1,4-dithiabutanediyl-2,2'-bis(6-tert-butyl-4-methylphenol) | 663910-59-6

• 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: 1,4-dithiabutanediyl-2,2'-bis(6-tert-butyl-4-methylphenol)
• 英文别名: 1,4-dithiabutanediyl-bis(6-tert-butyl-4-methylphenol)；1,4-dithiabutanediylbis(6-tert-butyl-4-methylphenol)；etbmpH2；Phenol, 2,2'-[1,2-ethanediylbis(thio)]bis[6-(1,1-dimethylethyl)-4-methyl-；2-tert-butyl-6-[2-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanylethylsulfanyl]-4-methylphenol
• CAS: 663910-59-6
• 化学式: C₂₄H₃₄O₂S₂
• 分子量: 418.665
• InChiKey: UUJSMYOPRQAQPJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  91.1
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,4-dithiabutanediyl-2,2'-bis(6-tert-butyl-4-methylphenol) 以 四氢呋喃 、 正戊烷 为溶剂， 生成 [Y(1,4-dithiabutanediylbis(6-tert-butyl-4-methylphenolato))(CH2SiMe3)(pyridine)2]
  参考文献：
  名称：

  含硫醚官能化双（酚）配体的稀土金属烷基和氢化物配合物：烯烃氢化硅烷化的高效催化剂

  摘要：

  具有三齿[OSO]型和四齿[OSSO]型双（酚醛）配体[[Ln（L）（CH 2 SiMe 3）（THF）n ]的稀土金属烷基络合物（LH 2 = 2,2' -硫代双（6-叔丁基-4-甲基苯酚）（tbmpH 2），1,3-二硫丙烷二基双（6-叔丁基-4-甲基苯酚）（mtbmpH 2），1,4-二硫代丁二烷基双（6-叔丁基） -4-甲基苯酚）（etbmpH 2）; Ln为Y（1 - 3），SC（4，5），路（7），何（9，10））是由三（烷基）配合物[Ln（CH 2 SiMe 3）3（THF）2 ]与相应的双（苯酚）通过烷烃消除反应合成的。通过NMR光谱法（Y，SC，Lu）和元素分析以及通过X射线晶体结构分析（烷基配合物进行了表征5，7）。[Lu（CH 2 SiMe 3）3（THF）2 ]与H 2 etbmp以1：2的比例反应导致双酚基桥接的双核络合物[Lu 2（etbmp）3（THF）的形成）2

  DOI：

  10.1021/om800161u

文献信息

• Rare earth metal complexes supported by 1,ω-dithiaalkanediyl-bridged bis(phenolato) ligands: synthesis, characterization and ring-opening polymerization catalysis of<scp>l</scp>-lactide
  作者：Haiyan Ma、Thomas P. Spaniol、Jun Okuda

  DOI：10.1039/b311604b

  日期：——

  Monomeric rare earth metal bis(phenolato) complexes [(Ls,s)LnN(SiHMe2)2}(THF)] (1a–4c) were isolated from the reaction of silylamido complexes [LnN(SiHMe2)2}3(THF)x] (Ln = Sc, x = 1; Ln = Y, Lu, x = 2) and one equivalent of tetradentate 1,ω-dithiaalkanediyl-bridged bis(phenol)s etbmpH2, ptbmpH2, edtbpH2 and pdtbpH2 in moderate to high yields. In contrast to the unsymmetrical scandium complexes 1a and

  单体的 稀土金属双（苯酚）络合物[（L s，s-硫）LN N（SiHMe 2）2 }（THF）]（1A-4C）从silylamido配合物[LN N（SiHMe反应分离2）2 } 3（ THF）x ]（Ln = Sc，x = 1; Ln = Y，Lu，x = 2）和一当量的四齿1，ω-二硫代烷二基桥接的双（酚）etbmpH 2，ptbmpH 2，edtbpH 2和pdtbpH 2中至高产。与不对称scan络合物1a和3a相反，the络合物2a，钇配合物1b和4b以及the配合物1c–4c表现出C s或C 2对称性，这是因为THF相对快速地解离。核磁共振室温下的时间刻度。通过X射线衍射研究证实了配合物2a和4b的单体结构。六坐标中心金属与四齿配体，甲硅烷基和一个四氢呋喃采用C 1对称构型，其两个氧供体的反式（O，O）或顺式（O，O）取向配体。发现2a和4b变形的八面体和三角棱柱配位几何。与2
• Aluminium alkyl complexes supported by [OSSO] type bisphenolato ligands: synthesis, characterization and living polymerization of rac-lactide
  作者：Haiyan Ma、Gianluca Melillo、Leone Oliva、Thomas P. Spaniol、Ulli Englert、Jun Okuda

