potassium benzylthiolate | 61671-44-1

• 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: potassium benzylthiolate
• 英文别名: potassium benzyl mercaptide；Potassium;phenylmethanethiolate
• CAS: 61671-44-1
• 化学式: C₇H₇S*K
• 分子量: 162.297
• InChiKey: JLSPRTCKFYWUMC-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.26
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  potassium benzylthiolate 以 乙醇 、 正己烷 为溶剂， 生成 (R)-2-benzylthio-3-methoxycarbonylpropionic acid
  参考文献：
  名称：

  Process for preparing 4-mercaptopyrrolidine intermediate compounds and a

  摘要：

  一种改进的制备4-巯基吡咯烷化合物[I]的方法：##STR1##其中R为H、低烷基或低烷酰基，R.sup.1为H或SH保护基，X为O或S，包括将卤代丁酸化合物[VI]或其盐与胺化合物[VII]或其盐反应，必要时随后进行硫代羰基化产物和/或去除保护基，所述4-巯基吡咯烷化合物[I]作为碳青霉烯类抗菌剂的中间体有用。

  公开号：

  US05629419A1
• 作为产物：
  描述：

  二苄基二硫 在 一水合肼 、 potassium hydroxide 作用下， 反应 2.0h， 生成 potassium benzylthiolate
  参考文献：
  名称：

  硫属取代基对1,3-二氯丙烯硫属化合物烯丙基重排过程的影响

  摘要：

  在水合氧化肼-KOH氧化还原体系中，用有机二卤化物处理1,3-二氯丙烯中的1,3-二氯丙烯基丙烯的形成受烯丙基重排的可能性控制。在碱的存在下，这种重排通过硫属基取代基部分稳定的碳负离子进行。在一系列取代基PhS> BnS> PhSe中，稳定作用的有效性以及因此发生重排的可能性有所不同。在氯的直接亲核取代阴离子PHSE的阶段-拥有最高的活动。

  DOI：

  10.1134/s1070428016050018
• 作为试剂：
  描述：

  S-benzyl O-ethylxanthate 、 偏二甲肼 在 potassium benzylthiolate 作用下， 反应 3.0h， 以70%的产率得到N,N-dimethyl ethyl thiocarbamate
  参考文献：
  名称：

  Barton, Derek H. R.; Boivin, Jean; Legreneur, Soizic, Journal of the Chemical Society. Perkin transactions I, 1984, # 5, p. 1005 - 1007

  摘要：

  DOI：

文献信息

• Chalcogenation of 1,4-dichlorobut-2-yne with organic dichalcogenides in the system hydrazine hydrate–KOH
  作者：E. P. Levanova、V. S. Vakhrina、V. A. Grabel’nykh、I. B. Rozentsveig、N. V. Russavskaya、A. I. Albanov、L. V. Klyba、N. A. Korchevin

  DOI：10.1007/s11172-015-1121-1

  日期：2015.9

  A reaction of organic dichalcogenides R2Y2 (R = Ph, Bn, Pr; Y = S, Se) with 1,4-dichlorobut-2-yne in the system hydrazine hydrate–KOH leads to four principal products: 1,4-bis(organylchalcogenyl)but-2-ynes, 1-organylchalcogenylbut-1-en-3-ynes, 4-organylchalcogenylbut-1-en-3-ynes, and 3(5)-methylpyrazole. The selectivity of the formation of individual products is determined by the ratio of the substrates used and the reaction temperature. A plausible mechanism of chalcogenation considered in the work agrees with the effect of the nature of chalcogene atoms and organic substituents R on stability of intermediates and products. The stabilization of carbanions by α chalcogene-containing groups corresponds to the following order: PhS > PhSe > BnS > BnSe > PrS.

  有机二磺酰亚胺R2Y2（R=Ph、Bn、Pr；Y=S、Se）与1,4-二氯丁炔-2在系统联氨氢水合物-KOH中的反应主要产生四种产物：1,4-双（有机磺酰亚胺基）丁炔-2、1-有机磺酰亚胺基丁烯-1-炔-3、4-有机磺酰亚胺基丁烯-1-炔-3和3(5)-甲基吡唑。单个产物的选择性取决于所用底物的比例和反应温度。本文考虑的加磺酰亚胺化作用的可行机制与磺酰亚胺原子和有机取代基R的性质对中间体和产物稳定性的影响相符。由α-磺酰亚胺基团稳定碳阴离子的顺序为：PhS > PhSe > BnS > BnSe > PrS。
• A NEW SYNTHETIC ROUTE OF β-HYDROXYALKYLPHOSPHONATES FROM β,γ-EPOXYALKYLPHOSPHONATES
  作者：Toshio Nagase、Takayuki Kawashima、Naoki Inamoto

  DOI：10.1246/cl.1984.1997

  日期：1984.11.5

  β-Hydroxyalkylphosphonates were synthesized from β,γ -epoxyalkylphosphonates and RMgX/ cat. CuI reagents, which is a new synthetic route for the various types of α- and/or γ-substituted β-hydroxyalkylphosphonates.

