| 摘要 |
<p>1282662 Bicyclo[3,1,0]hexan-3-one derivatives UPJOHN CO 10 March 1970 [14 March 1969] 58026/71 Divided out of 1282661 Heading C2C The invention comprises novel bicyclo[3,1,0]- hexan-3-ones of the formulµ wherein R 2 is H or C 1-10 alkyl, optionally substituted with 1 to 3 F atoms; R 3 and R 4 are H or C 1-4 alkyl; A is C 1-10 alkylene, optionally substituted by 1 or 2 F atoms, and with 1 to 5 C atoms between V and COOH and #C and OR 9 ; V is cis-CH=CH- or -C#C-; R 9 is H or 2- tetrahydropyranyl; R 12 and R 13 are C 1-4 alkyl; and #indicates attachment of and to cyclopentane ring in alpha and beta configuration and oxo or endo configuration with respect to the moiety attached to the cyclopropane ring; and their preparation. The carboxylic acids of the above formula in which V is cis-CH = CH- are obtained by hydrogenating the corresponding acids in which V is -C#C-, which are in turn obtained by oxidizing the corresponding primary alcohols, i.e. compounds of the formula above in which R 9 is H, resulting from the hydrolysis of the corresponding compounds in which R 9 is 2-tetra-hydropyranyl, obtained by reacting organic halides of the formula wherein X is Cl, Br or I in the presence of alkali metal alkoxides, alkali metal amides or alkali metal hydrides with the appropriate 2-unsubstituted-bicyclo[3,1,0]hexan-3-ones of the above formula, the latter being obtained by reacting the corresponding glycols with dialkyl ketones of the formula The following starting materials are also prepared:-endo-bicylo[3,1,0]hexan-3(and 2-)-ol-6- carboxylic acid methyl ester, endo-bicyclo- [3,1,0]hexan-3(and 2-)-ol-6-carboxylic acid methyl ester tetrahydropyran-2<SP>1</SP>-yl ethers, tetrahydropyran-2<SP>1</SP>-yl ethers of endo-6-hydroxymethylbioyclo[3,1,0]hexan-3-(and 2-)-ol, endobicyclo[3,1,0]hexan-3-(and 2-)-6-carboxaldehyde and endo-6-(cis- and trans-1-heptenyl)-bicyclo- [3,1,0]hexa-3-(and 2-)ol, endo-6-(cis- and trans- 1 - heptenyl) - bicyclo[3,1,0]hexan - 3 - (and 2-)- ol, endo-6-(cis- and trans-1-heptenyl)-bicyclo- [3,1,0]hexan - 3 - one, endo - 6 - (1,2 - dihydroxyheptyl-bicyclo[3,1,0]hexan-3-one, 1-tetrahydropyran - 2<SP>1 </SP>- yloxy - 4 - bromobutane, 7 - tetrahydropyran-2<SP>1</SP>-yloxyhept-2-yn-1-ol, 1-bromo-7- tetrahydropyran-2<SP>1</SP>-yloxyhept-2-yne, methyl 7- tetrahydropyran - 2<SP>1</SP> - yloxyhept - 2 - ynsulplonate, and endo-6-(1,2-dihydroxyheptyl)-2-(7- hydroxyhept - 2 - yn - # - yl) - bicyclo[3,1,0]- hexan-3-one.</p> |
