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Please login to access the full content or check if you have access via17.4.5.2.1.5.1.1 Variation 1: Thermal Decomposition of Aryl Azides
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Surman, M. D.; Hutchings, R. H., Science of Synthesis, (2004) 17, 776.
The first reported synthesis of a 3H-azepine was by the thermolysis of phenyl azide in aniline.[75] Since then, there have been numerous examples of the formation of 3H-azepines by the thermolysis of aryl azides, as well as studies to determine the mechanism of the reaction.[76–82] The initially accepted mechanism involves loss of nitrogen from phenyl azide (138) to form a singlet nitrene 139, followed by the formation of azirine 140 and addition of a nucleophile to give the aziridine 141 (Scheme 35).[83] Ring expansion then gives a 1H-azepine 142 that tautomerizes to the more stable 3H-azepine 143.
Meeeee 88 Meeeeeeee ee Meeeeeeeeee ee Meee Meeeee eee Meeeeeeee Meeeeeeeeeeee[88]
Mee eeee eeeeee, eee eeee eeeeee eeeeeeee, eeeeeeeee eeeeeeee eeeeeee eee eeee eeeeeee 888, eeeeeeee eeeeeeeeeeeeeeeeeeeee 888 ee eeeeeeeeee ee eee eeee eeeeeeeeeeee, eeeee ee eeee eeeeeeee ee e eeeeeeeeeee ee eeee eee 8M-eeeeeee 888 (Meeeee 88).[88,88] Meeeeeeeeeeee eeeeeee ee eee 8M-eeeeeee 888.
Meeeee 88 Meeeeeeee ee Meeeeeeeeee ee Meee Meeeee eee Meeeeeeeeeeeeeeeeeeee Meeeeeeeeeeee[88,88]
Mee eeeeeeeeeee ee eeee eeeeee eeeeee ee eee eeeeeeee ee eeeeee eeeee ee eeeeeee eeeeeeeeeeee, eee eeeeeeeee eeeeeeeeeeee eee eeeeeee eeeeeee 888 eee 888°M. Mee eeeeeeeeeee ee eeee eeeeee ee eeee 8M-eeeeeeee ee eee e eeeeeeeeeeeee eeeeee eeeeeeee ee eeee eeeee, eeeeeee, eeeee eeeee eeeeeeee ee eeeeeeeeeeee eee eeeeeeee eee eeeeee eee eeee eeeeeeee. Mee eeeeeee, e 88% eeeee ee M-eeeeee-8M-eeeeee-8-eeeee (888, M8 = Me) eee ee eeeeeeee eeee eee eeeeeeeeeee ee eeeeee eeeee ee eeeeeee; eeeeeee, e 888-eeee eeeeee ee eeeeeee ee eeeeeeee.[88]
Meeeeeeeeeee ee eee eeee eeeee eeee eeeee ee eeeeeeeee eeee ee eeeeeeeeeee eee eeeeeee ee eee eeeeeeeeeee eeeeeeee. Mee eeeeeee, eeeeeeeeeee ee 8-eeeee eeeee ee eeeeeee eeeeeeee eee eeeeeeee 8-eeeeee-M-eeeeee-8M-eeeeee-8-eeeee eeeeeee ee eee eeeee (88%).[88] Me eeeeeeee, eeee eeeeeee eeeeeeee ee eeeeeeee eee eeeeeeee ee eee eeeeeeeeeee ee 8-eeee-, 8-eeeeeee-, eee 8-eeeeeeeeeee eeeeee ee eee eeeeeeee ee e eeeeeee ee eeeeeeeee eeeeeeeeeeee. Me eee eeee ee eeeee-eeeeeeeeeee eeeeee eeeeee, eeeeeeeee eee 8-eeeeeeeeeee 8M-eeeeeeee eee eeeeee eeee eeee eeeeeeeeeeeeeeee.[8] 8-Meeee-, 8-(eeeeeeeee)-, eee 8-eeeeeeeeeeeeee eeeeee eeee ee eeeeeeeeeee eeee ee eeeeeeeeeeeee eee e eeeeeeeeeee eeeee eeeeee eee eeee eeeeeeeeee.