  β-羟基烷基磷酸盐是通过β,γ-环氧烷基磷酸盐与RMgX/催化剂CuI试剂合成的，这是一种新的合成不同类型的α和/或γ取代的β-羟基烷基磷酸盐的路线。
• Design and Synthesis of Sulfur Based Inhibitors of Matrix Metalloproteinase-1.
  作者：Tetsunori Fujisawa、Shinjiro Odake、Yuji Ogawa、Junko Yasuda、Yasuo Morita、Tadanori Morikawa

  DOI：10.1248/cpb.50.239

  日期：——

  Fibroblast collagenase (MMP-1), a member of the matrix metalloproteinases family, is believed to be a pathogenesis of arthritis, by cleaving triple-helical type II collagen in cartilage. From the similarity of the active site zinc binding mode with hydroxamate, we designed and synthesized α-mercaptocarbonyl possessing compounds (3—5), which incorporated various peptide sequences as enzyme recognition sites. The P4–P1 peptide incorporating compound (3) exhibited as potent inhibition as the hydroxamate (1) and the carboxylate (2) type inhibitors, with an IC50 of 10−6 M order against MMP-1. But the inhibitor (3) related compounds (6—8) displayed decreased or no inhibitory potencies. These results suggest that the existence of both the carbonyl and thiol groups might be critical for the inhibition, and the distance between the two functional groups is important for inhibitory potency. For Pn′ peptide incorporating compounds (4a—k), except for 4h and 4k, all compounds showed IC50 values under sub-nanomolar. Among them, for potent inhibition, Leu was better than Phe and Val as the P1′ amino acid, and the P2′ position amino acid was necessary, and preferentially Phe. Insertion of the Pn peptide into 4d or 4k, giving compounds 5a—c, did not increase the activities of 4d and 4k. Substitution of the mercapto group with other functional groups lost the activity of compound 4a. The stereochemical preference at the thiol-attached position was also determined by preparation of both isomers of 4a. It was found that the S configuration compound (36b) is approximately 100 times more potent than the corresponding R-isomer (36a).

  成纤维细胞胶原酶（MMP-1）是基质金属蛋白酶家族的一员，被认为是关节炎的病理机制之一，它通过切割软骨中的三重螺旋II型胶原蛋白发挥作用。基于其活性位点锌结合模式与羟肟酸的相似性，我们设计并合成了含有α-巯基羰基的化合物（3—5），这些化合物包含了作为酶识别位点的不同肽序列。包含P4–P1肽的化合物（3）表现出与羟肟酸（1）和羧酸（2）类型抑制剂相当的强抑制作用，对MMP-1的IC50值为10−6小于M的量级。然而，与抑制剂（3）相关的化合物（6—8）显示出下降或无抑制活性。这些结果表明，羰基和巯基的共存可能对抑制作用至关重要，并且这两个官能团之间的距离对抑制效能也很重要。对于Pn'肽的包含化合物（4a—k），除了4h和4k以外，所有化合物的IC50值均低于亚纳摩尔。其中，在强抑制作用方面，Leu作为P1'氨基酸优于Phe和Val，而P2'位的氨基酸是必要的，并且优先选择Phe。将Pn肽插入4d或4k生成化合物5a—c，并未增加4d和4k的活性。将巯基替换为其他官能团则失去了化合物4a的活性。通过合成4a的两种异构体还确定了在巯基连接位置的立体化学偏好，发现S构型的化合物（36b）的效能约为相应R-异构体（36a）的100倍。
• The Viologen Cation Radical Pimer: A Case of Dispersion‐Driven Bonding
  作者：Margarita R. Geraskina、Andrew S. Dutton、Mark J. Juetten、Samuel A. Wood、Arthur H. Winter

  DOI：10.1002/anie.201704959

  日期：2017.8

  The π bonds between organic radicals have generated excitement as an orthogonal interaction for designing self‐assembling architectures in water. A systematic investigation of the effect of the viologen cation radical structure on the strength and nature of the pimer bond is provided. A striking and unexpected feature of this π bond is that the bond strength is unchanged by substitution with electron‐donating

