Sulfonsyre- og karboksylgruppefrie aminodifenylindolyl-metan-fargestoffer.Sulfon- resp. karboksylgruppeholdige difenylindolylmetån-fargestoffer som egner seg til farging av ull og silke, er allerede kjent fra følgende patenter: tyske patenter nr. 604.429, 632.448, 635.465, 689.534, 694.444, 709.381, 718.705 og 889.498 samt fransk patent nr. 1.069.776.Oppfinnelsen vedrører sulfonsyre- og karboksylgruppefrie aminodifenylinolylmetan-fargestoffer til farging og trykking av materialer av polymerisater eller blandingspolymerisater av akrylnitril resp. vinylidencyanid, surt modifiserte aromatiske polyestere, lær, tannert bomull, syntetiske superpolyamider og -uretaner, til farging av ligninhoIdige fibre, skrivevæsker, stempelfarger, kulepennpastaer og til anvendelse i gummitrykk, idet fargestoffene erat de har formelhvori R betyr hydrogen, en alkyl-, aralkyl- eller arylrest, en nitro-, cyan-, karboksylsyreester- og eventuelt N-substituert karbonamid-, acyl- eller en alkylsulfonyl- eller arylsulfonylgruppe, Rog Rbetyr enten begge samtidig hydrogen eller R1 betyr en alkyl-, aralkyl-, cykloalkyl- eller arylrest ag Rbetyr en alkyl-, cykloalkyl- eller aralkylrest, R-j betyr hydrogen, en alkyl- eller arylgruppe, en karboksylsyreestergruppe, en eventuelt N-substituert karbonamidgruppe eller en alkoksygruppe, Rbetyr hydrogen, en alkyl-, aralkyl-, cykloalkyl- eller arylr-st, Z betyr hydrogen, halogen,. en lavere alkyl- eller lavere alkoksyrest og X betyr en anionisk rest og hvori de alifatiske, cykloalifatiske og aromatiske rester kan ha ytterligere substituenter som alkyl- og alkoksyrester (1-4 karbonatomer), benzyl, benzyloksy, fenyl, klorfenyl, metylfenyl, etylfenyl, nitrofenyl, cyanfenyl, fenyloksy, halogen, karboksylsyrealkylester-eller eventuelt N-alkylerte karbonamidgrupper (1 eller 2 karbonatomer i alkylresten), idet alkylgruppene kan være videre substituert med Cl, Br og OH, videre substituenter som cyan, nitro, hydroksylamino, metylsulfonyl, etylsulfonyl, benzolsulfonyl, p-toluolsulfonyl, acetoksy, propionyloksy, acetylamino, propionylamino, etylsulfpnyl-amino, metylsulfonylamino, benzoylamino, benzolsulfonylamino, benzoyl eller acetyl.En gruppe spesielt verdifulle fargestoffer innen rammen av de nye produkter med den generelle formel I tilsvarer formel. hvori R' betyr hydrogen eller en lavere alkylrest, R'og R'betyr enten begge samtidig hydrogen eller R-betyr en lavere alkylrest, benzyl eller en eventuelt med klor, brom, lavere alkyl- eller alkoksyrester videresubstituert fenylrest og R'betyr en lavere alkylrest eller benzylresten, R'betyr metyl, fenyl eller med klor., brom eller lavere alkyl- eller alkoksyrester substituert fenyl, R'betyr hydrogen, en lavere alkylrest eller benzyl, Z betyr et halogen, en lavere alkyl- eller en lavere alkoksyrest, og X betyr en anionisk rest. De nye fargestoffer fåes når man kondenserer 4-aminobenzofenoner med den generelle formelhvori R, Rog Rhar den ovenfor angitte betydning med indolderivater med den generelle formel. hvori Rj og Rhar den angitte betydning, i nærvær av sure kondensasjonsmidler til fargestoffer med formel (I) og herved velger utgangs-komponentene fri for sulfonsyre- og karboksylsyregrupper.Som utgangsmateriale til fremstilling av fargestoffene ifølge oppfinnelsen egner seg eksempelvis følgende aminobenzofenoner:. 4-aminobenzofenon, 4-N,N-dimetylaminobenzofenon, 4-N,N-dietylamino-benzofenon, 4-N,N-dibutylaminobenzofenon,. 4"-N-metyl'-N-bksetylamino-benzofenon, 4-N-metyl-N-kloretylaminobenzofenon, 4-N-metyl-N-cyanetylaminobenzofenon, 4-N-etyl-N-cyanetylaminobenzofenon, 4-N-etyl-N-kloretylaminobenzofenon, 4-N-etyl-N-oksetylaminobenzofenori, 4-N-butyl-N-oksetylaminobenzofenon, 4-N-butyl-N-kloretylaminobenzofenon, 4-N,N-dioksetylaminobenzofenon, 4-N,N-dikloretylaminobenzofenon, 4-N-metyl-N-benzylaminobenzofenon, 4-N-etylj-N-metylaminobenzofenon, 4-N-(4'-etoksyfenyl)-N-metylaminoberizofenon, 4-N-(2'-etoksyfenyl)-N-metylaminobenzofenon, 4-N-(4'-klorfenyl)-N-metylaminobenzofenon, 2- metyl-4-N,N-dietylaminobenzofenon, 2-klor-4-N,N-dietylaminobenzo-fenon, 2-metyl-4-N-oksetyl-N-etylaminobenzofenon, 2-klor-4'-N,N-dimetylaminobenzofenon, 2-brom-4'-N,N-dietylaminobenzbfenon, 3-klor-4'-N,N-dietylaminobenzofenon, 4-etyl-4'-N,N-dietylaminobenzofenon, 4-cyan-4'-N,N-dietylaminobenzofenon, 2-klor-4'-N-fenyl-N-metylaminobenzofenon, 2-klor-4'-N-(4"-etoksyfenyl)-N-metylaminobenzofenon, 3- klor-4•-N-fenyl-N-metylaminobenzofenon, 4-fenyl-4'-N-fenyl-N-metylaminobenzofenon, 4-etyl-4'-N-fenyl-N-metylamihobenzofenon, 