The effect of an alkoxy group on the kinetic and thermodynamic acidity of benzene and toluene
作者： Manfred Schlosser , Paola Maccaroni , Elena Marzi
DOI: 10.1016/S0040-4020(98)83011-1
关键词: Inductive effect 、 Toluene 、 Alkoxy group 、 Lone pair 、 Medicinal chemistry 、 Lithium diisopropylamide 、 Benzene 、 Photochemistry 、 Deprotonation 、 Chemistry 、 Lithium
摘要: 2-, 3- And 4-Methoxytoluene can be selectively metalated at an O-adjacent ortho position when butylithium or tert-butyllithium in the presence of sodium (potassium) tert-butoxide N,N,N',Nq,Nq-pentamethyldiethylenetriamine are employed as reagents. In contrast, lithium diisopropylamide 2,2,6,6-tetramethylpiperidide deprotonate benzylic a-position 2- and 3-methoxytoluene exclusively 4-methoxytoluene preferentially. These relative reactivities rationalized by interplay transition state stabilizing destabilizing forces (dipole matching metal coordination vs. lone pair repulsion). [on SciFinder (R)]
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sci-hub.se 参考文章(52)
A Mordini, V Snieckus), Advances in Carbanion Chemistry ,(1996)
D. D. Perrin, Dissociation Constants of Organic Bases in Aqueous Solution ,(1965)
Organometallics in synthesis : a manual : Wiley. ,(1994) , 10.1002/9781118750407
Robert E. Ireland, Wayne J. Thompson, The facile reduction of methoxyethoxymethyl esters with lithium triethylborohydride Tetrahedron Letters. ,vol. 20, pp. 4705- 4708 ,(1979) , 10.1016/S0040-4039(01)86689-2
John Lionel Simonsen, LXVII.—The nitration of 2- and 6-methoxy-m-tolualdehydes and m-toluic acids Journal of The Chemical Society, Transactions. ,vol. 113, pp. 775- 782 ,(1918) , 10.1039/CT9181300775
C. Schall, Ueber die mittelst der Tetrachlorkohlenstoff-Reaction aus den drei isomeren Kresolen darstellbaren Oxytoluylsäuren und die Oxydation der letzteren zu Oxyphtalsäuren (Phenoldicarbonsäuren) Berichte der deutschen chemischen Gesellschaft. ,vol. 12, pp. 816- 836 ,(1879) , 10.1002/CBER.187901201228
Alexander. McKillop, Brian P. Swann, Edward C. Taylor, Thallium in organic synthesis. XXXIII. One-step synthesis of methyl arylacetates from acetophenones using thallium(III) nitrate (TTN) Journal of the American Chemical Society. ,vol. 95, pp. 3340- 3343 ,(1973) , 10.1021/JA00791A043
Kim D. Summerhays, Steven K. Pollack, Robert W. Taft, Warren J. Hehre, Gas-phase basicities of substituted anilines. Inferences about the role of solvent in dictating site of protonation Journal of the American Chemical Society. ,vol. 99, pp. 4585- 4587 ,(1977) , 10.1021/JA00456A009
H. Küntzel, H. Wolf, K. Schaffner, Photochemical Reactions. Part 63 [1]. The photodecarbonylation of α‐aryl aldehydes Helvetica Chimica Acta. ,vol. 54, pp. 868- 897 ,(1971) , 10.1002/HLCA.19710540312
Michael Meot-Ner, L. Wayne Sieck, Proton affinity ladders from variable-temperature equilibrium measurements. 1. A reevaluation of the upper proton affinity range Journal of the American Chemical Society. ,vol. 113, pp. 4448- 4460 ,(1991) , 10.1021/JA00012A012