4-methyl-2-(trichloromethylsulfanyl)-thiazole | 89861-55-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 4-methyl-2-(trichloromethylsulfanyl)-thiazole
• 英文别名: 4-methyl-2-(trichloromethylsulfanyl)thiazole；2-tichloromethylsulfanyl-4-methylthiazole；5-methyl-2-trichloromethylthiothiazole；4-Methyl-2-[(trichloromethyl)sulfanyl]-1,3-thiazole；4-methyl-2-(trichloromethylsulfanyl)-1,3-thiazole
• CAS: 89861-55-2
• 化学式: C₅H₄Cl₃NS₂
• 分子量: 248.584
• InChiKey: FQBPYIUCODMBLT-UHFFFAOYSA-N

物化性质

• 沸点：
  235.7±50.0 °C(Predicted)
• 密度：
  1.60±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  11
• 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：
  66.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  4-methyl-2-[2-[(3R)-3-methylcyclopentyl]propan-2-ylsulfanyl]-1,3-thiazole 在 三氯溴甲烷 作用下， 以 乙醚 为溶剂， 反应 0.5h， 以86%的产率得到4-methyl-2-(trichloromethylsulfanyl)-thiazole
  参考文献：
  名称：

  Barton, Derek H.R.; Crich, David; Kretzschmar, Gerhard, Journal of the Chemical Society. Perkin transactions I, 1986, p. 39 - 54

  摘要：

  DOI：

文献信息

• 2,3-cis-Cyclization of 4-pentenoxyl radicals
  作者：Irina Kempter、Christine Schur、Katharina Huttenlochner、Ruth-Maria Bergsträßer、Benjamin Wolff、Thomas Kopf、Jens Hartung

  DOI：10.1016/j.tet.2016.07.001

  日期：2016.12

  which is the preferred conformation for transition structures for 2,3-trans-cyclization, stabilizes the double bond by delocalizing π-electrons into the σ*(C,O)-orbital. Along with energy decreases the affinity of π-electrons for forming a σ (C,O)-bond with the oxygen radical. In 2,3-cis-cyclization, a similar stabilizing effect cannot occur, because the allylic oxygen substituent and the alkene align

  当被烯丙基羟基，乙酰氧基或苯甲酰氧基取代时，4-戊氧基自由基选择性地环化2，3-顺式。取决于相对构型，位置和它们的化学性质，另外的取代基增加或减少2，3-顺式环化产物的分数。选择3-受体取代的戊氧基自由基来提供2,3-顺式环闭合产物的原因是烯丙基氧取代基与烯烃实体之间的次级轨道相互作用，在动力学上不利于5的2,3-反式-外-cyclization。将β-C，O键沿背斜取向与烯烃平面对齐，这是2,3-过渡结构的优选构象反式环化通过将π电子离域到σ*（C，O）轨道来稳定双键。随着能量的增加，π电子与氧自由基形成σ（C，O）键的亲和力降低。在2，3-顺式环化中，由于烯丙基氧取代基和烯烃排列在平面上，因此不会发生类似的稳定作用。烯丙基氧取代基的动力学作用在3-羟基壬基-1，8-二烯-5-氧基的环化中变得更加明显，有利于分子内向未取代的烯丙基双键加成三倍。
• Radical chemistry of thiohydroxamic acid esters
  作者：Derek H.R. Barton、Gerhard Kretzschmar

  DOI：10.1016/s0040-4039(00)94229-1

  日期：1983.1

  Thiohydroxamic esters in general decompose smoothly by a radical chain reaction to give carbon radicals which can be quenched in a synthetically useful manner.

  硫代异羟肟酸酯通常通过自由基链反应平稳地分解以产生碳原子团，其可以以合成上有用的方式被淬灭。
• Annulated and bridged tetrahydrofurans from alkenoxyl radical cyclization
  作者：Christine Schur、Harald Kelm、Thomas Gottwald、Arne Ludwig、Rainer Kneuer、Jens Hartung

  DOI：10.1039/c4ob01266f

  日期：——

  radicals sharing two or more carbon atoms with a cycloalkane cyclize in a predictable manner stereoselectively and regioselectively to afford in solutions of bromotrichloromethane cycloalkyl-fused or -bridged 2-bromomethyltetrahydrofurans in up to 95% yield. Stereoselectivity in alkenoxyl radical ring closures arises from cumulative steric effects. The substituent positioned the closest to the alkene carbon

