1-methyl-2-(methylsulfinyl)imidazole | 142132-87-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1-methyl-2-(methylsulfinyl)imidazole
• 英文别名: 2-methanesulfinyl-1-methyl-imidazole；N-methyl-2-(methylsulfinyl)imidazole；1-methyl-2-methylsulphinylimidazole；N-methyl-2-methylsulfinylimidazole；1-Methyl-2-methylsulfinyl-imidazole；1-methyl-2-methylsulfinylimidazole
• CAS: 142132-87-4
• 化学式: C₅H₈N₂OS
• mdl: MFCD18808377
• 分子量: 144.197
• InChiKey: SYZHBDIUGGHYNU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  54.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  三氯甲基锡 、 1-methyl-2-(methylsulfinyl)imidazole 以 氯仿 为溶剂， 以50%的产率得到MeSnCl3 * 1-methyl-2-(methylsulfinyl)imidazole
  参考文献：
  名称：

  含亚磺酰基的路易斯碱的锡（IV）到铂（II）配体转移反应

  摘要：

  反式-[PtCl（μ-Cl）（PEt 3）] 2中的Pt（II）中心被证明是从其几个Sn（IV）加合物中提取含亚磺酰基的Lewis碱并形成稳定的Pt（II）络合物。Ph 2 SnCl 2与（RSOCH 2）2型的二亚砜的六配位Sn（IV）加合物（RPr，Ph）以及1-甲基-2-（甲基亚磺酰基）咪唑（ImSOMe）具有由Pt（II）提取的含硫配体，形成S键键合的双铂络合物（在光谱和结构分析显示）。配体的抽象似乎是一个普遍的反应。仅当Sn（IV）前体变为锡部分呈强酸性的特别稳定的MeSnCl 3 -ImSOMe络合物时，反应才继续进行。

  DOI：

  10.1016/s0020-1693(97)05480-7
• 作为产物：
  描述：

  1-甲基-2-(甲硫基)咪唑 在 间氯过氧苯甲酸 作用下， 生成 1-methyl-2-(methylsulfinyl)imidazole
  参考文献：
  名称：

  金属催化的亚砜和硫化物亚胺的比较研究。

  摘要：

  提出了将各种金属催化剂与分离的或原位生成的亚氨基碘烷（PhI == NR）结合作为氮源对硫化合物进行胺化的比较研究。已经评估了金属催化剂对各种取代的亚砜的酰亚胺化的影响。此外，研究了硫的不同氧化态对亚硫胺和亚砜亚胺形成过程中氮转移氧化还原过程的反应性和选择性的影响。取决于特定的金属催化剂以及所使用的腈前体，硫化物/亚砜的亚胺化比率在5-氧噻吩和取代的对硫苯基亚砜的转化中变化。

  DOI：

  10.1002/chem.200700352

文献信息

• Biotransformation of organic sulfides. Part 12. Conversion of heterocyclic sulfides to chiral sulfoxides by <i>Helminthosporium</i> sp. NRRL 4671 and <i>Mortierella isabellina</i> ATCC 42613
  作者：Herbert L. Holland、Carl D. Turner、Peter R. Andreana、Doan Nguyen

  DOI：10.1139/cjc-77-4-463

  日期：——

  The enantioselective oxidation of a series of heterocyclic prochiral sulfides to chiral sulfoxides has been examined using the fungal biocatalysts Helminthosporium species NRRL 4671 and Mortierella isabellina ATCC 42613. Methylthiofuranyl and -thiophenyl substrates gave (S)-configuration products in low to moderate enantiomeric purity on biotransformation with H. species, but pyridyl sulfides with

  已经使用真菌生物催化剂 Helminthosporium 物种 NRRL 4671 和 Mortierella isabellina ATCC 42613 对一系列杂环前手性硫化物对映选择性氧化为手性亚砜进行了研究。甲基硫代呋喃基和-噻吩底物在低至中等纯度的生物反式转化中产生 (S)-构型产物与 H. 物种，但氮原子位于距硫中心 8-10 A 最佳距离的吡啶基硫化物产生高对映体纯度的 (S) 亚砜。M. isabellina 对适当取代的苯并噻烷底物的生物转化也产生了高对映体纯度的产物，但在硫处具有 (R) 构型。底物的可接受性以及 H. 物种和 M. 对硫氧化的构型。
• The methylation, oxidation and crystallographic characterization of imidazole derivatives
  作者：Gabriella Vampa、Stefania Benvenuti、Fabio Severi、Luca Malmusi、Luciano Antolini

  DOI：10.1002/jhet.5570320138

  日期：1995.1

  Compounds 2, 3 and 4 were synthesized and the crystal and molecular structures of 1 and 4 were determined. An hptlc technique for studying the methylation rate of 1 and the oxidation rate of 2 was applied.