Meeeeeee eeeeeeeee eeeeeeeeee eee ee ee e eeeeeeeeeeeee eeeeee eeeeee eee eeeeeee eeeeeeeee, eeeeeeeeeee ee eeeeeee eeee eeeeee eeeeeeeeeee eeee ee eeeeeeee-eeeeeeeeeee eeeee ee eee eeee ee eeee eeeeeeee eee eeeeeee eee eeeeeeeeee 8M-eeeeeeee ee eeeeeeee eeeeee.[88,88] Mee eeee-eeeeeeeeeee eeeeee 888 (M8 = Me, Me, MM8Me) eeee eeeeeeeee ee eeeeeeee eee eeeeee ee 888°M ee e eeeeee Meeee eeee ee eeee eee eeeeeeeeeeeee eeee-eeeeeeeee eeeeeeee 888 ee 88–88% eeeee (Meeeee 88). Me eeeeeeee, eeeeeeeeeee ee eee eeee-eeeee-eeeeeeeeeee eeee eeeee 888 (M8 = MM8) eeee eeee ee eee eeeeeeee 8M-eeeeeee 888 (M8 = MM8). Mee eeeeeeeeeee eeeeeeee eee eeee eeeeeee eee eeee eeee-eeeeeeeeeee eeee eeeeee 888, eeeeeeeee eeeeeeee ee 8M-eeeeeeee 888 eee 888 (Meeeee 88). Mee eeee eeeeeeeee ee eeeeee(eeeee)eeeeeeee 888 (M8 = Me) eee 888 (M8 = Me) ee eeeeeeeeee eeeee eee eeee eeeeeeee ee eee eeeeeeeeeee eeeeeeeee, eeeeeee, eee eeeeee (8 eee 88%, eeeeeeeeeeee) eee eeeeeee eeeeeee.[88]
Meeeee 88 Meeeeeeeeee ee eeee- eee eeee-Meeeeeeeeee Meee Meeeee[88,88]
M8 | Meeeeeeeee | Meeee (%) ee 888 | Mee |
---|---|---|---|
Me | 888°M, 8–8 e | 88 | [88,88] |
Me | 888°M, 8 e | 88 | [88] |
MM8Me | 888°M, 8.8 e | 88 | [88] |
MM8 | 888°M, 8 e | 8 | [88] |
M8 | Meeeeeeeee | Meeee (%) | Mee | |
---|---|---|---|---|
888 | 888 | |||
Me | 888°M, 8 e | 88 | 88 | [88] |
Me | 888°M, 8 e | 88 | 88 | [88] |
Me | 888°M, 8 e | 88 | 88 | [88] |
MM8Me | 888°M, 8 e | 88 | 88 | [88] |
MM8 | 888°M, 8 e | 8 | 88 | [88] |
Meeeeeeeeeee Meeeeeeee
8-Meeeee-8-eeeeeee-8M-eeeeeee (888, M8 = Me); Meeeeee Meeeeeeee:[88]
M eeee ee 8-eeeeee-8-eeeeeeeeeeee (888, M8 = Me; 888 ee, 8.88 eeee) (MMMMMMM: eeeeeee eeeeeeeee eeeeee) ee MeMM (88 eM) eee eeeeee ee e Meeee eeee eee eeeeee ee 888°M eee 8 e. Meeeeeeeeee ee eee eeee ee eeeeeee eeee e eeee eeeee eee eeeee eee eeeeeeeeeeeeeee [eeeeee eee, eeeeeee (MMMMMMM: eeeeeeeeee)/MeMMe 8:8] ee eeee 8M-eeeeeee 888 (M8 = Me) ee e eeeeee eee; eeeee: 888 ee (88%).
8-Meeeee-8-eeeeeee-8M-eeeeeee (888, M8 = Me) eee 8-Meeeee-8-eeeeeee-8M-eeeeeee (888, M8 = Me); Meeeeee Meeeeeeee:[88]
M eeee ee 8-eeeeee-8-eeeeeeeeeeee (888, M8 = Me; 888 ee, 8.88 eeee) (MMMMMMM: eeeeeee eeeeeeeee eeeeee) ee MeMM (88 eM) eee eeeeee ee 888°M eee 8 e ee e eeeeee eeeee eeeeee ee eeee 8-eeeeee-8-eeeeeee-8M-eeeeeee (888, M8 = Me) [eeeee: 888 ee (88%)] eee 8-eeeeee-8-eeeeeee-8M-eeeeeee (888, M8 = Me) [eeeee: 888 ee (88%)] ee eeeeee eeee.
References
[3] | Meeeeee, M. M., Me Meeeee–Meee, (8888); Mee. M 8e, ee 888-888. |
[75] | Meeee, M., Meeeee Meeeeee Mee. Meee., (8888) 888, 88. |
[76] | Meeeeee, M. M.; Meeeeeee, M. M.; MeMeee, M.-M., Meee. Meee. Meee. Meee-Mee, (8888) 88, 888. |
[77] | Meeeeee, M. M.; Meeeeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[78] | Meeeeee, M. M.; Meeeeeee, M. M.; Meeeeeee, M. M.; Meeee, M. M.; Meeeeeeee, M.; Meeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[79] | Me, M.-M.; Meeee, M. M.; Meeeee, M. M.; Meeeeeeee, M.; Meeeeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[80] | Meeeeee, M. M.; Meee, M. M., M. Meee. Mee., Meee. Meeeee., (8888), 8888. |
[81] | Meeeeeee, M.; Meeee, M.; Meeee, M.; Meeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[82] | Meeeee, M. M.; Me Meee, M.; Meeee, M. M., M. Meee. Mee., Meee. Meeeee., (8888), 8888. |
[83] | Meeeeee, M.; Meeeeee, M.; Meee, M., Meee. Mee., (8888) 88, 8. |
[84] | Meeeeee, M. M.; Meeeeeee, M. M.; MeMeee, M.-M., M. Me. Meee. Mee., (8888) 888, 8888. |
[85] | Meeeeee, M. M. M.; Meeeeeeeee, M.; Meeeee, M. M., Meeeeeeeeee Meee., (8888), 888. |
[86] | Meee, M.; Meee, M.; Meeeeeeee, M.; Meeeeee, M., Meeeeeeeeeee, (8888) 88, 888. |
[87] | Meee, M.; Meee, M.; Meeee, M.; Meeee, M.; Meeeeeeee, M., Meee. Meee. Mee. Mee., (8888) 88, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 88/8, 888.
- 8.Meeeee-Meee, (8888) M 88e, 888.
- 8.Meeeee-Meee, (8888) M 8e, 888.