Patent GB-713255-A (GB)
Title: Improvements in and relating to methine dyes
IPC: C09B23/14
Filed: 1951-04-09
Abstract: 1 : 8-Trimethylenequinaldinium iodide is prepared by adding paraldehyde (or aldol) in small portions to a refluxing solution of tetrahydroquinoline hydrochloride, ferric chloride, and anhydrous zinc chloride in absolute ethanol, and after removal of the alcohol and precipitation of metal hydroxides, adding sodium iodide and evaporating to dryness under reduced pressure.  1 : 8-(O-phenylene)-quinaldinium iodide is similarly prepared. 1-Methylquinaldinium perchlorate is prepared by adding peraldehyde dropwise to a refluxing mixture of N-methylaniline, o-nitrophenol, and concentrated hydrochloric acid, and finally precipitating with sodium perchlorate.  1-Methyl - 6 - chloroquinaldinium perchlorate, 1 : 8 - ethylenequinaldinium iodide, 1 : 8-(1 : 2) - cyclopentylenequinaldinium iodide, 1-phenylquinaldinium perchlorate (from diphenylamine and crotonaldehyde), 1-phenyllepidinium iodide (from diphenylamine and methylvinyl ketone), 1 : 8 - trimethylenelepidinium iodide, 1 : 8-ethylenelepidinium iodide, 1 : 8-o-phenylenelepidinium iodide, 1 : 8 - (3 : 4 : 5 : 6-tetrahydro - o - phenylene) - lepidinium iodide, and 1 : 8 - o - cyclopentylenelepidinium perchlorate are similarly prepared.  1 : 2 : 3 : 4 : 3a : 8b - Hexahydrocyclopentindole is prepared by reducing 1 : 2 : 3 : 4-tetrahydrocyclopentindole in alcohol with hydrogen in presence of Raney nickel.  1-Acetyltetrahydroquinoline is prepared by reacting acetic anhydride with tetrahydroquinoline.  1-Acetylindoline is similarly prepared.  1 - Ethoxalylacetyltetrahydroquinoline is prepared by adding sodium to a mixture of ethanol and xylene, cooling, adding 1-acetyltetrahydroquinoline and xylene, then ethyloxalate, and finally a ether solution of concentrated sulphuric acid. 1-Ethoxalylacetylindoline is similarly prepared.  4 - Carbethoxy - 1 : 8 - trimethylene - 2 - quinoline is prepared by adding 1-ethoxalylacetyltetrahydroquinoline portionwise to cooled concentrated sulphuric acid, and 4-carboxy-1 : 8-trimethylene-2-quinolone is prepared by refluxing this with aqueous sodium hydroxide.  4 - Carboxy - 1 : 8 - ethylene - 2 - quinoline is prepared by heating ethoxalylacetylindoline with phosphorus pentoxide and phosphoric acid.  1 : 8 - Trimethylylene - 2 - quinolone is prepared by refluxing 4-carboxy-1 : 8-trimethylene-2-quinolone and copper powder in isoquinoline.  1 : 8 - Ethylene - 2 - quinolone is similarly prepared.  1 : 8 - Trimethylene - 2 - thioquinolone is prepared by reacting 1 : 8-trimethylene-2-quinolone in pyridine with phosphorus pentasulphide.  1 : 8-Ethylene-2-thioquinolone is similarly prepared.  2 - Methylmercapto - 1 : 8 - trimethylene-quinolinium iodide is prepared by heating together 1 : 8 - trimethylene - 2 - thioquinolone and methyl p-toluenesulphonate, dissolving in water, and adding aqueous sodium iodide.  2 - Methylmercapto - 1 : 8 - ethylenequinolinium p-toluenesulphonate is similarly prepared.ALSO:A monomethine, carbocyanine, merocarbocyanine, styryl, or pyrrolocarbocyanine dye contains a quinoline nucleus having a bridge of atoms from the 1-position to the 8-position, the atom bridge completing a dihydropyrrole nucleus, a pyrrole nucleus carrying a fused-on ring, or a trihydropyridine nucleus.  