PROCESS FOR THE MANUFACTURE OF OPTICALLY ACTIVE BICYCLOALKANE DERIVATIVES

摘要

1352637 Indane and naphthalene derivatives SCHERING AG 19 April 1971 [20 March 1970 9 March 1971] 24060/71 Heading C2C Optically active compounds of the Formula I in which n represents 1 or 2, R 1 represents an aliphatic hydrocarbon group containing up to 4 carbon atoms, m represents 0, 1 or 2 and R 2 represents a hydrogen atom, a free or esterified carboxyl group, a free, etherified or esterified α- hydroxyalkyl group containing 2 to 4 carbon atoms, a haloalkenyl group containing 2 to 5 carbon atoms, a ketalized 1-oxoalkyl group containing 2 to 4 carbon atoms, an unsubstituted phenyl group or a phenyl group substituted by one or more substituents selected from halogen atoms and acylamino, alkyl, free amino, alkylamino, hydroxyl, alkoxy and acyloxy groups, are prepared by cyclizing a cycloalkane- 1,3-dione of the Formula II in a polar solvent in the presence of an optically active amino compound and of H+ ions, the optically active amino being used in an amount of at least 0À1 mole per mole of the cycloalkane- 1,3-dione. Examples of optically active amino compounds are optical antipodes of aminoacids such as proline, alanine and phenylalanine, and α-arylaminoalkanes such as α- phenylethylamine and α-(1-naphthyl)-ethylamine. The solvent may be, for example, a carboxylic acid, dimethylformamide or acetonitrile. H+ ions may be supplied by dilute mineral acids such as HCl or perchloric acid. The compound I formed may in the D- or L- form depending on which antipode of the optically active amino compound is present in the batch. Some of the products are claimed per se, namely (+) - 8a - n - butyl - 3,4,8,8a - tetrahydro - 1,6(2H,7H) - naphthalenedione, (+)- 7,7a - dihydro - 7a - ethyl - 1,5(6H) - indanedione, (+ ) - 7,7a - dihydro - 4,7a - dimethyl - 1, 5(6H) - indanedione, (+) - 7,7a - dihydro - 7amethyl - 4 - [21 - (meta - methoxyphenyl)- ethyl] - 1,5(6H) - indanedione, (+ ) - 7,7a - dihydro - 7a - methyl - 4 - [31,31 - (ortho - phenylenedioxy) - butyl] - 1,5(6H) - indanedione and (+) - 7,7a - dihydro - 7a - methyl - 4 - (31- chloro-21-butenyl)-1,5(6H)-indanedione. Starting materials and intermediates.-7,7a- Dihydro - 7a - methyl - 4 - [31,31 - (orthophenylenedioxy) - butyl] - 1,5(6H)-indanedione is prepared via 5,5 - (orthophenylenedioxy) - hexanoic acid ethyl ester, 5,5 - (ortho - phenylenedioxy) - hexan- 1 - ol, 5,5 - (ortho - phenylenedioxy) - hexanal, 7, 7 - (ortho - phenylenedioxy) - 1 - octen - 3 - ol, 7,7- (ortho - phenylenedioxy) - 1 - octen - 3 - one and 2 - methyl - [31- oxo - 71,71 - (ortho - phenylenedioxy) - octyl] - cyclopentane - 1,3 - dione. 7,7a- Dihydro - 7a - methyl - 4 - (31 - chloro - 21 - butenyl) - 1,5(6H) - indanedione is prepared via 4 - chloro - 3 - pentene - 1,1 - dicarboxylic acid diethyl ester, 5-chloro-4-hexenic acid, 5-chloro-4- hexen - 1 - ol, 5 - chloro - 4 - hexenal, 7 - chloro- 1,6 - octadien - 3 - ol, 7 - chloro - 1,6 - octadien- 3 - one and 2 - methyl - 2 - (31 - oxo - 71 - chloro- 61-octenyl)-cyclopentane-1,3-dione.