Патент USA US3090792код для вставки
United States Patent 0 l ice 3,090,782 Patented May 21, 1963 2 1 Q are the supplementary members of a heterocyclic ring system selected from the group consisting of indoline 3,090,782 PROCESS FOR THE PRODUCTION OF CYANINE DYESTUFFS Max Coenen, Gruiten, Rhineland, Oskar Weissel, Krefeld Urdingen, and Walter Wonder, Leverkusen, Germany, assignors to Farbcnfabriiren Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed Mar. 4, 1959, Ser. No. 797,057 Claims priority, application Germany Mar. 6, 1958 7 Claims. (Cl. Mil-240.6) The present invention is concerned with new cyanine and benzothiazole ring systems, R3 is a saturated alkyl radical with up to 18 carbon atoms, R, is an auxochrome group, R5 is a saturated alkyl radical with up to 4 carbon atoms, or a phenyl group, R6 is a hydrogen atom or a saturated alkyl radical with 10 up to 4 carbon atoms, and n is zero or the integer l, in the presence of an acidic condensing agent. More particularly, in Formula I the group dyestu?s and with a process for the production thereof. It is known to produce cyanine dyestuffs having a cyano radical (—CEN) in the alpha position on the I’A\\ methine chain by reacting quaternary cyclic ammonium 15 salts, which contain in the reactive position a thio-ether, -1~i b: may be, for instance, a seleno-ether or a substituted or unsubstituted amino group, in the presence of condensing agents which are usually basic, with either N-substituted heterocyclic cya nomethylene compounds or their salts or reacting them 20 with unsubstituted cyanomethylene heretrocyclic com pounds and quaternizing the thus formed cyanine bases. We have now found that cyanine dyestuffs, the methine wherein E1, E2, E3, and E4 may be, for instance, (methylidyne) chain of which is substituted by at least one cyano group, can be produced in a technically simple 25 manner and usually with excellent yields by reacting an aldehyde of the general formula: (I) ,a Rl-N—b (=o-cH),,.=e-oH0 2 —N (caHs) (C2H4CN), -N(C4Ha) lca?scl) —NHCOCH3, --NHCOC2H5 CN —NHCOC8H5(phenylcarbonylamino) wherein A are supplementary members of an indolenine —NHSO2C6H5(phenylsulfonamido), —COOH, —CN ring system, R, is a saturated alkyl radical with up to 18 carbon atoms, 35 R; is a substituent selected from the group consisting of (a) hydrogen, cyano, a lower alkoxycarbonyl radical (R—O~—OC--), the alkoxy radical of which contains not —CONHC6H5(phenylaminocarbonyl) , —SO2NHC2H5 more than 4 carbon atoms, or a carbamoyl (NH;CO—-) 40 Or an alkylcarhamoyl or arylcarbamoyl (R—-NH—-CO—) radical, or (b) a lower alkanoyl (R—CO--) radical hav~ ing not more than 4 carbon atoms, or a benzoyl radical, and m is zero or the integer l, with a compound of the general formula: (II) --COOCH3, —COOC3H5, —COOCgHq, —COOC,H9 —-COOC5H5(phen0xycarbonyl), —CONHCHa —C0NHC2H5, —CONHC3H7, ~CONHC4H9 N02; G1 and 6; may be, for instance, —CH3, —CgHs, —C3l-l7, —C4H9, —C8H5(phenyl); the group ,A,‘ further may be, for instance, 45 T-X wherein X is a radical selected from the group consisting of (a) a radical of the general formula: 50 wherein G1 and G2 have the same signi?cance as above. In Formula II the group (b) a radical of the general formula: __D._R4 (c) a radical of the general formula: """" "B ___‘“~ 55 —OH=O'E;OH:CH);:N—R: may be, for instance, l R: 60 (d) a radical of the general formula: ,Q\ —O=O—-—N—~R3 65 wherein B are the supplementary members