(2-hydroxy-5-methylphenyl)diphenylphosphine | 185509-29-9

• 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: (2-hydroxy-5-methylphenyl)diphenylphosphine
• 英文别名: (4-methyl-2-diphenylphosphanyl)phenol；2-(diphenylphosphanyl)-4-methylphenol；2-diphenylphosphanyl-4-methylphenol；5-methyl-2-phenoxydiphenylphosphine；2-diphenylphosphino-4-methylphenol；2-Diphenyl phosphanyl-4-methyl phenol
• CAS: 185509-29-9
• 化学式: C₁₉H₁₇OP
• 分子量: 292.317
• InChiKey: PKQQYUAHZNVQCC-UHFFFAOYSA-N

物化性质

• 沸点：
  414.5±38.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2-hydroxy-5-methylphenyl)diphenylphosphine 以 四氢呋喃 、 氘代氯仿 为溶剂， 生成 [Pd(2-diphenylphosphino-4-methylphenol)(SO2CH3)(μ-Cl)]2
  参考文献：
  名称：

  Kim, Jang Sub; Sen, Ayusman; Guzei, Ilia A., Journal of the Chemical Society. Dalton Transactions (2001), 2002, # 24, p. 4726 - 4731

  摘要：

  DOI：
• 作为产物：
  描述：

  2-溴-4-甲基苯酚 在 正丁基锂 、 乙醇 作用下， 反应 2.0h， 生成 (2-hydroxy-5-methylphenyl)diphenylphosphine
  参考文献：
  名称：

  P / O配体体系的合成，反应性和三级结构Ø -Phosphanylphenol衍生品

  摘要：

  C，O-二锂试剂1（M = M'= Li）或C，O-锂钠试剂1（M = Li，M'= Na）与氯膦的反应生成C，O-二取代产物2或膦基酚盐3其随后用ClSiMe 3处理，得到4-甲基-和大体积的4，6-二叔丁基取代的邻-膦酰基苯酚甲硅烷基醚4。这些被用于制备相应的邻膦基苯酚5，主要是P-不对称衍生物。使用1的局限性和副反应在上面的合成中进行了讨论。报告了酸碱性质，pH依赖于水/己烷的溶解度以及5个选定代表的在氧和磷处的取代反应。给出了通过用（1S）-（）-樟脑酰氯进行酯化来分离对映异构体的实例。红外研究表明分子内的PHO键和2 J（PC）在溶液中苯氧基的首选反式排列。在固态下，通过X射线结构分析检测分子间和分子内PHO键。该反式苯氧基的排列被保留。由于位阻，O取代基向磷原子倾斜，因此产生较大的贯穿空间耦合常数。然而，在庞大的取代的OSnMe 3部分8h中，PSn距离为336.9 pm

  DOI：

  10.1002/cber.19961291223

文献信息

• Complexes of phosphine–phenolate ligands with the [ReO]3+ and [Re(HNNC5H4N)(NNC5H4N)]2+ cores
  作者：Michael S. Kovacs、Peter Hein、Sherwin Sattarzadeh、Brian O. Patrick、Thomas J. Emge、Chris Orvig

  DOI：10.1039/b104274m

  日期：2001.10.11

  Complexes incorporating the [ReO]3+ core have been synthesised with ligands containing the new methyl substituted phosphine–phenolate PO and PO2 donor sets, (2-hydroxy-5-methylphenyl)diphenylphosphine (H(MePO)) and bis(2-hydroxy-5-methylphenyl)phenylphosphine (H2(Me2PO2)). The analogous tert-butyl ligands, (5-tert-butyl-2-hydroxyphenyl)diphenylphosphine (H(t-BuPO)) and bis(5-tert-butyl-2-hydroxyphenyl)phenylphosphine (H2(t-Bu2PO2)), were also prepared. Reaction of either mer-[ReOCl3(PPh3)2] or [NH4][ReO4] in CH3OH with H(MePO) led to formation of [ReOCl(MePO)2] (1) in good yield. Reaction of [NH4][ReO4] with H2(Me2PO2) in CH3OH afforded [ReO(Me2PO2)(H(Me2PO2))] (2), also in good yield. X-Ray crystallographic analyses of 1 and 2 demonstrated that both complexes are neutral and octahedral, and contain the oxo moiety. Two complexes have been structurally characterised from the reaction of (o-hydroxyphenyl)diphenylphosphine (HPO) with [Re(Hhypy)(hypyH)Cl3]: [Re(Hhypy)(hypy)(PO)(HPO)]Cl (3) and [ReCl(Hypy)(hypy)(PO)] (4) (hypy = NNC5H4N, Hhypy = HNNC5H4N, hypyH = NNC5H4NH). X-Ray crystallography demonstrated that both are Re(III) complexes; 3 is monocationic with an N3OP2 coordination sphere while 4 is neutral with a ClN3OP coordination sphere. [Re(Hhypy)(hypy)(HPO2)(H2PO2)]Cl (5) and [Re(Hhypy)(hypy)(H(Me2PO2))(H2(Me2PO2))]Cl (6) were synthesised by reaction of [Re(Hhypy)(hypyH)Cl3] in CH3OH with bis(o-hydroxyphenyl)phenylphosphine (H2PO2) and H2(Me2PO2) respectively. Compounds 5 and 6 were shown by 1H and 31P NMR spectroscopies to have the same N3OP2 coordination sphere as [Re(Hhypy)(hypy)(PO)(HPO)]Cl, with the addition of several uncoordinated, protonated phenolic donors.

