S-methyl O-phenyl carbonothioate | 13509-28-9

• 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: S-methyl O-phenyl carbonothioate
• 英文别名: S-ethyl O-phenyl carbonothioate；S-methyl-O-phenyl-thiocarbonate；O-phenyl-S-methyl thio carbonic acid ester；Thiokohlensaeure-S-methyl-phenylester；S-Methyl-O-phenylthiolcarbonat；S-Methyl-phenyl-thiocarbonat；Phenyl methylsulfanylformate
• CAS: 13509-28-9
• 化学式: C₈H₈O₂S
• 分子量: 168.216
• InChiKey: DLYZNVYLULHBQS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  S-methyl O-phenyl carbonothioate 在 磺酰氯 作用下， 反应 1.0h， 以78%的产率得到氯甲酸苯酯
  参考文献：
  名称：

  使用一氧化碳作为羰基来源合成氯甲酸苄酯（CbzCl）

  摘要：

  建立了一种新的非光气合成氯甲酸苄酯（CbzCl）的方法。通过在DBU（1,8-二氮杂双环[5.4.0]十一烷基-7-烯）存在下用一氧化碳和硫（或羰基硫）对苯甲醇进行羰基化反应，制得S-甲基O-苄基羰基硫代酸酯。使用碘甲烷收率好。然后，通过使用磺酰氯对S-甲基O-苄基硫代碳酸盐进行氯化，成功地合成了CbzCl衍生物，收率很高。

  DOI：

  10.1016/s0040-4020(02)01331-5
• 作为产物：
  描述：

  Potassium O-Phenylthiocarbonate 以95%的产率得到
  参考文献：
  名称：

  CHANYSHEV, N. T.;KALASHNIKOV, S. M.;POPOV, YU. N.;KRUGLOV, EH. A.;KURAMSH+, OSN. ORGAN. SINTEZ I NEFTEXIMIYA (YAROSLAVL),(1989) N5, S. 148-160

  摘要：

  DOI：

文献信息

• Synthesis of S-Aryl/Alkyl Thiolcarbonates from Disulfides and Chloroformates in the Presence of the Zn/AlCl3 System
  作者：Barahman Movassagh、Maryam Tavoosi

  DOI：10.1007/s00706-007-0778-z

  日期：2008.3

  A simple, general, and high yielding method has been developed for the synthesis of S -aryl/alkyl- O -aryl/alkyl thiolcarbonates from various chloroformates and disulfides by reductive cleavage of the S–S bond with a Zn/AlCl3 system in dry acetonitrile at 80°C.

  已经开发了一种简单，通用且高收率的方法，该方法可通过在Zn / AlCl 3系统中通过S–S键的还原裂解，从各种氯甲酸酯和二硫化物合成 S- 芳基/烷基 -O- 芳基/烷基硫代碳酸酯。在80°C干燥乙腈。
• Effect of substitution of oxygen by sulfur in the nonleaving group of a carbonate: kinetics of the phenolysis and benzenethiolysis of<i>S</i>-methyl aryl thiocarbonates
  作者：Enrique A. Castro、Margarita Aliaga、José G. Santos

  DOI：10.1002/poc.1192

  日期：2007.8

  are studied kinetically. The Brønsted plots (log kNversus nucleophile basicity) are linear for all reactions. The Brønsted slopes for 1 and 2 are, 0.51 and 0.66 (phenolysis) and 0.55 and 0.70 (benzenethiolysis), respectively. These values suggest a concerted mechanism for these reactions, as found in the corresponding carbonates. Namely, substitution of OMe by SMe in the nonleaving group does not change

