diethyl thiophene-2-carbonylphosphonate | 57777-09-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: diethyl thiophene-2-carbonylphosphonate
• 英文别名: Diethoxyphosphoryl(thiophen-2-yl)methanone
• CAS: 57777-09-0
• 化学式: C₉H₁₃O₄PS
• 分子量: 248.24
• InChiKey: HLMMLLRMUAVSEP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  80.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diethyl thiophene-2-carbonylphosphonate 在 sodium tetrahydroborate 、 盐酸羟胺 、 molybdenum(VI) oxide 作用下， 以 吡啶 、 甲醇 为溶剂， 反应 6.0h， 生成 膦酸,(氨基-2-噻嗯基甲基)-,二乙基酯
  参考文献：
  名称：

  A simple synthesis of 1-aminophosphonic acids from 1-hydroxyiminophosphonates with NaBH4 in the presence of transition metal compounds

  摘要：

  A new procedure has been developed for the synthesis of 1-aminophosphonic acids. Diethyl phosphonates are converted to hydroxyiminophosphonates when treated with hydroxylamine hydrochloride. Reduction of hydroxyiminophosphonates with NaBH4 in MeOH in the presence of MoO3 or NiCl2 and hydrolysis of 1- aminophosphonates gave 1-aminophosphonic acids in good yield.

  DOI：

  10.1016/0040-4039(95)02171-x
• 作为产物：
  描述：

  diethyl (2-thiophenyl)hydroxymethylphosphonate 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 以90%的产率得到diethyl thiophene-2-carbonylphosphonate
  参考文献：
  名称：

  Highly efficient and extremely simple protocol for the oxidation α-hydroxyphosphonates to α-ketophosphonates using Dess-Martin periodinane

  摘要：

  DOI：

  10.24820/ark.5550190.p011.213

文献信息

• Oxidative Deamination of α-Aminophosphonates and Amines by Zinc Dichromate Trihydrate (ZnCr2O7˙3H2O) under Solvent-Free Conditions at Room Temperature
  作者：Sara Sobhani、Mahdi Maleki

  DOI：10.1055/s-0029-1219174

  日期：2010.2

  A novel method for the rapid and efficient conversion of a variety ot α-aminophosphonates to α-ketophosphonates using ZnCr 2 O 7 ·3H 2 O via oxidative deamination under solvent-free conditions at room temperature is described. This method is also applicable to the rapid and highly selective oxidation of various types of ordinary amines (primary and secondary) to aldehydes and ketones in good to high

  描述了一种使用 ZnCr 2 O 7 ·3H 2 O 在室温下无溶剂条件下通过氧化脱氨基快速有效地将多种 α-氨基膦酸酯转化为 α-酮膦酸酯的新方法。该方法也适用于各种类型的普通胺（伯胺和仲胺）以良好到高产率快速和高选择性氧化成醛和酮。
• On the reaction of dialkyl acylphosphonate with 2-methylthiazolium salts.
  作者：AKIRA TAKAMIZAWA、YOSHIHIRO MATSUSHITA、HIROSHI HARADA

  DOI：10.1248/cpb.25.991

  日期：——

  Dialkyl acylphosphonate worked as an acylating agent on 2-methylthiazolium and thiazolinium salts in the presence of base, to give 2-acylidenethiazoline and thiazolidine derivatives, respectively. Dialkyl [1-aryl (alkyl)-1-dialkylphosphatomethyl] phosphonate was also isolated as a by-product in the same reaction. Dialkyl acylphosphonate afforded 2-acylidenethiazolines in better yield compared with acyl chlorides and showed on apparent affinity for carbanions. Application of diethyl benzoylphosphonate to 1, 2, 3-trimethylbenzimidazolium iodide, however, formed a dimeric salt, 1, 1', 3, 3'-tetramethyl-2, 2'-(2-phenyltrimethylene) di (benzimidazolium) diiodide in addition to 2-(1, 3-dimethylbenzimidazolin-2-ylidene) acetophenone. On the basis of the reactivity difference between the 2-methylthiazolium and 2-methylimidazolium salts and the kinetic experiments, the mechanism of the acylating reaction was proposed.

