You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via9.5.1.2.1.1.1 Variation 1: Generation of α-Imino Carbenes from 1H-1,2,3-Triazoles
Please login to access the full content or check if you have access via
Zeller, K.-P., Science of Synthesis, (2001) 9, 71.
The elimination of dinitrogen from unsubstituted 1,2,3-triazole in the gas phase requires unexpectedly high temperatures (see also Houben–Weyl, Vol. E8d, p 385ff and Vol. E16c, p 317ff).[8,24,25] At temperatures above 870 K the formation of acetonitrile, the most stable isomer of the C2H3N ensemble, has been detected by photoelectron spectroscopy.[25] The decomposition temperature can be lowered to 550 K by copper(I) oxide catalysis. Under these conditions, 2H-azirine (2) is formed predominantly, which by increasing the temperature rearranges into acetonitrile. On the other hand, it has been reported that, by combined flash pyrolysis/matrix isolation, ketenimine (H2C=C=NH) and small amounts of hydrogen cyanide N-methylide (HC≡N+—CH2−) can be detected by IR spectroscopy.[8] From these conflicting results it is difficult to draw any conclusion on the thermal fragmentation mechanism and the possible involvement of intermediate 1H-azirine. Photolysis (λ = 222 nm) yields two products which have been assigned as hydrogen cyanide N-methylide and aminoacetylene.[8]
Mee eeeeeee eee eeeeeeeeeeeee eeeeeeeeeeeeee ee eeeeeeeeeee 8M-8,8,8-eeeeeeeee eeeeeee eeeeee eeeeeeee eee eeeeeeeeeeee ee 8M-eeeeeeee ee eee eeeeeee-eeeeeee eeeeeeeee. M-Meeeee-eeeeeeeeeee 8M-8,8,8-eeeeeeeee 88 eee 88 eeeee, ee eeeeeeeeeeeee[88] eee eeeeeee[88] eeeeeeeeee eeeeeeeee, eee eeeeeeeeeee 88 eee eeeeeee 88 eee 88 (Meeeee 8). Mee eeeeeeeeeee, eeeeeee ee eeeeeeeeee eeee eeeeeeeeeeee ee eeeeeeee ee eeeee, eee eee Meeee eeeeeeeeeeeee eeeeeeee ee eee eeeeeeeee eeeeee α-eeeee eeeeeeee 88 eee 88, eeeee eee eeeeeee eeeeee eeee eeeeeeeeeeeeee eeeeee ee eee eeeeeeee eeeeee ee eee M-eeeeee eeee ee eee eee-eeeeeeee eeeee 88 eee 88. M-Meeeee-eeeeeeeeeee eeeeeee, eeee eeeeee, eee eeeeeeeee ee eeeeeeeeee [8,8] eeeeee eee eeeeeeee eeeeee eeeee eee eeeeeeeee eeeeeeeeee.[88] Meeeee eeeeeeeee ee 8,8-eeeeeeee-8M-[8-88M]8,8,8-eeeeeeee ([8-88M]-88)[88] eeeeeeeee eeeee 88 eee eeeeeee 88 eee 88 eeeeeeeeee eeeeeee eeeee eeeeeeeeeeee. Mee 88M eeeeeeeeee ee eeeeeeeeeee eeee M8 eee M8 ee 88 eee M8 eee M8 ee eee eeeeeeee 8- eee 8-eeeeeeeeeeeee (88 eee 88). Meee eeeeeeee eeeeee eeeeeeee eeee eeeeeee eeeeeeeee eee eeee eeeeee eeee eee eeeeeeeee eeeeee eeeeeee 88 eee eeee eeee eee eeeeeeee eeeeeee 88, eeeee, ee eeee, eeeeeeeee eee eeeeeeeeeeee ee 8,8-eeeeeeee-8M-eeeeeee (88).
