23516-38-3Relevant academic research and scientific papers
Reactions of epoxides prepared from some monoterpenes with acetic anhydride on aluminosilicate catalysts
Tatarova,Korchagina,Volcho,Salakhutdinov,Barkhash
, p. 1076 - 1082 (2007/10/03)
Reactions of epoxides prepared from α-, β-pinenes and camphene with acetic anhydride on aluminosilicate catalysts (clay K-10, zeolite β) were investigated affording various products of skeleton rearrangements: mono- and diacetates with five- and six-membered rings, and also with norbornane and pinane cores.
Diethoxytriphenylphosphorane: A Mild, Regioselective Cyclodehydrating Reagent for Conversion of Diols to Cyclic Ethers. Stereochemistry, Synthetic Utility, and Scope
Robinson, Philip L.,Barry, Carey N.,Kelly, Jeffery W.,Evans, Slayton A.
, p. 5210 - 5219 (2007/10/02)
Diethoxytriphenylphosphorane, Ph3P(OEt)2, prepared by reaction of triphenylphosphine and diethyl peroxide, is a "hydrolytically active" dioxyphosphorane which promotes mild cyclodehydration (40-110 deg C) of diols to cyclic ethers in neutral media.The regioselectivity in the closure of (S)-(+)-propane-1,2-diol and (R)-(-)-pentane-1,4-diol with Ph3P(OEt)2 is high (81-82 percent) while the cyclodehydration of (S)-(+)-phenylethane-1,2-diol gives racemized (+/-)-styrene oxide.Simple 1,2-, 1,4-, and 1,5-diols afford good yields of the cyclic ethers but 1,3-propanediol and 1,6-hexanediol give mainly 3-ethoxy-1-propanol and 6-ethoxy-1-hexanol, respectively with Ph3P(OEt)2.Tri- and tetra-substituted 1,2-diols afford the relatively stable 1,3,2-dioxaphospholanes (or ?-dioxyphosphoranes) in the presence of Ph3P(OEt)2, and, depending on conditions, the 1,3,2-dioxaphospholanes are selectively converted to epoxides, ketones or allylic alcohols.The carbonyl compounds arise from 1,2-hydride and 1,2-methyl migrations; the allylic alcohols are derived from thermolytic eliminations. trans-1,2-Cyclohexanediols afford essentially quantitative yields (>95 percent) of the cyclohexene oxides while cis-1,2-cyclohexanediol gives the stable 1,3,2-dioxaphospholane with Ph3P(OEt)2 which decomposes under thermal conditions to cyclohexanone (90 percent).Ph3P(OEt)2 is extremely useful for conversion of "sensitive" 1,2-diols to acidic and /or thermally labile epoxides as demonstrated by the quantitative conversion of 9,10-dihydro-trans-9,10-phenanthrenediol to 9,10-dihydrophenanthrene oxide and 2α,10-pinanediol to 2α,10-epoxypinane.
Cyclobutane Ring Opening of Pin-2(10)-ene with Mercury(II) Salts. A New, High-yield Synthesis of p-Mentha-1,8-dien-7-ol
Bluthe, Norbert,Ecoto, Jules,Fetizon, Marcel,Lazare, Sylvain
, p. 1747 - 1751 (2007/10/02)
The nucleophilic attack of pin-2(10)-ene-mercury(II) complex systems by water results in the opening of the four-membered ring leading to an allylic organomercury(II) derivative (11) with the p-menthane skeleton.This intermediate can be reduced by hydride to p-menth-1(2)-en-8-ol (6a) or can undergo an in situ SE2' elimination yielding p-menth-1(7)-en-8-ol (9a), in high yields. (-)-2,10-Epoxypinane (15) reacts with mercury(II) salts at room temperature, giving the diol (16) in a quantitative yield.Compound (16) is a suitable intermediate for convenient preparation of p-mentha-1,8-dien-7-ol (17) and its derivatives.
