Science of Synthesis

Aitken, R. A.; Aitken, K. M., Science of Synthesis, (2010) 41, 133.

In the Henry reaction, a nitroalkane anion adds to a carbonyl group to give a 2-nitro alcohol.[‌521‌] The reaction is also called the nitroaldol reaction. Nitromethane, nitroethane, and 2-nitropropane react with formaldehyde. Multiple alkylations occur when the nitroalkane is primary or secondary and sufficient carbonyl compound is used (‌Scheme 180‌).[‌522‌]

‌Meeeee 888‌ Meeeeeee ee Meeeee Meeeeeeeeeee eeee Meeeeeeeeeee[‌888‌]

Mee eeee eeeeee eeeeeeeeeee ee eee Meeee eeeeeeee ee eee eeeeeeee ee e eeeeeeeeeee ee eee eeeeeeee ee eeeeeeee eeeeeeee. Meee ee eeeeeeee eee eeeeeee eee eeeeeeeee eeeeeeeeeeee ee eee eeeeeeee eeeeeeee ee eee eeee ee eeeeee. Meeeeeee eee eeeee ee ‌Meeee 88‌. Meeee eeeeeeeee eee eeeeeeeee eeeeee ee ee eeeeeeee ee eeeee eee eeeeeeeeee eeee eeeeeee eeeee.

‌Meeee 88‌ Meeeeeee ee eee Meeee Meeeeeee[‌888‌–‌888‌]

M8	M8	M8	M8	Meeeeeeeee	Meeee (%)	Mee
MM8MM	Me	Me	M	M8M, M8MM8 (eee.), 88–88°M	–e	[‌888‌]
M	M	MM8MM8Me	M	eeeee MeMM8 eeee eee Me eeee ee MeM8MMM8MMM, eeeeeee, 88°M, 88 e	88	[‌888‌]
M	M	(MM8)8MM8	M	M	88	[‌888‌]
MM8Me	Me	M	M	MeMMe (eee.), MeMM, eeee eeeeeeee ee eeeee eeeeeeee, <88°M, eeee ee, 88 eee	88	[‌888‌]
Me	Me	M	M	MeMM (eee.), MeMM, ee, eeeeeeeee	88	[‌888‌]
MMMeMMe8	M	M	M	eeeeeee/M8M, M8MM8 (eee.), 888°M, 8 e	88	[‌888‌]
Me	M	Me	M	MeMe, MMM/MMMM, −88 ee 8°M, 8 e, eeee ee MMe	88e	[‌888‌]
M	M	(MM8)8		MeMe, MMM/MMMM, −88 ee −88°M, 8 e, eeee MeMM	88	[‌888‌]
M	M		M	eeee, 8 M MMM ee MeMM (eee.), ee, 8 e, eeee eeeeeeeeeeeeee eeee eeeee M8MM8	88	[‌888‌]
Me	Me	(MM8)8M(Mee)MM8MM=MM8	M	e-MeMM, e-MeMM/MeMM, 8°M ee ee, 88 e	88e	[‌888‌]
Me	Me	(MM8)8M(Mee)MM8M≡MMe	M	e-MeMM, e-MeMM/MeMM, 8°M ee ee, 88 e	88	[‌888‌]
M	M	Me	M	eeee, eeeeeeeeeeeeeee eeeeeeeee ee eeeeeeeeee eeeee, 8°M, eeee eeeeeeee ee eeeeeeee, ee, 8 e	88	[‌888‌]
(MM8)8MMe	M	(MM8)8MM8Me	M	MMM (eee.), MeMM, 8°M ee ee, eeeeeeeee	–e	[‌888‌]
Me	M	(MM8)8MM8Me	M	MMM, MMM, ee, 8–88 e	88	[‌888‌]
M	MM8	MM8MM	M	M8M, MeMM, ee, 88 e	88	[‌888‌]

e Meeee eee eeeeeeee.

e Meeee eeeeeeeeee ee MMM eeee eeeee eeeeeeee eeeeeee.

e Meeee ee eeeee eeeeeee eeeeeee, eeee eee eeeeeee eeee (MeM)8MMMe eee eeeeeeee ee eee eeeeeeeee eeeee ee 88% eeeee.

e Meeeeee eeeeeee eee eeeeeeeee eeeeeeee eeee eeeeeee eeeee eeeee Me8M; eeeeeee eeeee: 88%.

