Tetrahydrofuran → HCID 19899112, compound

HRID 1196685Notes

Reaction equation

HRID 1196685 reaction equation
[NH2-].[Na+].[Cl:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[C:14]3[C:15](=O)[CH2:16][CH2:17][CH:18]([C:20]([O:22][CH3:23])=[O:21])[CH2:19][C:13]=3[O:12][N:11]=2)=[CH:6][CH:5]=1.[Cl-].[NH4+].O1CCC[CH2:28]1>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[C:14]3[C:15](=[CH2:28])[CH2:16][CH2:17][CH:18]([C:20]([O:22][CH3:23])=[O:21])[CH2:19][C:13]=3[O:12][N:11]=2)=[CH:6][CH:5]=1

Participants

6

Reactant 4

HCID 8028Tetrahydrofuran2×HCID 24533Sodium amideHCID 25517Ammonium ChlorideHCID 19899036HCID 19899036, compound

Product 1

HCID 19899112HCID 19899112, compound

Reagents, catalysts & solvents 1

HCID 74505Methyltriphenyliphosphonium bromideCatalyst

Procedure

2.65 g of a mixture of methyltriphenylphosphonium bromide and sodium amide (approximately 6.3 mmol of each component) was stirred under nitrogen and 16 ml of dry tetrahydrofuran were added. After stirring at room temperature for 15 minutes, the mixture was cooled in ice and a solution of 1.85 g (5.79 mmol) of methyl 3-(4-chlorophenyl)-5,6,7,8-tetrahydro-4-oxo-4H-cyclohept[d]isoxazole-7-carboxylate in 11 ml of dry tetrahydrofuran was added dropwise. The mixture was stirred in the cold for 0.5 hour and then at room temperature for 3 hours. The mixture was treated with 10 ml of saturated aqueous ammonium chloride solution and then partially evaporated. The aqueous phase was extracted three-times with dichloromethane and the combined organic phases were dried over magnesium sulfate and evaporated. The residue was triturated with diethyl ether. The solid was filtered off and washed with diethyl ether and the filtrate was evaporated. The residue was chromatographed on silica gel using 50% ethyl acetate/hexane for the elution. There were obtained 1.06 g of methyl 3-(4-chlorophenyl)-5,6,7,8-tetrahydro-4-methylene-4H-cyclohept[d]isoxazole-7-carboxylate of melting point 113°-114° C.

Workup

  1. temperaturethe mixture was cooled in ice
  2. stirringThe mixture was stirred in the cold for 0.5 hour
  3. waitat room temperature for 3 hours
  4. custompartially evaporated
  5. extractionThe aqueous phase was extracted three-times with dichloromethane
  6. dry with materialthe combined organic phases were dried over magnesium sulfate
  7. customevaporated
  8. customThe residue was triturated with diethyl ether
  9. filtrationThe solid was filtered off
  10. washwashed with diethyl ether
  11. customthe filtrate was evaporated
  12. customThe residue was chromatographed on silica gel using 50% ethyl acetate/hexane for the elution

Sources & evidence

ORD record
ord-4b4995c3e3ae42f09400d1c6c4dfd3bb
Source dataset
uspto-grants-1992_05
Patent number
US05114960

Reaction notes

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