STUDY OF HYDROXYL PARTICIPATION IN ACYCLIC EPOXIDE SYSTEMS - ACID-CATALYZED REARRANGEMENTS OF TRANS-3,4-EPOXYPENTAN-1-OLS, AND CIS-3,4-EPOXYPENTAN-1-OLS, 4,5-EPOXYHEXAN-1-OLS, AND 5,6-EPOXYHEPTAN-1-OLS
STUDY OF HYDROXYL PARTICIPATION IN ACYCLIC EPOXIDE SYSTEMS - ACID-CATALYZED REARRANGEMENTS OF TRANS-3,4-EPOXYPENTAN-1-OLS, AND CIS-3,4-EPOXYPENTAN-1-OLS, 4,5-EPOXYHEXAN-1-OLS, AND 5,6-EPOXYHEPTAN-1-OLS
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DOI：
10.1071/ch9732521
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发表时间：
1973-01-01
影响因子：
1.1
通讯作者：
SWALLOW, WH
中科院分区：
文献类型：
--
作者：
COXON, JM;HARTSHOR.MP;SWALLOW, WH
反式和顺式-4，5-环氧己-1-醇和5，6-环氧庚-1-醇的酸催化重排显示出形成环醚的优先性：四氢呋喃>四氢吡喃>氧杂环庚烷。醚类产物是通过分子内羟基置换环氧化物氧而产生的，并伴有构型的反转。反式-和顺式-环氧戊-1-醇的反应得到反式-和顺式-2-甲基-四氢-呋喃-3-醇（8）和（9）的混合物。从每一个环氧化物中，一个甲基四氢呋喃醇必须通过仲环氧化物氧的亲核取代而产生，同时保持构型。
The acid-catalysed rearrangements of trans- and cis-4,5-epoxyhexan-1- ols and 5,6-epoxyheptan-1-ols demonstrate a preference for cyclic ether formation: tetrahydrofuran > tetrahydropyran > oxepan. The ether products arise by intramolecular hydroxyl displacement of the epoxide oxygen with inversion of configuration. Reactions of trans- and cis- epoxypentan-1-ols give a mixture of trans- and cis-2-methyl-tetrahydro- furan-3-ols (8) and (9). From each epoxide one methyltetrahydrofuranol must arise by nucleophilic displacement of the secondary epoxide oxygen with retention of configuration.