Meeee eeeeeeeee ee 8-eeee-eeeeeee[8.8.8]eeee-8-eee-8-eeeeeeeeeeee,[‌888‌] e eeeeeeeeee,[‌888‌] eee eeeeeeeeeeee (ee eeee ‌888‌)[‌888‌] eee eeeee ee ‌Meeeee 888‌.

‌Meeeee 888‌ Meeee Meeeeeeee ee Meeeeeeeeeee eeee Meeeee Meeeeeeee[‌888‌,‌888‌,‌888‌]

Meee eeeee eeeeeeeee ee eeeeeee eeeeeee eeeeeeeeee eee eeeeeeee, eee eeeeeeeeeeeeeeeee ee eee Meeee eeeeeeee eeeeeee eeeeeeeee. Meeee eeeeee eeeeeeee eeeeeeeee eeeeeee eee eeeeee ee eee eeeeeeee ee ee eeeeee eee eeeee e eeeeeeeeee eee eee eeeeeee eeeeeeeeeeee,[‌888‌] eeeeeee e eeeeee eeeeeeeeeeeeee eee eeee e eeee eeeeeeeeeeeeeeeeee eeee eeeee eeeeeee eeeeeeee eeeeeeeee[‌888‌] (‌Meeeee 888‌).

‌Meeeee 888‌ Meeeeeeeeeeeeee Meeee Meeeeeeee[‌888‌,‌888‌]

Meeee eeee eeee eeee eeee eeeee eeeee eee Meeee eeeeeeeee eeeee ee eee eeee eeeeeeeee eeeeeeeeeeeeee. Meeeeeee eeee eeeeeee eeeee ee ‌Meeeee 888‌, eee eeeeeee eee eeeeeeee ee eeeeeeeeeeee eeee eeeee eeeeeeeee ee eeeeeeeeeeee. Me ‌Meeeee 888‌ eee eeeee eeeeeee eeeeeeeeeeeeeee: M eeeeeeeeeee eeeeee eeee eee eeeeeeeee ee eeeeeeeeeeee,[‌888‌] eee eeeeeee eeeeeeeeeee eeeeee eeeee eeee e eeeeeeeeee eeeeee e eeeeee eeeeeee.[‌888‌] Meee, ee α,ω-eeeeeeeeeeeee eeee ee eee eeeeeeee eeeeeeeee,[‌888‌] eee e eeeeeeeeee eeeeee eeee eee eeeeeeeee ee eeeeeeeeeee.[‌888‌]

‌Meeeee 888‌ Meeeee Meeee Meeeeeeee[‌888‌,‌888‌,‌888‌,‌888‌]

Meeeeee ee eeee eeeeeee, eeeeeeeeee eeeeeeeeeeeee eeee eeeeee eeee ee eeeeee eeeeeeee eeeeeeeee. Me ‌Meeeee 888‌ eee eeeee e Meeee eeeeeeee eeeeeeee ee eeeeeeeee eeeeeeee ee eee eeeeeeeee eeeeeeeeeee,[‌888‌,‌888‌] ee eeeeeeeeeeeeeee eeeee-Meeeeee/Meeee eeeeeeee eeeeeee ee e eeeeeeeeeee,[‌888‌] eee e eeeeee Meee–Meeeee/Meeee eeeeeeee eeee eeee 8 eeeeeeeeeee ee eeeeeeeeeee.[‌888‌] Me eee eeee eeeeeee, eee eeeeeee eeeeee ee eeeeeeee eeeeeeee ee e eeeeee.[‌888‌]

‌Meeeee 888‌ Meeeee Meeee Meeeeeeee[‌888‌–‌888‌]

Meeeeeeeeeee Meeeeeeee

8-Meeee-8-eeeeeeeeeee-8-ee (‌888‌); Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeeeeeeeeeeeeeeeee eeeeeeee ee e eeeeeeee eeeee eeeeeeeeee eee ee eee eee eeee eeeeeeee.

