sodium 2-naphthalenethiolate | 39689-37-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: sodium 2-naphthalenethiolate
• 英文别名: Sodium naphthalene-2-thiolate；sodium;naphthalene-2-thiolate
• CAS: 39689-37-7
• 化学式: C₁₀H₇S*Na
• 分子量: 182.221
• InChiKey: ZYRDHUAJIQQRNX-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -0.25
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  sodium 2-naphthalenethiolate 在 samarium diiodide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 为溶剂， 反应 6.0h， 生成 2-萘硫醇
  参考文献：
  名称：

  Cyclizations and Rearrangements of Samarium Diiodide-Generated Vinyl Radicals

  摘要：

  Vinyl bromides 1, 5, 15, 20, 23, 27, 33a,b, 41a-c, 44a-c, 46a,b, 52a,b, 55a, 56a,b, and 60a,b react with samarium diiodide in THF and/or acetonitrile to give the corresponding vinyl radicals. Radicals 3, 7, and 16 afforded products deriving from cyclization on the adjacent triple bond in a 5-(pi-exo)exo, 6-(pi-endo)exo, and 6-(pi-exo)exo mode, respectively. Radical 7 undergoes competitive 1,5-hydrogen translocation. Vinyl radicals 21 and 24 readily cyclize on the proximal double bond, leading to 5- and 6-membered rings, respectively. Thienyl-substituted radical 28 leads to a product deriving from 5-exo cyclization on the thiophene ring and subsequent beta-fission of the C-S bond, whereas thienyl-substituted radicals 34a,b undergo almost exclusively 1,5-hydrogen translocation. Aryl-substituted radicals obtained from vinyl bromides 41, 44, 46, 52, and 55 do not form any products deriving from 5-exo or 6-exo cyclization (or ipso cyclization). Finally, naphthyl-substituted radicals 57a and 61a give only direct reduction products, whereas the radical 61b affords, in addition to the direct reduction product, a rearranged product deriving from a 1,3-radical migration of the naphthylthio group. Evidence is reported for the reduction of EWG-substituted benzene rings and thio-substituted naphthalene rings to radical anions, which can fragment on the side chain with the elimination of allyl radicals. alpha-Oxy(and alpha-thio)-substituted radicals deriving from 1,5-shift rearrange to alcohols (and thiols) through a Wittig rearrangement or a cyclization/fragmentation process.

  DOI：

  10.1021/jo00128a013
• 作为产物：
  描述：

  2-萘硫醇 在 dimsyl sodium 作用下， 以 氘代二甲亚砜 为溶剂， 生成 sodium 2-naphthalenethiolate
  参考文献：
  名称：

  硫酚盐的亲核反应性

  摘要：

  取代的硫酚盐的亲核反应性是通过在20°C下于DMSO中与一系列醌甲基化物（参比亲电试剂）反应的动力学来确定的。根据Mayr–Patz方程log k = s N（N + E）分析实验确定的二阶速率常数，以得出十个硫酚盐离子的亲核试剂特异性反应性参数N和s N。

  DOI：

  10.1021/acs.joc.1c00025

文献信息

• 2-Azabutadiene complexes of rhenium(<scp>i</scp>): <i>S</i>,<i>N</i>-chelated species with photophysical properties heavily governed by the ligand hidden traits
  作者：Adrien Schlachter、Frank Juvenal、Rodolphe Kinghat Tangou、Abderrahim Khatyr、Fabrice Guyon、Paul-Ludovic Karsenti、Carsten Strohmann、Marek M. Kubicki、Yoann Rousselin、Pierre D. Harvey、Michael Knorr

  DOI：10.1039/d0dt04183a

  日期：——

  The S,N-coordination of azabutadienes onto fac-Re(CO)₃X species creates moderately emissive complexes, which exhibit ultrafast and multiphasic deactivation kinetics of both their singlet and triplet (MLCT/ILCT) excited states.

