Reactivities of Stable Rotamers. XXXII. Chlorodecarboxylation of 3-(1,4-Dimethyl-9-triptycyl)-3-methylbutanoic Acid Rotamers
- 1 December 1993
- journal article
- research article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 66 (12) , 3790-3796
- https://doi.org/10.1246/bcsj.66.3790
Abstract
Rotational isomers of the title carboxylic acid were treated with lead(IV) acetate in the presence of lithium chloride or benzyltriethylammonium chloride in benzene. The ap-isomer afforded a chloride, which was expected from normal chlorodecarboxylation, in addition to a cyclized compound, which was produced by radical addition to a near-by benzene ring. By contrast, the sc-isomer afforded no normal chloride, but a benzylic chloride, which was formed by hydrogen transfer to the radical site in the 9-substituent from the benzylic position, was the main product. In addition, an acetonyl ester of the original sc-carboxylic acid and a small amount each of 1-acetoxymethyl compound and an olefin were obtained. Possible mechanisms of formation of these compounds are discussed on the ground of the stability of the benzylic radical and participation of a methyl group.Keywords
This publication has 16 references indexed in Scilit:
- Syntheses and Structures of 1,1-Dimethyl-1,2,6,10b-tetrahydro-6,10b-o-benzenoaceanthrylenes: Sterically Congested Triptycenes Carrying Five-Membered RingBulletin of the Chemical Society of Japan, 1993
- Reactivities of Stable Rotamers. XXXI. Bromine Addition to the Olefinic Moiety of Rotameric 1-(9-Fluorenyl)-2-(1-methylethenyl)naphthalenesBulletin of the Chemical Society of Japan, 1993
- Chiral Triptycenes Owing their Chirality to Hindered Rotation of a Bridgehead Substituent. Crystal Structure, Chromatographic Enantiomer Resolution, and Circular Dichroism Spectra.Acta Chemica Scandinavica, 1993
- Syntheses of and Restricted Csp3–Csp2 Bond Rotation in Triptycenes That Carry C4-Olefinic Substituent at 9-PositionBulletin of the Chemical Society of Japan, 1992
- Molecular Structure of 9-Chloromethyl-1,4-dimethoxytriptycene and Its Implications for the Presence of O···CH2C1 InteractionsBulletin of the Chemical Society of Japan, 1990
- Reactivities of Stable Rotamers. XXIV. Formation of Isomeric Ketones by Cydization of Rotameric 3-Methyl-3-(1,2,3,4-tetrahalo-9-triptycyl)butanoyl Chloride and Barriers to Isomerization of the KetonesBulletin of the Chemical Society of Japan, 1988
- Rotamer Populations and Molecular Structure of 9-Isobutyl-1,4-dimethoxytriptycene: Further Evidence for the Presence of CH3···O Hydrogen BondBulletin of the Chemical Society of Japan, 1988
- Reactivities of Stable Rotamers. XXII. Lewis Acid-Catalyzed Reactions of 3-(1,4-Disubstituted 9-Triptycyl)-3-methylbutanoyl Chloride: Isolation of Rotameric Ketones and Competition between Cyclizations to Substituted and to Unsubstituted Benzene RingsBulletin of the Chemical Society of Japan, 1988
- Implications of X-Ray Crystallographic Results of 1,2,3,4-Tetrachloro-9-(2-oxopropyl)triptycene RotamersBulletin of the Chemical Society of Japan, 1982
- The crystal structure of 1,2,3,4-tetrachloro-9-t-butyltriptyceneActa Crystallographica Section B: Structural Science, Crystal Engineering and Materials, 1975