6720-26-9Relevant articles and documents
Photochemical oxidation of phenanthrene sorbed on silica gel
Barbas, John T.,Sigman, Michael E.,Dabestani, Reza
, p. 1776 - 1780 (2007/10/03)
There have been relatively few detailed studies of PAH photochemical degradation mechanisms and products at solid/air interfaces under controlled conditions. Results from mechanistic studies on particulate simulants are important in understanding the fates of PAH sorbed on similar materials in natural settings. In this study, the photolysis of phenanthrene (PH) on silica gel, in the presence of air, has been carefully examined. Once sorbed onto the silica surface, PH is not observed to repartition into the gas phase, even under vacuum, and dark reactions of PH are not observed at the silica/air interface. Photolysis (254 nm) of PH leads to the formation of 2,2'-biformylbiphenyl (1), 9,10-phenanthrenequinone (2), cis-9,10-dihydrodihydroxyphenanthrene (3), benzocoumarin (4), 2,2'-biphenyldicarboxylic acid (5), 2-formyl-2'-biphenylcarboxylic acid (5), 2-formylbiphenyl (7),1,2-naphthalenedicarboxylic acid (8), and phthalic acid (9). These products account for 85-90% of the reacted PH. The photoproducts are independent of excitation wavelength (254 and 350 nm), and the reaction proceeds entirely through an initial step involving the addition of singlet molecular oxygen to the ground state of phenanthrene with subsequent thermal and/or photochemical reactions of the initially formed product. Singlet molecular oxygen is produced through quenching of the lowest triplet state of PH at the silica gel/air interface. The high material balance and detailed mechanistic information provided by this study serve as a standard for comparisons with the products and mechanism of PH photochemical oxidation on environmentally derived inorganic oxide particulates.
The mechanistic study and synthetic applications of the base treatment in the ozonolytic reactions
Hon, Yung-Son,Lin, Sheng-Wun,Lu, Ling,Chen, Yao-Jung
, p. 5019 - 5034 (2007/10/02)
The E1cb mechanism is the overwhelming process in the reaction of bases and ozonides. As a quenching agent in the ozonolysis of a variety of alkenes, the reactions involving triethylamine often gave better yields and proceeded faster than those involving methyl sulfide. On the other hand, in the presence of 4 A molecular sieves, the secondary amines reacted with mono- and 1,1-di-substituted ozonides to afford the reductive amination products in high yields. The formation of ammonium formate in the reaction mixture also supported the E1cb mechanism in the reaction of ozonide and amine.
A convenient and efficient workup of ozonolysis reactions using triethylamine
Hon,Lin,Chen
, p. 1543 - 1553 (2007/10/02)
Comparisons were made between triethylamine and methyl sulfide for their use as a quenching agent in the ozonolysis of a variety of alkenes. The reactions involving triethylamine often gave better yields and proceeded faster than those of involving methyl sulfide. The role of triethylamine played as base instead of reducing agent in the reaction.
Syntheses of Diphenic Anhydride-Mercury Compounds and Their Reaction with Nucleophilic Reagents
Takahashi, Teruo,Togashi, Shigeo,Morishita, Muneo,Takeda, Shiro
, p. 3020 - 3023 (2007/10/02)
Diphenic acid anhydride (1) is decarbonylated by prolonged heating with mercuric oxide (HgO) in acetic acid to give a diphenic anhydride-mercury compound (3).Since its infrared spectrum showed a shift of carbonyl adsorption to a very low wave number, the O-Hg linkage was considered to be in an ionic form (3'), with the carbon bonded to mercury becoming a carbonium ion.If this is the case, the compound would be expected to react with nucleophilic reagents and indeed 3 is reactive to KI, H2S and KCN.Keywords-diphenic anhydride-mercury compound; mercuration; carbon-mercury bond; carbonyl adsorptions; nucleophilic; the reaction mechanism; protonation
