BE629421A - - Google Patents

Description

       

   <Desc / Clms Page number 1>
 
 EMI1.1
 



  Nuuvuoux coloring * 'tu 1%, Jr! 1) t \ 1oxulniquCJ ot lour rr3 o r tin.
 EMI1.2
 



  The present invention relates to new dyes belonging to the 9é * rio dloxt.lnlqu., Their method of preparation, their application the tol- t4àrlo .Ii 1 \ the pigmontation of InlUbro8 do any strong ot, as induatriola products, loq : Mti ". Ot pigmontdot shades, with cos dyes.



  Lu Jo ^: nndcrcs5o n found that one ofctlort s1u "1j \ 1'L'llul (r;" l'Jl'ltnhdlr) (IUlr, l'1ulI'l, hardlyllomont IlI1III, lclla said to be able to rr ,. tft 14 10 ai nn C '' '\ Ù "nlo, do,.'" n 1) .1 (1 known, a dinnilo uxi-ript do jroupo arido sulfoniqtào ot r4p.-ndptnt Iii! '.) rrrIIJ1Cl 1

 <Desc / Clms Page number 2>

 
 EMI2.1
 
 EMI2.2
 in which
 EMI2.3
 I \ r1 ot Ar2 each represent tin rosto aryle which can prtor on a position nrtho with respect to IJr "lIrO Nil un euhvtltunt r"! 'I \ ph "h \ 4I has a fttflmo d'hydrntjtno at (him pout onnloolr d' other substituting * uuole dna los 4olo- ronts as well as d "It 1) t.4rl ') cyclo. cn << ent4 <,
 EMI2.4
 ot
 EMI2.5
 X ropr <! Mnto lo group 5mlno prlmalro or a secondary Qmino grtiulie nu tortiairo, or the groupo -CR whose symbol R r> presents a route alirht1quQ. cycl11ph'tl1U.

   ara-liphatiquo or, rom1tiquo, to obtain a compound corresponding to fornulo II
 EMI2.6
 
 EMI2.7
 of which Itquolto Arlt and Ar ,,, 'r |> r4 each have lo roet.n erylno Cor- ru <poftdar) t rotpuctlvurr, have o \ rl ot 4 ADÀ if X at the significance Indicated b about 14 formula V, Par X one dôoiqno in promior place dos gruz pot which derive from amino corresponding 3 the formula III

 <Desc / Clms Page number 3>

 
 EMI3.1
 
 EMI3.2
 in which
 EMI3.3
 RI ropr4oonto the hydragbno, a group alkylo or cyclou alkylo tfvontuollnmont substituting a groupa
 EMI3.4
 aralkylo or an arylo group,
 EMI3.5
 R2 ropr6sonto hydrogen, a substituted alkylo or cycloalkylo 6vontuollemont group, or a
 EMI3.6
 aralkyl group ot
 EMI3.7
 RI ot R2 can also form together, with ltozoto amine an hdtdrocycliquot nucleus, as examples of tolloi aminos, ammonia is montionnora,

   alkylamino dos such as methyl-, 61, hyl-, propyl-, isopropyl-, n-, aoc.-, tert.-butyl-, octyl- or ddcylamino, hydruxy .. alkyl amines, such as p-hydroxySthyl- or > -hydroxy. propylamino, alkoxyalkylaminos, commo 0 -, i (thoxy- or -6thoxySthylamino, or x -mGthoxyprop yl-, T -Jthoxypropyl- or iÎ-ph6noxypropylamino, dos -d16thylomino-olkylominoA, cycloalkylaminos,
 EMI3.8
 commo la cyolohoxylamino, dos aralkylaminos, commo la
 EMI3.9
 bonzylamino, dos arylaminos, by oxomplo la phanylamino or uno mdthyl-, <! thym-, dim0thyl-, mthoxy-, thoxy-,
 EMI3.10
 fluoro-, chloro-, bromo-, dichloro-, dibromo-, nitro-, carbamoyl- or dialkylamino-phnylamino, 1- or 2.

   
 EMI3.11
 naphthylamino, omlnopyrbnc or amino-anthracèno, on outro dos dialkyl-, dicycloalkyl- and dieralkyleminose for example dimJthyl-, dithyl-, dipropyl-, dibutyl-t di '- (- hydtnxy <ïthyl) -, dicyclohoxyl- f d1bonzyl- ot: N-mJthyl-N - hydl'Oxy4thyll \ ", 1no, N-alkyl back .... 'V ......: yclo-

 <Desc / Clms Page number 4>

 
 EMI4.1
 has 4 m # ikylûminos, such as N-methyl-N-cyclohoxylam1nc, dos N-41I <yl..N-orUkylm1nc9f as N-methylmyl-I.

   bonzylamino or dose 1-olkyl-N- * rylamincoo like N-ITIISthyl-N-phJnyl-omlno or N.Sttyltl-phûnyl-amino, or due to cyclic amines, coinmo pyrrolidino, lo pipdridinu nu la ml ' ) rphnl1not Lou dl'1xoxinoQ do formula II in losquollon X ddrivo do l'ommonia-
 EMI4.2
 /or/
 EMI4.3
 quo or uno alkylamino lnfrlour 7d'uno ph 5nylamino vauollomont portouso orbatituents on the nucleus have a particularly low solubility and are, for reason, preferred dioxaz1nos.



  When R, in the group -OR, ropruson-
 EMI4.4
 to an aliphatic rosto, it is before the beginning of a
 EMI4.5
 annuity alkylo inforiour, by oxomplo of the multhyla remainder,
 EMI4.6
 dthylo, propylo, isopropylo, n-, soc.L or tort.-butylo,
 EMI4.7
 but R can also roprisontar a rosto alkylo moyon to higher, like the remainder octylo, dcylo, dodcylo, tJtrodÓcylo, hux, 2decylo or octd6cylo.

   R pout egalomont Otro a hydroxyalkylo route, for example lo rest 2-hydroxythylo or lo rooto 3-hydraxypropylOt When
 EMI4.8
 is a cycloaliphatic rooto, R oot for example lo
 EMI4.9
 rooto cyclohoxylo. if it d <3aigno an oraliph5tiquo residue it is for example the bonzyle residue or a rosto methyl- or chlorobonzylo 1 as aromatic residues symboliode by Ri we can consider above all the phSnylo remainder as well as the rosto 2-, 3- or 4-mGthylphSnylo or lo rent 2-, 3- or 4-chlorophJny 10.



  Los rectos aryles Ar, ot Ar2, in formula I, belong to the oJrl0 bonzuniquo or to the 8Jr10 naphthiliniquo, less to the l..1rl0 bonzûni-

 <Desc / Clms Page number 5>

 
 EMI5.1
 quo Ilvi pwvunt dtru 1d (ntl'1UIJ or difwrunto one of the l0nttv 1 Il 'I! it Q'Il) nU'loUX qv ,: 1' d.rux ruettA 0rylu '\. ') iunt, J, td1t 1' f'I ')' 1 .r ;, mio ') ut' J t1 tU "Jn h rumplblae, cutting, un * rj'tr, p, 1 tl" 'n '. ortho por report au groups NU, Ar ot l \ r2 cW ienncnt par oxcl "1plo un croups ûlhor, un <3nuro thll) Jthr ou lo groupe hyrlroxyloo Cirro groupas' thora on p-itit onvh7or (YU'PxQ1'TIplo doe gDUpu * 0lcrxy, cycl (i 1c; 'Jxy, orIw, xy or i> ryloxv, on ... all d <J3 yr "upo 0lc, xy infri.; Ur9, cnvno 1" "group rn-hh) XY. Vth , xy, pipo: <7, h (, prr: oxy or n-, soce- or tort # -butryy, u don 1r) U orylcxy, comtnj ier Qxomple lo <JI ') Uf (1 r, nJnf, I ( ', r.Sthylpt; noxy or chlorophûnoxy.



  ! s other-is s.tntituinta Gvontuoln. uiuole d5nx rioo c'11 <.rfJnt .., which pruv4Jnt you find on Ar, ut r2 (or 4 \ rlt and Ar, 1) 3Tit psr OXGr1plo du5 groupe5 aliphatiquoi, cyç: lu 11 ph:) t.1ruv oroliphotiquû or ram't1quo ', else'. rjr 'UPQ uthura compo lo% grnupoa alcoxy, hydrxyolc "', xy, ir3l (; oxy u arylxy, dos fJrr:; Uf'108 thl" 'thor3, c rzrs, pr <.xor1plo loh .7rupr.sl: cy1thlù or arylthlo, on 'utrfl dosa hil) (jénosp lo gnupo nitro, cy0no or tr1flu ::: rt'tITAthyl11, lo gnupo amino prlm: 11ro, doo yfrUt "lo ;. carLomylos ut sul (..1Y 10 ..

   Jvùntuollomont suGrtitu3o ur l'0ztu, du% Jt., Uj1I'S entoro d'HI-1Q C: Hb ') xyl1ftuO, usters uy l1u,:,: rcid4 f ulfmlquof alkyl iulf .nylea, 3ryl, ulfonyljsp yl' .- :. jt acylon: r ,, * 3tylu "both taken here or more nrjo ot r! .n1- granting by oxonplo a ru **: corbacylo, un rosto de mono- ur, tvr of c2cL acid, ntqu * l un rosto carbmylo, thio- crt'2iT ..,. loJ) u '.3.trbzlr.ylù, m'lis de pr> Jfvronco un rcetu carbocylqo Cmno., "t'4rccyclon c') nrICMj,, \ r1 Qt Ace (uu ..ri 'ot -' 'r') c, ntion> sor.t by oxomplo a 1nid nucleus) 10.

 <Desc / Clms Page number 6>

 
 EMI6.1
 



  C "ltlrv f)) (1Jrlplo ,: do fretes carbacy! O9 on" w "U '' 'not'O do? Roatua d" <: hlvllhorb .., j (ylif1IJ (1'4ltjt \ tr4Iu n,' n tt \\ 1 f \ '1), m \ n .'- t'lU 1 "ly-h'.tmoc, aliyhatlquvn, cycln ..



  11ph ') Uqu (' ,,, rl1rhH1quo'l1u.: 1f Im, l1qu {'Ú, for example do routes do fornic acid do acStiquu acid, do acido pr'rl "' n1Ctuo , butyric acid, rio acid cyd / "\ holCyl-c2rb) .yl1qUQ, rio acid ph înyl IJJt1quo or aciefo bonzol'cluo. nus griupoo rt'r \ oQ! 1t.ur, do ocldo cor- nique, which can Ctro by (jxonpio dos c'natituantt of the group Ocylo and of the grsupo 'Yl'm'no, are los çjr-> upoi r .xSth xycarb, nylo or t :, xycarbcnylo, cycJohuxylxycorb groups, nylon, doR gr, ulx> a hon: "the" IC '". c7rbc, nyloo or doa groups phJn.') (ycDrtJ.1nylùG.



  Dos cxonploi do rc..tot1 torbom.yle or th1,) corbQf1 \ o'yloa a.nt loo groupos h-mlttlyl-, N-thyl ", 1-l, r ,, i, yl N-butyl-, N -cycihcxyl-, M-bcnzyl- -îu u-phJnylcarum, yl "9 nu ..th1or.rboyto.



  Dos ûxcniplot do routes 1,3.'Striazinylos oont loo rootos 4 * 6-bl9 "phunyl-f '1t6-Hfl phwnylaninc-f 4t6-ble- (2'- or 4'-cmorophônyl3nim) - or 4.6-bi6- mr > rrh011M-1, 3,9-triaziny '.- (2), Doo clrsr, t rUi) xozlniquc .. c nfiraco 1 the invention that one appreciates more rt1cullr (': -: on- '; are coux in which X ropréionto un (Jr JUP (:) lcl) xy 1nf, r1úur ot above all a cjrF0 art; ino, a groupo alkyl- amlno infcrlour or a group aryla, nlno.

