4-chlorobenzyl 4-methylbenzenesulfonate | 4450-67-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-chlorobenzyl 4-methylbenzenesulfonate
• 英文别名: 4-chlorobenzyl p-toluenesulfonate；p-chlorobenzyl p-tosylate；4-Chlorobenzyl tosylate；toluene-4-sulfonic acid-(4-chloro-benzyl ester)；Toluol-4-sulfonsaeure-(4-chlor-benzylester)；4-Chlor-benzyl-tosylat；(4-chlorophenyl)methyl 4-methylbenzenesulfonate
• CAS: 4450-67-3
• 化学式: C₁₄H₁₃ClO₃S
• 分子量: 296.774
• InChiKey: CFNIWCJEUPNISN-UHFFFAOYSA-N

物化性质

• 熔点：
  52 °C(Solv: ethyl ether (60-29-7))
• 沸点：
  438.8±33.0 °C(Predicted)
• 密度：
  1.310±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-chlorobenzyl 4-methylbenzenesulfonate 在 sodium azide 、 copper(ll) sulfate pentahydrate 、 potassium carbonate 、 sodium ascorbate 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.11h， 生成 1-(4-chlorobenzyl)-4-phenyl-1H-1,2,3-triazole
  参考文献：
  名称：

  A dicationic, podand-like, ionic liquid water system accelerated copper-catalyzed azide-alkyne click reaction

  摘要：

  In this work, an effective, task specific, dicationic, podand-like ionic liquid was synthesized and applied to improve the capability features of click reaction. Moreover, to broaden the scope and decreasing the serious limitations of preparation methods of organic azides, a simple green procedure for the preparation of alkyl azides, the fundamental starting materials in click reactions, from alcohols under solvent-free conditions and microwave irradiation has been reported, for the first time. (C) 2014 Mohammad Javaherian. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

  DOI：

  10.1016/j.cclet.2014.09.005
• 作为产物：
  描述：

  对甲苯磺酰氯 、 4-氯苯甲醇 在 sodium carbonate 作用下， 以 水 为溶剂， 反应 3.0h， 以77%的产率得到4-chlorobenzyl 4-methylbenzenesulfonate
  参考文献：
  名称：

  离子液体刷作为一种有效且可重复使用的非均相催化组件，用于纯净水中苯酚和醇的甲苯磺酸化†

  摘要：

  开发了一种非常有效且可重复使用的异质离子液体刷组件。该催化剂对纯净水中苯酚和醇的甲苯磺酸酯化显示出高催化活性。此外，该催化剂显示出优异的稳定性和可重复使用性，并且可以简单有效地回收和重复使用五次，而不会明显降低催化活性。

  DOI：

  10.1039/c7nj00141j

文献信息

• One-Pot Preparation of 3-Arylisoxazole-4,5-dicarboxylates from Benzylic Chlorides and Acetylenedicarboxylates
  作者：Taro Imai、Hideo Togo

  DOI：10.1002/ejoc.201701726

  日期：2018.3.22

  N‐methylmorpholine N‐oxide (NMO) and then NH2OH·HCl and potassium carbonate followed by the addition of Oxone® in the presence of acetylene derivatives to give the corresponding 3‐arylisoxazole‐4,5‐dicarboxylates in good to moderate yields. This one‐pot transformation used readily available materials and was performed under transition‐metal‐free conditions.

  先用N-甲基吗啉N-氧化物（NMO），然后用NH 2 OH · HCl和碳酸钾处理苯甲酰氯，然后在乙炔衍生物存在下加入Oxone®，得到相应的3-芳基异恶唑-4,5-二羧酸酯中等至中等的产量。这种一锅法改造使用了现成的材料，并在无过渡金属的条件下进行。
• Reversed Electron Apportionment in Mesolytic Cleavage: The Reduction of Benzyl Halides by SmI₂
  作者：Offir Yitzhaki、Shmaryahu Hoz

  DOI：10.1002/chem.201500519

  日期：2015.6.15

  and the effect of tosylate (OTs) as a leaving group. The latter does not tend to tolerate radical character on the oxygen atom. In the presence of a proton donor, the tolyl derivatives were the sole product, whereas in its absence, the coupling dimer was obtained by a SN2 reaction of the benzyl anion on the neutral substrate. The data also suggest that for the para‐CN and CO2Me derivatives in the presence

  苄基卤的自由基阴离子的裂解以这样的方式发生，即负电荷最终终止在离开的卤化物上而留下苄基的方式在化学上是根深蒂固的。通过研究取代的苄基溴化物和氯化物与SmI 2在THF中反应的动力学，发现底物被吸电子基团（CN和CO 2）对位取代能够与质子供体形成氢键并与sa阳离子配位的Me）以反向电子分配模式反应。即，卤化物以自由基形式离去。该结论基于发现的凸Hammett图，元素效应，质子供体效应以及作为离去基团的甲苯磺酸酯（OTs）的效应。后者不能容忍氧原子上的自由基特征。在质子供体的存在下，甲苯基衍生物是唯一的产品，而在其不存在，是由S取得的耦合二聚体Ñ中性基板上的苄基阴离子的2反应。数据还表明，对-CN和CO 2在存在质子供体的情况下的Me衍生物中，第一电子传递与质子传递耦合。
• Heterocyclic Ring and Carbocyclic Derivative
  申请人：Shionogi & Co., Ltd.

