36749-13-0Relevant articles and documents
The Mechanism of Ethylene Elimination from the Oxonium Ions CH3CH2CH=O+CH2CH3 and (CH3)2C=O+CH2CH3
Bowen, Richard D.,Derrick, Peter J.
, p. 1033 - 1039 (2007/10/02)
The reactions of the metastable oxonium ions CH3CH2CH=O+CH2CH3 and (CH3)2C=O+CH2CH3 are reported and discussed.Various mechanisms for ethylene elimination, which is the principal dissociation route for these ions, are considered.It is shown by means of 2H-labelling experiments and analysis of collision-induced dissociation spectra that routes involving ion-neutral complexes pre-empt 'conventional' mechanisms for these processes.In contrast, the behaviour of the lower homologues CH3CH2CH=OR+ and (CH3)2C=OR+ (R = H, CH3) is consistent with the operation of 'conventional' mechanisms for ethylene expulsion.This contrast is interpreted in energetic terms.The significance of these results for the chemistry of homologous and analogous 'onium' ions containing a Z+-R function (Z = O, S, NH, NCH3; R= CnH2n+1, n 2) is explained.
Nucleophilic Displacement with Heterocycles as Leaving Groups. Part 16. Reactions of Secondary Alkyl Primary Amines with 5,6,8,9-Tetrahydro-7-phenyldibenzoxanthylium Trifluoromethanesulphonate to give Intermediates Solvolysing without Rearrangement
Katritzky, Alan R.,Lopez-Rodriguez, Maria L.,Keay, James G.,King, Roy W.
, p. 165 - 170 (2007/10/02)
Representative secondary alkyl primary amines R1R2CHNH2 react with the title pyrylium cation in acetic acid, alcohols, phenols, and NN-dimethylaniline acting as nucleophilic solvents to give O- and C-(secondary alkyl) products.Absence of carbenium ion rearrangements is consistent with reaction via intimate ion-molecule pairs formed rapidly from the corresponding pyridinium cations.
ORGANOMETALLICS, PART VII. THE SYNTHESIS OF α,α-DISUBSTITUTED METHYL ETHERS BY REACTION OF ETHYLDIPHENYLORTHOFORMATE WITH ORGANOMAGNESIUM COMPOUNDS
Poncini, L.
, p. 215 - 224 (2007/10/02)
The reaction conditions are investigated for the production of pure α,α-disubstituted methyl esters.Crotyl- and ethyl-magnesium bromides on reaction with ethyldiphenylorthoformate in ether, under reflux conditions, yielded mixtures of mono- and disubstituted ethers; the former with total allylic transposition.Crotyl Grignard, at room temperature, gave only the monosubstituted mixed acetal.Acetylenic organomagnesiums produced high yields of pure α,α-disubstituted methyl ethers when the solvent was dichloromethane.Methyl vinyl and isopropenyl vinyl organomagnesiums in THF gave only disubstituted ethers.The products obtained are rationalized in terms of a mechanism incorporating a two-fold nucleophilic attack on the ethoxyphenoxycarbonium ion formed from the orthoformate by the organometallic anion, displacing two phenoxy groups to yield the α,α-disubstituted methyl ethers.
ACTION D'ORGANOMETALLIQUES SUR L'ORTHOFORMIATE DE DIPHENYLE ET D'ETHYLE. PREPARATION D'ACETALS MIXTES DE TYPE RCH(OC2H5)OC6H5
Barbot, F.,Miginiac, Ph.
, p. 1 - 16 (2007/10/02)
The reaction between an organometallic compound RM and the mixed orthoester (C6H5O)2CHOC2H5 gives either a mixed acetal RCH(OC2H5)OC6H5 or an ether R2CHOC2H5, depending on the structure of the organometallic compound used.