Me e 8.8 M eeee ee MeMe (88.8 eM, 88.8 eeee) ee MMM/MMMM (8:8; 888 eM) eeeee eeeee ee −88°M eee eeeee 8-eeeeeeeeeeee (8.88 e, 8.88 eM, 88 eeee). Mee eeeeeeeeee eee eeeeeee ee eeee ee −88°M eeee 88 eee eee eee eeeeeee eee eeeeeee 88 eee ee −88 ee −88°M. MeMMM (8.88 e, 8.88 eM, 88 eeee) eee eeee eeeee, eee eee eeeeeee eee eeeeeee eee 8 e ee −88°M. Meeee eeee eeee, ee eee eeeee eeeeee ee −88°M, eee e eeeeeee ee MeMM (8 eM, ee. 88 eeee) eee MMM (8 eM) eee eeeee. Mee eeeeeee eee eeeeee ee ee eee M8M (88 eM) eee eeeee. Mee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8×888 eM), eee eee eeeeeeee eeeeeeee eeee eeeeee eeee M8M (8×88–88 eM), eeeee (Me8MM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeee eeeeeeeee ee eeee ‌888‌; eeeee: 8.88 e (88%); ee 888°M/8.888 Meee; 8M MMM [MMe8 (MMMMMMM: eeeee), δ]: 8.8–8.8 (e, 8M), 8.88 eee 8.88 (8 e, 8M, eeeee ee eee eeeeeeeeeeeee 8:8, M = 8, 8 Me), 8.88 (ee, 8M, M = 8, 88 Me), 8.88 (ee e, 8M, MM), 8.8–8.8 (e, 8M), 8.88 (e, 8M, M = 8.8 Me).

(8M,8M)-8-Meeeeeeeee-8-eeeeeeeeeee-8-ee (‌888‌); Meeeeee Meeeeeeee:[‌888‌]

Me e eeeeeee ee (M,M)-‌888‌ (88.8 ee, 8.8888 eeee), MM (8.8 ee, 8.8888 eeee), eee MeMM8 (‌88‌; 88.8 μM, 8.88 eeee) ee eeeeeee (8.88 eM) eee 8 eM ee MMM (8.88 eM) eee eeeee MeMMM (88.8 μM, 8.888 eeee) ee 8°M. Mee eeeeeeeee eeeeeee eee eeeeeee eeeeeeeeee ee 8°M eee 88 e. Meee, eee. ee MM8Me eee eeeee, eee eee eeeeeee eeeee eee eeeeeeeee eeee MeMMe. Mee eeeeeeee eeee eeeee (MeMM8) eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee 8:88 ee 8:88) ee eeee ‌888‌; eeeee: 88.8 ee (88%); [α]M88 −8.8 (e 8.88, MMMe8); 8M MMM (MMMe8, δ): 8.88 (ee, 8M, M = 8.8, 8.8 Me), 8.88 (ee, 8M, M = 8.8, 8.8 Me), 8.88 (ee e, 8M), 8.88–8.88 (e, 8M), 8.88 (e, 8M, M = 8.8 Me), 8.88–8.88 (e, 8M). Meeeeee eeee MeMM/MMMe8 8:8 eeeeeee eee eeeeeeee ee ‌888‌; eeeee: 88.8 ee (88%). Meeeeeee eeeeeeeeeeeeeee ee ‌888‌ (eee/eeee = 88:8) eee eeeeeeeeee eeeee eeee eee eeeeeeee 8M MMM eeee ee eee eee eeeeeeee eeeeeeee. Mee eeeeeeeeeeee eeeeee ee ‌888‌ (88%) eee eeeeeeeeee ee eeeee ee eeeeee MMMM eeeeeeee [MMMMMMMMM MM-M; 8.88 ee (eeeeeeee)×88 ee (eeeeee); eeeeee/eMeMM 88:8; 8.8 eM·eee−8; eM (eeeee): 88.8 eee, eM (eeeee): 88.8 eee].

References