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Effects of amine nature and nonleaving group substituents on rate and mechanism in aminolyses of 2,4-dinitrophenyl X-substituted benzoates.
Second-order rate constants have been measured for the reactions of 2,4-dinitrophenyl X-substituted benzoates (1a-f) with a series of primary amines in 80 mol % H(2)O/20 mol % DMSO at 25.0 +/- 0.1Expand
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The Yukawa-Tsuno Relationship in Carbocationic Systems
Publisher Summary This chapter deals with reactions involving carbocationic transition states, in most cases forming intermediates having carbocationic centers at the conjugative position in the sideExpand
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Effect of amine nature on reaction rate and mechanism in nucleophilic substitution reactions of 2,4-dinitrophenyl X-substituted benzenesulfonates with alicyclic secondary amines.
Second-order rate constants have been measured for reactions of 2,4-dinitrophenyl X-substituted benzenesulfonates with a series of alicyclic secondary amines. The reaction proceeds through S-O andExpand
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Theoretical studies on empirical structure–reactivity relationship: the Yukawa–Tsuno equation
The substituent-dependent stabilization energies (δ X ΔE) of a series of α,α-R 1 R 2 benzyl cations were determined by means of ab initio calculation at the MP2/6-31G*//RHF/6-31G* + ZPE (scaledExpand
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Dynamics for reaction of an ion pair in aqueous solution: reactivity of carboxylate anions in bimolecular carbocation-nucleophile addition and unimolecular ion pair collapse.
[reaction: see text]. The sum of the rate constants for solvolysis and 18O-scrambling of 4-MeC6H4(13)CH(Me)18OC(O)C6F5 in 50/50 (v/v) trifluoroethanol/water, k(solv) + k(iso) = 1.22 x 10(-5) s(-1),Expand
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Theoretical study of substituent effects on gas‐phase stabilities of benzylic anions
The substituent effects on the relative gas-phase stabilities of 16 kinds of benzylic anion systems were determined theoretically using proton transfer reactions. The energies and geometries ofExpand
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The β-Silicon Effect. III. Substituent Effects of the β-Si-Aryl Moiety in the Solvolysis of 1-Aryl-2-(aryldimethylsilyl)ethyl 3,5-Dinitrobenzoates
Solvolysis rates of 2-[dimethyl(X-phenyl)silyl]-1-(Y-phenyl)ethyl 3,5-dinitrobenzoates were determined conductimetrically in 60% (v/v) aqueous ethanol. The effects of substituents X in theExpand
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