diethyl 2-oxo-1,1-difluoropropylphosphonate | 194097-01-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diethyl 2-oxo-1,1-difluoropropylphosphonate
• 英文别名: (1,1-Difluoro-2-oxopropyl)phosphonic acid diethyl ester；1-diethoxyphosphoryl-1,1-difluoropropan-2-one
• CAS: 194097-01-3
• 化学式: C₇H₁₃F₂O₄P
• 分子量: 230.148
• InChiKey: VUCCNJWIIFHFDN-UHFFFAOYSA-N

物化性质

• 沸点：
  244.3±40.0 °C(Predicted)
• 密度：
  1.217±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  乙基溴化镁 、 diethyl 2-oxo-1,1-difluoropropylphosphonate 以 四氢呋喃 为溶剂， 以48%的产率得到1,1-二氟-2-甲基丁-1-烯
  参考文献：
  名称：

  2-氧代-1,1-二氟膦酸二乙酯的制备和合成应用

  摘要：

  摘要 (溴二氟甲基)膦酸二乙酯 (EtO)2P(O)CF2Br 1 与活化锌反应生成 [(二乙氧基膦酰基)二氟甲基]溴化锌 (EtO)2P(O)CF2ZnBr 2 ，用各种酰化剂酰化得到二乙基 2 -oxo-1,1-二氟膦酸酯 (EtO)2P(O)CF2C(O)R 4 收率良好。膦酸酯4的处理，例如2-氧代-1,1-二氟丙基膦酸二乙酯(EtO)2P(O)CF2C(O)CH3 4a、二氟(二乙氧基膦酰基)丙酮酸乙酯(EtO)2P(O)CF2C(O)CO2Et 4e和N,N-二乙基二氟(二乙氧基膦酰基)乙酰胺(EtO)2P(O)CF2C(O)NEt2 4h，提供格氏试剂R'MgX。1,1-二氟烯烃分别为 R'(CH3)C[dbnd]CF2、R'(CO2Et)C[dbnd]CF2 和 R'(NEt2)C[dbnd]CF2。

  DOI：

  10.1080/10426509708043514
• 作为产物：
  描述：

  丙酮基膦酸二乙酯 在 Selectfluor 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以43%的产率得到diethyl 2-oxo-1,1-difluoropropylphosphonate
  参考文献：
  名称：

  Selective Synthesis of α-Fluoro-β-keto- and α-Fluoro-β-aminophosphonates via Electrophilic Fluorination by Selectfluor

  摘要：

  A series of alpha-mono- and alpha,alpha-difluoro-beta-ketophosphonates were synthesized in moderate to good yields with excellent selectivities via electrophilic fluorination by Selectfluor. Subsequently, synthetic potential of the obtained alpha-monofluoro-beta-ketophosphonates was demonstrated by their application in synthesis of alpha-monofluoro-beta-aminophosphonates, useful building blocks in the preparation of phosphapeptides.

  DOI：

  10.1021/jo102276y

文献信息

• NON-AQUEOUS ELECTROLYTE AND ELECTRICITY STORAGE DEVICE
  申请人：UBE INDUSTRIES, LTD.

  公开号：US20150372349A1

  公开（公告）日：2015-12-24

  The present invention provides a nonaqueous electrolytic solution capable of improving electrochemical characteristics in the case of using an energy storage device at a high temperature and further capable of inhibiting the gas generation as well as a capacity retention rate after a high-temperature cycle, and also to provide an energy storage device using the same. Disclosed are a nonaqueous electrolytic solution having an electrolyte salt dissolved in a nonaqueous solvent, the nonaqueous electrolytic solution containing a phenyl ester compound represented by the following general formula (I), and an energy storage device. (In the formula, R f represents a fluoroalkyl group having 1 to 6 carbon atoms; X represents a halogen atom; each of p and q is an integer of 1 to 4; and (p+q) is 5 or less. A has a structure represented by —S(═O) 2 —, —C(═O)—, —C(═O)—O—, —C(═O)-L 1 -C(═O)—, —C(═O)-L 2 -P(═O)(OR)—O—, or —P(═O)(OR)—O—. Y represents a fluorine atom, a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group; L 1 represents an alkylene group, an alkenylene group, an alkynylene group, or a direct bond; L 2 represents an alkylene group; and R represents an alkyl group. However, only when A is —S(═O) 2 —, Y may be a fluorine atom; and only when A is —C(═O)—, Y may be a hydrogen atom. At least one hydrogen atom in each group of the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, alkylene group, alkenylene group, and alkynylene group may be substituted with a halogen atom.)