  叠氮丁二烯与fac-Re(CO)₃X物种的S,N-配位形成中等发光的配合物，这些配合物的单重态和三重态（MLCT/ILCT）激发态的超快和多变失活动力学。

• Chemoselective Activation of Diethyl Phosphonates: Modular Synthesis of Biologically Relevant Phosphonylated Scaffolds
  作者：Pauline Adler、Amandine Pons、Jing Li、Jörg Heider、Bogdan R. Brutiu、Nuno Maulide

  DOI：10.1002/anie.201806343

  日期：2018.10

  Phosphonates have garnered considerable attention for years owing to both their singular biological properties and their synthetic potential. State‐of‐the‐art methods for the preparation of mixed phosphonates, phosphonamidates, phosphonothioates, and phosphinates rely on harsh and poorly selective reaction conditions. We report herein a mild method for the modular preparation of phosphonylated derivatives

  多年来，由于其独特的生物学特性和合成潜力，膦酸酯已经引起了相当大的关注。用于制备混合膦酸酯，膦酰胺，膦硫代酸酯和次膦酸酯的最新方法依赖于苛刻且选择性差的反应条件。我们在此报告了一种温和的方法，用于模块化制备膦酰化衍生物，其中一些表现出有趣的生物学活性，其基于三氟甲磺酸酐的化学选择性活化。该程序可以用广泛的O，S，N和C亲核试剂进行灵活甚至重复的取代。
• Phosphite‐thioether/selenoether Ligands from Carbohydrates: An Easily Accessible Ligand Library for the Asymmetric Hydrogenation of Functionalized and Unfunctionalized Olefins
  作者：Jèssica Margalef、Carlota Borràs、Sabina Alegre、Elisabetta Alberico、Oscar Pàmies、Montserrat Diéguez

  DOI：10.1002/cctc.201900132

  日期：2019.4.18

  phosphite‐thioether/selenoether ligands has been easily prepared from accessible L‐(+)‐tartaric acid and D‐(+)‐mannitol and applied in the M‐catalyzed (M=Ir, Rh) asymmetric hydrogenation of a broad number of substrates (46 in total). Its highly modular architecture has been crucial to maximize the catalytic performance. Improving most of the reported approaches, this ligand family presents a broad substrate

  可以轻松地从可及的L-（+）-酒石酸和D-（+）-甘露糖醇制备大量亚磷酸酯-硫醚/硒醚配体，并将其应用于M-催化的（M = Ir，Rh）不对称加氢反应中。大量的基材（总共46种）。其高度模块化的体系结构对于最大化催化性能至关重要。改进了大多数已报道的方法，该配体家族提供了广泛的底物范围。通过选择配体参数，因此在功能化和非功能化底物的广泛范围内都实现了高对映选择性（ee高达99％）。有趣的是，通常可以通过改变配体参数来获得氢化产物的两种对映异构体。
• Bifunctional 2-naphthyl propargylic sulfones exhibiting high DNA intercalating and alkylating activity
  作者：Wei-Min Dai、Chun Wo Chow、Ling Zhou、Atsushi Ishii、Chi Wai Lau、Quan Li、Wataru Hamaguchi、Sei-ichi Nishimoto

  DOI：10.1016/s0960-894x(99)00475-8

  日期：1999.10

  number of novel 2-naphthyl propargylic sulfones were synthesized as nucleic base alkylating agents. Extremely high DNA cleavage activity was observed for the sulfones with a free omega-hydroxyl group in the carbon chain in contrast to the ester conjugates possessing an additional intercalating unit.

  合成了许多新颖的2-萘基炔丙基砜作为核酸碱基烷基化剂。与具有额外插入单元的酯缀合物相反，对于在碳链中具有游离ω-羟基的砜，观察到极高的DNA裂解活性。
• One‐Pot Substitution‐Rearrangement Reaction of 2‐Chloroglycidic Ester: Effective Protocol for the Preparation of 3‐Arylsulfenyl‐2‐keto Ester
  作者：Takuzo Komiyama、Yutaka Takaguchi、Sadao Tsuboi

  DOI：10.1080/00397910500374914

  日期：2006.1

  Abstract The one‐pot substitution‐rearrangement reaction of 2‐chloroglycidic ester is reported. Treatment of 2‐chloroglycidic ester with sodium arylthiolate at room temperature results in the formation of 3‐arylsulfenyl‐2‐keto ester in excellent to good yields.

  摘要 报道了2-氯缩水甘油酯的一锅取代重排反应。在室温下用芳基硫醇钠处理 2-氯缩水甘油酯导致 3-芳基硫基-2-酮酯的形成，产率非常好。