  二烷基酰基膦酸酯作为酰基化试剂，在碱存在下与2-甲基噻唑盐和噻唑啉盐反应，分别生成2-酰亚氨基噻唑啉和噻唑烷衍生物。同时，反应中还分离得到了副产物：二烷基[1-芳基（烷基）-1-二烷基膦甲基]膦酸酯。与酰氯相比，二烷基酰基膦酸酯在生成2-酰亚氨基噻唑啉时产率更高，并显示出对碳负离子的明显亲和性。然而，将二乙基苯甲酰膦酸酯应用于1,2,3-三甲基苯并咪唑盐碘时，除了生成2-(1,3-二甲基苯并咪唑啉-2-亚基)苯乙酮外，还形成了二聚盐：1,1',3,3'-四甲基-2,2'-(2-苯基亚丙基)二(苯并咪唑盐)二碘化物。基于2-甲基噻唑盐和2-甲基咪唑盐之间的反应活性差异及动力学实验，提出了酰基化反应的机理。
• Asymmetric Direct Aldol Reaction of Functionalized Ketones Catalyzed by Amine Organocatalysts Based on Bispidine
  作者：Jie Liu、Zhigang Yang、Zhen Wang、Fei Wang、Xiaohong Chen、Xiaohua Liu、Xiaoming Feng、Zhishan Su、Changwei Hu

  DOI：10.1021/ja800839w

  日期：2008.4.1

  Organocatalysts containing primary-secondary amine based on bispidine and amino acid have been designed to catalyze the asymmetric direct aldol reaction of functionalized ketones including alpha-keto phosphonates, alpha-keto esters, as well as alpha,alpha-dialkoxy ketones as aldol reaction acceptors. The corresponding products with chiral tertiary alcohols were obtained in moderate to high yields (up

  含有基于双吡啶和氨基酸的伯仲胺的有机催化剂已被设计用于催化功能化酮的不对称直接醛醇反应，包括 α-酮膦酸酯、α-酮酯以及作为醛醇反应受体的 α,α-二烷氧基酮。以中等至高产率（高达 97%）和高对映选择性（高达 98% ee）获得具有手性叔醇的相应产物。过渡结构的理论研究表明，质子化哌啶对该反应的反应性和对映选择性很重要。
• Synthesis of Acylphosphonates by a Palladium-Catalyzed Phosphonocarbonylation Reaction of Aryl Iodides with Phosphites
  作者：Yusuke Masuda、Naoki Ishida、Masahiro Murakami

  DOI：10.1002/asia.201403260

  日期：2015.2

  Acylphosphonates are conveniently synthesized from aryl iodides by a palladium‐catalyzed reaction with dialkyl phosphites under an atmospheric pressure of carbon monoxide. The reaction demonstrates the first example of the use of phosphorus nucleophiles in related metal‐catalyzed carbonylation reactions.

  在一氧化碳的大气压下，通过钯催化与亚磷酸二烷基酯的反应，可以由芳基碘化物方便地合成酰基膦酸酯。该反应证明了在相关的金属催化的羰基化反应中使用磷亲核试剂的第一个例子。
• Catalytic, Asymmetric Synthesis of Phosphonic γ-(Hydroxyalkyl)butenolides with Contiguous Quaternary and Tertiary Stereogenic Centers
  作者：Marcus Frings、Isabelle Thomé、Ingo Schiffers、Fangfang Pan、Carsten Bolm

  DOI：10.1002/chem.201304331

  日期：2014.2.3

  yielding access to phosphonic γ‐(hydroxyalkyl)butenolides with excellent regio‐, diastereo‐ and enantiocontrol is reported. The simultaneous construction of up to two adjacent quaternary stereogenic centers by a catalytic asymmetric vinylogous Mukaiyama aldol reaction unites biologically and medicinally relevant entities, namely α‐hydroxy phosphonates and γ‐(hydroxyalkyl)butenolides. This is achieved by

  据报道，该方法可高收率地获得具有出色的区域，非对映和对映体控制能力的膦酸γ-（羟烷基）丁烯内酯。催化不对称乙烯基Mukaiyama aldol反应最多可同时构建两个相邻的四级立体异构中心，这些结构在生物学和医学上相关的实体，即α-羟基膦酸酯和γ-（羟烷基）丁烯醇内酯。这是通过利用易于获得的手性铜-亚磺酰亚胺催化剂对亲电子和亲核反应物表现出宽泛的官能团耐受性来实现的。还包括对影响观察到的对映选择性水平的潜在因素的讨论，对映选择性水平来自对映纯的亚砜亚胺配体。