of a 5 or 6 atom heterocyclic ring system, D is a phenylene radical, Z are the supplementary members of an indole ring 70 system, M has the same signi?cance as R2, 3,090,782 4 R1 in Formula I, and R3, L and T in Formula II may be, for instance, —-CH3, -C2H5, —-C3H7, ——C4H9, —-C5Hn, and so on to C18H31. R2 in Formula I may be, besides the signi?cance al ready speci?ed hereinbefore, for instance, -COOCH3i -—COOC2H5, -COOC3H7, —COOC4HB, —CONHz, —CONHCH3, —-CON(CH3)2, —-CONHC2H5, —CON(C2H5)2, --CONHC6H5 (phenylaminoearbonyl), 10 15 -—COCH3, —-COC2H5, -—COC4H9. R4 in Formula II may be, for instance, ——OCH3, -—N(C4H9) (C2H4Cl), —N(CH3) (C6H5) (methylphen ylamino), -—N(C2H5) (C6H5) (ethylphenylamino) -—N(CH3) (C6H4OCH3) (methylmethoxyphenylamino) . R5 and R6 in Formula 11 may be, besides the signi? 20 cance given above, for instance, —~CH3, —-C2H5, ——C3H7, and C4119. Suitable aldehydes of the mentioned type are, for ex ample, 1,3 ,3-trimethyl-Z-cyanomethylene-inodoline-w-aldehyde, 25 1, 3, 3 -trimethyl-5-chloro-Z-cyanomethylene indoline-w-aldehyde, 1,3,3 -trimethyl-5-methyl-2-cyanomethylene-indoline w-aldehyde, 1,3 ,3 -trimethyl-5-ethoxy-Z-cyanomethylene indoline-w-aldehyde, 1,3,3 -trimethyl-5<phenyl-2-cyanomethylene-indoline (ii-aldehyde, 1,3 ,3-trimethyl-S-carbornethoXy-2-cyan0rnethy1ene indoline-w-aldehyde, 35 1,3-dimethyl-3-ethyl-2-cyanomethylene-indoline-w aldehyde, 1-ethyl~3,3-dimethyl-5-methoxy-2-cyanomethylene indoline-w-aldehyde, 40 1-octadecyl-3 ,3 -dimethyl-Z-cyanOmethyIene-indoline w-aldehyde, 1,3,3 -trimethyl-S-dimethylamino-Z-cyanomethylene indoline-w-aldehyde, 1,3, 3-trimethyl-5,7-dimethoxy-2-cyanomethylene indoline-w-aldehyde, 1, 3 ,3 ,5 ,6-pentamethyl-2-cyanomethylene-indoline w-aldehyde, 1,3 ,3 -trimethyl-4-methoxy‘7-methyLZ-cyanomethylene indoline~w-aldehyde, 1,3 ,3 -trimethyl-6,7-benzo-2-cyanome thylene-indoline aldehyde, 1,3 ,3-trimethyl-2 (m,'y-dicyanopropenylidene ) - indoline-w-alclehyde and 1, 3 ,3-trimethy1-2d( 'y-cyanopropenylidene ) indoline-w aldehyde. Such aldehydes are obtainable, for example, by the action of N-methyl formanilide in the presence of phos phorus oxychloride on the corresponding cyanomethyl ene indoline derivatives, for examples, by the process de 60 70 scribed in US. patent application Serial No. 737,474, ?led May 26, 1958, now US. Patent No. 2,957,005. Suitable methylene bases of the hereinbefore speci?ed type are, for example, 1,3,3-trimethyl-2-methylene-ind0line, 1,3,3-trirnethyl-S-chloro-2-methylene-indoline, 1,3,3-trimethyl-5-methyl-2-methylene-indo1ine, 1,3,3-trimethyl-5-ethoxy-2-methylene~indoline, 1,3,3-trimethyl-5-phenyl-2-methylene-indoline, 1,3,3-trimetl1yl-5 -carb0rnethoXy~2-rnethylene-indoline, 1,3-dimethyl-3 -ethyl-2-methylene-indoline, 1 ethyl-3,3-dimethyl-S-methoxy-Z-methylene-indoline, 1 octadecyl-3,3-dimethyl-2-methylene-indoline, 1,3,3 -trimethyl-5 -dimethylamino-2-methylene-indoline, 1,3 ,3-trirnethyl-5,7-dimethoxy-2-methylene—indoline, 1,3,3,5,?-pentamethyl-Z-methylene-indoline, 3,090,782 1 ,3,3-trimethyl-4-methoxy-7-methyl-2-methylene indoline, A special class of new dyestuffs of the kind mentioned above corresponds to the following formula: l,3,3-trimethyl-6,7-benzo-2-methylene-indoline, l ,3,3 -trimethy‘l-Z-cyanomethylene-indoline, 1,3,3-trimethyl-5-chloro-Z-cyanomethylene-indoline, 1,3,3-trimethyl-5-rnethyl-2-cya.nomethylene-indoline, 1,3,3-trimethyl-5 -ethoxy-2-cyanomethylene-indoline, N wherein A, M, Q, R1, R3 and Y- have the signi?cance as 1 ,3, 3 ~trimethyl-5 -phenyl-2-cyanomethylene-indoline, described above. 