Confirmation of the ortho Substitution ... - ACS Publications

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1-01. 77

NOTES

ing material, only diene dimer as condensation product, b.p. 87.5-88' (15.0 mm.). CONTRIBUTION KO.175 FROM JACKSON LABORATORY E. I. DU PONTDE NEMOURS & Co. WILMINGTOS, DELAWARE

Confirmation of the ortho Substitution Rearrangement of the Benzhydryltrimethylammonium Ion by Sodium Amide B Y WALLACE R BRASEN'AND CHARLES R. HAUSER RECEIVEDFEBRUARY 28, 1955

One of the ortho substitution rearrangements of benzyl type quaternary ammonium ions by sodium amide in liquid ammonia reported recently,2 is that of the benzhydryltriniethylamnionium ion (I) t o form tertiary amine I V (88yo). This example is particularly remarkable3 since the reactive intermediate is carbanion I11 (an ylide),*not carbanion I1 which is presumably present in much higher co ncentratioii. CH3 (CsI1b),CHy( CII3)z

SaNHL

-+

CHs

-

1

t---( C6FIsLX-K(CI13), IIq

SH3

-c

i-

I

I1

The product was assigned structure IV because, on oxidation, it produced o-benzyl- and o-benzoylbenzoic acids. Lye have confirmed this assignment of structure bv unequivocally synthesizing tertiary aniirie 111 from o-benzoylbenzoic acid, passing through intermediates V and VI, and showing that it was identical with the tertiary amine obtained from the rearrangement of I.

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