  有机自由基之间的π键作为设计水中自组装结构的正交相互作用而产生了兴奋。提供了对紫精阳离子自由基结构对π键强度和性质的影响的系统研究。该π键的显着和出乎意料的特征是，通过用给电子基团或吸电子基团取代或增加共轭键，键强度不变。此外，空间大的N不会减弱相互作用烷基。理论模型表明，强分散力主导了基团之间的相互作用，使键合相互作用对取代基的不敏感性合理化：可极化的π基团的堆积导致有吸引力的分散力超过小分子的典型分散作用，并有助于克服库仑排斥使两种阳离子物质接触的过程。
• Novel dithioether–silver(<scp>i</scp>) coordination architectures: structural diversities by varying the spacers and terminal groups of ligands
  作者：Jian-Rong Li、Xian-He Bu、Jiao Jiao、Wen-Ping Du、Xiu-Hua Xu、Ruo-Hua Zhang

  DOI：10.1039/b416576b

  日期：——

  An investigation into the dependence of the framework formation of coordination architectures on ligand spacers and terminal groups was reported based on the self-assembly of AgClO4 and eight structurally related flexible dithioether ligands, RS(CH2)nSR (Lan, R = ethyl group; Lbn, R = benzyl group, n = 1–4). Eight novel metal–organic architectures, [Ag(La1)3/2ClO4]n (1a), [Ag2(La2)2(ClO4)2]2 (2a), [AgLa3ClO4]n (3a), [Ag(La4)2]ClO4}n (4a), [AgLb1ClO4]2 (1b), [Ag(Lb2)2]ClO4 (2b), [Ag(Lb3)3/2(ClO4)1/2](ClO4)1/2}n (3b) and [Ag(Lb4)3/2ClO4]n (4b), were synthesized and structurally characterized by X-ray crystallography. Structure diversities were observed for these complexes: 1a forms a 2-D (6,3) net, while 2a is a discrete tetranuclear complex, in which the AgI ion adopts linear and tetrahedral coordination modes, and the S donors in each ligand show monodentate terminal and μ2-S bridging coordination fashions; 3a has a chiral helical chain structure in which two homo-chiral right-handed single helical chains (Ag–La3–)n are bound together through μ2-S donors, and simultaneously gives rise to left-handed helical entity (Ag–S–)n. In 4a, left- and right-handed helical chains formed by the ligands bridging AgI centers are further linked alternately by single-bridging ligands to form a non-chiral 2-D framework. 1b has a dinuclear structure showing obvious ligand-sustained Ag–Ag interaction, while 2b is a mononuclear complex; 3b is a 3-D framework formed by ClO4− linking the 2-D (6,3) framework, which is similar to that of 1a, and 4b has a single, double-bridging chain structure in which 14-membered dinuclear ring units formed through two ligands bridging two AgI ions are further linked by single-bridging ligands. In addition, a systematic structural comparison of these complexes and other reported AgClO4 complexes of analogous dithioether ligands indicates that the ligand spacers and terminal groups take essential roles on the framework formation of the AgI complexes, and this present feasible ways for adjusting the structures of such complexes by modifying the ligand spacers and terminal groups.

  基于 AgClO4 和八种结构相关的柔性二硫醚配体 RS(CH2)nSR（Lan，R = 乙基；Lbn，R = 苄基，n = 1â4）的自组装，报告了配位体系结构的框架形成对配体间隔物和末端基团的依赖性的研究。八种新型金属有机结构：[Ag(La1)3/2ClO4]n (1a)、[Ag2(La2)2(ClO4)2]2 (2a)、[AgLa3ClO4]n (3a)、[Ag(La4)2]ClO4}n (4a)、[AgLb1ClO4]2 (1b)、合成了[Ag(Lb2)2]ClO4 (2b)、[Ag(Lb3)3/2(ClO4)1/2](ClO4)1/2}n (3b) 和 [Ag(Lb4)3/2ClO4]n (4b)。这些复合物的结构具有多样性：1a 形成了一个二维 (6,3) 网状结构，而 2a 则是一个离散的四核配合物，其中 AgI 离子采用线性和四面体配位模式，而每个配体中的 S 给体都呈现单价末端配位和 δ2-S 桥接配位方式；3a 具有手性螺旋链结构，其中两条同手性右手单螺旋链（AgâLa3â）n 通过δ¼2-S 供体结合在一起，同时产生左手螺旋实体（AgâSâ）n。在 4a 中，由桥接 AgI 中心的配体形成的左手和右手螺旋链通过单桥接配体进一步交替连接，形成一个非手性的二维框架。1b 具有双核结构，显示出明显的配体与 AgâAg 的相互作用，而 2b 则是单核复合物；3b 是 ClO4â 连接二维（6,3）框架形成的三维框架，与 1a 相似，而 4b 具有单双桥链结构，其中通过两个配体桥接两个 AgI 离子形成的 14 元双核环单元通过单桥接配体进一步连接。此外，将这些配合物与其他已报道的类似二硫醚配体的 AgClO4 配合物进行系统的结构比较表明，配体的间隔和末端基团对 AgI 配合物的框架形成起着至关重要的作用，这为通过改变配体的间隔和末端基团来调整这类配合物的结构提供了可行的方法。