1 , 3 , 3 -trimethyl-5 -carbometh oxy-2-cyanomethylene Speci?c preferred examples of compounds conform indoline, l,3-dimethyl-3-ethyl-2-cyanomethylene-indoline, 1-ethyl-3,3-dimethyl-S-methoxy-Z-cyanomethylene ing to this formula, whose preparations and uses are de scribed respectively in Examples 17, 16, 11, 10, and 19, are the following: indoline, l-octadecyl-3,3-dimethyl-2-cyanomethylene-indoline, l,3,3-trimethyl-5-dimethylamino-Z-cyanomethylene indoline, l,3,3~trimethyl-5,7-dimethoxy-2-cyan0methylene indoline, 1,3,3,5,6-pentamethyl-Z-cyanomethylene-indoline, 1,3,3-trimethyl-4-methoxy-7-methyl-2-cyanomethyl ene-indoline, and 1,3,3-trimethyl-6,7-benzo-2-cyano l M CH; C H; C Ha C H; + 15 Cl 611, 20 methylene-indoline. CH: CH; bluish red hm CH: CH; + Suitable reactive indoles are, for example, l-methyl-Z phenyl-indole and Z-methyl-indole. As examples of suit able quaternary cyclic ammonium salts there may be mentioned 2,3-dimethyl-benzthiazolinium salts. The mentioned cyanomethylene bases can be obtained, for example, by the action of cyanogen halides on the corresponding methylene indoline derivatives, for exam ple, by the process described in US. patent application 30 Serial No. 735,992, ?led May 19, 1958, now US. Patent No. 2,993,907. As acidic condensing agents there are advantageously used inorganic acid chlorides, such as phosphorus oxy chloride or thionyl chloride. Further suitable acidic con densing agents are organic acid chlorides and anhydrides, such as acetyl chloride and acetic anhydride, as well as concentrated mineral acids, such as sulphuric acid and phosphoric acid. In some cases it is recommended to use 40 glacial acetic acid-triethylamine as the condensing agent. Suitable solvents are, for example, aromatic; aliphatic and cycloaliphatic hydrocarbons, such as benzene, ligroin and cyclohexane, aliphatic, araliphatic and aromatic ethers, chlorinated aliphatic and aromatic hydrocarbons, such as chloroform and chlorobenzene, aliphatic ketones, such as acetone, as well as low molecular weight fatty acids, such as acetic acid. The reaction usually proceeds even at room tempera ture. In other cases it can be advantageous to increase the temperature somewhat to, for example, 40-100” C. A smooth reaction of this type of the aldehydes to be used according to the invention of the Formula I with compounds of the Formula II was not to be foreseen since it was to be expected that the reactivity of the aldehyde group would be strongly in?uenced by the 55 cyano group present on the same carbon atom in the same manner as the methylene hydrogen in the cyano methylene-indolines obtainable by the process according to US. Patent Application Serial. No. 735,992, methyl ene hydrogen of which is frequently inert in the case of 60 many reactions due to the cyano 0 group present so that, for example, alkylations or acylations were not success The dyestuffs obtainable according to the invention are ful. in the same way as the already known cyanine dyestulfs, According to the invention new dyestuffs of the general 65 valuable sensitizers for photographic silver halide emul‘ formula may be obtained. sions. Furthermore they are suitable for dyeing and printing materials such as ?bres, threads, strips and woven materials, made from polyacrylonitrile, acryloni 1 ON ' trile-containing mixed polymers or acetate rayon. The dyeings and printings obtained with the dyestuffs wherein A, X, R1, R2 and m have the same signi?cance 70 according to the invention on these materials are char as mentioned above and Y‘ is an anion, for instance, Cl’, Br’, 1', 80,", N03’, H2PO4', HPO4", C104’, CHaCOO’, C2H5COO', CCl3C0O', C6H5SO3', acterized by very good fastness and especially by excel lent stability to light and are clearly superior, in this re spect, to the already known dyestuffs of the Astraphloxine 75 type that are devoid of cyano radicals. 3,090,782 8 7 Example 3 Production of 2-(1,3,3-trimethy1-5-methoxy-indole)-2' It is known that the cyano group attached to the methine chain is saponi?ed very quickly and completely by heat ing in an aqueous acid medium. Since the free carboxylic (1',3 ’,3'-trimethyl-5’-methoxy-indole) -a-cyano-trimethine acids which result are immediately decarboxylated under cyanine chloride. the reaction conditions, compounds devoid of cyano radi cals can be very easily produced in this manner. Not only the rapid ability to hydrolyze of the cyano group but also the instability to light that is to be expected with the sensitizing effect appeared to exclude the use of these dyestuffs for the dyeing of textiles, for instance. It was, therefore, surprising, that the dyestu?s accord ing to the invention, containing cyano groups, are suitable for printing and dyeing material such as those speci?ed 12.8 grams 1,3,3-trimethyl-5-methoxy-2-cyanomethy1ene above. indoline-w-aldehyde, 10.2 grams 1,3,3-trimethyl-5-meth The dye baths and printing pastes can contain the usual 15 oxy-2-methylene-indoline and 7.5 grams phosphorus oxy additives, including levelling agents, such as substituted chloride are reacted in the presence of 20 milliliters chloro polyglycol ethers, condensation products of aromatic form in the same manner as in Example 2. Greenish sulpho acids or condensation products of ‘high molecular shining crystals are obtained. Yield: 19.2 grams, color of weight aliphatic amines with ethylene oxide, or dispersion solution in water: bluish-red. agents, such as fatty alcohol sulphonates, condensation 20 Example 4 products of high molecular weight alcohols and ethyl ene oxide or cellulose sulphite waste liquor products. Production of 2-(1,3,3-trimethyl-5-chloro-indole)-2’-(1', One can dye and print with these dyestuffs by the usual 3',3’-trimethyl - 5' - chloro - indole)-a-cyano-trimethine methods, for example, by boiling the materials to be dyed cyanine chloride. in aqueous dye baths, optionally with the addition of 25 acids, or by treating the materials with printing pastes containing the dyestuffs, and subsequently steam treating. The following examples are given for the purpose of illustrating the invention: 30 Example 1 Production of 2-(1,3,3,S-tetramethyl-indole)-2'-(1’,3', 3',S'-tetramethyl-indole)~a-cyano-trimethinecyanine chlo ride. CH3 CH5 CH3 CH3 1’ Cl (EH! CH5 red 13.0 grams 1,3,3-trimethyl-5-chloro-2~cyanomethylene-in doline-w-aldehyde, 10.4 grams 1,3,3-trimethyl-5echloro-2 35 methylene-indoline, 7.6 grams phosphorus oxychloride and 40 milliliters chloroform are heated together under re?ux for 30 minutes. The reaction mixture is evaporated to dryness. The so-obtained crude dyestuff is boiled with 50 milliliters water, ?ltered and washed with water. A 40 brown powder is obtained. Yield: 25.7 grams, color of solution in