  本发明提供了一种非水电解质溶液，能够在高温下使用能量存储装置时改善电化学特性，并且在高温循环后能够抑制气体生成以及保持容量保留率，还提供了使用该非水电解质溶液的能量存储装置。所述非水电解质溶液包含溶解在非水溶剂中的电解质盐，该非水电解质溶液包含下述通式（I）所代表的苯酯化合物，以及能量存储装置。（在该式中，Rf代表具有1至6个碳原子的氟烷基；X代表卤素原子；p和q中的每一个是1至4的整数；以及（p+q）不超过5。A具有由—S(═O)2—、—C(═O)—、—C(═O)—O—、—C(═O)-L1-C(═O)—、—C(═O)-L2-P(═O)(OR)—O—或—P(═O)(OR)—O—表示的结构。Y代表氟原子、氢原子、烷基、烯基、炔基或芳基；L1代表烷基、烯基、炔基或直链键；L2代表烷基；R代表烷基。但是，仅当A为—S(═O)2—时，Y可以是氟原子；仅当A为—C(═O)—时，Y可以是氢原子。上述烷基、烯基、炔基、芳基、烷基、烯基和炔基中的每一组中至少一个氢原子可以被卤素原子取代。）
• Synthesis of 1,1-Difluoroolefins Via Wittig-Horner-Emmons Reaction
  作者：Hou-Jen Tsai

  DOI：10.1080/10426500213415

  日期：2002.8

  (EtO)2P(O)CF2ZnBr, which was prepared from diethyl(bromodifluoromethyl)phosphonate (EtO)2P(O)CF2Br and zinc powder with an appropriate acylating reagents such as acetyl chloride CH3C(O)Cl, ethyl oxalyl chloride ClC(O)CO2Et, methyl oxalyl chloride ClC(O)CO2CH3, diethylcarbamoyl chloride ClC(O)NEt2, or ethyl chloroformate ClC(O)OEt in the solvent of monoglyme or triglyme gives diethyl 2-oxo-1,1-difluoropropylphosphonate

  N-二乙基二氟（二乙氧基膦基）乙酰胺（EtO）2P（O）CF2C（O）NEt2和（二乙氧基膦基）二氟乙酸乙酯（EtO）2P（O）CF2C（O）OEt分别以良好的产率出现。然而，在(EtO)2P(O)CF2C(O)CO2Et的制备中，如果在1.5%的溴化亚铜存在下，不使用乙腈作为助溶剂，在室温下进行酰化反应24小时，则类似观察到神经毒剂氟膦酸二乙酯 (EtO)2P(O)F 和 (EtO)2P(O)CF CFP(O)(OEt)2。用格氏试剂 R'MgX 通过 Wittig 处理 2-氧代-1,1-二氟膦酸二乙酯衍生物 (EtO)2P(O)CF2C(O)R（R CH3、CO2Et、CO2Me、NEt2、OEt）的 THF 溶液-Horner-Emmons 反应生成 1,1-二氟烯烃 R'(CH3)C CF2、R'(CO2Et)C CF2 和 R'(NEt2)C CF2。在制备 (EtO)2P(O)CF2C(O)CO2Et
• A reproducible and high-yielding cerium-mediated route to α,α-difluoro-β-ketophosphonates
  作者：Kevin Blades、Thierry P. Lequeux、Jonathan M. Percy

  DOI：10.1016/s0040-4020(97)00673-x

  日期：1997.7

  The addition of diethyldifluoromethylphosphonate to LDA containing cerium(III) chloride in THF generates an organometallic nucleophile that reacts efficiently with esters and DMF (1,2-addition) affording moderate to good yields of adducts, and extending considerably the range of compounds available containing the difluoromethylenephosphonate group. (C) 1997 Elsevier Science Ltd.
• PREPARATION AND SYNTHETIC APPLICATION OF DIETHYL 2-OXO-1,1-DIFLUOROPHOSPHONATES
  作者：Hou-Jen Tsai

  DOI：10.1080/10426509708043514

  日期：1997.3.1

  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

  摘要 (溴二氟甲基)膦酸二乙酯 (EtO)2P(O)CF2Br 1 与活化锌反应生成 [(二乙氧基膦酰基)二氟甲基]溴化锌 (EtO)2P(O)CF2ZnBr 2 ，用各种酰化剂酰化得到二乙基 2 -oxo-1,1-二氟膦酸酯 (EtO)2P(O)CF2C(O)R 4 收率良好。膦酸酯4的处理，例如2-氧代-1,1-二氟丙基膦酸二乙酯(EtO)2P(O)CF2C(O)CH3 4a、二氟(二乙氧基膦酰基)丙酮酸乙酯(EtO)2P(O)CF2C(O)CO2Et 4e和N,N-二乙基二氟(二乙氧基膦酰基)乙酰胺(EtO)2P(O)CF2C(O)NEt2 4h，提供格氏试剂R'MgX。1,1-二氟烯烃分别为 R'(CH3)C[dbnd]CF2、R'(CO2Et)C[dbnd]CF2 和 R'(NEt2)C[dbnd]CF2。
• Selective Synthesis of α-Fluoro-β-keto- and α-Fluoro-β-aminophosphonates via Electrophilic Fluorination by Selectfluor
  作者：Kinga Radwan-Olszewska、Francisco Palacios、Pawel Kafarski

  DOI：10.1021/jo102276y

  日期：2011.2.18

  A series of alpha-mono- and alpha,alpha-difluoro-beta-ketophosphonates were synthesized in moderate to good yields with excellent selectivities via electrophilic fluorination by Selectfluor. Subsequently, synthetic potential of the obtained alpha-monofluoro-beta-ketophosphonates was demonstrated by their application in synthesis of alpha-monofluoro-beta-aminophosphonates, useful building blocks in the preparation of phosphapeptides.