4-cyanophenyl chlorothionoformate | 66300-17-2

• 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-cyanophenyl chlorothionoformate
• 英文别名: 4-cyanophenyl chlorothioformate；4-cyanophenyl thiochloroformate；p-cyanophenyl chlorothionoformate；p-Cyanophenylchlorothionoformiat；O-(4-cyanophenyl) chloromethanethioate
• CAS: 66300-17-2
• 化学式: C₈H₄ClNOS
• 分子量: 197.645
• InChiKey: PKFKCAPVESCCFZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-cyanophenyl chlorothionoformate 在 奎宁环 、 potassium chloride 作用下， 以 phosphate buffer 、 水 为溶剂， 生成 4-羟基苯甲腈
  参考文献：
  名称：

  芳基氯硫代甲酸酯与奎宁环的反应。动力学研究

  摘要：

  苯基，4-氯苯基，4-氰基苯基和4-硝基苯基chlorothionoformates（奎宁环的反应中1，2，3，和4，分别地）经受在水溶液中的动力学研究中，在25.0℃下，和离子性强度为0.2 M（KCl）。通过分光光度法跟踪在底物平行水解中产生的相应酚盐阴离子/苯酚的释放来研究反应。在胺过量的情况下，发现伪一阶速率系数（k obs）。的曲线图ķ OBS与[胺]是线性的，斜率ķ Ñ。布朗斯台德型图（log k N与p ķ一个铵离子）是线性的，斜率β  = 0.26，0.22，0.19，和0.28，用于与反应1，2，3，和4，分别。斜率的大小表明这些机理是逐步的，决定速率的是两性离子四面体中间体（T ±）的形成。与p的双参数方程ķ一个亲核试剂和非离去基团的显示β Ñ  = 0.26和β NLG ＝ -0.16，也符合所提出的机制。另一方面，使用它们的硬度指数研究了这些硫代羰基底物及其羰基衍生

  DOI：

  10.1002/poc.1286
• 作为产物：
  描述：

  硫光气 、 4-羟基苯甲腈 在 sodium hydroxide 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 1.0h， 生成 4-cyanophenyl chlorothionoformate
  参考文献：
  名称：

  自由基O→C换位：苯酚转化为苯甲酸酯和苯甲酰胺的无金属工艺

  摘要：

  我们报告了通过新的自由基级联将苯酚转化为苯甲酸的酯和酰胺的无金属方法。二芳基硫代碳酸酯和硫代氨基甲酸酯可在单个高产率步骤中从苯酚获得，可在C═S部分的硫原子上选择性添加甲硅烷基。该添加步骤类似于Barton-McCombie反应的第一步，产生的碳原子团通过O进行1,2 O→C换位-新叶重排。可逆重排步骤中通常不利的平衡是通过O中心自由基中的高放热C-S键断裂而向前移动的，这提供了最终的苯甲酸酯或苯甲酰胺产品。由苯酚的无金属苯甲酸衍生物的制备为芳基三氟甲磺酸酯的金属催化的羰基化提供了潜在有用的替代方法。

  DOI：

  10.1021/jo102467j

文献信息

• Studies of the Thiocarbonyl Compounds. III. The Mechanism of the Thermal Rearrangement of Aryl Thionocarboxylates
  作者：Aritsune Kaji、Yoshiaki Araki、Koshin Miyazaki

  DOI：10.1246/bcsj.44.1393

  日期：1971.5

  The thermal rearrangement of aryl thionocarboxylates was kinetically investigated in diphenyl ether. The rate constants of the rearrangement of aryl N,N-dimethylthionocarbamates were well correlated with the σ− values, but the plots of the electron-releasing para-substituents deviated slightly on the lower side of the meta correlation line. A good linear free-energy relationship existed between the

  在二苯醚中对芳基硫羰羧酸酯的热重排进行了动力学研究。芳基 N,N-二甲基硫代氨基甲酸酯重排的速率常数与 σ− 值密切相关，但释放电子的对位取代基的图在元相关线的下侧略有偏差。芳基N,N-二甲基硫代氨基甲酸酯的重排与4-或5-取代的1-氯-2-硝基苯与哌啶的双分子亲核反应之间存在良好的线性自由能关系。通过使用从后一个反应中获得的取代基常数作为电子释放对位取代基常数，获得了相当好的 ρ-σ- 关系。芳基N重排之间也存在线性自由能关系，N-二甲基硫代氨基甲酸酯和芳基硫代苯甲酸酯，以及芳基 N,N-二甲基硫代氨基甲酸酯和 O-芳基 S-苯基二硫代碳酸酯的重排。反应常数的顺序是...
• Hydroxyphenylthiophosphoranylidene organophosphorus compounds
  申请人：Monsanto Company

  公开号：US04071584A1

  公开（公告）日：1978-01-31

  The present invention relates to a new hydroxyphenylthiophosphoranylidene organophoshorus compounds and to a process involving an unusual phenyl migration for their preparation. The general reaction for the preparation of the products of the present invention is set forth below: ##STR1## WHERE X is halogen (F, Cl, Br), NO.sub.2, CN, CO.sub.2 R', SO.sub.2 R', CF.sub.3 or ##STR2## R is phenyl, alkyl of 1 to 3 carbon atoms, or OR', and R' is alkyl of 1 to 6 carbon atoms. The compounds of the invention are useful as flame retardants, lubricating oil additives and as corrosion inhibitors.

