(hydroxy-phenyl-methyl)-phosphonic acid diisopropyl ester | 20386-43-0

• 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: (hydroxy-phenyl-methyl)-phosphonic acid diisopropyl ester
• 英文别名: (+/-) diisopropyl α-hydroxyphenylmetylphosphonate；diisopropyl (+/-)-[hydroxy(phenyl)methyl]phosphonate；(+/-)-diisopropyl phenyl(hydroxy)methylphosphonate；diisopropyl (α-hydroxybenzyl)phosphonate；diisopropyl 1-hydroxy-1-phenylmethylphosphonate；diisopropyl (1-hydroxyphenylmethyl)phosphonate；Di(propan-2-yloxy)phosphoryl-phenylmethanol
• CAS: 20386-43-0
• 化学式: C₁₃H₂₁O₄P
• 分子量: 272.281
• InChiKey: QCHMUMZWEDNROG-UHFFFAOYSA-N

物化性质

• 熔点：
  95-97 °C
• 沸点：
  377.9±35.0 °C(Predicted)
• 密度：
  1.131±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 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：

  (hydroxy-phenyl-methyl)-phosphonic acid diisopropyl ester 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 18-冠醚-6 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 58.08h， 生成
  参考文献：
  名称：

  Synthesis of chiral, nonracemic α-sulfanylphosphonates and derivatives

  摘要：

  Optically active alpha-sulfanylphosphonates and the corresponding methyl sulfides were prepared in three steps starting from chiral, nonracemic (ee 93-97%) alpha-hydroxyphosphonates obtained by enzymatic resolution. Reaction conditions for the reduction of racemisation-prone substrates were found to preserve the enantiomeric excesses. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00316-1
• 作为产物：
  描述：

  diisopropyl benzoylphosphonate 在 palladium 10% on activated carbon 、 氢气 作用下， 以 甲醇 为溶剂， 20.0 ℃ 、3.0 MPa 条件下， 反应 2.0h， 以69%的产率得到(hydroxy-phenyl-methyl)-phosphonic acid diisopropyl ester
  参考文献：
  名称：

  α-酮膦酸酯与手性钯催化剂的不对称氢化

  摘要：

  在大气压下，催化量的三氟乙酸钯 (II) 和 (R)-MeO-BIPHEP 在 2,2,2-三氟乙醇中促进二异丙基 α-酮膦酸酯 1 的不对称氢化，得到相应的 α-羟基膦酸酯 2以优异的产率和高达 55% ee 的中等对映选择性。外消旋α-芳基-α-羟基膦酸酯可以用钯碳作为催化剂制备。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

  DOI：

  10.1002/ejoc.200800943

文献信息

• Utilization of 1,3-Dioxolanes in the Synthesis of α-branched Alkyl and Aryl 9-[2-(Phosphonomethoxy)Ethyl]Purines and Study of the Influence of α-branched Substitution for Potential Biological Activity
  作者：Karel Pomeisl、Radek Pohl、Robert Snoeck、Graciela Andrei、Marcela Krečmerová

  DOI：10.1080/15257770.2018.1506884

  日期：2019.2

  Attachment of purine bases to dialkyl [(2-hydroxyethoxy)methyl]phosphonates was performed by Mitsunobu reaction. Final α-branched 9-[2-(phosphonomethoxy)ethyl]purines were tested for antiviral, cytostatic and antiparasitic activity, the latter one determined as inhibitory activity towards Plasmodium falciparum enzyme hypoxanthine-guanine-xanthine phosphoribosyltransfesase. In most cases biological activity

  摘要：研究了由取代的1,3-二氧戊环合成α-支链烷基和芳基取代的9- [2-（膦酰基甲氧基）乙基]嘌呤的方法。通过路易斯酸介导的1，3-二氧戊环的裂解，然后与亚磷酸二烷基酯或亚磷酸三烷基酯反应，制备关键的合成前体α-取代的[（2-羟基乙氧基）甲基]二烷基膦酸酯。在使用四氯化锡作为路易斯酸和亚磷酸三异丙酯的条件下，可获得最佳的制备产率。嘌呤碱与[（2-羟基乙氧基）甲基]膦酸二烷基酯的连接通过Mitsunobu反应进行。测试了最终的α支化9- [2-（膦酰基甲氧基）乙基]嘌呤的抗病毒，抑制细胞生长活性和抗寄生虫活性，后者被确定为对恶性疟原虫酶次黄嘌呤-鸟嘌呤-黄嘌呤磷酸核糖基转移酶的抑制活性。在大多数情况下，生物学活性只是微不足道的。
• Copper-Catalyzed Synthesis of α-Hydroxy Phosphonates from<i>H</i>-Phosphonates and Alcohols or Ethers
  作者：Zengxiang Zhao、Wanhua Xue、Yuxing Gao、Guo Tang、Yufen Zhao

  DOI：10.1002/asia.201201062

  日期：2013.4

  Easy PC: α‐Hydroxy phosphonates were synthesized by copper/tert‐butyl hydroperoxide (TBHP)‐catalyzed oxidative addition reactions of H‐phosphonates with alcohols or ethers. Diverse α‐hydroxy phosphonates were obtained from substituted benzyl alcohols or alkyl alcohols and alkyl ethers in moderate to good yields.