  DOI：10.1039/b416875e

  日期：——

  Aluminium alkyl complexes [(OSSO)AlR] (1–3: R = Me, Et) were isolated in good yields from the protonolysis reaction of AlR3 with the corresponding tetradentate 1,ω-dithiaalkanediyl-bridged bisphenols (1,4-dithiabutanediyl-bis(6-tert-butyl-4-methylphenol), etbmpH2; ortho-xylylenedithio-bis(6-tert-butyl-4-methylphenol), xytbmpH2). The monomeric structures of all three complexes were confirmed by X-ray diffraction studies. Complexes 1 and 2 have an isotypic packing arrangement. The aluminium center is coordinated by the etbmp ligand and one alkyl group with distorted trigonal bipyramidal geometry. Complex 3 shows Cs symmetry with square pyramidal geometry around the metal center. Substitution reaction of complex 1 with trityl alcohol gave the monomeric alkoxide complex [(etbmp)Al(OCPh3)] 4, which has a similar trigonal bipyramidal geometry around the aluminium atom as complex 1. In the presence of isopropanol, complexes 1–3 initiated the living ring-opening polymerization of rac-lactide (PDI = 1.03–1.06, Mw/Mn). The ligand structure influenced the tacticity of the obtained polymer, with complex 3 giving heterotactic-enriched polylactides.

  通过质子解反应，从AlR3与相应四齿1,ω-二硫代烷二基桥连双酚（1,4-二硫代丁二基-双(6-叔丁基-4-甲基苯酚)，etbmpH2；邻二甲苯二硫代-双(6-叔丁基-4-甲基苯酚)，xytbmpH2）反应中，得到了高产率的烷基铝配合物[(OSSO)AlR]（1-3：R = Me，Et）。所有三种配合物的单体结构通过X射线衍射研究得到证实。配合物1和2具有同型堆积排列。铝中心与etbmp配体和一个烷基基团配位，具有扭曲的三方双锥几何形状。配合物3显示出Cs对称性，金属中心周围具有四方锥几何形状。配合物1与三苯甲醇的取代反应得到单体烷氧化物配合物[(etbmp)Al(OCPh3)] 4，其铝原子周围具有与配合物1相似的三方双锥几何形状。在异丙醇存在下，配合物1-3启动了外消旋-乳酸的内酯开环活性聚合（PDI = 1.03–1.06，Mw/Mn）。配体结构影响了所得聚合物的构型，配合物3给出了富含异手性的聚乳酸。
• Lutetium alkyl and hydride complexes in a non-cyclopentadienyl coordination environment
  作者：Marcin Konkol、Thomas P. Spaniol、Małgorzata Kondracka、Jun Okuda

  DOI：10.1039/b710228n

  日期：——

  Lutetium alkyl complexes [Lu(L)(CH2SiMe3)(THF)n], which contain a sulfur-linked bis(phenolato) ligand such as 2,2′-thiobis(6-tert-butyl-4-methylphenolate) (L = tbmp, 1) or 1,4-dithiabutanediyl-bis(6-tert-butyl-4-methylphenolate) (L = etbmp, 2), were isolated from the reaction of the lutetium tris(alkyl) complex [Lu(CH2SiMe3)3(THF)2] with H2L. The monomeric structures of these complexes were confirmed by X-ray diffraction studies, showing distorted octahedral geometry around the metal centre. The reaction of [Lu(tbmp)(CH2SiMe3)(THF)2] (1) with alcohols ROH (R = iPr, CHPh2, CPh3) results in the formation of the corresponding alkoxide complexes [Lu(tbmp)(OR)(THF)n] (4–6). With PhSiH3 hydride complexes [Lu(L)(µ-H)(THF)n]2 (L = tbmp, 7; etbmp, 8) have been prepared in moderate to good yields. They adopt a dimeric form in the solid state as revealed by the X-ray crystal structure of 7. The reactivity of the hydride complexes and their catalytic activity in the ring-opening polymerisation of L-lactide and the hydrosilylation of alkenes are also discussed.

