| 摘要 |
<p>1384024 Prostaglandins; organocopper compounds G D SEARLE & CO 23 March 1973 [14 April 1972] 14152/73 Headings C2J and C2C [Also in Division C3] Compounds of Formula I in which X=-CH 2 -, -CH(OH)-, -CH(OSiAlk 3 )- or -CH(OCOY)-, Alk being C 1-7 alkyl, THP being tetrahydropyran-2-yl and Y being H or C 1-6 alkyl, R=H or Alk, R<SP>1</SP>=H or C 1-4 alkyl, R<SP>11</SP>=OH, OTHP, OAlkOAlk or OSiAlk 3 , Z=-CH=CH- or -CH 2 -CH 2 -, m=3 or 4, n=2-8 and the wavy lines represent the alternativeαor # configuration or the epimeric mixture, are prepared by reacting a compound of Formula II with an alkenyl copper compound of Formula III, IV or V optionally followed by hydrolysis of the protecting groups if desired. The following intermediates are prepared in the examples: methyl 3(RS) - hydroxy - 5 - oxo - 1- cyclopentene - 1 - heptanoate, methyl 3(RS)- (tetrahydropyran - 2 - yl)oxy - 5 - oxo - 1 - cyclopentene - 1 - heptanoate, methyl 3(R or S)- hydroxy - 5.- [(1 - carboxyisoamyl) - oxyimino]- 1 - cyclopentene - 1 - heptanoate, methyl 3(R or S) - hydroxy - 5 - oxo - 1 - cyclopentene - 1 - heptanoate, 3(RS) - (tetrahydropyran - 2 - yl) oxy - 1 - octyne, 3(RS) - (tetrahydropyran - 2 -yl) oxy - 1 - trans - octenyl iodide, 3(RS) - 1 - octen- 3 - ol, 3(RS) - (tetrahydropyran - 2 - yl)oxy - 1- octene, 1,2 - dibromo - 3(RS) - (tetrahydropyran- 2 - yl)oxy - octane, 3(RS) - (tetrahydropyran - 2- yl) - oxy - 1 - trans - octenyl bromide, 3(RS)- hydroxy - 1 - cis - octenyl iodide and 3(RS)- tetrahydropyran-2-yl)oxy-1-cis-octenyl iodide. 3 - (Tetrahydropyran - 2 - yl)oxy - 1 - alkenyl copper compounds are prepared by reaction of a 1 - halo - 3 - (tetrahydropyran - 2 - yl)oxy - 1- alkene with magnesium metal activated with mercuric chloride, followed by treatment with cuprous iodide. 3(RS)-(tetrahydropyran-2-yl) oxy-1-octenyl copper is prepared in Example 3A.</p> |
