Patent GB-1442107-A (GB)
IPC: C07C27/00
Filed: 1974-08-23
Abstract: 1442107 Polyenes F HOFFMANN-LA ROCHE & CO AG 23 Aug 1974 [24 Aug 1973] 37141/74 Heading C2C Novel compounds I wherein R 1  represents a 2,6,6-trimethyl-cyclohex-1-en-1-yl group or a phenyl group which is substituted in the 2- and 6-positions by a halogen atom or a lower alkyl or lower alkoxy group and in at least one of the 3-, 4- and 5-positions by a halogen atom or a hydroxy, lower alkyl, lower alkenyl, lower alkoxy, lower alkenoxy, lower alkanoyloxy, nitro, amino, mono(lower alkyl) amino, di(lower alkyl)amino, lower alkanoylamino or N-heterocyclic group, and R 2  represents a formyl, hydroxymethyl, alkoxymethyl, alkanoyloxymethyl, carboxyl, alkoxycarbonyl, alkenoxycarbonyl, alkynoxycarbonyl, carbamoyl, mono(lower alkyl)carbamoyl, di(lower alkyl)carbamoyl or N - heterocyclylcarbonyl group, are prepared by reacting a compound II with a compound III wherein one of the two symbols A and B represents the oxo group and the other represents a triarylphosphonium group of the formula -P[Y] 3 <SP>+</SP>Z<SP>-</SP>, in which Y represents an aryl group and Z represents the anion of an inorganic or organic acid, R 1  has the significance given in claim 1 and R 3  represents an alkoxymethyl, dialkoxymethyl, alkanoyloxymethyl, alkoxycarbonyl, alkenoxycarbonyl or alkynoxycarbonyl group when B represents the oxo group or R 3  represents a formyl, hydroxymethyl; alkoxymethyl, dialkoxymethyl, carboxyl, alkoxycarbonyl, alkenoxycarbonyl or alkynoxycarbonyl group when B represents the triarylphosphonium group, or reacting a compound IV with a compound V wherein D represents oxo, R 4  represents a formyl, carboxyl, alkoxycarbonyl, alkenoxycarbonyl, alkynoxycarbonyl, carbamoyl, mono- (lower alkyl)carbamoyl, di(lower alkyl) carbamoyl or N-heterocyclylcarbonyl group and E represents a dialkoxyphospinoxy group of the formula in which X represents an alkoxy group, or reacting a compound VI with a compound VII wherein R 1 , A and B have the significance given above and R 5  represents an alkoxymethyl, dialkoxymethyl, alkanoyloxymethyl, alkoxycarbonyl, alkenoxycarbonyl or alkynoxycarbonyl group when B represents the oxo group or R 5  represents a .hydroxymethyl, alkoxymethyl, dialkoxymethyl, carboxyl, alkoxycarbonyl, alkenoxycarbonyl or alkynoxycarbonyl group when B represents the triarylphosphonium group, or reacting a compound VIII with a compound IX wherein R 1 , D and E have the significance given above and R 6  represents an alkoxymethyl, dialkoxymethyl, alkanoyloxymethyl, alkoxycarbonly, alkenoxycarbonyl, alkynoxycarbonyl, carbamoyl, mono(lower alkyl)carbamoyl, di- (lower alkyl)carbamoyl or N-heterocyclylcarbonyl group, or reacting a compound X with a compound XI and saponifying a diacetal obtained and, if desired, esterifying or amidating a carboxylic acid obtained, or hydrolysing or amidating a carboxylic ester obtained, or reducing a carboxylic acid obtained or a carboxylic acid ester obtained to the corresponding alcohol and if desired etherifying or esterifying the resulting alcohol, or saponifying an alcohol ester obtained, or oxidizing an alcohol or alcohol ester obtained to give the corresponding carboxylic acid. Lower signifies a group containing up to 6 carbon atoms. The following intermediates and starting materials are prepared in the examples: 6- methyl - 8 - (2,6,6 - trimethyl - cyclohex - 1- en - 1 - yl) - octa - 5,7 - dien - 2 - one, 6 - methyl- 8 - (4 - methoxy - 2,3,6 - trimethylphenyl)- 5,7 - octa - 5,7 - dien - 2 - one, 6 - methyl - 8- (3 - chloro - 2,4,6 - trimethylphenyl) - octa- 5,7 - dien - 2 - one, 3 - ethoxycarboxyl - 6 - methyl - 8 - (2,6,6 - trimethylcyclohex - 1 - en- 1 - yl) - octa - 5,7 - dien - 2 - one, 3 - ethoxycarbonyl - 6 - methyl - 8 - (3 - chloro - 2,4,6- trimethylphenyl) - octa - 5,7 - dien - 2 - one, 1 - chloro - 3 - methyl - 5 - (4 - methoxy - 2,3,6- trimethylphenyl) - penta - 2,4,- diene, 1- bromo - 3 - methyl - 5 - (3 - chloro - 2,4,6 - trimethylphenyl) - penta - 2,3 - diene, ethyl 3- methyl - 5 - (3 - chloro - 2,4,6 - trimethylphenyl) - 2,4 - pentadienoate and 3 - methyl- 5 - (3 - chloro - 2,4,6 - trimethylphenyl) - 2,4- pentadien-1-ol. Pharmaceutical compositions having antineoplastic, anti-inflammatory, anti-allergic and anti-dermatitis activity, for oral, parenteral or topical administration, comprise a compound I together with a pharmaceutical carrier.