3-benzyl-4,5-dimethylthiazol-3-ium bromide | 28048-27-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 3-benzyl-4,5-dimethylthiazol-3-ium bromide
• 英文别名: 3-benzyl-4,5-dimethylthiazolium bromide；3-Benzyl-4,5-dimethyl-1,3-thiazol-3-ium;bromide
• CAS: 28048-27-3
• 化学式: Br*C₁₂H₁₄NS
• 分子量: 284.22
• InChiKey: MQUDCDLKFPTCMB-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  32.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-benzyl-4,5-dimethylthiazol-3-ium bromide 、 2-甲基苯甲醛 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 生成 (E)-(3-benzyl-4,5-dimethyl-1,3-thiazol-2-ylidene)-(2-methylphenyl)methanolate
  参考文献：
  名称：

  Electron-Transfer Properties of Active Aldehydes of Thiamin Coenzyme Models, and Mechanism of Formation of the Reactive Intermediates

  摘要：

  The active aldehydes 2a-c(-) derived from the reaction of 3-benzylthiazolium salts (1a(+): 3-benzyl-4-methylthiazolium bromide, 1b(+): 3-benzyl-4;5-dimethyIthiazolium bromide, 1c(+): 3-benzylthiazolium bromide) with o-tolualdehyde in the presence of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) are stable in deaerated MeCN at 298 K because of the steric bulkiness of the o-methyl group, which prohibits benzoin condensation with a second aldehyde molecule. The one-electron oxidation of fourteen different active aldehydes (2a-n(-)) derived from various aldehydes occurs at -0.98 to -0.77 V vs. SCE in deaerated MeCN at 298 or 233 K and leads to formation of the corresponding radical intermediates (2a-n(.)), which have been characterized by electron spin resonance (ESR spectroscopy. The rapid rates of electron exchange between 2a-c(-) and 2a-c(.) were determined by the linewidth variations of the ESR spectra of 2a-c(.) in the presence of different concentrations of 2a-c(-), demonstrating the efficient electron-transfer properties of the active aldehydes. The electron transfer from 2a(-) to an outer-sphere one-electron oxidant, [Co-II(phen)(3)](2+) (phen = 1,10-phenanthroline), whose one-electron reduction potential (E-red(o) = -0.97 V) is about the same as the one-electron oxidation potential of 2a(-) (E-ox(o) = -0.96 V), occurs efficiently to yield the corresponding Co-I complex. The observed rate constants for formation of [Co-I(phen)(3)]' agree with those for formation of the active aldehyde examined independently. This agreement indicates that rate-determining formation of 2a(-), which is a very strong reductant, precedes the highly efficient electron transfer from 2a(-) to [Co-II(phen)(3)](2+).

  DOI：

  10.1002/(sici)1521-3765(19991001)5:10<2810::aid-chem2810>3.0.co;2-f
• 作为产物：
  描述：

  4,5-二甲基噻唑 、 溴甲苯 以 乙醚 为溶剂， 以87 %的产率得到3-benzyl-4,5-dimethylthiazol-3-ium bromide
  参考文献：
  名称：

  N-杂环卡宾：噻唑基-Cu(I)配合物：微波辅助合成及其在A3反应中用作催化剂

  摘要：

  摘要 开发了一种简单的方法，涉及 3-苄基噻唑鎓/苯并噻唑溴化物与氧化亚铜的微波辅助反应，用于合成四种新型 N-杂环卡宾 (NHC)：噻唑基/苯并噻唑基-Cu(I) 配合物。配合物的结构可以根据IR、1H和13建立13C NMR 研究和元素分析。代表性的NHC：苯并噻唑亚基-Cu(I)络合物被用作苯乙炔与仲胺和醛的微波辅助A3反应的催化剂，以优异的收率获得新的取代的炔丙胺。在 DFT 水平上对 A3 模型反应的理论研究揭示了炔烃与 NHC-Cu(I) 络合物的初始配位，随后攻击仲胺与醛反应生成的亚胺离子。在催化剂存在下，活化自由能垒（ΔG #）降低了约。3 kcal mol -1。

