diethyl (((diphenylmethylene)amino)methyl)phosphonate | 122570-91-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: diethyl (((diphenylmethylene)amino)methyl)phosphonate
• 英文别名: diethyl N-(diphenylmethylene)aminomethylphosphonate；Diethyl ((diphenylmethylene)amino)methylphosphonate；N-(diethoxyphosphorylmethyl)-1,1-diphenylmethanimine
• CAS: 122570-91-6
• 化学式: C₁₈H₂₂NO₃P
• 分子量: 331.351
• InChiKey: NOVOZMJGMNDVGJ-UHFFFAOYSA-N

物化性质

• 沸点：
  423.7±37.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  47.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl (((diphenylmethylene)amino)methyl)phosphonate 在 盐酸 作用下， 以 乙醚 为溶剂， 反应 6.0h， 生成 diethyl (1-aminomethyl)phosphonate hydrochloride
  参考文献：
  名称：

  Oxidative Deprotection of Diphenylmethylamines

  摘要：

  [GRAPHICS]The diphenylmethyl amino protecting group can be efficiently removed by initial oxidation of the amine to an imine by 2,3-dichloro-5,6-dicyanobenzoquinone. The resulting imine can then be easily hydrolyzed under mildly acidic conditions. This method is particularly well suited for the preparation of alpha-amino phosphinates and alpha-amino phosphonates.

  DOI：

  10.1021/ol990956i
• 作为产物：
  描述：

  1-(二苯基甲基氨基)甲基膦酸二乙酯 在 4 A molecular sieve 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 苯 为溶剂， 反应 1.0h， 生成 diethyl (((diphenylmethylene)amino)methyl)phosphonate
  参考文献：
  名称：

  Oxidative Deprotection of Diphenylmethylamines

  摘要：

  [GRAPHICS]The diphenylmethyl amino protecting group can be efficiently removed by initial oxidation of the amine to an imine by 2,3-dichloro-5,6-dicyanobenzoquinone. The resulting imine can then be easily hydrolyzed under mildly acidic conditions. This method is particularly well suited for the preparation of alpha-amino phosphinates and alpha-amino phosphonates.

  DOI：

  10.1021/ol990956i

文献信息

• Catalytic Enantio- and Diastereoselective Cyclopropanation of 2-Azadienes for the Synthesis of Aminocyclopropanes Bearing Quaternary Carbon Stereogenic Centers
  作者：Xinxin Shao、Steven J. Malcolmson

  DOI：10.1021/acs.orglett.9b02692

  日期：2019.9.20

  We report the catalytic enantio- and diastereoselective preparation of aminocyclopropanes by the cyclopropanation of terminal and (Z)-internal 2-azadienes with donor/acceptor carbenes derived from α-diazoesters. The resulting cyclopropanes bear quaternary carbon stereogenic centers vicinal to the amino-substituted carbon and are formed as a single diastereomer in up to 99:1 er and 97% yield with 0

  我们报道了通过末端和( Z )-内部2-氮杂二烯与源自α-重氮酯的供体/受体卡宾的环丙烷化，催化对映和非对映选择性制备氨基环丙烷。所得环丙烷带有与氨基取代碳相邻的季碳立构中心，并以高达 99:1 er 和 97% 产率形成单一非对映异构体，其中使用 0.5 mol% 的 Rh 2 (DOSP) 4 和仅1.5当量的重氮试剂。内部氮杂二烯的转化提供了具有三个连续立体中心的环丙烷。
• Enantioselective synthesis of substituted α-aminophosphonates catalysed by <scp>d</scp>-glucose-based crown ethers: pursuit of the origin of stereoselectivity
  作者：Son Truong Pham、Zsolt Rapi、Péter Bakó、Imre Petneházy、András Stirling、Zsuzsa Jászay

  DOI：10.1039/c7nj03345a

  日期：——

  N-protected aminomethylenephosphonate onto acrylic acid derivatives and trans-β-nitrostyrene. Among these crown ethers, three are new. Michael adducts were formed with good to excellent enantio- and diastereoselectivities. Combined MM and QM calculations have revealed that suitable side arms on the crown ether beneficially affect the position of the central sodium cation, which in turn helps enhance the stereocontrol

  将几种与苯基-β- D-吡喃葡萄糖苷退火的单氮杂-15-冠-5型大环化合物用作手性催化剂，用于将N-保护的氨基亚甲基膦酸酯对映体选择性加成到丙烯酸衍生物和反式-β-硝基苯乙烯上。在这些冠醚中，有三个是新的。迈克尔加合物形成的对映选择性和非对映选择性都很好。MM和QM的组合计算表明，冠醚上合适的侧臂有利地影响了中央钠阳离子的位置，进而通过允许底物与催化剂之间的紧密接触，有助于增强立体控制。
• Synthesis of Diethyl (1-Aminoalkyl)phosphonates Under Solid-Liquid Phase-Transfer Catalysis Conditions
  作者：J. P. Genet、J. Uziel、A. M. Touzin、S. Juge

  DOI：10.1055/s-1990-26782

  日期：——

  Alkylations of the stable diethyl N-(diphenylmethylene) aminomethylphosphonate (1) under solid-liquid phase-transfer catalysis (PTC) with or without solvent to give N-(diphenylmethylene) aminomethylphosphonic esters 2 are described. Acidic hydrolysis of 2 afforded diethyl (1-aminoalkyl)phosphonates 3 in good yields.

  在固液相转移催化（PTC）条件下，稳定的二乙基N-(二苯基亚甲基)氨基甲基膦酸酯（1）的无溶剂或有溶剂烷基化反应得到了N-(二苯基亚甲基)氨基甲基磷酸酯2。酯2的酸性水解以良好的产率提供了二乙基(1-氨基烷基)膦酸酯3。
• Phase-Transfer-Catalyzed Asymmetric Michael Addition of (Iminomethyl)phosphonates to α,β-Unsaturated Ketones: Access to α-Aminophosphonic Acid Derivatives
  作者：Jin-Shan Li、Han-Feng Cui、Ke-Feng Zhang、Jing Nie、Jun-An Ma

  DOI：10.1002/ejoc.201700249

  日期：2017.5.3

  The asymmetric Michael addition reaction of (iminomethyl)phosphonates to α,β‐unsaturated ketones in the presence of a chiral dinuclear N‐spiro ammonium salt as a phase‐transfer catalyst (PTC) was developed. This method successfully provided optically active α‐aminophosphonic acid derivatives in good to high yields with excellent diastereoselectivities and moderate to good enantioselectivities.

  在手性双核N-螺铵盐作为相转移催化剂（PTC）的存在下，开发了（亚氨基甲基）膦酸酯与α，β-不饱和酮的不对称迈克尔加成反应。该方法成功地以良好的高收率提供了具有出色的非对映选择性和中等至良好对映选择性的旋光性α-氨基膦酸衍生物。
• Synthesis of α -aminophosphonic acids by Pd(O) alkylation of diethyl aminomethylphosphonate schiff bases.
  作者：J.P. Genet、J. Uziel、S. Juge

  DOI：10.1016/s0040-4039(00)80546-8

  日期：1988.1

  γ, δ -Unsaturated α -amino phosphonic acids are obtained by alkylation of Schiff bases , in the presence of a palladium catalyst under neutral or basic conditions in THF or DME, using allylic carbonates, esters or halides (50–80 % yields).

  γ，δ不饱和α -氨基膦酸由席夫碱的烷基化获得，在钯催化剂存在下在THF或DME中性或碱性条件下的存在下，使用烯丙基碳酸酯，酯或卤化物（50-80％产率）。