Cyclodecene oxide

A systematic study has confirmed the low activity of EHs toward cycloalkene oxides (1,2-epoxycycloalkanes, 10.123) [184], In the presence of mouse liver microsomal EH, activity was very low for cyclopentene oxide and cyclohexene oxide (10.123, n = 1 and 2, respectively), highest for cyclo-heptene oxide (10.123, n = 3), and decreased sharply for cyclooctene oxide (10.123, n = 4) and higher homologues. Mouse liver cytosolic EH showed a different structure-activity relationship in that the highest activity involved cyclodecene oxide (10.123, n = 6). With the exception of cyclohexene oxide, which exhibited an IC50 value toward microsomal EH in the p.M range, cycloalkene oxides were also very weak inhibitors of both microsomal and cytosolic EH. 

Reaction with cyclic epoxides. The reaction of epoxides of medium-size rings with base (lithium di- -alkylamides) has been extensively studied by Cope and by Crandall (1, 610 611 2, 247). Two products are usually obtained an allylic alcohol formed by -elimination and a bicyclic alcohol derived from a carbene intermediate formed by a-elimination. Boeckman has now found that the ciirbcnc pathway is highly favored if n-butyllithium (3 equiv.) is used as base and if (he reaction is conducted at low temperatures, —78 to 25° in the case of cis-eyelooctene oxide (1) and m-cyclodecene oxide. The oxide of cyclododecene,... 

The reaction of a substituted ylide with an aldehyde usually leads to dominant or exclusive formation of the trans-oxiran. Thus, tetra-methylenesulphoniumbenzylides reacted with substituted benzaldehydes to afford only the frans-oxirans (57)." Townsend and Sharpless" demonstrated that the cycle of reactions from trans-cyclodecene oxide to the hydroxysul-phonium salt (58) and back occurred with less than 3% crossover to the... 

Cyclodecanediol has been prepared by the hydrogenation of sebacoin in the presence of Raney nickel or platinum, by the reduction of sebacoin with aluminum isopropoxide or lithium aluminum hydride, and by the oxidation of cyclodecene with osmium tetroxide and pyridine. ... 

Although 0s04 is thought of as a specific oxidant for cis alkenes there are a few examples of hydroxylation of trans alkenes, e.g. cis- and frans-cyclodecene can be hydroxylated to the respective cis and irons diols.597 The Os04-alkene-pyridine reaction can be made catalytic by the use of suitable secondary oxidants such as H202, C103 , Bu OOH, A-morpholine A-oxide, I04 , 02 and CIO-. S54... 

The full report on the synthesis of the hexano-bridged oxepin (140) has now appeared and further work has been reported on its oxidative cleavage to give cyclodecenes and cyclodecadienes, and on some addition reactions. The structure of the dehydration product of 2,6-di-t-butyl-4-phenyl-l-(p-tolyl)cyclohexa-2,5-diene-l,4-diol, previously postulated as a fully unsaturated oxepin, has now been confirmed by X-ray analysis. ... 

It is also possible to carry out permanganate oxidation in organic solvents by using crown ethers or phase transfer agents to effect solubilization of permanganate salts. Studies with 5-decene and cyclodecene revealed that mixtures of carboxylic acids, diones, ketols, and diols were obtained but that the ratio of the various products could be influenced by the amount of oxidant used. 

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