Hydrochloric Acid → 4,4-Diphenyl-2-formyl-3-(nitromethyl)cyclohexanone

HRID 1196263Notes

Reaction equation

HRID 1196263 reaction equation
[C:1]1([C:7]2([C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)[CH2:12][CH2:11][C:10](=[O:13])[C:9]([CH:14]=[O:15])=[CH:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[N+:22]([CH3:25])([O-:24])=[O:23].[OH-].C([N+](C)(C)C)C1C=CC=CC=1.Cl>O1CCCC1.C(O)(C)(C)C.CO.C(OCC)(=O)C.O>[C:1]1([C:7]2([C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)[CH2:12][CH2:11][C:10](=[O:13])[CH:9]([CH:14]=[O:15])[CH:8]2[CH2:25][N+:22]([O-:24])=[O:23])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

10

Reactant 4

HCID 313Hydrochloric AcidHCID 6375NitromethaneHCID 66854Benzyltrimethylammonium hydroxideHCID 537947534,4-Diphenyl-2-formyl-2-cyclohexen-1-one

Product 1

HCID 540830574,4-Diphenyl-2-formyl-3-(nitromethyl)cyclohexanone

Reagents, catalysts & solvents 5

HCID 887MethanolSolventHCID 962WaterSolventHCID 6386tert-ButanolSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
20 °C

Procedure

A solution of 4,4-diphenyl-2-formyl-2-cyclohexen-1-one (29 g) and nitromethane (5.7 cc) in a mixture of tetrahydrofuran (250 cc) and tert-butanol (500 cc) is treated with a 35% strength solution (6.93 cc) of benzyltrimethylammonium hydroxide in methanol and stirred at 20° C. for 18 hours. The reaction mixture is diluted with ethyl acetate (500 cc) and water (2000 cc) and acidified to pH 2 with hydrochloric acid. The aqueous phase is extracted with ethyl acetate (200 cc) and the combined organic phases are washed with water (500 cc) and saturated sodium chloride solution (250 cc), then dried over magnesium sulphate and concentrated to dryness under reduced pressure (2.7 kPa). The crystallized residue is stirred in a mixture (100 cc) of cyclohexane and ethyl acetate (80:20 by volume) and the crystals are drained and washed with the same mixture (20 cc) and with isopropyl ether (2×50 cc). 4,4-Diphenyl-2-formyl-3-(nitromethyl)cyclohexanone (24.7 g) is obtained in the form of cream-colored crystals, m.p. 188° C.

Workup

  1. extractionThe aqueous phase is extracted with ethyl acetate (200 cc)
  2. washthe combined organic phases are washed with water (500 cc) and saturated sodium chloride solution (250 cc)
  3. dry with materialdried over magnesium sulphate
  4. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)
  5. stirringThe crystallized residue is stirred in a mixture (100 cc) of cyclohexane and ethyl acetate (80:20 by volume)
  6. washwashed with the same mixture (20 cc) and with isopropyl ether (2×50 cc)

Sources & evidence

ORD record
ord-b44ce0bea8534cb48d4fb4da9a58c4fc
Source dataset
uspto-grants-1992_05
Patent number
US05112988

Reaction notes

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