1,2 hydrogen shift and other thermally induced free radical reactions in x-irradiated methyl. cap alpha. -D-glucopyranoside single crystals. An ESR-ENDOR study

Journal Article · Thu Jun 26 00:00:00 EDT 1980 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100450a010· OSTI ID:6873435

Madden, K P; Bernhard, W A

Upon warming single crystals of methyl ..cap alpha..-D-glucopyranoside x-irradiated at 77 K, three free radical reactions have been observed. At approx. 190 K the deprotonated primary hydroxyalkyl radical, centered at C6, converts by a 1,2 hydrogen shift to a C5-centered secondary oxyalkyl radical. Further warming to approx. 230 K causes a conversion of the C5 secondary oxyalkyl radical to a primary hydroxyalkyl radical, centered at C2, opening the pyranose ring. It is postulated that the C2 radical, at approx. 320 K, abstracts a hydrogen from C5, re-forming the C5 secondary oxyalkyl radical. Thus a chain reaction is propagated through the crystal until terminated in yet another free radical product. This latter free radical has been characterized by ENDOR but its structure is uncertain.

• Research Organization: Univ. of Rochester, NY
• OSTI ID: 6873435
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 84:13; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
CARBOHYDRATES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DATA
ELECTROMAGNETIC RADIATION
ELECTRON SPIN RESONANCE
ENDOR
EXPERIMENTAL DATA
INFORMATION
IONIZING RADIATIONS
LOW TEMPERATURE
MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADICALS
RESONANCE
X RADIATION