Notable Substituent Effects on the Rate Constant of Thermal Denitrogenation of Cyclic Azoalkanes : Strong Evidence for a Stepwise Denitrogenation Mechanism
Australian Journal of Chemistry Volume 63 Issue 12
Page 1615-1618
published_at 2010-12-06
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| File | |
| Title ( eng ) |
Notable Substituent Effects on the Rate Constant of Thermal Denitrogenation of Cyclic Azoalkanes : Strong Evidence for a Stepwise Denitrogenation Mechanism
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| Creator |
Ishihara Chizuko
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| Source Title |
Australian Journal of Chemistry
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| Volume | 63 |
| Issue | 12 |
| Start Page | 1615 |
| End Page | 1618 |
| Abstract |
The thermal denitrogenation rates (k) of a series of 7,7-dimethoxy-1,4-diaryl-2,3-diazabicyclo[2.2.1] hept-2-ene derivatives 2 with a variety of aryl groups (p-CNC6H4, C6H5, p-MeC6H4, p-MeOC6H4) were determined to investigate the denitrogenation mechanism. A linear correlation (r=0.988) between the relative rate-constant (log k(rel)) of the denitrogenation reaction and Arnold's sigma(.)(alpha) parameter for benzylic-type radical-stabilization was observed. However, the relative rate-constant was not correlated with the substituent effect on the lifetime of the resulting singlet diradicals DR2. These results indicate that the rate-determining step of denitrogenation of 7,7-dimethoxy-2,3-diazabicyclo[2.2.1] hept-2-ene derivatives involves stepwise C-N bond cleavage.
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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/CH10281
[NCID] AA00555860
[DOI] http://dx.doi.org/10.1071/CH10281
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