methyl-phosphonic acid n-butyl ester | 1832-55-9

• 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: methyl-phosphonic acid n-butyl ester
• 英文别名: methanephosphonous acid mono-n-butyl ester；methylphosphonic acid monobutyl ester；mono-n-butyl ester methanephosphonate；methyl phosphonic acid n-butyl ester；butyl hydrogen methylphosphonate；n-butyl methylphosphonic acid；butoxy(methyl)phosphinic acid
• CAS: 1832-55-9
• 化学式: C₅H₁₃O₃P
• 分子量: 152.13
• InChiKey: GZUFHXSFPZCNJA-UHFFFAOYSA-N

物化性质

• 沸点：
  116-117 °C(Press: 0.1 Torr)
• 密度：
  1.0842 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  9
• 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：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-羟基-3-丁烯腈 、 methyl-phosphonic acid n-butyl ester 在 新癸过氧酸叔丁酯 作用下， 反应 3.0h， 以12.5 g的产率得到n-butyl(3-cyano-3-hydroxypropyl)methylphosphinate
  参考文献：
  名称：

  TW2016/525

  摘要：

  公开号：
• 作为产物：
  描述：

  二-N-甲烷膦酸酯 在 sodium hydroxide 作用下， 生成 methyl-phosphonic acid n-butyl ester
  参考文献：
  名称：

  水解碱性磷酸酯I.Étude质性

  摘要：

  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。

  DOI：

  10.1016/s0022-328x(00)88699-4

文献信息

• 一种甲基次磷酸单烷基酯的合成方法
  申请人：四川福思达生物技术开发有限责任公司

  公开号：CN108752378A

  公开（公告）日：2018-11-06

  本发明公开了一种甲基次磷酸单烷基酯的合成方法，属于有机合成技术领域。针对现有技术中MDP合成收率低，反应条件苛刻等问题，本发明所述方法通过合成甲基次磷酸来生成甲基次磷酸单烷酯,避开了MDP的合成。本发明采用了常见的试剂，先进行甲基化，然后再进行酯化生成了甲基次磷酸单烷酯。整个生成过程控制点少，不会出现MDP合成过程中收率低等技术难题，开创了一种全新的甲基次磷酸单烷基酯的合成路线，更容易实现工业化生产。
• Microwave-Assisted Ionic Liquid-Catalyzed Selective Monoesterification of Alkylphosphonic Acids—An Experimental and a Theoretical Study
  作者：Nikoletta Harsági、Réka Henyecz、Péter Ábrányi-Balogh、László Drahos、György Keglevich

  DOI：10.3390/molecules26175303

  日期：——

  It is well-known that the P-acids including phosphonic acids resist undergoing direct esterification. However, it was found that a series of alkylphoshonic acids could be involved in monoesterification with C2–C4 alcohols under microwave (MW) irradiation in the presence of [bmim][BF4] as an additive. The selectivity amounted to 80–98%, while the isolated yields fell in the range of 61–79%. The method developed is a green method for P-acid esterification. DFT calculations at the M062X/6–311+G (d,p) level of theory (performed considering the solvent effect of the corresponding alcohol) explored the three-step mechanism, and justified a higher enthalpy of activation (160.6–194.1 kJ·mol−1) that may be overcome only by MW irradiation. The major role of the [bmim][BF4] additive is to increase the absorption of MW energy. The specific chemical role of the [BF4] anion of the ionic liquid in an alternative mechanism was also raised by the computations.

  众所周知，包括膦酸在内的P-酸不易直接酯化。然而，发现一系列烷基膦酸在微波（MW）辐射下与C2-C4醇在[bmim][BF4]存在下可以进行单酯化反应。选择性达到80-98％，而分离收率在61-79％的范围内。所开发的方法是一种绿色的P-酸酯化方法。在M062X/6-311+G(d,p)理论水平上进行的DFT计算（考虑了相应醇的溶剂效应）探索了三步机制，并证明了较高的活化焓（160.6-194.1 kJ·mol-1），只有通过MW辐射才能克服。[bmim][BF4]添加剂的主要作用是增加MW能量的吸收。计算还提出了离子液体中[BF4]阴离子的特定化学作用在另一种机制中的作用。
• Surface Mediated Synthesis of Unsymmetrical <i>O,O</i>-dialkyl Alkyl Pyrophosphonates using Neutral Alumina: Potential Chemical Weapons Convention Related Compounds
  作者：Rajesh Kumar、Devendra K. Dubey、Arvind K. Gupta、M.P. Kaushik

