Benzidine rearrangements. 17. The concerted nature of the one-proton p-semidine rearrangement of 4-methoxyhydrazobenzene

Journal Article · Wed Sep 22 04:00:00 EDT 1982 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00383a031· OSTI ID:6203667

Shine, H J ^[1]; Zmuda, H; Kwart, H; Horgan, A G; Brechbiel, M

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1. Texas Tech. Univ., Lubbock

The nitrogen kinetic isotope effects (KIE) for the acid-catalyzed rearrangement of 4-methoxyhydrazobenzene (1b) into the p-semidine (4-methoxy-4'-aminodiphenylamine, 2b) and o-semidine(2-amino-5-methoxydiphenylamine, 3b) have been measured and are 1.0296 (av) and 1.074 (av), respectively. The carbon KIE for formation of 2b was found to be 1.039 (av). The results show that p-semidine formation is a concerted process. Rearrangements were carried out in 60% aqueous dioxane under conditions of earlier kinetic work. Mixtures of 1b and (/sup 15/N, /sup 15/N')1b were used for the nitrogen KIE, measured mass spectrometrically with isolated N-benzoyl-2b, and mixtures of 1b and (4'-/sup 14/C)1b for the carbon KIE, measured with scintillation counting on isolated N-benzoyl-2b. The method of carbon labeling did not allow for a measurement of the KIE for formation of 3b.

• OSTI ID: 6203667
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 104:19; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
AMINES
AROMATICS
BENZIDINE
CARBON ISOTOPES
CHEMICAL REACTION KINETICS
HYDRAZONES
ISOTOPE EFFECTS
ISOTOPES
KINETICS
NITROGEN ISOTOPES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
REACTION KINETICS
SYNTHESIS