2-[5-(4-Methoxy-phenyl)-[1,2]dithiol-(3Z)-ylidenemethyl]-pyridine | 141511-40-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-[5-(4-Methoxy-phenyl)-[1,2]dithiol-(3Z)-ylidenemethyl]-pyridine
• 英文别名: 2-[(Z)-[5-(4-methoxyphenyl)dithiol-3-ylidene]methyl]pyridine
• CAS: 141511-40-2
• 化学式: C₁₆H₁₃NOS₂
• 分子量: 299.417
• InChiKey: GVHWGTSONWYMAY-GDNBJRDFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  72.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-[5-(4-Methoxy-phenyl)-[1,2]dithiol-(3Z)-ylidenemethyl]-pyridine 在 sodium nitrite 作用下， 以 溶剂黄146 、 乙腈 为溶剂， 反应 0.17h， 以40%的产率得到5-(4-Methoxy-phenyl)-3-pyridin-2-yl-7λ⁴-[1,2]dithiolo[1,5-b][1,2,5]oxathiazole
  参考文献：
  名称：

  (Pyridinylmethylidene)dithioles: synthesis, structure, and reactivity

  摘要：

  Spectral characteristics, an X-ray crystal structure, and molecular orbital calculations indicate that (pyridinylmethylidene)dithioles 3, prepared from butadiynyl precursors 4 and hydrogen sulfide in basic methanol, are analogous in their bonding to the parent 1-aza-6,6a-lambda-4-dithiapentalenes 1 which, according to ab initio studies at the Hartree-Fock level, is best represented as an (iminomethylidene)dithiole. An interaction between the sulfur and the nitrogen atoms is evident from the significant polarization of the S-S bond in those isomers where the nitrogen is proximal to the dithiole moiety. A comparison of the calculated structures of 1 and 3 with experimental data, as well as preliminary calculations on the related system trithiapentalene 2, suggest that ab initio methods using a single determinant are inadequate to describe these hypervalent sulfur systems. For example, an asymmetric structure is calculated to be the minimum energy form for 2 in contradiction to experimental results. Electrophilic substitutions, ring rearrangement, and reaction with electron acceptors are described for 3.

  DOI：

  10.1021/jo00040a032
• 作为产物：
  描述：

  2-((4-methoxyphenyl)buta-1,3-diyn-1-yl)pyridine 在 sodium hydroxide 、 硫化氢 作用下， 以 甲醇 为溶剂， 反应 15.0h， 以55%的产率得到2-[5-(4-Methoxy-phenyl)-[1,2]dithiol-(3Z)-ylidenemethyl]-pyridine
  参考文献：
  名称：

  (Pyridinylmethylidene)dithioles: synthesis, structure, and reactivity

  摘要：

  Spectral characteristics, an X-ray crystal structure, and molecular orbital calculations indicate that (pyridinylmethylidene)dithioles 3, prepared from butadiynyl precursors 4 and hydrogen sulfide in basic methanol, are analogous in their bonding to the parent 1-aza-6,6a-lambda-4-dithiapentalenes 1 which, according to ab initio studies at the Hartree-Fock level, is best represented as an (iminomethylidene)dithiole. An interaction between the sulfur and the nitrogen atoms is evident from the significant polarization of the S-S bond in those isomers where the nitrogen is proximal to the dithiole moiety. A comparison of the calculated structures of 1 and 3 with experimental data, as well as preliminary calculations on the related system trithiapentalene 2, suggest that ab initio methods using a single determinant are inadequate to describe these hypervalent sulfur systems. For example, an asymmetric structure is calculated to be the minimum energy form for 2 in contradiction to experimental results. Electrophilic substitutions, ring rearrangement, and reaction with electron acceptors are described for 3.

  DOI：

  10.1021/jo00040a032

文献信息

• (Pyridinylmethylidene)dithioles: synthesis, structure, and reactivity
  作者：Kevin T. Potts、Susan A. Nye、Kennith A. Smith

  DOI：10.1021/jo00040a032

  日期：1992.7

  Spectral characteristics, an X-ray crystal structure, and molecular orbital calculations indicate that (pyridinylmethylidene)dithioles 3, prepared from butadiynyl precursors 4 and hydrogen sulfide in basic methanol, are analogous in their bonding to the parent 1-aza-6,6a-lambda-4-dithiapentalenes 1 which, according to ab initio studies at the Hartree-Fock level, is best represented as an (iminomethylidene)dithiole. An interaction between the sulfur and the nitrogen atoms is evident from the significant polarization of the S-S bond in those isomers where the nitrogen is proximal to the dithiole moiety. A comparison of the calculated structures of 1 and 3 with experimental data, as well as preliminary calculations on the related system trithiapentalene 2, suggest that ab initio methods using a single determinant are inadequate to describe these hypervalent sulfur systems. For example, an asymmetric structure is calculated to be the minimum energy form for 2 in contradiction to experimental results. Electrophilic substitutions, ring rearrangement, and reaction with electron acceptors are described for 3.