6-(1-methylbenzene)-2-(2'-pyridyl)pyridine | 185610-09-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 6-(1-methylbenzene)-2-(2'-pyridyl)pyridine
• 英文别名: 6-(α-methylbenzyl)-2,2'-bipyridine；6-(1-methylbenzyl)-2,2'-bipyridine；6-(1-phenylethyl)-2,2'-bipyridine；2-(1-phenylethyl)-6-pyridin-2-ylpyridine
• CAS: 185610-09-7
• 化学式: C₁₈H₁₆N₂
• 分子量: 260.338
• InChiKey: VCHQCURBUZHHBU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  6-(1-methylbenzene)-2-(2'-pyridyl)pyridine 以 水 、 丙酮 、 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Synthesis and characterization of gold(III) adducts and cyclometallated derivatives with 6-benzyl- and 6-alkyl-2,2′-bipyridines

  摘要：

  The reaction of a series of 6-substituted-2,2'-bipyridines HL (N(2)C(10)H(7)R, R = CH(2)Ph, CHMePh, CMe(2)Ph, CH(2)Me, CMe(3) or CH(2)CMe(3)) with HAuCl4 or Na[AuCl4] has been investigated. Under different experimental conditions, salts [H(2)L][AuCl4], adducts [Au(HL)Cl-3] or cyclometallated derivatives [Au(L)Cl][X] (X = AuCl4, BF4 or PF6) have been isolated. The cyclometallated species arise from direct activation of a C-H bond either of a phenyl or a methyl substituent. The structures of an adduct [Au{N2C10H7(CHMePh)-6}Cl-3] and two metallated species [Au{N2C10H7(CMe(2)C(6)H(4))-6}Cl][AuCl4] and [Au{N2C10H7(CMe(2)CH(2))-6}Cl][BF4] . 0.5H(2)O have been determined by X-ray diffraction. In the adduct the gold atom is bonded to the nitrogen atom of the unsubstituted pyridine ring: a long-range interaction with the other nitrogen atom is observed, Au ... N 2.758(4) Angstrom. In the two cyclometallated species the bipyridines act as tridentate N,N,C anions, giving a [5,6] and a [5,5]-fused ring system, respectively. In [Au{N2C10H7(CMe(2)C(6)H4)-6}Cl](+) the hexaatomic N,C ring adopts a boat-like conformation: the structure reveals a rather short interaction between one hydrogen of the Me group in axial position and the gold atom, Au ... H2.62 Angstrom. The pentaatomic N,C ring in [Au{N2C10H7(CMe(2)CH(2))-6}Cl](+) is not planar: the co-ordination around the gold atom is essentially square planar. The new cyclometallated complexes [Au(N,N,C)Cl](+) are compared with those derived from similarly substituted pyridines described previously.

  DOI：

  10.1039/dt9960004217
• 作为产物：
  描述：

  (1-溴乙基)苯 在 palladium bis[bis(diphenylphosphino)ferrocene] dichloride 、 1,2-二溴乙烷 、 lithium chloride 作用下， 以 四氢呋喃 为溶剂， 反应 19.66h， 生成 6-(1-methylbenzene)-2-(2'-pyridyl)pyridine
  参考文献：
  名称：

  铂（II）选择性激活sp2 / sp3或乙烯基/芳基碳氢键的计算和实验研究：异构环戊铂化合物的几何形状和相对稳定性

  摘要：

  Cyclometalating ligands 6-(1-phenylethyl)-2,2'-bipyridine (L4), 6-(1-phenylvinyl)-2,2'-bipyridine (LS), and 6-(prop-1-en-2-yl)-2,2'-bipyridine (L6) were synthesized by the Negishi coupling of 6-bromo-2,2'-bipyridine with the corresponding organo-zinc reagents. The reaction of L4 with K2PtCl4 produced only the cycloplatinated compound 4a via sp(2) C-H bond activation. The reactions of L5 and L6 produced exclusively the cycloplatinated compounds 5b and 6a, respectively, via vinylic C-H bond activation. DFT calculations were performed on 12 possible cycloplatination products from the reaction of N-alkyl-N-phenyl-'2,2'-bipyridin-6-amine (alkyl = methyl (L1), ethyl (L2), and isopropyl (L3)) and L4 L6. The results show that compounds 1b-3b resulting from the sp(3) C-H bond activation of L1-L3 are thermodynamic products, and their relative stability is attributed to the planar geometry that allows for a better conjugation. Similar reasoning also applies to the stability of products from vinylic C-H bond activation of L5 and L6. The relative stability of isomeric cycloplatinated compounds 4a and 4b may be due to the different strengths of C-Pt bonds. The steric interaction is the major cause of severe distortion from a planar coordination geometry in the cycloplatinated compounds, which leads to instability of the corresponding cyclometalated products and a higher kinetic barrier for C-H bond activation.

  DOI：

  10.1021/acs.organomet.5b00326

文献信息

• Optically active nitrogen ligans
  作者：C. Botteghi、C. Chelucci、G. Chessa、G. Delogu、S. Gladiali、F. Soccolini

  DOI：10.1016/s0022-328x(00)99687-6

  日期：1986.4

  The reduction of acetophenone by hydrogen transfer from isopropranol is catalyzed by rhodium(I) complexes containing optically active 2-(2′-pyridyl)pyridines. Optical yields up to 15% have been obtained.

