N-(2,6-dimethylphenyl)-1-(pyridin-2-yl)ethan-1-imine | 270928-26-2

• 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: N-(2,6-dimethylphenyl)-1-(pyridin-2-yl)ethan-1-imine
• 英文别名: N-(2,6-dimethylphenyl)-1-pyridin-2-ylethanimine
• CAS: 270928-26-2
• 化学式: C₁₅H₁₆N₂
• 分子量: 224.305
• InChiKey: ZKDUUTZTRMFWEO-UHFFFAOYSA-N

物化性质

• 沸点：
  354.9±42.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  25.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(2,6-dimethylphenyl)-1-(pyridin-2-yl)ethan-1-imine 在 lithium hexamethyldisilazane 作用下， 以 氘代四氢呋喃 、 正己烷 为溶剂， 反应 24.0h， 生成 {κ-N,N-N(C₆H₃(2-Me)CH₂C(Me)(2-py))}Li
  参考文献：
  名称：

  第一行过渡金属和锂吡啶-烯-酰胺络合物，具有N-和C-异构体以及基于苄基CH键的配体活化

  摘要：

  Ene-amines Z-3-(2-pyridyl)-1-aza(2,6-Pr-i(2)-Ph)propene, (pynac)H, and 2-(2-pyridy1)-1-aza(2,6-R,R'-Ph)propene, (pyEA-ArRR')H, were synthesized by condensation procedures; corresponding lithium or potassium ene-amides were prepared via standard deprotonation protocols. Addition of 2 equiv of (pynac)H to {(Me3Si)(2)N}(2)Fe(THF) or 2 Li(pynac) to FeBr2(THF)(2) afforded (pynac)(2)Fe (1), while treatment of CrCl2(THE)(2), MnCl2, FeBr2(THF)(2), and CoCl(2)py(4) with 2 equiv of (pyEA-(ArPr2)-Pr-i)K afforded pseudotetrahedral (pyEA-(ArPr2)-Pr-i)(2)M (2-M, M = Cr, Mn, Fe) and (pyEA-(ArPr2)-Pr-i)(2)Co-py (2-Co-py). Diamagnetic (kappa-C,N-pyEA-(ArPr2)-Pr-i)(3)Co (3) was prepared in low yield (similar to 7%) from CoCl2, and its Co-C(sp(3)) linkages are unusually low in field strength. Reactivity studies yielded little clean reactivity, but thermolysis of 2-Co-py afforded the bis-indolamide derivative -{kappa-N,N-N(C6H3(2-Pr-i)CMe2C(Me)(2-py)}(2)Co (5-Co), and related thermolyses of 2-M (M = Cr, Mn, Fe), conducted on NMA. tube scales, generated related 5-M (M = Cr, Mn, Fe) at roughly the same rates. This observation prompted thermolyses of (pyEA-ArRR')Li, which rearrange to their corresponding indolamides in >90% yields. Rate studies, accompanied by KLE and EIE observations, revealed that an initial hydrogen transfer is reversible and is likely to correspond to an anionic rearrangement, whereas C-C bond formation is rate-determining, as suggested by accompanying calculations. X-ray structure determinations of 1, 2-Fe, 2-Co-py, 3, and 5-Co were conducted.

  DOI：

  10.1021/acs.organomet.5b00385
• 作为产物：
  描述：

  2-乙酰基吡啶 、 2,6-二甲基苯胺 以 乙醇 为溶剂， 生成 N-(2,6-dimethylphenyl)-1-(pyridin-2-yl)ethan-1-imine
  参考文献：
  名称：