4- metyl-4'-N-(4"-etoksyfenyl)-N-metylaminobenzofenon, 4-metyl-4 * - N,N-dimetylaminobenzofenon, 4-metyl-4'-N-fenyl-N-metylaminobenzofenon, 4-cyan-4'-N,N-dimetylaminobenzofenon, 4-karbometoksy-4'-N,N-dimetyl-aminobenzofenon, 4-metylsulfonyl-4 *-N-fenyl-N-metylaminobenzofenon.Egnede indolderivater er eksempelvis: 2-metylindol, 2-fenylindol, 2,5-dimetylindol, 2-metyl-5-klorindol, 2-fenyl-5-.metylindol, 2-fenyl-5-klorindol, 1,2-dimetylindol, 1-metyl-2-fenylindol, 1,2,5-trimetylindol, 1,5-dimetyl-2-fenylindol, l,2-dimetyl-5-klorindol, l-metyl-2-fenyl-5-klorindol, l-etyl-2-metylindol, l-etyl-2-fenylindol, l-etyl-2,5-dimetylindol, l-etyl-2-fenyl-5-metylindol, l-etyl-2-metyl-5-klorindol, l-etyl-2-fenyl-5-klorindol, l-benzyl-2-metylindol, l,4,7-trimetyl-2-fenyl-indol, l-n-butyl-2-fenylindol, l-iso-utyl-2-(4'-klorfenyl)-4,6-dimetylindol, l-cyanetyl-2-metylindol, l-cyanetyl-2-fenylindol.Egnede sure kondensasjonsmidler er eksempelvis: Saltsyre, svovelsyre, fosforsyre, fosforoksyklorid, tionylklorid, fosgen,. sinkklorid, aluminiumklorid, tinnklorid eller p-toluensulfonsyre.Reaksjonen kan utføres i nærvær eller fravær av et inert oppløsningsmiddel. Egnede oppløsningsmidler er eksempelvis klorbenzen, o-diklorbenzen, toluen, xylen, benzen, ligroin, dioksan, cykloheksan, tetraklorkarbon, kloroform og i noen tilfelle også metanol, etanol og aceton.Reaksjonen gjennomføres vanligvis ved forhøyet temperatur, f.eks. ved 40-l60°C, fortrinnsvis ved 70-120°C.De anioniske rester X~ kan være såvel uorganiske som organiske ioner. Eksempelvis kan nevnes Cl", Br ,.J , CRSO, C^-SO", p-toluensulfonat-, HSO", benzensulfonat-, p-klorbenzen-sulfonat, fosfat-, acetat-, formiat-, propionat-, oksalat-, laktat-, maleinat-, krotonat-, tartrat-, citrat-, NO^ , perklorat-, ZnCl^ • Typen av de anioniske rester er uten betydning for fargestoffenes egenskaper for så vidt det dreier seg om sterkt fargeløse rester som ikke influerer uheldig på fargestoffenes oppløselighet.Ifølge en ytterligere fremgangsmåte lar en del av fargestoffet ifølge oppfinnelsen seg også danne i nærvær av kondensasjonsmidler ved kondensasjon av benzoylindoler med den generelle formel. med aromatiske aminer med den generelle formelhvori R, Rog Rhar den angitte betydning, mens Rbetyr en alkyl-, cykloalkyl- eller aralkylrest, og Rg betyr en alkyl-, cykloalkyl-, aralkyl- eller arylrest. Som benzoylindoler med den generelle formel IV egner seg til fremstilling av fargestoffene ifølge oppfinnelsen eksempelvis: l-metyl-2-fenyl-3-benzoylindol, 1,2-dimetyl-3_benzoylindol, 1,2,5-trimetyl-3-benzoylindol, 1,5-dimetyl-2-fenyl-3-benzoylindol, 1,2-dimetyl-3-benzoyl-5-klorindol, l-metyl-2-fenyl-3-benzoyl-5_klorindol, l-etyl-2-metyl-3-benzoylindol, l-etyl-2-fenyl-3-benzoylindol, l-benzyl-2-metyl-3-benzoylindol, l,4,7-trimetyl-2-fenyl-3-benzoyl-indol, l-n-butyl-2.-fenyl-3-benzoylindol, l-cyanetyl-2-metyl-3- benzoylindol, l-cyanetyl-2-fenyl-3-benzoylindol, l-metyl-2-(2 klorfenyl)-3-benzoylindol, l-metyl-2-fenyl-3-(3'-klorbenzoyl)-indol, l-metyl-2-fenyl-3-(4'-metylbenzoyl)-indol, 1,2-dimetyl-3-(2klorbenzoyl)-indol, l,2-dimetyl-3-(3rklorbenzoyl)-indol, 1,2-dimetyl-3-(4'-metylbenzoyl)-indol og l-etyl-2-fenyl-3-(2'-klorbenzoyl)-indol.Egnede aromatiske aminer med den generelle formel (V) er eksempelvis: N,N-dimetylanilin, N,N-dietylanilin, N,N-dibutylanilin, N-metyl-N-oksetylanilin, N,N-dioksetylanilin, N-metyl-N-kloretylanilin, N,N-dikloretylanilin, l-N-etyl-N-oksetylamino-3-metylbenzen, 1-N-etyl-N-kloretylamino-3-metylbenzen, N-butyl-N-oksetylanilin, 3klor-l-N,N-dietylanilin, 3klor-l-N,N-dimetylanilin, N-metyl-N-benzylanilin, N-etyl-N-benzylanilin, l-N-etyl-N-benzylamino-3-metylbenzen, N-metyldifenylamin, N-etyldifenylamin, N-cyanetyldifenylamin, N-(4-etoksyfenyl)-N-metylanilin, 3-metoksy-l-N,N-dimetylanilin og 3-etoksy-l-N,N-dietylanilin.Som sure kondensasjonsmidler for denne fremgangsmåte egner seg spesielt fosforoksyklorid, tionylklorid, fosgen, sinkklorid, aluminiumklorid o.l.En ytterligere egnet fremgangsmåte til fremstilling av. de nye fargestoffer består i at man kondenserer benzanilidet med den generelle formel. hvori R har den angitte betydning, mens Rbetyr hydrogen eller en alkylrest, og Rg betyr en aromatisk rest, med aromatiske aminer med den generelle formel (V) i nærvær av sure kondensasjonsmidler og deretter uten isolering av mellomproduktet, med indoler med den generelle formel (III). Som benzanilid (VI), som er egnet for denne fremgangsmåte kan det eksempelvis nevnes: Benzanilid, 2-klorbenzanilid, 3-klorbenzanilid, 2-metylbenzanilid, 3-metylbenzanilid, 