Patent GB-1313390-A (GB)
Title: Radiation-sensitive polymers
IPC: C08F8/00
Filed: 1970-07-31
Abstract: 1313390 Indenyl and benzylidene furanone compounds EASTMAN KODAK CO 31 July 1970 [1 Aug 1969] 37151/70 Heading C2C [Also in Divisions C3 and G2] In examples, the following preparations are disclosed:-(1) 1 - benzylidene - 3 - indenecarboxylic acid is prepared by reacting 3-indenecarboxylic acid with benzaldehyde in toluene in the presence of piperidine and glacial acetic acid; (2) 1 - p - nitrobenzylidene - 3 - indene carboxylic acid is prepared as in (1), using p-nitrobenzaldehyde; (3) 1-p-methoxybenzylidene-3-indene carboxylic acid is prepared by reacting p - anisaldehyde with 3 - indene oarboxylic acid in methanol in the presence of potassium methoxide; (4) methyl 1-p-carboxybenzylidene - 3 - indene - carboxylate is prepared by reacting p-carboxybenzaldehyde with methyl 3-indene-carboxylate as in (1); (5) p - (3 - methoxy - carbonyl - 1 - indenylidenemethyl) cinnamic acid is prepared by the procedure of (4) using p-formyl cinnamic acid instead of p-formyl benzoic acid; (6) 2-ethylhexyl 3-indene-carboxylate is produced by reacting 2-ethyl-1-hexanol with 3-indene carboxylic acid, and is used to produce p[3-(2-ethyl hexyl carbonyl)-1-indenylidene methyl] cinnamic acid by reacting it with p-formyl cinnamic acid; (7) 1-benzylidene-3-indenecarbonyl chloride by reacting the product of Example (1) with oxalyl chloride; (8) methyl-1-[p-(2-chlorocarbonyl vinyl) benzylidene]-3-indene carboxylate is produced as in (7) from the product of Example (5); (9) the products of Examples (2), (3) and (4) are reacted with oxalyl chloride as above to produce the acid chlorides; (10) the product of Example (6) is treated as above; (16) furfurylidene-3-indene carboxylic acid is produced by reaction between 3-indene carboxylic acid and 2-furaldehyde; (17) methyl-1- (5 - formyl - furfurylidene) - 3 - indene - carboxylate is produced from methyl 1-furfurylidene)-3-indene-carboxylate by a Vilsmeier reaction in D.M.F. and in the presence of phosphonyl chloride and, finally, KOH; (18) the product from (17) is reacted with 3-indenecarboxylic acid to produce methyl 1-[5-(3- carboxyl - 1 - indenylidenemethyl)furfurylidene]-3-indene carboxylate; (19) the product of (18) is made into the 3-indene-carbonyl chloride form by reaction with oxalyl chloride; (22) 4,7 - dimethyl - 1 - p - isopropylbenzylidene - 3- indene carboxylic acid is made by reaction between 4,7-dimethyl-3-indene-carboxylic acid and p-isopropylbenzaldehyde, and p-(4,7-dimethyl - 3 - methoxycarbonyl - 1 - indenylidenemethyl) cinnamic acid is produced by reacting methyl 4,7-dimethyl-3-indene-carboxylate and p-formyl cinnamic acid; (23) the first product of (22) is reacted with oxalyl chloride to give the acid halide; (26) 3-methoxycarbonyl - 5 - [p - (2 - carboxyvinyl)benzylidene]-4-phenyl-2(5H)-furanone is produced by reaction of 3-methoxycarbonyl-4-phenyl-2(5H)- furanone and p-formyl cinnamic acid; (27) the above product is reacted with oxalyl chloride to produce the acid chloride; (28) 5-(p-carboxybenzylidene) - 3 - cyano - 4 - phenyl - 2(5H)- furanone is reacted with oxalyl chloride to produce the 5-(p-chlorocarbonylbenzylidene)- derivative; and (29) 5-[p-(2-carboxyvinyl)- benzylidene] - 3 - cyano - 4 - phenyl - 2(5H)- furanone is treated as in (28) to produce the corresponding derivative. The compounds prepared above fall within the scope of any one of the formulae  wherein R 1  is a substituted or unsubstituted aromatic or furyl group; each R 2  is H, alkyl or alkoxy; R 3  is alkoxy-carbonyl or cyano; R 4  is aryl; X is a carbonyloxy, oxycarbonyl, or amido linkage; Z is an arylmethylidene group, and m and n are each 0 or 1.