MECHANISM OF BENZIDINE AND SEMIDINE REARRANGEMENTS. PART IX. SUBSTRATE- ISOTOPE EFFECTS ON KINETICS AND PRODUCTS OF ACID REARRANGEMENT OF 1,1'-HYDRAZONAPHTHALENE

Journal Article · Sat Sep 01 04:00:00 EDT 1962 · Journal of the Chemical Society (England) Divided into J. Chem. Soc. A, J. Chem. Soc. B, etc.

DOI:https://doi.org/10.1039/jr9620003299· OSTI ID:4777954

Banthorpe, D V; Hughes, E D; Ingold, C; Humberlin, R

1,1'-Hydrazonaphthalene, as well as its 2,2'- and 4,4'dideutero- derivatives, the preparation of which is described, were rearranged with acid in 60%'' aqueous dioxan, and comparisons were made of rearrangement rates and product proportions. The same hydrazo-compounds were rearranged with acid in 95% aqueous ether-ethanol, and comparisors were made of product proportions. In the conditions of these comparisons, three products alone are formed, the single 4,4'- ring-coupled product, naphthidine, and the pair of 2,2'-ring-coupled products, dinaphthyline, and its cyclised relative, dibenzocarbazole, all in substantial, easily measurable, amounts. In the dioxan solvent, neither 2-deuteration nor 4- deuteration affects the overall rate of rearrangement. In both solvents, neither 2- nor 4-deuteration affects the ratio of 4,4'- to total 2,2'-ringcoupled products. In both solvents, 2-deuteration, but not 4-deuteration, does change the internal ratio of the two 2,2'-ring-coupled products, the shift being large, and in favor of the carbazole. Conclusions are drawn concerning The activation of the aromatic proton losses, and their disposition among the product-forming steps of rearrangement. (auth)

• Research Organization: University Coll., London
• NSA Number: NSA-16-032989
• OSTI ID: 4777954
• Journal Information: Journal of the Chemical Society (England) Divided into J. Chem. Soc. A, J. Chem. Soc. B, etc., Journal Name: Journal of the Chemical Society (England) Divided into J. Chem. Soc. A, J. Chem. Soc. B, etc.; ISSN JCSOA
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

AROMATICS
CHEMISTRY
CONFIGURATION
DEUTERIUM COMPOUNDS
ETHANOL
ETHERS
ISOTOPE EFFECTS
MEASURED VALUES
NAPHTHALENE
ORGANIC NITROGEN COMPOUNDS
PREPARATION
REACTION KINETICS
SOLVENTS
WATER