  含光学活性的2-（2'-吡啶基）吡啶的铑（I）配合物可催化从异丙醇中氢转移引起的苯乙酮还原。已获得高达15％的光学产率。
• Palladium(II) and platinum(II) derivatives with chiral 2,2′-bipyridines. X-ray structure of C18H15ClN2Pd; C- and N-intramolecular coordination in a six-membered metallacycle
  作者：Giovanni Minghetti、Maria A. Cinellu、Giorgio Chelucci、Serafino Gladiali、Francesco Demartin、Mario Manassero

  DOI：10.1016/0022-328x(86)80181-4

  日期：1986.6

  with Na2[PdCl4] and K2[PtCl4] give the 1 : 1 adducts (LH)MCl2 (M = Pd, 1; M = Pt, 2) and the metallated species (L′)MCl (M = Pd, 3; M = Pt, 4), respectively. In complexes 3 and 4, the deprotonated bipyridine behaves as a tridentate ligand; there is coordination to the metal through the two nitrogen atoms and the ortho-carbon atom of the phenyl ring to give a six-membered metallacycle. The X-ray structure

  （+）-（S）-5-s，丁基-2,2'-联吡啶（LH）和6-（1-甲基苄基）-2,2'-联吡啶（L'H）与Na 2的反应[ PdCl 4 ]和K 2 [PtCl 4 ]给出1：1加合物（LH）MCl 2（M = Pd，1 ; M = Pt，2）和金属化物质（L'）MCl（M = Pd，3 ; M）。 M = Pt，4）。在配合物3和4中，去质子化的联吡啶表现为三齿配体。通过两个氮原子和邻位金属之间存在配位-苯环的碳原子形成六元金属环。配合物3的X射线结构表明，钯原子周围的配位从通常的正方形平面几何形状向四面体变形。
• Computational and Experimental Study on Selective sp²/sp³ or Vinylic/Aryl Carbon–Hydrogen Bond Activation by Platinum(II): Geometries and Relative Stability of Isomeric Cycloplatinated Compounds
  作者：Yumin Li、Jeffrey Carroll、Bradley Simpkins、Deepak Ravindranathan、Christopher M. Boyd、Shouquan Huo

  DOI：10.1021/acs.organomet.5b00326

  日期：2015.7.13

  Cyclometalating ligands 6-(1-phenylethyl)-2,2'-bipyridine (L4), 6-(1-phenylvinyl)-2,2'-bipyridine (LS), and 6-(prop-1-en-2-yl)-2,2'-bipyridine (L6) were synthesized by the Negishi coupling of 6-bromo-2,2'-bipyridine with the corresponding organo-zinc reagents. The reaction of L4 with K2PtCl4 produced only the cycloplatinated compound 4a via sp(2) C-H bond activation. The reactions of L5 and L6 produced exclusively the cycloplatinated compounds 5b and 6a, respectively, via vinylic C-H bond activation. DFT calculations were performed on 12 possible cycloplatination products from the reaction of N-alkyl-N-phenyl-'2,2'-bipyridin-6-amine (alkyl = methyl (L1), ethyl (L2), and isopropyl (L3)) and L4 L6. The results show that compounds 1b-3b resulting from the sp(3) C-H bond activation of L1-L3 are thermodynamic products, and their relative stability is attributed to the planar geometry that allows for a better conjugation. Similar reasoning also applies to the stability of products from vinylic C-H bond activation of L5 and L6. The relative stability of isomeric cycloplatinated compounds 4a and 4b may be due to the different strengths of C-Pt bonds. The steric interaction is the major cause of severe distortion from a planar coordination geometry in the cycloplatinated compounds, which leads to instability of the corresponding cyclometalated products and a higher kinetic barrier for C-H bond activation.
• Synthesis and characterization of gold(<scp>III</scp>) adducts and cyclometallated derivatives with 6-benzyl- and 6-alkyl-2,2′-bipyridines
  作者：Maria Agostina Cinellu、Antonio Zucca、Sergio Stoccoro、Giovanni Minghetti、Mario Manassero、Mirella Sansoni

  DOI：10.1039/dt9960004217

  日期：——

  The reaction of a series of 6-substituted-2,2'-bipyridines HL (N(2)C(10)H(7)R, R = CH(2)Ph, CHMePh, CMe(2)Ph, CH(2)Me, CMe(3) or CH(2)CMe(3)) with HAuCl4 or Na[AuCl4] has been investigated. Under different experimental conditions, salts [H(2)L][AuCl4], adducts [Au(HL)Cl-3] or cyclometallated derivatives [Au(L)Cl][X] (X = AuCl4, BF4 or PF6) have been isolated. The cyclometallated species arise from direct activation of a C-H bond either of a phenyl or a methyl substituent. The structures of an adduct [AuN2C10H7(CHMePh)-6}Cl-3] and two metallated species [AuN2C10H7(CMe(2)C(6)H(4))-6}Cl][AuCl4] and [AuN2C10H7(CMe(2)CH(2))-6}Cl][BF4] . 0.5H(2)O have been determined by X-ray diffraction. In the adduct the gold atom is bonded to the nitrogen atom of the unsubstituted pyridine ring: a long-range interaction with the other nitrogen atom is observed, Au ... N 2.758(4) Angstrom. In the two cyclometallated species the bipyridines act as tridentate N,N,C anions, giving a [5,6] and a [5,5]-fused ring system, respectively. In [AuN2C10H7(CMe(2)C(6)H4)-6}Cl](+) the hexaatomic N,C ring adopts a boat-like conformation: the structure reveals a rather short interaction between one hydrogen of the Me group in axial position and the gold atom, Au ... H2.62 Angstrom. The pentaatomic N,C ring in [AuN2C10H7(CMe(2)CH(2))-6}Cl](+) is not planar: the co-ordination around the gold atom is essentially square planar. The new cyclometallated complexes [Au(N,N,C)Cl](+) are compared with those derived from similarly substituted pyridines described previously.