diisopropyl vinylphosphonate | 4472-27-9

• 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: diisopropyl vinylphosphonate
• 英文别名: 2-[ethenyl(propan-2-yloxy)phosphoryl]oxypropane
• CAS: 4472-27-9
• 化学式: C₈H₁₇O₃P
• 分子量: 192.195
• InChiKey: SIXWLMJAXPTYJY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  diisopropyl vinylphosphonate 在 三氟甲磺酸 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以92%的产率得到乙烯基膦酸
  参考文献：
  名称：

  布朗斯台德酸催化的将膦酸酯选择性转化为膦酸的湿法和干法工艺。

  摘要：

  已经开发了通过布朗斯台德酸催化的将膦酸酯转化为膦酸的“湿”法和两种“干”法。因此，在水的存在下，通常可以在140°C的温度下，通过三氟甲基磺酸（TfOH）催化，将一系列烷基，烯基和芳基取代的膦酸酯水解成相应的膦酸，产率高（湿法）。另一方面，使用膦酸酯的特定取代基，可以在没有水的条件下在较温和的条件下实现向相应膦酸的转化（干燥过程）。因此，在80℃下在甲苯或苯中以高收率平稳地进行了二苄基膦酸酯向相应膦酸的转化。此外，也可以在反应条件下将苄基膦酸酯RP（O）（OR'）（OBn）选择性转化为相应的单膦酸RP（O）（OR'）（OH）。通过生成二异丁烯进行脱烷基叔丁基膦酸酯和TfOH的相关催化即使在室温下也能以高至高收率得到相应的膦酸。Nafion对这些反应也显示出高催化活性。通过使用Nafion作为催化剂，可以通过简单的方法容易地大规模制备膦酸。

  DOI：

  10.1021/acs.joc.0c00550
• 作为产物：
  描述：

  (2-氯乙基)膦酸二异丙酯 在 三乙胺 作用下， 生成 diisopropyl vinylphosphonate
  参考文献：
  名称：

  Kolesnikow; Rodionowa, Vysokomolekulyarnye Soedineniya, 1959, vol. 1, p. 641,644

  摘要：

  DOI：

文献信息

• ORGANOPHOSPHORUS COMPOUND AND FLAME RETARDANT AGENT COMPRISING SAME, AND METHOD FOR PRODUCING ORGANOPHOSPHORUS COMPOUND
  申请人：Maruzen Petrochemical Co., Ltd.

  公开号：US20200270288A1

  公开（公告）日：2020-08-27

  An object is to provide a novel organophosphorus compound which can impart flame retardancy to an amorphous resin in a smaller addition amount without deteriorating heat resistance and transparency, and also can be applied to a wide range of resins, a flame retardant containing the same, and a method for producing an organophosphorus compound. An organophosphorus compound represented by the following general formula (1) (wherein R 1 and R 2 are independently hydrogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, or an alkylaryl group having 7 to 15 carbon atoms, R 3 and R 4 are independently an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an alkylaryl group having 7 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an aralkyloxy group having 7 to 15 carbon atoms, or an alkylaryloxy group having 7 to 15 carbon atoms, provided that R 3 and R 4 may be bound to each other to form a ring, and m and n are independently 1, 2, 3 or 4), a flame retardant containing the same, and a method for producing an organophosphorus compound.

  提供一种新型有机磷化合物，可以在较小的添加量下赋予无定形树脂阻燃性能，而不会降低耐热性和透明性，同时也可以应用于广泛范围的树脂中，包括含有相同化合物的阻燃剂，以及一种生产有机磷化合物的方法。所述有机磷化合物由以下通用式(1)表示（其中R1和R2分别为氢、具有1至15个碳原子的烷基基团、具有6至12个碳原子的芳基基团、具有7至15个碳原子的芳基烷基基团或具有7至15个碳原子的烷基芳基基团，R3和R4分别为具有1至15个碳原子的烷基基团、具有6至12个碳原子的芳基基团、具有7至15个碳原子的芳基烷基基团、具有7至15个碳原子的烷基芳基基团、具有1至15个碳原子的烷氧基、具有6至12个碳原子的芳氧基、具有7至15个碳原子的芳基烷氧基或具有7至15个碳原子的烷基芳氧基，其中R3和R4可以结合形成环，m和n分别为1、2、3或4），包含相同化合物的阻燃剂，以及一种生产有机磷化合物的方法。
• Synthesis of β-Aminophosphonates and Study of Their Acid-Base Properties and Phase Distribution in Water-Organic Solvent Systems
  作者：R. A. Cherkasov、V. I. Galkin、N. G. Khusainova、O. A. Mostovaya、A. R. Garifzyanov、G. Kh. Nuriazdanova、N. S. Krasnova、E. A. Berdnikov

  DOI：10.1007/s11178-005-0370-0

  日期：2005.10

  New and previously known β-aminoethylphosphonates were synthesized by addition of primary and secondary amines to vinylphosphonates, and their IR and NMR spectra were examined. Diethyl 2-diethylaminoethylphosphonate and diethyl 2-morpholinoethylphosphonate were found to be stronger bases than the corresponding aminomethylphosphonates, but all these are weaker bases than their precursors, nonphosphorylated amines. Distribution constants of β-aminophosphonates between water and some organic solvents were determined and compared with those of their α-amino homologs.