Dyes of the general formula: <FORM:0713255/IV(c)/1> wherein r is I and wherein R is a substituted or unsubstituted alkyl group (including an aralkyl group) or aryl groups, X is an acid radical, Z represents the atoms necessary to complete a dihydropyrrole nucleus, a pyrrole nucleus carrying a fused-on ring or a trihydropyridine nucleus Z1 represents the atoms necessary to complete a pyridine nucleus, Z2 represents the non-metallic atoms necessary to complete a 5-or-6-membered heterocyclic nucleus, D1 represents the atoms to complete a benzene nucleus, L is a substituted or unsubstituted methine group, and d is 1 or 2, are prepared by condensing a cyclammonium quaternary salt containing a methyl group in the a - or g -position with a quaternary salt of the general formula: <FORM:0713255/IV(c)/2> (II) preferably in the presence of a basic condensing agent and a reaction medium such as a lower molecular weight alcohol, and with heating.  3-ethyl-1\sv : 8\sv-ethylene-thia-2\sv-cyanine iodide is prepared by heating together 1 : 8-ethylene-2-thioquinolone and methyl p-toluene sulphonate, adding 2-methylbenzthiazole ethiodide, ethyl alcohol, and triethylamine, and refluxing. 1-ethyl-1\sv : 8\sv-trimethylene-2 : 2\sv-cyanine iodide is similarly prepared.  Dyes of the above general formula 1, wherein n is 2, can be prepared by reacting a cyclammonium quaternary salt containing in the a - or g -position a b -arylaminovinyl (e.g. b -acetanilidovinyl) group or a b -alkyl-or b -arylmercaptovinyl group (e.g. b -methylmercaptovinyl or b -methylmercaptobutenyl) with a cyclammonium quaternary salt of the general formula:  <FORM:0713255/IV(c)/3> (III) 3-Ethyl-1\sv : 8-ethyleneoxa-2-carbocyanine iodide is prepared by refluxing together 1 : 8-ethylquinaldinium iodide, b -acetanilidovinyl-benzoxazole ethiodide, ethyl alcohol, and triethylamine, and 9-ethyl-1\sv : 8\sv-ethylene-3-methylthia-2-carbocyanine iodide by refluxing together 1 : 8 ethylenequinaldinium iodide, 2-(2-methylmercaptobutenyl)-benzthiazole methiodideethyl alcohol, and triethylamine.  Dyes of the general formula: <FORM:0713255/IV(c)/4> (IV) wherein n is 1 and D1, Z, X, L, Z2 R, and d are as before are prepared by condensing a cyclammonium quaternary salt containing in a - or g - position a thioether group (e.g. alkylthio, aralkylthio, or arylthio) or a halogen atom (e.g. a chlorine, bromine, or iodine atom) with a cyclammonium quaternary salt of the general formula:  <FORM:0713255/IV(c)/5> (V) 1-Ethyl-1\sv : 8\sv-trimethylene-2 : 4\sv-cyanine iodide is prepared by refluxing together 1 : 8 trimethylenelepidium iodide, 2-iodoquinoline ethiodide, ethyl alcohol, and triethylamine. 1-ethyl-1\sv : 8\sv-ethylene-2 : 4\sv cyanine iodide, and 1-ethyl-1\sv : 8\sv-o-phenylene-2 : 4\sv-cyanine perchlorate are similary prepared. Dyes of the general formula (IV), wherein n is 2, are prepared by condensing a cylammonium quaternary salt of the general formula V above with a cyclammonium quaternary salt containing in the a - or b - position a b -arylaminovinyl or a b -alkyl- or b - aryl-mercaptovinyl group.  3-Ethyl-1\sv : 8\sv-trimethyleneoxa-4\sv-carbocyanine iodide is prepared by refluxing together 1 : 8-trimethylenelepidinium iodide, 2-b -acetanilidovinylbenzoxazole ethiodide, ethyl alcohol, and triethylamine.  