Patent GB-1102891-A (GB)
Title: Process for the preparation of heterocyclammonium betaines
IPC: C07D277/84
Filed: 1965-04-26
Abstract: Cyanine and merocyanine dyes are prepared by condensing in the presence of a basic condensing agent a sulphobetaine of the Formula I <FORM:1102891/C4-C5/1> wherein R represents an alkyl, substituted alkyl, aryl or substituted aryl group, Z represents the atoms necessary to complete a substituted or unsubstituted 5- or 6-membered heterocyclic ring which may be fused with a substituted or unsubstituted benzene, hydrogenated benzene naphthalene or thionaphthene ring, R1 represents hydrogen or an alkyl, aralkyl or aryl group, m is 0 or 1 and n is 0 or 1 with a quaternary compound of the formula <FORM:1102891/C4-C5/2> where R2 represents an alkyl, substituted alkyl, aryl or substituted aryl group, Z1 is the same as Z in Formula I, d is 0 or 1 and X is an acid anion, or with a heterocycle of the formula <FORM:1102891/C4-C5/3> where R3 represents an alkyl or aryl group and Q represents <FORM:1102891/C4-C5/4> group, where R4 is hydrogen, an alkyl, aryl, substituted aryl, substituted amino, substituted carbonamido, substituted sulphonamido, substituted sulphamyl or substituted carbamyl group, R5 is hydrogen, an alkyl or aryl group and W represents a sulphur, oxygen or selenium atom. Examples 11-15 relate to the preparation of 1,11 - diethyl - 2,21 - cyanine bromide, 11 - ethyl - 3 - methylthia - 21 - cyanine bromide, 3 - carboxymethyl - 11 - ethylthia - 21 - cyanine bromide, 3 - ethyl - 5 - [(1 - sulphobutyl) - 4(1H) - pyridylidene] - rhodanine and 3 - ethyl - 5 - [(4 - sulphobutyl - 4(1H) - pyridylidene) - rhodanine.  1 - Ethyl - 2 - [3 - ethyl - 4 - phenyl - (4 - oxazolin - 2 - ylidene) - methyl] quinolinium iodide and 1 - ethyl - 11 - a  - hydroxypropyl-2,21-cyanine iodide are also specified.ALSO:Heterocycloammonium sulphobetaines of the formula <FORM:1102891/C2/1> wherein R represents an alkyl group, substituted alkyl group, an aryl group or a substituted aryl group, Z represents the atoms necessary to complete a substituted or unsubstituted 5- or 6-membered heterocyclic ring which may be fused with a substituted or unsubstituted benzene, hydrogenated benzene, naphthalene or thionaphthene ring, R1 represents hydrogen or an alkyl, aralkyl or aryl group, m is 0 or 1 and n is 0 or 1, are made by reacting an aqueous solution of an alkali metal sulphite or metabisulphite with a quaternary ammonium salt of the Formulae II or III <FORM:1102891/C2/2> or <FORM:1102891/C2/3> wherein Y represents halogen, a phenoxy group or -SR2, where R2 is defined as R above, X is an acid anion, or when R in Formula II represents a sulpho group and X an hydroxyl ion, the internal anhydride of such a quaternary salt. Preferred compounds are those derived from pyridine and quinoline, but other specified heterocycles are thiazole, benzothiazole, thionaphtheno - 71,61,4,5 - thiazole, naphthothiazole, oxazole, benzo- and naphtho - oxazole, selenazole, benzo- and naphtho-selenazole, thiazoline, 3,3 - dialkylindolenine, imidazole, benzo- and naphtho-imidazole.  The heterocyclic ring or carbocyclic rings fused thereto may be substituted, e.g. by halogen, alkyl, aryl, 2-thienyl, hydroxy, alkoxy or dioxymethylene groups.  The group R may be substituted by carboxy or sulpho groups.  The sulphobetaines are used in the synthesis of dyes (see Division C4).  The phosphorodichloridyl compounds of the Formula III may be prepared by reacting a ketone of the formula <FORM:1102891/C2/4> with phosphorous oxychloride.  The quaternary ammonium methyl sulphates of the Formula II wherein R is a methyl group are prepared by treating the free base with dimethyl sulphate.  The internal anhydride of the compound of the Formula III corresponding to4-phenoxy-1-(4-sulphobutyl) pyridinium hydroxide is prepared by reacting 4-phenoxypyridine with 1,4-butane sultone. 4-Chloroquinoline may be prepared by treating quinoline N-oxide with phosphorous oxychloride.