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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 18, Number 8
BKCSDE 18(8)
August 20, 1997 

Theoretical Studies on the Nucleophilic Substitution Reactions of 1-Phenylethyl Chlorides
Wang Ki Kim, Wang Sun Ryu, Hyeong Yeoun Park, In-Suk Han, Chang Kon Kim, Ikchoon Lee*
Nucleophilic substitution reactions of 1-phenylethyl chlorides (1-PEC; YC6H4CH(CH3)Cl) with phenoxides (XC6H4O-) and thiophenoxides (XC6H4S-) are investigated theoretically using the PM3 method. The Bronsted α and β values are greater for the phenoxides indicating a more advanced reaction in the transition state (TS) than for the thiophenoxides. This is supported by a greater magnitude of ρX (- 6.4 ∼ - 7.4) and ρ XY (- 0.76) for the phenoxides than for the thiophenoxides (ρX = - 3.6 ∼ - 4.4 and ρXY = - 0.60). The percentage bond order changes, %Δn≠, suggest that the extents of bond making and breaking are similar for the phenoxides and hence the TS is symmetrical, but bond making is somewhat greater than bond cleavage for the thiophenoxides indicating an unsymmetrical TS. The reactions in the gas phase for both nucleophile series proceed by a SN2 mechanism with a tight TS and negative charge development on the reaction center carbon, Cα. The reactions in water investigated with model systems of benzyl and 1-phenylethyl chlorides using the Cramer-Truhlar solvation model (PM3-SM3) indicate that the reactions of 1-PEC are far more complex due to enhanced stabilization of the carbocation by the methyl substitution for a benzylic hydrogen.
868 - 873
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