Patent GB-816014-A (GB)
Title: Process of making diaryloxyazole quaternary salts, diaryloxazole quaternary salts made thereby, cyanine dyes containing a diaryloxazole nucleus made from such salts and photographic silver halide emulsions containing such dyes
IPC: C09B23/02
Filed: 1956-12-06
Abstract: Diaryl oxazole quaternary halides of the formula <FORM:0816014/IV (b)/1> wherein R represents an alkyl, aralkyl or aryl group, "Hal" represents halogen and R1 and R2 represent aryl groups, are prepared by reacting a compound of the formula <FORM:0816014/IV (b)/2> or the keto form thereof, or the acid addition salts of such compounds, with an acetyl halide preferably in the presence of a dehydrating agent such as acetic or propionic anhydride.  R may represent methyl, ethyl, n-propyl, isopropyl, n-butyl, n-amyl, n-octyl, n-dodecyl, benzyl, phenyl, ortho-, meta- or para-tolyl or paramethoxyphenyl.  R1 and R2 may represent phenyl, ortho-, meta- or para-tolyl, para-chlorophenyl or para-methoxyphenyl.  The halogen anion may be replaced by other anions (X) such as perchlorate, thiocyanate, benzenesulphonate, para - toluenesulphonate, ethylsulphate and methylsulphate.  The products in which X represents halogen or other anions may also be reacted with alkyl isoformanilides such as with ethyl isoformanilides to yield compounds of the formula <FORM:0816014/IV (b)/3> wherein R3 represents a mononuclear aromatic group such as phenyl or tolyl.  The examples describe the preparation of 2 : 3-dimethyl-4 : 5-diphenyloxazolium perchlorate, 3-ethyl-2-methyl - 4 : 5 - diphenyloxazolium perchlorate, 2 - methyl - 3 - octyl - 4 : 5 - diphenyloxazoliumiodide, 2 : 21 - anilinovinyl - 3 - octyl - 4 : 5 - di - phenyloxazoliumiodide, 3 - butyl - 2 - methyl-4 : 5 - diphenyloxazoliumiodide, 2 - methyl-3 : 4 : 5 - triphenyloxazoliumiodide, 2 : 21-anilinovinyl - 3 : 4 : 5 - triphenyloxazoliumiodide, 3 - butyl - 4 : 5 - di - 41 - methoxyphenyl - 2 - methyloxazolium perchlorate and 2 : 21-anilinovinyl - 3 - butyl - 4 : 5 - di - 41 - methoxyphenyloxazolium perchlorate. N-Methyldesylamine hydrochloride and N-ethyldesylamine hydrochloride are prepared by reacting benzoin with methylamine hydrochloride and ethylamine hydrochloride respectively.  N - Butyl - 4 : 41 - dimethoxydesylamine hydrochloride is prepared by reacting 4 : 41-dimethoxybenzoin and butylamine with phosphorus pentoxide and saturating the product with hydrogen chloride.  Specifications 585,707, [Group IV], and 813,178 are referred to.ALSO:Cyanine dyes of the formula <FORM:0816014/IV (c)/1> and merocyanine dyes of the formula <FORM:0816014/IV (c)/2> wherein R represents alkyl, aralkyl or aryl groups, R1 and R2 represent aryl groups, X represents an anion, d is 0 or 1, Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing 5 or 6 atoms in the ring when d=0 or containing 6 atoms in the ring when d=1, R4 represents an alkyl or substituted alkyl group but, when Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the oxazole series, may also represent an aryl group, and Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing 5 or 6 atoms in the ring, are prepared by standard methods from compounds of the formul <FORM:0816014/IV (c)/3> <FORM:0816014/IV (c)/4> <FORM:0816014/IV (c)/5> <FORM:0816014/IV (c)/6> in which R3 is an aryl group such as phenyl or tolyl and X1 is an anion.  R may represent methyl, ethyl, n-propyl, isopropyl, n-butyl, n-amyl, n-octyl, n-dodecyl, benzyl, phenyl, ortho-, meta- or para-tolyl or para-methoxyphenyl.  R1 and R2 may represent phenyl, ortho-, meta-and para-tolyl, para-chlorophenyl or para-methoxyphenyl.  Specifications 585,707, [Group IV], and 813,178 are referred to.