   Let’s say the case where X is a lower alkoxy oreurc, the '. col-ranti ort do trh b, our propriutiîs tlnct'-rialos especially when loura roat <fs Ar. ' ot, \ t2: are to, toli phiînylbnoû which

 <Desc / Clms Page number 7>

 we position para with respect to the nitrogen atom of
 EMI7.1
 Axtziniquoe ring do not bear a substituent or bear a lower cicanoylamino, aroylamino or lower alkoxy-carbonyl group which, in the para position relative to the oxygen atom, are devoid of a substituent or carry a chlorine atom or a group
 EMI7.2
 alkt, lq6u lower alkoxy.



   The dinnilos of formula 1 which can be used as starting material in the present process are obtained, for example, by reaction of diamido or
 EMI7.3
 of a 2,5-bis-halo-1 4-bonzoquinono- 3,6-dicarboxyliquo acid dioator with the aminos Ar1-NH2 ot Ar-NH, for example in a lower alcohol, such as methanol.

   
 EMI7.4
 or ethonol # optionally there is an acid neutralizing agent, such as an alkali hydroxide, for example sodium hydroxide, oxides or hydroxydos of alkaline-torrous metals, for example magnesium oxide, an alkali carbonate, a alkaline soil of an inferior coarse acid, by oxomplo sodium acetate, or tortarian bases, such as, for example, pyridino.
 EMI7.5
 



  The diamidos of 2,5-bis-halo 1 4-bonzoquino-3-dicarboxylic acids are new compounds. We obtain them by oxemplo from dos diostors of 2,5-bis-halogno-1, 4..dialcor.y-bonzèno-3.6-dicarboxyliquaa known by saponification of the dioster on diorboxylic acid, transformation of last co its diamido,
 EMI7.6
 then d6slkylation of the dialkoxy compound dihydroxy compound ot oxidation of codornior on quinone.



   As for the 2,5-bis- acid diootors
 EMI7.7
 halooono-1t4-bonzoquinono-3t6-dicarboxyliquos are

 <Desc / Clms Page number 8>

 
 EMI8.1
 prepared by known methods, for example by treating a dietter of 2.ihydroxy-tdrdphtftllquo 4cido with chloro or bromo, 4vontuollo, Mnt in an organic solvent, or by causing chloro or bromine vapor to act with a diostor auccinylo-oucciniquo ot then oxidizing for example with nitric acid, optionally proonco an organic solvent.



   He recommended to isolor los dianiles
 EMI8.2
 of formula I thus prepared before the convorting of dioxazin compounds of formula II. However
 EMI8.3
 it is possible, in many cases, to transform the substances used for their preparation even without isolating cos dianilos, directly into dioxaziniquos dyes of formula II.



   The condensation of compounds of formula
 EMI8.4
 I on dyes din; caziniquos do formula II is done in inortos organic solvents, dvontuollomont the presence of acids or do compounds releasing acid dos,
 EMI8.5
 if necessary, oxidizing agents are pronounced, heated. back organic solvents inortos appro-
 EMI8.6
 pries are by oxomplo dos aromatic hydrocarbons optionally halogenated, oppartoriant d: rie bon- zdniquo or nophtoldnique, for example xylènos, loc di- ot tri-chlorobonzbnos, naphthaline or cliloronaphtholbnes, dos alcohols ot their ostors, as for example lldenos , proponol, butanol, ethy'- I6no-01ycol, as well as acetates, bonzoatos or phthalatoa,

 <Desc / Clms Page number 9>

 
 EMI9.1
 As acids suitable by oxomplo
 EMI9.2
 acidos ;; "lj <:. i. '::

  1 concentrated minerals, such as sulfuric acid or polyphosphoric acid, as well as strong organic acids; ,, such as dl- or tri-halog6.o-ac6tlquos acids.



  Don examples of compounds releasing back #cidot are one particular ion helogenurae of 4cido4 carboxyliquot or fâulf-3ririuot, compo the chloruro do bonzoylo, the chlorurut of rndthyl- or chloro-bonzoylo, the chloride of the acid btnz4nQ- or -m6thylbvntna- sulfoniquo, chlorides of acidoa, like lo chloruro do thlonylo or lo pqntoçhliruru do phosphorus, ot dgalo mont dou chloride rr '&U1l1qu'J!;, t CO! MO lo aluminum chloride, chloruro do for or 1Q chloride of zinc.



  Loe chlorides m /, tal11quQ, are then applied will 4- QQu \ 'imont a pr6eunca of the bottom'. Has 32ot '<?% "Ri. Ijl'lJrJ, c" r: -. the at pyrid1no.



  Cornu ï'i '.- tW * of appropriate oxidation *} 1 one montionnern by oxomplo the oxygen of the oit as well as dos cortpno3s nltr6s tot1qlJs, not3rr, have lu nitro- bonzbno u the nlttobnzno-3ul acid (onlquo .



  The choice of media for the condensation conditions is made according to the offset body used.



  Clo% t thus, for example, the dianiloa law do formula I in which Ar, ot 1r2 each tontionnont, one position ortho I) ir relative to the roupo tlH, a 4ttivr combo substituting group, are heated tu% v2nt3geuse-Qnt in a ndlango constituted
 EMI9.3
 an organic solvent inorto ot an agent releasing a

 <Desc / Clms Page number 10>

 
 EMI10.1
 acid # to de tompJroturcs do here at 300 * Ct do preforenco do 140 20 <y * Ct When using dianilue do formula I containing acylamino groups and a dih3loydnur'o acido OI'1 '} " lnlquo coruno agent release an acid, it should not be forgotten that it is produced under a ctcnnQa of * acyloi rumps and the ocylo4 groupos do l'Qcy13mlnoqu1nono do formulo 1 ot caux do llhloo, 1nuN of acido are not idantiqtioso Lo4 dionilos do formula 1 in losquol4 Ar,

   and AD2 rupr6e each have a 4-ocylamino - phonylo meteo containing a Zthor group in po4ltion4 2 and 9, can Ctro condane3 already cold with the formation of dioxozinu corruspondanto, dîna due acidot, in particular mont in closed acid * n) (Y9Jn. minerals concontrS :, as the acid sul (uriquc. In the heart of this condensation loo grouros acylaMino are (r4Qu8mnent saponifias en grourue minot Il o% t duilorent poe siblo do tr:

  ! nlltOr1liOt 00 dianiloef by heating in solvents of "1nlquo. 1 invrtos, .n other additives, one dioxazinic compounds of formula 11. f The di3nils of formula 1 in lusquole Ar, and the ropz are each an aromatic stream
 EMI10.2
 carrier of a hydroxylo group on ortho position by
 EMI10.3
 report or groupo tA !, can our condontot on horn put dioxaziniquos of formula II to the care of an organic solvent / by oxonplo in lldth3nol or 113cido 2cu'tiquo
 EMI10.4
 
 EMI10.5
 glacial, d4j à clos tonpôraturc-a rol-àtivirent bjetote Dianiloa law of formula 1 in which Ar, ot Ar2 ropN are each an aromatic restl, containing an atom of nycH, '. orltno in position ortho by

 <Desc / Clms Page number 11>

 
 EMI11.1
 compared to the NH group, are advantageously condonode in an organic solvent,

   we presume from an agent
 EMI11.2
 oxidation ot evontuollomont of an agent releasing an acid @
A variant of the present proceeds from
 EMI11.3
 preparation of coloranloK8zinlquoonllto saponifior on acido dicarboxyliquo corresponding to a compound corresponding to the following formula IV
 EMI11.4
 in which
 EMI11.5
 Ar, 'ot Ar2l roprd are each an arylene roste which may carry a substituent * ij8uole in dye lot * and contain do h4 tdl'oQ) 18 five ootniunudo, CL R roprdaonto un roato eliphatiquo, CycloDl1 ", hot.1quo, 1araliphitiquo or aromatic , a tranformor eo diacido on chloruro or acid bromide / dicarboxy1j.c "make roagir co last 3voc the ammoniaquo or an ominu prinniro or socondairg or an alcohol aliphatiquot cycloaliphotiquo,

   3raliph3tiquo or aromatic
The starting body do formula IV corresponding to the composas do formulo II conformoa to
 EMI11.6
 the invention in lusquels X ddoigno lo groupo .on, ot they can therefore be prepared by the first proceeds conformo to the invontion.

 <Desc / Clms Page number 12>

 
 EMI12.1
 



  OQ9 examples of primary 3minos. or cocond3iren which can be used according to the invention have been given, including the comments rol3tifs to X. The saponification (see above) of the dloxozinc-9.1o- dicarboxyliquo acid ostor of formula IV on dicarboxyliquo acid
 EMI12.2
 The transformation of the dicarboxylic acid or its chloro-ruro or bromide is carried out in 70-95% sulfuric acid and the conversion of dicarboxylic acid co-dornior on amido of formula II is carried out by known methods.



   Los compounds dioxaziniquos do formulo II conforming to the invontion are obtained in back rondomonts
 EMI12.3
 lov8. In general they are already crystallized in the hot mdlango r <3actionnol, almost completely in a very pure formo. They are pr <2are los propridt68 closed charac- teristics ooloranto dloQ1nlquoa, pr olcamplu uno unulour 1J1 (J \ JfJ # * # - an IJf> l.uHl1n It'Jt111 i'toi'tu aulfuriqun onn'j "nt '! '! nl') t IIIdtl Ut "" 1 du nt! 18 Tr'1UIC ('11 ". isolated by filtration and purified by washing the precipitate in organic solvents and bases or aqueous acids.



   Loo dyes dioxaziniquoa hardly soluble in organic solvents are used as pigmontairos dyes. At the end of the cotto they put
 EMI12.4
 advantageouromont under uno formo finomont di8porso ot, for cola, ilo are dissolved by oxqmplu in an acido ot roprdcipitdo under a formo finomont divided by dilution dos solutions with water. Common solvents can be considered for example sulfuric acid, back acid
 EMI12.5
 sulfoniquos or aliphatic or aromatic carboxylic acids.

   The state of fine, - division. pout also

 <Desc / Clms Page number 13>

 
 EMI13.1
 be obtained by grinding, advantageously in the presence of auxiliary * do grinding roof quo back soil # minerals or orpeniquoe tueceptible to be again eliminated by back tolvontig and 4vontuollement in proaence of themiliairu 'due to grinding uppl <ïmcntairo9j COMno dot solvent% organic , dot acidos or dot basais It is possible to use a solid or liquid organic solvent in the arrblantq tcmperpturo.

   The colors * pigmuntoiroà isolated from the roctionnol mixture ot tGch6i are for example crushed ovoc of calcium chloride d: vt, ydr0t6 or with naked sodium sulphoto from
 EMI13.2
 
 EMI13.3
 sodium chloride, on yr, Ssanco of hydrocarbons elinh4 tiquoi or aramatiquoa, dvuntuolloment chlorinated and / or nitnîtt conro cyclolb-ix3no, lo @ bonzbne, toluenep lo naphtholbnup lo = no-, di- or trirbcrn.fna, le .4tr * - chlor4thano or nitrnbonzènop do cdtonos 3liphltiluos oxeriple lnr-irivuros, corro pir / if-tc4tonot or Mno3lcools 4lipti3tiqtàa, lower t *), pir oitonplo lo tTor7? * Fyth-nol or lt'thoxxy ou'th compos, '$ agotiop eonwo dim'thyl- or l4thyl-anilino, 14 quinoi'ino or dimthyltorimmidot In bion dei ton we can also% riliorûr 1-irs plgmunta by grinding with organic solvents, suuls without addition of the solo .



