One-electron vs. two-electron oxidations. Vanadium(V) and manganese(III) oxidations of cyclobutanol

Abstract

chloroplatinic acid. The mixture was stirred for 16 hr at room temperature. The pentane was removed by distillation through a 24-in. spinning-band column yielding the product, 3.1 g (60g/), bp 102", n S o~ 1.4288 (lit.8 bp 103-105", 122% 1.4340). lt1,2-Trimethyl-l-silacyclohexane (1). 1-(Trichlorosily1)-5-ch1orohexane.-To 20 g (0.16 mol) of 5-chloro-I-hexene in 250 ml of cyclohexane were added 60 g (0.50 mol) of trichlorosilane and 3.6 g of dibenzoyl peroxide catalyst. The temperature of the mixture was maintained at 65' for 90 hr. The solvent and excess trichlorosilane were removed by atmospheric distillation, and the product, bp 110-112° (0.12 mm), was isolated by vacuum distillation. The reaction yield was 21 g (87%). The product was converted to trimethyl-n-hexylsilane for characterization (see below).Trimethyl-n-hexylsilane.-To 50 g of l-(trichlorosilyl)-5chlorohexane was added 50 ml of 3 A4 methylmagnesium bromide in ether. The mixture was stirred at ambient temperature for 1 hr, then poured over cracked ice, and extracted with two 50ml portions of ether. The ether was removed by distillation, and the product, bp 195-197", n Z 5~ 1.4123, was distilled. The 1-(trimethylsily1)-.i-chlorohexane wa5 treated with magnesium in ether, and the resulting Grignard reagent was hydrolyzed with HzO. The product was distilled and shown to be trimethyl-nhexylsilane by comparison of its spectra (nmr, ir) with those of an authentic sample prepared from the reaction of n-hexylmagnesium bromide and trimethyl~hlorosilane.1~Attempted Ring Closure of 1-(Trichlorosilyl)-5-chlorohexane .-To a large excess of -Mg in 500 ml of ether was added 20 g (0.063 mol) of l-(trichlorosilyl)-5-chlorohexane. The mixture was heated at reflux overnight, and then 35 g (0.25 mol) of methyl iodide was added. The mixture wa5 again heated at reflux for

One-electron vs. two-electron oxidations. Vanadium(V) oxidation of cyclobutanols

“…Calcd for C12H16N405: C , 48.64; H, 5 Oxidation of 2,2-dimethylcyclobutanol in the presence of acrylonitrile. Anal.…”

“…(5) Is there evidence for the formation of an oxidant-substrate intermediate? (1) Does the oxidation of cyclobutanol proceed through a free radical intermediate?…”

Free-Radical Rearrangements

“…Similarly, thermolysis of cyclobutyl hypochlorite gives 4-chlorobutanal, which then undergoes further reactions (520). Many oxidation reactions of cyclopropanols and cyclobutanols also afford ring-opened products by free-radical mechanisms (500,(521)(522)(523)(524)(525)(526)(527)(528)(529)(530)(531)(532)(533)(534). Many oxidation reactions of cyclopropanols and cyclobutanols also afford ring-opened products by free-radical mechanisms (500,(521)(522)(523)(524)(525)(526)(527)(528)(529)(530)(531)(532)(533)(534).…”

The oxidation of alcohols by sodium ruthenate

“…This compound may be used to distinguish between one-and two-electron transfer oxidants (16,22). With I-electron transfer agents such as chromium(IV), cerium(IV), manganese(III), and vanadium(V), carbon-carbon bond cleavage occurs and non-cyclic products are obtained.…”