  本发明涉及一种新的羟基苯基硫代磷烯有机磷化合物，以及涉及一种涉及其制备的不寻常苯基迁移的过程。本发明产品的制备的一般反应如下所示：其中X为卤素（F、Cl、Br）、NO.sub.2、CN、CO.sub.2 R'、SO.sub.2 R'、CF.sub.3或R为苯基、1至3个碳原子的烷基或OR'，R'为1至6个碳原子的烷基。该发明的化合物可用作阻燃剂、润滑油添加剂和防腐剂。
• Preparation of Alkyl and Aryl Chlorodifluoromethyl Ethers Using BrF3
  作者：Youlia Hagooly、Revital Sasson、Michael J. Welch、Shlomo Rozen

  DOI：10.1002/ejoc.200800231

  日期：2008.6

  Both alkyl and aryl chlorothioformates could readily be obtained from the corresponding alcohols and thiophosgene. These families of compounds were treated with BrF3 to form the corresponding alkyl and aryl chlorodifluoromethyl ethers in 60–85 % yields. The method is suitable for constructing a variety of aliphatic as well as electron-deficient aromatic chlorodifluoromethyl ethers. The reactions proceed

  烷基和芳基氯硫代甲酸酯可以很容易地从相应的醇和硫光气中获得。这些化合物家族用 BrF3 处理形成相应的烷基和芳基氯二氟甲基醚，产率 60-85%。该方法适用于构建多种脂肪族和缺电子芳香族氯二氟甲基醚。反应在温和的条件和短的反应时间下进行。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Antibacterial penem derivatives
  申请人：HOECHST UK LIMITED

  公开号：EP0069377A2

  公开（公告）日：1983-01-12

  Penem derivative of the formula 1 in which R is hydrogen or a carboxyl esterifying group, R1 is phenyl, napthyl, thienyl, pyridyl, quinolyl or isoquinolyl being unsubstituted or substituted by one, two or three of the same or different substituents selected from halogen, hydroxy, amino, nitro, cyano, azido, alkyl, alkoxy, alkanesulfenyl, alkanesulfinyl, alkanesulfonyl, alkanoyl, alkoxycarbonyl, alkanoyloxy, carbamoyl, ureido, carba- moyloxy, alkanoylamino, aminosulfamoyl, sulfamoyl, guani- dino, trifluormethyl, trifluormethanesulfenyl, trifluor- methanesulfinyl, trifluormethanesulfonoyl and formyl, which may be substituted by one, two or three lower alkyl groups being the same or different. R2 represents a hydrogen atom or a optionally protected hydroxyl group, or a salt thereof, process for the production thereof and antibacterial pharmaceutical preparations comprising them.

  式 1 的 Penem 衍生物 其中 R 是氢或羧基酯化基团、 R1 是苯基、萘基、噻吩基、吡啶基、喹啉基或异喹啉基，未被取代或被一个、两个或三个相同或不同的取代基取代，这些取代基选自卤素、羟基、氨基、硝基、氰基、叠氮基、烷基、烷氧基、烷亚磺酰基、烷亚磺酰基、烷酰基、烷氧羰基、烷酰氧基、氨基甲酰基、脲基、羧基、烷酰氨基、氨基磺酰基、磺酰基、胍基、三氟甲基、三氟甲磺酰基、三氟甲亚磺酰基、三氟甲磺酰基和甲酰基，它们可被一个、两个或三个相同或不同的低级烷基取代。 R2 代表氢原子或受保护的羟基、 或其盐、 其生产工艺和包含它们的抗菌药物制剂。
• Kinetics and Mechanisms of the Reactions of 3-Methoxyphenyl, 3-Chlorophenyl, and 4-Cyanophenyl 4-Nitrophenyl Thionocarbonates with Alicyclic Amines
  作者：Enrique A. Castro、Leonardo Leandro、Nicolas Quesieh、José G. Santos

  DOI：10.1021/jo0157371

  日期：2001.9.1

  The reactions of 3-methoxyphenyl, 3-chlorophenyl, and 4-cyanophenyl 4-nitrophenyl thionocarbonates (1, 2, and 3, respectively) with a series of secondary alicyclic amines are studied kinetically in 44 wt % ethanol-water at 25.0 degreesC and an ionic strength of 0.2 M (KCl). Pseudo-first-order rate coefficients (k(obsd)) are obtained for all reactions (amine excess was used). The reactions of compound 1 with piperidine, piperazine, and 1-(2-hydroxyethyl)piperazine and of compounds 2 and 3 with these amines and morpholine exhibit linear k(obsd) versus amine concentration plots with slopes (k(1)) independent of pH. In contrast, the plots are nonlinear upward for the reactions of substrate I with morpholine, 1-formylpiperazine, and piperazinium ion and of substrates 2 and 3 with the two latter amines. For all these reactions, a reaction scheme is proposed with a zwitterionic tetrahedral intermediate (T +/-), which can be deprotonated by an amine to yield an anionic intermediate (T-). When the nonlinear plots are fit through an equation derived from the scheme, rate and equilibrium microcoefficients are obtained. The Bronsted-type plots for k(1) are linear with slopes of beta (1) = 0.22, 0.20, and 0.24 for the aminolysis of 1, 2, and 3, respectively, indicating that the formation of T+/- (k(1) step) is rate-determining. The k(1) values for these reactions follow the sequence 3 > 2 > 1, which can be explained by the sequence of the electron-withdrawing effects from the substituents on the nonleaving group of the substrates.