Nucleophilic substitution at centers other than carbon: reaction at the chlorine of N-chloroacetanilides with triethylamine as the nucleophile
The reaction between triethylamine (TEA) and a series of para-substituted N-chloroacetanilides has been studied in aqueous solution buffered to pHs between 1 and 5. The exclusive product derived from the aromatic moiety is the corresponding acetanilide. The reaction occurs via two parallel pseudo-second-order paths, one acid catalyzed (the Orton-like mechanism), the other uncatalyzed. The uncatalyzed reaction is accelerated by the presence of electron-withdrawing substituents on the aromatic ring and can best be represented as nucleophilic displacement at chlorine. It therefore appears to be the prototype of a convenient class of reactions for the study of displacement reactions at chlorine. The rho value for this reaction is 3.87, indicating substantial negative charge buildup in the aromatic ring during of the transition state. The acid-catalyzed reaction is more complex, presumable involving a protonation equilibrium for the N-chloroacetanilide prior to the rate-determining step similar to that in the Orton reaction. 15 references, 2 figures, 3 tables.
- Research Organization:
- New York Univ., NY
- DOE Contract Number:
- AC02-81ER60015
- OSTI ID:
- 5863367
- Journal Information:
- J. Org. Chem.; (United States), Journal Name: J. Org. Chem.; (United States) Vol. 49:26; ISSN JOCEA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
AMIDES
AMINES
AQUEOUS SOLUTIONS
AROMATICS
BUFFERS
CHEMICAL REACTION KINETICS
CHLORINATED AROMATIC HYDROCARBONS
CHROMATOGRAPHY
CORRELATIONS
DATA
DATA ANALYSIS
DISPERSIONS
EXPERIMENTAL DATA
HALOGENATED AROMATIC HYDROCARBONS
INFORMATION
KINETICS
LEAST SQUARE FIT
LIQUID COLUMN CHROMATOGRAPHY
MATHEMATICAL MODELS
MAXIMUM-LIKELIHOOD FIT
MIXTURES
MONITORING
NUMERICAL DATA
NUMERICAL SOLUTION
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PH VALUE
REACTION KINETICS
SEPARATION PROCESSES
SOLUTIONS