diethyl (1-hydroxy-1-(4-trifluromethyl)phenyl-ethyl)phosphonate | 1360147-11-0

• 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 (1-hydroxy-1-(4-trifluromethyl)phenyl-ethyl)phosphonate
• 英文别名: diethyl 1-hydroxy-1-(4-trifluoromethyl)phenylethylphosphonate；diethyl 1-hydroxy-1-(4-trifluoromethylphenyl)ethylphosphonate；diethyl 1-hydroxy-1-(4-trifluromethyl)phenyl-ethylphosphonate；1-Diethoxyphosphoryl-1-[4-(trifluoromethyl)phenyl]ethanol
• CAS: 1360147-11-0
• 化学式: C₁₃H₁₈F₃O₄P
• 分子量: 326.252
• InChiKey: WIVOXZVREBJIPJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  21
• 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：
  7

反应信息

• 作为产物：
  描述：

  4'-三氟甲基苯乙酮 、 亚磷酸二乙酯 在 Y[N(SiMe₃)₂](κ²-C₆H₅C(O)NC₆H₃(ⁱPr)₂)₂(THF) 作用下， 以 neat (no solvent) 为溶剂， 反应 0.67h， 以83%的产率得到diethyl (1-hydroxy-1-(4-trifluromethyl)phenyl-ethyl)phosphonate
  参考文献：
  名称：

  酰胺化物稀土金属酰胺的合成，表征及其对醛和未活化酮的氢膦酰化反应的催化活性

  摘要：

  两种新型酰胺化稀土类金属酰胺LN [N（森达3）2 ]（κ 2 -L 1）2（THF）（L 1  = C 6 H ^ 5 C（O）NC 6 H ^ 3（我PR）2） （Ln = Yb（1），Y（2））通过苯甲酰胺配体HL 1与Ln [N（SiMe 3）2 ] 3的简单甲硅烷基胺消除反应制备。在60°C下于四氢呋喃中溶解。这些配合物通过元素和单晶X射线衍射分析得到了很好的表征，钇配合物2也通过NMR光谱分析得到了表征。调查酰胺化稀土类金属氨化的催化行为，包括两个新的复合物1，2和三种已知的酰胺化物二价稀土金属酰胺{LN [N（森达3）2 ]（μ -O：κ 2 -L 1）（THF）} 2（Ln = Yb（3），Eu（4））和Eu 2 [N（SiMe 3）2 ] 2（μ -O：κ 2 -L 2）2（THF）3（L 2  = C 6 H ^ 5 C（O）NC 6 H ^ 3（Me）的2）（5），表

  DOI：

  10.1016/j.poly.2014.04.018

文献信息

• Highly Efficient Hydrophosphonylation of Aldehydes and Unactivated Ketones Catalyzed by Methylene-Linked Pyrrolyl Rare Earth Metal Amido Complexes
  作者：Shuangliu Zhou、Zhangshuan Wu、Jiewei Rong、Shaowu Wang、Gaosheng Yang、Xiancui Zhu、Lijun Zhang

  DOI：10.1002/chem.201102207

  日期：2012.2.27

  characterized by 1H NMR spectroscopic analyses. The structures of complexes 2, 3, 4, and 6 were determined by single‐crystal X‐ray analyses. Study of the catalytic activities of the complexes showed that these rare earth metal amido complexes were excellent catalysts for hydrophosphonylations of aldehydes and unactivated ketones. The catalyzed reactions between diethyl phosphite and aldehydes in the presence

  通过甲硅烷基胺消除反应制备了一系列带有亚甲基连接的吡咯基-酰胺基配体的稀土金属酰胺配合物，在无溶剂条件下，液态底物在醛和未活化酮的氢膦酰化反应中显示出很高的催化活性。的治疗[（ME 3 Si）的2 N] 3 LN（μ-Cl）的锂（THF）3与2-（2,6--ME 2 ç 6 ħ 3 NHCH 2）C 4 H ^ 3 NH（1，1个当量）在甲苯，得到相应的式三价稀土金属酰胺（μ-η 5：η 1）：η 1-2-[（2,6-Me 2 C 6 H 3）NCH 2 ]（C 4 H 3 N）LnN（SiMe 3）2 } 2 [Ln = Y（2），Nd（3），Sm（4），Dy（5），Yb（6）]，产量适中。所有化合物均通过光谱法和元素分析充分表征。钇配合物的特征还在于1 H NMR光谱分析。复合物的结构 2，3，4，和6由单晶X射线分析确定。配合物催化活性的研究表明，这些稀土金属酰胺配合物是醛和未活化
• Lanthanide anilido complexes: synthesis, characterization, and use as highly efficient catalysts for hydrophosphonylation of aldehydes and unactivated ketones
  作者：Chengwei Liu、Qinqin Qian、Kun Nie、Yaorong Wang、Qi Shen、Dan Yuan、Yingming Yao

  DOI：10.1039/c4dt00522h

  日期：——

  Lanthanide anilido complexes stabilized by the 2,6-diisopropylanilido ligand have been synthesized and characterized, and their catalytic activity for hydrophosphonylation reaction was explored. A reaction of anhydrous LnCl3 with 5 equivalents of LiNHPh-iPr2-2,6 in THF generated the heterobimetallic lanthanide–lithium anilido complexes (2,6-iPr2PhNH)5LnLi2(THF)2 [Ln = Sm(1), Nd(2), Y(3)] in good isolated yields. These complexes are well characterized by elemental analysis, IR, NMR (for complex 3) and single-crystal structure determination. Complexes 1–3 are isostructural. In these complexes, the lanthanide metal ion is five-coordinated by five nitrogen atoms from five 2,6-diisopropylanilido ligands to form a distorted trigonal bipyramidal geometry. The lithium ion is coordinated by two nitrogen atoms from two 2,6-diisopropylanilido ligands, and one oxygen atom from a THF molecule. It was found that these simple lanthanide anilido complexes are highly efficient for catalyzing hydrophosphonylation reactions of various aldehydes and unactivated ketones to generate α-hydroxyphosphonates in good to excellent yields (up to 99%) within a short time (5 min for aldehydes, 20 min for ketones). Furthermore, the mechanism of hydrophosphonylation reactions has also been elucidated via1H NMR monitoring of reaction.