4-metylbenzanilid, 2-metoksy-benzanilid, 2-etoksybenzanilid, 2,4-dimetylbenzanilid, 2,5-diklorbenzanilid og 2,6-diklorbenzanilid.Som aromatiske aminer (V) er for denne fremgangsmåte egnet de samme forbindelser som de som ble angitt for annen fremgangsmåte. Som indolforbindelser kan det anvendes de som er angitt som egnet ved første fremstillingsmåte. Som sure kondensasjonsmidler egner seg også her fosforoksyklorid, tionylklorid, fosgen, sinkklorid, aluminiumklorid o.l.Produktene som fåes ifølge fremgangsmåten er meget verdifulle fargestoffer som kan anvendes til fargning og trykking av materialer av lær, tannert bomull, celluloseacetat, syntetiske super-polyamier og -polyuretaner, såvel som til fargning av ligninholdige fibre som kokos, jute og sisal. De er videre egnet til fremstilling av skrivevæske, stempelfarge, kulepennpastaer og lar seg også anvende i gummitrykk. De egner seg fremfor alt godt til fargning og trykking av materialer som helt eller delvis består av polymerisert akrylnitril og/eller vinylidencyanid, eller av sure modifiserte aromatiske polyestere. De utmerker seg her ved meget gode lysekthet, våt-, friksjons- og sublimeringsekthet. De har videre et meget godt trekk-forhold på disse fibre og har en god overfargningsekthet. Fargestoffene danner med anioniske utfellingsmidler som lerjord, tannin, fosforwolfram (molybden)-syrer, lysekte pigmenter, som fordelaktig kan anvendes i papirtrykk.I forhold til det i eksempel 1 i tysk patent. nr. 632.448 omtalte fargestoff av 4-klor-2',5'-dimetyl-benzofenon-diklorid og N-metyl-ot-fenylindol, som ble avsmeltet med p-fenetidin, utmerker de nærmest sammenlignbare fargestoffer ifølge oppfinnelsen seg, som ved nitrogen istedenfor hydrogenatom har en metylgruppe med en betraktelig forbedret oppløselighet: Fargestoffet fra eksempel 1 i tysk patent nr. 632.448 har en oppløselighet på 0,52 g/l., mens fargestoffet ifølge oppfinnelsen har en oppløselighet på 2,84 g/l.Eksempel 1.378 vektdeler N-fenyl-N-metylaminobenzofenon, 27,2 vektdeler l-metyl-2-fenylindol og 35 vektdeler fosforoksyklorid oppvarmes sammen ved 100°C og holdes i 3 timer ved denne temperatur. Den ennå varme smelter setter man til 600 volumdeler 50°C varmt vann og innstiller ved tilsetning av 140 volumdeler 20%- ig natriumacetat-oppløsning pH-verdien på 2. Deretter fullstendiggjør man fargestoffets utfelling ved tilsetning av 30 vektdeler koksalt og lar blandingen omrøre noen timer. Den dannede fargeharpiks adskilles, oppløses i. 4000 volumdeler kokende vann, oppløsningen klares med aktivkull og fargestoffet, etterat oppløsningen har avkjølt seg noe, utfelles ved tilsetning av 90 volumdeler av en oppløsning av sinkklorid i den ~~ samme vektmengde vann. Fargestoffet omrøres noen tid, suges fra og vaskes med 10%- lg koksaltoppløsning. Det således dannede fargestoff tilsvarer formelen. CH. ZnCl3 <£>. I. CH. og farger fibre av polyakrylnitril i et lysekte, blåaktig grønt.Man kommer likeledes til verdifulle fargestoffer, når man i ovennevnte eksempel i stedet for l-metyl-2-fenylindol anvender de ekvivalente mengder av de i følgende tabell oppførte indolderivater.l-n-butyl-2-fenyl-6-metylindol Blåaktig grønn l-n-butyl-2-fenylindol Noe dempet blåaktig grønn Eksempel 2. 45 vektdeler 4-N,N-dimetylaminobenzofenon, 41,4 vektdeler l-metyl-2-fenylindol og 50 vektdeler fosforoksyklorid has sammen og oppvarmes i 3 timer ved 100°C. Den ennå varme smelte helles ut på 1000 volumdeler vann av 50°C og reaksjonsblandingen innstilles på pH-verdien 2 med 320 volumdeler 20%- ig natriumacetatoppløsning. Etterat oppløsningen har avkjølt seg, utfeller man fargestoffet ved tilsetning av 100 vektdeler koksalt og 150 volumdeler av en oppløsning av sinkklorid i samme vektmengde vann. Til ytterligere rensing oppløser man fargestoffet i kokende vann, klarer med aktivkull og feller det ved tilsetning av 30 volumdeler sinkkloridoppløsning. Det således dannede fargestoff'farger fibre av polyakrylnitril i et lysaktig grønnaktig blått.Gjennomfører man omsetningen etter den ovenfor angitte fremgangsmåte med de i følgende tabell oppførte aminobenzofenoner og indolderivater så får man likeledes fargestoffer som utmerker seg ved meget gode fargemessige egenskaper.Eksempel 3. 