Phosphorus oxychloride → HCID 86695083, compound
Reaction equation
O[C:2]1[N:3]=[CH:4][N:5]=[C:6]2[C:13]=1[C:12]1[C@H:11]([CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16])[CH2:10][CH2:9][C:8]=1[S:7]2.P(Cl)(Cl)([Cl:22])=O>O1CCOCC1>[Cl:22][C:2]1[N:3]=[CH:4][N:5]=[C:6]2[C:13]=1[C:12]1[C@H:11]([CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16])[CH2:10][CH2:9][C:8]=1[S:7]2Participants
Reactant 2
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 110 °C
Procedure
To a 50-mL round-bottom flask was added ethyl 2-[(3S)-12-hydroxy-7-thia-9,11-diazatricyclo[6.4.0.0[2,6]]dodeca-1(12),2(6),8,10-tetraen-3-yl]acetate (16.2, 560 mg, 2.01 mmol, 1.00 equiv), dioxane (10 mL) and phosphoroyl trichloride (3.5 mL). The reaction was stirred for 4 h at 110° C. under nitrogen. After concentration under reduced pressure, the resulting solution was poured dropwise into saturated aqueous NaHCO3 and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with brine and dried over sodium sulfate. After evaporation in vacuo, the residue was purified by column chromatography on silica gel with ethyl acetate/petroleum ether (1:7) to afford ethyl 2-[(3S)-12-chloro-7-thia-9,11-diazatricyclo[6.4.0.0[2,6]]dodeca-1(12),2(6),8,10-tetraen-3-yl]acetate (16.3, 550 mg, 92%) as a yellow oil.
Workup
- concentrationAfter concentration under reduced pressure
- additionthe resulting solution was poured dropwise into saturated aqueous NaHCO3
- extractionextracted with ethyl acetate (3×50 mL)
- washThe combined organic layers were washed with brine
- dry with materialdried over sodium sulfate
- customAfter evaporation in vacuo
- customthe residue was purified by column chromatography on silica gel with ethyl acetate/petroleum ether (1:7)
Sources & evidence
- ORD record
- ord-b53cd0135eb34b19a271d4bf8fc44645
- Source dataset
- uspto-grants-2015_12
- Patent number
- US09212190B2
Reaction notes
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