87841-92-7Relevant academic research and scientific papers
Mechanism of Epoxidation of Norbornene with α-Hydroperoxy Diazenes
Osei-Twum, Emmanuel Y.,Warkentin, John
, p. 4725 - 4729 (1985)
Thermolysis of α-hydroperoxy diazenes 1a-1c (Me2C(OOH)N=NR: 1a, R = CH2CF3; 1b, R = CH2CH2OCH3; 1c, R = CH2CH2OC6H5) at 50 deg C in benzene containing norbornene or in neat norbornene affords exo-(2R)-norbornane and exo-norbornene epoxide as major products and exo,exo-(2R)-3-hydroxynorbornane as a minor product.The reaction kinetics and the effects of deuteration of the hydroperoxy function on the distribution of products points to a radical chain process for the hydroalkylation and for the epoxidation.The other major product is formed by a competitive radical chain reaction.
Hydroxyalkylation with α-Hydroperoxydiazenes. Alcohols from Olefins and Carbonyl Compounds from Enol Ethers
Osei-Twum, Emmanuel Y.,McCallion, Doug,Nazran, Avtar S.,Panicucci, Rick,Risbood, Prabhakar A.,Warkentin, John
, p. 336 - 342 (2007/10/02)
Alkyl(1-hydroxy-1-methylethyl)diazenes 2a-f were prepared in solution by autoxidation of the corresponding hydrazones of acetone.Thermolysis of the diazenes at 50-80 deg C in alkenes leads to alcohols.For example, 2b decomposes in 1,1-diphenylethene to afford 5-hydroxy-5,5-diphenylpentanenitrile.Alkenes with abstractable allylic hydrogens gave analogous products, but in very low yield.Thermolysis of a diazene 2 in an enol ether solvent leads to an aldehyde or a ketone.Thus, 2a decomposes in 1-ethoxyethene and in 2-methoxypropene to afford, respectively, 4,4,4-trifluorobutanal and 5,5,5-trifluoro-2-pentanone.Yields lie in range from 50percent to 70percent.The thermolysis of 2 in alkenes involves radical intermediates and radical chain hydroxyalkylation of alkene double bonds.In one chain-propagating step, R*, generated from 2, adds to the alkene.The adduct radical so formed propagates by inducing decomposition of 2 by attack at hydroxyl oxygen.According to this mechanism, initial products from enol ethers are hemiacetals or hemiketals which do not survive the reaction conditions but decompose to the corresponding carbonyl compounds.Preliminary evidence for this mechanism is presented.