water: scarlet-red. A mixture of 120 grams 1,3 ,3,S-tetramethyl-Z-cyanometh Example 5 ylene-indoline-w-aldehyde, 93.5 grams 1,3,3,5-tetrameth Production of 2-(1,3,3 - trimethyl-S-carbomethoxy-in yl-2~methylene-indoline and 200 milliliters chloroform are dole)-Z'-(1',3',3'-trimethyl - indole)-ot-cyano - trimethine heated to boiling and 75 grams phosphorus oxychloride cyanine chloride. added dropwise in the course of 25 minutes. The reac tion ‘mixture is subsequently heated under re?ux for a Example 2 Production of 2-(1.3,3-trimethyl-5-methoxy-indole)-2' CH: CH; further 15 minutes, evaporated to dryness and the residual crude dyestutf recrystallized from water. Metallic shining 50 crystals are obtained. Yield: 181 grams, color of solu tion in water: scarlet red. 55 \ omooo l/ CH: OH! + o \ 01 bluish red (1',3',3’-trimethyl-indole)-a-cyano - trimethine - cyanine 17.1 grams of dyestuft are obtained when 13.1 grams 1,3,3 chloride. trimethyl-5-carbomethoxy-Z-cyanomethylene - indolinc-w / on, aldehyde ‘and 8.7 grams 1,3,3-trimethyl~2-methylene-in on, doline were reacted and recovered in the same manner as \ 60 described in Example 2. A ?ne crystalline powder is ob tained. Color in methanol: bluish-red. Example 6 Production of 2-(1,3,3-trimethyl-5,7-dimethoxy-indole) bluish-red 65 A mixture of 12.8 grams 1,3,3-trimethyl-5-methoxy-2 2’-(1’,3',3'-trimethyl - 5' - chloro - indole)-a-cyano-tri methine-cyanine chloride. cyanomethylene-indoline~w-aldehyde, 8.7 grams 1,3,3-tri methyl-2-methylene-indoline and 20 milliliters chloroform is mixed in the course of 2 minutes with 7.5 grams phos phorus oxychloride. The ‘mixture automatically warms 70 up to boiling point. It is boiled under re?ux for an addi tional period of 5 minutes, then evaporated to dryness and the residual crude idyestul’f recrystallized from water. Crystals having a metallic sheen are obtained. Yield: 75 By the reaction of 6.8 grams 1,3,3-trimethyl-5,7-dimeth 22.0 grams, color of solution in water: bluish-red. 8,090,782 V grams of dyestulf. This is a brown powder. methanol: bluish-red. zene is mixed with 6.0 grams thionyl chloride and heated under re?ux for 10 minutes. After cooling the dyestutf formed is ?ltered off with suction and washed with ben zene. The dyestuff is in the form of red-brown crystals. Yield: 21.0 grams, color of the solution in water: red Color in Example 7 Production of 2-(1,3,3,5,6-pentamethyl-indolc)-2’-(1‘,3’, orange. 3'-trimethyl-S’ecarbomethoxy - indole)-a-cyanotrimethine cyanine chloride. on, on, on. \0/ CH + / / ‘EN ’ Example 11 Production of 2-(l,3,3-trimethyl-S-methoxy-indole)-2' ( 1', 3’,3 ',5 ’-tetramethy1-indole ) ~a-7-dicyano-trimethine-cy anine chloride. o o 0 CH; O=O—OH=0H-C on 10 \O \ - on, 10 ene-indoline-w-aldehyde and 11.6 grams l,3,3-trimethyl-5— chloro-2-cyanomethylene-indoline in 100 milliliters ben oxy-2ecyanornethylene-indoline-w-aldehyde and 5.2 grams 1,3,3-trimethyl-2-methylene-indoline in accordance with the method described in Example 2 there is obtained 8.6 - CH3 Cl \\ N N bluish d5. $11, red CH3 \ * CHaO By the reaction of 6.6 grams l,3,3,5,6—pentamethyl-2 l bluish cyanometihylene-w-aldehyde and 5.7 grams 1,3,3-trimethyl CH; CH: red 5-carbomethoxy-2-tnethylene~indoline in accordance with 20 12.8 grams 1,3,3-trimethyl-S-methoxy-Z-cyanomethylene the method described in Example 2, 7.8 grams of dyestu? indoline-w-aldehyde, 10.6 grams 1,3,3,5-tetramethyl-2-cy are obtained. This is a ?ne crystalline powder. Color in ianomethylene-indoline and 6.0 grams thionyl chloride are methanol: bluish-red. reacted in the presence of 100 milliliters benzene in the Example 8 manner described in Example 5. The dyestutf is obtained Production of 2~(1-ethyl-3,3-dimethyl-5-methoxy-in in the form of dark red crystals. Yield: 24.3 grams, color of solution in water: bluish-red. dole)'2’-(l’~ethyl-3',3'-dimethyl - 5' - methoxy-indole)-a cyano-trirnethineeyanine chloride. 