  含有硫桥联双酚配体的镥烷基配合物[Lu(L)(CH2SiMe3)(THF)n]，如2,2'-硫代双(6-叔丁基-4-甲基酚盐)(L = tbmp，1)或1,4-二硫杂环丁二基双(6-叔丁基-4-甲基酚盐)(L = etbmp，2)，由镥三烷基配合物[Lu(CH2SiMe3)3(THF)2]与H2L反应分离得到。这些配合物的单体结构通过X射线衍射研究得到证实，显示金属中心周围扭曲的八面体几何构型。[Lu(tbmp)(CH2SiMe3)(THF)2](1)与醇ROH(R = iPr, CHPh2, CPh3)反应生成相应的烷氧化物配合物[Lu(tbmp)(OR)(THF)n](4-6)。与PhSiH3反应，以中等至良好产率制备了氢化物配合物[Lu(L)(µ-H)(THF)n]2(L = tbmp，7; etbmp，8)。它们在固态中采用二聚形式，正如7的X射线晶体结构所示。还讨论了氢化物配合物的反应性和它们在L-乳酸开环聚合以及烯烃的氢硅化反应中的催化活性。
• Indium Complexes Supported by 1,ω-Dithiaalkanediyl-Bridged Bis(phenolato) Ligands: Synthesis, Structure, and Controlled Ring-Opening Polymerization of<scp>l</scp>-Lactide
  作者：Ilja Peckermann、Andreas Kapelski、Thomas P. Spaniol、Jun Okuda

  DOI：10.1021/ic900161w

  日期：2009.6.15

  observed for 4 and 5. The isopropoxy complexes [In(L)(OiPr)] (L = etbbp, 6; etccp, 7) were synthesized starting with indium tris(isopropoxide). Complex 6 crystallized as homochiral dimer of pseudo-octahedral fragments with bridging μ2-alkoxide ligands, but in solution two diastereomers were observed. The isopropoxy complexes efficiently initiated the ring-opening polymerization of l-lactide in toluene

  铟双（苯酚）配合物[在（L）R（THF）Ñ ]（L = 1,4- dithiabutanediylbis（4,6-二-叔-butylphenolato）（etbbp），R =氯，Ñ = 0，1 ; L ＝ 1，3-二硫代丙二基双（6-叔丁基-4-甲基苯酚基）（mtbmp），R ＝ Me，n＝1、2； L ＝ 1，4-二硫代丁二基双（6-叔丁基-4-基）甲基苯酚）（etbmp），R = Me中，ñ = 0，3 ; L = etbbp，R = CH 2森达3，ñ = 0，4 ; L = 1,4- dithiabutanediylbis 4,6-二（2- -苯基-2-丙基）苯酚基}（etccp），R = CH 2 SiMe 3，Ñ = 0，5）从三氯化铟或从相应的三（烷基）配合物和四齿1的1个当量，ω-dithiaalkanediyl桥连双（酚）LH制备2。烷基铟配合物的单体性质通过配合物[I
• A binaphtolate titanium complex featuring a linear tetradentate [OSSO]-bis(phenolato) ligand: Synthesis and partial hydrolysis to a homochiral dinuclear complex
  作者：Geert-Jan M. Meppelder、Thomas P. Spaniol、Jun Okuda

  DOI：10.1016/j.jorganchem.2006.02.006

  日期：2006.7

  Reaction of [(R)-C20H12O2}Ti((OPr)-Pr-i)(2)] with 1,4-dithiaalkanediyl-2,2'-bis(6- tert-butyl-4-methyl-phenol) affords the chiral-at-metal complex [(R)-C20H12O2} Ti(C6H2O-'Bu-6-Me-4)(2)S(CH2)(2)S}] (1) in low diastereomeric excess. Complex I can be partially hydrolyzed to give a dinuclear species [mu-(R)-C20H12O2}-mu-O-(Lambda)-Ti[(C6H2O-Bu-t-6-Me-4)(2)S(CH2)(2)S]}(2)] (2), in which the two titanium centers are homochiral. The molecular structure of 1 and 2 was confirmed by single crystal X-ray analysis, which shows C-2-symmetry in both complexes. (c) 2006 Elsevier B.V. All rights reserved.