2-(1-hydroxy-3-phenylprop-2-enyl)-5,5-dimethyl-1,3,2-dioxaphosphinane 1-oxide | 279669-06-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: 2-(1-hydroxy-3-phenylprop-2-enyl)-5,5-dimethyl-1,3,2-dioxaphosphinane 1-oxide
• 英文别名: 1-(5,5-Dimethyl-2-oxo-1,3,2lambda5-dioxaphosphinan-2-yl)-3-phenylprop-2-en-1-ol；1-(5,5-dimethyl-2-oxo-1,3,2λ5-dioxaphosphinan-2-yl)-3-phenylprop-2-en-1-ol
• CAS: 279669-06-6
• 化学式: C₁₄H₁₉O₄P
• 分子量: 282.276
• InChiKey: BLQQTWJALLMIHP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(1-hydroxy-3-phenylprop-2-enyl)-5,5-dimethyl-1,3,2-dioxaphosphinane 1-oxide 在 氯化亚砜 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 生成 2-[(E)-3-chloro-3-phenylprop-1-enyl]-5,5-dimethyl-1,3,2lambda5-dioxaphosphinane 2-oxide
  参考文献：
  名称：

  Chlorophosphonates:  Inexpensive Precursors for Stereodefined Chloro-Substituted Olefins and Unsymmetrical Disubstituted Acetylenes

  摘要：

  New chlorophosphonates bearing a 1,3,2-dioxaphosphorinane ring which are useful for the stereospecific synthesis of 5-chlorofurfuryl substituted olefins and chloro-substituted dienes have been obtained by an easy, inexpensive route. The utility of some of these in the synthesis of ferrocenyl- and anthracenyl-substituted unsymmetrical acetylenes has been explored. The structures of the phosphonates (OCH2CMe2CH2O)P(O)CH2(C4H2ClO) (4) and (OCH2Me2CH2O)P(O)-(CH=CHCH(Cl)Ph (7) have been determined; in addition, the stereochemistry of (5-chlorofurfuryl)-CH=CH(4-ClC6H4) (13b) and 2,4-Cl2C6H3-CH=CH-CH=C(Ph)Cl (14a) is unambiguously proved by the X-ray structure determination.

  DOI：

  10.1021/jo991946y
• 作为产物：
  描述：

  2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷 在 水 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 14.0h， 生成 2-(1-hydroxy-3-phenylprop-2-enyl)-5,5-dimethyl-1,3,2-dioxaphosphinane 1-oxide
  参考文献：
  名称：

  Chlorophosphonates:  Inexpensive Precursors for Stereodefined Chloro-Substituted Olefins and Unsymmetrical Disubstituted Acetylenes

  摘要：

  New chlorophosphonates bearing a 1,3,2-dioxaphosphorinane ring which are useful for the stereospecific synthesis of 5-chlorofurfuryl substituted olefins and chloro-substituted dienes have been obtained by an easy, inexpensive route. The utility of some of these in the synthesis of ferrocenyl- and anthracenyl-substituted unsymmetrical acetylenes has been explored. The structures of the phosphonates (OCH2CMe2CH2O)P(O)CH2(C4H2ClO) (4) and (OCH2Me2CH2O)P(O)-(CH=CHCH(Cl)Ph (7) have been determined; in addition, the stereochemistry of (5-chlorofurfuryl)-CH=CH(4-ClC6H4) (13b) and 2,4-Cl2C6H3-CH=CH-CH=C(Ph)Cl (14a) is unambiguously proved by the X-ray structure determination.

  DOI：

  10.1021/jo991946y

文献信息

• FeCl3 catalysed regioselective allylation of phenolic substrates with (α-hydroxy)allylphosphonates
  作者：MANDALA ANITHA、RAMESH KOTIKALAPUDI、K C KUMARA SWAMY

  DOI：10.1007/s12039-015-0903-1

  日期：2015.8

  Electrophilic allylation of phenolic substrates including salicylaldehydes with (α-hydroxy) allylphosphonates is presented. It is observed that catalytic FeCl3 is sufficient to accomplish the allylation. Interestingly, the reaction led to the formation of allylphosphonates in addition to vinylphosphonates, depending upon the substituent. The vinylphosphonates obtained here are E-isomers. More importantly

  提出了包括水杨醛的酚类底物与（α-羟基）烯丙基膦酸酯的亲电子烯丙基化。观察到催化FeCl 3足以完成烯丙基化。有趣的是，取决于取代基，该反应导致除了乙烯基膦酸酯之外还形成烯丙基膦酸酯。此处获得的乙烯基膦酸酯为E-异构体。更重要的是，该反应相对于酚类底物区域选择性地发生。当使用水杨醛或（2-羟基-苯基）芳基甲酮时，形成取代的烯丙基膦酸酯。通过单晶X射线晶体学提供了烯丙基膦酸酯以及乙烯基膦酸酯形成的确凿证据。 通过使用甚至催化量的FeCl 3，使用膦酰基烯丙基醇实现了酚类底物的区域选择性烯丙基化。乙烯基膦酸酯和烯丙基膦酸酯均获得，其比例取决于底物。
• Easy and Stereoselective Synthesis of Cyclopropyl-Substituted Phosphonates via α-Chlorophosphonates
  作者：K. Kumara Swamy、K. Pavan Kumar、R. Rama Suresh、N. Satish Kumar

  DOI：10.1055/s-2007-966032

  日期：——

  reaction of inexpensive α-chlorophosphonates with alkyl acrylates in the presence of sodium hydride is reported. Reaction with dimethyl maleate or fumarate also leads to cyclopropyl-substituted phosphonates. These reactions take place via Michael addition of acrylate, dimethyl maleate, or fumarate to the phosphonate carbanion, followed by expulsion of the chloride ion.

  报道了在氢化钠存在下，通过廉价的 α-氯膦酸盐与丙烯酸烷基酯的反应，简便地立体选择性合成环丙基膦酸盐。与马来酸二甲酯或富马酸二甲酯的反应也产生环丙基取代的膦酸盐。这些反应通过将丙烯酸酯、马来酸二甲酯或富马酸加成到膦酸负碳离子上，然后排出氯离子而发生。
• Synthesis and anticancer activity of new class of bisphosphonates/phosphanamidates
  作者：Y.B. Kiran、C. Devendranath Reddy、D. Gunasekar、C. Suresh Reddy、Annette Leon、Luiz C.A. Barbosa

  DOI：10.1016/j.ejmech.2007.05.014

  日期：2008.4

  Novel bis-heterocyclic bisphosphonates/phosphonamidates were synthesized utilizing the Pudovick reaction. The employment Of Nb2O5 as catalyst was found to increase the yields and purity of the bisbenzoxazaphosphine derivatives (13a-h). Their anticancer activity studies in vitro, on three human tumor cell lines NCI-H460 (lung large cell), MCF-7 (breast adenocarcinoma), and SF-268 (central nervous system glioblastoma), showed that bis-[3-(3-chloro-4-fluorophenyl)-2-oxo-3,4-dihydro-2H-2 lambda(5)-benzo[e][1,3,2]oxazaphosphinin-2-yl]arylmethanes (13a-h) and [(4-chlorophenyl)-(hydroxyamidophosphinoyl)-methyl]phosphonic acid (14) exhibited significant anticancer activity. (c) 2007 Elsevier Masson SAS. All rights reserved.