- Electronic and steric effects controlling efficiencies of photoaddition reactions of fullerene C60with N-α-trimethylsilyl-N-alkyl-N-benzylamines
-
Single electron transfer (SET)-promoted photoaddition reactions between fullerene C60and both various alkyl (Me, Et, i-Pr, t-Bu)- and para-substituted (p-Me, p-OMe, p-F, p-CF3) arene ring containing, N-α-trimethylsilyl-N-alkyl-N-benzylamines were explored to gain information about photoproduct profiles and how the electronic and steric nature of the amine substrates influence reaction efficiencies. The results show that visible light (λ?>?540?nm) irradiation of 10% EtOH-toluene solutions containing C60and N-α-trimethylsilyl-N-alkyl-N-benzylamines produce 1-aminomethyl-1,2-dihydrofullerenes as a sole photoproduct. In addition, SET-promoted photoaddition reactions of unsubstituted and para-electron donating group substituted arene ring containing N-α-trimethylsilyl-N-alkyl-N-benzylamines take place to give photoproducts more efficiently than those containing para-electron withdrawing group substituted arene rings. Moreover, although steric factors are less significant than the electronic nature of the amine substrates in governing reaction efficiencies, sterics do play a significant role in photoreactions of electron deficient amine substrates.
- Jeong, Ho Cheol,Lim, Suk Hyun,Sohn, Youngku,Kim, Young-Il,Jang, Hoeun,Cho, Dae Won,Mariano, Patrick S.
-
supporting information
p. 949 - 954
(2017/02/19)
-
- Intermediate in Sommelet-Hauser Rearrangement of N,N-Dimethylbenzylammonium N-Methylides
-
Formation of benzylammonium N-methylides by fluoride anion induced desilylation of dimethyl(4-substituted benzyl)ammonium halides (1) and 3-substituted benzyl analogues (6) was examined to isolate 5--6-methylene-1,3-cyclohexadienes (isotoluene intermediates, 3,8,10) in the Sommelet-Hauser rearrangement.Some isotoluenes were isolated and their structures were confirmed by 1H NMR analysis.The stability of the isotoluenes was dependent on the electron-donating effects of the substituents on the conjugated bonds, and 3-methoxy-substituted isotoluene 3a was the most stable compound studied.
- Shirai, Naohiro,Watanabe, Yoko,Sato, Yoshiro
-
p. 2767 - 2770
(2007/10/02)
-