19,7 vektdeler 4-aminobenzofenon og 14,5 vektdeler 1,2-dimetylindol innføres i 200 vektdeler alkohol og reaksjonsblandingen blandes ved 30°C med 50 vektdeler konsentrert saltsyre (d = 1,19). Etterat man har oppvarmet blandingen til 80°C, omrører man den i 3 timer ved denne temperatur. Deretter avdestilleres 120 volumdeler alkohol og det mørkfargede residuum settes til en blanding av 250 volumdeler mettet koksaltoppløsning og 250 vektdeler is. Man lar fargestoffsuspensjonen omrørenatten over, suger den fra og renser fargestoffet ved omkrystallisering fra vann og utfelling med koksalt.I stedet for 1,2-dimetylindol lar seg med fordel også anvende de følgende indoler til fremstilling av fargestoffer ifølge den ovennevnte fremgangsmåte.- Erstatter man 4-aminobenzofenon med kjernesubstituerte 4-aminobenzofenon og omsetter disse på den omtalte måte med indoler får man ved fargning av polyakijylnitril følgende fargetoner:. Eksempel 4.Polyakrylnitrilfibre innbringes ved 40°C i badforhold. 1:40 i et vandig bad som pr. liter inneholder 0,75 g 30#-ig. eddiksyre, 0,38 g natriumacetat og 0,3 g av det i eksempel 1 beskrevne aminodifenylindolylmetanfargestoff. Man oppvarmer i løpet av 20-30. min. til koking og holder badet i 30-60 min. ved denne temperatur. Deretter spyles og tørkes polyakrylnitrilfibrene. Man får en blåaktig grønn fargning av meget god lysekthet, som dessuten utmerker seg ved en meget god overfargningsekthet i eddiksurt og svovelsur bad.Eksempel 5». Av 2 vektdeler av aminodifenylindolylmetanfargestoffet,. hvis fremstilling ble omtalt i eksempel 2, 60 vektdeler glycerin,. 20 vektdeler vann og 20 vektdeler sprit tilberedes en stempelfarge,. som gir klare, utmerkede trykk.Eksempel 6.Ostindisk bastardlær, som på vanlig måte er forberedt til fargning farges i badforhold 1:10 med 1% av det i eksempel 2 omtalte fargestoff som på forhånd var deigdannet med den samme. mengde 30#-ige eddiksyre ved 40°C i 45 min. i walkekar. Læret opp-rettes på kjent måte. Man får en grønnaktig blå fargning med gode ekthetsegenskaper.Eksempel 7 .19,7 vektdeler benzanilid og 22,7 vektdeler N-metyl-4-etoksydifenylamin oppvarmes med 40 vektdeler fosforoksyklorid i 3 timer ved 100°C. Deretter inrifører man 20,7 vektdeler l-metyl-2- j i. fenylindol og oppvarmer videre i 3 timer ved 100°C. Den ennå varme smelte uttas på 1000 volumdeler vann og innstilles på pH 2 med 275 volumdeler 20/S-ig natriumacetatoppløsning. Blandingen lar man etteromrøre i flere timer, skiller ut fargeharpiksen, oppløser den i 3000 volumdeler kokende vann.under tilsetning av 300 volumdeler iseddik og klarer oppløsningen med aktivkull. Fra oppløsningen feller man fargestoffet ved tilsetning av 50 volumdeler av en oppløsning av sinkklorid i samme vektdel vann.Fargestoffet farger materialer av polyakrylnitril i en blåaktig grønn farge med meget gode ekthetsegenskaper.Eksempel 8.Sure modifiserte polyglykoltereftalatfibre og typen DACR0N 64 (DuPont), resp. slik de er beskrevet i belgisk patent nr. 549.179 og i US-patent nr. 2.893-816, innbringes ved 20°C i badforhold 1:40 i et vandig bad som pr. liter inneholder 3 g natriumsulfat, 0,5 - 2 g av en oleylpolyglykoleter (50 mol etylenoksyd), 2,5-5 g difenyl og 0,3 g av fargestoffet med formelen i eksempel 1, og innstilles med eddiksyre til en pH-verdi på 4,5-5. Man oppvarmer i løpet av 30 min. ved 98°C og holder badet i 60 min. ved denne temperatur. Deretter spyles og tørkes fibrene. Man får en blåaktig grønn fargning med meget gode ekthetsegenskaper.Eksempel 9.Sure modifiserte polyglykoltereftalatfibre som i eksempel 8 innbringes ved 20°C i badforhold 1:40 i et vandig bad som pr. liter inneholder 6-10 g natriumsulfat, 0,5- 1 g oleylpolyglykoleter (50 mol etylenoksyd), 0-15 g dimetyl-benzyl-dodecyl-ammoniumklorid og 0,3 g av fargestoffet med formelen i eksempel 1, og innstilles med eddiksyre til pH 4-5. Man oppvarmer i løpet av 30 min. ved 120°C og holder badet i 60 min. ved denne temperatur.Deretter spyles og tørkes fibrene. Man får en blåaktig grønn fargning med meget gode ekthetsegenskaper.Ved fremgangsmåten ifølge eksemplene 8 og 9 lar også samtlige andre i de forangående eksempler nevnte fargestoffer seg farge på sure modifiserte aromatiske polyesterfibre, idet det oppnås fargetoner, som er like eller tilsvarende de på polyakrylnitril.Sulfonic acid and carboxyl group-free aminodiphenylindolyl-methane dyes. Carboxyl group-containing diphenylindolylmethane dyes suitable for dyeing wool and silk are already known from the following patents: German Patents Nos. 604,429, 632,448, 635,465, 689,534, 694,444, 709,381, 718,705 and 889,498 and French Patent No. 1,069,776. relates to sulfonic acid and carboxyl group-free aminodiphenylinolylmethane dyes for dyeing and printing materials of polymers or mixed polymers of acrylonitrile resp. vinyl residency, acid-modified aromatic