7478-95-7Relevant academic research and scientific papers
EFFECT OF GUEST CATIONS ON THE PHOTO-SOLVOLYSIS OF 4'-(1-ACETOXY)ETHYLBENZO-15-CROWN-5
Suzuki, Atsushi,Tada, Masaru
, p. 515 - 516 (1980)
Photo-solvolysis of 4'-(1-acetoxy)ethylbenzo-15-crown-5 (1) in methanol is depressed by the complex formation of the crown ether moiety with alkali metal ions.This effect is accounted for by the destabilization of excited state of 1 and benzyl cation from 1.
Site-Selective Alkoxylation of Benzylic C?H Bonds by Photoredox Catalysis
Lee, Byung Joo,DeGlopper, Kimberly S.,Yoon, Tehshik P.
supporting information, p. 197 - 202 (2019/11/26)
Methods that enable the direct C?H alkoxylation of complex organic molecules are significantly underdeveloped, particularly in comparison to analogous strategies for C?N and C?C bond formation. In particular, almost all methods for the incorporation of alcohols by C?H oxidation require the use of the alcohol component as a solvent or co-solvent. This condition limits the practical scope of these reactions to simple, inexpensive alcohols. Reported here is a photocatalytic protocol for the functionalization of benzylic C?H bonds with a wide range of oxygen nucleophiles. This strategy merges the photoredox activation of arenes with copper(II)-mediated oxidation of the resulting benzylic radicals, which enables the introduction of benzylic C?O bonds with high site selectivity, chemoselectivity, and functional-group tolerance using only two equivalents of the alcohol coupling partner. This method enables the late-stage introduction of complex alkoxy groups into bioactive molecules, providing a practical new tool with potential applications in synthesis and medicinal chemistry.
Effect of pH on the mechanism of OClO· oxidation of aromatic compounds
Svenson, Doug,Kadla, John F.,Chang, Hou-Min,Jameel, Hasan
, p. 761 - 766 (2007/10/03)
Contrary to previous reports, the reaction mechanism of chlorine dioxide (OClOC·) with benzyl alcohols involves both radical cation and benzyl radical mechanisms dependent on pH. The primary reaction product between OClOC· and 1-(3,4-dimethoxy-phenyl) ethanol at pH 8 is 3,4-dimethoxyacetophenone. At pH 4 no acetophenone was observed; the majority of the degradation products were chlorinated and aromatic ring-oxidized compounds. A primary kinetic isotope effect (kH/kD = 2.05) was observed in the reaction of OClOC· with 1-(3,4-dimethoxy-phenyl)-(1-2H) ethanol at pH 8, but was absent at pH 4 (kH/kD ≈ 1). Similarly, the corresponding methyl ether (4-(1-methoxy)ethyl-1,2-dimethoxybenzene) was substantially less reactive at pH > 6. On the basis of these results, competing pH-dependent reaction mechanisms have been proposed, where at high pH OClOC· reacts with benzyl alcohols via a OClOC·-benzyl alcohol complex.
ANOMALOUS REDUCTION OF ALIPHATIC-AROMATIC KETONES BY THE COMPLEX HYDRIDES OF BORON
Dem'yanovich, V.M.,Khlebnikov, V.A.
, p. 255 - 259 (2007/10/02)
During the reduction of XC6H4COCH3 by the action of sodium borohydride or potassium borohydride in a water-methanol medium the ethers XC6H4CH(OCH3)CH3 and not the corresponding alcohols were obtained.The formation of the ethers indicates that the O-Calkyl (and not O-B) bond is broken in the intermediate tetraalkoxyborate if a stable carbocation of the benzylic type, further stabilized by an electron-donor group at the ortho or para position of the benzene ring, is formed.
