Patent GB-891767-A (GB)
Title: Improvements in or relating to photographic dye-developers of the anthraquinone series
IPC: C09B1/28
Filed: 1958-08-14
Abstract: Amines of the formula <FORM:0891767/IV (b)/1> where R is hydrogen or alkyl or the R's are joined to form an ethylene or propylene linkage to complete a 5 or 6 carbon cycloaliphatic ring and Y is a possibly alkyl-substituted ortho- or para-dihydroxyphenyl group, are made by condensing a dialkoxybenzaldehyde with a ketone of the formula <FORM:0891767/IV (b)/2> hydrogenating the unsaturated product, condensing the ketone with hydroxylamine, hydrogenating the oxime so formed to obtain an amine and hydrolysing the alkoxy groups. Alternatively, the ketone condensation product may be reductively aminated to the amine with ammonia and hydrogen.  Benzaldehydes specified are the 2 : 5- and 3 : 4-dimethoxy compounds and ketones mentioned are acetone, methyl-ethyl ketone, diethyl ketone, phenyl acetone, cyclopentanone and cyclohexanone.  In an example, acetone and 2 : 5-dimethoxybenzaldehyde are reacted to form 1 : 5-bis-(21 : 51-dimethoxy phenyl)-penta-1 : 4-dien-3-one which is hydrogenated to give 1 : 5-bis-(21 : 51-dimethoxyphenyl)-3-pentanone, the oxime of which is hydrogenated to form 1 : 5-bis-(21 : 51-dimethoxyphenyl)-3-pentylamine hydrochloride which is hydrolysed to yield 1 : 5-bis-(21:51-dihydroxyphenyl)-3-pentylamine hydrobromide.  Amines of the formula <FORM:0891767/IV (b)/3> where Y has the meaning given above, R1 is hydrogen, methyl or ethyl, R2 is hydrogen or alkyl and R3 is alkylene are prepared by condensing an amine of the structure <FORM:0891767/IV (b)/4> where Y1 is a dialkoxy derivative of Y, with an aldehyde or ketone of the formula <FORM:0891767/IV (b)/5> hydrogenating the resulting imine and hydrolysing the alkoxy groups.  An aldehyde which may be used is b -2 : 5-dimethoxyphenyl-propionaldehyde.  In an example, 2 : 5-dimethoxyphenethylamine is reached with 2 : 5 dimethoxyphenylacetone and simultaneously hydrogenated and the product obtained is hydrolysed to yield a  - methyl - b , b 1 - bis - (2 : 5 - dihydroxy - phenyl)-diethylamine hydrobromide.ALSO:The invention comprises dye developers of the formulae <FORM:0891767/IV (c)/1> <FORM:0891767/IV (c)/2> wherein one or two X1's are radicals of the formula <FORM:0891767/IV (c)/3> the remainder being an alkyl, alkoxy or nitro group or a halogen or hydrogen atom; X is a <FORM:0891767/IV (c)/4> radical; n is 1 or 2; Y is an unsubstituted, alkyl-substituted or halogen-substituted ortho or para dihydroxyphenyl group; each R is hydrogen, alkyl or an aryl group, or both R's together represent an ethylene or propylene group to complete a cycloaliphatic ring; R1 is hydrogen, methyl or ethyl; R2 is hydrogen or alkyl; R3 is alkylene; and Z is hydrogen, hydroxyl, halogen, cyano, carboxylic acid, sulphonic acid, alkyl, aryl, aryloxy, alkoxy, sulphonamido or carboxamido.  The dye developers are made by condensing a sulphonic acid, halogen, nitro, hydroxyl, alkoxy or amino substituted anthraquinone with an amine of the formula <FORM:0891767/IV (c)/5> or by condensing an alpha-halogen or nitrosubstituted anthraquinone with an amine of the formula <FORM:0891767/IV (c)/6> the condensations being carried out so that 1 or 2 mols of the amines are present in the condensation products. When dye-developers of formula (A) containing the substituted amino group in the 1- and 4-positions are desired, leuco-quinisarin may be reacted with an amine of formula (C) and the resulting leuco-compound oxidised.  Examples are given.  Specification 804,974 is referred to.