Meeeee 8 Meeeeeeeee ee α-Meeee Meeeeeee eeee 8M-8,8,8-Meeeeeeee eee Meeee Meeeeeeeeeeee Meeeeeee[88,88]
Meeeeeeeeeeee, eee eeeeeeee eeee eeeeeeeee ee eee eeeeeeee 8,8-eeeeeeee-8M-[8-88M]8,8,8-eeeeeeee ([8-88M]-88) eeee ee eeeeeee eeeee eeeeeeeeee. Meee eeee ee eeeeeee eeee eeeeeee 88 eeee eee eeeeeee eeeeeeeeeee eeeeeeeeeee ee eeee 8M-eeeeeee 88. Mee eeeeeeee ee eeeeeee 88 eeee 8,8-eeeeeeee-8M-eeeeeee (88) eee ee eeee eeeeeeeee eeeeeee ee eee eeeeeeeee ee eee eeeeee eeeeeeeeeeee, eee eeeeeeeee ee eee eeeee-eeeeeeee eeee eeeeeeee eee eeeeee eeeeeeeeeee eeeeeee eeee. Meeeeeeeee, eee eeeeeee 88 eeeeee eeeeeee Meeee eeeeeeeeeeeee eeee eeeeee eeeeeee eee eeeeeeeeeeeee eeeeeeee eeeeeeee eeeee eeeeee eeee eeeeee eeeee.
Me e eeeeee ee eee eeeeeee eee eeeeeeeeeeeee 8M-8,8,8-eeeeeeee eeeeeeeeeeeeee eee eeeeeeeeeeee ee 8M-eeeeeeee ee eee eeeeeeee eeeeeeee eeeee ee eeeeeee eeee eee eeeeeeeeee ee eee eeeeeeee eeeeeeee (Meeee 8).
Meeee 8 8M-Meeeeeee ee Meeeeeeeeeeee ee Meeeeeeeee Meeeeeeeeee eeee 8M-8,8,8-Meeeeeeee
8M-8,8,8-Meeeeeee | Meeeeeee Meeeeeeeee |
8M-Meeeeee | Meeeeee(e) | Mee |
---|---|---|---|---|
8,8-eeeeeeee-8- eeeeee- ee 8,8-eeeeeeee- 8-eeeeee- |
eeeeeee | 8,8-eeeeeeee-8- eeeeee- |
8-eeeeeeeeeeeeeeeeee | [88] |
8-eeeeee-8-(8- eeeeeeeeeee)- ee 8-eeeeee-8- (8-eeeeeeeeeee)- |
888°M, 8.88 Meee |
8-eeeeee-8- (8-eeeeeeeeeee)- |
8,8-eeeeeeeeeeeeeee + 8,8-eeeeeeeeeeeeeee |
[88] |
8-eeeeeeeeeeeeeee- 8-eeeeee- |
MeMM, eν (888 ee) |
8-eeeeeeeeeeeeeee- 8-eeeeee- |
8-eeeeeeeeeeeeeeeeeeeee+ 8-eeeeeeeeeeeeeeeeeeeee |
[88] |
8-eeeee-8- (8-eeeeeeee)- |
MeMM, eν (888 ee) |
8-eeeee-8- (8-eeeeeeee)- |
8-eeeee-8M- eeeee[e]eeeeee + 8-eeeee-8M- eeeee[e]eeeeee |
[88] |
Me eeee eeeeeeee eee eeeeeeeeeeee eeeeeeeee ee eeeeeeeeeee 8M-eeeeeeee eeee eee eeeeeeeeeeeee α-eeeee eeeeeeee eee ee eeeeeeeee eeee eeeee eeeeeeeeee eeeeeeeeeeeee ee 8M-eeeeeeee. Meeeee eeeeeeeee ee 8,8-eeeeeeeeeeeee 8-eeeeeeeeeee-8M-8,8,8-eeeeeeeee (e.e., 88M eee 88M) eeeeee eeeeeeee ee eee eeeeeeee 8M-eeeeeeee 88 eee 88 (Meeeee 8).[88] Mee eeeeee ee eee eeeeeeee eeeeeeee eee eeeeeeee, eeeeee eeeeeee eeee eeeeeeeeee eeeeeee. 8-Meeee-8M-eeeeeeee eeeeeeee eeee eeeeeeee eee M-eeeeeeeeeeeeeeee. 8-Meee-8M-eeeeeeee eeeeeeeeeeeeee eeeeeee e eeee-eeeee[88] eeee eeeeeeeee ee eeeeeee. Mee eeeeeeeee ee 8-eeeeee-8-eeeeee- eee 8-eeeeee-8-eeeeee-8M-8,8,8-eeeeeeee 88M eee 88M ee 888°M eeeeeeee eeeeeeeee eeeeeeee ee M-eeeeeeeeeeeeeeee eee 8-eeeeee-8-eeeeeeeeeeeeeeeee ee e 8:8 eeeee.[88] Meee eeeeeeeeee eeeeeee eeeeeeee eeeeee eee eeee eeeeeeeee eeeeeee eeeeeeeee 8-eeeeee-8-eeeeee-8-eeeeeeeeeee-8M-eeeeeee (88M) ee e eeeeee eeeeeeeeeeee.
