2,6-dichlorophenol lithium | 144428-99-9

• 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: 2,6-dichlorophenol lithium
• 英文别名: lithium 2,6-dichlorophenoxide；Lithium;2,6-dichlorophenolate
• CAS: 144428-99-9
• 化学式: C₆H₃Cl₂O*Li
• 分子量: 168.936
• InChiKey: BNBQNQMWLVAQFE-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -0.93
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  23.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,6-dichlorophenol lithium 、 Mo(N-2,6-i-Pr2C6H3)(CHCMe2Ph)(OTf)2(DME) 在 pyridine 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以58%的产率得到Mo(CHCMe2PH)(N-2,6-diisopropylphenyl)(O-2,6-dichlorophenoxide)2(pyridine)
  参考文献：
  名称：

  Monoadducts of imido alkylidene complexes, syn and anti rotamers, and alkylidene ligand rotation

  摘要：

  Complexes of the type M(CH-t-Bu)(NAr)(OR)2 (M = Mo, W; Ar = 2,6-C6H3-i-Pr2; OR = OCMe(CF3)2, OCMe2(CF3)) form five-coordinate adducts upon addition of PMe3 or quinuclidine. PMe3 attacks the C/N/O face of the pseudotetrahedral complexes to give chiral TBP species in which the phosphine is bound in an axial position and the imido and alkylidene ligands lie in the equatorial plane. Two isomers containing syn and anti rotamers of the alkylidene ligand are observed. The syn rotamer forms first; the anti rotamer is the final product. PMe3 binds weakly when OR = O-t-Bu and is lost readily in vacuo. Quinuclidine adds to either the C/O/O face or N/O/O face to give an achiral syn isomer and to the C/N/O face to give an anti chiral TBP species analogous to that formed for the PMe3 adduct. An equilibrium mixture of syn and anti forms is observed with time. An X-ray structure of syn-Mo(CH-t-Bu)(NAr)[OCMe(CF3)2]2(PMe3) shows that the t-Bu group points toward the imido ligand and the phenyl ring of the imido ligand lies approximately in the equatorial plane in a relatively crowded coordination environment (a = 10.979 (4) angstrom, b = 17.945 (7) angstrom, c = 18.375 (8) angstrom, beta = 106.34 (3)degrees, Z = 4, V = 3474 (4) angstrom 3, rho = 1.490 g/cm3, R = 0.037, R(w) = 0.045). Pyridine adducts of Mo complexes containing the 2,6-dichlorophenoxide ligand also have been characterized. Three isomers of five-coordinate molybdenum or tungsten complexes containing a cis- or trans-2-butenylidene ligand and quinuclidine are found at equilibrium, syn and anti rotamers of the chiral core previously described and a syn rotamer with an achiral core. An X-ray structure of anti-W(trans-CHCH = CHMe)(NAr)[OCMe(CF3)2]2(quin) showed the expected trigonal-bipyramidal core with alkylidene and imido ligands occupying equatorial sites and OCMe(CF3)2 ligands occupying one axial and one equatorial site (a = 12.972 (9) angstrom, b = 18.049 (7) angstrom, c = 15.038 (9) angstrom, beta = 92.07 (3)degrees, Z = 4, V = 3518 (6) angstrom 3, rho = 1.673 g/cm3, R1 = 0.038, R(w) = 0.040). The only significant difference between the structure of this anti adduct and the syn adduct described above is that the anti adduct is markedly less crowded in the equatorial plane. Syn and anti rotamers in five-coordinate adducts have been shown to interconvert after losing the base in several cases. The barrier to rotation of the alkylidene ligand has been measured in several four-coordinate species and shown to lie in the range DELTA-G-double-ended-dagger 298 = 15-18 kcal mol-1. These findings are discussed in relation to the proposed mechanism of olefin metathesis by pseudotetrahedral complexes of the type M(CHR')(NAr)(OR)2.

  DOI：

  10.1021/om00052a033

文献信息

• Aryloxide derivatives of tungsten oxytetrachloride as ring-opening metathesis polymerization catalysts
  作者：Andrew Bell

  DOI：10.1016/0304-5102(92)80155-a

  日期：1992.10

  Pure WOCl4-x (OAr)x complexes (x = 1, 2, 3 or 4; OAr = aryloxide, e.g., −OC6H3-2,6-Me2 were prepared in essentially quantitative yields by reacting tungsten oxytetrachloride (WOCl4) with the stoichiometric amount of the parent substituted phenol or lithium aryloxide. A structural study of WOCl2(OC6H3-2,6-Pri2)2 and WO(OC6H3-2,6-Me2)4 procatalysts showed them to have pseudo-square-pyramidal geometry

  纯WOCL 4- X（OAR）X复合物（X = 1，2，3或4; OAR =芳氧基，例如，-OC 6 H ^ 3 -2,6-ME 2由钨oxytetrachloride反应以基本上定量的产率制备（化学计量的母体取代的苯酚或芳基氧化锂的WOCl 4）WOCl 2（OC 6 H 3 -2,6-Pr i 2）2和WO（OC 6 H 3 -2,6-Me 2）4前催化剂显示它们在钨中心周围具有伪正方形的金字塔形几何形状（参见WOCl 4）。甲反式的2,6- diisopropylphenoxide配体排列被发现为WOCL 2（OC 6 H ^ 3 -2,6-PR我2）2前催化剂。二环戊二烯（DCPD）通过WOCl 3（OAr），WOCl 2（OAr）2和WOCl（OAr）3与氢化三烷基锡（R 3 SnH）或氢化三芳基锡（Ar ）的开环复分解聚合（ROMP）3SnH），进行了评估。纯净的基于四氧化钨的前催化剂，即被氢化锡活化的WOCl
• Pure tungsten oxyphenolate complexes as DCPD polymerization catalysts
  申请人：HERCULES INCORPORATED