  After the troyila we eliminate the * ouxiliiroo s 1 * s sole min4ràux are by cxonplo dissolved 13ne water and batch
 EMI13.4
 
 EMI13.5
 orginiquüo auxiliaries are # ïvontuollonont chaso'e by distillation or by cntroinomont the water vaporf Cn thus obtained due piclnontm finamont disporave, twinte rouo, orarogce bordooux, blouo
 EMI13.6
 or violet, which have purity and tinctorial power:

 <Desc / Clms Page number 14>

 
 EMI14.1
 romerquablos and which will penetrate a texture more
 EMI14.2
 mowing on comparison of raw product *.

   They have
 EMI14.3
 usable for the spraying of rubber, lacquer, oxamplo do vornis3antl, ot plastic material, as well as polyvinyl chloride, They are very suitable for the preparation of impro colors, lon for improv. .Tlon paper as usual for tolnturo including viscose-based roatilrct matto and celluloute Lot lmprQI1on. produced with these dyes you are told by a great intunity of the tinting as well as by the good properties of solidity to solvents 10 overginturo, to the aeration and to the chlorine. The following examples illustrating the requesting invention without any limitation being
 EMI14.4
 scope.

   Unless otherwise indicated, the parts * including
 EMI14.5
 it is question in cos exumplai uluntundont a weight4o
 EMI14.6
 
 EMI14.7
 maintains at 1.2 tOmrQtUro a'Qouim- tion for 2 hours with stirring, 12 pàrtios do 1-, mino, 9dfûthoxy-4-bonzoylmlnobezino, 10.8 part of dianilidc do Ilieidu 2.5..dibromo-t, 4-bonzoquinono- 3.6-dicarboxyliquo ot 5, "> part of acutato of sodium crist3llisj in 300 part of 3thanol # One tdp3re by hot filtration 10 p-Scipit3 * lare forffti, it is washed

 <Desc / Clms Page number 15>

 
 EMI15.1
 avocado of 13thanol in 4oc of water and it is dried * Ch obtains 15.7 parts of a dianilù of violet brown color which melts at 258 C.



   To transform the dioxazin compound lo dianilo is heated in 200 parts of dichlorobonzèno with 10 parts of benzoylo chloride,
 EMI15.2
 for 1 hour, at 17O-175 C. Lo pigment formed is then separated: by hot filtration, washed with do 1o-dichlorobenzno do 16thanol and water, ot .4chJ.



  Twelve parts of a crystalline product are obtained which has a green metallic luster and which dissolves in concentrated sulfuric acid with a cloudy color. To obtain a fine division it is ground with sodium chloride and calcium chloride. announces a potito quantity of the petroleum fraction
 EMI15.3
 boiling at 180-2200C.

   After removing the sol and the solvent, a violet pigment is obtained which has a large
 EMI15.4
 tinctorial power and good properties of fastness to light, heat, b surge and migration *
 EMI15.5
 The 2.5-! Librnmo-t .4-bonzoquinone.3.6-ciicarboxylic acid dianilido used is an orange-brown compound which is insoluble in common organic solvents and which decomposes at 255 c.

   Cn the
 EMI15.6
 prepared from the diostor gthyliquo of the aid 2 / known / dibromo-1.4-dimethoxybonzno3.6-dicarboxylic acid passing through dicarboxyliquo acid (F. 265 Cîr dicarbnxyliquo acid dichloride (F - 136 C), the di - anilide (melting point not at 316 C), demethylating with aluminum chloride to obtain the dihydroxylic compound (frittago at 260 C) and then oxidizing the latter to obtain quinono corrospon.

 <Desc / Clms Page number 16>

 
 EMI16.1
 



  Oh obtains dos pigmenta douvs! O proper analogues here one temploco, in this oxomplo, = los 12 parts c'e 1-dmino.5-dithoxy.l-benx0yl- 8 '! Iino-bontè'1o by 13 parts cic. t..Gm1no-2 .ithoxy ..



  -4 - ', 41-chlorobonzoylariino) -bonzèno or by 12.6 parts of 1-3mlno-ô 5-c! Iôthoxy-4- (4' -mwthylbon2oylamlno) -
 EMI16.2
 bonzno. EXAMPLE?' .
 EMI16.3
 
 EMI16.4
 We molntlont, the tontpfaturo of the reflux
 EMI16.5
 for 1 hour, with stirring, 6.1 parts of 1-ami-
 EMI16.6
 n0-2.4-dl- (2'-mdthylphJnoxy) -bonzr.o. 3.5 parts of 2,5-dibrcmo-1,4-bonfcoquinono-3 6 dicorboxyliquo acid diamido and 0.4 part of magnesium oxide in 100 parts of 4t $ iibnol. an separates by f iltration !! hot the dianilo forms, of tinted btun rougo p41o, it is washed with lthonol ot with water, ot it is dried.
 EMI16.7
 Cyclication leading to compound
 EMI16.8
 dioxoziniquo 09t offactuo thormiquomont 1 for cola we heat the dianilo donated 100 parts of chloron4phthalene laying 30 minutes h 220â.

   230 C, A red bordoaux violot solution is formed in loquolle the dioxaainiquo criétalliso compoed at the same time all in the form of fine needle syrup On lo e5paro pir ocoor3go a zou, we wash it with othor monoethyliquo of 1'4thY- lèmo-glycol ot a mGlangu, in the volume report

 <Desc / Clms Page number 17>

 
 EMI17.1
 9 i 1, dfdthor mono6thyliqua do l'3ethyleno-glycol ot d'uno losiivo do ebudo caustiquo normal, until Co râ that the otücoylo colorless filtrate to finish on'4 "1'1'1 lo'lavo oncoro with diluted acetic acid and water ot on lo tcho.



  After grinding cor.-ine c. '' Written 'with oxonfpio 011 obtiont a pigment cic tointo vivo, ratrgo brown, t which has an excellent solidity to the lumibro, to the phalcur, to the migration and to the surtointuro. In the tabloou 1 cl-Dossouo we have fndiqued dèaxozinos analogous * do tointo viVo t the .colonno A contains the substitute ¯ #; it dolon formula II, coloino B indicated the color
 EMI17.2
 This solution of the dioxazinic compound in the concentrated sulfuriauo acid and the clonno C indicates the color
 EMI17.3
 of the solution of the composa dioxaziniquo (lins lo chlorē nahtaibno boiling.
 EMI17.4
 

 <Desc / Clms Page number 18>

 
 EMI18.1
 T A B L E A U T
 EMI18.2
 NO Substitute X according to.

   Color of the Color of the sol- 13 formula Et A solution in lution in sulphu- cliloronaphtholene acid
 EMI18.3
 
<tb> riquo <SEP> concentrate <SEP> boiling <SEP> C
<tb>
 
 EMI18.4
 : # 7 * $ ffî 1 ... rMCH3. Burgundy blue, m -NH-CH2 CH3 burgundy blue 3 -rll CH2 -Çy burgundy blue 4 "'Z'-CH2 -.C1 burgundy blue, ..tr'HCI -i2 -y) blue ny bordeaux, - '#.' "6 ci blue bordeaux 7 -tû .... II ..1 blue .. bordeaux '-. & f CH 8 -tJfi - CIi3' blue green purple pulling '
 EMI18.5
 
<tb> on <SEP> the red <SEP>
<tb>
 
 EMI18.6
 9 -N 2..C; f (0'2 bordeaux blue Vhj-CIY
 EMI18.7
 
<tb>
<tb>
 
 EMI18.8
 10 -N 0 bordeaux blue Ci? - "'' 2 / CH2'CH2 bordeaux blue r \ H2 1 bordeaux blue" 1 .2

 <Desc / Clms Page number 19>

 
 EMI19.1
 T A ,, (. A U. 1 ("" 1 t,
 EMI19.2
 lie 'Suh'- t 1 tu ,, -. t -Y -in 1) 1I1, 'If of Color d. the 50 ..



  In f 0 ri "': U 1 Q II A! J 0 1.; T1 (' \ r; \ <1 n lotion Han3 lo l'nrj'1c 'iul:' u- cli Io ror ai> -i ta 1, no r) quc: -nr, C ,, w,! Re bouiln't ¯¯¯¯¯¯¯¯ B 12 "; 11-10 t! C ';? blue vurt red pulling
 EMI19.3
 
<tb> on <SEP> the brown <SEP>
<tb>
 
 EMI19.4
 13 Wfj'- Ci3 blou v, rt rojt) o pulling
 EMI19.5
 
<tb> on <SEP> the brown <SEP>
<tb>
 
 EMI19.6
 i 1 "ij blou vrt violot tirant 00 5ur 1 TOU'JO 15 - Nli .. Cfl2 .... Cll3 bordeaux blue 1 6 .. Nf! .. Ol.2..p blue border
 EMI19.7
 
<tb> CI <SEP> It <SEP>
<tb>
 
 EMI19.8
 1 7 N y.! . eu wn j ,, bordeaux cil 18 .. N ¯ ("1 blou rouelo has 19 ..

   N ¯0 blue T \ j "U (', I i ,, -C'j 12 -Cf LJ -O! I

 <Desc / Clms Page number 20>

 
 EMI20.1
 Cl obtains the dyes di 'xozinl-1'.Jo, proccd, lentg an making rtS - "' Jlr 14s di.1i'c! I,! Taci!,: 2.5-! Ibr) 1: 1 -1 ..; -bc Il r) q U 1 n,) no- 3. 6-d 1 ..; 8 rb /) X y 11 '11.; 1) C'J r- rQ 'p' mu8ots with lo 1 -amim-2 .- (i.! - ('- <' '. thYiph << nox' /) - bonzno ol7n lo nras6: describes the Qx0mpl 1. These qUinonQs are obtained from the ustur c: i6thyid, urJ to acid 2, 'S..llbrorm-1, 1-! i ^ rCthxyblnz? nu-3,6.-li-. carboxyliquo solon lo prr) çéd6 described in ilexomplo 1.



  All of these products are yellowish to brown in color and they are hardly soluble in the usual barley solvents. EXAMPLE 3;
 EMI20.2
 
 EMI20.3
 We condonoo 11.1 portion of '-amino- 2.h diphenoxy-bonrna ot 10.1 partios of dianilido c1o 2.5-rlibrmo-1.-bonzoquinono-3,6-icorboxyliquo as indicated in oxomplo 2, to get lo composa dinnilo and start from co dorniort we prepare lo composa 1! i: (Q7.! nlquQ by cycli (.1tion.

   We thus obtain 9.5 partio3 of dye in fine form @ dark red needles, the analysis of which agrees exactly with the
 EMI20.4
 The finnulc illculated CI \ 4H..2sN'106 'By grinding we prescribe mineral soils, such as chloride, calcium, we obtain a pigment of lively color, red bordeaux,
 EMI20.5
 who o uno great solidity? light, migration, aurtointuro and heat.

