Paper
PREPARATION AND SYNTHETIC APPLICATION OF DIETHYL 2-OXO-1,1-DIFLUOROPHOSPHONATES
Published Mar 1, 1997 · Hou‐Jen Tsai
Phosphorus Sulfur and Silicon and The Related Elements
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Abstract
Abstract Reaction of diethyl(bromodifluoromethyl)phosphonate (EtO)2P(O)CF2Br 1 with activated zinc gave [(diethoxyphosphonyl)difluoromethyl]zinc bromide (EtO)2P(O)CF2ZnBr 2, which was acylated with various acylating agents to afford diethyl 2-oxo-1,1-difluorophosphonates (EtO)2P(O)CF2C(O)R 4 in good yields. Treatment of phosphonates 4 such as diethyl 2-oxo-1,1-difluoropropylphosphonate (EtO)2P(O)CF2C(O)CH3 4a, ethyl difluoro(diethoxyphosphonyl)pyruvate (EtO)2P(O)CF2C(O)CO2Et 4e and N,N-diethyldifluoro(diethoxyphosphonyl)acetamide (EtO)2P(O)CF2C(O)NEt2 4h with Grignard reagents R′MgX provided. 1,1-difluomlefins R′(CH3)C[dbnd]CF2, R′(CO2Et)C[dbnd]CF2 and R′(NEt2) C[dbnd]CF2, respectively.
Diethyl 2-oxo-1,1-difluorophosphonates (EtO)2P(O)CF2C(O)R4 can be synthesized to produce 1,1-difluomlefins, which can be used in various applications.
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