Triphenylphosphine → 4-Chloro-3-(4-methyl-2-oxo-1-piperazinyl)-5-nitrobenzonitrile
Reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C.[Cl:34][C:35]1[C:40]([N+:41]([O-:43])=[O:42])=[CH:39][C:38]([C:44]#[N:45])=[CH:37][C:36]=1[NH:46][C:47](=O)[CH2:48][N:49]([CH2:51][CH2:52][OH:53])[CH3:50]>C1COCC1.CCOC(C)=O.O>[Cl:34][C:35]1[C:40]([N+:41]([O-:43])=[O:42])=[CH:39][C:38]([C:44]#[N:45])=[CH:37][C:36]=1[N:46]1[CH2:47][CH2:48][N:49]([CH3:50])[CH2:51][C:52]1=[O:53]Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 3
Procedure
To a solution of triphenylphosphine (252 mg, 0.959 mmol) in THF (2 mL) was added DIAD (0.187 mL, 0.959 mmol). The reaction mixture was stirred for 10 min. Then a solution of N-(2-chloro-5-cyano-3-nitrophenyl)-2-((2-hydroxyethyl)(methyl)amino)acetamide (120 mg, 0.384 mmol) in THF (2 mL) was added drop wise. The reaction mixture was then stirred at room temperature for 2 h. LC-MS indicated the desired peak, but the reaction was about ˜80% complete. It was diluted with EtOAc and water. The aqueous layer was extracted with EtOAc and the combined organic layer was washed with water, brine, dried over Na2SO4, filtered and concentrated. Purification via silica gel chromatography (0-100% EtOAc in Hexanes, 12 g) gave 4-chloro-3-(4-methyl-2-oxopiperazin-1-yl)-5-nitrobenzonitrile (40 mg) as a off-white solid.
Workup
- stirringThe reaction mixture was then stirred at room temperature for 2 h
- extractionThe aqueous layer was extracted with EtOAc
- washthe combined organic layer was washed with water, brine
- dry with materialdried over Na2SO4
- filtrationfiltered
- concentrationconcentrated
- customPurification via silica gel chromatography (0-100% EtOAc in Hexanes, 12 g)
Sources & evidence
- ORD record
- ord-e0c7873ec59c46e7b6b81792a4cb7541
- Source dataset
- uspto-grants-2016_03
- Patent number
- US09273057B2
Reaction notes
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