  合成了包含 [ReO]3+ 核心的配合物，使用了含有新甲基取代膦-酚类 PO 和 PO2 供体组的配体，包括 (2-hydroxy-5-methylphenyl)diphenylphosphine (H(MePO)) 和 bis(2-hydroxy-5-methylphenyl)phenylphosphine (H2(Me2PO2))。类似的叔丁基配体，也准备了 (5-tert-butyl-2-hydroxyphenyl)diphenylphosphine (H(t-BuPO)) 和 bis(5-tert-butyl-2-hydroxyphenyl)phenylphosphine (H2(t-Bu2PO2))。在 CH3OH 中用 H(MePO) 反应 mer-[ReOCl3(PPh3)2] 或 [NH4][ReO4] 可以良好地产生 [ReOCl(MePO)2] (1)。用 H2(Me2PO2) 处理 [NH4][ReO4] 也能在 CH3OH 中很好的得到 [ReO(Me2PO2)(H(Me2PO2))] (2)。对 1 和 2 的 X 射线晶体学分析表明，这两个配合物都是中性的八面体结构，并包含氧基。通过 (o-hydroxyphenyl)diphenylphosphine (HPO) 与 [Re(Hhypy)(hypyH)Cl3] 的反应，两个配合物被结构上表征为：[Re(Hhypy)(hypy)(PO)(HPO)]Cl (3) 和 [ReCl(Hypy)(hypy)(PO)] (4)（hypy = NNC5H4N，Hhypy = HNNC5H4N，hypyH = NNC5H4NH）。X 射线晶体学表明，两个都是 Re(III) 配合物；3 为单阳离子，具有 N3OP2 配位环境，而 4 是中性的，具有 ClN3OP 配位环境。通过在 CH3OH 中将 [Re(Hhypy)(hypyH)Cl3] 与 bis(o-hydroxyphenyl)phenylphosphine (H2PO2) 和 H2(Me2PO2) 反应合成了 [Re(Hhypy)(hypy)(HPO2)(H2PO2)]Cl (5) 和 [Re(Hhypy)(hypy)(H(Me2PO2))(H2(Me2PO2))]Cl (6)。通过 1H 和 31P NMR 光谱分析证明，化合物 5 和 6 具有与 [Re(Hhypy)(hypy)(PO)(HPO)]Cl 相同的 N3OP2 配位环境，并增加了一些未配位的质子化酚类供体。
• Nickel Chelate Complexes of 2-Alkylphenylphosphanylphenolates: Synthesis, Structural Investigation and Use in Ethylene Polymerization
  作者：Joachim Heinicke、Manuela Koesling、Robert Brüll、Wilhelm Keim、Hans Pritzkow

  DOI：10.1002/(sici)1099-0682(200002)2000:2<299::aid-ejic299>3.0.co;2-j

  日期：2000.2

  solvents, but in contrast to 1a–c, yielding 4, a sparingly soluble green trans-bis(P–O-chelate) nickel complex 6d is formed. Complexes formed in situ from 1 or 2 and Ni(COD)2 in toluene catalyze the polymerization of ethylene. The cyclopentadienyl (P∩O) complexes 3, however, are too stable to be active in this process. The crystal and molecular structure of 3c and 4c are described.

  2-二苯基膦酰基-和 2-烷基苯基膦酰基-4-甲基苯酚 1 或它们的甲硅烷基醚 2 与等摩尔量的茂镍在苯中反应，优选得到橙棕色抗磁性环戊二烯基镍螯合物 [η-CpNi(P∩O)] (3)。添加第二个等价物 1 或 2 得到顺式双 (P∩O-螯合物) 4a–c (R = Ph, Me, iPr) 或不对称顺式双 (P∩O) 的 (RR) 和 (SS) 非对映异构体O-螯合物) 5，而对于较大的取代衍生物 1d 或 2d (R = tBu)，第二步受到阻碍或延迟。1d 对极性溶剂中的镍盐的反应性仍然很高，但与 1a-c 相比，产生 4，形成了微溶的绿色反式双（P-O-螯合）镍络合物 6d。由 1 或 2 和 Ni(COD)2 在甲苯中原位形成的配合物催化乙烯聚合。环戊二烯基 (P∩O) 配合物 3, 然而，在这个过程中太稳定了。描述了3c和4c的晶体和分子结构。
• <i>O</i> ‐Acylated 2‐Phosphanylphenol Derivatives – Useful Ligands in the Nickel‐Catalyzed Polymerization of Ethylene
  作者：Dmitry G. Yakhvarov、Kaleswara R. Basvani、Markus K. Kindermann、Alexey B. Dobrynin、Igor A. Litvinov、Oleg G. Sinyashin、Peter G. Jones、Joachim Heinicke

