Patent GB-627353-A (GB)
Title: Improvements in acylacetanilides useful as dye intermediates
IPC: C07D317/00
Filed: 1947-05-01
Abstract: m-Dialkoxymethyl- and m-alkylenedioxy-methyl-acylacetanilides of the formula <FORM:0627353/IV (a)/1> (R1 is acyl; Y1 and Y2 are either together -O-R2-O-, where R2 is alkylene of 2-4 carbon atoms, or are each -OR3, where R3 is substituted or unsubstituted alkyl of 1-4 carbon atoms, or a benzyl group; the benzene ring may be further substituted) may be reacted with hydroxyl polymers such as polyvinyl alcohol, partly hydrolysed polyvinyl acetate, partly substituted polyvinyl acetals, cellulose acetate, and cellulosic yarns and filters to form immobile dyestuff intermediates for colour photography and fast dyes for textile dyeing.  Specification 535,341 is referred to.ALSO:m-Dialkoxymethyl- and m-alkylenedioxy-methyl-acylacetanilides of the formula <FORM:0627353/IV (b)/1> (where R1 is acyl, e.g. acetyl, benzoyl; Y1 and Y2 are either together -O-R2-O- where R2 is alkylene of 2, 3, or 4 carbon atoms, or are each -OR3, where R3 is substituted or unsubstituted alkyl of 1 to 4 carbon atoms, or a benzyl group; and where any of the free positions in the benzene ring may contain substituents) are prepared by condensing the appropriate aminobenzene derivative with a keto-ester R1.CH2.CO.OR4, where R4 is an alkyl group, e.g. methyl or ethyl.  Ketene dimer may be used in place of the keto-ester.  The condensation is preferably carried out by heating at 100-140 DEG  C. in a high-boiling solvent, e.g. xylene or chlorobenzene, in the presence of an alkaline catalyst, e.g. pyridine or sodium hydroxide, and distilling off the alcohol R4OH as formed by the reaction.  Specified keto-esters are various acetoacetates, ethyl picolinyl acetate, ethyl furoylacetate, ethyl propionyl acetate, ethyl g :g -diethoxy-acetoacetate, ethyl oxalacetate, methyl and ethyl benzoylacetate and ethyl o-anisoyl-acetate.  The acetal groups represented by Y1 and Y2 are derived from alkanols of 1 to 4 carbon atoms and 1 : 2- and 1 : 3-diols of 2 to 4 carbon atoms.  Specified acetals are the dimethyl, diethyl, di-b -chloroethyl, di-isopropyl, dibenzyl, and those derived from ethylene glycol, 1 : 3-propylene and 1 : 3-butylene glycols. Specified m-aminobenzaldehydes of which the acetals are formed are 2-chloro-3-amino- and 4-methyl-3-aminobenzaldehyde and 3-amino-2-formylbenzenesulphonic acid.  The acetal group of any of the products may be hydrolysed to a free aldehyde group.  In the examples: (1) m-aminobenzaldehyde ethylene glycol acetal is reacted with a boiling mixture of ethyl benzoylacetate and sodium hydroxide solution in chlorobenzene to give m-benzoylacetamidobenzaldehyde ethylene glycol acetal, which may be hydrolysed with hydrochloric acid in acetone to the free aldehyde; and (2) ethyl acetoacetate is treated in the same way to give the m-acetoacetamidobenzaldehyde acetal.  In example (3), m-aminobenzaldehyde dimethyl acetal is reacted in a similar manner with ethyl furoylacetate to give m-furoylacetamidobenzaldehyde dimethyl acetal.  The dimethyl and diethyl acetals of m-nitrobenzaldehyde are prepared by the use of dimethyl sulphite and ethyl orthoformate respectively.  Catalytic reduction of the products gives the acetals of m-aminobenzaldehyde.  Specification 535,341 is referred to.ALSO:m-Dialkoxymethyl and m-alkylenedioxymethyl acylacetanilides of the formula: <FORM:0627353/IV (c)/1> (where R1 is acyl, Y1 and Y2 are together -O-R2-O- where R2 is alkylene of 2-4 carbon atoms or are each -OR3 where R3 is alkyl of 1-4 carbon atoms which may be substituted or a benzyl group, and the benzene ring may be further substituted) are condensed with a diazonium salt, an aromatic nitroso compound, or a p-phenylenediamine in the presence of an oxidising agent to give a dyestuff.  Compounds of the above formula may be reacted by acetal interchange with hydroxyl polymers such as partially hydrolysed polyvinyl acetate, polyvinyl acetals, cellulose acetate and cellulosic yarns and filters and used to produce fast colours.