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Rück-Braun, K.; Priewisch, B., Science of Synthesis, (2007) 31, 1326.
A broad range of nitrosoarenes bearing a tertiary amino group in the para position can be synthesized in good to excellent yields by nitrosation of the corresponding tertiary arylamines. Often a solution of an equimolar amount of sodium nitrite in water is gradually added at 0–10°C to the arylamine in hydrochloric acid,[24] but in some cases the addition of an alcohol as a cosolvent may be necessary. The concentration of hydrochloric acid should be high enough to ensure precipitation of the 4-nitrosylated arylamine as its hydrochloride salt (Scheme 10),[25–31] from which the free amine 13 may be subsequently liberated by the addition of a base such as ammonium hydroxide or aqueous sodium hydroxide.[25,26] Nitrosation of tertiary arylamines may also be effected using alkyl nitrites or nitrosonium ethyl sulfate, generated in situ from ethyl nitrite and sulfur trioxide, as nitrosating reagents.[27,28] Alternatively, nitrosyl chloride can be generated in situ from sodium nitrite and tin(IV) chloride pentahydrate in dichloromethane and this allows nitrosations to be carried out in non-alcoholic organic solvents.[29] Substituents ortho to the tertiary amino group impede nitrosation (see Houben–Weyl, Vol. 10/1, p 1042), and para-substituted tertiary amines also do not normally undergo ring nitrosation.[32]
Meeeee 88 Meeeeeeeeee ee Meeeeeee Meeeeeeeee[88–88]
M8 | M8 | M8 | M8 | Meeeeeeeee | Meeee (%) | eee (°M) | Mee |
---|---|---|---|---|---|---|---|
Me | (MM8)8MMMe | MMe | M | MeMM8, MMe, M8M, 8–8°M, 8.8 e, eeee MM8MM | eeeee | 888–888 | [88] |
(MM8)8MM | (MM8)8MM | M | M | MeMM8, MMe, M8M, 88–88°M, 8 e, eeee ee 88% MeMM | 88 | 888–888 | [88] |
Me | (MM8)8MM | Me | M | eMeMMM, eMeMM, M8MM8, <8°M, 8 e | 88e | 88 (eee) | [88] |
Me | eeeeeeeeeeee-8-ee | M | M | MeMM8, MeMM, MMe, M8M, 88–88°M, 8 e, eeee ee 88% MeMM | 88 | 88–88 | [88] |
Me | Me | M | M | MeMM8, MeMe8•8 M8M, MM8Me8, 8 e | 88 | e.e. | [88] |
eMe | eMe | M | M | MeMMM, MM8, MM8Me8, −88 ee 88°M, 8 e, eeee ee Me8MM8 | 88 | 88–88 | [88] |
Me | (MM8)8MMMe | Me | M | MeMM8, MMe, M8M, 8–8°M, 8.8 e, eeee MM8MM | 88 | 888–888 | [88] |
Me | Me | M | M | MeMM8, MMe, M8M, 8°M ee ee, 8–8 e | 88–88e | e.e. | [88] |
(MM8)8MMe | MM8M(Me)=MM8 | M | M | MeMM8, MMe, M8M, 88–88°M, 8 e, eeee ee 88% MeMM | 88 | 88–88 | [88] |
Me | Me | Me | Me | MeMM8, MMe, M8M, 8°M, 8 e, eeee ee MeMM | 88 | 888–888 | [88] |
e e.e. = eee eeeeeeee.
e Mee eeeeeeee ee eeeeeeee ee e eeeeeeeeeee eeee.
e Mee eeeeeeee ee eeeeeeee ee e eeeeeeeeeeeee eeee.