 <Desc / Clms Page number 21>

 
 EMI21.1
 



  T) in '; . tt; 1 :, ') \ J 1 r': 1 "'4J' \ 'f' JI? N rseeufiblG! <" # Pi |> rt '.' #,! ... 'i il1. "N,'. 'iu, i JII'J "Î 1' ni U- ') tf.' ;. t. '<-' 'V' ''" "') 1" 1., "1"' 1 \ 11 ". #hfliU lu pr l./'I, ,, ', r1' -) r. He'!. , .1 .t ... 1.12 t 1 r.n 1 int! TrlJ'1 1 # Jur.-iHt j3tt 'i..lr1 -u 7IH ""' J -'u 'H') nl1g utilln. ' t 15, .. 1 u. "'1': nu .." t ') ¯-jt .., r lU'! 1 ') r.11'j, 11': ', 1 rr =: 3, , r, ti U ". la c'jl.; 'jr! o la." .1IJt1 n rat (: ', 1' nr.t., t r.s4i ^ d; .w: = ¯rrj .J "" 1 '') 1 '! 1' .'Jlr; ri'l'J cr, c: 4r, tr '"t 1'): 1 rrv # 1r.: l'j '; :) 1'1 rs-iura'" # un-: r "'Jll1f1 #! #': 1y rur -j # '.; 1 l' / V1 "'/ IJ stn' 'f1' la" '1 "', 7lnr 1,1: ri fer, * 'j Il'). 1 fi i 'I).'].

 <Desc / Clms Page number 22>

 
 EMI22.1
 



  T ri 1, t '(I, 1 1 il
 EMI22.2
 11 .. 1q! ... . #,. roVr eT .... yn. ¯ w pr "1 .. n t .-. T., .. t ..



  , ttl 1! 'nr a ltr' jf lym .. :: 1: '; iw ,! : Iy le si bl, eu "D \ J ..) run fun blrtu wheel:. [[[Rj ... www, 2r.r." I br.r.fe cl ... Yr 16., i! shot a 3, j -o- ci lw r0Ui's) t 1 1, -4 :, tn'Ir! .. # 1 '^ ..a .. (:., Cl brown Joua. M..u # .. , - # Iro'vle tlr.ir-.t jur Ocl roH ton G1 cli, ir .1 .., # ,, ..., r <!.: Oci

 <Desc / Clms Page number 23>

 
 EMI23.1
 y T-6 MLEAU Il (Continued)
 EMI23.2
 ? 1 Grouo NII-Ar1 Color of Color of Color "ans a3lon tor- dianil the solution uno leaf
 EMI23.3
 
<tb> in <SEP> acid <SEP> of <SEP> choride
<tb>
<tb> sulfuric <SEP> from <SEP> pcly-
<tb>
<tb> concentrate <SEP> vinyl
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> NH <SEP> OCH,

   <SEP> blue <SEP> purple <SEP> blue <SEP> purple
<tb>
<tb>
<tb> CCH3
<tb>
 
 EMI23.4
 0 -lH OC -} {5 dark brown blue violet
 EMI23.5
 
<tb>. will go <SEP> on
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 2 <SEP> 5 <SEP> the red <SEP>
<tb>
 
 EMI23.6
 coliti
 EMI23.7
 
<tb> 9 <SEP> -NH # <SEP> CI <SEP> brown <SEP> blue <SEP> red
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> deep
<tb>
<tb>
<tb> ci
<tb>
 
 EMI23.8
 COtNH- <ci .N4 .. 9 Mi.Q Ci r'.U1 blue red 0 - / ¯ \ deep pulling on o -0 lo bl: u CONH-Ç% ch3 1 -wH CH3 brown 1.1 gold ", rougo f 0 3 pref * n pulling on -0 '. blue.



  -N: i-r- <. CONH - Q- 01 brown blue i? -'0 brown blue round
 EMI23.9
 
<tb> O <SEP> deep
<tb>
 

 <Desc / Clms Page number 24>

 
 EMI24.1
 A 9 L E A U II (Continued)
 EMI24.2
 N Group NM..w% rl Color of Color of Color in according to Eozr '. cfz: flo the solution one sheet
 EMI24.3
 
<tb> mule <SEP> in <SEP> acid <SEP> of <SEP> chloride
<tb>
<tb>
<tb> sulfuric <SEP> from <SEP> poly-
<tb>
<tb>
<tb> concentrate <SEP> vinyl
<tb>
 
 EMI24.4
 IE
 EMI24.5
 
<tb>
<tb>
 
 EMI24.6
 cOrrH.

   C: a3
 EMI24.7
 
<tb> -NH¯ <SEP> brown <SEP> blue <SEP> red
<tb> deep
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 14 <SEP> -NH- @ <SEP> brown <SEP> blou <SEP> purple
<tb> deep <SEP> pulling <SEP> on
<tb> 0- @ <SEP> the red <SEP>
<tb>
<tb>
<tb>
 
 EMI24.8
 S02CH3 15 -wh-O ..,
 EMI24.9
 
<tb> brown <SEP> purple <SEP> orange
<tb>
<tb>
<tb> red
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 16 <SEP> -NH- @ <SEP> brown <SEP> purple <SEP> orange
<tb>
<tb>
<tb>
<tb> o- <SEP> red
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Ci
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 0 <SEP> @ <SEP> brown <SEP> blue <SEP> red
<tb>
 
 EMI24.10
 N # 'troubled day

 <Desc / Clms Page number 25>

 
 EMI25.1
 TA BLE A¯U II (S-ui te 1 @
 EMI25.2
 N6 (iroupe? H.1r Color of Color of Color donations colon f0r "dianile 18 solution one

  leaf
 EMI25.3
 
<tb> mule <SEP> i <SEP> in <SEP> acid <SEP> do <SEP> chloride
<tb>
<tb>
<tb> sulfuriquo <SEP> from <SEP> poly-
<tb>
<tb> concentrate <SEP> vinyl
<tb>
 
 EMI25.4
 18 '' P 'red blue strand
 EMI25.5
 
<tb> dark
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> CH3
<tb>
<tb>
<tb> 19-NH - # - S- # <SEP> bran <SEP> viotet <SEP> voiolot
<tb>
<tb> trouble
<tb>
 
 EMI25.6
 :

  - <D 90-
 EMI25.7
 
<tb> 20 <SEP> -NH- # <SEP> brown <SEP> blue <SEP> red
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> @ <SEP> bend <SEP> pulling
<tb>
<tb>
<tb>
<tb>
<tb> 0 @ <SEP> on <SEP> on
<tb>
<tb>
<tb>
<tb> red
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> CO-
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 21 <SEP> -NH - # - 0- = <SEP> brown <SEP> blue <SEP> red <SEP> pulling
<tb>
 
 EMI25.8
 P-110 shot, -. Nt on blou 0- <D on K - ci vort C0 ir. ("'22' W 1" "- .. (T 0CO brown blue red tirîrt
 EMI25.9
 
<tb> 0 <SEP> @ <SEP> on <SEP> the blue <SEP>
<tb>
 

 <Desc / Clms Page number 26>

 
 EMI26.1
 EXAMPLE 4
 EMI26.2
 
 EMI26.3
 heated to 220-wj, with stirring, 16.6 parts.! 0 1-¯rino - phnoxy-r1-bcrnzeylamin-chlorobcnzna, 8.3 parts of 2.5-ciohloro-1.4..benzoquinono- acid dianilido ab-c.lictrboxylituo ot 8,

  2 parts of acetate duo sodium anhydro Liane 200 parts c! O chloron5phtlèno, ot one maintains \ the tomp- r3turo indicated for a half-hourtf The m3lango rV'cti4nnal then prond a ifinto rougo pulling on the blou cfn '"nj3me time that precipitates the compound 1110) (0% 1n1- that form. It is separated by filtration 1 hot and then carried out the additional operations tol- los as described in ex-complete 2. We obtain 16.5 partios
 EMI26.4
 of a red product pulling on the brown which, crushed ovoc
 EMI26.5
 back mineral soils, such as chloride and calcium, conf-
 EMI26.6
 tituo a purple pigment with good strength *
 EMI26.7
 to the light and!) migration.

   If one uses lo 1-amino.2-athoxy-7-bon: oylamino-5-nthylbonzno at the liou of t., Zminc, -2-phnoxy-l..bon = oylamino-5-chloro-
 EMI26.8
 bonzno, we get a pigment that pulls a little more
 EMI26.9
 on lo blou and possessing zoos propri.! t'ia analogues.



  The 2.5-dichloro-1.4.banaoquinone3.6-c! Icarboxylic acid dianllid is prepared from the known 2.5-dinhloro-1,4-dim; thoxybcnzAno-3,6-dicarbuxylic acid ester, by the ocmo przc4'di that the corresponding dibrorrN compound describes the) fomple 1.

 <Desc / Clms Page number 27>

 
 EMI27.1
 



  EXAMPLE 5: reflux heating for 2 hours, with stirring, -M prti0 'RlQ 1-amino - :. 5-! I.tthoxy. 4-h <) n2oylain''bonno, 1,3 part * d'ostur rl1thy11- quo f! O inic: u 2.9-! Ibrm.-i, .t¯u: nnno - .. 6dicartoxy l1qu.) ot. 1,6?) Part :: 'oxydo do m: 1gnJo1um in 400 parts c!' .; thanol. Lo precipitated cr1Dt \ lin, dark, which was forrrr ', is sJpor'! Filtration pot! <hot, add ethanol ot with o: 1 or s3chS. We thus obtain 2A, 9 parts of a compooû dianilo which, for atro transfarm4, we compose dioxaxiniquo, heated oat laying one- houro 170-175 "C in 250 parts cto-lichloro-bonzne avoc z partioa c; c: (; hl \ 1rur '.ï bonzoylo.

   The pigment fo ost,:>. P.:l by filtration 1001lC, it obt washes with 1, 2-dichlorobwn: î> no, '(' g l'1; h: 1n'l ot c'o l ' oau ot it is aûchû. obtains 22 partij <; of a product in beautiful crystals, having m welat ml :: Ü} 1rl'lO seen: '<' atr hr''nzo <LI ') n.'lYh1 4 ]. 'non- t'lt t'II r.nrri'tipiMv! N 11 f <1rrmdlJ (\ 111 vni.u,
 EMI27.2
 
 EMI27.3
 Proyû 3voc of sodium chloride or
 EMI27.4
 chloruro do calcium, in the presence! 'a (? small amount
 EMI27.5
 do xylbno or uno huilo m1nrlo, the crystalline product forma, lorquo lo sel and lo reviver have <? tt! úlim1.- naked, a blou pigment p0JJnt a great intanoitû do tinta ot po bonnos pl'orr1, Hs do solidity the luminosity, the heat, 1 the aurtointuro ot 1.3 migra- tion.

   ni cbtiont un pigmont douu dfaucet bonnoe pro

 <Desc / Clms Page number 28>

 
 EMI28.1
 / (! Zf pri3t s Q similar nuance ai we replace in cot example, lu <-amino-2.5-di <'thoXY # t-bon2oyla'nino-' bonxno f.ar 2 - '.,' I parts do t-anino-3.'5- <il'httxy-- (.1chlott.mznylam: n) -banzâna.



  An.y3 .: inontiro for C3pHZOtt71C12 Calculation C t 5) d li-.3 # 38 N t?, 2 Found! t C 1 5e) f1't f It: '3.33 t N =? 35 l'oitor <.irrf: thyliqua of acid 2.5-') ibnmo-1.4-quimne-3.6-die3rboxyliquo (F a 250- 251 OC)
 EMI28.2
 use in this example gets you for example by
 EMI28.3
 rnination of 1 f ostur dimcthyllque do acido z5-
 EMI28.4
 
 EMI28.5
 dihydroxy-t 5rpht3liquo ci2ne acido ac <5tiquo glacial. ,.
 EMI28.6
 



  EXAMPLE If we replace, in oxomplo 5, the
 EMI28.7
 1-amino-2.5-di <jthoxy¯4-bûnzoylamino-bonzî> nQ by 20.2 partios of 1-imino -, - '4.5-ditthoxy-4-Ocdtylômino- bonzbnop we obtain 17.7 parts of a dianilo compound do color fonco. The product is heated 170 C in 200 nartios elra-dichlornhonzàno ot, \ cotto t'jmp '! Ratu- ru, on 01 (utu gonito rii) ljttte, on uno tiotjrgp -1 portion! (read rhlfirtlro d'nowtylo t abjura du cotte additif'n read mullongu r4lotinntiol nu colore on yiolute lrrta rofroi '' dinaomont on oûporo by filtr2tion Io dye dioxaziniquo form, it is lavo avocado of Jtheiol nt water ot it is dried * 8.3 parts of a crystallized product are thus isolated which, crushed with mineral scia, constitutes a violet pigmont having great tinctorial power and good fastness to light and to surtointuro.



