<α-(methylthio)>benzenacetic acid | 55843-16-8

• 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: <α-(methylthio)>benzenacetic acid
• 英文别名: (α-(methylthio))benzeneacetic acid；a-(methylthio)phenylacetic acid；α-(methylthio)-α-phenylacetic acid；2-(methylthio)-2-phenylacetic acid；α-Methylmercapto-phenylessigsaeure；2-(Methylsulfanyl)-2-phenylacetic acid；2-methylsulfanyl-2-phenylacetic acid
• CAS: 55843-16-8
• 化学式: C₉H₁₀O₂S
• mdl: MFCD07787609
• 分子量: 182.243
• InChiKey: XEPIKYPNVRIQJA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.222
• 拓扑面积：
  62.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  <α-(methylthio)>benzenacetic acid 在 N-氯代丁二酰亚胺 、 2,3-二脱氧胞啶 作用下， 以 四氯化碳 为溶剂， 反应 2.0h， 生成 chloro-methylsulfanyl-phenyl-acetic acid phenyl ester
  参考文献：
  名称：

  Synthesis of benzofuranones related to diazonamide via an intramolecular Pummerer reaction

  摘要：

  Treatment of in situ generated 2-thiolaethyl-2-chloro-2-phenylacetyl aryl esters with SnCl4 (catalytic) resulted in the formation of the corresponding 3-thiomethylbenzofuran-2-ones. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)02386-7
• 作为产物：
  描述：

  (+/-)-2-methylthio-2-phenylacetonitrile 在 potassium phosphate buffer 、 Rhodococcus sp. AJ₂₇₀ 作用下， 反应 120.0h， 以15%的产率得到<α-(methylthio)>benzenacetic acid
  参考文献：
  名称：

  Enantioselective biotransformations of racemic α-substituted phenylacetonitriles and phenylacetamides using Rhodococcus sp. AJ270

  摘要：

  Rhodococcus sp. AJ270 is an efficient whole-cell system able to catalyze the stereoselective conversions of racemic alpha-substituted phenylacetonitriles and amides under very mild conditions into enantiopure carboxylic acids and derivatives. The nitrile hydratase involved generally has a broad substrate spectrum against phenylacetonitriles irrespective of the electronic nature of the alpha-substituent while the amidase is very sensitive to both the electronic and steric factors of the substituent of amides. The overall enantioselectivity of nitrile hydrolysis is mainly determined by the combination of selectivities of nitrile hydratase and of amidase, with the latter being a major contributor. The amidase has high S-enantiocontrol against amides while the nitrile hydratase exhibits low R-selectivity against nitriles. The scope and limitations of this enantioselective biotransformation process are discussed. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00025-2

文献信息

• [EN] BORONIC ACID DERIVATIVES<br/>[FR] DÉRIVÉS D'ACIDE BORONIQUE
  申请人：MERCK PATENT GMBH

  公开号：WO2020020858A1

  公开（公告）日：2020-01-30

  The present invention relates to α-amino boronic acid derivatives. These compounds are useful for inhibiting the activity of immunoproteasome (LMP7) and for the treatment and/or prevention of medical conditions affected by immunoproteasome activity such as inflammatory and autoimmune diseases, neurodegenerative diseases, proliferative diseases and cancer.

  本发明涉及α-氨基硼酸衍生物。这些化合物对抑制免疫蛋白酶体(LMP7)的活性以及治疗和/或预防受免疫蛋白酶体活性影响的医疗状况，如炎症性和自身免疫疾病、神经退行性疾病、增殖性疾病和癌症，具有用处。
• Ni/Ir-Catalyzed Photoredox Decarboxylative Coupling of S-Substituted Thiolactic Acids with Heteroaryl Bromides: Short Synthesis of Sulfoxaflor and Its SF₅ Analog
  作者：Oleksandr S. Kanishchev、William R. Dolbier

  DOI：10.1002/chem.201701627

  日期：2017.6.7

  bonds between alkyl chains and aromatic systems, including electron‐deficient heteroaryls, which are known to be challenging coupling partners. In this article, we disclose the Ni/Ir‐catalyzed photoredox decarboxylative coupling of readily available S‐substituted thiolactic acids with electron‐deficient heteroaryl bromides, which resulted in the formation of simple but otherwise not easily accessible

  Metallaphotoredox交叉偶联反应最近成为构建C（sp 2）-C（sp 3）烷基链与芳族系统（包括缺乏电子的杂芳基）之间的键，这些键已知是挑战性的偶合伙伴。在本文中，我们公开了易于获得的S取代硫代乳酸与缺电子的杂芳基溴的Ni / Ir催化的光氧化还原脱羧偶联，这导致形成简单但不易获得的带有烷基硫醚侧链的杂芳烃。为了证明该偶联反应的实际应用，我们已经证明了它在一步合成最近销售的杀虫剂Sulfoxaflor的关键中间体的合成中以及SF 5 -Sulfoxaflor的短合成中的有效性。
• Correlation of rates of uncatalyzed and hydroxide-ion catalyzed ketene hydration. A mechanistic application and solvent isotope effects on the uncatalyzed reaction
  作者：John Andraos、A Jerry Kresge