30 Example 12 Production of 2-(1,3,3-trimethyl-indole)-2'-(l',3’,3’-tri methyl-indole ) -aq-dicyano-pentamethine-cyanine perchlo rate. By the reaction of 6.8 grams l-ethyl~3,3-dimethyl-S-meth oxy-Z-cyanomethylene-indoline-w-aldehyde with 5.5 grams l-cthyl-3,3-dimethyl - 5 - rnethoxy-Z-rnethylene-indoline according to the method described in Example 2, 9.5 40 2.3 grams 1,3,3-trimethyl-2-(uq-dicyano-propenylidene)~ indoline-w-aldehyde, 1.5 grams 1,3,3-trirnethyl-2-methyl ene-indoline, 1.3 grams phosphorus oxychloride and 35 grams of dyestuff are obtained. This is in the form of metallic shining crystals. Color in methanol: bluish-red. Example 9 Production of 2-(1 ,3,3-trimethyl-5-phenyl~indole)-2'-( l ’, milliliters chloroform are heated together under re?ux for two hours. The reaction mixture is then evaporated to dryness. The residue is taken up in 150 milliliters meth anol, ?ltered and mixed with 10 milliliters 10 percent am 3’, '~tritnethyl - 5' - methoxy-indole)-a-cyano-trimethine cyanine chloride. CH3 \ / CH1 CH1 CH3 N éHl 2111: bluish red By the reaction of 7.6 grams 1,3,3-trimethyl-5-phenyl-2 cyano-methylene-indolinew-aldehyde with 5.1 grams 1,3,3 monium perchlorate. The dyestutf perchlorate precipi trimethyl-S-methoxy-Z-methylene - indollne according to with isopropanol. methanol: violet. tates out as a blue powder. the method described in Example 2, 9.7 grams of dyestuff are obtained. This is a brown crystalline powder. Color 60 in methanol: bluish-red. (3'-methyl~benzthiazole)-a-cyano - trimethine - cyanine methylsulphate. 3’,3'-trimethyl~indole)-a-'y-dicyano - trimethine - cyanine 65 chloride. OH; 0 Example 13 Production of 2-(1,3,B-trimethyl-S-methoxy-indole)-2' Example 10 Production of 2-( l,3,3~trimethyl-5-chloro-indole)-2'-(1', CH; 7 It is separated olf and washed Yield: 2.0 grams, color of solution in OH: CH: OH: \ 1‘ 0 C1 70 N/ t... a... \N/ (‘1H5 | CH3 red-orange A mixture of 2.6 grams 1,3,3-trimethyl-S-methoxy-Z-cy nno-methylene-indolmew-aldehyde, 2.8 grams 2,3-dimeth A solution of 11.3 grams 1,3,3-trimethyl-2-cyanomethyl 75 yl-benzthiazolium-mcthyl-sulphate, 1.0 gram triethylamine 3,090,782 12 11 time, the dyestu? precipitates. The mixture is diluted with 100 milliliters benzene, the precipitate is separated and and 20 milliliters glacial acetic acid is heated under re?ux for 15 minutes. The reaction mixture is then diluted with 50 milliliters hot water. After cooling, the dyestuff, which is obtained in the form of metallic shining crystals, is separated o?'. Yield: 4.1 grams, color of solution in methanol: bluish-red. Washed with benzene. One obtains a light orange pow der. Yield: 24.3 grams, color of solution in water is scarlet red. Example 17 Example 14 Production of 2—(1,3,3-trimethyl-indole)-3'-(1’,-methyl 2'-phenyl-indole)-a—cyano-dimethine-cyanine perchlorate. Production of 2-(1,3,3-trimethyl - 5 - methoxy-indole) 2’-( l’,3’,3'-tnimethyl - 5'-methoxy-indole) - a?