  We obtain a pigmont of similar shade ot of bnnaa rrnpri: te if, in this example, we replace the dimithyl ostor of 2,5-ciibromo acid. 1.1 quinone-3 * 6-dicirboxyliquo by 5,1 parts of dibutylic uter of lraciclr 2,5rcl, tchloro-1, i..quinona-3.f
 EMI28.8
 tUc :) rboxy l1rtuo.

 <Desc / Clms Page number 29>

 
 EMI29.1
 



  Anclyso '! L << mont3ir <t for C36H4001Jl4 Calcula t C r 62,7 *) t N t'), 1 JN 8,14 Trouva t C <62,73 J Ii t 5,75 t N t 8,17 .



  The dlbutyliquo attcr of 2.5- dichloru1.1-quinon acid - :. h ... iicorLoxylictue (melting point s 1) 'f C) is obtained from the chlorftt1 "n ester of the dlhut'111'1uo ester do the acidt '(tihydroxy-trphtnmue of which lteclda àc6tiquv glacial * F.XI! MP # 7 1 Cn heats at: flow for 1 shock *, under Ayit4tiorie 24 parts of l..min.5-dithxy-rnznyl-
 EMI29.2
 àminc-t-enZr-0, 16,4 p "tt1 do not choose d1 (! thyl1rl '.) O of the 1 \ ri says J,: -dltTOr7-1 .¯uinnnr-3.f-cllcor: f , y, yll.i ct 16.5 r, / \ rt1.u "jt" 'xyde # - do: r,.; r, r: y l1 dam -500 parts d'itiflr, vl, Lf pdf; 1 +6 f ^ nCd:) f "'r" I:

   is. ! 6pt6 par t'ilt.r,) t1., 1 ', i .tad, lava c'1VQ df't i' << thtncl ut Jft water and '.4rr. <! <Lr. r, twr, t '<O, 4 portion of the cor.po <i4 d1itr.Sh quo one: yjli *, l' '' 'r' ..l1u! 'f;' Jq (1 J '? "0 pOndl \ ft 0 'i ura". D:, r.',, "1,; :: '.: w, jt-" 11rt .. ():' \ zr, e. L: aws!: R on la -ert raturc 1 \! 1Ü ianto, An lava lildtticirr) lo! 1 l'rnu and "1), 4, zt-fie C". rictit-nt, a pr-dult ..; r1.t "i- H6;. 4 :: 1: \ .rl.'1'I1l1q1J" 1'1, broy4 8Voc du - ^. hlU: -sIa, jf1 <, where \ 1 ': 1t11 "1 lr..ycre, (jrnn ur,; r l1.1' on *. 1: 1 (t! J, do ..t) ir.t, \ 'intr ,. u, who has 1'Q / 11tQ5 pripri4t <î'i do i1! té la l ': "' 1Ltf !, In -> ur * eir.turo, \ la ë: ta le'Jr fJt.:. la - ,! -.



  't'a t 1' (\.



  If gold, rl): '11' l .1 ('d * n <i ^ ¯9ô tXB, "Nia los .lA j: tt. <1-a; nl ..; t, 5-ii" ?.!, x; .-: - Een: afamino t-ttn :). n tr 1, .. 1 ..att1 (.. '. o, 1'. '} lidt' I l 'ci'1o 3 -nino- 4-p: nowr-tcnzol ';: o, we W! in¯ a pi.iment rcuyc: Jol1'J has the <u7tntr.

 <Desc / Clms Page number 30>

 
 EMI30.1
 



  The dldt.hyl ester of 2. *, dibromr1, d-quinono-3.6-tiicerhoxylic acid (fution point <! <7C) can be produced for example by brortrition due to didthylic aster of Gucdnylo-succlnlqut acid with brOIT'Q vapor and subsequent oxidation with dry concentrated nitric acid in ethenol, EXAMPLE a 1
 EMI30.2
 Condensation is carried out by heating
 EMI30.3
 rorlux laying an houro 24 parts of 1-Amino-ii 5 - -; dirttt, oxy-4-bonoylemino-bonr, no, 1, parts of 2.5-dichlorn-1 acid dibutyl ester, A..qulnono-3.6- iicarhaxyllqua and 1rW parts of nayneslum oxide in 400 parts of ethanol.

   After filtration, 1..va \ ') 8 with Athynol and the eu and s4uhaje one obtains ï3 pertiao of a dark crystalline product which splits at 218-22t) OC, nor the heat to T-1yS. for a *. 1 hour in 160 will leave I 1, 2-dichlcro-tenzbno aver. '5 l &quot;' fIrt.1o'lo duo tor.zoyle chloride. The dye f4rm6 ost itpinê JAr uisoralo:. cold, wash 1 1'4t! inrk,) l and water ut% 6ch6.



  Ch obtains 1-191 parts of a crystalline product which has a metallic luster (tall1quo, bronze color. By pre-grinding mineral soils, together with calcium chloride, a mixture is obtained. u6r.o! T: we \ pure, blue, of tointo vive, which has, tr, 11do 5 the lU1tu. the aurtointuro and the ch810 ir * Or \ obtains éq4lenont doa p11cnh of blueberry and oe shades: .6dart es propris " lJul f} r ... ne% si one t'f! Y1.pllt (; l), in cot oxenplo, the dlbu- oitor typical of 2.-dtctloxo-1.-uin acid ,: na-.sh- dicarGoxyliqua par ies esturn lr.diqt: 4-, dsr, q column II of 4; at> lt: alJ ::. atc4 .., 0 rl'lrç la ct'l1 ('1 in a mentions the number of parts of the ester used, in

 <Desc / Clms Page number 31>

 
 EMI31.1
 li '; 01.) / \: \ <:: l; n "' 'ulo'jr' - 'r!;, \' l '. 1.) W: .rr. IV law 1.' /" . '. 11., \ ",' 'L' '' '. L \ lj'.I) l';" '! 1} lr' (.k ',: -l ::' "" 0r .. , '1 .i \)' I1 "xa ;; i'w..
 EMI31.2
 



  ', m iv (1 ## -.- #) il 0 ,; tt, r lue rl? ü v: l - '. 11! t Ct <, CO! cl ..- i'T.: i-ic .'.- ruu- Mj1 ;. ' f N ', 00 mo-1.' "# - '# iui .-. or.o-1 ..''- 1- t-uv?!!', 7- '! ¯1C12' (?; ' ll; U: Ht 'S, * O | 1 = 1.1 (F -. 11- ..' .;) 3 23.2 ojlvir ri ty 1 L- 1 u - :. l.:uLc f; i7O, .î0 | qu.j de Î J1W 2.'i- HtO, '-' '! 16 Jbni'; '"-! .-! - qnin- li-'Viv5; #" J''1,11 ! m-: 3, r: -id.Wt.cx- H s # "', -! #' (NiS'-! Llquo (F - -1 '")
 EMI31.3
 
<tb>
<tb>
 
 EMI31.4
 ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ ¯¯¯ ¯¯ ¯¯ ¯¯¯¯ .- --...
 EMI31.5
 



  The esters ', Jibro: r / 3 ;, I'nt.i 1nn6'J in column II;' get p <v. brodât Ion, 1l "; -here de.." '1 ..: - j droxytf, r0.l'r: t. ::: l.r1'1C: l;,) rtl'Îp,) nf \: , tr, .i :: ln. 1 'a t.-' m'1 i'tUi glacint.



  GX! 2MPL 1: nndense car. heating .. \ reflux; 'on lint 2 hourc: s 23 parts 10 lr.1!' 1110. "" ¯, 1! Itthn) (y - :-( 3t .., - i dirtef, irylbnzoyl, 7n, inn ) -rer, z << r, aS% ,. i P.:lf,1I: '. i,'), -., '"', l '' 'brl) ITI () - l.-1- qUlonrh: -3 .f, -Jiî; Qrl'.Jx ',' lirj '; o ot 1,' '' '' \ i) ct, \ "'1 of oxide do '11 <1ÍJn ((; iu11 d :: 1r., 1rc party.; -, \ ':: h1n .... l. 1.0 j dtontlo l'lin'd .br:, nu o'.t l'.b ct: r \ l. Jf1t5 - # 1 / 'J "C .1,1 :)' 1 3QJ r, 't'ti''j du 1..2-dlt; hl.'r"': "'I',;:; - '! I' ;, yes * tntr,: dtJl tjoutt'1; 0outt. ("R.% I ,,., R ,,.,; C, t" 1 t ";:". I '(: : 1t.uro, ctans 6 p, 1ril '!', TjW '.! LlrWr: (Jo tllr.yl .. (>. 1.) 1 <;'.,: Refroi-ir # j HXD1 "1 !: , on 6IJ, 11 "jn7L: ilvl7'¯tf. lo dye f) r '- <0 \ 1

 <Desc / Clms Page number 32>

 
 EMI32.1
 v1 lo live dV (! r do l '6th \ 1ncl 0 of 1', 1: 1.

   Apr; <if,:. 3 y on., Tt1 (..,: 1 "} 1 j.3ttie" d '. R: -l - ,. 1r,' .: 5V'J:; ': TC do -: rī; x. \! -: 1, *;,: talli '"l': t, '1, Il.t)' 1Ïn '!'" r '#jlvi' 4,: ni.'W 'ī a. ni ') Tf1I ::: t dt ..' ..r "j11: H: (f blC" ..: o, ri "') r1tJ:) - hl (1! lon +' ir,:; '. # , 'r) tick \ la' '1'j "E:' r1 J 1 :: -, i; r * ## 1 # -. 1 14 # ro 't. b 1 "1 1.:; d; r:.



  Cr. obtains ck-s "i'iiWf.t1. d '' 'J, r. 1¯ Lennon Ul'tiô' - # '# -: n11" <J'J ..' 3 si, TJ 1 î. o du - ;. m #.: - ii-;, c! thoxy - .. 1¯l, -3 ', 1¯r; i ^ t'qtiy: c; -zoyl: m ::;} - t ; t,;., no '' 'Ir:' ..1 +. Ei 'FJ 11)'; '1min <:. of the fomulo q1: n ..: r ': 11o
 EMI32.2
 
 EMI32.3
 indicated in tbl <) 1u below In column I the number of parts of 1min0, dlr.- has been entered, column II the color of the dinxor rt. inique ot clind la colonnu III 1.,; rfaultat tj "t ': JnlJy'Jo 61t: rront: lÍro.
 EMI32.4
 

 <Desc / Clms Page number 33>

 
 EMI33.1
 



  NOT*. 1 i1 k4 t 1 in - ..........., ... T ---......... T .. & ".. tf - ..: -" ; 1 J 1 19 "" ';, read ") .rCt: iīs tlflJ:) l'; ull 60 ,!" '.' "1, fA A,; '\!) Trl" "" {. t 0 ,. "y! 77 'Jt03 2 2" "': J.i '!) .rjl. IJl'", -: ilr. il * 5 1 "'7"' 1 p), '0 7,1'j \ ##' tlrrt tr '.. IJ'1, I <7, <"1 6r90' .ur lo t" "'I ) C1 3 2.8 ..cil) .J: ') .. ('.) Mou rluvr 1 (, I ,, '/ J 01,7 7, I \ C "## tr, gv- <0' #) , ##> î 4.61 7,? <).