  稳定的2,6-二异丙基苯胺配体的镧系金属苯胺复合物已被合成和表征，并探讨了其在磷化氢化反应中的催化活性。无水LnCl3与5个等摩尔的LiNHPh-iPr2-2,6在THF中的反应生成了异质双金属镧系-锂苯胺复合物(2,6-iPr2PhNH)5LnLi2(THF)2 [Ln = Sm(1), Nd(2), Y(3)]，收率良好。这些复合物通过元素分析、红外光谱、核磁共振（对于复合物3）和单晶结构测定进行了良好的表征。复合物1-3是同构的。在这些复合物中，镧系金属离子由来自五个2,6-二异丙基苯胺配体的五个氮原子协调，形成四面体畸变的三角双锥几何结构。锂离子则由两个2,6-二异丙基苯胺配体中的两个氮原子和一个THF分子中的氧原子协调。研究发现，这些简单的镧系苯胺复合物在催化各种醛和未活化酮的磷化氢化反应中具有高效率，能够在短时间内（醛为5分钟，酮为20分钟）生成α-羟基磷酸酯，收率良好至优异（高达99%）。此外，磷化氢化反应的机制也通过氢核磁共振监测反应得到了阐明。
• Synthesis, structure, and catalytic activity of novel trinuclear rare-earth metal amido complexes incorporating μ–η⁵:η¹bonding indolyl and μ₃-oxo groups
  作者：Song Yang、Xiancui Zhu、Shuangliu Zhou、Shaowu Wang、Zhijun Feng、Yun Wei、Hui Miao、Liping Guo、Fenhua Wang、Guangchao Zhang、Xiaoxia Gu、Xiaolong Mu

  DOI：10.1039/c3dt51107c

  日期：——

  temperatures of 75–80 °C afforded the novel trinuclear rare-earth metal amido complexes incorporating the indolyl ligand in μ–η5:η1 bonding modes and a μ3-O group, which is believed to originate from cleavage of the THF ring based on experimental results. Reactions of 2-(1H-indol-3-yl)-N-((1-methyl-1H-pyrrol-2-yl)methylene)ethanamine with rare-earth metal(III) amides [(Me3Si)2N]3REIII(μ-Cl)Li(THF)3 (RE = Yb

  不同吡咯基官能化的吲哚与稀土金属（III）酰胺[（Me 3 Si）2 N] 3 RE III（μ-Cl）Li（THF）3（RE = Yb，Er，Dy，Eu， Y）生产了各种稀土金属酰胺配合物。的反应ñ - （（1- ħ吡咯-2-基）亚甲基）-2-（1- ħ吲哚-3-基）乙胺与稀土类金属氨化物[（ME 3 Si）的2 N] 3 RE III（ μ-Cl）Li（THF）3（RE =镱，铒，镝，铕，Y）在甲苯或THF中，在75-80°的温度下C获得结合了新颖的三核稀土金属络合物酰胺吲哚基配体在μ-η 5：η 1种接合模式和一个μ 3 -O基团，其被认为是由根据实验结果的THF环的裂解来发起。2-（1 H-吲哚-3-基）-N -（（1-甲基-1 H-吡咯-2-基）亚甲基）乙胺与稀土金属（III）酰胺[（Me 3 Si）的反应2 N] 3 RE III（μ-Cl）Li（THF）3（RE =镱，镝）中
• Synthesis and Characterization of Organolanthanide Complexes with a Calix[4]-pyrrolyl Ligand and Their Catalytic Activities toward Hydrophosphonylation of Aldehydes and Unactivated Ketones
  作者：Shuangliu Zhou、Hengyu Wang、Jian Ping、Shaowu Wang、Lijun Zhang、Xiancui Zhu、Yun Wei、Fenhua Wang、Zhijun Feng、Xiaoxia Gu、Song Yang、Hui Miao

  DOI：10.1021/om2008925

  日期：2012.3.12

  The alkali metal salt free dinuclear trivalent lanthanide amido complexes (eta(5):eta(1):eta(5):eta(1)-Et-8-calix[4]-pyrrolyl)LnN-(SiMe3)(2)}(2) (Ln = Nd (2), Sm (3), Gd (4)) were prepared through the silylamine elimination reactions of calix[4]-pyrrole [Et2C(C4H2NH)](4) (1) with 2 equiv of [(Me3Si)(2)N](3)Ln(mu-Cl)Li(THF)(3) (Ln = Nd, Sm, Gd) in toluene at 110 degrees C. The complexes were fully characterized by elemental, spectroscopic, and single-crystal X-ray analyses. Studies on the catalytic activity of the new lanthanide amido complexes revealed that these complexes can be used as efficient catalysts for hydrophosphonylation of aldehydes and unactivated ketones, affording the products in high yields by employing a low catalyst loading (0.1 mol %) at room temperature in a short time (20 min). Noteworthy is that it is the first application of calix[4]-pyrrolyl-supported lanthanide amides as catalysts to catalyze the hydrophosphonylation of aldehydes and unactivated ketones under mild conditions.