-dicyano 10 trimethine-cyanine-chloride. A mixture of 12.8 grams 1,3,3-trimethyl-5-methoxy 20 Z-cYanomethyIene-indoline-w-aldehyde, 11.4 grams 1,3,3 trimethyl-S - methoxy~2 - cyanomethylene-indoline, 7.7 orange-red grams phosphorus oxychloride and 20 milliliters chloro A solution of 10.0 grams l,3,3-trimethyl-2-cyanomethyl form are refluxed for 10 minutes. Then the chloroform ene-indoline-w-aldehyde, 8.3 grams l-methyl-Z-phenyl-in dole and 4 milliliters phosphorus oxychloride in 40 milli and the unreacted phosphorus oxychloride are distilled oil, ?rst under atmospheric pressure and ?nally under liters chloroform is heated under re?ux for 60 minutes. reduced pressure. The remaining raw dyestuff is re The reaction mixture is then evaporated to dryness. The crystallized in 800 milliliters water. On obtains a brown residual crude dyestu?' is dissolved in 500 milliliters meth powder. Yield: 16.0 grams, solution color in water: anol and precipitated out as the perchlorate with 70 milli bluish red. liters 10 percent ammonium prechlorate solution. The Example 18 dyestutf perchlorate is separated oil and washed with a 30 little methanol. The dyestulf is a red-brown powder. Production of 2-(1,3,3,5-tetramethyl-indole)-2'-(l',3’, Yield: 17.0 grams, color of solution in methanol: orange 3',5'-tetramethyl-indole) - aq-dicyano - trimethine-cy red. anine-chloride. 1,. t Example 15 Production of 2-(l,3,3-trimethyl-indole)-3'-(2'-methyl indole)-wcyano-dimethine-cyanine chloride. 40 scarlet red 12.0 grams l,3,3,5-tetramethyl-2 - cyanornethylene-in doline-w-aldehyde, 10.6 grams 1,3,3,5-tetramethyl-2-cy ano-methylene-indoline and 7.7 grams phosphorus oxy 6.4 grams phosphorus oxychloride is added dropwise in chloride are reacted according to Example 17. The raw the course of 5 minutes to a solution of 9.5 grams 1,3,3 dyestu? is recrystallized in 350 milliliters water. trimethyl-Z-cyanomethylene-indoline-w~aldehyde and 5.5 obtains a red powder. Yield: 13.6 grams, solution color in Water is scarlet red. grams a-methyl-indole in 50 milliliters chloroform. The reaction mixture is then heated under re?ux for an addi The following examples demonstrate the dyeing process tional period of 5 minutes and subsequently evaporated to dryness. with some new dyestuffs. The residue is preferably heated up with a Example 19 1 part by weight of the dyestuff of the formula: little water. After cooling, the undissolved dyestuff is separated off. It is in the form of ‘a brown powder. Yield: 13.1 grams, color of solution in methanol: orange red. 0E. Example 16 CH3‘) Production of 2-(1,3,3,5 - tetramethyl-indole)-2-(1', 3',3',-trimethyl-5-chloroindole)-|x,'y - dicyano-trimethine cyanine-chloride. CH3 CH8 One 60 on, /c\ OH: \0/ \ N/ G=C—CH=(|3—O/ 0N CN \N ([JH I + \ OH. é H1 + 1 I ol bluish red is dissolved in 300 parts by weight of water. 3 parts by weight 30% acetic acid and one part by weight sodium acetate are added to the solution. 100 parts by weight of a woven textile made from polyacrylonitrile or an acrylonitrile-containing mixed polymer are immersed in this dye solution at about 50° C., the temperature in 12.0 grams 1,3,3,5-tetramethyl—Z-cyanomethylene- in 70 creased in the course of 20 to 30 minutes to boiling point and dyeing carried out at the boiling temperature for doline-w-aldehyde and 11.6 grams 1,3,3-trimethyl-5- chlo ro-2-cyanomethylene-indoline are dissolved in 50 milli liters hot benzene, and after cooling the solution 6.0 grams thionylchloride are added. The mixture auto matically warms up to the boiling point. one to one and half hours. After washing and drying, a strong bluish-red dyed material is obtained, which possess excellent fastness and an exceptionally good sta After a short 75 bility to light. 