  4 20,3 r'.I1, ... '; (()'; lIl hlou c.!: Nl 'l' 5i7 () () 4, r., 4 "J tnuvî t 1H ///", 7 ") 1 / .1 1C - /: jk: cr.xar3 violât r;" 1 .; 'J II: 1' .J. "),) #; A fi rc 1 found l ':, 11,7') 4,1-tf}, Q 6 21,7" "'U]; f / \ tlf / 'J c "]' 'Jll" U "I)' ,; 1., 10 7 ##: i \ ¯ / t t W i, 72 4.41 7 '.; 7 27.2 -f-il, -; fi./ \ -Cl violet. c51: y: "), '10 1, .n 1, ...



  \ ## tf ") '4'l1, l') '", VI 3t 1 /., 1 .: 8 2'T "'; .lll.,. '0 ... (' - '.. ^ 1 11 <. '1 c: r: 1J1' Cl ri, ';.



  ..... 1 U #. / T Cl bzz
 EMI33.2
 t: XL; .UU.



  1 fi ')', yl1'jlJ'J FI; .f '). "<.;'. '. <:'): -Il: n '/ li .. quti do the acid'" J- iLrrr # 1, '' # rilr.cr.c- 3 1 - -J itr:) X '/ liqqite (F .t'Y :). -, i the rjr. ir'-ro o: to d-'irl * t't; <cpl Cri "t: t. 1 ..;. read i.'j''r; '. J'. 'o. ;;" " <bIo'J, II '. </ f "r.".' '. igTt> n * .T 3p * i1' / ji> 3 *. lu liou t., 1 '1: ./ r, (ll ,. 'k!' # -.! ...? # * ## ili-r - ': - -.-- 1, -'-.'; jinc: '-) ..'- if-n. ') r' .. '', H :;, "> *. '.'. li'-; or 'r.tit.'a * i r <.- #; # r. i f.l .-- 1 ..- ..; ''., -. ", o'iivjm,

 <Desc / Clms Page number 34>

 
 EMI34.1
 aat'T tit c y rio * x y] cia il nt., 2. '. iit, rccr-1.4 tluinnra-3, h-riiwr;

   <,, cyl1 1> uof p'tcr (il bon? y 1 tzitit- #! # l'ecluo?, 5-dihrnmo-1, t..3uirnne 3, liicnrt., xyt lquof Ot'r (10. l 'acid <> #r> -dlbromo- <- <! ino-3.' <cnroxyHquc, e-, acid tur 2,., - <iltrmo-, lf | ulnr> f, o-.l # (> - <1 1 cil -1 oxy y 1 id uo, cr: er di-ictlnrlbRnzylique 14, acid 2 l> -tUbroii - 1.-4uinono-.j, t4..dicarhoxyliquo otcr dij-, ttl, ylbon: ylictue fetcido 2. <librfn'- 't .iquinonr-3.6-.dicar'nxyl iquo, estor 1 :(' 1 ',. iWdir ttyll..i, hGryliqua de 1 db''nm- < - '') ulnno-3.f'-dit'r: '<(Yli.ju <*, nt read from the act dibro- mo-1.-4 .- (;' ji: n'nc- ' t.-dic.trh <'xYl 1 i.jiic.

   CXL'.TU: ni 1 on rcr.pl.ii.Cf 1 irQxcpl '">, 1 <1- arinn:,' a-.lim, 't! ,, Xy-, i., (,, , tt..iiy; hy; t..nylar, in,) 1¯ bn; .. na by? .y; 1 pbttlut, do 1-4-nir.o -. '. "j-dliT.' ' t> .rxy # î- (it-m, ttiylbanzr, oxnlfon 1 nino? -tenzrn ct ni on op.r conro dderit 1 tox ^ rrpio), or, obtains a ri; 7-slow violet which, however, did not rns all flit IAS good prnt, rictt 'of solidity ut:,% Ei lrenta ôcict'it' "..ru: 3: the 9. th obtains, in nirrxz! v! '' * an3i> -jv: t if one: vntlcv, dar '-et ctcnrlo, the' -a '?.'. '# * .'- dinthc) (y -'} - ('- fr / tlbfnx? "- t (. # 3n'T. 131. i :: c -) - n?! 'N <} P') r 1 '), de -r.ir.o <.'.'''- * i "!' Ox ' /#'.(.-hydr!'y- prnplonyl3 ".inn) -boni> 'no.

 <Desc / Clms Page number 35>

 



  EXAMPLE 12
Boil at reflux for 5 hours
 EMI35.1
 12.8 portion of 1-mino-2m6thoxy.d-bon = oylmino. nothylbcnzno, S, 0'S parts of ubtqr d1Jthyllquo do acido 2,5> -dlchloro-1, 4-quinonc-3.6-dic3rboxyliqu (ra 195OCs prepared by chlorination of ostor dlthyl1- quo of dihydroJ \ y acid ..tcSrdpht: .ll1quo in lo tdtra chloruro de carbon) ot 4.5 parts of anhydrous sodium ketate in 200 partioa of ethanol. The ionile compound formed, which has a reddish brown tint, is filtered off by hot filtration, washed with alcohol and with water or dried. 17.3 portios are obtained.

   Op produced is heated with 200 parts of 1,2-dichloro- bonzno with 5.5 parts of chloruro do bonzoyle, weight
 EMI35.2
 For 3 hours, h 170-175 "C. Then the dye formed is filtered off at 1000 ° C., washed, the (5thanol at the olu ot the cochu. 0.2 parts of the ester are obtained. 2.c.-dibunroyl acid dithyl .. amino-3.7-.dimGthyl-triyheno-dioxezino-7.1C - dicarboxy liquc After grinding with calcium chloride, the body forms a purple pigmont.
 EMI35.3
 



  If the 1 '* amino-2-muthoxy- -bonzoylamino-.5-mdthylbonztno was completed with 13.9 portions of 1-amino-.2-rtx'.thoxy..t-bonzoylamino- -chlorobenvèno, a pigment is obtained. analogue of burgundy red shade.



  EXAMPLE 13:
 EMI35.4
 By operating as oxomplo 12 pnJcd of which 13.9 parts of amino - rt3thoxy -... bonzoylainino-5-chlorobontèno ot 9.6 parts of oator dithyl1qllo of 2.5-dibrotro-1.4- acid are condensed quinone-3.6-

 <Desc / Clms Page number 36>

 
 EMI36.1
 dicorboxyliquo with 4.5 portions of anhydrous sodium ardttto to obtain the compound dianilo quo on cyclioo onnuitos On 101010 thus 1't, 3 PlHilv & (lt4pntor d1mûthyllquQ do ocldo 2,6-dibonzoyJamino-3.7-dichloro-triphnc -dioxozino-9.10-dicarboxyliquo from which we can obtain, after grinding with a soil, a rouyo bordoaux pigment.



   -If we replace in cot exmeple lo
 EMI36.2
 1-amino-2-mCthoxy-1-bonzoylamino-5-chlorobonzèno per 12.8 parts of 1-nmino-2 - mtdthoxy-4-bonzoylamino-5-s. nxïthylbonzëno, obtains a pigmont violot doud do 1. bonnog propriGt6a analogues, EXAMPLE 14;
Reflux is heated for 2 hours 2.1
 EMI36.3
 parts of 3-amino-4-mGthoxybonzophdnono (P = 99-1 OO C) with 8.2 from oator div'tlyliqut) do 1 forido 1 2 .5-dibromci-1.-I..q (ilnono -3.6-dienrt) oxyl iquo on pru! Ioncu 1 do 0.9 part of oxida do magnGeiumfi5ns 200 parts: of uthanol, Lo precipita fnrmû, rougo ororgo, ast sdpard by hot filtration, washed with ethanol ot h the water
 EMI36.4
 ot suchJ.

   Lo dianilo thus obtained, which melts at 217 C, crst heated dono 50 parts of 1.I-dichlorobonzèno cvoc 2.5 parts of bonzoylo chloride, laying 4 houloci at 170-175 C, In lo milando ractinnnol rt) fro3dip The crystalline dioxaziniquo dye forms a brick red product which dissolves in sulfuric acid concontrd with a deep coloration.
 EMI36.5
 In the hot 1.2-dichlorobonzno it 90 dissolves avoc uno yellow color ot uno fluorosconce vorto.



   If we replace, in this example, the 3-
 EMI36.6
 amino-4-meuthoxybonzophSnono by los aminary6uivantcap we obtain 1

 <Desc / Clms Page number 37>

 
 EMI37.1
 Avoc 4, that part fo-aniaidinu, un a Inn (1û dl ') n11! J c1 "tointu roniu tilciu4 fondant .11a (% (0 t, le.' H tir 1111 1: 4 ilurnlor, un c .. He , 1) l ') nt tt 1,) w'},. Xlnlrtuo qui lin dlnaout dani l4rifn tuifutiquu concentrated with uno staining vort birtu. D-ins da solvent * ofl) '\ nlqut: 1I hot 14 dye prunonto uno vivo flucrosconcea Avoc 12,2 pZrtiG9 dU bi4: tlar 0CI ^ a4yli que du 4-lno-rJGI ") clnOl, a composition ditnilo do tointo ljgèromont t'ltqnc hrun, fondant 2 'bOC, ot,!) from do co dornicr, a red-brown dioxawiniqua dye which itu (dissolves. don los snivor.ta organiquoa with uno c; olorHlol1 ornce ot qui pri "3, ntQ une vivo f1'Jl) roc (lnco.



  EMJtf: 1 i A, 5 will start from co: -, oa ': dianilo prûporâ according to uxúmplCl 7 5 start from 1-nnino-ar-ii.thoxy hcnzc, yl' \ 1I)! R \ cib.H ', z'-n7 bed of 1 ns tur di +. ', l1qu') 1 laci- of 2,5-ibra;, u, -1 ,, .. qutnnrf = !.> - flco: 5oxylirJua, have introduced 9 ' JS d / itJtcr, 11. '. Tt finomont rHJ1'lrh ,. dini 150 partios of icid. ul: "a;: ique 1C -, * 4 '. Au tx)'. du 20 houms lu tc.p, r '} tu1 (, onbiînt on vono lo rvîljnrjo rr.t1N' '', l blou gray on 15f1O port1 <J! of cold esu, the c () 1 ') 4nt d1o;:' 1 '\ 1'l'J (J for -.>! prû.: being then under forrtb d *' jn end rrr. lp1t. l, tOI / deep, 'zor anvîtio- ri.-ri; tl1! ntlo (\' 1f (1, r., \ tjtn 1 '1 UtvrV jlJPt4r' '.f 1 (JOltfu UJ1ftr1q ,,' I, folfn on lorvl; l0iin av c do l'olTr, () n1 ") qu (. 'lir5 ft1r'lt1nl \. 1-.v, iti à llui t oij # ch3 ..



  9 <J, we get ## f 0 partioo drue; blou dye pulling on the reugu qui ',' 7 d1! 1 "u'Jt dam la nitrnbonzbno hot with unu r; olC ': 1c') t!., n deep blue.

 <Desc / Clms Page number 38>

 
 EMI38.1
 



  EXAMPLE 16 t 01 rh: auuffo h 9O C laying 5 ha4tue, on lu *> 3ln of uau, Ul lmrliua (1 ') clirtpogj dtanflu PrJI) QrJ bol (-, n l'uxumplu 9 1 putir du t..aminc : .5clidthmyl 3cv'tylaminot) onzbtioo dîna W70 pirtice dficidtt trictilor- rjc, ïtique, b Il oc fozma uno eolution blou vert N which one adds 1000 partua of otu coldo t the colrrant << io- <x3zinIquo formu then precipitates in forma with a prJci- pit.l blcu purple.