polyesters, leather, tinned cotton, synthetic superpolyamides and urethanes, for dyeing lignin-containing fibers, writing fluids, stamps, ballpoint pen pastes and for use in rubber printing, the dyes having the formula wherein alkyl, R or aryl radical, a nitro, cyano, carboxylic acid ester and optionally N-substituted carbonamide, acyl or an alkylsulfonyl or arylsulfonyl group, R 2 R represents either simultaneously hydrogen or R 1 means an alkyl, aralkyl, cycloalkyl or aryl radical ag R represents an alkyl, cycloalkyl or aralkyl radical, R 1 represents hydrogen, an alkyl or aryl group, a carboxylic acid ester group, an optionally N-substituted carbonamide group or an alkoxy group, R represents hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical. , Z means hydrogen, halogen ,. a lower alkyl or lower alkoxy radical and X represents an anionic radical and in which the aliphatic, cycloaliphatic and aromatic radicals may have additional substituents such as alkyl and alkoxy acid radicals (1-4 carbon atoms), benzyl, benzyloxy, phenyl, chlorophenyl, methylphenyl, ethylphenyl, nitrophenyl, cyanophenyl, phenyloxy, halogen, carboxylic acid alkyl ester or optionally N-alkylated carbonamide groups (1 or 2 carbon atoms in the alkyl radical), the alkyl groups may be further substituted by Cl, Br and OH, further substituents such as cyano, nitro, hydroxylamino, methylsulfonyl, ethylsulfonyl, ethylsulfonyl , benzolsulfonyl, p-toluolsulfonyl, acetoxy, propionyloxy, acetylamino, propionylamino, ethylsulfonylamino, methylsulfonylamino, benzoylamino, benzolsulfonylamino, benzoyl or acetyl.A group of particularly valuable dyes within the scope of the formula I corresponds to the general products. wherein R 'represents hydrogen or a lower alkyl residue, R' and R 'mean either both hydrogen or R- represents a lower alkyl residue, benzyl or an optionally substituted phenyl residue with chlorine, bromine, lower alkyl or alkoxy acid and R' means a lower alkyl radical or benzyl radical, R 'represents methyl, phenyl or with chlorine, bromine or lower alkyl or alkoxy acid substituted phenyl, R' represents hydrogen, a lower alkyl radical or benzyl, Z represents a halogen, a lower alkyl or a lower alkoxy radical, and X represents an anionic residue. The new dyes are obtained by condensing 4-aminobenzophenones of the general formula wherein R, Rog Rhar is as defined above with indole derivatives of the general formula. wherein Rj and Rhar have the stated meaning, in the presence of acidic condensing agents for dyes of formula (I) and thereby select the starting components free of sulfonic acid and carboxylic acid groups. The following aminobenzophenones are suitable as starting material for the preparation of the dyes according to the invention: 4-aminobenzophenone, 4-N, N-dimethylaminobenzophenone, 4-N, N-diethylamino-benzophenone, 4-N, N-dibutylaminobenzophenone,. 4 "-N-methyl'-N-oxyethylamino-benzophenone, 4-N-methyl-N-chloroethylaminobenzophenone, 4-N-methyl-N-cyanethylaminobenzophenone, 4-N-ethyl-N-cyanethylaminobenzophenone, 4-N-ethyl- N-chloroethylaminobenzophenone, 4-N-ethyl-N-oxyethylaminobenzophenone, 4-N-butyl-N-oxyethylaminobenzophenone, 4-N-butyl-N-chloroethylaminobenzophenone, 4-N, N-dioxetylaminobenzophenone, 4-N-ethenol, 4-N 4-N-methyl-N-benzylaminobenzophenone, 4-N-ethyl-N-methylaminobenzophenone, 4-N- (4'-ethoxyphenyl) -N-methylaminoberizophenone, 4-N- (2'-ethoxyphenyl) -N-methylaminobenzophenone, 4-N- (4'-chlorophenyl) -N-methylaminobenzophenone, 2-methyl-4-N, N-diethylaminobenzophenone, 2-chloro-4-N, N-diethylaminobenzophenone, 2-methyl-4-N-oxetyl -N-ethylaminobenzophenone, 2-chloro-4'-N, N-dimethylaminobenzophenone, 2-bromo-4'-N, N-diethylaminobenzphenone, 3-chloro-4'-N, N-diethylaminobenzophenone, 4-ethyl-4 ' -N, N-diethylaminobenzophenone, 4-cyano-4'-N, N-diethylaminobenzophenone, 2-chloro-4'-N-phenyl-N-methylaminobenzophenone, 2-chloro-4'-N- (4 "-ethoxyphenyl) -N-methylaminobenzophenone, 3-chloro-4 • -N-phenyl-N-methylaminobenzophen one, 4-phenyl-4'-N-phenyl-N-methylaminobenzophenone, 4-ethyl-4'-N-phenyl-N-methylamihobenzophenone, 4-methyl-4'-N- (4 "-ethoxyphenyl) -N- methylaminobenzophenone, 4-methyl-4 * - N, N-dimethylaminobenzophenone, 4-methyl-4'-N-phenyl-N-methylaminobenzophenone, 4-cyano-4'-N, N-dimethylaminobenzophenone, 4-carbomethoxy-4'- N, N-dimethyl-aminobenzophenone, 4-methylsulfonyl-4 * -N-phenyl-N-methylaminobenzophenone. Suitable indole derivatives are, for example: 2-methylindole, 2-phenylindole, 2,5-dimethylindole, 2-methyl-5-chloroindole, 