Optical monoisomers of biphenylphosphoric acids, procedures for separation of racemate from racemate and their use for separation of racemic bases

摘要

1360946 Binaphthyl phosphate resolving agents RICHARDSON-MERRELL SpA 9 March 1972 [18 March 1971] 11041/72 Headings C2C and C2P The invention comprises optical isomers of formula (wherein R and R 1 are each H, F, Cl, Br, NO 2 or C 1-8 alkyl, with the proviso that the two 1,2- naphthylene radicals are both unsubstituted or are identically substituted) and the corresponding bi(5,6,7,8-tetrahydronaphthyl) compounds; and their preparation by conventional resolution of the racemates thereof using basic optically active resolving agents such as cinchonine, cinchonidine, brucine, quinine, quinidine, morphine, strychnine, ephedrine or -phenylethylamine. Optical resolution of racemic organic amines is effected by conventional procedures using the inventive compounds as resolving agents. Many organic amines are specified. Clomiphene is separated into the cis- and transisomers thereof using the inventive compounds or racemates thereof as resolving agents. Racemates of the inventive compounds are prepared from the corresponding 1,1SP1/SP-binaphthalene-2,2SP1/SP-diols by reaction with POCl 3 /py, and hydrolysis of the resulting pyridine salts with HCl. Methyl esters of the resulting racemic binaphthylphosphoric acids may be prepared by reaction with diazomethane. In Example 10 5,5SP1/SP,6,6SP1/SP,7,7SP1/SP,8,8SP1/SP - octahydro - 1,11 - binaphthalene - 2,2SP1/SP- diyl phosphorochloridate is also prepared. 3,31 - Dimethyl - 1,1SP1/SP - binaphthalene - 2,2SP1/SP- diol is prepared from 3-methyl-2-naphthol by reaction with FeCl 3 (Ex. 3). 6,6SP1/SP- Dibromo - 1,1SP1/SP - binaphthalene - 2,2SP1/SP- diol and the corresponding 6,6SP1/SP-difluoro and 6,6SP1/SP- dichloro compounds are prepared from the 6,6SP1/SP- unsubstituted compound by reaction with elementary halogen (Ex. 5). 6,6SP1/SP - Dinitro - 1,1SP1/SP - binaphthalene - 2,2SP1/SP-diol is prepared from the corresponding 6,6SP1/SP-unsubstituted compound by reaction with HNO 3 /HOAc (Ex. 7). 5,5SP1/SP,6,6SP1/SP,7,7SP1/SP,8,8SP1/SP - Octahydro - 1,1SP1/SP- binaphthalene-2,21-diol is prepared by catalytic hydrogenation of the corresponding fully unsaturated compound (Ex. 9).