4113-66-0Relevant articles and documents
Substituted Oxazoles: Synthesis via Lithio Intermediates
Whitney, Scott E.,Rickborn, Bruce
, p. 3058 - 3063 (2007/10/02)
Reactions of 2-α-, 2-, 4-, and 5-lithiooxazoles are used to prepare various substituted derivatives.Previously unrecognized time dependence for the reaction of a 2-lithiooxazole with benzaldhyde is described, and a rationale for this behavior is offered.Competitive reactions occur when the readily available 2,5-diphenyloxazole is treated with n-butyllithium.Deprotonation of the ortho position of the 2-phenyl group and addition of n-butyl to the 2-position of the oxazole compete with the desired 4-lithiation.The use of sec-butyllithium/catalytic lithium tetramethylpiperidide allows preferential formation of 4-lithio-2,5-diphenyloxazole.This intermediate has been converted to the 4-bromo, -methyl, -hydroxybenzyl, -benzoyl, and -trialkylsilyl derivatives.Lithiation of 2,4-diphenyloxazole and subsequent trimethylsilylation occur readily at the 5-position.Deprotonation of 2-alkyloxazoles occurs at the α-carbon in preference to ring sites.Further reaction of an α-phenyl-2-oxazolemethanol methoxymethyl ether with base and acetyl chloride leads to an acyloin derivative.Chromic acid oxidation is used to prepare both 2- and 4-benzoyloxazoles.The formation of an 2-ethoxyoxazole from 2-oxazolone vis Meerwein salt chemistry is described.
Investigation of Thermally Induced α-Deoxysilylation of Organosilylated Hydroxylamine Derivatives as a General Method for Nitrene Production
Chang, Young Hwan,Chiu, Fang-Ting,Zon, Gerald
, p. 342 - 354 (2007/10/02)
A variety of organosilylated hydroxylamine derivatives have been synthesized and studied as possible nitrene generators by thermally induced α-deoxysilylation: GN(OR')SiR3 GN + R'OSiR3, where G = EtO2C, ArCO, ArSO2, Me, H, and Ph2PO.The methods used to assess nitrene formation include trapping product characterization, substitutent variation, kinetic activation parameter measurements, Hammett studies, and solvent effects.While the latter two types of precursors were only briefly investigated because of their marked resistance to fragmentation, the combined data for the remaining compounds are consistent with the intermediacy of a nitrene.The existence of alternative deoxysilylation pathways is discussed in some cases, and for comparison with the nitrogen systems reported herein, kinetic activation parameters for α-deoxysilylation about carbon and silicon have been determined.