diethyl <(diethylcarbamoyl)methyl>phosphonate | 3699-76-1

• 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: diethyl <(diethylcarbamoyl)methyl>phosphonate
• 英文别名: Diethyl 2-(diethylamino)-2-oxoethylphosphonate；2-diethoxyphosphoryl-N,N-diethylacetamide
• CAS: 3699-76-1
• 化学式: C₁₀H₂₂NO₄P
• 分子量: 251.263
• InChiKey: WBLDKEWTTNXBRQ-UHFFFAOYSA-N

物化性质

• 沸点：
  106 °C(Press: 0.17 Torr)
• 密度：
  1.0988 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  16
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl <(diethylcarbamoyl)methyl>phosphonate 在 对甲苯磺酰叠氮 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 以56%的产率得到α-diazo-α-(diethoxyphosphoryl)-N,N-diethylacetamide
  参考文献：
  名称：

  α-重氮-α-(二烷氧基磷酰基)乙酰胺和-乙酸盐的区域选择性和立体选择性二铑(II)-催化的分子内C-H插入反应

  摘要：

  α-重氮-α-（二烷氧基磷酰基）乙酸酯和 -乙酰胺分别通过二铑（II）催化的分子内碳氢插入反应以中等至高产率提供了 α-（二烷氧基磷酰基）内酯和内酰胺。在α-重氮-α-（二烷氧基磷酰基）乙酰胺的情况下，观察到显着偏好形成γ-内酰胺，立体控制有利于反式非对映异构体。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  DOI：

  10.1002/ejoc.200300330
• 作为产物：
  描述：

  diethyl ethynylphosphonate 在 水 作用下， 以 乙醇 为溶剂， 反应 0.5h， 生成 diethyl <(diethylcarbamoyl)methyl>phosphonate
  参考文献：
  名称：

  Addition of Secondary Amines to Alkynephosphonates

  摘要：

  Addition of secondary amines to diethyl alkynephosphonates, catalyzed by Cu(I) salts, proceeds regio- and stereospecifically and yields diethyl (E)-2-diethylaminooalkenephosphonates. The E configuration was established by analysis of the vicinal coupling constants between the phosphorus and carbon nuclei in the C-13 NMR spectra of the reaction products and model compounds: (3)J(PC) is 6-10 Hz at the cis arrangement of the coupled nuclei and 16 Hz or higher at the trans arrangement. In all the diethyl diethylaminoalkenephosphonates obtained, (3)J(PC) is about 5 Hz, suggesting cis addition.

  DOI：

  10.1023/b:rugc.0000018649.77735.cf

文献信息

• Iron-Catalyzed Regio- and Stereoselective Substitution of γ,δ-Epoxy-α,β-unsaturated Esters and Amides with Grignard Reagents
  作者：Takeshi Hata、Rie Bannai、Mamoru Otsuki、Hirokazu Urabe

  DOI：10.1021/ol100022w

  日期：2010.3.5

  When γ,δ-epoxy-α,β-unsaturated esters or amides were treated with 2 equiv of Grignard reagents in the presence of 10−24 mol % FeCl2, regio- and stereoselective substitution of the epoxide moiety with the Grignard reagent occurred to give exclusively δ-hydroxy-γ-alkyl or aryl-α,β-unsaturated esters or amides in good yields.

  当在10−24 mol％FeCl 2存在下用2当量的Grignard试剂处理γ，δ-环氧-α，β-不饱和酯或酰胺时，发生了用Grignard试剂对环氧部分进行区域和立体选择性取代仅以高收率得到δ-羟基-γ-烷基或芳基-α，β-不饱和酯或酰胺。
• Catalytic hydrogenation of α,β-unsaturated carboxylic acid derivatives using copper(<scp>i</scp>)/N-heterocyclic carbene complexes
  作者：Birte M. Zimmermann、Sarah C. K. Kobosil、Johannes F. Teichert

  DOI：10.1039/c8cc09853k

  日期：——

  air-stable copper(I)/N-heterocyclic carbene complex enables the catalytic hydrogenation of enoates and enamides, hitherto unreactive substrates employing homogeneous copper catalysis and H2 as a terminal reducing agent. This atom economic transformation replaces commonly employed hydrosilanes and can also be carried out in an asymmetric fashion.

  简单且空气稳定的铜（I）/ N-杂环卡宾络合物能够实现烯酸酯和烯酰胺的催化氢化，这是迄今为止使用均相铜催化和H 2作为末端还原剂的非反应性底物。这种原子经济的转变代替了常用的氢硅烷，并且也可以以不对称的方式进行。
• Rhodium‐Catalyzed Asymmetric Synthesis of β‐Branched Amides
  作者：Zhao Wu、Joshua D. Laffoon、Trang T. Nguyen、Jacob D. McAlpin、Kami L. Hull

  DOI：10.1002/anie.201610500

  日期：2017.1.24

  synthesis of chiral β‐branched amides is reported through the highly enantioselective isomerization of allylamines, followed by enamine exchange, and subsequent oxidation. The enamine exchange allows for a rapid and modular synthesis of various amides, including challenging β‐diaryl and β‐cyclic.

  据报道，烯丙胺的高度对映选择性异构化，随后的烯胺交换和随后的氧化，是一步合成手性β-支链酰胺的一般不对称路线。烯胺交换可快速模块化地合成各种酰胺，包括具有挑战性的β-二芳基和β-环状。
• Novel products
  申请人：Zoecon Corporation

  公开号：US03948996A1

  公开（公告）日：1976-04-06

  Aliphatic di-unsaturated esters and acids, and derivatives thereof, substituted with thiol (mercapto) or hydrocarbon thio group useful for the control of insects.

  脂肪族二不饱和酯和酸及其衍生物，其中用巯基(硫醇)或烃硫基取代，用于控制昆虫。
• Cyclic analogues of insect juvenile hormone
  作者：Karel Hejno、František Šorm

  DOI：10.1135/cccc19801734

  日期：——

  The preparation and the juvenilization effect of some derivatives of 3,7-dimethyl-9-(5-methyl-2-oxolanyl)-2,6-nonadenoic, 3,7-dimethyl-9-(5-methyl-2-oxolanyl)-2-nonenoic (methyl, ethyl and isopropyl ester, monomethyl and dimethylamide) and 3,7-dimethyl-9-(-methyl-2-oxolanyl)-2,4-nonadenoic acid (methyl, ethyl and isopropyl ester) have been described.

  已经描述了3,7-二甲基-9-(5-甲基-2-氧杂环戊基)-2,6-壬二酸、3,7-二甲基-9-(5-甲基-2-氧杂环戊基)-2-壬烯酸(甲基、乙基和异丙酯,单甲基和二甲基酰胺)以及3,7-二甲基-9-(-甲基-2-氧杂环戊基)-2,4-壬二酸(甲基、乙基和异丙酯)的制备和一些衍生物的幼态化效应。