   It is separated by filtration, it is 21, vo in water, with a normal solution of carbonate of <odiun at I1 new avoc do lta2ug then we lo iavc N the qttDnnl and we lo abchue We obtain 803 pirtioe of a pigmont blou pulling on the rouyop of a great tinctorial power, which has a good sc, liditi the light, with the colvntug to the turtointuro ot the chileuro The product is obtained if it is used, with the liou of the trichlonctiquo acid, 200 p3rHu '! of acid) dichloracutiquo or a s.fl: ngc do cos sweet acid. f: XEMI'lk 17 H 90 "C laying S hours, on lo water bath, 5 parts of ditnilc prypir according to oxomplu 6 from 1-amirn:. 'S-cJithoxy-l..actyl - * minobonzbnop in 100 parts of polyphosphoriciuco aciJo We add 000 partieu of cold c u to the milingu rction-;

   noi, co which precipitates the dye ftYrN August forrw from a trScltlt3 vtotott Apr5 i flltritlon, lvajo to 1 rosu ot aSctvu, we obtain i F) Jltlor. of an iilynont
 EMI38.2
 of violotto shade.



  EXAMPLE 10
 EMI38.3
 In him conditiona clüc.-Ittis a l'xatlo 5, we condonao 7.4 portt35 of 1-amino.5-dtGttoxy1

 <Desc / Clms Page number 39>

 
 EMI39.1
 benroylaminobonzbno # 6.8 part, from 1-amino-3.5- dir # thoxy..ol1-bonzoYlamlnobenz & no ,. 8.05 parts of 2,5-dichloro-1,4-quinono 3.6-dicarboxylic acid diethyl ester with 1 part of magnesium oxide.



  17.2 parts of the dianil compound are obtained. The cyclication and isolation of the dioxaziniquo pigment occurs
 EMI39.2
 do éyalomont as in Example 5. We obtain 11.6 per-. tios of a crystallized product with 6 flash mt8111quo which, mixed with a salt, constitutes a blue pigment of great tinctorial power which has great fastness to light, to overdyeing and to migration, EXAMPLE 19:
3.2 parts of 2.5- acid diethyl ester were heated to 170-175 ° C. for 3 hours.
 EMI39.3
 clichloro-1.4-quinonc-3,6-dica:

  rlioxyliqtio ot 6 parts of 1-amino-2.5-dicthoxy-1-benxoylaminabonznG in 100 parts of o-dichlorobonzéno, On laieso cooled? lo reaction mixture at 100 C ot the dye formed is separated by filtration. After washing / 1.2-dichloro-
 EMI39.4
 bonzèno, ethanol and t of Qt; 6 tO: 10, 2.6 parts of crystals with metallic sparkle are obtained: this is the compound described in Example 7.



    EXAMPLE 20:
The reflux temperature is heated
 EMI39.5
 for one hour, 11.5 parts of 2-aminonaphthalene and 12.8 parts of 2.5-diehloro-1.4-quinono-3.6-dicarboxyltO diethyl ester in 200 parts of alcohol. It then forms a red precipitate
 EMI39.6
 orange. After filtration, washing with ltethW ol ct: water and drying, 19.1 parts of the compound are obtained.

 <Desc / Clms Page number 40>

 dianile which melts at around 250 C ot which this solidifio
 EMI40.1
 again a dciat-.etllic dioxazinic body is heated to 18O-19O C for 4 hours, 5.4 parts of the dionl1o compound in 50 parts of nitrobonzono.



  After cooling down, the dye formed is absorbed by filtration, washed with ethanol and with / and dried. With water / 2.4 parts of a product are obtained under
 EMI40.2
 formo of crystals dclt mdtolliquo which, after grinding. with a neck, constitutes a blue pigment of great purity and great tinctorial power.
 EMI40.3
 



  Avoc 16.8 parts of 3..amfno-9..Ethylcarr bazolo with the liou of 2-aminonophto2lono, it does form a dye dioxaziniquo blou.



   If we start with 11.5 parts of 1-omino- nophtalbno and 15.3 parts of dimethyl oator
 EMI40.4
 do the ocido 2.5-dibromo-1.4-quinonc-3.6-.dicnrhoxytiquo ot if one operates as described above, one obtains, commo with 10 2-aminonaphthalene, a pigmont analoguo, violot tending to red.



    EXAMPLE 21:
110 C is heated for 10 hours in 100 parts of glacial acetic acid, 6.4 parts of
 EMI40.5
 5-nitro-amino-1-hydroxybenzeno 8,2 parts of diethyl oator of 2,5-dibromo-1 4-quinono-3 .6-dicarboxylic acid ot 3.7 parts of sodium acetate. The dioxazinic dye is then formed in diroctomont. We
 EMI40.6
 the sdparo by hot filtration, loosened with alcohol and water and then dried. 7.8 parts of a product of a dark color are obtained, the elementary analysis of which corresponds to the ostor didthyliquo

 <Desc / Clms Page number 41>

 
 EMI41.1
 do l'çI, du? .Q..dlr, S! rv..triphèno..dioxazinr-9.10. dlc: 'Jtboxyl1'II ,.].

   He will say donations cldQ lulfUl1ry "", r.nilçol ^ r t îvoc nnc. deep hluu coloring ot dar.e 10 nltt "", t; ol1:,. 1m '! at: lV ') C uno coloring rouyo, Au c'Jllr') dv la rcim: tin ovoc hydroo'Ufito do sodium 11 'III for ... CINO dn 1 ^ lnv do tint olivo, which will turn to b 1 (ttJ ln. 11 (\ c; ú lor ') do oxidation.



  : 1 we start from "6.4 p ') rUtJ8 do 4-nitro- 2-Tt <noph <' nol ci Jc 7.6 parts of oator dlthyl1quo du ltd (j (J. ') - dU' : "I!) () - '.4 .. (ulnono-3.6-dlcorboxyUquo ot i1 1'011 opî-rj corro McrJtt below, we obtain 7.2 p3rUo3 of a criatllic6 product, from') tolnto brown f \ J / J ", 'hnt 11n:' Jl '/' iç '' # lt'nontalfo (at we accortl ouzo the ouïr r J 1, /; UI'Ill q '.': '] #> l '') ddu 3.7-dinitro-trlphbno.- lloxzS; v :-). 1 ili Wttox liue.



  U a !:, va- u4. z 2
 EMI41.2
 
 EMI41.3
 Lr. said august in 1x portiot o'acme sulfuric JO IC parts of aster didthyllquo do 101-.idu triph, tfn-di ^ xazinr-.1G-dicorboxyliquo, pr4- par, 6 co "n << d4ctit .'r i 'cxsplo 1.1, second paregnpho, ut on --h% Ltf! o 5 Is: -' '?: for 15 heurta, Cn vorao il blue solution nro: or. on a liter of chiudo water, we yhparo by filtration l 'dicarhoxyliquo acid which 3 (rcipit' we le- ive to osu ot it is dried * We obtain part ', of a tn - rnsé of func4o tint which, dcr-ts- "on a li-iiior filter, peconto a Jclat

 <Desc / Clms Page number 42>

 
 EMI42.1
 nôtalllquo green.

   Corner forma do Print color ..prpJI ':' tt'p: '1r d': l: 1y :: lrJO of the suht: 1nclJ with duo oil A c of hydrated alunlno- il rrJ ' iontc a nunco violut brown, L'3! l '/': c of the acid dic: l1bo) ('Ill1u Monno loi r' #. ulta # J, ioivW: W: Calculated it: J 6,., ' r II j 2.01 j M 1 7.5 Found t 0 t 69'IJH t 2.82 | N! 7.3 "'.
 EMI42.2
 
 EMI42.3
 in 4.r3rrifor-x cet], -: 1 (h: un hlofUt1) .j'1- cido corrc-.pOtdtnt, in 2CO parts of o-dichloro- bcnzàno with 50: C't.L ::; d 'chloruro do thion / lc ot uno: rC4? lt: lnntriL:, lC7r, lâ "J0 rhoo ;; r" t't1, and on,; n ', 0 c'mplttJ "', cnt by distillation lo! llarn: L do tl ::. ^, vlc on 0x05, ', ln "Ij \ Jtl. , 3u ullu a lut lin d <:! # '# 9 "ir- tlo? 7h r-ct" lor: a, l11n (t1i'i1 1 X'; -> 3r * i '.' S \ i '. J..jic1 \:;: C- benzene ot on chaufo 19 '' iT-n rJ1CU ,: ',,' pctd-: rt 2 h'lIrc <;) 170 * C.

   Lo dye closed! ost vni>; ito 9.t.i: by filtraticn 5 ctand, l2v î avoc do 1o-: icr: lorbonzhno and do I'vth5n; çt:; ct ,. Lo H-p-r.t-.1onr1l1dn. do l'2 ': idc tripne ... Jiox7zlnc-.t â-.d: co: ^ OXy; iu constitutes a brown p liront', 7tfjy # i-'Uv of a gr ') nd .: olidi the light and t1 1rti? n.



  If we make rVw; ir the chloruo of 3'.ldv.- with the diJthy1in (J at 11vu the p-chlonni tir ..). one obtains a similar r1lJ: 1ùnt do nusr.,; e.

 <Desc / Clms Page number 43>

 
 EMI43.1
 iXE1. ',? U: .. 3
 EMI43.2
 
 EMI43.3
 , 51 one:, :: - nlac ,, l'oxonpio <!, l'ostor di.;:! '- y l1quc of triphne-dioxazine-4,10-dicarboxyliu0 acid by the c5tar dithyliqU0 do J'ocido 3.7- dibon / .oyl-triphôncdiox3-! ino-Q.10-dicarboxyliquol one obtains the acid dic1rh0xyllqUQ corresponding to the formula
 EMI43.4
 next
 EMI43.5
 
 EMI43.6
 #lui, '¯1.'nt d' .- gnuiour d'1I'lpt'tJl'm, preieuntu uno nuano'i vioiot pulling on Vu rouge.

   Avoc the chloruro rIo thionylo we prt >>.: 1,) chloride of acidu, as in example 2i, ot one makes rgir co dornior with the aniline to obtain lo phûnylamido corresponding to the column obtained from cotte manlrc. c () n6titu an onion of a reddish brown shade with uno bonno so11- iJl1 with solvent. isnWilt.n. f11
 EMI43.7
 

 <Desc / Clms Page number 44>

 We heat at 110 C laying 4 hoursoa,
 EMI44.1
 in 150 p.1rt.1o '. acid sc .- 'tiquc: glacial, 6C partioa do -nit.r., - 2 -,) minf "J-' -hycirnxyb (I1;! 0nO, 10,1 part lys of dianilido of acid 2 , -dihromc-1.l-bcnzoquinono 3.6-dicarboxylidue and 3.6 parts of actato do aodium anhydro.

   The dioxazinic dye then formed is sd-oar6 by hot filtration, washed in ethanol and water and dried, 5 parts of a dark dye product are obtained which dissolves in sulfuric acid concentrated with uno coloring. dark blue.After broyogo with a ground it constitutes a purple pigmont, of great tinctorial power.



  EXAMPLE 25
 EMI44.2
   gold. maintains at the retiux temperature for 1 hour, with stirring, 6 parts of 2-naphthylamino, 8.3 parts of the dionilide of the acid 2,5-
 EMI44.3
 dichloro-1.4-bonzoquinono-1.6-.jicrjrhoxyliquo ot z parts of crystalliguous sodium acûtato. Lo c; lanilo form'3, do tointo dark brown <5, is cûpar by hot filtration, washed with ethanol and olu ot 9ch. We lo -; hQuf (0 onaulto 5 '? I! I.30nC laying 2 hourou in 200 oartios of chloronipht14no, then we lo rofold 100 C ot on lo sSpara by fil tr "' \ t1on.