2-phenyl-5-methylindole, 2-phenyl-5-chloroindole, 1,2-dimethylindole, 1-methyl-2-phenylindole, 1,2,5-trimethylindole, 1,5-dimethyl-2-phenylindole, 1 , 2-dimethyl-5-chloroindole, 1-methyl-2-phenyl-5-chloroindole, 1-ethyl-2-methylindole, 1-ethyl-2-phenylindole, 1-ethyl-2,5-dimethylindole, 1-ethyl -2-phenyl-5-methylindole, 1-ethyl-2-methyl-5-chloroindole, 1-ethyl-2-phenyl-5-chloroindole, 1-benzyl-2-methylindole, 1,4,7-trimethyl-2 -phenyl-indole, 1n-butyl-2-phenylindole, 1-iso-methyl-2- (4'-chlorophenyl) -4,6-dimethylindole, 1-cyanethyl-2-methylindole, 1-cyanethyl-2-phenylindole. Suitable acid condensas ionic agents are, for example: hydrochloric acid, sulfuric acid, phosphoric acid, phosphorus oxychloride, thionyl chloride, phosgene ,. zinc chloride, aluminum chloride, tin chloride or p-toluenesulfonic acid. The reaction may be carried out in the presence or absence of an inert solvent. Suitable solvents are, for example, chlorobenzene, o-dichlorobenzene, toluene, xylene, benzene, ligroin, dioxane, cyclohexane, tetrachlorocarbon, chloroform and in some cases also methanol, ethanol and acetone. The reaction is usually carried out at elevated temperature, e.g. at 40-160 ° C, preferably at 70-120 ° C. The anionic residues X ~ can be both inorganic and organic ions. Examples which may be mentioned are Cl ", Br, .J, CRSO, C 2 -SO", p-toluenesulfonate, HSO ", benzenesulfonate, p-chlorobenzene sulfonate, phosphate, acetate, formate, propionate, oxalate , lactate, maleinate, crotonate, tartrate, citrate, NO 2, perchlorate, ZnCl 2 • The type of anionic residues is irrelevant to the properties of the dyes in the case of strongly colorless residues which do not adversely affect According to a further process, a part of the dye according to the invention can also be formed in the presence of condensing agents by condensation of benzoylindoles of the general formula, with aromatic amines having the general formula wherein R, Rog Rhar has the meaning given, while R -, cycloalkyl or aralkyl radical, and R 9 represents an alkyl, cycloalkyl, aralkyl or aryl radical As benzoylindoles of the general formula IV are suitable for the preparation of the dyes according to the invention, for example: 1-methyl-2-phenyl-3-benzoylindole , 1,2-dimethyl-3-benzo ylindole, 1,2,5-trimethyl-3-benzoylindole, 1,5-dimethyl-2-phenyl-3-benzoylindole, 1,2-dimethyl-3-benzoyl-5-chloroindole, 1-methyl-2-phenylindole 3-benzoyl-5-chloroindole, 1-ethyl-2-methyl-3-benzoylindole, 1-ethyl-2-phenyl-3-benzoylindole, 1-benzyl-2-methyl-3-benzoylindole, 1,4,7-trimethylindole 2-phenyl-3-benzoyl-indole, 1n-butyl-2,-phenyl-3-benzoylindole, 1-cyanethyl-2-methyl-3-benzoylindole, 1-cyanethyl-2-phenyl-3-benzoylindole, 1-methyl -2- (2 chlorophenyl) -3-benzoylindole, 1-methyl-2-phenyl-3- (3'-chlorobenzoyl) -indole, 1-methyl-2-phenyl-3- (4'-methylbenzoyl) -indole, 1,2-Dimethyl-3- (2-chlorobenzoyl) -indole, 1,2-dimethyl-3- (3-chlorobenzoyl) -indole, 1,2-dimethyl-3- (4'-methylbenzoyl) -indole and 1-ethyl-2 -phenyl-3- (2'-chlorobenzoyl) -indole. Suitable aromatic amines of the general formula (V) are, for example: N, N-dimethylaniline, N, N-diethylaniline, N, N-dibutylaniline, N-methyl-N -oxetylaniline, N, N-dioxethylaniline, N-methyl-N-chloroethylaniline, N, N-dichloroethylaniline, 1N-ethyl-N-oxethylamino-3-methylbenzene, 1-N-ethyl-N-chloroethylamino-3-methylbenzene, N -butyl-N-oxethylaniline, 3-chloro- 1N, N-diethylaniline, 3-chloro-1N, N-dimethylaniline, N-methyl-N-benzylaniline, N-ethyl-N-benzylaniline, 1N-ethyl-N-benzylamino-3-methylbenzene, N-methyldiphenylamine, N-ethyldiphenylamine, N-cyanethyldiphenylamine, N- (4-ethoxyphenyl) -N-methylaniline, 3-methoxy-1N, N-dimethylaniline and 3-ethoxy-1N, N-diethylaniline. Acidic condensing agents for this process are particularly suitable for phosphorus oxychloride, thionyl chloride, , zinc chloride, aluminum chloride, etc.An further suitable process for the preparation of. the new dyes consist of condensing the benzanilide with the general formula. wherein R is as defined, while R represents hydrogen or an alkyl residue, and Rg represents an aromatic residue, with aromatic amines of the general formula (V) in the presence of acidic condensing agents and then without isolation of the intermediate, with indoles of the general formula ( III). Examples of benzanilide (VI) suitable for this process are: Benzanilide, 2-chlorobenzanilide, 3-chlorobenzanilide, 2-methylbenzanilide, 3-methylbenzanilide, 4-methylbenzanilide, 2-methoxybenzanilide, 2-ethoxy, 2-ethoxy 4-dimethylbenzanilide, 