20818-81-9Relevant articles and documents
A Spectroscopic, Kinetic, and Product Study of the (CH3)2C(OH)CH2O2 Radical Self Reaction and Reaction with HO2
Boyd, Andrew A.,Lesclaux, Robert,Jenkin, Michael E.,Wallington, Timothy J.
, p. 6594 - 6603 (1996)
A flash photolysis technique was used to measure the UV absorption spectrum of the peroxy radical (CH3)2C(OH)CH2O2 formed in the (CH3)3COH/Cl/O2 reaction system and to study the kinetics of its self reaction and reaction with the HO2 radical at room temperature and above: 2(CH3)2C(OH)CH2O2 -> 2(CH3)2C(OH)CH2O + O2 (5a); 2(CH3)2C(OH)CH2O2 -> (CH3)2C(OH)CH2OH + (CH3)2C(OH)CHO + O2 (5b); (CH3)2C(OH)CH2O2 + HO2 -> (CH3)2C(OH)CH2OOH + O2 (8).The spectrum of the radical resembles that of other β-hydroxyl substituted peroxy radicals in form and magnitude.Use of this and other known absorption cross sections in an appropriate chemical model of the system allowed k5, the branching ratio α (=k5a/k5), and k8 to be derived as a function of temperature (T = 306-398 K) by an iterative procedure involving the simulation of experimental decay traces recorded at several wavelengths: k5 = (1.4 +/- 0.6)E-14exp cm3 molecule-1 s-1; α = 0.59 +/- 0.15 (no discernible temperature dependence over this range); k8 = (5.6 +/- 2.0)E-14exp cm3 molecule-1 s-1.These expressions yield values for k5 and k8 of 4.8 and 14E-12 cm3 molecule-1 s-1 at 298 K, confirming the phenomena both of enhanced self reaction reactivity upon β-OH substitution and of a large rate coefficient for the reaction of all >/= C2 peroxy radicals with HO2.Product studies of reaction 5, using an FTIR-smog chamber system, confirmed the assumed reaction mechanism in 700 Torr of air at 296 K, namely the unique formation of the peroxy radical of interest, rapid decomposition of the alkoxy radical (formed in reaction 5a) through C-C bond scission, and subsequent reaction with O2 to yield formaldehyde and acetone (and HO2).A similar fate for the (CH3)2C(OH)CH2O radical is expected as part of the degradation of tert-butyl alcohol (TBA) and isobutene under tropospheric conditions.Furthermore, the product distribution results, when combined with the extrapolated k5 and k8 values, allow α be determined as 0.60 +/- 0.07 at 296 K, consistent with the value obtained from the flash photolysis study.As part of the smog chamber work, a relative rate technique was used to measure the rate coefficient for the reaction of Cl atoms with (CH3)2C(CH2Cl)OH as (9.2 +/- 1.1)E-12 cm3 molecule-1 s-1 at 296 K.
Synthesis of novel triplet drugs with 1,3,5-trioxazatriquinane skeletons and their pharmacologies. 3: Synthesis of novel triplet drugs with the bis(epoxymethano) or bis(dimethylepoxymethano) structure (double-capped triplet)
Wada, Naohisa,Fujii, Hideaki,Koyano, Koji,Hirayama, Shigeto,Iwai, Takashi,Nemoto, Toru,Nagase, Hiroshi
, p. 7551 - 7554 (2013/02/23)
Novel double-capped triplet drugs, which have one pharmacophore unit and two epoxymethano or dimethylepoxymethano structures (termed cap or diMe-cap structures, respectively) were synthesized. Key intermediate oxazoline 16 derived from acetone enabled the
Enzymes in organic synthesis, 15. - Short enzymatic synthesis of L- fucose analogs
Fessner, Wolf-Dieter,Go?e, Claudius,Jaeschke, Georg,Eyrisch, Oliver
, p. 125 - 132 (2007/10/03)
A short enzymatic route for the synthesis of L-fucose analogs modified at the nonpolar terminus is reported. In particular, fucose derivatives bearing extended linear (1b) and branched (1e) saturated, or various unsaturated (1c, 1d) aliphatic chains have been prepared, in order to increase hydrophobic contacts. The rather general approach involves a sequential application of the recombinant enzymes L-fuculose 1-phosphate aldolase (FucA) and L-fucose ketol isomerase (FucI) from E. coli. Enantiomerically pure L-fucose analogs have been prepared in up to 30% overall yield starting from the appropriate hydroxyaldehyde precursors and dihydroxyacetone phosphate as readily available components. Unsaturated 2- hydroxyaldehydes have been efficiently prepared by alk(en/yn)yl Grignard addition to cinnamaldehyde followed by controlled ozonolysis of the styrene fragment.