  阳离子双（吡啶并嘧啶）钴（II）配合物的合成，表征和晶体结构

  摘要：

  摘要配体2,6-二甲基-N-（吡啶-2-基亚甲基）苯胺C14H14N2（L1），2,6-二甲基-N-（1-（吡啶-2-基）亚乙基）苯胺C15H16N2（L2）和2通过缩合反应获得了6-6-异丙基-N-（1-（吡啶-2-基）亚乙基）苯胺C19H24N2（L3）。CoCl2·6H2O与相应的配体L1-L3在新的盐甲氧基三（二甲基氨基）六氟磷酸phosphate [CH3OP（NMe2）3] + PF6-的存在下反应，收率很高，双[2,6-二甲基]络合物-N-（吡啶-2-基亚甲基）苯胺]六氟磷酸钴（II）C28H28ClCoF6N4P（C1），双[2,6-二甲基-N-（1-（吡啶-2-基）亚乙基）苯胺]苯胺]氯钴（II ）六氟磷酸盐C30H32ClCoF6N4P（C2）和双-[2,6-二异丙基-N-（1-（吡啶-2-基）亚乙基）苯胺]六氟磷酸钴（II）C38H48ClCoF6N4P（C3）。所有

  DOI：

  10.1016/j.ica.2014.12.019

文献信息

• Alternating ethylene-norbornene copolymerization catalyzed by cationic organopalladium complexes bearing hemilabile bidentate ligands of α-amino-pyridines
  作者：Ya-Chi Lin、Kuo-Hsuan Yu、Shou-Ling Huang、Yi-Hung Liu、Yu Wang、Shiuh-Tzung Liu、Jwu-Ting Chen

  DOI：10.1039/b912068h

  日期：——

  Cationic methylpalladium complexes with hemilabile bidentate ligands of alpha-amino-pyridines, in the form of [R(1)HNCR(2)H(o-C(6)H(5)N)]Pd(Me)(NCMe)}(BF(4)) (R(1) = (i)Pr, (t)Bu, Ar R(2) = H, Me) have been found to be effective precursors for catalytic copolymerization of ethylene and norbornene under mild conditions. The copolymer products exhibit predominant alternating microstructures which are

  阳离子甲基钯配合物与[R（1）HNCR（2）H（oC（6）H（5）N）] Pd（Me）（NCMe）}（ BF（4））（R（1）=（i）Pr，（t）Bu，Ar R（2）= H，Me）被发现是在温和条件下乙烯和降冰片烯催化共聚的有效前体。共聚物产物显示出主要的交替微观结构，这通过NMR和质谱以及根据Finman-Ross关系的动力学分析证明。
• Bis-alkoxycarbonylation of styrene by pyridinimine palladium catalysts
  作者：Claudio Bianchini、Hon Man Lee、Giuseppe Mantovani、Andrea Meli、Werner Oberhauser

  DOI：10.1039/b108804c

  日期：2002.4.2

  Pyridinimine-modified Pd(II) complexes of general formulae (N-N′)Pd(Y)2 catalyze the methoxycarbonylation of styrene to give dimethyl phenylsuccinate as the largely major product [N-N′ = py-2-C(R)N(2,6-R′C6H3), R = H, Me; R′ = Me, i-Pr; 6-Mepy-2-C(H)N[2,6-(i-Pr)2C6H3]; py-2-C(H)N(C6H5); Y = acetate, trifluoroacetate]. The influence of various catalytic parameters on the overall conversion of styrene to carbonylated products and on the product selectivity has been studied by systematically varying the type of palladium initiator, the concentrations of organic oxidant (1,4-benzoquinone) and protic acid (p-toluenesulfonic acid), and the CO pressure. By an appropriate choice of the structure of the pyridinimine ligand and of the reaction parameters, turn-over numbers as high as 96 and selectivities in dimethyl phenylsuccinate as high as 98% were obtained. In particular, the overall conversion of styrene is controlled by the steric properties of the alkyl substituents on the imine aryl group, while the nature of the substituent (H or Me) on the imine carbon influences the selectivity. The addition of 2 equivalents of TsOH to the catalytic mixtures generally increased the styrene conversion but lowered the selectivity in dimethyl phenylsuccinate due to greater production of methyl 3,6-diphenyl-4-oxohexanoate. Further additions of TsOH (up to 6 equivalents) resulted in better selectivities and lower conversions for all precursors.