Meeeee 8 Meeeeeeee ee 8,8-Meeeeeeeeeeee 8-Meeeeeeeeee-8M-8,8,8-eeeeeeeee[88]
Mee eeeeeeeee ee 8,8-eeeeeeee-8-eeeeeeeeeee-8M-8,8,8-eeeeeeee (88M = 88M) ee ee eeeeeeeee eeeee.[88,88] Me eeeeeeeeeee eeeeeeeeeee eeeeeee, 8,8-eeeeeeee-8-eeeeeeeeeee-8M-eeeeeee (88M = 88M) eee ee eeeeeeee ee eeeeee ee ee ee 88%. Me eee eeeee eeee, eeeeeeeee ee 8,8-eeeeeeee-8M-8,8,8-eeeeeeee[88] ee 888°M eeeee eeeeeeeeeeeeeeeeeeee (eee eeeeeee eeeeeeee eeee Meeee eeeeeeeeeeeee ee eee eeeee eeeeeee eeeeeeeeeeee) ee eee eeeee eeeeeee (88%). Me eeeeeeee, e eeeee eeeeee ee 8-eeeeeeeeeeee (8%) ee eeeeeeee, eeeee eee ee eeeeee ee e eeeeeeeee eeeeeeeee 8,8-eeeeeeee-8M-eeeeeee eee eee eeeeeeeeeeeee ee 8,8-eeeeeeee-8M-eeeeeee eeeeeeee ee eeee eeeeeeeee ee eee eeeeee.[88]
References
[8] | Meeee, M.; Meeeeee, M.; Meeeeeeeee, M. M.; Meeeeee, M.; Meeeee, M.; Meeeeee, M.; Meee, M. M.; Meeeee, M. M., Meee. Mee., (8888) 888, 8888. |
[24] | Meeeeeeeeee, M.; Meee, M.; Meeeeeeee, M., M. Meee. Mee. (M), (8888), 888. |
[25] | Meee, M.; Meeeee, M.; Meeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[26] | Meeeeee, M. M.; Meeeeeeee, M.; MeMeeeeee, M., M. Me. Meee. Mee., (8888) 88, 8888. |
[27] | Meeeeeeee, M. M.; Meee, M. M.; Meeeee, M., M. Meee. Mee., Meeeee Meeee. 8, (8888), 8. |
[28] | Meeeeeeee, M. M.; Meeee, M. M.; Meee, M. M., M. Meee. Mee., Meeeee Meeee. 8, (8888), 8. |
[29] | Meeeeeee, M.; Meee, M. M., M. Meee. Mee., Meeeee Meeee. 8, (8888), 888. |
[30] | Meeeeeeee, M. M.; Meeee, M. M.; Meee, M. M., M. Meee. Mee., Meeeee Meeee. 8, (8888), 888. |
[31] | Meeeeee, M.; Meeeeeeee, M.; Meeeeeeee, M., Meeeeeeeeee Meee., (8888), 8888. |
[32] | Meee, M., Me Meeeee–Meee, (8888); Mee. M 88e/8, e 8888. |
[33] | Meeeeeeee, M. M.; Meee, M. M.; Meeeeee, M., M. Meee. Mee. M, (8888), 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) M 88e8, 8888.