Sodium hydride → 3-Oxa-tricyclo[3.2.2.02,4]nonane-2-carboxylic acid N-(4-nitro-3-trifluoromethyl-phenyl)-hydrazide

HRID 1591703Notes

Reaction equation

HRID 1591703 reaction equation
[H-].[Na+].[N+:3]([C:6]1[CH:11]=[CH:10][C:9]([NH:12][C:13]([C:15]23[O:21][CH:20]2[CH:19]2[CH2:22][CH2:23][CH:16]3[CH2:17][CH2:18]2)=[O:14])=[CH:8][C:7]=1[C:24]([F:27])([F:26])[F:25])([O-:5])=[O:4].C1(P([NH:42]O)(C2C=CC=CC=2)=O)C=CC=CC=1>CN(C=O)C>[N+:3]([C:6]1[CH:11]=[CH:10][C:9]([N:12]([C:13]([C:15]23[O:21][CH:20]2[CH:19]2[CH2:18][CH2:17][CH:16]3[CH2:23][CH2:22]2)=[O:14])[NH2:42])=[CH:8][C:7]=1[C:24]([F:27])([F:25])[F:26])([O-:5])=[O:4]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 419256DiphenylphosphinylhydroxylamineHCID 235461863-Oxa-tricyclo[3.2.2.02,4] nonane-2-carboxylic acid (4-nitro-3-trifluoromethyl-phenyl)-amide

Product 1

HCID 235461873-Oxa-tricyclo[3.2.2.02,4]nonane-2-carboxylic acid N-(4-nitro-3-trifluoromethyl-phenyl)-hydrazideYield 15.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
70 °C

Procedure

NaH (60% in mineral oil, 7.9 mg, 0.20 mmol, 1.4 eq) was added to the solution of 11E (50 mg, 0.14 mmol, 1 eq) in DMF (3 mL). The reaction mixture was heated at 70° C. for 2 h. The reaction was cooled to rt and diphenylphosphinylhydroxylamine (52 mg, 0.22 mmol, 1.6 eq, made according to the procedure of Colvin, E. W. et.al. Tetrahedron Lett. 23, 3835-6 (1982)) was added. The reaction mixture was stirred at rt overnight and quenched by addition of water (3 mL) and extracted with EtOAc (2×20 mL). The combined organics were washed with H2O (25 mL), dried over Na2SO4 and concentrated under reduced pressure. Purification by flash chromatography on silica gel eluting with 10% EtOAc/CH2Cl2 gave 8.0 mg (0.022 mmol, 15.4%) of compound 11F as a yellow solid. HPLC conditions: 93% at 3.54 min (YMC S5 ODS 4.6×50 mm, 10%-90% aqueous methanol over 4 minute gradient with 0.2% H3PO4, detecting at 220 nm).

Workup

  1. temperatureThe reaction was cooled to rt
  2. addition23, 3835-6 (1982)) was added
  3. customquenched by addition of water (3 mL)
  4. extractionextracted with EtOAc (2×20 mL)
  5. washThe combined organics were washed with H2O (25 mL)
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated under reduced pressure
  8. customPurification by flash chromatography on silica gel eluting with 10% EtOAc/CH2Cl2

Sources & evidence

ORD record
ord-83f1c18afb0c479996ad48ddb5a43549
Source dataset
uspto-grants-2007_11
Patent number
US07291637B2

Reaction notes

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