scholarly journals Kinetic Studies of Bimolecular Nucleophilic Substitution. II. Structural Effects of Alkyl Halides on the Rate of SN2 Reactions —A Reinvestigation of the Linear Free-Energy Relationships for the Structural Variation of the Alkyl Groups

1967 ◽  
Vol 40 (8) ◽  
pp. 1905-1908 ◽  
Author(s):  
Kunio Okamoto ◽  
Issei Nitta ◽  
Tetsuo Imoto ◽  
Haruo Shingu
Keyword(s):  
Free Energy ◽  
Structural Variation ◽  
Kinetic Studies ◽  
Alkyl Halides ◽  
Linear Free Energy Relationships ◽  
Structural Effects ◽  
Sn2 Reactions ◽  
Linear Free Energy ◽  
Alkyl Groups ◽  
Energy Relationships

Transition state analysis. I. Correlation between solvent stretching frequencies and C vs. O product ratios in alkylation of ambient anions. A new explanation for the observed product ratios

1970 ◽  
Vol 48 (13) ◽  
pp. 2120-2123 ◽  
Author(s):  
Donald C. Wigfield
Keyword(s):  
Free Energy ◽  
Phenolic Compounds ◽  
Ground State ◽  
Metal Cation ◽  
Alkyl Halide ◽  
Alkyl Halides ◽  
Linear Free Energy Relationships ◽  
Linear Free Energy ◽  
Energy Relationships ◽  
Alkylation Reactions

A new explanation is presented for the O to C product ratios observed in alkylation reactions of ethyl acetoacetate and related enolic and phenolic compounds, based on a Hammond postulate analysis of the nature of the transition states involved. The explanation not only covers the effects of solvent and the nature of the metal cation, but also encompasses the previously unexplained effect of the alkyl halide structure. From the latter effect, ground state interaction between solvent and alkyl halide is predicted. Evidence consistent with this interaction is found in linear free energy relationships between the ΔΔG‡ (C vs. O) values for various alkyl halides and the stretching frequency of the solvent (S=O of DMSO; P=O of HMPA) when measured as alkyl halide solutions.

Linear free energy relationships in CN bond dissociations in molecular ions of 4-substitutedN-(2-furylmethyl)anilines in the gas phase

2007 ◽  
Vol 42 (11) ◽  
pp. 1496-1503 ◽  
Author(s):  
Eduardo A. Solano Espinoza ◽  
Elena Stashenko ◽  
Jairo Martínez ◽  
Uriel Mora ◽  
Vladimir Kouznetsov
Keyword(s):  
Free Energy ◽  
Gas Phase ◽  
Molecular Ions ◽  
Linear Free Energy Relationships ◽  
Linear Free Energy ◽  
Energy Relationships
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