  DOI：

  10.1080/10426507.2023.2193403
• 作为试剂：
  描述：

  tert-butyl 4-bromobenzylidenecarbamate 、 (E)-ethyl 3-(2-formylphenyl)acrylate 在 caesium carbonate 、 3-benzyl-4,5-dimethylthiazol-3-ium bromide 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以62%的产率得到
  参考文献：
  名称：

  N-Heterocyclic carbene-catalyzed tandem aza-benzoin/Michael reactions: on site reversal of the reactivity of N-Boc imines

  摘要：

  我们开发了一种串联 NHC 催化的偶氮苯甲酸/迈克尔反应，作为高效生产二氢茚酮和含吡咯烷酮的三环化合物的方法。这种新颖的反应模式涉及叔丁基芳基（甲苯基）甲基氨基甲酸酯作为亲电体和亲核体在同一碳上发生反应。

  DOI：

  10.1039/c0cc01769h

文献信息

• Reactivity of the thiazolium C2 ylide in aprotic solvents: novel experimental evidence for addition rather than insertion reactivity
  作者：Yao Tsung Chen、Frank Jordan

  DOI：10.1021/jo00017a010

  日期：1991.8

  Two thiazolium compounds were synthesized specifically labeled at their C2 positions: 3,4,5-trimethyl[2-C-13]thiazolium nitrate and 3-benzyl-5-(beta-ethoxyethyl)-4-methyl[2-C-13]thiazolium bromide, with a view to examine their pathways leading to dimerization in strongly basic medium using C-13 NMR. On addition of less than 1 equiv of base the N-methyl ion first formed an unsymmetrical dimer in which the C2 atoms of two molecules were bonded to each other and only one of them still carried a hydrogen; that unsymmetrical dimer upon addition of excess base lost the remaining hydrogen at C2 and was converted to a mixture of syn and anti symmetrical dimers in nearly equal amounts. The sequence of observations on addition of base to the N-methyl derivative is consistent with nucleophilic addition of the conjugate base to a second thiazolium ion at its C2 position. Since the unsymmetrical dimer is formed first, rather than the symmetrical dimer, the latter cannot result from direct dimerization of two conjugate bases (ylides) by a carbene mechanism. Instead, a carbanion-addition mechanism was further supported by two experiments. A ''crossover'' experiment was designed in which unsymmetrical dimers were detected in Me2SO on addition of limiting potassium tert-butoxide to thiazolium ions containing [2-C-13]-H and [2-C-12]-D, under conditions such that there was little H/D exchange observed at the C2 position. Also, N-3-alkenylthiazolium ions were synthesized, that, if carbenic reactivity had existed, would have resulted in formation of cyclopropanes. In preference to the intramolecular reaction, intermolecular unsymmetrical dimers resulted in each case, consistent with nucleophilic addition. On addition of base to the N-benzylthiazolium ion, the first product to be detected by C-13 NMR was the syn/anti symmetrical dimer mixture (again bonded via the C2 atoms), that underwent a [1,3]-sigmatropic rearrangement of one of the benzyl groups from N3 to C2. According to H-1 NMR recorded within minutes of mixing, the unsymmetrical dimer precedes the symmetrical one for this salt as well. The reactivity of the C2 ylide derived from the N-methyl and N-benzylthiazolium ions can be rationalized according to an ionic addition reaction, implying that the related thiamin (vitamin B1) conjugate base (ylide) behaves similarly.
• Concise Assembly of Highly Substituted Furan-Fused 1,4-Thiazepines and Their Diels−Alder Reactions with Benzynes
  作者：Hanfeng Ding、Yiping Zhang、Ming Bian、Weijun Yao、Cheng Ma

  DOI：10.1021/jo702299m

  日期：2008.1.1

  A facile and highly efficient three-component reaction of thiazole or benzothiazole carbenes, disubstituted ketenes, and activated alkynes is disclosed. With this methodology, a polysubstituted ring system containing furo[2,3-c]thiazepine core can be constructed from simple and readily accessible starting materials in good yields. The scope and limitation of this transformation were investigated in detail by using various thiazole carbene, ketene, and alkyne components. Furthermore, the synthetic utilities of these unique polyheterocyclic compounds were demonstrated via their Diels-Alder reactions with benzynes to furnish thiazepine-fused 7-oxanorbornadiene derivatives in excellent yields.
• A Ring-Expansion Methodology Involving Multicomponent Reactions: Highly Efficient Access to Polysubstituted Furan-Fused 1,4-Thiazepine Derivatives
  作者：Cheng Ma、Hanfeng Ding、Yiping Zhang、Ming Bian

