<2-D>pyridine N-oxide | 22527-04-4

• 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: <2-D>pyridine N-oxide
• 英文别名: 2-deuteropyridine N-oxide；pyridine-2-d N-oxide；Pyridin-2D1-N-oxid；Pyridin-2D-N-oxid；2-Deuterio-1-oxidopyridin-1-ium
• CAS: 22527-04-4
• 化学式: C₅H₅NO
• 分子量: 96.0929
• InChiKey: ILVXOBCQQYKLDS-QYKNYGDISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.2
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  25.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  <2-D>pyridine N-oxide 在 氨 、 sodium amide 作用下， 生成 吡啶-N-氧化物
  参考文献：
  名称：

  摘要：

  The kinetic isotope effects in deuterium and tritium exchange in benzene, fluorobenzene, pyridine, pyridine N-oxide, and quinoline with a solution of an alkali metal amide in liquid ammonia k(D)(NH3)/k(T)(NH3) were determined, where k(D)(NH3) and k(T)(NH3) are the experimental rate constants of protodedeuteration and protodetritiation, respectively. The variation of the tritium exchange rates in benzene in going from NH3 to ND3 (k(T)(NH3) and k(T)(ND3)) was evaluated. The deviation of the observed ratios k(D)(NH3)/k(T)(NH3) and k(H)(ND3)/k(T)(ND3) from the maximum possible values corresponding to the Swan-Shaad equation suggests the reaction mechanism in which both elementary stages, ionization of the CH acid and diffusion separation of the complex of the carbanion with the ammonia molecule, are partially limiting. A small decrease in the secondary isotope effect of the solvent, defined as k(T)(ND3)/k(T)(NH3) as compared to the theoretical maximum of 2.4, is assumed to be due to similar structures of the transition state and the equilibrium carbanion. A theoretical explanation was given for the observed dependences of the primary isotope effect of the substrate on pK(a) for deutero (tritio) derivatives of fluorobenzene [4D(t) < 3D(t) < 2D(t)], for reactions in the series pyridine-2D(t) < pyridine-3D(t) < quinoline3D(t), and for hydrogen exchange in pyridine-2D(t) N-oxide (k(D)(NH3)/k(T)(NH3) similar to 1).

  DOI：

  10.1023/a:1013134511332
• 作为产物：
  描述：

  吡啶-N-氧化物 在 bis(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate 、 重水 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 氯苯 为溶剂， 反应 1.0h， 生成 <2-D>pyridine N-oxide
  参考文献：
  名称：

  定向C ？使用阳离子铑（I）催化剂在C-8位的喹啉N-氧化物的H烯基化

  摘要：

  阳离子铑催化的烯基化反应在喹啉N-氧化物的C-8位置进行。区域选择性的CH键活化是通过N-氧化物部分的阴离子氧的直接作用来实现的，可以通过还原处理很容易地将其除去。以中等至高收率获得了多种8-烯基化的喹啉N-氧化物。

  DOI：

  10.1002/adsc.201400223

文献信息

• Visible-Light-Induced C2 Alkylation of Pyridine <i>N</i>-Oxides
  作者：Wen-Man Zhang、Jian-Jun Dai、Jun Xu、Hua-Jian Xu

  DOI：10.1021/acs.joc.6b02891

  日期：2017.2.17

  A photoredox catalytic method has been developed for the direct C2 alkylation of pyridine N-oxides. This reaction is compatible with a range of synthetically relevant functional groups for providing efficient synthesis of a variety of C2-alkylated pyridine N-oxides under mild conditions. Mechanistic studies are consistent with the generation of a radical intermediate along the reaction pathway.

  已经开发了用于氧化吡啶N-氧化物的直接C 2烷基化的光氧化还原催化方法。该反应与一系列合成相关的官能团相容，以在温和的条件下提供各种C 2-烷基化的吡啶N-氧化物的有效合成。机理研究与沿着反应途径产生自由基中间体是一致的。
• Palladium‐Catalyzed Regioselective Dehydrogenative C–H/C–H Cross‐Coupling of Pyrroles and Pyridine <i>N</i> ‐Oxides
  作者：Shanshan Liu、C. Christoph Tzschucke

  DOI：10.1002/ejoc.201600680

  日期：2016.7

  The palladium-catalyzed cross-dehydrogenative coupling of N-alkylpyrroles and pyridine N-oxides gave the corresponding pyrrolylpyridine N-oxides. Cu(OAc)2·H2O as a co-catalyst with air as the terminal oxidant led to preferential coupling in the β-position, whereas AgOAc as the stoichiometric oxidant resulted in preferential coupling in the α-position. N-(Benzyloxymethyl)pyrrole derivatives were deprotected

  N-烷基吡咯和吡啶N-氧化物的钯催化交叉脱氢偶联得到相应的吡咯基吡啶N-氧化物。Cu(OAc)2·H2O作为助催化剂，空气作为末端氧化剂导致β位优先偶联，而化学计量氧化剂AgOAc导致α位优先偶联。N-(苄氧基甲基)吡咯衍生物通过氢解和碱水解脱保护。
• Photochemistry of pyridine -oxides
  作者：Christian Lohse、Linda Hagedorn、Angelo Albini、Elisa Fasani

  DOI：10.1016/s0040-4020(01)81710-5

  日期：1988.1

  Photolysis of pyridine N-oxide (1a) in aqueous basic solution yields the anion of 5-hydroxypentadienenitrile (2a). Kinetic data are obtained from flash photolytic measurements. The reaction is extended to twenty substituted pyridine N-oxides, including deuterated derivatives, as well as 10 other experimental conditions (amines as the base in organic solvents).

  吡啶N-氧化物（1a）在碱性水溶液中的光解产生5-羟基戊二烯腈（2a）的阴离子。动力学数据是从快速光解测量获得的。反应扩展到二十个取代的吡啶N-氧化物，包括氘代衍生物，以及10个其他实验条件（以胺为有机溶剂中的碱）。
• Preparation and microwave spectra of [18O] pyridine N-oxide and deuterated pyridine N-oxides. Complete molecular structure of pyridine N-oxide
  作者：G.O. Sørensen、Å. Tang-Pedersen、E.J. Pedersen

  DOI：10.1016/0022-2860(83)85020-0

  日期：1983.9

  Abstract [18O] Pyridine N-oxide and the monodeuterated species have been prepared and their microwave spectra investigated for J-values up to 10. The complete rs structure is determined from these data combined with data from earlier measurements on the 13C- and the 13N-substituted species [1]. The NO bond length obtained here is intermediate between the typical single and double bond lengths found

  摘要 [18O] 吡啶 N-氧化物和单氘化物质已经制备出来，并研究了它们的微波光谱，其 J 值高达 10。完整的 rs 结构由这些数据结合早期对 13C- 和 13N 的测量数据确定。 -取代的物种[1]。此处获得的 NO 键长介于其他气相分子结构中的典型单键和双键长度之间。发现吡啶N-氧化物的CNC部分的结构与吡啶结构的相应部分显着不同。
• Direct Dehydrative <i>N</i>-Pyridinylation of Amides
  作者：Jonathan William Medley、Mohammad Movassaghi

  DOI：10.1021/jo802355d

  日期：2009.2.6

  Electrophilic activation of secondary amides with trifluoromethanesulfonic anhydride in the presence of 2-fluoropyridine followed by introduction of a pyridine N-oxide derivative and warming affords the corresponding N-pyridinyl tertiary amide derivatives. A mechanism supported by in situ monitoring and deuterium labeling experiments is discussed.