13275-25-7Relevant articles and documents
Oxidation of (CD3)2C.X Radicals. I. Reaction of Propane and Isopropyl Radicals with Atomic Oxygen
Washida, Nobuaki
, p. 3739 - 3750 (1987)
The raection of oxygen atoms with propane-1,1,1,3,3,3-d6, (CD3)CH2, in a fast-flow system was studied with a photoionization mass spectrometer.Isopropyl-d6 radicals, (CD3)2CH, formed by the initial hydrogen abstraction at the 2-position were detected directly. The subsequent reaction of (CD3)2C.H radicals with atomic oxygen proceeds by both an deuterium abstraction (61percent) and an oxygen addition reaction (39percent).The product in the deuterium abstraction was CD2CHCD3 and those in the oxygen addition were (CD3)2CO (18percent) and CD3CHO (21percent). Competitition experiments show that (CD3)2C.H radicals react (0.029 +/- 0.004) times as fas with O2 as with O(3P).In the presence of an excess of O2, CD2CHCD3 was observed in decreased yield (20percent) and (CD3)2CO and CD3CHO increased to 32 and 44percent, respectively.The rate data for Reaction 3 were fitted by an Arrhenius expression: k3=(2.0+1.0-0.7)*10-10 exp-1)/RT> cm3 molecule-1 s-1 (381-627 K).The rate constant of Reaction 3 obtained from the yields of products was 7.9*10-15 cm3 molecule-1 s-1 at 298 K.
Mild and selective deuteration and isomerization of alkenes by a bifunctional catalyst and deuterium oxide
Erdogan, Guelin,Grotjahn, Douglas B.
supporting information; experimental part, p. 10354 - 10355 (2009/12/08)
(Figure Presented) H/D exchange is achieved at allylic positions of alkenes using D2O in acetone and alkene isomerization catalyst 1, which features a bifunctional imidazolylphosphine. The basic nitrogen of the latter is thought to deprotonate an alkene substrate coordinated to the CpRu center; at this stage the protonated nitrogen could undergo H/D exchange with deuterium oxide. An exceptional degree of deuteration is achieved at positions accessible to isomerization, with a high degree of control. Using biphasic settings one can literally wash out reactive protons on the substrate without using organic solvents.
