Piperidine → (Z)-2-[3-(4-Fluoro-phenyl)-2-nitro-allyl]-[1,3]dioxolane

HRID 606616Notes

Reaction equation

HRID 606616 reaction equation
[N+:1]([CH2:4][CH2:5][CH:6]1[O:10][CH2:9][CH2:8][O:7]1)([O-:3])=[O:2].[F:11][C:12]1[CH:19]=[CH:18][C:15]([CH:16]=O)=[CH:14][CH:13]=1.N1CCCCC1>C1(C)C=CC=CC=1>[F:11][C:12]1[CH:19]=[CH:18][C:15](/[CH:16]=[C:4](\[N+:1]([O-:3])=[O:2])/[CH2:5][CH:6]2[O:10][CH2:9][CH2:8][O:7]2)=[CH:14][CH:13]=1

Participants

5

Reactant 3

HCID 8082PiperidineHCID 680234-FluorobenzaldehydeHCID 108880592-(2-Nitroethyl)-1,3-dioxolane

Product 1

HCID 59008413(Z)-2-[3-(4-Fluoro-phenyl)-2-nitro-allyl]-[1,3]dioxolane

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

In a flask equipped with a Dean-Stark trap and a reflux condenser, a solution of 2-(2-nitro-ethyl)-[1,3]dioxolane (162.5 g, 1.1 mol) in toluene (1.2 L) was treated with 4-fluorobenzaldehyde (124 g, 1.0 mol) followed by piperidine (15 mL, 0.15 mol). The solution was heated at reflux under N2 for 16 h, then was cooled to rt and washed with water (2×300 mL) and satd. aq. NaCl (2×300 mL). Charcoal and MgSO4 were added, and the suspension was stirred for 1 h. Filtration and concentration of the filtrate provided the title compound, which was used in the next reaction without further purification. 1H NMR (400 MHz, CDCl3): 8.15 (s, 1H), 7.70-7.65 (m, 2H), 7.18-7.10 (m, 2H), 5.23 (t, J=4.5, 1H), 4.10-3.80 (m, 4H), 3.26 (d, J=4.5, 2H). The (Z)-olefin geometry was confirmed by nuclear Overhauser effect (NOE) studies (Stott et al. J. Magn. Reson. 1997, 125, 302-324) with a mixing time of 0.8 sec. When proton at 8.15 ppm was selectively inverted, NOE was observed at 3.25 ppm and 7.65 ppm.

Workup

  1. customIn a flask equipped with a Dean-Stark trap and a reflux condenser
  2. temperatureThe solution was heated
  3. temperatureat reflux under N2 for 16 h
  4. washwashed with water (2×300 mL)
  5. additionCharcoal and MgSO4 were added
  6. filtrationFiltration and concentration of the filtrate

Sources & evidence

ORD record
ord-efe184608fce4eb9be3eb312895c36cd
Source dataset
uspto-grants-2011_03
Patent number
US07915404B2

Reaction notes

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