3-tert-butyl-3-(3-tert-butyl-2-hydroxy-6-methylphenyl)-5-methyl-4-trifluoromethylphenol | 940273-35-8

• 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: 3-tert-butyl-3-(3-tert-butyl-2-hydroxy-6-methylphenyl)-5-methyl-4-trifluoromethylphenol
• 英文别名: H2[Biphen(CF3)]；3,3'-Di-tert-butyl-5,5'-bis(trifluoromethyl)-6,6'-dimethylbiphenyl-2,2'-diol；6-tert-butyl-2-[3-tert-butyl-2-hydroxy-6-methyl-5-(trifluoromethyl)phenyl]-3-methyl-4-(trifluoromethyl)phenol
• CAS: 940273-35-8
• 化学式: C₂₄H₂₈F₆O₂
• 分子量: 462.476
• InChiKey: YSJKCVDLIIWDOG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  32
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  3-tert-butyl-3-(3-tert-butyl-2-hydroxy-6-methylphenyl)-5-methyl-4-trifluoromethylphenol 、 W(N-t-Bu)(CH-t-Bu)(Me₂pyrrolide)₂(pyridine) 以 苯 为溶剂， 反应 24.0h， 以56%的产率得到W(N-t-Bu)(CH-t-Bu)(Biphen_CF3)(py)
  参考文献：
  名称：

  含叔丁基酰亚胺配体的钼和钨亚烷基配合物的合成

  摘要：

  A variety of molybdenum or tungsten complexes that contain a tert-butylimido ligand have been prepared. For example, the o-methoxybenzylidene complex W(N-t-Bu) ( CH-o-MeOC6H4) (C1)(2)(py) was prepared through addition of pyridinium chloride to W(N-t-Bu)(2)-(CH2-o-MeOC6H4)(2), while Mo(N-t-Bu)(CH-o-MeOC6H4)(ORF)(2)(tBuNI-12) complexes (ORF = 006F(3) or OC(CF3)(3)) were prepared through addition of two equivalents of RFOH to mo(N-t-Bu)(2)(CH2-o-MeOC6H4)(2). An X-ray crystallographic study of Mo(N-t-Bu)(CH-o-MeOC6H4)[0C(CF3)(3)]2(t-BuNH2) showed that the methoxy oxygen is bound to the metal and that two protons on the tert-butylamine ligand are only a short distance away from one of the CF3 groups on one of the perfluoro-tert-butoxide ligands (H center dot center dot center dot F = 2.456(17) and 2.467(17) A). Other synthesized tungsten tert-butylimido complexes include W(N-t-Bu) (CH-o-MeOC6H4)(pyr)(2)(2,21-bip-yridine) (pyr = pyrrolide), W(N-t-Bu) (CH-o-MeOC6H,t)(pyr)(OHMT) (OHMT = 0-2,6-(mesity1)(2)C6H3), W(N-t-Bu) (CH-t-Bu) (OH_MT)(C1)(py) (py = pyridine), W(N-t-Bu) (CH-t-Bu) (OHMT)(Cl), W(N-t-Bu) (CH-t-Bu)(PYr)(0DFT)(PY), W(N-t-Bu) (CH-t-Bu)(OHMT)(2), and W(N-t-Bu) (CH-t-Bu) (ODFT)(2) (ODFT = 0-2,6- (C6F5)(2)C6H3). Interestingly, W(N-t-Bu)(CH-t-Bu)(OHMT)(2) does not react with ethylene or 2,3-dicarbomethoxynorbomadiene. Removal of pyridine from W(N-t-Bu) (CH-t-Bu)(Biphencp3)(pyridine) (Biphencp3 = 3,3'di-tert-buty1-5,5'-bistrifluoromethy1-6,6'-dimethyl-1,1'-biphenyl-2,2'-diolate) with B(C6F5)(3) led to formation of a five-coordinate 14e neopentyl complex as a consequence of CH activation in one of the methyl groups in one tert-butyl group of the Biphenc F-3 ligand, as was proven in an X-ray study. An attempted synthesis of W(N-t-Bu) (CH-t-Bu)(Biphenme) (Biphenme = 3,3'-di-tertbuty1-5,5',6,6'-tetramethy1-1,1'-biphenyl-2,2'-diolate) led to formation of a 1:1 mixture of W(N-t-Bu)(CH-t-Bu)(Biphenme) and a neopentyl complex analogous to the one characterized through an X-ray study. The metallacyclobutane complexes W(N-t-Bu) (C3H6)(Pyrrolide)(0DFT) and W(N-t-Bu) (C3H6) (ODFT)(2) were prepared in reactions involving W(N-t-Bu)(CH-tBu)(pYr)(2)(biPY), ZnC12(dioxane), and one or two equivalents of DFTOH, respectively, under 1 atm of ethylene.

