N-hydroxypyridine-2(1H)-thione tetraethylammonium salt | 22574-14-7

• 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: N-hydroxypyridine-2(1H)-thione tetraethylammonium salt
• 英文别名: 1-Oxidopyridine-2-thione;tetraethylazanium
• CAS: 22574-14-7
• 化学式: C₅H₄NOS*C₈H₂₀N
• 分子量: 256.412
• InChiKey: ARWJXNZCJAXGMK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.45
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  58.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  toluene-4-sulfonic acid pent-4-enyl ester 、 N-hydroxypyridine-2(1H)-thione tetraethylammonium salt 以 N,N-二甲基甲酰胺 为溶剂， 反应 14.0h， 以31%的产率得到N-(4-Pentenyl-1-oxy)pyridine-2(1H)-thione
  参考文献：
  名称：

  Ring Closure Reactions of Substituted 4-Pentenyl-1-oxy Radicals. The Stereoselective Synthesis of Functionalized Disubstituted Tetrahydrofurans

  摘要：

  N-(Alkyloxy)pyridine-2( VT)-thiones 3 and benzenesulfenic acid O-esters 5 have been synthesized from substituted 4-pentenols 1 or the derived tosylates. Compounds 3 and 5 are efficient sources of free alkoxy radicals 6 which undergo synthetically useful fast ring closure reactions 6 --> 8 [k(exo) = (2 +/- 1) x 10(8) s(-1) to (6 +/- 2) x 10(9) s(-1) (T = 30 +/- 0.2 degrees C)]. Tetrahydrofurfuryl radicals 8 can be trapped with, e.g., hydrogen or chlorine atom donors to afford either trans- or cis-disubstituted tetrahydrofurans 10 or 12 depending on the substitution pattern of the 4-pentenyloxy radical. Substituted tetrahydropyrans 11 or 13 are formed in the minor 6-endo-trig cyclization. According to the data of competition kinetics, the observed stereoselectivities in free alkoxy radical cyclizations arise from steric interactions between the substituents in the transition state of the ring closure reactions. Alkyl substituents cause small differences in the measured relative rate constants of B-exo cyclizations which are reminiscent of the data obtained from the rearrangements of alkyl-substituted 5-hexenyl radicals. Likewise, a stereochemical model for oxygen radical cyclization is proposed where the pentenyloxy chain adopts a six-membered, chairlike transition state with the alkyl substituents preferentially situated in the pseudoequatorial positions leading to 2,5-trans-, 2,4-cis-, and 2,3-trans-substituted tetrahydrofurfuryl radicals 8 as the major intermediates.

  DOI：

  10.1021/jo00126a021
• 作为产物：
  描述：

  1-氧化-2-巯基吡啶 、 四乙基氢氧化铵 以94%的产率得到
  参考文献：
  名称：

  HAY, BENJAMIN P.;BECKWITH, ATHELSTAN L. J., J. ORG. CHEM., 54,(1989) N8, C. 4330-4334

  摘要：

  DOI：

文献信息

• On the SelectiveO-Alkylation of Ambident Nucleophiles – The Synthesis of Thiohydroxamic AcidO-Esters by Phase-Transfer Reactions
  作者：Jens Hartung、Rainer Kneuer、Michaela Schwarz、Ingrid Svoboda、Hartmut Fueß

  DOI：10.1002/(sici)1099-0690(199901)1999:1<97::aid-ejoc97>3.0.co;2-k

  日期：1999.1

  N-(alkoxy)pyridine-2(1H)-thiones and N-(alkoxy)thiazole-2(3H)-thiones. Four issues have been addressed and the following conclusions can be drawn: (i) Thiones 1 and 5 exist as O–H acids in the solid state. (ii) According to NMR investigations (1H, 13C), the thione structures should be largely retained in CDCl3, [D6]DMSO, and CD3OD solutions of acids 1, 3–5, as is also the case for pyridinethione salts 2a–h. (iii)

