diethyl (3-methyl-3-butenyl)phosphonate | 71071-55-1

• 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 (3-methyl-3-butenyl)phosphonate
• 英文别名: diethyl (3-methylbut-3-en-1-yl)phosphonate；(2-Methyl-but-1-en-4-yl)-phosphonsaeure-diethyleste；<2-Methyl-but-1-en-4-yl>-phosphonsaeure-diethylester；diethyl 3-methylbut-3-enylphosphonate；4-Diethoxyphosphoryl-2-methylbut-1-ene
• CAS: 71071-55-1
• 化学式: C₉H₁₉O₃P
• 分子量: 206.222
• InChiKey: NZDNKISOEZVILP-UHFFFAOYSA-N

物化性质

• 沸点：
  70 °C(Press: 15 Torr)
• 密度：
  1.0094 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  diethyl (3-methyl-3-butenyl)phosphonate 在 吡啶 、 三甲基溴硅烷 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以96%的产率得到3-methyl-3-butenylphosphonic acid
  参考文献：
  名称：

  Synthesis of Prenyl Pyrophosphonates as New Potent Phosphoantigens Inducing Selective Activation of Human Vγ9Vδ2 T Lymphocytes

  摘要：

  gamma9delta2T cells represent the most abundant population of human blood gammadeltaT lymphocytes. They produce and promote strong cytotoxic activity against many pathogens that are implicated in several human infectious diseases. Their activation requires their exposure to small phosphorus-containing antigens in the family of prenyl pyrophosphates and their related biosynthetic precursors such as isopentenyl pyrophosphate (IPP) and dimethylallyl pyrophosphate (DMAPP), which are naturally occurring metabolites in mycobacteria and several other microbial pathogens. The broad specificity in the recognition of these molecules by the T-lymphocyte population expressing a Vgamma9Vdelta2 cell receptor might facilitate their manipulation by designing small potent synthetic agonist ligands. In this paper, we describe the synthesis and the biological evaluation of new pyrophosphonate compounds as new isosteric analogues of natural prenyl pyrophosphates. Several prenyl and alkenyl pyrophosphonate with different chain lengths and degrees of insaturation (24-28, 48-50, and 64-66) were tested as well as the alkoxymethylpyrophosphonic analogue of IPP (compound 76) as its closest isostere. Several of them appeared to be better activators of Vgamma9Vdelta2 T cell proliferation than IPP. These results open the perspective of a potential use of isoprenoides pyrophosphonates as specific immunoregulatory molecules.

  DOI：

  10.1021/jm049861z
• 作为产物：
  描述：

  4-mesyloxy-2-methylbutene 在 lithium bromide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 diethyl (3-methyl-3-butenyl)phosphonate
  参考文献：
  名称：

  Synthesis of Prenyl Pyrophosphonates as New Potent Phosphoantigens Inducing Selective Activation of Human Vγ9Vδ2 T Lymphocytes

  摘要：

  gamma9delta2T cells represent the most abundant population of human blood gammadeltaT lymphocytes. They produce and promote strong cytotoxic activity against many pathogens that are implicated in several human infectious diseases. Their activation requires their exposure to small phosphorus-containing antigens in the family of prenyl pyrophosphates and their related biosynthetic precursors such as isopentenyl pyrophosphate (IPP) and dimethylallyl pyrophosphate (DMAPP), which are naturally occurring metabolites in mycobacteria and several other microbial pathogens. The broad specificity in the recognition of these molecules by the T-lymphocyte population expressing a Vgamma9Vdelta2 cell receptor might facilitate their manipulation by designing small potent synthetic agonist ligands. In this paper, we describe the synthesis and the biological evaluation of new pyrophosphonate compounds as new isosteric analogues of natural prenyl pyrophosphates. Several prenyl and alkenyl pyrophosphonate with different chain lengths and degrees of insaturation (24-28, 48-50, and 64-66) were tested as well as the alkoxymethylpyrophosphonic analogue of IPP (compound 76) as its closest isostere. Several of them appeared to be better activators of Vgamma9Vdelta2 T cell proliferation than IPP. These results open the perspective of a potential use of isoprenoides pyrophosphonates as specific immunoregulatory molecules.

