Intramolecular hydrogen bonding of novel o-hydroxythioacetophenones and related compounds evaluated by deuterium isotope effects on 13C chemical shifts.
A new class of compounds, the 2-hydroxythioacetophenones, and related compounds have recently been synthesized. The hydrogen-bond system has been characterized by NMR chemical shifts and deuterium isotope effects on these as well as by DFT calculations. Use of solid-state (13)C NMR has enabled measurements of the intrinsic deuterium isotope effects of the most abundant tautomer of beta-thioxoketones. The compounds show very interesting long-range deuterium isotope effects on the thiocarbonyl carbon. The intramolecular hydrogen bonds of o-hydroxythioacetophenones are found to be slightly stronger than those of the corresponding acetophenones. The reactivity and stability of the compounds can be related to hydrogen bonding and to the presence of electron donating substituents.
Nguyen
Trung Thanh
TT
Department of Organic Chemistry, University of Natural Sciences, National University of HoChiMinh City, 227 Nguyen Van Cu St, Dist 5, HoChiMinh City, Vietnam.
Le
Thach Ngoc
TN
Duus
Fritz
F
Hansen
Bjarke K V
BK
Hansen
Poul Erik
PE
D002247:Carbon Isotopes; D003903:Deuterium / Q000737:chemistry*; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy / Q000379:methods* / Q000592:standards*; D015394:Molecular Structure; D010636:Phenols / Q000737:chemistry*; D012015:Reference Standards; D012680:Sensitivity and Specificity; D013871:Thiones / Q000737:chemistry*
D002247:Carbon Isotopes; D010636:Phenols; D013871:Thiones; D003903:Deuterium