iPrN=C{P(C6H4Me-4)2}(NHiPr) | 1012332-99-8

• 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: iPrN=C{P(C6H4Me-4)2}(NHiPr)
• 英文别名: 1-bis(4-methylphenyl)phosphanyl-N,N'-di(propan-2-yl)methanimidamide
• CAS: 1012332-99-8；914388-34-4
• 化学式: C₂₁H₂₉N₂P
• 分子量: 340.448
• InChiKey: LSXCQOFWNFWRDI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  24.4
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  二对甲苯膦 、 N,N'-二异丙基碳二亚胺 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 以99%的产率得到iPrN=C{P(C6H4Me-4)2}(NHiPr)
  参考文献：
  名称：

  Alkali-metal-catalyzed addition of primary and secondary phosphines to carbodiimides. A general and efficient route to substituted phosphaguanidines

  摘要：

  诸如nBuLi和(Me3Si)2NK等有机碱金属化合物作为磷烷P-H键加成到碳二亚胺上的优异催化剂前体，提供了一种通用的、原子经济性的合成取代磷胍途径，且对芳香族C-Br和C-Cl键具有良好的耐受性。

  DOI：

  10.1039/b609198a

文献信息

• Half-sandwich rare-earth metal tris(alkyl) ate complexes catalyzed phosphaguanylation reaction of phosphines with carbodiimides: an efficient synthesis of phosphaguanidines
  作者：Wangyang Ma、Ling Xu、Wen-Xiong Zhang、Zhenfeng Xi

  DOI：10.1039/c5nj01136a

  日期：——

  Half-sandwich Y/Li ate complex displays better catalytic activity for phosphaguanylation reaction of phosphines with carbodiimides than the neutral yttrium complexes.

  半夹 Y/Li 配合物在磷胍基化反应中显示出比中性钇配合物更好的催化活性。
• Alkali-metal-catalyzed addition of primary and secondary phosphines to carbodiimides. A general and efficient route to substituted phosphaguanidines
  作者：Wen-Xiong Zhang、Masayoshi Nishiura、Zhaomin Hou

  DOI：10.1039/b609198a

  日期：——

  Organo alkali metal compounds such as nBuLi and (Me3Si)2NK act as excellent catalyst precursors for the addition of phosphine P–H bonds to carbodiimides, offering a general and atom-economical route to substituted phosphaguanidines, with excellent tolerability to aromatic C–Br and C–Cl bonds.

  诸如nBuLi和(Me3Si)2NK等有机碱金属化合物作为磷烷P-H键加成到碳二亚胺上的优异催化剂前体，提供了一种通用的、原子经济性的合成取代磷胍途径，且对芳香族C-Br和C-Cl键具有良好的耐受性。
• Half-Sandwicho-N,N-Dimethylaminobenzyl Complexes over the Full Size Range of Group 3 and Lanthanide Metals. Synthesis, Structural Characterization, and Catalysis of Phosphine PH Bond Addition to Carbodiimides
  作者：Wen-Xiong Zhang、Masayoshi Nishiura、Tomohiro Mashiko、Zhaomin Hou

  DOI：10.1002/chem.200701300

  日期：2008.2.27

  (7). The reaction of 6 or 7 with Ph2PH in THF yielded 4 and the phosphaguanidine iPrN=C(PPh2)NHiPr (3a). These results suggest that the catalytic formation of a phosphaguanidine compound proceeds through the nucleophilic addition of a phosphide species, which is formed by the acid-base reaction between a rare-earth metal o-dimethylaminobenzyl bond and a phosphine P--H bond, to a carbodiimide, followed