  一般公式为 (N-N′)Pd(Y)2 的吡啶亚胺修饰的 Pd(II)配合物催化苯乙烯甲氧羰基化生成二甲基苯基琥珀酸酯作为主要产物 [N-N′= 吡啶-2-C(R)N(2,6-R′C6H3), R= H, Me; R′= Me, i-Pr; 6-Mepy-2-C(H)N[2,6-(i-Pr)2C6H3]; 吡啶-2-C(H)N(C6H5); Y= 乙酸酯, 三氟乙酸酯]。通过系统改变钯引发剂类型、有机氧化剂(1,4-苯醌)和质子酸(对甲苯磺酸)的浓度以及 CO 压力,研究了各种催化参数对苯乙烯转化成羰基化产物及其产物选择性的影响。通过适当选择吡啶亚胺配体的结构和反应参数,获得了高达 96 的转换数和高达 98%的二甲基苯基琥珀酸酯选择性。特别是苯乙烯的总体转化受亚胺芳基上烷基取代基的立体性质控制,而亚胺碳上的取代基(H 或 Me)的性质影响选择性。向催化混合物中加入 2 当量的 TsOH 通常会增加苯乙烯的转化率,但由于甲基 3,6-二苯基-4-氧代己酸酯的产量增加,降低了二甲基苯基琥珀酸酯的选择性。进一步添加 TsOH(高达 6 当量)使所有前体的选择性更好,转化率更低。
• Synthesis, structures of (aminopyridine)nickel complexes and their use for catalytic ethylene polymerization
  作者：Ya-Chi Lin、Kuo-Hsuan Yu、Ya-Fan Lin、Gene-Hsiang Lee、Yu Wang、Shiuh-Tzung Liu、Jwu-Ting Chen

  DOI：10.1039/c2dt30151b

  日期：——

  A series of α-aminopyridines in the form of (2,6-C6H3N)(R1)(CHR2NR3R4) (R1 = R2 = H R3 = H R4 = iPr (L1a), R4 = tBu (L1b), R4 = Ph (L1c), R4 = 2,6-Me2C6H3 (L1d), R4 = 2,6-iPr2C6H3 (L1e), R1 = R2 = H R3 = R4 = Et (L1f), R1 = H R2 = Me R3 = H R4 = iPr (L2a), R4 = Ph (L2c), R4 = 2,6-Me2C6H3 (L2d), R4 = 2,6-iPr2C6H3 (L2e), R1 = Me R2 = H R3 = H R4 = 2,6-iPr2C6H3 (L3e)) and β-aminopyridines in the form of (2-C6H4N)(CH2CH2NR1R2) (R1 = H R2 = iPr (4a), R2 = tBu (L4b), R1 = R2 = Et (L4f)) have been prepared. Their corresponding halonickel complexes 1a–4f are synthesized by ligand substitution from (DME)NiBr2 and the molecular structures are characterized. Four types of coordination modes include four-coordinate mononuclear species with one ligand, five-coordinate mononuclear species with two ligands, five-coordinate dinuclear species with two ligands, and a six-coordinate polymeric framework were determined by X-ray crystallography. Using methylaluminoxanes (MAO) as the activator, the nickel complexes can catalyze ethylene polymerization under moderate pressure and ambient temperature. The activity reaches 105 g PE mol−1 Ni h. The PE products with high branching and high crystallinity have Mn ∼ 103 with PDI < 2.