  DOI：10.1139/v00-032

  日期：2000.4.1

  Rates of hydration of a number of ketenes were measured in neutral and basic solution using flash photolytic techniques, and rate constants for their uncatalyzed, k_uc, and hydroxide-ion catalyzed, k_HO, reactions were determined. These results, plus additional data from the literature, were found to provide the remarkably good correlation log k_uc= -3.21 + 1.14 log k_HO, which spans 10 orders of magnitude in reactivity and includes 31 ketenes. This good correlation implies that uncatalyzed and hydroxide-ion catalyzed ketene hydraton occur by similar reaction mechanisms, which for the hydroxide-ion catalyzed process is known to involve nucleophilic attack on the carbonyl carbon atom of the ketene. Rate constants for phenylhydroxyketene, on the other hand, do not fit this correlation, which suggests that the mechanistic assignment upon which these rate constants are based may not be correct. Solvent isotope effects on these uncatalyzed ketene hydrations are weak; most are less than k_H/k_D= 2. It is argued that these isotope effects are largely, if not entirely, secondary in nature and that they are consistent with both a reaction mechanism in which nucleophlic attack of a single water molecule on the ketene carbonyl carbon atom produces a zwitterionic intermediate and also a mechanism that avoids this intermediate by passing through a cyclic transition state involving several water molecules.Key words: ketene hydration, rate correlation, nucleophilic attack, solvent isotope effects, phenylhydroxyketene.

  一些酮烯的水合速率在中性和碱性溶液中使用闪光光解技术进行了测量，确定了它们的非催化反应速率常数k_uc和羟基离子催化反应速率常数k_HO。这些结果以及来自文献的额外数据发现，提供了非常好的相关性log k_uc= -3.21 + 1.14 log k_HO，涵盖了10个数量级的反应性，并包括31个酮烯。这种良好的相关性意味着非催化和羟基离子催化的酮烯水合反应通过类似的反应机制发生，对于羟基离子催化的过程已知涉及对酮烯的羰基碳原子的亲核攻击。另一方面，苯羟基酮烯的速率常数不符合这种相关性，这表明这些速率常数所基于的机械分配可能不正确。这些非催化酮烯水合反应的溶剂同位素效应较弱；大多数小于k_H/k_D= 2。据认为，这些同位素效应在很大程度上，如果不是完全地是次要的性质，并且它们与既涉及单个水分子对酮烯羰基碳原子的亲核攻击产生带电中间体的反应机制一致，也与通过涉及几个水分子的环状过渡态而避免这种中间体的机制一致。关键词：酮烯水合，速率相关性，亲核攻击，溶剂同位素效应，苯羟基酮烯。
• Metalation reactions
  作者：S. Cabiddu、C. Floris、S. Melis、P.P. Piras、F. Sotgiu

  DOI：10.1016/s0022-328x(00)87069-2

  日期：1982.9

  The products from the reaction between n-butyllithium and benzylalkyl and β-phenethylalkyl sulfides followed by carbonation, have been investigated by GLC/MS analysis. With benzylalkyl sulfides metalation occurs at the benzylic position, and the corresponding carboxylic acid can be isolated, but side products from Wittig like rearrangement, cleavage of the thioether bond, and aliphatic and aromatic

  通过GLC / MS分析研究了正丁基锂与苄基烷基之间的反应产物以及β-苯乙基烷基硫醚随后发生碳酸化的产物。在苄基烷基硫醚上，金属化发生在苄基位置，可以分离出相应的羧酸，但也获得了来自Wittig的副产物，如重排，硫醚键的裂解以及脂族和芳族取代。从β-苯乙基硫化物未获得苄基金属化或类似Wittig的重排产物：相反，硫醚键断裂，发生脂族和芳族取代。
• A Convenient Method for Preparation of 2-(Methylthio)alkanoic Acids and Their Related Compounds Using the Carbanions of Substituted Malonic Esters
  作者：Katsuyuki Ogura、Hiroshi Itoh、Toshio Morita、Kunio Sanada、Hirotada Iida

  DOI：10.1246/bcsj.55.1216

  日期：1982.4

  Starting from alkyl- or aryl-substituted malonic esters prepared by various methods, 2-(methylthio)alkanoic acids are synthesized by successive treatment with sodium ethoxide and with S-methyl methanethiosulfonate, followed by alkaline hydrolysis which causes concurrent decarboxylation. Production of 2-(phenylthio)alkanoic acids is also achieved in a similar manner.

  从通过各种方法制备的烷基或芳基取代的丙二酸酯开始，通过依次用乙醇钠和 S-甲基甲硫代磺酸盐处理合成 2-（甲硫基）链烷酸，然后进行碱水解，同时引起脱羧作用。2-(苯硫基)链烷酸的生产也以类似的方式实现。