Azetidines. 5. Reaction of 1,1,3,3-tetramethyl- and 1-benzyl-1,3,3-trimethylazetidinium ions with butyllithium and phenyllithium. Deuterium labeling as a mechanistic probe

Journal Article · Fri Jun 06 04:00:00 EDT 1980 · J. Org. Chem.; (United States)

DOI:https://doi.org/10.1021/jo01300a046· OSTI ID:6927806

Wills, M T; Wills, I E; Von Dollen, L; Butler, B L; Porter, J

The reactions of 1,1,3,3-tetramethylazetidinium iodide (1) and 1-benzyl-1,3,3-trimethylazetidinium bromide (7) with butyllithium and with phenyllithium were studied in ether. The products from the reaction of 1 with butyllithium were 1,3,3-trimethylpyrrolidine (2), 3,3-dimethyl-4-(methylamino)-1-butene (3), 1-(dimethylamino)-2,2-dimethylheptane (4), neopentylpyrrolidine (5), and 1-(dimethylamino)-2,2-dimethylcyclopropane (6). With phenyllithium, 1 gave 2 and 1-(dimethylamino)-2,2-dimethyl-3-phenylpropane (11). With butyllithium, 7 gave 2-phenyl-1,4,4-trimethylpyrrolidine (8), 1-benzyl-3,3-dimethylpyrrilidine (9), and 1-neopentyl-2-phenylpyrrolidine (10). The reaction of phenyllithium with 7 gave only 8 and 9. Mechanistic information was obtained by labeling 1 with deuterium in three different ways: N-methyl-d/sub 3/,2,2-d/sub 2/, and N-methyl-d/sub 3/-2,2-d/sub 2/. A primary kinetic isotope effect of 9.4 was found for the formation of 2 from 1-N-methyl-d/sub 3/. When 2 was formed from 1-2,2-d/sub 2/, a secondary kinetic isotope effect of 1.17 was measured. The formation of 4 from 1-2,2-d/sub 2/ was accompanied by a primary kinetic isotope effect of 4.7, suggesting a carbene intermediate. Ylide carbanions involving decomposition to a carbene carbanion in the formation of 3 and an azomethine ylide in the formation of 5 and 9 are probable intermediates. It is postulated that the azomethine ylides react with ethylene formed from the reaction of butyllithium with the solvent ether by means of a concerted (4 + 2) cycloaddition reaction. A primary kinetic isotope effect of 20 was found for the formation of pentylbenzene from dibenzyldimethylammonium bromide and butyllithium.

• Research Organization: California Polytechnic State Univ., San Luis Obispo
• OSTI ID: 6927806
• Journal Information: J. Org. Chem.; (United States), Journal Name: J. Org. Chem.; (United States) Vol. 45:12; ISSN JOCEA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400303* -- Organic Chemistry-- Isotope Exchange & Isotope Separation-- (-1987)
ALKALI METAL COMPOUNDS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
DEUTERIUM
HYDROGEN ISOTOPES
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
LITHIUM COMPOUNDS
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
STABLE ISOTOPES
SYNTHESIS