3-ethyl-1\sv : 8\sv-trimethylenethia-4\sv-carbocyanine iodide, 3-ethyl-1\sv : 8\sv-ethyleneoxa-4\sv-carbocyanine iodide, 3-ethyl-1\sv : 8\sv-ethylenethia-4\sv-carbocyanine iodide, 3-ethyl-1\sv : 8\sv-o-phenyleneoxa-4\sv-carbocyanine iodide, 3-ethyl-1\sv : 8-o-phenylene - thia-4\sv-carbocyanine iodide, 1\sv : 8\sv-[(1 : 2)-cyclopentylene)-3-ethylthia-4\sv-carbocyanine perchlorate and 3-ethyl-1\sv : 8\sv-(3 : 4 : 5 : 6-tetrahydro-o-phenylene) oxa-4\sv-carbocyanine perchlorate are similary prepared.  Dyes of the general formula:  <FORM:0713255/IV(c)/6> (VI) wherein Q represents the atoms to complete a 5-membered heterocyclic ring, and D1, Z, Z, and L are as before, are prepared by condensing a cyclammonium quaternary salt of the general formula III with a heterocyclic compound of the general formula:  <FORM:0713255/IV(c)/7> (VII) wherein R4 is H or an acyl group and R5 an aryl group.  3-Ethyl-5-[(1 : 8-trimethylene-2 (1)-quinolylidene)-ethylidene]-rhodanine is prepared by refluxing together 1 : 8-trimethylenequinaldinium iodide, 5-acetanilidomethylene-3-ethyl - rhodanine acetic anhydride, and triethylamine.  3-Ethyl-5-[C1 : 8-o-phenylene-2(1) quinolylidene)-ethylidene]-rhodanine and 5-[1 : 8-trimethylene-2(1)-quinolylidene)-ethylidene]-1 : 3- diethyl-2-thiobarbituric acid are similary prepared.  Dyes of the general formula:  <FORM:0713255/IV(c)/8> (VIII) wherein D1, Z, L, and Q, are as above, are prepared by condensing a cyclammonium quaternary salt of the general formula V with a compound of the general formula VII.  Dyes of the general formula:  <FORM:0713255/IV(c)/9> (IX) wherein R, and R2 are alkyl groups and D1, Z, Z1, and X are as before, are prepared by condensing a cyclammonium quaternary salt of the general formula III with the appropriate aldehyde. 2-p-Dimethyl-aminostyryl-1 : 8-trimethylenequinolinium iodide is prepared by refluxing together 1 : 8-trimethylene-quinaldinium iodide, p-dimethylamino-benzaldehyde, ethyl alcohol and piperidine. Dyes of the general formula:  <FORM:0713255/IV(c)/100> (X) wherein R1, R2, D1, Z and X are as before, are prepared by condensing a cyclammonium quaternary salt of the general formula V with the appropriate aldehyde 4-p-Dimethylaminostyryl-1 : 8-trimethylenequinolinium iodide is prepared by refluxing together 1 : 8-trimethylenelepidinium iodide, p-dimethylamino-benzaldehyde, ethyl alcohol, and piperidine.  4-p-Dimethylaminostyryl-1 : 8-o-phenylenequinolinium perchlorate, and 4-p-dimethylaminostyryl-1 : 8-o-phenylenequinolinium perchlorate, 4-p-dimethylaminostyryl-1 : 8-[(1 : 2)-cyclopentylene]-4-p-dimethylaminostyryl-ethylenequinolinium iodide, quinolinium perchlorate, and 4-p-dimethylaminostyryl-1 : 8-(3 : 4 : 5 : 6-tetrahydro-o-phenylene)-quinolinium iodide are similary prepared.  Dyes of the general formula:  <FORM:0713255/IV(c)/111> (XI) wherein Q1 represents the atoms to complete a heterocylic nucleus of the pyrrole series and R3 is a substituted or unsubstituted alkyl group (including an aralkyl group) or aryl group, and D1, Z, Z1, X and L are as before defined, are prepared by condensing a cyclammonium quaternary salt of the general formula III with an aldehyde of the general formula:  <FORM:0713255/IV(c)/122> (XII) 1\sv : 8\sv-Ethylene-2 : 5-dimethyl-1-phenyl-3-pyrrolo- 2\sv-carbocyanine iodide is prepared by refluxing together 1 : 8-ethylenequinaldinium iodide 2 : 5 dimethyl-1-phenyl-pyrrol