Methyl-cyanothiolformat | 57361-47-4

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代羰基化合物
• 英文名称: Methyl-cyanothiolformat
• 英文别名: [(Methoxycarbonyl)thio] cyanide；methyl thiocyanatoformate
• CAS: 57361-47-4
• 化学式: C₃H₃NO₂S
• 分子量: 117.128
• InChiKey: LPGKEDPOWNKBJX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  75.4
• 氢给体数：
  0
• 氢受体数：
  4

制备方法与用途

用途 

硫氰基甲酸甲酯是杀菌剂甲基硫菌灵的中间体。

生产方法 

其制备方法是在合成釜内加入定量溶剂，经冷却后加入定量的硫氰化钠和催化剂，釜温在10～15℃，加入计量的氯甲酸甲酯，然后自然升温并保温搅拌数小时，得到硫氰基甲酸甲酯。反应方程式：ClCOOCH₃+NaSCN[催化剂]→SCNCOOCH₃+NaCl

反应信息

• 作为产物：
  描述：

  potassium thioacyanate 、 氯甲酸甲酯 生成 Methyl-cyanothiolformat
  参考文献：
  名称：

  The Thermal Decomposition of Alkoxycarbonyl Thiocyanates and Isothiocyanates

  摘要：

  烷氧羰基硫氰酸酯和异硫氰酸酯已在降压条件下在240-375°C的温度下热分解。初级体系主要产生烷基硫氰酸酯，而次级和三级体系产生烷基异硫氰酸酯。讨论了在将初级醇转化为初级烷基硫醇以及次级和三级醇转化为三级烷基胺中使用此反应的可行性。

  DOI：

  10.1139/v75-126

文献信息

• Conformational Behavior of CH₃OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study
  作者：Sonia Torrico-Vallejos、Mauricio F. Erben、Mao-Fa Ge、Helge Willner、Carlos O. Della Védova

  DOI：10.1021/jp912044r

  日期：2010.3.18

  Pure methoxycarbonylsulfenyl cyanide, CH3OC(O)SCN (I), and rnethoxycarbortylsulfenyl thiocyanate, CH3OC(O)SSCN (II), were prepared by reacting liquid CH3OC(O)SCl with either AgCN or AgSCN, respectively. Compounds I and II were characterized by H-1 NMR, CG-MS, and vibrational (FTIR and FT-Raman) techniques. The conformational properties have been Studied by using vibrational spectroscopy I infrared (gaseous, liquid, and Ar matrix isolated), Raman (liquid) spectroscopy.] together with quantum chemical calculations at the B3LYP and MP2 methods with the extended 6-311++G** and aug-cc-pVTZ basis sets. Compound 1 exhibits a conformational equilibrium at room temperature having the most stable form C, symmetry with a synperiplanar (syn) orientation of the carbonyl double bond (C=O) with respect to both the CH3O- and -SCN groups (syn-syn). Several bands assigned to a second conformer have been observed ill the IR matrix spectra. This rotamer presents an antiperiplanar orientation of the thiocyanate group (syn-anti). Evaluating the equilibrium compositions at different temperatures by quenching the gas phase MiXtUreS as Ar matrices allowed LIS to determine the conformational enthalpy difference Delta H-0 = H-(syn-anti)(0) - H-(syn-syn)(0) = 0.80(18) kcal mol(-1). A similar conformational behavior has been determined for compound II. Thermodynamic properties were also computed at the high-level G2MP2 and G3 model chemistry methods. The importance of mesomeric (resonance) and anomeric (hyperconjugation) electronic interaction in the conformational behavior is evaluated by using the NBO approach for both species.