Photo-oxidative Fragmentation of Some alpha-Alkyl Substituted 4-Methoxybenzyl Alcohols and Methyl Ethers Sensitized by TiO2.
摘要:
The TiO2-catalyzed photo-oxidation of some alpha-alkyl substituted 4-methoxybenzyl alcohols and ethers [4-MeOPhCH(OR)Y] has been investigated in MeCN, in the presence of Ag2SO4. When Y=t-Bu, the intermediate radical cation undergoes exclusive C-alpha-H bond cleavage (leading to the corresponding ketone) if R = Me, but predominantly C-alpha-C-beta bond cleavage (leading to 4-MeOPhCHO) if R=H. The C-alpha-H bond cleavage path is also the major one when Y= i-Pr and R=H. For the substrates where Y=CH(OMe)Me or CH(OH)Me, exclusive C-C bond cleavage is observed when R is either H or Me. A similar situation holds when the photo-oxidations are carried out in the presence of oxygen, however a change in the outcome of the reaction has been observed for the substrates where R=Me and Y=t-Bu or CH(OMe)Me, which both form 4-MeOC6H4CO2Me as the exclusive product. These results are interpreted on the basis of the structural effects on the fragmentation reactions of the intermediate radical cations, the stability of the formed carbon radicals and carbocations, as well as the possible reactions of the former with oxygen.
Electrochemical cleavage of the double bond of 1-alkenylarenes
作者:Yu. N. Ogibin、A. B. Sokolov、A. I. Ilovaiskii、M. N. �linson、G. I. Nikishin
DOI:10.1007/bf00957996
日期:1991.3
A study has been made of the electrochemical cleavage of the double bond of propenylbenzene (Ia) and p-propenylanisole (Ib), which takes place upon anodic oxidation of (Ia, b) in alcoholic solutions of sodium trifluoroacetate and other electrolytes and which leads to conversion of (Ia, b) to benzaldehyde dialkylacetals. Conditions are found that provide for highly selective (> 80%) conversion of (Ib) and p-propenyltoluene to p-methyl- and p-methoxybenzaldehyde dimethylacetals.
Electrochemical methoxylation of allyl and propenyl derivatives of phenol and phenol ethers
作者:Isidoro Barba、Rafael Chinchilla、Cecilia Gomez
DOI:10.1021/jo00297a051
日期:1990.5
BARBA, ISIDORO;CHINCHILLA, RAFAEL;GOMEZ, CECILIA, J. ORG. CHEM., 55,(1990) N0, C. 3270-3272