  Easy PC：α-羟基膦酸酯是通过铜/叔丁基氢过氧化物（TBHP）催化的H-膦酸酯与醇或醚的氧化加成反应合成的。从取代的苄醇或烷基醇和烷基醚以中等到良好的产率获得了多种α-羟基膦酸酯。
• The Preparation of Dialkyl 1-Hydroxyalkylphosphonates in the Reaction of Trialkyl Phosphites with Oxonium Salts Derived from Aldehydes or Ketones
  作者：Mirosław Soroka、Waldemar Goldeman

  DOI：10.1055/s-2006-950200

  日期：——

  The reaction of trialkyl phosphites with aldehydes or ketones in the presence of hydrogen chloride gives dialkyl 1-hydroxy-alkylphosphonates via Arbusov-like reaction of oxonium salts derived from aldehydes or ketones. This reaction is a very convenient instant method for the preparation of dialkyl 1-hydroxyalkyl-phosphonates with a good yield as an alternative to the well-known Abramov reaction.

  亚磷酸三烷基酯与醛或酮在氯化氢存在下的反应通过衍生自醛或酮的氧鎓盐的 Arbusov 样反应得到 1-羟基烷基膦酸二烷基酯。该反应是制备 1-羟烷基-膦酸二烷基酯的一种非常方便的即时方法，作为众所周知的 Abramov 反应的替代方法，该反应具有良好的收率。
• Mechanistic approach for expeditious and solvent-free synthesis of α-hydroxy phosphonates using potassium phosphate as catalyst
  作者：Makarand A. Kulkarni、Uday P. Lad、Uday V. Desai、Satish D. Mitragotri、Prakash P. Wadgaonkar

  DOI：10.1016/j.crci.2012.10.009

  日期：2013.2

  Résumé An extremely simple, high yielding, highly rapid and solvent-free protocol has been described for hydrophosphylation of aldehydes using potassium phosphate as catalyst. Easy commercial availability of the reusable catalyst, operational simplicity at ambient temperature and avoidance of conventional work-up as well as purification procedure makes this solvent-free protocol a near-ideal synthesis. Supplementary Materials: Supplementary material for this article is supplied as a separate file: mmc1.pdf

  摘要 描述了一种极其简单、高产量、高速且无溶剂的醛类羟基磷化方法，使用磷酸钾作为催化剂。该可重复使用的催化剂易于商业获取，在常温下操作简单，并且避免了传统的后处理和纯化过程，使该无溶剂方案成为一种近乎理想的合成方法。 补充材料： 本文的补充材料以单独文件形式提供：mmc1.pdf
• Enzymes in organic chemistry, part 1: Enantioselective hydrolysis of α-(acyloxy)phosphonates by esterolytic enzymes
  作者：Yong-Fu Li、Friedrich Hammerschmidt

  DOI：10.1016/s0957-4166(00)86021-8

  日期：1993.1

  exclusively hydrolyzed to give optically pure alcohols (S)-(−)-3a and (S)-(−)-3b. Lipases AP 6 and F-AP 15 were used to prepare phosphonates (S)-(−)-3b, (S)-(+)-3d and (S)-(−)-3e on a preparative scale with an enantiomeric excess of 81%, 87%, and 89%, respectively. The absolute configurations ofthe α-hydroxyphosphonates were assigned by Horeau's method and 1H-NMR spectroscopy of Mosher's derivatives

  制备α-羟基膦酸酯（±）-3并转化为酯（±）-5。测试了八种脂肪酶以及猪肝酯酶，作为双相系统中α-（酰氧基）膦酸酯的对映选择性水解的催化剂。他们中的两个被证明是有用的。以脂肪酶F-AP 15和α-（乙酰氧基）苯基甲基膦酸酯（±）-5a和（±）-5b为底物可获得最高的对映选择性。（S）-对映异构体专门水解，得到光学纯的醇（S）-（-）- 3a和（S）-（-）- 3b。脂肪酶AP 6和F-AP 15用于制备膦酸酯（S）-（-）- 3b，（S）-（+）- 3d和（S）-（-）- 3e在制备规模上，对映体过量分别为81％，87％和89％。α-羟基膦酸酯的绝对构型通过Horeau法和Mosher衍生物的1 H-NMR光谱确定。