   C1'-I thus obtiont the corresponding dioxaziniquo dye in the form of a green
 EMI44.4
 crystalline substance, with a tallic flash

 <Desc / Clms Page number 45>

 
 EMI45.1
 di4% nut fI ... "... l '') <; 1clll buityririiiie cnnnlJt '\ trl1 -1VQQ uno staining ht'tuo ot which, bioy> 5 Ivuc of chloride cf" calcium, constituted a pli7mont do gr-ind tinc- torial power which Q uno bonno iolidit4 to migration.



  Avoc 0, "parts do 3-an <ino-9 - <! Thylcir- bQ1Q au liou du l-jm1nonrhtlônQ il 4Q formo an ilinxàzjfiic dye violât pondant doo pv <) pri'ït'3 <Qn 1 t> r] Uf ) 0.



  UX1: MPLe 26
 EMI45.2
 
 EMI45.3
 At 260 part of pyridino we added avoc
 EMI45.4
 p \ Jt1on, 7Q..OOr.C, M portion of chlo1 '\. lro of alumi- nium, then 20 parts of the diinilo corresponding to the following formula 1
 EMI45.5
 
 EMI45.6
 The temperature of 1T'Jhn (l (, j r '!' T: tionnol oot slowly lIort4u 1 tc :, the heart turns ancott to brown rougo 5u iiititit \ pr} M v'r wW ntrS laying fl houroa in Rotroijit S 0 C ot in diluo svoc; 00 partita of ocidQ hydrochloride b1norrnol. 200 parts of ocido hydrochloride are added once to the rttvln7o concentrated on lo diluo then with water up to 1 liter.

 <Desc / Clms Page number 46>

 
 EMI46.1
 



  & q pxzicipitS ost avparG by filtration, washed with water ot 3 ch î. On.,) Bt14) l "It 15.5 parts of crude product q'.io on t'cçr \ t ') tli';" d "m, f" 'f' \ prtia.s 1'o- <11 ('hlnro- 1) lilll "\\" Apv1'} ta '' '\' '' \. '.. "l \ 1 ,) q "I1, \., pm.lult ri '.



  11 (ltlafv. 'Tt t' "7 (l'vUtl: j7i'i: nl.nll 3" nt.Uflt 5naly.lnuoïp state,> pure nt <EXAMPLE 27 i Pan3 c7 p ': lrtl5 of acid 3ulfuriquc t10 ². On <u qoii * 10 t> irtlon dt4,3tur dt'thyliquo de l'Or.id <rl rll'hnQ- \ H 0) (\ TIt ..... I '). Il .; .d! t; 'HIHJ) (Y Il quo, prp0 r <3 "u11'" t7 ptf'r '1,' rP. Pllllj, .nrtl1 '.1, d: UICUCDn f) t'.IIrQIJ1:' ph! i, ot on c) vauf l0 '1 IC ..' IIJ "C ponlhnt. 1 '} hourott We vorao the solution bl! J'J orford in a hot water lltru, we s.'pirc pot f11r 'tlf1n l'îcldo dicarboxyli- quo qui pr.'cirit, on 10 lavc 1 l'vu ut on 10 5iCho, On trins t'orne ot drj \} on chloride l' c1do corrvs- pondant, dano 2 <X -Trti -.a 1'o - J1 ..: hl () r,) bt) n% nt,) avoc?) 0 parts, Jo ctilorurq d <;

   # M'nvlo Lt uno traco do | x> nt3chlorurc ûo pî.jphiir, pu! we (,; h!; 50 completely by, - 't' ti U 1 ':. hn the chloride? do thi4nylo vn (..xcb. ot we add a solution of S, partial of sodium mJthy lto don 100 parts of thy11quù alcohol. We heat the mixture f.:::ctlon"'l.:>l laying 10 hcuroa or bath where, we filter 'hot, we lvo brought! Ot i ou and? n:! 0ChtJ.

   C nbt; orr, a brown product 1 "'.) IIQo. Noua for- * Jo t irw- 11'1.11 \ i}'). 1'jl s4 dissolved in acid 'Iu1fur ltJ (.') N" : It r \ 3v uno color blou pritttW, #>), L: 1. at m, .., 1 .t'n dt'JMQJ1n1'1u,) 1r'1- loç'j 'have added, to m.:11n J ,; , 1 <: t1'1nr. \ Jl prv>: <5- tooth, chioruro; J t drt'J tr: c-tfn,: - diaxaxine-f.10- dicarboxyliquo, une; 0! "Ti,) r..J. "> n, fJ will start from crystalline sodium acetate- 'in UX) f', rtior, iso- alcohol

 <Desc / Clms Page number 47>

 
 EMI47.1
 PrOPY! IquO, ot if one nrocfcdc otherwise as described above ;.



  EXAMPLE 28:
To prepare a color for improvisation
 EMI47.2
 graphic sions on m. :: l: 1nge, in the l1xour three cylinders, 2 parts of the pigment prepared by oxomplo 6 from t-anino-: 2.5-dithoxy .. '1-acutylamino-benzene and do l' acid dimethyl ester 2.5. dxbrama-i .'- çuinone ... 6-dlcar! oxyliquc, pigment which was ground with a sol, with 36 parts of alumina hydrate, 60 parts of vomit with linseed oil of medium viscosity ot 0.2 part of cobalt linoleate.



  Avocated colorant paste can be produced in purple imprints possessing a great intensity of color as well as good light fastness * EXAMPLE 29;
We mix together 67 parts of chloru- ro do polyvinylo, 33 partioa do naphtalato do dioctylo,
 EMI47.3
 2 parts of dilaurato of dibuyl-G3ta1, 2 parts of titanium dioxide ot 0.6 part of pinewood prepared solon loxemplo 2 from 1-amino..di- (2'- methylphenoxy) -benzènc, pigment which we have crushed with a ground, ot one worked the whole with the rollers laying 10 to 15 minutes at 140 C. With the mixture obtained one pout to manufacture red excavations of chloride of polyvinylo having very good properties of solidity the migration and the light.



    EXAMPLE 30 t
We grind for 48 hours, in a mill, 10 parts of bioxydo do titano, 35 per-

 <Desc / Clms Page number 48>

 tios of a 60% solution of a modified urec-alkyd resin in a mixture of 1; 1 of xylbno and of butanot, 10 parts of turpentine and 5 parts of xylene, with 2 parts of the pigment prepared according to Example 3 from 1-amino-2,4-diphenoxybonzene and 2,5-dibromo-1,4-benzoquinone-3,6-dicarboxyliquo acid dianilide. If we pour the coloria lacquer on the back of aluminum foils and pass in the oven at 120 C for one hour,

   Lacquos are obtained which are distinguished by a red nuance which is very rosy and pure, possessing very good properties of aoliditd to light, heat and over-stitching.


    

Claims (1)

SUMMARY The present invention comprises in particular l) A process for preparing dyes EMI49.1 la: .. o1ril 'd: oxa :: in ;; ue, solon loquol on condensa, p-r de') T't: cd :,; known, a dianilo devoid of do #jrouro cH .. '1u.lt',) nlr; uù and corresponding to the following formula I EMI49.2 in which Ar. ot Ar2 each represent a rosto aryl which contains a replaceable substituent or a hydrogen stome in an ortho position to the NH group ot which may include other substituents customary in EMI49.3 the dyes as well as dos hdt-roryclos i condansés, ot EMI49.4 X represented the minl1Priiro group or a secondary amino group or tortiairo or lo groupo 'of which the 5yrnbolo R doaigno an aliphoatic, cycloaliphatiquo, araliphatiquo or aromatic riieto. to obtain a compound answering the following formula II EMI49.5 <Desc / Clms Page number 50> in which EMI50.1 Ar1 'and Ar2t each represent lo r <. ::; tc Jry10t10 corresponding roc; noct.i.v \.' RTK: r, t art ot Ar2, and X has the meaning mentioned above in connection with formula I. 2) Dci1Odr.:s of execution of proc4d <? '* n4- cifitf under 1, presenting los nartic-ilDri4.'g', \ J1 w} nt (prinos odpardmcnt or 0010n loo divonus coihinataons possible ta) we use dianilos of formula I in losquols Ar1 ot Ar2 contionnont each, as substitutable substitute. a dther group ortho portion to the HH group; b) we used back dianils of formula 1 EMI50.2 in the group Ar, ot Ar2 each represent an oato / oc 1 4 am noph6nylo carrying an ûthor group in positions 2 and 5 c) three diiniloa dc formulu 1 are used in losquols Ar and Ar2 each contain an; esto 2-aicoxy .. r-açylamino - o-halogûno-.ph6nyle d) one uses dos dianilos of formula 1 in looquole R rupr <Î3onto a groupu ilkylo lnfSriAlr / o) one uses dos dianilos do formula: in loaquolo X roprGaonto a lower alkylamino group) f) dianils of formula I are used EMI50.3 in louquols X ropr6onto a 14vontuollom phdnylamino group carrying substituents on 10 ring. 3) A variant of the procedure specified under 1, l according to loquollo we saponify we acid dicar- <Desc / Clms Page number 51> EMI51.1 hoxyU't 'crzwsrlnarst ir, c') mr> ('rjr'1n {J: lnt la forr, ulo LV satvrit, EMI51.2 EMI51.3 J: m'1 11'ttJ011J i * T] * t ot '\ fr rr ,, r.¯, ent ,, nt nacun un nsto arylbno which pouf, contain dc.' .. 5uL <stltuantt> 'JtJlJúh in 1 :; .lornt t da "h, a ': rocycl1qtJQ () r. {1,! 1 iuS ut R r:; rrunt un r.; st,) '11 ipMtiquo, cyc11): ll1ph.: at1quo,' H": : l1r, h ':. \ rpJC or': \ rot1quo, we tranifomo 1. ' G 1dCJ di ("rbf) (Y l1q1JO obtained we chloride on bl1m'Jro <J1 ') ddù dicirboxy liquo ot we make r .-' J 1 this djrnicr dvoc do l'irrcnisquo or uno 1: nir, t \; J1 "zL or r; r, j, fr: tu un 3liph3tiquu alcohol, cyclo- 1li) tj'HlqIJ!;, Aroliphatiquo or 5ro; at.iquo. 't1) a t i t.r.r du r, rC), J'J1t ... industrial nou- EMI51.4 calves t EMI51.5 a) The to1or: lnt3 devoid of do groupa EMI51.6 acido sulfoniquo ot corresponding to formula II, EMI51.7 EMI51.8 in which EMI51.9 AT?' and <"vr <> 1 rpr: .ont <: nt each an arylfcno residue which can bear usual substituents in dyes as well as hotûrocyclos C> r.don5v.'5, t <Desc / Clms Page number 52> EMI52.1 X ropr: 1f) ntll le -jioupo!>! #> L no prtimiro or tin groupa 1mlnr) '.l',: <1r.d, ir ,, .JI) #orllslfo or lj 1t ') IJ (\ I ,! - * 'l "ins l"' lUll1 1 R 'i'-il'iiv-1 un r), i to al tt;' 1 '1,' ") 1 \ d, tl '!' JQ. 1l ': lll'lhO "t. ! '!': <} .111 '"1.1) 1,% 11 b) Ic-j.". Ir .. do t, 0ut09: Jorto,> who have (ît - * tints ot pigncnU'c-i "t the help of: dyes s P0 ci fi under -1 a),