(6Z)-2-甲基-6-(亚硝基甲基亚基)-1H-吡啶 | 1195-40-0

• 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
• 中文名称: (6Z)-2-甲基-6-(亚硝基甲基亚基)-1H-吡啶
• 中文别名: 2-吡啶甲醛-6-甲基肟
• 英文名称: 6-methyl-2-pyridinecarboxaldehyde oxime
• 英文别名: 6-methyl-2-hydroxyiminomethyl-pyridine；6-methylpyridine-2-carbaldehyde oxime；6-methylpyridin-2-carbaldehyde oxime；6-methylpyridine-2-carbaldehydeoxime；6-methylpicolinaldehyde oxime；6-methylpyridine-2-aldoxime；N-[(6-methylpyridin-2-yl)methylidene]hydroxylamine
• CAS: 1195-40-0
• 化学式: C₇H₈N₂O
• mdl: MFCD04037756
• 分子量: 136.153
• InChiKey: OIKGFMHISSQNRL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.142
• 拓扑面积：
  45.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (6Z)-2-甲基-6-(亚硝基甲基亚基)-1H-吡啶 在 Oxone 、 sodium hexamethyldisilazane 、 乙酸酐 、 碳酸氢钠 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 水 、 异丙醇 、 甲苯 为溶剂， 反应 64.5h， 生成 2-methyl-6-(1-(4-(methylsulfonyl)phenyl)-4-(trifluoromethyl)-1H-imidazol-2-yl)-pyridine
  参考文献：
  名称：

  Selective Cyclooxygenase-2 Inhibitors:  Heteroaryl Modified 1,2-Diarylimidazoles Are Potent, Orally Active Antiinflammatory Agents

  摘要：

  A series of heteroaryl modified 1,2-diarylimidazoles has been synthesized and found to be potent and highly selective (1000-9000-fold) inhibitors of the human COX-2. 3-Pyridyl derived COX-2 selective inhibitor (25) exhibited excellent activity in acute (carrageenan induced paw edema, ED50 = 5.4 mg/kg) and chronic (adjuvant induced arthritis, ED50 = 0.25 mg/kg) models of inflammation. The relatively long half-life of 25 in rat and dog prompted investigation of the pyridyl and other heteroaromatic systems containing potential metabolic functionalities. A number of substituted pyridyl and thiazole containing compounds (e.g., 44, 46, 54, 76, and 78) demonstrated excellent oral activity in every efficacy model evaluated. Several orally active diarylimidazoles exhibited desirable pharmacokinetics profiles and showed no CI toxicity in the rat up to 100 mg/kg in both acute and chronic models. The paper describes facile and practical syntheses of the targeted diarylimidazoles. The structure-activity relationships and antiinflammatory properties of a series of diarylimidazoles are discussed.

  DOI：

  10.1021/jm0000719
• 作为产物：
  描述：

  6-甲基-2-吡啶甲醛 在 盐酸羟胺 、 sodium acetate 作用下， 以 乙醇 、 水 为溶剂， 生成 (6Z)-2-甲基-6-(亚硝基甲基亚基)-1H-吡啶
  参考文献：
  名称：

  6-甲基吡啶-2-甲醛肟在羧酸镍（ii）化学中的应用：五和六核配合物的合成，结构和磁性†

  摘要：

  指某东西的用途 6-甲基吡啶-2-甲醛已研究了镍（II）化学中的配体（6-mepaoH），并在温和条件下分离了三个新簇。根据金属原料盐的性质和反应条件，Ni II / 6-mepaoH系统提供了对络合物[Ni 6（O 2 CPh）6（6-mepao）6 ]（1），[Ni 6（O 2 CMe）6（6-mepao）6 ]（2）和[Ni 5（3-Cl-BzO）4（6-mepao）4（6-mepaoH）2（N 3）2 ]（3），其中3-CL-BZO -是3-氯阴离子。化合物1和2是六核配合物[Ni 6（O 2 C-R）（oximato）6 ]家族的两个新成员，而化合物3则表现出不寻常的不规则领结拓扑，包括末端叠氮基桥。三种化合物的结构已通过单晶X射线晶体学确定。进行了1-3温度可变的直流磁化率研究。数据表明配合物1和2的反铁磁交换和配合物3的亚铁磁相互作用。

  DOI：

  10.1039/c1dt10657k

文献信息

• Nanocrystalline CeO₂ as a Highly Active and Selective Catalyst for the Dehydration of Aldoximes to Nitriles and One-Pot Synthesis of Amides and Esters
  作者：Anastasia Rapeyko、Maria J. Climent、Avelino Corma、Patricia Concepción、Sara Iborra

  DOI：10.1021/acscatal.6b00272

  日期：2016.7.1

  The dehydration of aldoximes into nitriles has been performed in the presence of various metal oxides with different acid–base properties (Al2O3, TiO2, CeO2, MgO). The results showed that a nanocrystalline CeO2 was the most active catalyst. An in situ IR spectroscopy study supports a polar elimination mechanism in the dehydration of aldoxime on metal oxide catalysts, in which Lewis acid sites and basic