  一系列α-氨基吡啶类化合物(2,6-C6H3N)(R1)(CHR2NR3R4)(R1 = R2 = H, R3 = H, R4 = iPr (L1a), R4 = tBu (L1b), R4 = Ph (L1c), R4 = 2,6-Me2C6H3 (L1d), R4 = 2,6-iPr2C6H3 (L1e), R1 = R2 = H, R3 = R4 = Et (L1f), R1 = H, R2 = Me, R3 = H, R4 = iPr (L2a), R4 = Ph (L2c), R4 = 2,6-Me2C6H3 (L2d), R4 = 2,6-iPr2C6H3 (L2e), R1 = Me, R2 = H, R3 = H, R4 = 2,6-iPr2C6H3 (L3e))和β-氨基吡啶类化合物(2-C6H4N)(CH2CH2NR1R2)(R1 = H, R2 = iPr (4a), R2 = tBu (L4b), R1 = R2 = Et (L4f))已被合成。通过配体取代反应从(DME)NiBr2合成相应的卤化镍配合物1a–4f,并由X射线晶体学表征其分子结构。通过X射线结晶学确定了四种配位模式,包括单核四配位物种与一个配体、单核五配位物种与两个配体、双核五配位物种与两个配体以及六配位的聚合框架。使用甲基铝氧烷(MAO)作为活化剂,镍配合物可以在中等压力和室温下催化乙烯聚合。活性达到105 g PE mol−1 Ni h。具有高度支化和高度结晶性的PE产品,Mn ∼ 103,PDI < 2。
• Synthesis and X-ray Crystal Structures of Zinc Complexes Supported by Chelating Ligands: Various Reactions of α-Iminopyridines with ZnEt₂
  作者：Haimang Wang、Zhiqiang Guo、Jihong Yang、Wei Cao、Yupeng Hua、Xuehong Wei、Jianfeng Li

  DOI：10.1002/zaac.201800120

  日期：2018.7.17

  redox‐noninnocent ligand. The substituents on the imino function of α‐IPs have important impact on the reaction selectivity with diethylzinc. For the α‐IPs with a hydrogen substituent on the imino carbon, reduction occurred for the non‐bulky N‐substituents phenyl and 2‐methylphenyl groups, whereas alkyl addition and coupling reactions can be selectively achieved for the sterically bulky N‐substituents 2,6‐dimethylphenyl

  α‐氨基吡啶（α‐IP）是重要的氧化还原非清纯配体。α-IP的亚氨基官能团上的取代基对与二乙基锌的反应选择性有重要影响。对于亚氨基碳上具有氢取代基的α-IPs，非大体积N-取代基苯基和2-甲基苯基的还原反应发生，而空间较大的N-取代基2可以选择性地实现烷基加成和偶联反应2。 6-二甲基苯基或2,4,6-三甲基苯基。但是，对于亚氨基碳上具有CH 3取代基的α-IP，无论N为何，都会发生去质子化反应2-甲基苯基或2,6-二甲基苯基的取代基。所有产品均经过分离，并通过单晶X射线衍射进行表征。还讨论了这些反应的可能机理。
• Highly Active Iminopyridyl Iron-Based Catalysts for the Polymerization of Isoprene
  作者：Obaid H. Hashmi、Yohan Champouret、Marc Visseaux

  DOI：10.3390/molecules24173024

  日期：——

  (II) complexes were developed to investigate their application in the controlled coordinative polymerization of isoprene. The modulation of steric and electronic properties within this family of ligands/pre-catalysts has shown to influence the stereo-selectivity and activity of the polymerization of isoprene after activation. Upon activation with various co-catalysts such as AliBu3/[Ph3C][B(C6F5)4],

  500 h-1) 并具有各种立体/区域规则。在异戊二烯聚合过程中，给电子和吸电子基团的存在极大地影响了催化剂的活性和立体选择性。当用 AliBu3/[Ph3C][B(C6F5)4] 激活时，配合物 6-[(2,6-Me2-C6H3)N=C(Me)]-2-C6H5N}FeCl2 (C1) 和 6 -[(2,6-iPr2-C6H3)N=C(Me)]-2-C6H5N}FeCl2 (C2) 表现出中等的 trans-1,4 选择性 (>67%) 而带有相关醛亚氨基吡啶配体的铁基系统6-[(2,6-Me2-C6H3)N=C(H)]-2-C6H5N}FeCl2 (C3) 和 6-[(2,6-iPr2-C6H3)N=C(H)] -2-C6H5N}FeCl2 (C4) 被发现在低温下（-40 °C 时 >86%）具有显着的 cis-1,4 选择性。另一方面，三元 6-[(3,