Mechanisms of Elimination Reactions. II. Rates of Elimination from Some Substituted 2-Phenylethyl Bromides and 2-Phenylethyldimethylsulfonium Bromides<sup>1</sup>

Saunders, William H.; Williams, Richard A.

doi:10.1021/ja01571a030

Cited by 51 publications

(21 citation statements)

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“…Later works have pointed out that the bonding changes need not be synchronous, although they occur in a single elementary step. Proton transfer at the transition state may be more advanced than the C-X bond breakage, or vice versa (2)(3)(4)(5). The possible variations in transition-state structure can be represented by means of a More O'Ferrall -Jencks diagram (6)(7)(8).…”

Section: Introductionmentioning

confidence: 99%

Valence bond calculations on the transition state for the E2 reaction of fluoride ion with ethyl fluoride Implications for the More O'Ferrall Jencks diagram

Wu¹,

Shaik²,

Saunders

2005

Can. J. Chem.

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A valence bond self-consistent field (VBSCF) calculation has been carried out on the bimolecular elimination (E2) reaction of fluoride ion with ethyl fluoride. The transition state was first optimized at HF/6-31+G and the resulting orbitals were used in the VBSCF calculation. A transition-state hybrid consisting of four structures (, and F-H -CH 2 -CH 2 + F -) for a total of eight resulted in an energy slightly below Hartree-Fock. A full-space VBSCF calculation utilizing 50 structures showed that the eight structures give a sufficiently accurate wave function. The transition state is dominated by chargeseparated structures, leading to a greater degree of charge separation than in either the reactant or product complex. Therefore, the transition state does not evolve synchronously from the reactants, and explicit allowance should be made for this fact when applying descriptions of the reaction path, such as that in the More O'Ferrall -Jencks diagram.

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Section: Introductionmentioning

confidence: 99%

Valence bond calculations on the transition state for the E2 reaction of fluoride ion with ethyl fluoride Implications for the More O'Ferrall Jencks diagram

Wu¹,

Shaik²,

Saunders

2005

Can. J. Chem.

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“…74,155 By contrast, substitution is insignificant when the β-protons are benzylic. 156 Evidence for ylide formation and subsequent intramolecular elimination has also been found in sulfonium systems treated with organometalics. 157 Five-membered cyclic sulfonium salts treated with such bases (thiolanium salts) may fragment to ethylene and an alkyl vinyl sulfide via a cycloreversion (Fig.…”

Section: Pyridinium Ionic Liquidsmentioning

confidence: 92%

Stability of ionic liquids in Brønsted-basic media

2020

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“…The reactions were carried out in 50ml volumetric flasks in a thermostatted bath at 60°C as described by Saunders and Williams (23). An accurately weighed amount (ca.…”

Section: Elimination Reactionsmentioning

confidence: 99%

Isotope effect studies on elimination reactions. VII. The stereochemistry of elimination from 2-phenylethylammonium ions

Bourns¹,

Frosst²

1970

Can. J. Chem.

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The stereochemistry of the base-promoted elimination reactions of 2-phenylethyltrimethylalnmonium and 2-phenylethyldimethylanilinium ions has been investigated using both ethoxide ion in ethanol and t-butoxida in t-butyl alcohol as base-solvent systems. The proton magnetic resonance spectroscopic analysis of the deuterated styrene products formed from the react~ons of the tlzreo-2-phenylethylammonium-1,2-d, ions established that elimination proceeds more than 95 % by an anti process.

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Mechanisms of Elimination Reactions. II. Rates of Elimination from Some Substituted 2-Phenylethyl Bromides and 2-Phenylethyldimethylsulfonium Bromides¹

Cited by 51 publications

References 1 publication

Valence bond calculations on the transition state for the E2 reaction of fluoride ion with ethyl fluoride Implications for the More O'Ferrall Jencks diagram

Valence bond calculations on the transition state for the E2 reaction of fluoride ion with ethyl fluoride Implications for the More O'Ferrall Jencks diagram

Stability of ionic liquids in Brønsted-basic media

Isotope effect studies on elimination reactions. VII. The stereochemistry of elimination from 2-phenylethylammonium ions

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Mechanisms of Elimination Reactions. II. Rates of Elimination from Some Substituted 2-Phenylethyl Bromides and 2-Phenylethyldimethylsulfonium Bromides1

Cited by 51 publications

References 1 publication

Valence bond calculations on the transition state for the E2 reaction of fluoride ion with ethyl fluoride  Implications for the More O'Ferrall  Jencks diagram

Valence bond calculations on the transition state for the E2 reaction of fluoride ion with ethyl fluoride  Implications for the More O'Ferrall  Jencks diagram

Stability of ionic liquids in Brønsted-basic media

Isotope effect studies on elimination reactions. VII. The stereochemistry of elimination from 2-phenylethylammonium ions

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Product

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Mechanisms of Elimination Reactions. II. Rates of Elimination from Some Substituted 2-Phenylethyl Bromides and 2-Phenylethyldimethylsulfonium Bromides¹

Valence bond calculations on the transition state for the E2 reaction of fluoride ion with ethyl fluoride Implications for the More O'Ferrall Jencks diagram

Valence bond calculations on the transition state for the E2 reaction of fluoride ion with ethyl fluoride Implications for the More O'Ferrall Jencks diagram