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    • 10. 发明专利
    • FR2115445B1
    • 1978-02-10
    • FR7142514
    • 1971-11-26
    • UPJOHN CO
    • KELLY R C
    • C07C405/00C07D263/04C07D307/93C07D307/935C07D317/12C07D317/14C07D317/26C07D319/06C07D319/16A61K27/00C07C61/00
    • 1369254 Bicyclohexane and tricyclooctane derivatives UPJOHN CO 1 Nov 1971 [27 Nov 1970] 58575/73 Divided out of 1369251 Heading C2C The invention comprises optically active compounds of the formulae or the mirror images thereof, or racemic compounds thereof, wherein R 1 and R 2 are C 1-4 alkyl or together form wherein R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are H, C 1-4 alkyl or phenyl; with the proviso that not more than one of the Rs is phenyl and the total number of carbon atoms is from 2 to 10, x is 0 or 1, # indicates the attachment of the radical to the cyclopropane ring in exo or endo configuration, and R 12 and R 13 each are H, Br or Cl, optically active bicyclo[3,1,0]hex-2-ene-6-carboxaldehyde and an oxazolidine thereof with an optically active ephedrine, and an oxazolidine of an optically active compound of the formula or of the mirror image thereof with an optically active ephedrine. The bicyclo[3,1,0]hex-2-ene- 6-carboxaldehyde acetals of the above formula are obtained by reacting the aldehyde with the appropriate alcohols or glycols, and the resulting acetals may be then reacted with ketenes of the formula R 10 R 11 C=C=O to give tricyclooctanones of the above formula in which R 12 is Br or Cl and R 13 is H, Br or Cl, which may be converted to tricyclooctanones of the same formula in which R 12 and R 13 are H by treatment with zinc dust, and a racemic mixture so obtained may be resolved by reacting with an optically ephedrine, separating the resulting oxazolidines and hydrolysing the separated oxazolidine. Optically active bicyclo[3,1,0]hex-2-ene-6-carboxaldehyde is prepared in a similar manner. dl - Endo - bicyclo[3,1,0]hex - 2 - ene - 6 - carboxaldehyde is reacting bicyclo[2,2,1]hepta-2,5- diene with peracetic acid.