400-52-2Relevant academic research and scientific papers
Oxidative Fragmentation of Saturated Hydrocarbons. II. Oxidative Fragmentation of 1,3,5-Trimethyladamantane
Krasutskii,Baula,Botov
, p. 985 - 989 (2007/10/03)
Oxidation of 1,3,5-trimethyladamantane and 7-hydroxy-1,3,5-trimethyladamantane by perfluoroperoxybutyric acid in perfluorobutyric acid is accompanied by fragmentation of the adamantane polyhedron with formation of cis-1,3,5-trimethyl-cis-3,5-bis(perfluorobutanoyloxymethyl)cyclohexaneacetic acid. The reaction of tert-butyl alcohol with perfluoroperoxyacetic acid simulates well the process of oxidative fragmentation of adamantane and its derivatives. The mechanisms of these transformations are discussed.
Oxymetallation. Part 23. Peroxymercuriation of Bicycloalkanes
Bloodworth, A. J.,Chan, Kam Hung,Cooksey, Christopher J.,Hargreaves, Neville
, p. 1923 - 1930 (2007/10/02)
The peroxymercuriations of bicycloalkanes, n = 2-4, have been carried out using mercury(II)acetate and a one-fold excess of t-butyl hydroperoxide in dichloromethane with 20 molpercent of perchloric acid as catalyst, the products being isolated, after anion exchange, as the organomercury(II)bromides.Small amounts of acetoxymercurials are also formed but are easily removed by silica chromatography.Bicyclopentane reacts by exclusive cleavage of the zero-bridge to give cis-1-bromo-mercurio-3-t-butylperoxycyclopentane 4, but competing isomerisation to cyclopentene consumes ca. 50percent of the cyclopropane.Reaction in neat t-butyl hydroperoxide without perchloric acid gives only the peroxymercurial 4.This has been converted into 2,3-dioxabicycloheptane 2a by iododemercuriation then reaction with silver trifluoroacetate.Bicycloheptane reacts by exclusive cleavage of the one-bridge to give cis- and trans-1-bromomercuriomethyl-2-t-butylperoxycyclohexanes 28 and 29, which have been reduced with alkaline sodium borohydride to afford the corresponding 1-methyl compounds 32 and 33.Bicyclohexane reacts by both zero-bridge and one-bridge cleavage to give the γ-peroxymercurials trans-1-bromomercuriomethyl-2-t-butylperoxycyclopentane 10 and 1-bromomercurio-3-t-butylperoxycyclohexane 13.Also formed is a similar amount of the isomeric β-peroxymercurials 1-bromomercuriomethyl-1-t-butylperoxycyclopentane 11 and trans-1-bromomercurio-2-t-butylperoxycyclohexane 14 yet neither starting cyclopropane nor product γ-peroxymercurial is isomerised by perchloric acid.These unusual rearrangements are also obtained with n-butyl hydroperoxide but not with methanol, butanol or acetic acid as nucleophile.They do not take place with other strong acid catalysts, and are inhibited by 2,6-di-t-butyl-4-methylphenol and promoted by di-t-butyl peroxyoxalate.Reaction in neat t-butyl hydroperoxide at 60 deg C without perchloric acid gives only the γ-peroxymercurials 10 and cis-13.Iododemercuriation of the cis-1,3-cyclohexane derivative cis-13. then reaction with silver trifluoroacetate, gives mainly 3-t-butoxycyclohexanone 27 rather than 6,7-dioxabicyclooctane.
CONVERSION OF BICYCLOPENTANE INTO 2,3-DIOXABICYCLOHEPTANE VIA t-BUTYL PEROXYMERCURIATION
Bloodworth, A. J.,Hargreaves, Neville
, p. 2783 - 2784 (2007/10/02)
Bicyclopentane has been converted in 45 percent yield into 2,3-dioxabicycloheptane by the sequence t-butyl peroxymercuriation, iodomercuriation, epimerisation of the resultant 1-t-butylperoxy-3-iodocyclopentane, and reaction of the trans isomer with silver trifluoroacetate.
Oxidative Displacement of Halogen from Alkyl Halides by Phenyliodine(III) Dicarboxylates
Gallos, John,Varvoglis, Anastasios
, p. 1999 - 2002 (2007/10/02)
The reaction of alkyl iodides with aryliodine(III) dicarboxylates affords as the main product the ester derived through substitution of iodine by an acyloxy group; in some cases α-iodoalkyl esters are also formed along with other minor products.Certain reactive bromides and chlorides react along similar lines.The mechanism of these reactions is briefly discussed.