  DOI：

  10.1021/jm049861z

文献信息

• 8π Electrocyclic Reaction of Phosphonate Derivatives: Access to Seven-Membered Cross-Conjugated Cyclic Trienes
  作者：Hiroki Saito、Ranmaru Kato、Kazutada Ikeuchi、Takahiro Suzuki、Keiji Tanino

  DOI：10.1021/acs.orglett.1c03815

  日期：2021.12.17

  An anionic 8π electrocyclic reaction of 4-(diethoxyphosphoryl)-1,3,6-heptatriene derivatives was developed. Under the influence of a base, the substrate underwent deprotonation at the C5 position followed by the 8π electrocyclization of the resulting heptatrienyl anion. The subsequent Horner–Wadsworth–Emmons reaction in one pot, following the addition of an aldehyde, resulted in the production of the

  开发了 4-（二乙氧基磷酰基）-1,3,6-庚三烯衍生物的阴离子 8π 电环反应。在碱的影响下，底物在 C5 位置进行去质子化，然后对所得庚三烯阴离子进行 8π 电环化。在加入醛后，随后在一个锅中进行 Horner-Wadsworth-Emmons 反应，生成 3-亚烷基-1,4-环庚二烯衍生物。电环反应以立体定向的方式进行，导致两个相邻立体中心的立体控制形成。
• Phosphonates useful as modulators of t $g(g)9$g(d)2 lymphocyte activity
  申请人：Montero Jean-Louis

  公开号：US20060241087A1

  公开（公告）日：2006-10-26

  The invention concerns novel phosphonate derivatives, preparation method, use thereof as ligands modulating T γ9δ2 lymphocyte activity and pharmaceutical compositions comprising them.

  这项发明涉及新型膦酸酯衍生物，其制备方法，以及将其用作调节T γ9δ2淋巴细胞活性的配体和包含它们的药物组合物。
• Synthesis of Phosphonomethyl Tetrahydrofurans via the Mori–Tamaru Reaction of Phosphonodienes
  作者：Rishi R. Paudel、Jeremy N. Ridenour、Nigam P. Rath、Christopher D. Spilling

  DOI：10.1021/acs.orglett.0c01080

  日期：2020.5.15

  (the Mori-Tamaru reaction) gives hydroxy vinyl phosphonates in good yields with excellent control of the relative stereochemistry. Base-induced cyclization of the vinyl phosphonates yields phosphonomethyl-substituted tetrahydrofurans. Inversion of the hydroxyl stereochemistry by Mitsunobu reaction and then cyclization yields a different set of phosphonomethyl-substituted tetrahydrofuran diastereoisomers

  镍催化的膦酰基二烯还原至醛的还原反应（Mori-Tamaru反应）可很好地控制相对立体化学，从而获得高产率的羟基乙烯基膦酸酯。碱诱导的乙烯基膦酸酯的环化产生膦酰基甲基取代的四氢呋喃。通过Mitsunobu反应反转羟基立体化学，然后环化，得到另一组膦酰基甲基取代的四氢呋喃非对映异构体。
• Phosphonates useful as modulators of T-gamma-9-delta-2 activity
  申请人：Montero Jean-Louis

  公开号：US20100204184A1

  公开（公告）日：2010-08-12

  The invention concerns novel phosphonate derivatives, preparation method, use thereof as ligands modulating T γ9δ2 lymphocyte activity and pharmaceutical compositions comprising them.

  这项发明涉及新型膦酸盐衍生物、其制备方法，以及将其用作调节T γ9δ2淋巴细胞活性的配体和包含它们的制药组合物。
• Savignac,P. et al., Synthetic Communications, 1979, vol. 9, p. 487 - 496
  作者：Savignac,P. et al.

  DOI：——

  日期：——