Extreme sensitivity of grandisal to acids

Attempted purification of synthetic racemic grandisal1 by silica gel chromatography resulted in severe decomposition. The nature of this reaction was studied on silica gel and in an ether solution ofp-toluenesulfonic acid. The same products resulted from both reaction systems, although in different...

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Bibliographic Details
Published in:Journal of chemical ecology 1987-07, Vol.13 (7), p.1725-1738
Main Authors: Webster, F.X, Zeng, X.N, Silverstein, R.M
Format: Article
Language:English
Subjects:
ACIDE ORGANIQUE
ACIDOS ORGANICOS
AISLAMIENTO (TECNICA)
ALCOHOLES
ALCOHOLS
ALCOOL
ALDEHIDOS
ALDEHYDE
ALDEHYDES
Biochemistry. Physiology. Immunology
Biological and medical sciences
CHEMISTRY
CHIMIE
Curculionidae
DEGRADATION
DETERIORO
Fundamental and applied biological sciences. Psychology
Insecta
Invertebrates
ISOLATION
ISOLEMENT
ORGANIC ACIDS
Physiology. Development
PISSODES
QUIMICA
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Summary:Attempted purification of synthetic racemic grandisal1 by silica gel chromatography resulted in severe decomposition. The nature of this reaction was studied on silica gel and in an ether solution ofp-toluenesulfonic acid. The same products resulted from both reaction systems, although in different ratios. Five racemic, rearrangement products were isolated by preparative GC and identified as follows: (1RS, 3SR, 6RS)-1-methyl-5-methylenebicyclo[4.2.0]octan-3-ol (4); (1RS, 3RS, 6RS)-1-methyl-5-methylenebicyclo[4.2.0]octan-3-ol (5); (1RS,3RS,6RS)-1,5-dimethylbicyclo[4.2.0]oct-4-en-3-ol (6); (1RS,3SR,6RS)-1,5-dimethylbicyclo[4.2.0]oct-4-en-3-ol(7); and 3-methyl-7-methylenecyclooct-3-en-l-ol (8). The stereochemical assignments are based on our proposed mechanism, which also accounts for all products observed. The racemic bicyclic enone (3) was a by-product of grandisol (2) oxidation.
ISSN:0098-0331
1573-1561
DOI:10.1007/BF00980213