8,090,782 14 13 Example 20 1 part by weight of the dyestuff having the formula whose preparation is described in Example 17 herein and (b) a 1,3,3-trialkyl-Z-cyanomethyleneindoline of the formula before: Gi CH; CH: CH: \ / CH: G5 * / a 10 l. bluish red in which formulae is dissolved in 3000 parts by weight of water and used in the manner described in Example 19 hereinbefore for 15 dyeing 100 parts by weight of polyacrylonitrlle thread, R1 and R5 are each an alkyl radical having up to 18 if desired with the addition of a levelling and/or disper sion agent. A material is obtained which is dyed with a G1 and G, are each a radical of the group consisting carbon atoms, of alkyl and phenyl, and clear bluish red and possesses very good fastness and an especially good light stability. 20 Example 21 1 part by weight of the dyestuff having the formula E3 is a radical of the group consisting of hydrogen, lower alkyl, lower alkoxy, and halogen. 3. A cyanine dyestuff of the formula whose preparation is described in Example 18 herein 25 30 4. A cyanine dyestuff of the formula is dissolved in 3000 parts by weight of water. 100 parts 35 by weight of material made from polyacrylonitrile or a mixed polymer containing acrylonitrile are placed on this dye solution at about 50° C., the temperature is increased within a period of 20 to 30 minutes ‘to boiling point and maintained at this temperature for l to 1% hours. After 40 washing and drying, a material is obtained dyed with a very clear scarlet shade which possesses very good fast ness and an excellent stability to light. We claim: 1. A cyanine dyestu? of the formula 45 G: G: G1 G: 011, \ / CH; CH3 CH: 5. A cyanine dyestutf of the formula CH; CH; CH] t 6. A cyanine dyestuff of the formula in which 55 R1, R3, 6;, and G2 are each lower alkyl, E3 is a radical of the group consisting of hydrogen, lower OHl 011g 0 HI alkyl, lower alkoxy, and halogen, and Y" is an anion. 2. A process for the production of a cyanine dyestuff which comprises mixing in an inert solvent in the pres 60 ence of an ‘acidic condensing agent at a temperature be tween room temperature and about 100° C., approximate ly equimolecular amounts of 65 (a) a cyanomethyleneindoline carboxaldehyde of the formula 1 70 75 7. A cyanine dyestu? of the formula OH: [CHO / OH: Cg: / CHI O / N $11; a an \ (SH; (References on following page) 3,090,782 15 16 References Cited in the ?le of this patent FOREIGN PATENTS UNITED STATES PATENTS 2,158,287 Konig _______________ __ May 16, 1939 2,165,337 Brooker ______________ __ July 11, 1939 2,345,094 BI'OOk?I' et a1 _________ .... Mar. 28, 1944 2 ’ 542401 ’ Doyle etal ____________ __ Feb. 20 ’ 1951 2’848’296 ‘Heller """"""""" "' Aug‘ 19’ 1958 620,802 Great Britain _________ __ Mar. 30, 1949 éusma —————————————— -— Df-l 1;’ £1‘; 5 2,893,816 Tsang _________________ .._ July 7, 1959 2,918,369 2,953,561 Dorrenbos ____________ __ Dec. 22, 19159 10 Dorrenbos ___________ __ Sept. 20, 1960 1 "many -------------- -- “ Y 1 OTHER REFERENCES . . Dyes, vol. Venkatararnan: The Chem1stry of Synthetic II, page 1175, Academic Press Inc., N.Y., 1952.