  在具有不同酸碱性质的各种金属氧化物（Al 2 O 3，TiO 2，CeO 2， MgO）存在下，醛肟肟脱水成腈。结果表明，纳米晶CeO 2是活性最高的催化剂。原位红外光谱研究支持醛肟在金属氧化物催化剂上脱水的极性消除机制，其中涉及路易斯酸位和碱性位。路易斯酸位点干预肟在催化剂表面的吸附，而表面碱位点负责C1-H键的裂解。因此，纳米晶CeO 2的酸碱性质负责高催化活性和选择性。使用纳米级二氧化铈以良好的收率（80-97％）将各种醛肟（包括烷基醛和环烷基醛肟）脱水成相应的腈，从而得到稳定且可重复使用的催化剂。另外，已经表明，使用纳米二氧化铈作为催化剂，通过一锅法可以从2-吡啶并肟中以高收率获得各种药理上重要的产物，例如吡啶甲酸酰胺和吡啶甲酸烷基酯衍生物。
• Examination of cobalt, nickel, copper and zinc(ii) complex geometry and binding affinity in aqueous media using simple pyridylsulfonamide ligandsElectronic supplementary information (ESI) available: experimental details for [M(L2)2], [M(L3)2] and [M(L4)2] (M = Zn, Cu, Ni, Co); species distribution plots. See http://www.rsc.org/suppdata/nj/b2/b206279h/
  作者：Aileen Congreve、Ritu Kataky、Mark Knell、David Parker、Horst Puschmann、Kanthi Senanayake、Lisa Wylie

  DOI：10.1039/b206279h

  日期：2003.1.8

  The sixteen neutral ML2 complexes of Co, Ni, Cu and Zn(II) with the p-toluenesulfonamide and trifluoromethylsulfonamide derivatives of 2-aminomethylpyridine (L1, L2) and its 6-Me homologue (L3, L4) have been characterised by low temperature X-ray crystallography (100–120 K). Complexes of Co and Zn invariantly adopted a distorted tetrahedral geometry and whilst Cu(II) complexes of L2, L3 and L4 also took up a distorted tetrahedral geometry, that with L1 was square planar. A database survey of the distortion from limiting tetrahedral/square planar geometry has been carried out, aided by a simple geometric analysis. The trifluoromethylsulfonamide ligands (L2 and L3) were less basic, e.g. log K1 7.51(3) for L2vs. 12.23(6) for L1 (80% MeOH/H2O) and afforded a weaker ligand field, exemplified by the position of the visible d–d transition in Cu(II) complexes and the ease of reduction of the Cu(II) centre: E1//2 values (MeCN vs. Ag/AgCl) are −430, −137, +55 and −240 mV for Cu(L1)2, Cu(L2)2, Cu(L3)2 and Cu(L4)2. Ligand protonation and stepwise formation constants have been measured for L1–L3 and derived species distribution diagrams reveal that for complexes with L2 and L3, the predominant species present at pH 7.4 when zinc was in the nanomolar range was ZnL2.

  使用低温度X射线晶体学(100-120 K)对16种Co, Ni, Cu和Zn(II)与p-甲苯磺酰胺和三氟甲基磺酰胺衍生物的2-氨基甲基吡啶(L1, L2)及其6-甲基类似物(L3, L4)的中性ML2络合物进行了表征。Co和Zn络合物的结构恒定为扭曲四面体几何结构,而Cu(II)络合物的L2, L3和L4也采用扭曲四面体几何结构,但与L1的络合物则是四方平面结构。利用简单的几何分析辅助,对偏离极限四面体/四方平面几何结构的扭曲进行了数据库调查。三氟甲基磺酰胺配体(L2和L3)的碱性较弱,例如L2的log K1值为7.51(3),而L1为12.23(6)(80%MeOH/H2O),并且产生了更弱的配体场,例如Cu(II)络合物中可见d-d跃迁的位置和Cu(II)中心还原的容易程度:E1//2值(MeCN vs. Ag/AgCl)分别为-430, -137, +55和-240 mV用于Cu(L1)2, Cu(L2)2, Cu(L3)2和Cu(L4)2。对L1-L3及其衍生物种的配体质子化和逐步生成常数进行了测量,所得物种分布图揭示,对于L2和L3的络合物,当锌浓度为纳摩尔范围时,pH 7.4下存在的主要物种是ZnL2。
• Prediction of Catalyst and Substrate Performance in the Enantioselective Propargylation of Aliphatic Ketones by a Multidimensional Model of Steric Effects
  作者：Kaid C. Harper、Sarah C. Vilardi、Matthew S. Sigman