  DOI：

  10.1021/acs.organomet.5b00633

文献信息

• Molybdenum Imido Alkylidene Metathesis Catalysts That Contain Electron-Withdrawing Biphenolates or Binaphtholates
  作者：Rojendra Singh、Constantin Czekelius、Richard R. Schrock、Peter Müller、Amir H. Hoveyda

  DOI：10.1021/om061134+

  日期：2007.5.1

  We have prepared new Mo(NR)(CHCMe2Ph)(diolate) complexes (R = 2,6-i-Pr2C6H3, 2,6-Me2C6H3, 1-adamantyl, or 2-CF3C6H4) that contain relatively electron-withdrawing binaphtholate (3,3'-bis(9-anthracenyl), 3,3'-bispentafluorophenyl, or 3,3'-bis(3,5-bis(trifluoromethyl)phenyl)) or biphenolate (3,3'-di-tert-butyl-5,5'-bistrifluoromethyl-6,6'-dimethyl-1,1'-biphenyl-2,2'-diolate) ligands. We also have prepared new monomeric Mo(NR)(CHCMe2Ph)(2,5-dimethylpyrrolide)(2) complexes and have treated them with biphenols or binaphthols in order to prepare several Mo(NR)(CHCMe2Ph)(diolate) species. In one case the new Mo(NR)(CHCMe2Ph)(diolate) complexes could be prepared only through reaction of a binaphthol [3,3'-bis(pentafluorophenyl)binaphthol] with a bis(2,5-dimethylpyrrolide) complex. The pyrrolide approach can be employed either to isolate catalysts on a preparative scale or to generate catalysts in situ. Several simple preliminary ring-closing metathesis reactions show that the new complexes are catalytically competent.
• Synthesis of Molybdenum and Tungsten Alkylidene Complexes that Contain a <i>tert</i>-Butylimido Ligand
  作者：Hyangsoo Jeong、Richard R. Schrock、Peter Müller

  DOI：10.1021/acs.organomet.5b00633

  日期：2015.9.14

  A variety of molybdenum or tungsten complexes that contain a tert-butylimido ligand have been prepared. For example, the o-methoxybenzylidene complex W(N-t-Bu) ( CH-o-MeOC6H4) (C1)(2)(py) was prepared through addition of pyridinium chloride to W(N-t-Bu)(2)-(CH2-o-MeOC6H4)(2), while Mo(N-t-Bu)(CH-o-MeOC6H4)(ORF)(2)(tBuNI-12) complexes (ORF = 006F(3) or OC(CF3)(3)) were prepared through addition of two equivalents of RFOH to mo(N-t-Bu)(2)(CH2-o-MeOC6H4)(2). An X-ray crystallographic study of Mo(N-t-Bu)(CH-o-MeOC6H4)[0C(CF3)(3)]2(t-BuNH2) showed that the methoxy oxygen is bound to the metal and that two protons on the tert-butylamine ligand are only a short distance away from one of the CF3 groups on one of the perfluoro-tert-butoxide ligands (H center dot center dot center dot F = 2.456(17) and 2.467(17) A). Other synthesized tungsten tert-butylimido complexes include W(N-t-Bu) (CH-o-MeOC6H4)(pyr)(2)(2,21-bip-yridine) (pyr = pyrrolide), W(N-t-Bu) (CH-o-MeOC6H,t)(pyr)(OHMT) (OHMT = 0-2,6-(mesity1)(2)C6H3), W(N-t-Bu) (CH-t-Bu) (OH_MT)(C1)(py) (py = pyridine), W(N-t-Bu) (CH-t-Bu) (OHMT)(Cl), W(N-t-Bu) (CH-t-Bu)(PYr)(0DFT)(PY), W(N-t-Bu) (CH-t-Bu)(OHMT)(2), and W(N-t-Bu) (CH-t-Bu) (ODFT)(2) (ODFT = 0-2,6- (C6F5)(2)C6H3). Interestingly, W(N-t-Bu)(CH-t-Bu)(OHMT)(2) does not react with ethylene or 2,3-dicarbomethoxynorbomadiene. Removal of pyridine from W(N-t-Bu) (CH-t-Bu)(Biphencp3)(pyridine) (Biphencp3 = 3,3'di-tert-buty1-5,5'-bistrifluoromethy1-6,6'-dimethyl-1,1'-biphenyl-2,2'-diolate) with B(C6F5)(3) led to formation of a five-coordinate 14e neopentyl complex as a consequence of CH activation in one of the methyl groups in one tert-butyl group of the Biphenc F-3 ligand, as was proven in an X-ray study. An attempted synthesis of W(N-t-Bu) (CH-t-Bu)(Biphenme) (Biphenme = 3,3'-di-tertbuty1-5,5',6,6'-tetramethy1-1,1'-biphenyl-2,2'-diolate) led to formation of a 1:1 mixture of W(N-t-Bu)(CH-t-Bu)(Biphenme) and a neopentyl complex analogous to the one characterized through an X-ray study. The metallacyclobutane complexes W(N-t-Bu) (C3H6)(Pyrrolide)(0DFT) and W(N-t-Bu) (C3H6) (ODFT)(2) were prepared in reactions involving W(N-t-Bu)(CH-tBu)(pYr)(2)(biPY), ZnC12(dioxane), and one or two equivalents of DFTOH, respectively, under 1 atm of ethylene.