Patent GB-1001067-A (GB)
Title: Improvements in or relating to sensitized photographic silver halide emulsions and to new sensitizing dyes
Inventor: LIBEER MARCEL JAN
IPC: C09B23/02
Filed: 1962-04-13
Abstract: The invention comprises asymmetrical cyanine dye salts of formula <FORM:1001067/C4-C5/1> where A is methylene, substituted methylene or <FORM:1001067/C4-C5/2> where Y represents the atoms to complete a benzene or substituted benzene ring, n is 2 or 3, R1 and R2 are alkyl, substituted alkyl, allyl, aryl, substituted aryl, benzyl, substituted benzyl or cycloalkyl, X is an acid radical, r and m are 1 and 2 and Z represents the number of atoms to complete a heterocyclic nucleus containing 5 or 6 atoms.  The invention also comprises merocyanine dyes of formula <FORM:1001067/C4-C5/3> wherein A, n and R1 are the same as above and P and Q are cyano or together complete a heterocyclic ketomethylene nucleus. The cyanine dye salts may be prepared by condensing a 1 : 5-cyclomethylene tetrazolium quaternary salt of formula <FORM:1001067/C4-C5/4> where R1, n, A and X are as above with a cycloammonium quaternary salt of formula <FORM:1001067/C4-C5/5> wherein R2, X, Z and m are as above and D is alkyl- or aryl-mercapto, b -alkyl- or b -aryl-mercaptovinyl, b -arylaminovinyl, b -acetanilidovinyl or b -p-tolusulphamilido group, or with a heterocyclic base of formula <FORM:1001067/C4-C5/6> where R2, Z and m are as above and Y is an aryl-N = group. The merocyanine dyes may be prepared by condensing the 1 : 5-cyclomethylene tetrasodium quaternary salt of the above formula with a heterocyclic compound of formula <FORM:1001067/C4-C5/7> where P and Q are as above and E is alkoxy, arylimino or an acetarylido group.  3 - Ethyl - 4,5 - dihydrotetrazole - quinolinium iodide is reacted with 2-(b -anilethylidene) -3-ethyl - 5 - phenyl - 2,3 - dihydrobenzoxazole; 1,3 - diethyl - 2[b  - (p - tolusulphoanilido)vinyl]-5 - cyano benzimidazolium chloride; 2 - [b -(acetanilido)vinyl] - 3 - ethyl - 5 - phenyl benzothiazolium iodide; 2-methylmercapto-3-methylbenzothiazolium methyl sulphate; 2-(b -anilethylidene) - 3 - ethyl - 2,3 - dihydrobenzselenazole or 2-[b -(acetanilido)vinyl]-3-ethyl naphtho - [1 : 2 - d] - thiazolium iodide to produce the appropriate cyanine dye.  Cyanine dyes are also prepared by reacting 1-ethyl or 1-methyl-6,7 - dihydro - 5H - pyrrolotetrazolium ethyl or alkyl sulphate with 2-(b -anilethylidene) -3-ethylthiazolidine; 2 - b  - (acetanilido) - vinyl - 3-ethyl-benzoxazilium iodide or 2-(b -anilethylidene) - 3 - ethyl - 2,3 - dihydrobenzthiazole. Other cyanine dyes are prepared by reacting 1 - ethyl - 5,6,7,8 - tetrahydrotetrazolopyridinium ethyl sulphate with 2-(b -(anil)-ethylidene - 3 - ethyl - 5,6 - dimethyl - 2,3 - dihydrobenzoxazole and reacting 1,3-diethyl-2-[b -(p-tolusulphanilido)vinyl] - 5,6 - dichlorobenzimidazolium chloride with 3-ethyl-7-chloro-4,5-dihydrotetrazoloquinolinium iodide. Merocyanine dyes are prepared by reacting 3-ethyl-5-acetanilidomethylene-2-thio-2,4-thia-or oxa-zolidonedione with 1-ethyl, allyl or methyl-6,7-dihydro - 5U - pyrrolotetrazolium ethyl or methyl sulphate; 3-ethyl-4,5-dihydrotetrazoloquinolinium iodide or with 7-methyl or 7-chloro-3 - ethyl - 4,5 - dihydrotetrazoloquinolinium iodide. Other merocyanine dyes prepared are by reacting 3-ethyl-4,5-dihydrotetrazoloquinolinium iodide with acetanilido methylene acetonitrile and by reacting 1-methyl-5-phenyl-5,6,7,8 - tetrahydrotetrazolopyridinium iodide with 1 - ethyl - 3 - methyl - 5 - acetanilidomethylene-2-thio-2,4-imidazolidione.  Specification 955,962 is referred to.ALSO:The quaternary alkyl sulphate or iodide salts of 1-alkyl-dihydro-5H-pyrrolo tetrazole, 1-alkyl - 5,6,7,8 - tetrahydropyridotetrazole and 3 - alkyl 4 - 5 - dihydroquinolo - tetrazole are prepared by reacting the deterocyclic compound with dialkyl sulphate or methyl iodide.  1-methyl - 5 - phenyl - 5,6,7,8 - tetrahydropyrido-tetrazolaumiodide is prepared by heating 5-phenyl-pyridotetracole with methyl iodide and then reducing with Raney nickel.  3-ethyl-7-methyl - 4,5 - dihydroquinolinetetrazolaumiodide prepared by refluxing 1,6-dimethyl-2-quinoline with phosphorus oxy- and penta-chlorides to give 2-chloro-6-methyl quinoline which is refluxed with hydrazine to produce 2-hydracino-6-methyl quinoline.  This is reacted with nitrous acid 7-methyl-quinoline-tetracole which on reaction with methyl iodide and reduction with Raney nickel gives the desired salt.  3 - ethyl - 7 - chloro - 4,5 - dihydroquinolino-tetrazolium iodide is prepared as above starting with 1-methyl-6-chloro-2-quinoline. Specification 955,962 is referred to.