2-Methylpentane → Ethyl 4-(4-nitrophenoxy)cyclohexanecarboxylate

HRID 1713831Notes

Reaction equation

HRID 1713831 reaction equation
[OH:1][CH:2]1[CH2:7][CH2:6][CH:5]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:4][CH2:3]1.[H-].[Na+].F[C:16]1[CH:21]=[CH:20][C:19]([N+:22]([O-:24])=[O:23])=[CH:18][CH:17]=1.CCCC(C)C>CN(C=O)C.CCOC(C)=O.O>[N+:22]([C:19]1[CH:20]=[CH:21][C:16]([O:1][CH:2]2[CH2:3][CH2:4][CH:5]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:6][CH2:7]2)=[CH:17][CH:18]=1)([O-:24])=[O:23]

Participants

8

Reactant 4

HCID 78922-MethylpentaneHCID 9590p-FluoronitrobenzeneHCID 24758Sodium hydrideHCID 86973Ethyl 4-hydroxycyclohexanecarboxylate

Product 1

HCID 57435335Ethyl 4-(4-nitrophenoxy)cyclohexanecarboxylate

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolvent3×HCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of ethyl 4-hydroxycyclohexanecarboxylate (2.0 g, 11.6 mmol) in DMF (3 ml) was added in one portion to a stirred suspension of sodium hydride (60% dispersion in mineral oil, 490 mg, 12.2 mmol) in DMF (15 mL) at 0° C. under an argon atmosphere. The mixture was stirred at 0° C. for 10 minutes and then warmed to room temperature and stirred for 20 minutes and then a solution of 1-fluoro-4-nitrobenzene (1.24 mL, 11.6 mmol) in DMF (2 mL) was added in one portion. The reaction mixture was stirred at room temperature for 2 h and then heated at 110° C. for 24 h. The solution was concentrated in vacuo to leave a residue that was taken up in EtOAc (250 mL) and water (150 mL) was added. The layers were separated and the organic layer was washed with H2O (2×100 mL) and brine (50 mL) and then dried (MgSO4) and concentrated in vacuo to leave an oil. The oil was taken up in a mixture of hot EtOAc and isohexane (1:1) and left for 20 h. Filtration, followed by concentration in vacuo of the filtrate left an oil, which was purified by column chromatography, using 10-40% EtOAc in isohexane as eluent, to give crude ethyl 4-(4-nitrophenoxy)cyclohexanecarboxylate as an off white solid that was used without further purification.

Workup

  1. temperaturewarmed to room temperature
  2. stirringstirred for 20 minutes
  3. stirringThe reaction mixture was stirred at room temperature for 2 h
  4. temperatureheated at 110° C. for 24 h
  5. concentrationThe solution was concentrated in vacuo
  6. customto leave a residue that
  7. customThe layers were separated
  8. washthe organic layer was washed with H2O (2×100 mL) and brine (50 mL)
  9. dry with materialdried (MgSO4)
  10. concentrationconcentrated in vacuo
  11. customto leave an oil
  12. waitleft for 20 h
  13. filtrationFiltration
  14. concentrationfollowed by concentration in vacuo of the filtrate
  15. waitleft an oil, which
  16. customwas purified by column chromatography

Sources & evidence

ORD record
ord-fc471e0a19fc49a7a124bf22adb31a82
Source dataset
uspto-grants-2010_09
Patent number
US07795283B2

Reaction notes

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