  DOI：10.3184/030823408x318316

  日期：2008.5

  The surface mediated synthesis of unsymmetrical O,O’- dialkyl alkyl pyrophosphonates from O-alkyl alkylphosphonic acid is described. These pyrophosphonates are listed in schedule 2B4 of Chemical Weapon Convention (CWC). The effect of the presence of chromatographic grade of Al₂O₃on the phosphorylation of a series of alkyl phosphonic acids has also been investigated. For phosphonic acids having different alkyl groups, it was observed that higher yields of the more hindered pyrophosphonates were formed in the presence of Al₂O₃. This method has an advantage over the conventional methods in terms of easy work-up, reduced reaction time and high yields.

  介绍了以 O-烷基烷基膦酸为原料，通过表面介导合成非对称 O,O'-二烷基烷基焦磷酸盐的方法。这些焦磷酸盐被列入《化学武器公约》（CWC）附表 2B4。此外，还研究了色谱级 Al2O3 的存在对一系列烷基膦酸磷化的影响。对于具有不同烷基的膦酸，观察到在 Al2O3 的存在下形成的受阻程度较高的焦磷酸盐的产率较高。与传统方法相比，该方法具有操作简便、反应时间短和产率高等优点。
• Organophosphorus chemistry. Part 1. The synthesis of alkyl methylphosphonic acids
  作者：Christopher M. Timperley、Michael Bird、Ian Holden、Robin M. Black

  DOI：10.1039/b007077g

  日期：——

  Several alkyl hydrogen methylphosphonates of structure RO(HO)P(O)Me were synthesised by a three-stage route [R = i-Pr, n-Bu, i-Bu, s-Bu, pinacolyl Me3C-CH(Me)-, cyclopentyl and cyclohexyl]. Trimethyl phosphite was transesterified with alcohols in the presence of sodium catalyst to give the mixed phosphites (MeO)2POR in 6–64% yield. Treatment of these with methyl iodide gave alkyl methyl methylphosphonates

  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％。
• Dimethoxytriadinylation LC–MS/MS of Novichok A-Series Degradation Products in Human Urine
  作者：Akinori Yamaguchi、Hajime Miyaguchi、Manabu Tokeshi

  DOI：10.1021/acs.analchem.1c04634

  日期：2022.3.22

  Novichok A-series compounds, novel nerve agents, pose an increasing threat to citizens worldwide; however, no analytical methods have been reported for detecting their hydrolysis products. Herein, a screening method was developed to detect and identify Novichok A-series degradation products (hydrolysates of A230, A232, A234, A262, and one related compound) and alkyl methylphosphonic acids (RMPAs, conventional nerve agent hydrolysates) using liquid chromatography–tandem mass spectrometry (LC–MS/MS). We identified a suitable derivatization reagent, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM), and optimized the reaction conditions. The derivatized esters of Novichok A-series degradation products were stable and easily detected. We used this derivatization to achieve the first analytical method for Novichok hydrolysis products in urine (0.40–4.0 ng/mL). The detection limits of the RMPAs (0.1–0.4 ng/mL) were comparable to those presented in previous reports involving pentafluorobenzylation or direct LC–MS/MS. The applicability of the newly developed method was evaluated by analyzing urine samples from the OPCW Fifth Biomedical Proficiency Test.

  Novichok A系列化合物，这些新型神经毒剂，对全球公民构成日益严重的威胁；然而，目前尚未报告检测其水解产物的分析方法。在此，我们开发了一种筛选方法，通过液相色谱–串联质谱（LC–MS/MS）检测和鉴定Novichok A系列降解产物（A230、A232、A234、A262及一种相关化合物的水解产物）和烷基甲基膦酸（RMPAs，即传统神经毒剂的水解产物）。我们确定了一种合适的衍生化试剂，4-(4,6-二甲氧基-1,3,5-三嗪-2-基)-4-甲基吗啉氯化物（DMTMM），并优化了反应条件。Novichok A系列降解产物的衍生化酯稳定且易于检测。我们利用这一衍生化方法首次实现了对尿液中Novichok水解产物的分析（0.40–4.0 ng/mL）。RMPAs的检测限（0.1–0.4 ng/mL）可与之前报告的五氟苯基化或直接LC–MS/MS的结果媲美。通过分析来自OPCW第五届生物医学能力测试的尿液样本，评估了新开发方法的适用性。