tetramethyl (dichloromethylene)bisphosphonate | 19929-29-4

• 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: tetramethyl (dichloromethylene)bisphosphonate
• 英文别名: tetramethyl dichloromethanediphosphonate；Dichlormethylen-diphosphonsaeure-tetramethylester；Dichloro-bis(dimethoxyphosphoryl)methane
• CAS: 19929-29-4
• 化学式: C₅H₁₂Cl₂O₆P₂
• 分子量: 301.0
• InChiKey: RVDYNQGIJXIAAA-UHFFFAOYSA-N

物化性质

• 沸点：
  300.4±42.0 °C(Predicted)
• 密度：
  1.449±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  tetramethyl (dichloromethylene)bisphosphonate 以 aqueous ether 为溶剂， 以90%的产率得到<(dimethoxyphosphino)dichloromethyl>phosphonic acid monomethyl ester
  参考文献：
  名称：

  Partial esters of (Di) chloromethanediphosphonic acid useful for

  摘要：

  式（I）中新型药理活性双膦酸衍生物，其中 R.sup.1、R.sup.2、R.sup.3 和 R.sup.4 独立地为 C.sub.1 -C.sub.22 -烷基、C.sub.2 -C.sub.22 -烯基、C.sub.2 -C.sub.22 -炔基、C.sub.3 -C.sub.10 -环烷基、C.sub.3 -C.sub.10 -环烯基、芳基、芳基烷基、硅基和氢，且 R.sup.4 与氢不同，Q.sup.1 为氢、氟、氯、溴或碘，Q.sup.2 为氯、溴或碘，包括化合物的立体异构体，如几何异构体和光学活性异构体，以及化合物的药学上可接受的盐。

  公开号：

  US05376649A1
• 作为产物：
  描述：

  四甲基亚甲基二磷酸酯 在 sodium hypochlorite 、 碳酸氢钠 作用下， 以 甲醇 为溶剂， 反应 0.17h， 以85%的产率得到tetramethyl (dichloromethylene)bisphosphonate
  参考文献：
  名称：

  Bisphosphonic compounds. Part 3. Preparation and identification of tetraalkyl methylene- and (α-halomethylene)bisphosphonates by mass spectrometry, NMR spectroscopy and X-ray crystallography

  摘要：

  The preparation and identification of tetraalkyl methylenebisphosphonates {XYC[P(O)(OR)2]2; X = Y = H, Cl or Br and R = alkyl} have been studied. Detailed procedures are given for the synthesis of XYC[P(O)(OR)2]2 (X = Y = H; R = hexyl; X = Y = Cl or Br and R = Me). H-1, C-13 and P-31 NMR data are reported including 1J(CH), 2J(CP), 3J(CP) and 2J(PP) coupling constants. The fragmentation of 19 XYC[P(O)(OR)2]2 has been studied in the gas phase. The solid state structures are given for two compounds (X = Y = Cl, R = Pr(i) and X = Y = Br, R = Me).

  DOI：

  10.1039/p29920000835

文献信息

• An improved synthetic method and the first crystal structures for (dihalomethylene)bisphosphonate partial esters
  作者：Jouko J. Vepsäläinen、Jussi Kivikoski、Markku Ahlgrén、Heikki E. Nupponen、Esko K. Pohjala

  DOI：10.1016/0040-4020(95)00314-x

  日期：1995.6

  A new general and selective strategy for the synthesis of (dihalomethylene)bisphosphonic acid (XYMBP) partial alkyl esters (PE) with high selectivity and purity has been developed. Preparation is started from selected XYMBP tetraesters using tertiary or secondary amines as dealkylating reagents leading to trialkyl or P,P′-dialkyl XYMBP PEs, respectively. The solid state structures are given for three

  已开发出一种新的具有选择性和高纯度的合成（二卤代亚甲基）双膦酸（XYMBP）偏烷基酯（PE）的新的通用和选择性策略。使用叔胺或仲胺作为脱烷基剂，从选定的XYMBP四酯开始制备，分别生成三烷基或P，P'-二烷基XYMBP PE。给出了以下三种化合物的固态结构：Cl 2 C [P（O）（OPr i）（O - Na +）] [P（O）（O - Na +）2 ]和Cl 2 C [P （O）（OPr i）（O − X +）] 2，其中X = Na +或H2 Ñ +（CH 2 CH 2）2 O.
• Relative reactivities of tetraalkyl esters of methylene bisphosphonic acid
  作者：David W. Hutchinson、Graeme Semple

  DOI：10.1016/s0022-328x(00)99591-3

  日期：1986.1

  The synthesis in high yield of tetraisopropyl esters of C-alkylated methylene bisphosphonic acids can be achieved by the alkylation of the thallium salts of tetraisopropyl esters of the parent methylene biphosphonic acids. Yields of C-alkylated products are markedly reduced when the tetraethyl or tetramethyl esters are used in this reaction. From a study of the 13C and 31P NMR spectra of the methylene

  C-烷基化的亚甲基双膦酸的四异丙酯的高产率合成可以通过母体亚甲基双膦酸的四异丙酯的th盐的烷基化来实现。当在该反应中使用四乙基或四甲基酯时，C-烷基化产物的产率显着降低。通过对亚甲基双膦酸酯及其阴离子的13 C和31 P NMR光谱进行研究，发现这种反应性差异归因于空间因素。
• Bisphosphonic compounds VIII. A facile and selective one-pot synthesis of P,P-dialkyl (dichloromethylene)bisphosphonate partial esters
  作者：Jouko Vepsäläinen、Heikki Nupponen、Esko Pohjala

  DOI：10.1016/0040-4039(96)00605-3

  日期：1996.5

  The preparations of P,P-dialkyl partial esters of (dichloromethylene)bisphosphonic acid from readily available tetraesters with good selectivity and purity have been developed.

  已经开发了由容易获得的具有良好的选择性和纯度的四酯制备（二氯亚甲基）双膦酸的P，P-二烷基偏酯的方法。
• McKenna, Charles E.; Khare, Anil; Ju, Jing-Yue, Phosphorus, Sulfur and Silicon and the Related Elements, 1993, vol. 76, # 1-4, p. 139 - 142
  作者：McKenna, Charles E.、Khare, Anil、Ju, Jing-Yue、Li, Zeng-Min、Duncan, Greg、et al.

  DOI：——

  日期：——
• McKenna, Charles E.; Khawli, Leslie A.; Ahmad, Wan-Yaacob, Phosphorus and Sulfur and the Related Elements, 1988, vol. 37, p. 1 - 12
  作者：McKenna, Charles E.、Khawli, Leslie A.、Ahmad, Wan-Yaacob、Pham, Phuong、Bongartz, Jean-Pierre

  DOI：——

  日期：——