  DOI：10.1002/ejic.200801121

  日期：2009.3

  of ethylene, the precatalysts are activated. Catalysts 2Ni and 3a–dNi convert ethylene nearly quantitatively, 2Ni slowly, and 3a–dNi rapidly, into linear polyethylene with vinyl and methyl end groups, and in the latter case, C(O)R end groups are also detectable. This proves insertion of Ni0 into the O–C(O)R bond of 3a–d ligands for formation of the primary catalyst. Termination of the first chain growing

  标题配体通过 2-二苯基膦酰基-4-甲基苯酚 (1) 的 O-酰化或直接通过 2-溴-4-甲基苯酚的双锂化并逐步与 ClPPh2 和 ClP(O)Ph2 或 RC(O)Cl 偶联制备(R = Me, tBu, Ph, 4-MeOC6H4) 得到二苯基次膦酸酯 2 和羧酸酯 3a-d。3b-d 的 X 射线晶体结构分析显示其中对苯基取代基旋转远离酯基的构象，并且 C(O)O π 平面几乎垂直于苯酚环 π 平面。O-酰化磷酰苯酚 2 和 3a-d 与 Ni(1,5-cod)2（与 1 一样）形成高活性催化剂，用于乙烯聚合，而磷酰苯基醚在相同条件下不会产生催化剂。原因是在乙烯存在下与镍 (0) 前体化合物一起加热时 O-酰基键断裂。前体是 P 配位的 NiO 配合物，它们在室温下形成，例如从 3d 和 Ni(cod)2（摩尔比为 2:1）获得的 4d，并通过多核 NMR 光谱表征。在乙烯存在下加热时，预催化剂被活化。催化剂
• Reaction of Acyl(hydrido)cobalt(III) Complexes with (2-Diphenylphosphanyl)phenol and Influence of Chelating Ligands Containing Hard/Soft Donor Atoms on the Stability of Cobalt Complexes
  作者：Hongjian Sun、Xiaoyan Li、Hans-Friedrich Klein、Ulrich Flörke、Hans-Jürgen Haupt

  DOI：10.1021/om0489960

  日期：2005.5.1

  (Acylphenolato)hydridocobalt(III) complexes by reaction with (2-diphenylphosphanyl) phenol deliver (2-diphenylphosphanyl)phenolatocobalt(III) complexes with a 2-acylphenolato chelating ligand as co-ligand (complexes 2, 4−6, and 10−12). Depending on the substituents in the chelating ligands trans/cis-isomers were detected by NMR and IR spectroscopy. Complex 2 was shown by X-ray crystallography to attain

  （Acylphenolato）hydridocobalt（III）配合物通过与（2-二苯基膦基）苯酚递送（2-二苯基膦基）phenolatocobalt（III）配合物用2-acylphenolato螯合配体作为助配位体（复合物2，4 - 6，和10 - 12）。根据螯合配体中的取代基，通过NMR和IR光谱检测反式/顺式异构体。复杂2通过X射线晶体学显示获得八面体结构。在特定条件下，获得了取代的（2-羟甲基）苯酚和（2-二苯基膦基）苯酚-钴（I）配合物。提出了可能的反应途径。将讨论含硬/软供体原子的螯合配体对钴配合物稳定性的影响。
• [EN] APPLICATION OF STAUDINGER LIGATION IN PET IMAGING<br/>[FR] APPLICATION D'UNE LIGATURE DE STAUDINGER EN IMAGERIE TEP
  申请人：SIEMENS MEDICAL SOLUTIONS

  公开号：WO2011123444A1

  公开（公告）日：2011-10-06

  A method for generating a radiolabeled tracer. The method includes providing a phosphine molecule having at least one carbocyclic, aromatic, or pyrrolidinyl ring with an OH substitute. The OH of this phosphines molecule is then condensed with an acid to produce a phosphine ester. Staudinger ligation is then performed to generate the radiolabeled tracer by treating the phosphine ester with a radiolabeled azide having a PET radioisotope moiety

  一种生成放射性标记示踪剂的方法。该方法包括提供至少具有一个环烷基、芳香基或吡咯烷基的磷化物分子，该分子上含有一个OH取代基。然后将该磷化物分子的OH与酸缩合以产生磷酸酯。最后，通过使用带有PET放射性同位素基团的放射性偶氮酰基化合物与磷酸酯进行斯陶丁格反应，生成放射性标记示踪剂。