Diethyl chlorophosphate → HCID 87097481, compound
Reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[C:13]([O:14][CH3:15])=[CH:12][CH:11]=[CH:10][C:9]=1[O:16][CH3:17].C([Li])CCC.[P:23](Cl)([O:28][CH2:29][CH3:30])([O:25][CH2:26][CH3:27])=[O:24]>>[CH3:17][O:16][C:9]1[CH:10]=[CH:11][CH:12]=[C:13]([O:14][CH3:15])[C:8]=1[C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[P:23](=[O:24])([O:28][CH2:29][CH3:30])[O:25][CH2:26][CH3:27]Participants
Conditions
- Temperature
- -78 °C
Procedure
To a 250-mL round-bottom flask equipped with a magnetic stir bar was added 2′-bromo-2,6-dimethoxybiphenyl (see Buchwald SL, Journal of the American Chemical Society 2005;127:4685-4696)(7.02 g, 24.0 mmol, 1 equiv). Degassed, anhydrous tetrahydrofuran was added (80 mL) followed by N,N,N′,N′-tetramethylethylene-1,2-diamine (4.31 mL, 28.7 mmol, 1.2 equiv). The resulting solution was cooled to −78 ° C., and then n-butyllithium (11.5 mL, 28.7 mmol, 1.2 equiv, 2.5 M hexanes) was added in a dropwise fashion. After the addition of 5 mL of n-butyllithium the reaction slurry could no longer be stirred. The reaction flask was warmed to 0 ° C. at which point the slurry became free-flowing. The remainder of the n-butyllithium (˜6.5 mL) was added over the course of 10 minutes. The reaction was stirred for 90 minutes at 0 ° C., and then the aryllithium intermediate was quenched with diethyl chlorophosphate (4.15 mL, 28.7 mmol, 1.2 equiv).
Workup
- customTo a 250-mL round-bottom flask equipped with a magnetic stir bar
- customDegassed
- additionanhydrous tetrahydrofuran was added (80 mL)
- temperatureThe reaction flask was warmed to 0 ° C. at which point the slurry
- stirringThe reaction was stirred for 90 minutes at 0 ° C.
Sources & evidence
- ORD record
- ord-d778e6c45cf3433a820256abf3d0607d
- Source dataset
- uspto-grants-2015_12
- Patent number
- US09200021B2
Reaction notes
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