S-methyl 1-piperidinecarbothioate | 3012-97-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: S-methyl 1-piperidinecarbothioate
• 英文别名: S-methyl-1-piperidinecarbothioate；S-methyl piperidinecarbothioate；piperidine-1-carbothioic acid S-methyl ester；Piperidin-1-thiocarbonsaeure-S-methylester；N,N-Pentamethylen-thiocarbaminsaeure-S-methylester；S-methyl piperidine-1-carbothioate
• CAS: 3012-97-3
• 化学式: C₇H₁₃NOS
• 分子量: 159.252
• InChiKey: UGXAFPLXOSEFRX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  45.6
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2933399090

反应信息

• 作为反应物：
  描述：

  S-methyl 1-piperidinecarbothioate 在 sodium hydroxide 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 24.0h， 生成 S-(piperidine-1-ylcarbonyl)cysteine
  参考文献：
  名称：

  Identification of a S-Hexahydro-1H-azepine-1-carbonyl Adduct Produced by Molinate on Rat Hemoglobin β₂ and β₃ Chains in Vivo

  摘要：

  Molinate is a thiocarbamate herbicide used in the rice industry for over 25 years, and regulatory reports have shown that administration of molinate results in reproductive toxicity in male rats. Previous in vitro studies indicate that molinate undergoes oxidative metabolism, forming reactive electrophilic intermediates capable of undergoing nucleophilic addition by protein nucleophiles. On the basis of in vitro studies, carbamylation of an active site serine residue in Hydrolase A has been proposed to be the mechanism responsible for the observed testicular toxicity. The experiments presented here utilize hemoglobin to characterize covalent protein modifications produced in vivo by molinate. Rats were dosed intraperitoneally with molinate as a function of exposure duration, Examination of globin from molinate-treated rats by HPLC demonstrated a new peak in the isolated samples and, when collected and analyzed using MALDI-TOF MS, revealed a 126 Da increase in mass relative to the native beta(3) chain. Digestion of the globin using Glu-C and analysis by MALDI-TOF MS revealed two modified peptide fragments at m/z 2743 and 4985 consistent with a 126 Da increase to peptide fragments [122-146] and [102-146] in the unmodified beta(2) and beta3 chains of globin. Using selected reaction monitoring LC/MS/MS, S-hexahydro-1H-azepine-1-carbonyl cysteine HHAC-Cys) was identified in the globin hydrolysates isolated from the molinate-treated rats, but not in the control samples, and the quantity of adduct exhibited a cumulative dose response. These experiments demonstrate the ability of molinate to covalently modify proteins in vivo in a dose dependent manner. For hemoglobin this modification was a carbamylation at Cys-125 similar to the modification produced by disulfiram and NIV-diethyldithiocarbamate. The ability of molinate to covalently modify cysteine residues provides a potential mechanism to account for enzyme inhibition following molinate exposure and suggests that enzymes with cysteine residues in their active site may be inhibited by molinate.

  DOI：

  10.1021/tx015564a
• 作为产物：
  描述：

  Piperidine-1-carboselenoate;piperidin-1-ium 在 sulfur 作用下， 以 四氢呋喃 为溶剂， 生成 S-methyl 1-piperidinecarbothioate
  参考文献：
  名称：

  在硒催化剂的存在下，由胺，一氧化碳，元素硫和烷基卤化物新型合成S-烷基硫代氨基甲酸酯

  摘要：

  硒化羰基化物在低温下容易与元素硫反应，以高收率形成羰基硫化物，硒代氨基甲酸盐的铵盐与元素硫的反应可立即转化为硫代氨基甲酸盐。除了这些重要发现以外，基于硒对胺与一氧化碳羰基化的高催化活性，还开发了一种方便的新方法，用于合成S-烷基硫代氨基甲酸酯，方法是将胺与一氧化碳和元素硫进行羰基化。在温和条件下存在硒催化剂，然后将硫代氨基甲酸酯的铵盐与烷基卤化物烷基化。

  DOI：

  10.1016/s0040-4020(01)85637-4

文献信息

• Solvent-Free Synthesis of Urea Derivatives from Primary Amines and Sulfur under Carbon Monoxide and Oxygen at Atmospheric Pressure
  作者：Takumi Mizuno、Masatoshi Mihara、Takeo Nakai、Toshiyuki Iwai、Takatoshi Ito

  DOI：10.1055/s-2007-990793

  日期：2007.10

  was developed. With these reactions, an environmentally benign synthesis of urea derivatives could be carried out in good to excellent yields from primary amines and sulfur at ambient pressure of carbon monoxide and oxy-gen. For example, N, N′-dioctylurea was prepared in 99% yield from two equivalents octylamine and one equivalent sulfur in the presence of carbon monoxide (1 atm) at 80 °C and oxygen

  开发了一种针对绿色和可持续化学的无溶剂羰基化和氧化系统。通过这些反应，可以在一氧化碳和氧气的环境压力下以良好至优异的产率从伯胺和硫进行环境友好的尿素衍生物合成。例如，在 80 °C 的一氧化碳 (1 atm) 和室温下的氧气 (1 atm) 存在下，由两个当量的辛胺和一个当量的硫以 99% 的收率制备 N,N'-二辛基脲，完全没有溶剂。
• Facile S-alkyl thiocarbamate synthesis by a novel DBU-assisted carbonylation of amines with carbon monoxide and sulfur
  作者：Takumi Mizuno、Junko Takahashi、Akiya Ogawa

  DOI：10.1016/s0040-4020(03)00031-0

  日期：2003.2

  A novel DBU-assisted carbonylation of amines with carbon monoxide and sulfur has been developed for the synthesis of S-alkyl thiocarbamates. In the presence of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), S-alkyl thiocarbamates are synthesized in excellent yields from amines, carbon monoxide, sulfur, and alkyl halides under mild conditions (1 atm, 20°C). In the absence of DBU, however, no formation of

  已经开发了一种新颖的DBU辅助的胺与一氧化碳和硫的羰基化反应，以合成硫代氨基甲酸酯的S-烷基。在DBU（1,8-二氮杂双环[5.4.0]十一碳-7-烯）的存在下，š -烷基硫代氨基甲酸盐在选自胺，一氧化碳，硫，和烷基卤化物在温和条件下高收率合成（1个大气压， 20°C）。然而，在不存在DBU的情况下，未观察到S-烷基硫代氨基甲酸酯的形成。本DBU辅助的羰基化反应还可用于苯硫威和邻苯甲酸（除草剂）和氨基甲酰氯的新合成方法。
• Kinetics and mechanisms of the reactions of S-methyl chlorothioformate with pyridines and secondary alicyclic amines
  作者：Enrique A. Castro、Margarita Aliaga、Marcela Gazitúa、José G. Santos

  DOI：10.1016/j.tet.2006.03.013

  日期：2006.5

  Brønsted-type plot, in agreement with a stepwise mechanism and a change in the rate-limiting step, from formation of a zwitterionic tetrahedral intermediate (T±) at high pKa to its breakdown at low pKa. The reaction of the same substrate with secondary alicyclic amines shows a linear Brønsted-type plot of slope 0.23, which is in accordance with a stepwise mechanism where formation of T± is the rate-determining

  S-甲基氯硫代甲酸甲酯的吡啶解反应显示了一个双相布朗斯台德型图，与逐步机理和限速步骤的变化相一致，从在高p K a的两性离子四面体中间体（T ±）形成到其分解在低p K a时。相同底物与脂环族仲胺的反应显示出斜率0.23的线性布朗斯台德图，这符合逐步机理，其中T ±的形成是确定整个p K a范围的速率决定步骤。
• 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.