-@-,ii-i-ino-iiap'iitliileiie iii '0'00 I)artE@ of NY]@eiie 'Lhe Lclclitioii of 6 pii-ts of phos1)hortis trielilorl(le zid the r e,,i c'Lio,@-i -I)rodiiet is I)tirlCiecl iii tti(, iii,,iiii,,er iii 'I'l-io p-,-iapli'L-Iii,laiiiicle of 3-1i)-droxA"- cliplieiiAl@iii-iine-c,irl)oxylic acid of ti' le probable fori;@uli: El_<@D_c 0_1\ TIT_( OH ci-ystall@@zes froni clitoro-beiizeiie iii colorle,-s iieedles iiieltiii,)@ j7t 208' (i,,iicorrectecl). Ei.,ag)?p7e 3 22.9 1),irts o-c' c@irbox.),Iie ac-ld ai@(,, ill@@eiaise coil(lelised Al,itll 12.'-) pirts o'L' dia.@@-@;ls@l(li.-.io iii tLe I)reseiiec,, of '000 Plr,L:s o f alicl C) pai-ts of 1)1',osl)l@-ior,,is ti-ieliloi.-Icle. The iieAApi.,o,-,Iilict isolatej ,is abo-@Te rei,)resei,,ts AvIlell reci-yst,illized f-voiii oi-tlio-clielilopo -beiizeil.@@ .edd;sli (,oloi,e,-t above 3-101 (uncoiTect(lCL) . it COPPOSI)Ollcls to the pro'@,)able T-oriiLiil,,i OTI 0 OH ocl@13 Ei Taii@1)7e 22.9 parts of 3-1,1y(lroxy-clil)l,ell.)"illlline@,.9 1).ii-Is of na btlia!eT-le, 6 liii-@lls o-f pliospilorus ti-leii,lor-. p like 1)oiyder iiieltiii- at 210-212o (uiicori-eeted). 6 To L iiii:@ture of 1.")2 ])arts of 3-hydrox),-4'cli loro-(Ijpliei-iA,],,iiiiiiie-carb-,xvlie -.cid@ 61.5 11-jillo-3-JIV(Iro]@- Y-1-11-let]13TI 1),irts o-l' 6-,I" -benzoie tiii@d 1000 1)"Il.ts of- toliieiie, 30 ptrts OT-lis tr' liloiicle ai-c sloA-@,-Iy 'iiti,o- !IO le dii,c(,(l )I-. C)O-'@0'). Tlieii the i,eactioii ilill@,@s is to 110' foi- al)oiit 8 1-..oiii,s, thei-eafter 1101@(lell(Id @ilkiliiie ivitli sodi so I Ititioii ,,,iicl fi@cecl toliie,.i(,, stcaii-i distillatioii. The reiiaiiiii-t(,- iic,-cirl),)xylic qe;d 's clissolv(,.J i@oitioii iii a (@qiistic socli lye, filtei-ed and I)reei,)Itateci b of carl)oiiie acid. It is eqsilv soltibl(, iii soda lye, ver.), cliffi- 11.0 cultl v solubic,. eveii i-ii the hot, iii iiiost of i@lie oi@,gaiiie It corresponcis to the prob,,,ible foi-iiiiila: ci- -NTI-r- -0 O-NH- 0 rf 1 2,@l 0 H CH3 Exo?ii,7)7e 24.3 I)ai-ts of allililiil)e-(,arbox3,llc .1 acid, , 11 parts of I part-

1,868)612 3 amino-pl-ienol, 6 parts of phosphortis trichloride and 500 parts of toluene are condensed as described aboi,e. The formed parahydroxy-anilide of 3-hydrox y-2'-methyl-diphenylamine-c,,trboxylic acid of the pro'bable formula: <D>-NH- -CO-NFE-<@::>-OH uH3 OH C, shows when crystallized fron-i xylene the melting point 230-@931 (uncorrected). Eyxa,n?,p7e 8 78 pirts of the soditim salt of 3-hydroxydipheni,la mine-car.boxylic acid and 46 parts of- pal@a-nitro-aniline are mixed with 750 parts of xylep-e ,tnd thei,, gradually ivith 20 parts of phosphorlis triel-iloride' The temper,tture is kept at 110' for soiiie hours. Thei-i the mass is reiidered alk-,tline mith sodasolution, the X3TIelle Is blown off by means of ste,tn'l and the reactioii product is puri-fied by dissolvin,- it in catistic soda lye and precipitatidgwithcarbonicacid. Thenewparanitro-aiiilide of 3-hydroxy-diphln3TIamiDecarboxylic acid of the probable foriiiula: <:D-NH-<@:>-CO-NH-<@@>-NO2 Oil cryst,illizes froin glacial acetic acid in 3,ellowish green needles melting at 211-212'. Exay2?,ple 9 76.3 parts of 3-hydroxy-diphenylaiiiinecarboxylic - Leid iiid 120 parts of thionylchloride are introduced into 1000 parts of 40 ligroiiie and the mixture is lieated to boiliiig tintil it is dissolved. Then the lio,,roine and the excess of thionyl-chloride are distilled off iii vactio. The residlie is mixed with 750 ,5 parts of toliiei-ie and 35.7 parts of orthotoliiidiiie iiid the mixtiire is boiled until the evol.ution of bydrochloric@ acid has ceased. The mass is inixed witli soda-solutioii iiiitil beinc, alkqliiie ai-id freed from tolueiie by t--, 50 steam. The re,,tctioii prodtict is purified as described above. It represents the orthotoli.iidicle of - 3-h,)Tdroxvdiplienylamine-carboxylic acid of the probable formula: NT]i 0 O-NH H ancl er3rstallizes from glacial acetic acid in leaflets melting at 185'. 60 F,xa,in,ple 10 305.5 parts of N-acetyl-3-h ydroxy-4'clilorodiphenylamiiie-c,trboxylic acicl., prep,,tred by longer boiling 3-liydroxy-4'-chloro65 diphenylaiii,"ne-carboxylic acicl witli an excess of acetic acid InhyOride, ap-d 138 parts of ineta-n itro-,tii;.I;.,-,e ,re iii@-,--o,-!Liced iiato 3000 parts of ortlio-dichlo ro-be-Tlze--@-ie. At 60-i'O' 60 parts o'L i)hosphoplis trichloricle are -,,radually dropped iii. Thp- P.-,@tss is maiii'L,,tilled at 1100 for soire hours, iiliixed Y,,ith aii excess of doiible-i,,oriiaal caustic pot,@sli-lye. Orthodichloro-beiizene is reiiioved b i.iitroy ducii-ig steani a-.id 'Uhe reiiia,'@iiin- filtered solutn uion is stturate,-L iiit,-i e,,t@.boii---c acid. Thereby mett-iiitro,),nilicle of 3"hy@,.rox@,-4'-eliloro-, diphenvl-am iiie-carboxylic teid precii)itates. It corresponds to the probable formtila: CI-C>-Nlll-<:D-IC O-NH-C> OH N02 It c,.ystallizes froii.-i oi-tllo-dichloro-beizeiie aid i-iielts -@t 203'. co Exa???@@v7e 11 ITI'LO t iiiix'LtTre o.@-263.5 parts of 3-hydroxy-i; teid, 4 chlovo - dil)heii-ilaii ite - carboX@Tlie 138 arts of 4-iiitrot,-iiline aiid. 11,00 parts of toliieiie, 60 I)-Irts of 1)laospho,,,tis trieliloride lire ara(iiiallIT i--Ei'uroclue-ld qt 6040'. Tiieil I M 4 teiiil)ei-ature is aiiitained at 110',for so,i,er,il liours LT-.itil tl-ie evolution of hydrochloric i,cid lias ce,@ised. The reaction mass is ren(lored ,tlkc-Lline b.)Tmeajas o-f soda,,tiid f e froii-i toltier@e by s"-ell1ii-I. The formed ,traiiitro-,inilicle of 3- hydroxy-4'-cl-iloro-d pheiiiTJam@,i@e-c,,trboxylic aci_d is ptiriflei as cleC." 0 scribedtl)ove. Iteorr-,spoiidstothe,prob,-ble -l'orn,itila: Cl<@D-NH C 0 -1\1 1-1- C2 - <@:7>- <: :>", I I io5 OH ,il(l iiielts wh@,ii reeryst,,tllized from o7cli-eblorobepzone at 229'. Exalnp7e 12 A ii-iixtiire of- 2C,@'.5 -@-,,lrts of 3-ji-,,C,troxv-41 C @"Cid 17,2.5 of 6-ch , lor -4-iiitto-,,inili,.,ie Iii@l 1500 L 0 pcirts of xi,-le7le is ti@c-alu-od C@O p@-,rts o-L' i-IospliorLis trieliloride ai-id the reiction iiiass - workecl up tsdescrib-,-d, i,,q ti).e for is egoing exan-iples. The or@'ho-chloro-pari-ii-Ltro-anilide of 3hydro@xy-4'-ehlorodi-p!ienylaiiiiiie-carbo-,,,-flic @-.-D acid th-Lis formed corresl)onds to ',-he probable f ormtila: ci-- -NH- C O-NH N02 OH It melts ivheii recrystallized froiii glaci-al II.Cetic acid or froiii pyridiii,-, et 240'. The folloiving table sliows the propei@ties