  化合物2,3和4的合成和晶体和分子结构1和4进行了测定。用于研究的甲基化率的HPTLC技术1和的氧化速率2涂布。
• Iron(II) Triflate as an Efficient Catalyst for the Imination of Sulfoxides
  作者：Olga García Mancheño、Jonathan Dallimore、Andrew Plant、Carsten Bolm

  DOI：10.1021/ol900660x

  日期：2009.6.4

  The challenging imination of benzyl-, sterically demanding alkyl-, and heteroaryl-substituted sulfoxides has been studied. Iron(II) triflate was identified as a highly efficient and robust catalyst for sulfur imination reactions. A variety of sulfoxides and sulfides were efficiently iminated with sulfonyliminoiodinanes (PhI═NSO2R) at room temperature to give the corresponding sulfoximines and sulfilimines

  已经研究了具有挑战性的亚苄基，空间上需要的烷基和杂芳基取代的亚砜的亚砜。三氟甲磺酸铁（II）被认为是用于硫磺化反应的高效且坚固的催化剂。多种亚砜和硫化物与sulfonyliminoiodinanes（PhI═NSO被有效亚胺化2在室温下R），得到相应的亚磺酰亚胺和sulfilimines在良好的产率和短的反应时间。
• Casey; Gairns; Geraghty, Synlett, 2000, # 12, p. 1721 - 1724
  作者：Casey、Gairns、Geraghty、Kelly、Murphy、Walker

  DOI：——

  日期：——
• Mechanism of the Asymmetric Sulfoxidation in the Esomeprazole Process: Effects of the Imidazole Backbone for the Enantioselection
  作者：Muthu Seenivasaperumal、Hans-Jürgen Federsel、Kálmán J. Szabó

  DOI：10.1002/adsc.200800753

  日期：2009.4

  Abstractmagnified imageThe asymmetric sulfoxidation reaction of imidazole‐based prochiral sulfides was studied to explore the mechanistic details of the highly efficient esomeprazole process, which is one of the few industrial scale catalytic asymmetric procedures. The synthetic studies revealed that the smallest subunit governing the selectivity in the esomeprazole process is an imidazole ring. Thus, by using the esomeprazole procedure methyl imidazole sulfide could be oxidized as efficiently as its several functionalized derivatives, including pyrmetazol. However, alkylation of the imidazole nitrogen led to a major drop of the enantioselectivity. Our atmospheric pressure chemical ionization‐mass spectrometry (APCI/MS) studies indicate that addition of small amounts of water to the reaction mixture facilitates the formation of mononuclear titanium species, which are the active catalytic intermediates of the selective oxidation reaction. One of the most important features of the esomeprazole procedure is that amine additives increase the enantioselectivity of the oxidation process. The NMR studies of the presumed reaction intermediates show that under catalytic conditions the amines are able to coordinate to titanium and dissociate the coordinated imidazole substrate. The density functional theory (DFT) modelling studies provided new insights in the mechanism of the asymmetric induction. It was found that the oxidation requires a lower activation energy if the imidazole sulfide precursor does not coordinate to titanium. Two possible reaction paths were explored for this out of sphere oxidation mechanism. The most important interaction governing the enantioselection is hydrogen bonding between the NH of the imidazole ring and the chiral tartrate ligand on titanium. Furthermore, the oxidation reaction imposes an important structural constraint to the TS structure involving a linear arrangement of the peroxide oxygens and the sulfur atom. This constraint and the N coordination of imidazole leads to a very strained structure for the inner sphere mechanism of the oxidation, which leads to a much higher activation barrier than the corresponding out of sphere process, and therefore it is unlikely.