  已经研究了环硫异羟肟酸 1 和 3-5 的 O-烷基化，以期开发一种合成 N-(烷氧基)吡啶-2(1H)-硫酮和 N-(烷氧基)噻唑-2( 3H)-硫酮。已经解决了四个问题，可以得出以下结论：（i）硫酮 1 和 5 以固态的 O-H 酸存在。(ii) 根据 NMR 研究 (1H, 13C)，硫酮结构应主要保留在酸 1、3-5 的 CDCl3、[D6]DMSO 和 CD3OD 溶液中，吡啶硫酮盐 2a-h 也是如此. (iii) 吡啶硫酮盐的 O-烷基化与 S-烷基化竞争发生。然而，如果在极性非质子介质中用硬烷基化试剂处理具有大抗衡阳离子（例如 M = NBu4）的硫代异羟肟酸盐，则选择性 O-烷基化是可能的。(iv) 作为硫代异羟肟酸四丁基铵，例如 2f，在环硫异羟肟酸 O-酯的合成中非常有用，我们开发了一种使用相转移条件直接从酸 1 制备 N-（烷氧基）吡啶-2（1H）-硫酮的有效方案（
• A Radical Version of the Bromo- and the Iodocyclization of Bis(homoallylic) Alcohols— The Synthesis of Halogenated Tetrahydrofurans by Stereoselective Alkoxyl Radical Ring Closures
  作者：Jens Hartung、Rainer Kneuer、Stefanie Laug、Philipp Schmidt、Kristina Špehar、Ingrid Svoboda、Hartmut Fuess

  DOI：10.1002/ejoc.200300107

  日期：2003.10

  A new synthesis of bromo- and iodomethyl-substituted tetrahydrofurans has been devised. The sequence starts with the conversion of aryl-functionalized bis(homoallylic) alcohols 1 into N-alkenoxythiazole-2(3H)-thiones 6 or pyridine-2(1H)-thiones 7. When photolyzed in the presence of appropriate trapping reagents, thiones 6 and 7 efficiently liberated substituted 4-penten-1-oxyl radicals 2, which underwent

  已经设计了溴和碘甲基取代的四氢呋喃的新合成。该序列从芳基官能化的双（高烯丙基）醇 1 转化为 N-链烯氧基噻唑-2(3H)-硫酮 6 或吡啶-2(1H)-硫酮 7 开始。 6 和 7 有效地释放了取代的 4-penten-1-oxyl 自由基 2，其经历了合成有用的 5-exo-trig 环化。环化自由基 3 被 BrCCl3 或足够的碘原子供体（n-C4F9I 或 2-碘-2-甲基丙二酸二乙酯）捕获，以提供卤环化产物 4 或 5。该策略已应用于合成 3-、4 -, 或 5-苯基取代的 2-(1-溴-1-甲基乙基)四氢呋喃 4a-c (75-90%, 36-96% de)，它们不能作为极性的主要产品，例如 NBS 介导的溴环化。从 N-链烯氧基吡啶-2(1H)-硫酮 7 和合适的碘原子供体开始，以类似的方式制备芳基取代的 2-碘甲基四氢呋喃 5 (46-80%)。非对映异构纯碘化物 cis-5
• Hartung, Jens; Hiller, Margit; Schmidt, Philipp, Liebigs Annalen, 1996, # 9, p. 1425 - 1436
  作者：Hartung, Jens、Hiller, Margit、Schmidt, Philipp

  DOI：——

  日期：——
• Hartung, Jens; Hiller, Margit; Schmidt, Philipp, Chemistry - A European Journal, 1996, vol. 2, # 8, p. 1014 - 1023
  作者：Hartung, Jens、Hiller, Margit、Schmidt, Philipp

  DOI：——

  日期：——
• Balancing Conjugational Stabilization and Torsional Strain. The Solid-State Structure of a 2-Thioalkyl-Substituted Pyridine N-Oxide
  作者：J. Hartung、I. Svoboda、H. Fuess

  DOI：10.1107/s0108270196007019

  日期：1996.11.15

  The solid-state geometry of 2-(1-phenyl-4-penten-1-yl-thio)pyridine N-oxide, C16H17NOS, provides an insight into the spatial arrangement of the 2-thioalkyl side chain. The N2-C7-S8 bond angle [112.0(2)degrees] shows a significant and unprecedented distortion from the expected value of 120 degrees towards the pyridine N-oxide O atom. The substituents of the thioether are arranged to allow conjugational interaction of the lone pairs on sulfur and the heteroaromatic nucleus on one side, and a minimization of conformational strain between the pyridyl and the alkenyl groups on the other side.