Oxidative Breaking of Long-Chain Acetylenic Enol Ethers of Glycerol of the Marine SpongesRaspailia pumila and of Model Compounds with Aerial Oxygen
作者:Graziano Guella、Ines Mancini、Francesco Pietra
DOI:10.1002/hlca.19870700521
日期:1987.8.12
The raspailynes (novel long-chain enol ethers of glycerol having the enol ethers double bond conjugated in sequence, to an acetylenic and an olefinic bond, isolated from the North-East-Atlantic sponges Raspailia pumila and R. ramosa) are stable under normal hydrolytic conditions for enol ethers. In contrast, when their solutions are evaporated, these lipids such as raspailyne Bl (=(−))-3-[(1Z,5Z)-(tetradeca-1
raspailynes(具有从头到北大西洋海绵Raspailia pumila和R. ramosa分离的乙炔和烯键的烯醇醚双键序列共轭的甘油的新型长链烯醇醚)在正常水解条件下是稳定的烯醇醚的条件。相反,当它们的溶液蒸发时,这些脂质如雷帕西林Bl(=(-))-3-[(1 Z,5 Z)-(十四烷基-1,5-二烯-3-炔基)氧基] -1 ,2-丙二醇;(- 2)在正常实验室日光条件下与空中O 2迅速反应,C = C烯醇醚键断裂,得到1- O-甲酰甘油(3)和醛(例如(-)- 2的tridec-4-en-2ynal(4))。该反应必须由三重态O 2引起,因为热生成的单重态O 2对溶液中的(-)- 2没有影响。用模型化合物1-甲氧基戊二烯-1-en-3-yn-5-ol(6a)及其5- O证明了仅存在与炔基基团偶联的烯醇醚部分是造成这种现象的原因。-乙酰基或5 - O-四-氢吡喃基衍生物6b和6c。耐水解条件和单线态O