2-Nitropropane → HCID 21842710, compound

HRID 1737311Notes

Reaction equation

HRID 1737311 reaction equation
[Na].[N+:2]([CH:5]([CH3:7])[CH3:6])([O-:4])=[O:3].[CH:8]1[CH:9]=[CH:10][C:11]([CH:16]=[O:17])=[C:12]([CH:14]=[O:15])[CH:13]=1.OS(O)(=O)=O.[CH3:23]O>O>[CH3:23][O:15][CH:14]1[C:12]2[C:11](=[CH:10][CH:9]=[CH:8][CH:13]=2)[CH:16]([C:5]([CH3:7])([N+:2]([O-:4])=[O:3])[CH3:6])[O:17]1

Participants

7

Reactant 5

HCID 3982-NitropropaneHCID 887MethanolHCID 1118Sulfuric AcidHCID 4807PhthalaldehydeHCID 5360545Sodium

Product 1

HCID 21842710HCID 21842710, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Sodium metal (12.4 g, 0.539 g atm) is added to MeOH, (1 L) at 10° C. over 90 min. When a clear solution is obtained the cold water bath is removed and 2-nitropropane (256 mL, 2.85 mol) is added, followed by orthophthalaldehyde (120 g, 0.895 mol). The resulting solution is stirred at rt overnight. The solution is acidified by adding 1 N H2SO4 to pH 2. White solids precipitate. The mixture is filtered, and the filter cake is washed with MeOH and discarded. The filtrate is stirred at rt for 3 h and then made basic by adding 3 N NaOH. The solution is then concentrated in vacuo to remove the MeOH. The resulting aqueous solution is extracted twice with Et2O. The combined organic layers are washed once with water, dried (MgSO4) and concentrated in vacuo. Kugelrohr distillation of remaining solvent at 50° C. (oil pump vacuum) leaves 195 g (106% of theoretical, 86% pure by GC) of a brown liquid, which is used as such in the next step. The ratio of diastereoisomers is 1:1 (1H NMR). A portion of the crude material can be purified by flash chromatography over silica gel (9:1 cyclohexane/EtOAc) to give pure 71 as a pale yellow oil. 1H NMR(CDCl3) 7.42-7.36(m, 3), 7.17-7.12(m, 1), 6.25 and 5.88(isomer I, d and dd, 1 total, J=2.4, 0.6, respectively), 6.01 and 5.72 (isomer II, s and d, 1 total, J=0.6), 3.58 and 3.37 (isomers I and II, respectively, 2s, 3 total), 1.57 and 1.56 and 1.55 and 1.48 (4s, 6 total); 13C NMR (CDCl3) 138.77, 138.51, 137.57, 129.82, 129.67, 129.21, 129.13, 123.41, 122.09, 107.32, 107.01, 90.52, 86.77, 56.14, 54.03, 22.51, 22.14, 21.73, 20.96; IR (neat) 1543, 1464, 1398, 1373, 1348, 1113, 1094, 1026, 974, 756;MS, m/z 206 [(M+H)+, base peak], 190, 149; Anal. Calcd for C12H15NO2 : C,60.75; H,6.37; N,5.90. Found: C,60.48; H,6.28;N,6.00.

Workup

  1. customis removed
  2. filtrationThe mixture is filtered
  3. washthe filter cake is washed with MeOH
  4. stirringThe filtrate is stirred at rt for 3 h
  5. additionby adding 3 N NaOH
  6. concentrationThe solution is then concentrated in vacuo
  7. customto remove the MeOH
  8. extractionThe resulting aqueous solution is extracted twice with Et2O
  9. washThe combined organic layers are washed once with water
  10. dry with materialdried (MgSO4)
  11. concentrationconcentrated in vacuo
  12. distillationKugelrohr distillation of remaining solvent at 50° C. (oil pump vacuum)
  13. customleaves 195 g (106% of theoretical, 86% pure by GC) of a brown liquid, which
  14. customA portion of the crude material can be purified by flash chromatography over silica gel (9:1 cyclohexane/EtOAc)

Sources & evidence

ORD record
ord-c5b80b94d2434b98b2758af941eaaa37
Source dataset
uspto-grants-1999_10
Patent number
US05962469

Reaction notes

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