Demethylation of an Allene Bearing Two Dimethoxythioxanthene Groups by Oxidation via a Vinyl Cation Intermediate
Australian Journal of Chemistry Volume 63 Issue 12
Page 1638-1644
published_at 2010-12-06
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| File | |
| Title ( eng ) |
Demethylation of an Allene Bearing Two Dimethoxythioxanthene Groups by Oxidation via a Vinyl Cation Intermediate
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| Creator |
Yamaguchi Torahiko
Fuku-en Shin-ichi
Sugawara Shun
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| Source Title |
Australian Journal of Chemistry
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| Volume | 63 |
| Issue | 12 |
| Start Page | 1638 |
| End Page | 1644 |
| Abstract |
With the objective of preparing an isolable triplet carbene, we have carried out the oxidation of an allenic compound bearing two thioxanthene moieties (5). Relatively weak oxidants such as Ph3C+BF4 – gave 8, which is the conjugate acid of 5, as a result of a one-electron oxidation followed by hydrogen abstraction, whereas relatively strong oxidants such as SbCl5 furnished a dicationic ketal (9) as a consequence of oxidation and demethylation. Computations on the supposed dicationic intermediate suggest that the singlet state is more stable than the triplet state by 6.7 kcal mol–1 and that the reason for this peculiarity is because the singlet state is essentially a vinyl cation stabilized by a coordinating methoxy group.
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| NDC |
Chemistry [ 430 ]
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| Language |
eng
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| Resource Type | journal article |
| Publisher |
CSIRO Publishing
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| Date of Issued | 2010-12-06 |
| Rights |
Copyright (c) 2010 CSIRO
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| Publish Type | Author’s Original |
| Access Rights | open access |
| Source Identifier |
[ISSN] 0004-9425
[DOI] 10.1071/CH10297
[NCID] AA00555860
[DOI] http://dx.doi.org/10.1071/CH10297
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