  DOI：10.1021/ja4001807

  日期：2013.2.20

  The effectiveness of a new asymmetric catalytic methodology is often weighed by the number of diverse substrates that undergo reaction with high enantioselectivity. Here we report a study that correlates substrate and ligand steric effects to enantioselectivity for the propargylation of aliphatic ketones. The mathematical model is shown to be highly predictive when applied to substrate/catalyst combinations

  新的不对称催化方法的有效性通常取决于以高对映选择性进行反应的不同底物的数量。在这里，我们报告了一项研究，该研究将底物和配体空间效应与脂肪族酮丙炔化的对映选择性相关联。当应用于训练集之外的底物/催化剂组合时，该数学模型显示出高度预测性。
• Optimized strategies to synthesize β-cyclodextrin-oxime conjugates as a new generation of organophosphate scavengers
  作者：Romain Le Provost、Timo Wille、Ludivine Louise、Nicolas Masurier、Susanne Müller、Georg Reiter、Pierre-Yves Renard、Olivier Lafont、Franz Worek、François Estour

  DOI：10.1039/c0ob00931h

  日期：——

  A new generation of organophosphate (OP) scavengers was obtained by synthesis of β-cyclodextrin-oxime derivatives 8–12. Selective monosubstitution of β-cyclodextrin was the main difficulty in order to access these compounds, because reaction onto the oligosaccharide was closely related to the nature of the incoming group. For this purpose, non-conventional activation conditions were also evaluated. Intermediates 5 and 7 were then obtained with the better yields under ultrasounds irradiation. Finally, the desired compounds 8–10 were obtained from 5–7 in high purity by desilylation using potassium fluoride. Quaternarisation of compounds 8 and 9 was carried out. OP hydrolytic activity of compounds 8–12 was evaluated against cyclosarin (GF) and VX. None of the tested compounds was active against VX, but these five cyclodextrin derivatives detoxified GF, and the most active scavengers 10 and 11 allowed an almost complete hydrolysis of GF within 10 min. Even more fascinating is the fact that compounds 9 and 10 were able to hydrolyze enantioselectively GF.

  通过合成δ²-环糊精-肟衍生物 8â12 获得了新一代有机磷（OP）清除剂。δ-环糊精的选择性单取代是获得这些化合物的主要困难，因为与寡糖的反应与进入基团的性质密切相关。为此，我们还对非常规活化条件进行了评估。在超声波照射下，中间体 5 和 7 得到了较好的产率。最后，通过使用氟化钾进行脱硅处理，从 5â7 得到了高纯度的所需化合物 8â10 。对化合物 8 和 9 进行了季铵化处理。评估了化合物 8â12 针对环沙林（GF）和 VX 的 OP水解活性。所测试的化合物中没有一种对 VX 具有活性，但这五种环糊精衍生物对 GF 具有解毒作用，其中活性最高的清除剂 10 和 11 几乎能在 10 分钟内完全水解 GF。更令人着迷的是，化合物 9 和 10 能够对映选择性地水解 GF。
• The synthesis and magnetic and spectral studies of some lanthanide(III) chelates of 6-methyl pyridine-2-aldoxime
  作者：M. Mohan、J.P. Tandon、N.S. Gupta

  DOI：10.1016/0022-1902(81)80021-8

  日期：1981.1

  A series of trivalent lanthanide chelates of the type [Ln(HMPOX)3(X)2](X) (where Ln3+ = La, Pr, Nd, Sm, Gd or Dy; HMPOX = 6-methylpyridine-2-aldoxime and X− = NO3 or Cl) have been synthesised by the direct reaction of 6-methylpyridine-2-aldoxime with lanthanide(III) nitrates or chlorides in 2,2′-dimethoxypropane and ethanol. These chelates have been characterized by analysis, molar conductance, X-ray

  [Ln（HMPOX）3（X）2 ]（X）类型的一系列三价镧系元素螯合物（其中Ln 3+ = La，Pr，Nd，Sm，Gd或Dy； HMPOX = 6-甲基吡啶-2-醛肟并且X − = NO 3或Cl）是通过6-甲基吡啶-2-醛肟与硝酸镧或氯化镧（III）在2,2'-二甲氧基丙烷和乙醇中的直接反应合成的。这些螯合物的特征在于分析，摩尔电导，X射线粉末衍射图，磁，电和振动光谱研究。分析数据表明，化学计量比为1：3（金属：配体），乙醇中的摩尔电导数据表明所有镧系元素（III）螯合物中的1：1电解质。具有HMPOX的镧系元素（III）螯合物是X射线同构的。磁矩值与Van Vleck值几乎没有偏差。在室温下在甲醇中记录的电子光谱受配体吸收带的支配，并且仅显示出轻微的偏移并显着增强了带的强度。红外光谱数据表明中性HMPOX配体分子通过吡啶氮和肟基团氮原子的顺式配位，以及硝酸根与所有镧系元素（III）螯合物的单齿硝酸盐配位。