Syntheses and Structures of 1,1-Dimethyl-1,2,6,10b-tetrahydro-6,10b-o-benzenoaceanthrylenes: Sterically Congested Triptycenes Carrying Five-Membered Ring
- 1 July 1993
- journal article
- research article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 66 (7) , 2088-2096
- https://doi.org/10.1246/bcsj.66.2088
Abstract
Sterically compressed title compounds which carry a five-membered ring condensed to the triptycene skeleton were synthesized by the Diels-Alder reaction of 1,1-dimethyl-1,2-dihydroaceanthrylene with a benzyne. The structures of three compounds were determined by X-ray crystallography. The molecules have several abnormal bond lengths and angles in addition to significant deformation of the benzene rings as well as the triptycene skeleton to avoid the eclipsed conformation about C(1)–C(10b) and C(1)–C(2) bonds. The effects of the substituents at the 7—10 positions are rather small, but an interesting bond angle deformation is found on comparison of the C(10a)–C(10)–substituent bond angles. Molecular mechanics calculation was performed for the dimethoxy compound to compare the calculated structure with the X-ray structure. Molecular flexibility of the unsubstituted compound was discussed on the basis of MM2 calculation.Keywords
This publication has 9 references indexed in Scilit:
- 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
- A molecular mechanics study of cyclopropanes within the MM2 and MM3 force fieldsJournal of the American Chemical Society, 1992
- 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
- Restricted Rotation Involving the Tetrahedral Carbon. XLIV. Atropisomers of 2,3-Dichloro-9-(1-hydroxy-1-methylethyl)triptycene and Related CompoundsBulletin of the Chemical Society of Japan, 1983
- Chemistry of diazoacenaphthenones and diazoacenaphthenesThe Journal of Organic Chemistry, 1982
- Steric effects. A study of a rationally designed systemJournal of the American Chemical Society, 1980