  公开号：EP0480447A2

  公开（公告）日：1992-04-15

  This invention relates to a two component catalyst system for polymerization of metathesis polymerizable cycloolefins, comprising (a) a tungsten compound of the formula WOX4-x(OAr)x wherein X represents chlorine, bromine or fluorine, Ar represents a hindered phenyl ring having 1-5 substituents and x = 1, 2 or 3; and (b) an activator compound that preferably is triphenyltin hydride or trialkyltin hydride, preferably a tributyltin hydride. Among the preferred molecules or groups that are substituted on the phenyl ring of the tungsten compound include chlorine, bromine, phenyl, methoxy and isopropyl. Ar may also represent a multisubstituted phenyl group such as 2,4-dichloro-6-methyl phenyl.

  本发明涉及一种用于偏聚可聚合环烯烃聚合的双组分催化剂体系，包括 (a) 式 WOX4-x(OAr)x 的钨化合物，其中 X 代表氯、溴或氟，Ar 代表具有 1-5 个取代基的受阻苯基环，x＝1、2 或 3；以及 (b) 一种活化剂化合物，最好是三苯基氢化锡或三烷基氢化锡，最好是三丁基氢化锡。 在钨化合物的苯基环上被取代的优选分子或基团包括氯、溴、苯基、甲氧基和异丙基。Ar 也可以代表多取代苯基，如 2,4-二氯-6-甲基苯基。
• 一种双核茂金属化合物及其制备方法和应用
  申请人：拓烯科技(衢州)有限公司

  公开号：CN113788862A

  公开（公告）日：2021-12-14

  本发明公开了一种双核茂金属化合物，其制备方法包括有以下步骤：氮气氛围下，将金属氯化物溶解于无水溶剂中，并冷却至‑40～‑20℃搅拌均匀；随后将锂盐一次性加入到反应釜中，加料完毕后，恢复至室温继续搅拌16～24h进行反应；反应结束后，将反应液进行无水无氧过滤，收集得到滤液；将滤液经真空干燥后析出固体；将固体溶于少量的无水溶剂中，并在‑40～‑20℃下静置析出晶体；随后分离晶体，并真空干燥，得到所需的双核茂金属化合物。与现有技术相比，本发明的双核茂金属化合物能够提高催化活性和环烯烃单体插入率。
• Tetrahydrofuran Adducts of a Chlorobismuthate(III) Anion and Antimony Triiodide
  作者：S. C. James、N. C. Norman、A. G. Orpen、M. J. Quayle

  DOI：10.1107/s0108270197004009

  日期：1997.8.15

  Tetrahydrofuran (thf) adducts of a chlorobismuthate(III) and of antimony triiodide have been pre and characterized by X-ray crystallography. The former compound, bis[tetrakis(tetrahydrofuran-O)-lithium(I)] di-mu-chloro-bis[trichloro(tetrahydrofuran-O)-bismuthate(III)], [Li(C4H8O)(4)](2)[Bi2Cl8(C4H8O)(2)], contains centrosymmetric edge-shared bi-octahedral dianions with the formula [Bi2Cl6(thf)(2)(mu-Cl)(2)](2-) in which the thf ligands occupy terminal sites at 90 degrees to the Bi-2(mu-Cl)(2) plane; the cations are [Li(thf)(4)](+). The latter structure, triiodo(tetrahydrofuran-O)antimony(III), [SbI3(C4H8O)], comprises a polymeric arrangement of SbI3(thf) units, the antimony centres being bridged alternately by pairs of I atoms and pairs of thf ligands.
• Efficient Norbornene (NBE) Incorporation in Ethylene/NBE Copolymerization by Half-Titanocene Catalysts Containing Chlorinated Aryloxo Ligands
  作者：Weizhen Zhao、Qing Yan、Ken Tsutsumi、Kotohiro Nomura

  DOI：10.1021/acs.organomet.6b00242

  日期：2016.6.13

  Synthesis and structural: analysis of a series of half-titanocenes containing chlorinated phenoxy ligands of the type Cp'TiCl2(OAr) "[Cp' = Cp, Ar = 2,6-Cl2C6H3 (1), 2,4,6-ClO6H2 (2), C6Cl5 (3); Cp' = indenyl, Ar = 2,6-C12C6H3 (4), 2,4,6-Cl3C6H2 (5), C6Cl5 (6)] and CpTiMe2(OAr) [Ar = 2,4,6-O3C6H2=(9), C6Cl5 (10)] have been explored. The T1 O bond distances in 1H3 are apparently longer than those of the reported aryloxo-modified half-titanocenes, and the Ti O C(in phenyl) angles in 1-3 are also rather small: The Cp analogues (1-3) exhibited higher catalytic activities than the reported (indenyl)TiCl2(O-2,64r2C(6)H(3)) in ethylene copolymerization with norbornene (NBE) in the presence of MAO; these complexes (1-3) also showed better NBE incorporation than those repOrted previously.