Permanganate–periodate Oxidation: Part Vii. The Oxidation of Some Acyclic Monoterpenes

Abstract

The reaction of permanganate-periodate with 1-decene and 1-octadecene in aqueous suspension or media containing tert-butanol has been studied. CIO-compounds are oxidized almost quailtitatively with the aqueous reagent. Myrcene, cis-ocimene, citronellol, citronellal, citronellic acid, geraniol, nerol, linalool, and linalyl acetate are all oxidized in high yield to the predicted products. These can serve conveiliently for chemical identification of the aliphatic terpenes when isolated from mixtures by gas-liquid chromatography. The reaction may also be useful in locating the ',LC-label in tracer studies.

Permanganate–periodate oxidation. Part VIII. The oxidation of some cyclic mono-olefins and monoterpenes

“…271.5-223" (lit. (20) When the reaction was carried out in 30% tert butyl The quantitative and preparative oxidation procedures solution, virtually all the camphene reacted but were described in detail previously (1,7,12). Tables I in addition to camphenilone, a neutral compound of and 11 list the purity of the starting materials as deter-much higher retention time (not the same as the derived mined by g.l.c., the amount of tert butyl alcohol used, dial or ketol) and a larger amount of acidic products the results obtained after 1,6,24, 144, and 196 h reaction were time (the data obtained after 0.5,2,3,48,72,96, and 120 h are not included), as well as the products obtained in the preparative oxidations.…”

“…Ketones and esters were found to be stable towards the reagent (at pH 7 to 8), whereas alcohols reacted slowly (12). With water-insoluble olefins good results were obtained when the reaction was carried out in aqueous tert butyl alcohol solutions (10-50 %) (1,11,12).…”

“…We reported briefly (6) on the excellent yields of sabina ketone and nopinone which may be obtained from sabiilene and P-pinene respectively, and that the oxidation proceeds at a satisfactory rate in aqueous suspension. Our previous studies (1,(7)(8)(9)(10)(11)(12) have shown that the oxidation of an olefinic double bond proceeds in a predictable manner, involving hydroxylation of the double bond by a permanganate ion (via a TC complex and hypomanganate ester (13) (see also Wiberg and Geer (14)), followed by periodate cleavage of the diol or ketols thus formed, and subsequent slower oxidation of the resulting …”

A Practical Route to a Complex Bis-Steroidal Diene Intermediate Using a Microwave Assisted Heck-Reaction

“…Scheme 4 Reactions and conditions: (a) K 2 CO 3 (3 equiv), NaIO 4 (4.7 equiv), KMnO 4 (0.4 equiv), t-BuOH-H 2 O (1:1), 30 min, 25°C, 94%; (b) CH 2 N 2 , CH 2 Cl 2 , 25°C, >99%; (c) HO-(CH 2 ) 2 -OH-CH 2 Cl 2 (1:1), PTSA (2.1 equiv), 96 h, 25°C, 91%; (d) LiAlH 4 (2.5 equiv), THF, 10 min, 25°C, >99%; (e) o-NO 2 PhSeCN (1.2 equiv), PBu 3 (1.2 equiv), THF, 3 H, 25°C, 82%; 13 (f) H 2 O 2 (35%), THF, 24 h, 25°C, 90%. For the preparation of the ring-open steroid 13 we could rely on the well established Lemieux-Rudloff-oxidation 12 which performed best as compared to various other protocols and generated keto-acid 12 in 94% yield starting from the unsatured ketone 11 (Scheme 4). This in turn was easily available from hecogenin.…”

Postulated intermediates and activated complexes in the permanganate ion oxidation of organic compounds

“…Alternatively, permanganate ion would attack the sulfur atom of the thiocarbonyl group or mecaptan 101a, 10lb.The kinetics and mechanisms of the permanganate ion oxidation of thiocarbonyl compounds, thiols, sulfides, sulfoxides, disulfides, sulfinic acids, and sulfenic acids are under investigation TM'; 3 o XIII. PERMANGANATE ION-PERIODATE ION SYSTEM a9,[231][232][233][234][235][236][237][238][239][240][241][242][243] Cleavage of carbon-carbon double bonds takes place smoothly with periodate ion and catalytic amounts of permanganate ion in neutral solution231-243. This general method is useful both preparatively and analytically.…”