Hydrochloric Acid → 2-(alpha-Hydroxy-3-nitrobenzyl)cyclohexanone

HRID 2209516Notes

Reaction equation

HRID 2209516 reaction equation
[O:1]1CCN(C2CCCCC=2)CC1.[N+:13]([C:16]1[CH:17]=[C:18]([CH:21]=[CH:22][CH:23]=1)[CH:19]=[O:20])([O-:15])=[O:14].Cl.[C:25]1(C)[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1>>[OH:20][CH:19]([CH:26]1[CH2:27][CH2:28][CH2:29][CH2:30][C:25]1=[O:1])[C:18]1[CH:21]=[CH:22][CH:23]=[C:16]([N+:13]([O-:15])=[O:14])[CH:17]=1

Participants

5

Reactant 4

HCID 313Hydrochloric AcidHCID 1140TolueneHCID 74493-NitrobenzaldehydeHCID 69589Morpholine, 4-(1-cyclohexen-1-yl)-

Product 1

HCID 41108432-(alpha-Hydroxy-3-nitrobenzyl)cyclohexanone

Procedure

1-Morpholino-1-cyclohexene (13.28 g) was added dropwise to a stirred solution of 3-nitrobenzaldehyde (10.0 g) and 65 mL of dry toluene, under nitrogen. After stirring at room temperature for 5 days the mixture was treated with 75 mL of 5N HCl, stirred an additional 15 minutes and the layers separated. The aqueous phase was extracted with three additional 75 mL portions of toluene, the toluene extracts were dried (MgSO4), filtered and the solvent evaporated. The resulting yellow oil which turned greenish on standing overnight was chromatographed, with methylene chloride as elutent, to yield 2-(α-hydroxy-3-nitrobenzyl)cyclohexanone (6.35 g) as a yellow oil; MS (CI, CH4): m/z=250(M+1). The yellow oil was dissolved in ethyl ether (50 mL) and treated with 50 mL of concentrated hydrochloric acid. After stirring overnight the layers were separated and the aqueous phase extracted with ethyl ether. The combined extracts were dried (MgSO4), filtered and evaporated to yield crude 2-(3-nitrophenyl)methylenecyclohexanone as low melting orange crystals (4.69 g), which were used without further purification. NMR CDCl3): 1.79-1.89 (m,2, CH2), 1.93-2.01 (m,2, CH2), 2.56-2.60 (m,2, CH2), 2.82-2.87 (m,2, CH2), 7.47 (s,1, olefinic), 7.58 (t,1, J= 7.9, Ar), 7.69 (d,1, J=7.7, Ar), 8.19 (d,1, J=8.9, Ar), 8.24 (s,1, Ar); MS (CI, CH4): m/z=232(M+1).

Workup

  1. stirringstirred an additional 15 minutes
  2. customthe layers separated
  3. extractionThe aqueous phase was extracted with three additional 75 mL portions of toluene
  4. dry with materialthe toluene extracts were dried (MgSO4)
  5. filtrationfiltered
  6. customthe solvent evaporated
  7. waiton standing overnight
  8. customwas chromatographed, with methylene chloride as elutent,

Sources & evidence

ORD record
ord-1b071799051e44d4b287c82b7d5cb47d
Source dataset
uspto-grants-1995_10
Patent number
US05455253

Reaction notes

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