  这些半三明治稀土金属氨基苄基络合物可作为有效的催化剂前体，用于催化将各种膦MH键与碳二亚胺催化加成，形成一系列对芳族碳-卤素键具有优异耐受性的磷胍衍生物。观察到催化活性的显着增加，这是由于金属尺寸的增加，总体趋势为La> Pr，Nd> Sm> Gd> Lu> Sc。2-La与1当量的Ph2PH反应生成相应的磷化物络合物[Me2Si（C5Me4）（NC6H2Me3-2,4,6）} La（PPh2）（thf）2]（4），从苯，得到二聚体类似物[Me2Si（C5Me4）（NC6H2Me3-2,4,6）} La（PPh2）] 2（5）。在THF中将4或5加至iPrN = C = NiPr，得到磷胍盐配合物[Me2Si（C5Me4）（NC6H2Me3-2,4,6）} La iPrNC（PPh2）NiPr}（thf）]（6），其在醚上重结晶后，得到醚配位的结构可表征的类似物[Me2Si（C5Me4）（NC6H2Me3-2
• Synthesis of Bis(NHC)-Based CNC-Pincer Rare-Earth-Metal Amido Complexes and Their Application for the Hydrophosphination of Heterocumulenes
  作者：Xiaoxia Gu、Lijun Zhang、Xiancui Zhu、Shaowu Wang、Shuangliu Zhou、Yun Wei、Guangchao Zhang、Xiaolong Mu、Zeming Huang、Dongjing Hong、Feng Zhang

  DOI：10.1021/acs.organomet.5b00628

  日期：2015.9.28

  The bis(NHC) (NHC = N-heterocyclic carbene)-based CNC-pincer rare-earth-metal amido complexes LRE[N(SiMe3)(2)](2) (L = 4-CH3-2-R-[N(CH)(2)CN]}C6H3](2)N; L2, R = CH3; L3, R = CH(CH3)(2)) were synthesized and characterized, and their catalytic activities toward hydrophosphination of heterocumulenes were developed. Reactions of bis[2-(3-methylimidazolium)-4-methylphenyl]amine diiodide (H3L2I(2)) or bis[2-(3-isopropylimidazolium)-4-methylphenyl]amine diiodide (H3L2I(2)) with 5 equiv of NaN(SiMe3)(2) followed by treatment with 1 equiv of RECl3 in THF at -78 C afforded the bis(NHC)-based CNC-pincer rare-earth-metal amido complexes LRE[N(SiMe3)(2)](2) (L2 = [4-CH3-2-CH3-[N(CH)(2)CN]}C6H3](2)N, RE = Y (1), Eu (2), Er (3); L-3 = [4-CH3-2-(CH3)(2)CH-[N(CH)(2)CN]}C6H3](2)N, RE = Y (4), Er (5), Yb (6)). Complexes 46 can also be prepared by stepwise reactions of H3L-3I-2 with n-BuLi in THF followed by reactions with [(Me3Si)2N]3RE(mu-Cl)Li(THF)3. Stepwise reactions of H3L3I(2) with n-BuLi in THF followed by treatment with [(Me3Si)(2)N](3)RE(mu-Cl)Li(THF)(3) generated the bis(NHC)-based CNC-pincer rare-earth-metal amido complexes L2RE[N-(SiMe3)(2)](2) (RE = Y (1), Er (3)) together with the fused-heterocyclic compound 3,8,9-trimethyl-8a,9-dihydro-8H-benzo[4,5]imidazo[2',1':2,3]imidazo[1,2-a]imidazo[2,1-c]quinoxaline (7), which formed through carbene CC and CN coupling. Attempts to prepare complexes of the type LRE[N(SiMe3)(2)](2) by reaction of H3L3I(2) with [(Me3Si)(2)N](3)Yb(mu-Cl)Li(THF)(3) in THF, however, afforded mixed complexes of the bis(NHC)-based CNC-pincer ytterbium complex L3Yb[N(SiMe3)(2)](2) (6) and the unexpected bis(NHC)-based CNC-pincer monoamido ytterbium iodide L3YbI[N(SiMe3)(2)] (8). Investigation of the catalytic activity of complexes 16 and 8 indicated that all complexes displayed high activity toward the addition of the phosphine PH bond to heterocumulenes, producing the corresponding phosphaguanidines, phosphaureas, and phosphathioureas, which represents the first example of bis(NHC)-based CNC-pincer type rare-earth-metal amido complexes as catalysts for the catalytic addition of the phosphine PH bond to heterocumulenes with high efficiency in the presence of a low catalyst loading at room temperature