methyl pinacolyl methylphosphonate | 7040-59-7

• 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: methyl pinacolyl methylphosphonate
• 英文别名: 3-[methoxy(methyl)phosphoryl]oxy-2,2-dimethylbutane
• CAS: 7040-59-7
• 化学式: C₈H₁₉O₃P
• 分子量: 194.211
• InChiKey: IVTOWMZAZSBKOT-UHFFFAOYSA-N

物化性质

• 沸点：
  103 °C(Press: 20 Torr)
• 密度：
  0.981±0.06 g/cm3(Predicted)
• 保留指数：
  1200;1208;1200;1208;1197.4;1200;1204.9;1208.3

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  methyl pinacolyl methylphosphonate 在 甲醇 作用下， 以 氯仿 为溶剂， 反应 12.0h， 生成 替诺福韦
  参考文献：
  名称：

  有机磷化学。第1部分。烷基甲基膦酸的合成

  摘要：

  通过三步路线合成了结构RO（HO）P（O）Me的几种烷基氢甲基膦酸酯[R =  i -Pr，n -Bu，我-Bu，s -Bu，pinacolyl Me 3 C-CH（Me）-，环戊基 和 环己基]。 亚磷酸三甲酯 被酯交换 酒类 在钠存在下 催化剂得到6–64％的混合亚磷酸酯（MeO）2 POR。用这些治疗甲基碘以66–95％的收率得到烷基甲基甲基膦酸酯RO（MeO）P​​（O）Me。可选择的脱甲基 这些化合物的 溴三甲基硅烷， 其次是 甲醇分解甲硅烷基磷酯RO（Me 3 SiO）P（O）Me生成氢膦酸酯 收率为60–97％。

  DOI：

  10.1039/b007077g
• 作为产物：
  描述：

  3,3-二甲基-2-丁醇 在 sodium 作用下， 反应 2.0h， 生成 methyl pinacolyl methylphosphonate
  参考文献：
  名称：

  有机磷化学。第1部分。烷基甲基膦酸的合成

  摘要：

  通过三步路线合成了结构RO（HO）P（O）Me的几种烷基氢甲基膦酸酯[R =  i -Pr，n -Bu，我-Bu，s -Bu，pinacolyl Me 3 C-CH（Me）-，环戊基 和 环己基]。 亚磷酸三甲酯 被酯交换 酒类 在钠存在下 催化剂得到6–64％的混合亚磷酸酯（MeO）2 POR。用这些治疗甲基碘以66–95％的收率得到烷基甲基甲基膦酸酯RO（MeO）P​​（O）Me。可选择的脱甲基 这些化合物的 溴三甲基硅烷， 其次是 甲醇分解甲硅烷基磷酯RO（Me 3 SiO）P（O）Me生成氢膦酸酯 收率为60–97％。

  DOI：

  10.1039/b007077g

文献信息

• Inhibition of Plasma Cholinesterase by O-Alkylfluorophosphonates
  作者：Jiří Cabal、Jiří Kassa、Jiří Patočka

  DOI：10.1135/cccc19970521

  日期：——

  Inhibition of plasma cholinesterase by three methylfluorophosphonates (MFF), sarin, soman and cyclosin, and by the products of their hydrolysis and alcoholysis was examined. Inhibition by phosphonic acids and by methyl esters derived from MFF was purely competitive while that by MFF was irreversible. The rate of phosphorylation of cholinesterase by MFF differs, depending on the structure of the alkoxy group in the MFF and decreases in the sequence soman-sarin-cyclosin. The affinity values of MFF, phosphonic acids and methyl esters of phosphonic acid for cholinesterase are comparable. The in vitro kinetic parameters suggest that plasma cholinesterase might act as a natural detoxicating agent in cases of poisoning with the above inhibitors of acetylcholinesterase.

  三种甲基氟磷酸酯（MFF），沙林、索曼和环磷酯以及它们的水解和醇解产物对血浆胆碱酯酶的抑制作用进行了研究。磷酸酯和来自MFF的甲基酯的抑制作用是纯竞争性的，而MFF的抑制作用是不可逆的。MFF对胆碱酯酶的磷酰化速率取决于MFF中烷氧基团的结构，并且在索曼-沙林-环磷酯序列中逐渐降低。MFF、磷酸酯和磷酸甲酯对胆碱酯酶的亲和力值是可比较的。体外动力学参数表明，血浆胆碱酯酶可能在上述乙酰胆碱酯酶抑制剂中中毒的情况下起着天然解毒剂的作用。
• Hydrolyse Basique de phosphonates I. Étude qualitative
  作者：Henri Christol、Michel̀e Levy、Claude Marty

  DOI：10.1016/s0022-328x(00)88699-4

  日期：1968.6

  The hydrolysis of phosphonates by alkali in aqueous dioxane has been studied. The symmetrical phosphonates are hydrolysed with loss of one ester group to form a monoacid. With the mixed phosphonates the better leaving group is replaced.