Mee eeeeeee ee eee eeeeeeee ee eeeee eeeeeeeee ee eee eeeeeeeeee eeeeeeee, ee eeeeeeeeeee ee eee eeeeee ee eeeeee eeeeeee eeee M,M-eeeeeeeeeeeeeee ee eeeeeeeeeeee eeee; eeee, eeeee eeeeee eeeeee eeeeeee eeeee ee eee eeeeeeeee ee eeeeeeeeeeeee eee M-eeeeeeeeee eeeeeeee 88–88 eeeee eeee M,M-eeeeeeee-8-eeeeeeeeeeeeee (88) (Meeeee 88),[88] e eeeeeee ee eee eeeeeeeeeee eeeeeee eeeeee eeeeeeeeeee eeeeeee ee M,M,M′,M′-eeeeeeeeeeeeeeeeeee-8,8′-eeeeeee.[88,88]
Meeeee 88 Meeeeeeeee ee eee Meeeeeeeeee ee M,M-Meeeeeeeeeeeeee[88]
Meeeeeeeeeee Meeeeeeee
M,M-Meeeeee-8-eeeeeeeeeeeeee Meeeeeeeeeeee (88, M8 = M8 = Me; M8 = M8 = M); Meeeeee Meeeeeeee:[88]
MeMM8 (8.88 e, 88 eeee) ee M8M (88 eM) eee eeeeee ee 8°M eee eeeee ee eeeeeeee eeee 8–8 e, eeee eeeeeeee, ee e eeee ee M,M-eeeeeeeeeeeeee (88.8 e, 88 eeee) ee eeeee MMe (88 eM) eee M8M (88 eM) eeee eee eeeeeeeeee ee −88 ee −8°M ee ee eee/eeee eeee. Meeeee eee eeeeeeee eee eeeeeeeeeee ee eee eeeeeee eee eeeeeeeee eeeeeeeee ee eeee ee eee eee eeee eeeee 8°M. Meee eee eeeeeeee eee eeee, eee eeeeeee eee eeeeeee ee eeee ee ee eeee 8–8 e, eee eeee eee eeee-eeeeeee eeeeeeeeeee eeee eee eeeeee eee eeeeeeeee ee eeeeeeeeee, eeeeee eeee eeeeeee, eee eeeee ee 88°M ee eeeeeeee eeeeee. Meee eeeeeeee eee eeeeeeeeeee ee eee MeMM (88 eM) eee Me8M (888–888 eM) eee eeeee ee eeeeeeeeeee eee eeeee eeeeeeee ee eeeeee-eeeee eeeeeeee; eeeee: 8–8 e (88–88%).
References
[24] | Meeee, M.; Meeeeee, M. M., Mee. Meeee., Meee. Mee. M, (8888), 888. |
[25] | Meee, M. M.; Meeeeeee, M. M.; Meeeeeeeee, M. M.; Meeeeee, M. M.; Meeee, M. M.; Meeee, M. M.; Meeeee, M. M.; Meee, M. M.; Meeee, M. M.; Meeeeee, M. M.; Meeeeee, M. M.; Meeeee, M. M.; Meeeeeeeeee, M., M. Me. Meee. Mee., (8888) 88, 8888. |
[26] | M'Meeee, M. M.; Meee, M. M.; Meeeee, M. M., M. Me. Meee. Mee., (8888) 88, 8888. |
[27] | Mee, M. M.; Meeeeeee, M. M.; Meeeeeeeee, M. M.; Meeeeee, M. M., Mee. Meee. Meee, Mee. Meee., (8888), 888; Meee. Meee. Meee., (8888) 88, 888. |
[28] | Meeeeee, M.; Meeeeeeee, M.; Meeeeeee, M., MM 888 888, (8888); Meee. Meeee., (8888) 888, 8888. |
[29] | Méeeeeèe, M.; Máeeáee, M., Meeeeeeee, (8888), 8888. |
[30] | Meeeeeeee, M. M.; Meeeeeee, M. M.; Meeeeee, M. M.; Meeeeeee, M. M.; Meeeeeee, M. M.; Meeeeeee, M. M.; Meeeeeee, M.; Meeeeeee, M. M.; Meeee, M. M.; Meeeeeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[31] | Mee, M.; Meee, M., MM 88 88 888, (8888); Meee. Meeee., (8888) 888, 88888. |
[32] | Meeeeee, M. M.; Meeee, M. M.; Meeeeee, M.; Meeeeeee, M.; Meeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[33] | Meeeeee, M. M.; Meeeeeeee, M. M., M. Meee. Mee., (8888), 888. |
[34] | Meee, M.-M.; Meeeeeeee, M., Meee. Mee. Meee. Me., (8888), 8888. |
[35] | Meeeeee, M.; Meeeeeeee, M. M.; Meeeeeeeeee, M., Meeeeeeeeee, (8888) 88, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 88/8, 8888.
- 8.Meeeee-Meee, (8888) M 88e8, 888.