  公开号：US20160024072A1

  公开（公告）日：2016-01-28

  The present invention provides novel compounds having a P2X 3 and/or P2X 2/3 receptor antagonistic effect, e.g. a compound of Formula (I): wherein R 2 is a hydrogen atom or the like; ring A is five- to seven-cycloalkane or the like; C is a carbon atom; Q 1 and Q 2 are carbon atoms or the like; R 9a and R 9b are carbon atoms or the like; R 6 is cycloalkyl or the like; R 7 is a group represented by the formula: wherein ring D is benzene or the like; carbon atom a and b are carbon atoms; ring B is an aromatic carbocyclic ring or the like; s and s′ are 0 or the like; R 9 and R 9′ are halogen or the like, or the like, or its pharmaceutically acceptable salt.

  本发明提供了具有P2X3和/或P2X2/3受体拮抗作用的新化合物，例如Formula (I)的化合物：其中R2是氢原子或类似物；环A是五至七环烷或类似物；C是碳原子；Q1和Q2是碳原子或类似物；R9a和R9b是碳原子或类似物；R6是环烷基或类似物；R7是由以下公式表示的基团：其中环D是苯或类似物；碳原子a和b是碳原子；环B是芳香族碳环或类似物；s和s'为0或类似物；R9和R9'是卤素或类似物，或其药用可接受盐。
• Nucleophilic substitution reaction of benzyl benzenesulfonates with anilines in MeOH-MeCN mixtures-I
  作者：Ikchoon Lee、Won Heui Lee、Se Chul Sohn、Choong Shik Kim

  DOI：10.1016/s0040-4020(01)96365-3

  日期：1985.1

  Kinetic studies on nucleophilic substitution reaction of benzyl tosylates with anilines are reported. The reaction was found to proceed via a dissociative SN2 mechanism with less than 50 % bond formation and extensive bond breaking at the transition state. It was found that positive charge development at the benzylic carbon is substantial and para-substituent effect on the substrate is predominantly

  报道了甲苯磺酸苄基酯与苯胺的亲核取代反应的动力学研究。发现该反应通过离解S N 2机理进行，其中少于50％的键形成和在过渡态的大量键断裂。已经发现，苄基碳上的正电荷发展是充分的，并且对底物的对位取代作用主要是共振型的。更好的亲核试剂，底物上的吸电子基团和极性更大（MeCN含量较高）的溶剂有助于形成键。发现底物，亲核试剂和溶剂遵循RSP。
• Catalyst and process for preparing low-viscosity and color-reduced polyisocyanates containing isocyanurate groups
  申请人：DEGUSSA AG

  公开号：US20030187178A1

  公开（公告）日：2003-10-02

  A low-viscosity polyisocyanates and polyisocyanates of reduced color containing isocyanurate groups is prepared by a process comprising, partially trimerizing aliphatic and/or cycloaliphatic diisocyanates in the presence of 0.02 to 2% by weight, based on the weight of the diisocyanate starting material, of at least one trimerization catalyst of formula (I) 1 wherein and wherein substituents A, B, C, D, and E simultaneously or independently of one another are hydrogen, chloro, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl, hydroxyl, (R 5 ) 3 SiO—, (R 5 ) 2 N—, —COOH, (R 5 ) 2 N—CH 2 — or phenyl, it being 5 possible for any two adjacent radicals selected from the group A, B, C, D and E to form a conjoint 5- or 6-membered saturated or unsaturated ring which may also include nitrogen, sulfur or oxygen heteroatoms; F is hydrogen, methyl or fluoro; G is hydrogen, methyl or fluoro; R 2 and R 3 simultaneously or independently of one another are C 1 -C 18 -alkyl or R 1 ; R 4 is hydrogen, methyl, C 2 -C 18 -alkyl, C 3 -C 8 -cycloalkyl or C 2 -C 12 -alkoxy; R 5 is C 1 -C 18 -alkyl; Y − is R 6 COO − ; R 6 is hydrogen or a branched or unbranched aliphatic or araliphatic C 1 -C 12 -alkyl radical, and then removing excess diisocyanate from the reaction medium.

  通过部分三聚脂肪族和/或环脂肪族二异氰酸酯在至少一种式(I)的三聚催化剂的存在下进行部分三聚化反应，其中所述催化剂的重量为二异氰酸酯起始物的重量的0.02至2％。所述催化剂的式子如下：其中，取代基A、B、C、D和E可以同时或独立地是氢、氯、C1-C4-烷基、C1-C4-烷氧基、C1-C4-烷氧羰基、羟基、(R5)3SiO-、(R5)2N-、-COOH、(R5)2N-CH2-或苯基，其中任意相邻的两个基团A、B、C、D和E中选择的基团可以形成共轭的5-或6-成员饱和或不饱和环，该环还可以包括氮、硫或氧杂原子；F为氢、甲基或氟；G为氢、甲基或氟；R2和R3可以同时或独立地是C1-C18烷基或R1；R4为氢、甲基、C2-C18烷基、C3-C8环烷基或C2-C12烷氧基；R5为C1-C18烷基；Y-为R6COO-；R6为氢或支链或非支链的脂肪族或芳基脂肪族C1-C12烷基基团，然后从反应介质中去除多余的二异氰酸酯，从而制备含有异氰酸酯基团的低粘度聚异氰酸酯和降低颜色的聚异氰酸酯。