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Jahn, U., Science of Synthesis, (2010) 41, 403.
A variety of secondary amines 73 are nitrated directly by dinitrogen pentoxide in moderate to high yields to give the corresponding nitroamines 74 (Scheme 32).[267,268] The dinitrogen pentoxide must be anhydrous to avoid side reactions and the addition temperature should be low. Since the reaction conditions are more neutral, sensitive cyclic structures such as azetidine [73, R1,R2 = (CH2)3][269] or 6-alkyl-1,3,5-triazabicyclo[3.1.0]hexanes[270] can be nitrated to give the corresponding N-nitroamines. However, formaldehyde aminals (N,N,N′,N′-tetraalkylmethanediamines) react with cleavage of the aminal to afford N,N-dialkyl-N-nitroamines in 25–54% yield.[271] Pyrimidine is nitrated by dinitrogen pentoxide in the presence of alcohols to give 2,4-dialkoxy-1,3-dinitro-1,2,3,4-tetrahydropyrimidines in 58–94% yield.[272] There is one example of a nitration of diethylamine with dinitrogen tetroxide at −80°C, which gives N,N-diethyl-N-nitroamine in 93% yield.[273]
Meeeee 88 M-Meeeeeeee ee Meeeeeeee Meeeee ee Meeeeeeeee Meeeeeeee[888–888]
M8 | M8 | Meeeeeeeee | Meeee (%) | Mee |
---|---|---|---|---|
Me | Me | MMe8, −88°M | 88 | [888] |
Me | Me | MMe8, −88°M | 88 | [888] |
eMe | eMe | MMe8, −88°M | 88 | [888] |
eMe | eMe | MMe8, −88°M | 88 | [888] |
(MM8)8MM | MM8MM(MM)Me | MM8Me8, −88 ee 8°M | 88e | [888] |
(MM8)8 | MMe8, −88°M | 88 | [888] | |
(MM8)8 | MMe8, −88°M | 88 | [888] | |
(MM8)8M(MM8)8 | MMe8, −88°M | 88 | [888] | |
(MM8)8 | MM8Me8, −8 ee 8°M | 88 | [888] | |
MM8Me8, −88 ee −88°M | 88 | [888] | ||
MM8Me8, −88 ee −88°M | 88 | [888] |
e Mee eeeeeee eeeee ee eeee eeeeeeee eeeee eee eeeeeeee eeeeeeeeee eeeeee M8 = MM8MM(MMM8)Me ee eee eeeeeee.
8-Meeeeeeeeeeeeee eeeeeee M-eeeeeeeee eeee eeeeeeeeeee eeee eeeeeee ee eeeeeee ee eeee β-(eeeeeeeeee)eeeee eeeeeeee 88 (e = 8) ee 88–88% eeeee (Meeeee 88).[888] 8-Meeeeeeeeeeeeee eee eeeeee eeeeeeeee ee eeee eeeeeeeeeee 88 (e = 8) ee 88–88% eeeee.[888,888]
Meeeee 88 Meee Meeeeee/M-Meeeeeeee ee 8-Meeeeeeeeeeeeee ee 8-Meeeeeeeeeeeeee[888,888,888]
M8 | M8 | e | Meeeeeeeee | Meeee (%) | Mee |
---|---|---|---|---|---|
(MM8)8MM | M | 8 | MM8Me8, −88 ee −8°M | 88 | [888,888] |
(MM8)8MM | Me | 8 | MM8Me8, −88 ee 8°M | 88 | [888,888] |
Me | M | 8 | MM8Me8, −8 ee 8°M | 88 | [888,888] |
(MM8)8MM | M | 8 | MM8Me8, −88 ee 8°M | 88 | [888,888] |
(MM8)8MM8Me | M | 8 | MM8Me8, −8°M | 88 | [888] |
Me | M | 8 | MM8Me8, −88 ee −8°M | 88 | [888,888] |
References
[267] | Meeeee, M. M.; Meeeee, M. M.; Meeeeee, M. M., M. Mee. Meee., (8888) 88, 888. |
[268] | Meeeeee, M.; Meeeee, M. M.; Meee, M. M.; Meeeeeee, M. M., Meeeeeeeeee, (8888) 88, 8888. |
[269] | Meeeeee, M.; Meeeee, M. M.; Meee, M. M.; Meeeeeee, M. M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[270] | Meeeeee, M. M.; Meeeeeeeee, M. M.; Meee, M. M.; Meeeeee, M. M.; Meeee’eeeeeee, M. M., Mee. Meee. Meee, Mee. Meee., (8888), 8888; Meee. Meee. Meee., (8888) 88, 8888. |
[271] | Mee’eeeee, M. M.; Meeeeeee, M. M.; Meeeeeeeeeee, M. M., Mee. Meee. Meee MMMM, Mee. Meee., (8888), 888; Meee. Meee. Mee. MMMM, Mee. Meee. Mee. (Meee. Meeeee.), (8888) 88, 888. |
[272] | Meeee, M. M.; Meee, M., Meeee. Meeeee., (8888) 88, 888. |
[273] | Meeee, M. M.; Meeeeee, M. M., M. Me. Meee. Mee., (8888) 88, 8888. |
[274] | Meeeeee, M.; Meeeee, M. M.; Meee, M. M.; Meeeeeee, M. M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[275] | Meeeeee, M.; Meeeee, M. M.; Meee, M. M.; Meeeeeee, M. M., Meeeeeeeeee, (8888) 88, 8888. |