cap alpha. -deuterium isotope effects in benzyl halides. 2. Reaction of nucleophiles with substituted benzyl bromides. Evidence for a change in transition-state structure with electron-donating substituents
Journal Article
·
· J. Am. Chem. Soc.; (United States)
Rates and ..cap alpha..-D isotope effects have been determined for the following substrates and nucleophiles: p-methoxybenzyl bromide (Et/sub 3/N, SCN/sup -/, N/sub 3//sup -/, OH/sup -/, S/sub 2/O/sub 3//sup 2 -/), benzyl bromide (Et/sub 3/N, SCN/sup -/, N/sub 3//sup -/, OH/sup -/, S/sub 2/O/sub 3//sup 2 -/), and p-nitrobenzyl bromide (Et/sub 3/N, SCN/sup -/, N/sub 3//sup -/, S/sub 2/O/sub 3//sup 2 -/). In nearly all cases the second-order rate constant for each nucleophile goes through a minimum for the unsubstituted compound while the ..cap alpha..-D isotope increases monotonically in the squence p-NO/sub 2/ > p-H > p-OCH/sub 3/. These results are consistent with an increasing looseness of the S/sub N/2 transition state as the substituent on the aromatic ring becomes more electron donating. 4 figures, 3 tables.
- Research Organization:
- Univ. of Maryland, Catonsville
- OSTI ID:
- 6934872
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 102:21; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Tue Apr 03 23:00:00 EST 1984
· J. Am. Chem. Soc.; (United States)
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OSTI ID:6549633
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Sun Dec 31 23:00:00 EST 1961
·
OSTI ID:4702899
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Thesis/Dissertation
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Wed Dec 31 23:00:00 EST 1975
·
OSTI ID:7256990
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
ALPHA REACTIONS
AROMATICS
ARYL RADICALS
BENZYL RADICALS
BINDING ENERGY
CHARGED-PARTICLE REACTIONS
DEUTERIUM
ELECTRONS
ELEMENTARY PARTICLES
ENERGY
FERMIONS
HALOGENATED AROMATIC HYDROCARBONS
HYDROGEN ISOTOPES
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LEPTONS
LIGHT NUCLEI
NUCLEAR REACTIONS
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
RADICALS
REACTION KINETICS
STABLE ISOTOPES
VALENCE
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
ALPHA REACTIONS
AROMATICS
ARYL RADICALS
BENZYL RADICALS
BINDING ENERGY
CHARGED-PARTICLE REACTIONS
DEUTERIUM
ELECTRONS
ELEMENTARY PARTICLES
ENERGY
FERMIONS
HALOGENATED AROMATIC HYDROCARBONS
HYDROGEN ISOTOPES
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LEPTONS
LIGHT NUCLEI
NUCLEAR REACTIONS
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
RADICALS
REACTION KINETICS
STABLE ISOTOPES
VALENCE