  动力学研究了S-甲基4-硝基苯基硫代碳酸酯（1）和S-甲基2,4-二硝基苯基硫代碳酸酯（2）在水中的酚解和苯硫解。对于所有反应，布朗斯台德图（log k N与亲核试剂碱性之间的关系）是线性的。1和2的Brønsted斜率分别为0.51和0.66（酚醛）和0.55和0.70（苯硫解）。这些值表明了这些反应的协调机制，如在相应的碳酸盐中发现的。即，用S代替O Me我在非离开小组中并没有改变机制。版权所有©2007 John Wiley＆Sons，Ltd.
• Phenolysis and aminolysis of 4-nitrophenyl and 2,4-dinitrophenyl S-methyl thiocarbonates in aqueous ethanol
  作者：Enrique A. Castro、Margarita E. Aliaga、Marjorie Cepeda、José G. Santos

  DOI：10.1002/kin.20562

  日期：2011.7

  linear with slope (β) values in the 0.5–0.7 range, in accordance with concerted mechanisms. Comparison of the SA aminolysis of 1 with the same one carried out in water shows that the change of solvent from water to aqueous ethanol destabilizes the zwitterionic tetrahedral intermediate, changing the mechanism from stepwise to concerted. This destabilization is greater than that due to the change from SA

  的反应小号甲基ø - （4-硝基苯基）硫代碳酸酯（1）和小号甲基ø - （2,4-二硝基苯基）硫代碳酸酯（2）具有一系列次级脂环族（SA）的胺和酚经受动力学研究。在亲核试剂过量的情况下，获得伪一级速率系数（k obs）。在恒定pH下，相对于游离亲核试剂浓度的k obs曲线与斜率k N呈线性关系。Brønsted图（log k N与亲核试剂p K a）的反应是线性的，根据协调的机理，其斜率（β）值在0.5–0.7范围内。SA 1的氨解与在水中进行的SA氨解的比较表明，溶剂从水变为乙醇水溶液会破坏两性离子四面体中间体的稳定性，从而将机理从逐步转变为一致。该去稳定作用大于由于SA胺变为喹啉核苷而引起的去稳定作用。对于酚醛反应，k N乙醇水溶液中的值小于水中相同反应的值。考虑到亲核试剂是阴离子，该结果是出乎意料的，因为阴离子应在极性更大的溶剂中更稳定。该结果由以下事实解释：酚盐反应物具有在芳环中离
• Solvent-assisted thiocarboxylation of amines and alcohols with carbon monoxide and sulfur under mild conditions
  作者：Takumi Mizuno、Toshiyuki Iwai、Yoshio Ishino

  DOI：10.1016/j.tet.2005.06.114

  日期：2005.9

  DMSO or DMF as a solvent strongly accelerated the thiocarboxylation of amines and alcohols with carbon monoxide and sulfur. Under mild conditions (1 atm, 20 degrees C), this thiocarboxylation of amines assisted by DMSO with carbon monoxide and sulfur has been developed into a practical and convenient synthetic method for S-alkyl thiocarbamates in good to excellent yields, including EPTC, thiobencarb, orbercarb, and molinate (herbicides). DMF also showed the similar solvent effect. NMP slightly decreased the effect for the thiocarboxylation of amines, and the yield of S-alkyl thiocarbamate was lowered in DMAc. Surprisingly, no formation of S-alkyl thiocarbamate was observed at the use of the other solvents, such as THF, hexane, toluene, AcOEt, MeCN, MeOH, and H2O. The present solvent-assisted thiocarboxylation with carbon monoxide and sulfur could be also applied to a new synthesis of S-alkyl O-alkyl carbonothioates from alcohols under mild conditions (1 atm, 20 degrees C) in DMF using DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). (c) 2005 Elsevier Ltd. All rights reserved.
• Chanyshev, N. T.; Kalashnikov, S. M.; Kuramshin, E. M., Journal of general chemistry of the USSR, 1990, vol. <2> 60, # 11, p. 2300 - 2307
  作者：Chanyshev, N. T.、Kalashnikov, S. M.、Kuramshin, E. M.、Naimushin, A. I.、Imashev, U. B.

  DOI：——

  日期：——