  DOI：10.1002/anie.200602836

  日期：2006.11.27
• Electron-Transfer Properties of Active Aldehydes of Thiamin Coenzyme Models, and Mechanism of Formation of the Reactive Intermediates
  作者：Ikuo Nakanishi、Shinobu Itoh、Shunichi Fukuzumi

  DOI：10.1002/(sici)1521-3765(19991001)5:10<2810::aid-chem2810>3.0.co;2-f

  日期：1999.10.1

  The active aldehydes 2a-c(-) derived from the reaction of 3-benzylthiazolium salts (1a(+): 3-benzyl-4-methylthiazolium bromide, 1b(+): 3-benzyl-4;5-dimethyIthiazolium bromide, 1c(+): 3-benzylthiazolium bromide) with o-tolualdehyde in the presence of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) are stable in deaerated MeCN at 298 K because of the steric bulkiness of the o-methyl group, which prohibits benzoin condensation with a second aldehyde molecule. The one-electron oxidation of fourteen different active aldehydes (2a-n(-)) derived from various aldehydes occurs at -0.98 to -0.77 V vs. SCE in deaerated MeCN at 298 or 233 K and leads to formation of the corresponding radical intermediates (2a-n(.)), which have been characterized by electron spin resonance (ESR spectroscopy. The rapid rates of electron exchange between 2a-c(-) and 2a-c(.) were determined by the linewidth variations of the ESR spectra of 2a-c(.) in the presence of different concentrations of 2a-c(-), demonstrating the efficient electron-transfer properties of the active aldehydes. The electron transfer from 2a(-) to an outer-sphere one-electron oxidant, [Co-II(phen)(3)](2+) (phen = 1,10-phenanthroline), whose one-electron reduction potential (E-red(o) = -0.97 V) is about the same as the one-electron oxidation potential of 2a(-) (E-ox(o) = -0.96 V), occurs efficiently to yield the corresponding Co-I complex. The observed rate constants for formation of [Co-I(phen)(3)]' agree with those for formation of the active aldehyde examined independently. This agreement indicates that rate-determining formation of 2a(-), which is a very strong reductant, precedes the highly efficient electron transfer from 2a(-) to [Co-II(phen)(3)](2+).
• N-Heterocyclic carbene: thiazolylidene–Cu(I) complexes: microwave-assisted synthesis and use as catalyst in A3 reaction
  作者：Nosheen Beig、Varsha Goyal、R. K. Bansal

  DOI：10.1080/10426507.2023.2193403

  日期：2023.8.3

  bromides with cuprous oxide has been developed for the synthesis of four new N-heterocyclic carbene (NHC): thiazolylidene/benzothiazolylidene–Cu(I) complexes. Structures of the complexes could be established on the basis of the IR, 1H, and 13C NMR studies and elemental analysis. A representative NHC:benzothiazolylidene–Cu(I) complex was used as catalyst for the microwave-assisted A3 reaction of phenylacetylene

  摘要 开发了一种简单的方法，涉及 3-苄基噻唑鎓/苯并噻唑溴化物与氧化亚铜的微波辅助反应，用于合成四种新型 N-杂环卡宾 (NHC)：噻唑基/苯并噻唑基-Cu(I) 配合物。配合物的结构可以根据IR、1H和13建立13C NMR 研究和元素分析。代表性的NHC：苯并噻唑亚基-Cu(I)络合物被用作苯乙炔与仲胺和醛的微波辅助A3反应的催化剂，以优异的收率获得新的取代的炔丙胺。在 DFT 水平上对 A3 模型反应的理论研究揭示了炔烃与 NHC-Cu(I) 络合物的初始配位，随后攻击仲胺与醛反应生成的亚胺离子。在催化剂存在下，活化自由能垒（ΔG #）降低了约。3 kcal mol -1。