  通过在乙烯基膦酸盐中加入伯胺和仲胺，合成了新的β-氨基乙基膦酸盐和以前已知的β-氨基乙基膦酸盐，并研究了它们的红外光谱和核磁共振光谱。研究发现，2-二乙氨基乙基膦酸二乙酯和 2-吗啉基乙基膦酸二乙酯是比相应的氨基甲基膦酸盐更强的碱，但所有这些碱都比它们的前体--非磷酸化胺弱。测定了 β-氨基膦酸盐在水和一些有机溶剂中的分布常数，并将其与α-氨基同系物的分布常数进行了比较。
• Mono and double Mizoroki–Heck reaction of aryl halides with dialkyl vinylphosphonates using a reusable palladium catalyst under aqueous medium
  作者：Han-Sheng Lee、Shao-Hsuan Pai、Wei-Ting Liao、Xin-Jing Yang、Fu-Yu Tsai

  DOI：10.1039/c7ra06464k

  日期：——

  reusable Pd-catalyzed mono and double Mizoroki–Heck reactions of aryl halides and dialkyl vinylphosphonates using iPr2NH as a base in aqueous medium under air were developed. For aryl iodides, the reaction could be conducted at 80 °C under a low catalyst loading (0.1–1 mol%). When aryl bromides were applied, however, a greater amount of catalyst (5 mol%) and a longer reaction time at 120 °C were required.

  使用i Pr 2操作简单且可重复使用的Pd催化的芳基卤化物和乙烯基乙烯基膦酸二烷基酯的单和双Mizoroki-Heck反应在空气中在水性介质中开发了以NH为碱的物质。对于芳基碘化物，该反应可以在80°C的低催化剂负载量（0.1-1 mol％）下进行。然而，当使用芳基溴化物时，需要更大量的催化剂（5mol％）和更长的在120℃下的反应时间。简单地改变乙烯基二膦酸二烷基酯作为限制剂就可以高收率地形成2，2-二芳基乙烯基膦酸。反应后，残留的水溶液可重复用于Mizoroki-Heck单反应和双反应，使反应更绿色，并减少贵金属的浪费，并使用有害的有机溶剂作为反应介质。
• Synthesis and hybridization of oligonucleotides modified at AMP sites with adenine pyrrolidine phosphonate nucleotides
  作者：Dominik Rejman、Petr Kočalka、Radek Pohl、Zdeněk Točík、Ivan Rosenberg

  DOI：10.1135/cccc2009022

  日期：——

  Three structurally diverse types of the protected pyrrolidine nucleoside phosphonates were prepared as the monomers for the introduction of pyrrolidine nucleotide units into modified oligonucleotides on the solid phase. Two different chemistries were used for incorporation of modified and natural units: the phosphotriester method for the former, i.e., monomers containing N-phosphonoalkyl and N-phosphonoacyl moieties attached to the pyrrolidine ring nitrogen atom, and phosphoramidite chemistry for the latter. Since the synthesized pyrrolidine nucleoside phosphonic acids are close mimics of the 3′-deoxynucleoside 5′-phosphates, the incorporation of one modified unit into oligonucleotides gives rise to one 2′,5′ internucleotide linkage. A series of nonamers containing two or three modified units, as well as the fully modified adenine 15-mer, were synthesized in reverse order, i.e., from the 5′ to the 3′ end of the strand. The measurement of thermal characteristics of the complexes of modified nonamers with the complementary strand revealed a destabilizing effect of the introduced modification. The modified adenine homooligonucleotide, was found to form the most stable complex with oligothymidylate of all the tested modified oligonucleotides in terms of ΔT_m per modification.

  三种结构多样的保护吡咯烷基核苷酸膦酸酯被制备为单体，用于在固相上引入吡咯烷核苷酸单元到修饰寡核苷酸中。采用两种不同的化学方法来合成修饰和天然单元：前者采用磷酸三酯法，即含有连接到吡咯烷环氮原子的N-膦酸烷基和N-膦酸酰基的单体，后者采用磷酸酰胺化学方法。由于合成的吡咯烷基核苷酸膦酸是3'-去氧核苷酸5'-膦酸的近似物，因此将一个修饰单元引入到寡核苷酸中会产生一个2',5'间核苷酸连接。一系列包含两个或三个修饰单元的九聚体以及完全修饰的腺嘌呤15聚体是以相反的顺序合成的，即从链的5'端到3'端。测量修饰九聚体与互补链形成的复合物的热特性表明，引入修饰会导致复合物不稳定。在所有测试的修饰寡核苷酸中，修饰腺嘌呤同源寡核苷酸与寡胸苷酸形成的复合物具有最稳定的ΔTm值。
• Pyrrolidine N-alkylphosphonates and related nucleotide analogues: synthesis and stereochemistry
  作者：Dominik Rejman、Radek Pohl、Petr Kočalka、Milena Masojídková、Ivan Rosenberg

  DOI：10.1016/j.tet.2009.02.071

  日期：2009.5

  4-dihydroxypyrrolidine derivatives were synthesized and exploited as synthons for the preparation of hydroxypyrrolidine nucleoside phosphonic acids, the 3′-deoxynucleoside 5′-phosphate analogues. Simultaneously, an alternative route, the N-phosphoalkylation of the preformed pyrrolidine nucleosides employing Mannich- and Michael-type reactions, was investigated to obtain desired nucleotide analogues. In contrast to

  合成了N-膦酰基烷基-反式-3,4-二羟基吡咯烷衍生物，并将其用作合成子来制备羟基吡咯烷核苷膦酸，即3'-脱氧核苷5'-磷酸类似物。同时，研究了另一种途径，即利用曼尼希和迈克尔型反应对预先形成的吡咯烷核苷进行N-磷酸烷基化，以获得所需的核苷酸类似物。与后一种方法相反，前一种方法很可能由于亲核置换过程中存在两个可能的S N 2过渡态而形成了两个非对映异构体。通过NMR光谱研究了所制备的核苷酸类似物的立体化学。