2,5-dichlorobenzanilide and 2,6-dichlorobenzanilide. As aromatic amines (V), the same compounds as those indicated for another process are suitable for this process. As indole compounds, those indicated as suitable in the first method of preparation can be used. Phosphorus oxychloride, thionyl chloride, phosgene, zinc chloride, aluminum chloride etc. are also suitable as acidic condensing agents. The products obtained according to the process are very valuable dyes which can be used for dyeing and printing materials of leather, tinned cotton, cellulose acetate, synthetic super-polyamers and polyurethane. , as well as for dyeing lignin-containing fibers such as coconut, jute and sisal. They are further suitable for the production of writing fluid, stamp paint, ballpoint pen pastes and can also be used in rubber printing. Above all, they are well suited for dyeing and printing materials which consist wholly or partly of polymerized acrylonitrile and / or vinylidencyanide, or of acid-modified aromatic polyesters. They are distinguished here by very good light fastness, wet, friction and sublimation fastness. They also have a very good draw ratio on these fibers and have a good over-dyeing fastness. The dyes form with anionic precipitants such as clay soil, tannin, phosphorous tungsten (molybdenum) acids, lightfast pigments, which can be advantageously used in paper printing. Compared to that in Example 1 of the German patent. No. 632,448 discloses dyes of 4-chloro-2 ', 5'-dimethyl-benzophenone dichloride and N-methyl-ot-phenylindole, which were melted down with p-phenetidine, the almost comparable dyes according to the invention being distinguished, as in the case of nitrogen instead of hydrogen atom has a methyl group with a considerably improved solubility: The dye from Example 1 of German Patent No. 632,448 has a solubility of 0.52 g / l., while the dye according to the invention has a solubility of 2.84 g / l. Example 1,378 parts by weight of N-phenyl-N-methylaminobenzophenone, 27.2 parts by weight of 1-methyl-2-phenylindole and 35 parts by weight of phosphorus oxychloride are heated together at 100 ° C and kept for 3 hours at this temperature. The still hot melt is added to 600 parts by volume of 50 ° C hot water and by adding 140 parts by volume of 20% sodium acetate solution the pH value is adjusted to 2. Then the precipitation of the dye is completed by adding 30 parts by weight of common salt and allowing the mixture to stir. timer. The color resin formed is separated, dissolved in 4000 parts by volume of boiling water, the solution is clarified with activated charcoal and the dye, after the solution has cooled somewhat, is precipitated by adding 90 parts by volume of a solution of zinc chloride in the same amount by weight of water. The dye is stirred for some time, sucked off and washed with 10% - 1 g of saline solution. The dye thus formed corresponds to the formula. CH. ZnCl3 <£>. I. CH. and dyes fibers of polyacrylonitrile in a light-true, bluish green. Valuable dyes are also obtained, when in the above example instead of 1-methyl-2-phenylindole the equivalent amounts of the indole derivatives listed in the following table are used. 2-phenyl-6-methylindole Bluish green ln-butyl-2-phenylindole Some muted bluish green Example 2. 45 parts by weight of 4-N, N-dimethylaminobenzophenone, 41.4 parts by weight of 1-methyl-2-phenylindole and 50 parts by weight of phosphorus oxychloride are combined. and heated for 3 hours at 100 ° C. The still hot melt is poured onto 1000 parts by volume of water at 50 DEG C. and the reaction mixture is adjusted to pH 2 with 320 parts by volume of 20% sodium acetate solution. After the solution has cooled, the dye is precipitated by adding 100 parts by weight of common salt and 150 parts by volume of a solution of zinc chloride in the same amount by weight of water. For further purification, the dye is dissolved in boiling water, clarified with activated charcoal and precipitated by adding 30 parts by volume of zinc chloride solution. The dye thus formed dyes fibers of polyacrylonitrile in a light greenish blue. If the reaction is carried out according to the above procedure with the aminobenzophenones and indole derivatives listed in the following table, dyes which are distinguished by very good color properties are also obtained. Example 3. 