  与环烷烃共享两个或更多个碳原子的4-戊氧基自由基以可预测的方式立体选择性和区域选择性地环化，从而在溴三氯甲烷中的环烷基稠合的或桥连的2-溴甲基四氢呋喃溶液中的产率高达95％。烷氧基自由基闭环中的立体选择性是由累积的空间效应引起的。位置最接近烯烃碳的取代基受到氧自由基的攻击，发挥了最强的立体定向作用。这主要电感指南5-外-cyclization 2,3-反式-或2,4-顺式-选择性。远离受攻击的π键的取代基是次级电感器。相对变压器中的次级电感-配置增强了初级电感器的立体声分化；一个顺式-构型次级电感器降低这种效果。次级电感器不能推翻类似尺寸的初级电感器的引导效果。分子内的4-戊烯氧基基团向环己烯键合的外亚甲基基团或环内双键的加成是顺式进行的，这是由非对映体纯的溴代双环[2.2.1]庚基环化的四氢呋喃从动木基乙氧基基团合成而来的。根据理论，烷氧基自由基环化成环内π键的实验性2,3-顺式特异性来自与2
• Synthesis and structural characterization of the isomuscarines
  作者：Irina Kempter、Britta Frensch、Thomas Kopf、Ralph Kluge、René Csuk、Ingrid Svoboda、Hartmut Fuess、Jens Hartung

  DOI：10.1016/j.tet.2013.12.085

  日期：2014.3

  Four diastereomers of 2-[(trimethylammonium)-methyl]-5-methyltetrahydrofuran-3-ol, trivially named isomuscarine, allo-isomuscarine, epi-isomuscarine, and epiallo-isomuscarine, were prepared as bromide salts from 2,4-like and 2,4-unlike diastereomers of 3-(4-hydroxyhex-5-en-2-oxy)-4-methylthiazole-2(3H)-thione. The strategy for constructing the tetrahydrofuran nucleus of the isomuscarines uses alkenoxyl radical 5-exo-bromocyclization, occurring 2,3-cis-selectively for the 2,4-like-4-hydroxyhex-5-en-2-oxyl radical, and 2,3-trans-selectively for the 2,4-unlike diastereomer. A fraction of 4hydroxyhex-5-en-2-oxyl radicals cyclizes 6-endo-selectively providing 5-bromo-2-methyltetrahydropyran-4-ols in yields between 3 and 15%. Substituting trimethylamine for bromide in 5-exo-bromocyclized products furnishes isomuscarine bromides, which were structurally characterized by X-ray diffraction and NMR-spectroscopy. (C) 2014 Elsevier Ltd. All rights reserved.
• Synthesis of enantiopure (2R)-configured muscarine alkaloids via selective alkoxyl radical ring-closure reactions
  作者：Jens Hartung、Rainer Kneuer

  DOI：10.1016/j.tetasy.2003.06.006

  日期：2003.10

  A new synthesis of (-)-muscarine, (+)-allo-muscarine, (-)-epi-muscarine, and (-)-epiallo-muscarine has been devised which utilizes selective alkoxyl radical cyclizations for constructing tri-substituted tetrahydrofuran units. Photolysis of (2R,3S)-N-(3-benzoyloxy-5-hexen-2-oxy)-4-methylthiazole-2(3H)thione in the presence of BrCCl3 provided (2R,3S,5S)-3-benzoyloxy-5-broniomethyl-2-methyltetrahydrofuran as the major product and the corresponding (2R,3S,5R)-isomer as the minor. These building blocks were converted into enantiomerically pure (+)-allo-muscarine (from the major alkoxyl radical cyclization product) and (-)-muscarine (from the minor product). Temperature and substituent effects on the diastereoselectivity of the underlying alkoxyl radical cyclization have been investigated. (-)-epi-Muscarine and (-)-epiallo-muscarine have been prepared likewise, starting from (2R.3R)-ev-(3-benzoyloxy-5-hexen-2-oxy)-4-metliylthiazole-2(3H)thione. (C) 2003 Published by Elsevier Ltd.