  已经研究了在二恶烷水溶液中碱将膦酸酯水解的方法。对称的膦酸酯水解而失去一个酯基，形成一元酸。用混合的膦酸酯，更好的离去基团被取代。
• Stereochemistry of some reactions between alkyl S-methyl methylphosphonothioates and chiral alkoxides
  作者：C. Richard Hall、Thomas D. Inch、Colin Pottage、Nancy E. Williams

  DOI：10.1016/s0040-4020(01)96731-6

  日期：1985.1

  te and (+)-pinacolyl alkoxide competitive and highly stereoselective displacements of O-alkyl and S-methyl occur, both reactions being with inversion of configuration. With the enantiomeric S-(-) ethyl (and methyl) S-methyl methylphosphonothioates and (+)-pinacolyl alkoxide the reactions, although still competitive, are no longer stereoselective. In contrast similar reactions with the sodium salt of

  在R-（+）乙基（或甲基）S-甲基甲基硫代磷酸酯和（+）-频哪醇烯醇盐的竞争下，发生O-烷基和S-甲基的立体选择性置换，这两个反应均与构型反转有关。用对映体S-（-）乙基（和甲基）S-甲基甲基硫代磷酸酯和（+）-频哪醇醇盐，反应尽管仍然具有竞争性，但不再是立体选择性的。相反，与（-）-薄荷醇钠盐的类似反应（可能被认为是（+）-频哪醇醇盐的镜像）在S-（-）上发生高度立体选择性，而在R-（+ ）对映体。当甲醇盐为亲核试剂时，未观察到乙醇，频哪醇醇盐和薄荷醇醇盐将烷基硫代甲基硫代磷酸烷基酯中的O-烷基取代。
• New simulators in the prophylaxis against soman poisoning: structural specificity for the depot site(s)
  作者：Herman P M Van Helden、Henk P Benschop、Otto L Wolthuis

  DOI：10.1111/j.2042-7158.1984.tb04379.x

  日期：2011.4.12

  The oxime HI−6 is effective as an antidote in the soman poisoned (6–8LD50) rat, however, successfully treated animals subsequently show a gradual relapse of signs of poisoning and eventually die after several hours. The relapse is caused by the reappearance of soman at specific sites, after having been elsewhere in the body. Diaphragms isolated from poisoned rats successfully treated with HI−6 also showed a ‘secondary’ relapse of poisoning. Eight compounds chemically related to soman-soman-simulators–-have been tested as prophylactic agents, for their potency in preventing the reappearance of poisoning. The idea was that such compounds may block the non-synaptic binding sites for soman. Three of the 8 compounds proved very effective, which gave some insight into the chemical structure needed for this type of prophylactic action.

  氢肟HI-6在中毒（6-8LD50）的老鼠中作为解毒剂是有效的，但成功治疗的动物随后显示出中毒症状的逐渐复发，并在几个小时后死亡。复发是由特定部位的索曼再次出现引起的，在此之前，它已经在身体的其他部位。用HI-6成功治疗的中毒老鼠分离的膈肌也显示出毒性的“次生”复发。已经测试了与索曼相关的8种化合物-索曼模拟剂-作为预防剂，以防止中毒症状的复发。这样的化合物可能会阻止索曼的非突触结合位点。其中8种化合物中的3种被证明非常有效，这为这种预防性行动所需的化学结构提供了一些见解。

• PREPARATION, DERIVATIZATION WITH TRIMETHYLSILYLDIAZOMETHANE, AND GC/MS ANALYSIS OF A “POOL” OF ALKYL METHYLPHOSPHONIC ACIDS FOR USE AS QUALITATIVE STANDARDS IN SUPPORT OF COUNTERTERRORISM AND THE CHEMICAL WEAPONS CONVENTION
  作者：Michael D. Crenshaw、David B. Cummings

  DOI：10.1080/10426500490459632

  日期：2004.6

  There are hundreds of nerve agents in the class of alkyl methylphosphonofluoridates covered by Schedule 1 of the CWC (Chemical Weapons Convention). Hydrolysis of these sarin-like nerve agents results in all equal number of alkyl methylphosphonic acids. These allkyl methylphosphonic acids are persistent and provide good evidence of specific agent production or use. In order to support the CWC and counterterrorism activities, it is desirable to have ready access to each of these hydrolysis products for use as qualitative standards. A means for simultaneously producing multiple alkyl methylphosphonates from methylphosphonic acid and the corresponding alcohols was developed. Derivatization of these alkyl methylphosphonic acids with trimethylsilyldiazomethane yields the corresponding methyl esters which are suitable for GC/MS analysis.

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