19 7 parts by weight of 4-aminobenzophenone and 14.5 parts by weight of 1,2-dimethylindole are introduced into 200 parts by weight of alcohol and the reaction mixture is mixed at 30 DEG C. with 50 parts by weight of concentrated hydrochloric acid (d = 1.19). After heating the mixture to 80 ° C, it is stirred for 3 hours at this temperature. Then 120 parts by volume of alcohol are distilled off and the dark residue is added to a mixture of 250 parts by volume of saturated brine and 250 parts by weight of ice. The dye suspension is allowed to stir overnight, sucked off and the dye is purified by recrystallization from water and precipitation with brine. Instead of 1,2-dimethylindole, the following indoles can advantageously also be used for the preparation of dyes according to the above process. 4-aminobenzophenone with core-substituted 4-aminobenzophenone and reacting these in the manner described with indoles, the following tones are obtained by dyeing polyacrylonitrile :. Example 4. Polyacrylonitrile fibers are introduced at 40 ° C in bath conditions. 1:40 in an aqueous bath as per. liters contains 0.75 g 30 # -ig. acetic acid, 0.38 g of sodium acetate and 0.3 g of the aminodiphenylindolylmethane dye described in Example 1. You heat up in 20-30. my. for boiling and holding the bath for 30-60 min. at this temperature. The polyacrylonitrile fibers are then rinsed and dried. You get a bluish green coloration of very good lightfastness, which is also distinguished by a very good over-staining fastness in acetic acid and sulfuric acid baths. Example 5 ». Of 2 parts by weight of the aminodiphenylindolylmethane dye ,. whose preparation was described in Example 2, 60 parts by weight of glycerin ,. 20 parts by weight of water and 20 parts by weight of alcohol are prepared in a stamp color. which gives clear, excellent prints.Example 6.Indian bastard leather, which is prepared in the usual way for dyeing, is dyed in a bath ratio of 1:10 with 1% of the dye mentioned in Example 2 which had previously been dough-formed with the same. amount of 30 # -acetic acetic acid at 40 ° C for 45 min. and walkekar. The doctrine is corrected in a known manner. A greenish blue coloration is obtained with good authenticity properties. Example 7. 19.7 parts by weight of benzanilide and 22.7 parts by weight of N-methyl-4-ethoxydiphenylamine are heated with 40 parts by weight of phosphorus oxychloride for 3 hours at 100 ° C. Then 20.7 parts by weight of 1-methyl-2-phenylindole are introduced and further heated for 3 hours at 100 DEG C. The still hot melt is taken out on 1000 parts by volume of water and adjusted to pH 2 with 275 parts by volume of 20 .mu.g of sodium acetate solution. The mixture is allowed to stir afterwards for several hours, the color resin is separated, it is dissolved in 3000 parts by volume of boiling water, with the addition of 300 parts by volume of glacial acetic acid and the solution is treated with activated carbon. From the solution, the dye is precipitated by adding 50 parts by volume of a solution of zinc chloride in the same part by weight of water. The dye dyes polyacrylonitrile materials in a bluish green color with very good authenticity properties. Example 8. Acid modified polyglycol terephthalate fibers and type DACR0N 64 . as described in Belgian Patent No. 549,179 and in U.S. Patent No. 2,893-816, are introduced at 20 ° C in a bath ratio of 1:40 into an aqueous bath as per liters contains 3 g of sodium sulfate, 0.5 - 2 g of an oleyl polyglycol ether (50 mol of ethylene oxide), 2.5-5 g of diphenyl and 0.3 g of the dye of the formula in Example 1, and is adjusted with acetic acid to a pH value at 4.5-5. You heat up within 30 min. at 98 ° C and hold the bath for 60 min. at this temperature. The fibers are then rinsed and dried. A bluish green coloration is obtained with very good authenticity properties. Example 9. Acid modified polyglycol terephthalate fibers as in Example 8 are introduced at 20 ° C in a bath ratio of 1:40 in an aqueous bath as per liters contains 6-10 g of sodium sulfate, 0.5-1 g of oleyl polyglycol ether (50 moles of ethylene oxide), 0-15 g of dimethyl-benzyl-dodecyl-ammonium chloride and 0.3 g of the dye of the formula in Example 1, and is adjusted with acetic acid to pH 4-5. You heat up within 30 min. at 120 ° C and holds the bath for 60 min. at this temperature.Then the fibers are rinsed and dried. A bluish green coloration is obtained with very good authenticity properties. In the process according to Examples 8 and 9, all the other dyes mentioned in the preceding examples can also be dyed on acid-modified aromatic polyester fibers, color tones equal to or similar to those of polyacrylonitrile being obtained.