Ethyl formate → 7-(3-Bromophenyl)-2-(hydroxymethylene)-9-(4-(trifluoromethyl)phenylsulfonyl)-9-azabicyclo[3.3.1]nonan-3-one

HRID 2061614Notes

Reaction equation

HRID 2061614 reaction equation
[CH3:1][CH2:2][O-:3].[Na+].[Br:5][C:6]1[CH:7]=[C:8]([CH:12]2[CH2:19][CH:18]3[N:20]([S:21]([C:24]4[CH:29]=[CH:28][C:27]([C:30]([F:33])([F:32])[F:31])=[CH:26][CH:25]=4)(=[O:23])=[O:22])[CH:14](C[C:16](=[O:34])[CH2:17]3)[CH2:13]2)[CH:9]=[CH:10][CH:11]=1.C(OCC)=O>C1COCC1.[NH4+].[Cl-]>[Br:5][C:6]1[CH:7]=[C:8]([CH:12]2[CH2:13][CH:14]3[N:20]([S:21]([C:24]4[CH:25]=[CH:26][C:27]([C:30]([F:32])([F:33])[F:31])=[CH:28][CH:29]=4)(=[O:23])=[O:22])[CH:18]([CH2:17][C:16](=[O:34])[C:1]3=[CH:2][OH:3])[CH2:19]2)[CH:9]=[CH:10][CH:11]=1

Participants

6

Reactant 3

HCID 8025Ethyl formateHCID 2723922Sodium ethoxideHCID 673032167-(3-Bromophenyl)-9-(4-(trifluoromethyl)phenylsulfonyl)-9-azabicyclo[3.3.1]nonan-3-one

Product 1

HCID 673031627-(3-Bromophenyl)-2-(hydroxymethylene)-9-(4-(trifluoromethyl)phenylsulfonyl)-9-azabicyclo[3.3.1]nonan-3-one

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 25517Ammonium ChlorideSolvent

Procedure

21% NaOEt (6 ml, 16.1 mmol) was added to a solution of 7-(3-Bromophenyl)-9-(4-(trifluoromethyl)phenylsulfonyl)-9-azabicyclo[3.3.1]nonan-3-one (90) (2.28 g, 4.54 mmol) and ethyl formate (6 ml, 74.5 mmol) in THF (20 ml). The solution was placed into a preheated oil bath at 60° C. After stirring for 30 min, the solution was cooled to ambient temperature, diluted with saturated aqueous NH4Cl, and extracted with EtOAc. The combined organic extracts were dried over MgSO4, filtered, and concentrated to afford 7-(3-bromophenyl)-2-(hydroxymethylene)-9-(4-(trifluoromethyl)phenylsulfonyl)-9-azabicyclo[3.3.1]nonan-3-one. Hydrazine monohydrate (3 ml) was added to a solution of 7-(3-bromophenyl)-2-(hydroxymethylene)-9-(4-(trifluoromethyl)phenylsulfonyl)-9-azabicyclo[3.3.1]nonan-3-one and glacial acetic acid (1 ml) in EtOH (20 ml). After stirring for 18 h, the solution was concentrated to afford compound 92.

Workup

  1. customThe solution was placed into a preheated oil bath at 60° C
  2. extractionextracted with EtOAc
  3. dry with materialThe combined organic extracts were dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-af228f87e7af4796ab62ba7b5be9323f
Source dataset
uspto-grants-2012_10
Patent number
US08283358B2

Reaction notes

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