Spirodienone Derivatives of a Spherand-Type Calixarene
- 10 April 2001
- journal article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 66 (9) , 2891-2899
- https://doi.org/10.1021/jo001648x
Abstract
Oxidation of the spherand-type calixarene 4 with 1 or 2 equiv of phenyltrimethylammonium tribromide/base afforded mono- and bis(spirodienone) derivatives (8b and 9, respectively). The spirodienone groups are derived from the oxidation of two phenols connected by a common methylene group. NOESY data indicated that 9 possesses a “head to tail” arrangement of the spirodienone groups. Oxidation of 4 with 3 equiv of the oxidizing reagent afforded two tris(spirodienone) calixarene derivatives 11 and 10 with C1 and C3 symmetries, respectively. The same tris(spirodienone) products were obtained by oxidation of 9 with I2/aq KOH. Tris(spirodienone) 11 displayed NOE cross-peaks in the NOESY NMR spectrum consistent with a nonalternant disposition of carbonyl and ether groups. Upon heating 10 and 11 isomerize in the solid state and in solution. The major component in the equilibration mixtures is 11, indicating that this is the thermodynamically more stable tris(spirodienone) isomer.Keywords
This publication has 23 references indexed in Scilit:
- Stereochemistry of a Spherand-Type CalixareneThe Journal of Organic Chemistry, 2001
- Medium-sized cyclophanes. Part 46.1 The preparation and novel [3.3]- and [1.5]-sigmatropic rearrangements of [n.2]cyclophanes having a spiro skeleton †Journal of the Chemical Society, Perkin Transactions 1, 1998
- An Efficient Method for Synthesis of the Bis(spirodienone) Derivative of p-tert-Butylcalix[4]arene and Effect of para Substituents on the Analogous ReactionJournal of Chemical Research, 1998
- Partial OH → Me Replacement in the Calixarene Scaffold: Preparation, Conformation, and Stereodynamics of Tetra-tert-butyl-25,27-dihydroxy-26,28-dimethylcalix[4]arene and Its Dimethyl Ether DerivativeThe Journal of Organic Chemistry, 1997
- Isolation of a Cyclic Octamer in the Caesium Hydroxide Catalysed Calixarene Condensation of a DihydroxybiphenylJournal of Chemical Research, 1997
- Synthesis and reactions of large-ring spiro-dienone calixarene derivativesPublished by Walter de Gruyter GmbH ,1996
- Diastereoselective Functionalization of a Spherand‐Type CalixareneEuropean Journal of Inorganic Chemistry, 1994
- Proximal intraannular modifications of calix[4]arene via its spirodienone derivativeJournal of the Chemical Society, Chemical Communications, 1993
- A conformational study of the calixspherand and its complexes with alkalimetal cationsJournal of the Chemical Society, Perkin Transactions 2, 1992
- Oxepinobenzofurans—The True Nature of Sterically Hindered “Benzoxetes”Angewandte Chemie International Edition in English, 1978