2-((4-methoxyphenyl)buta-1,3-diyn-1-yl)pyridine | 22779-13-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-((4-methoxyphenyl)buta-1,3-diyn-1-yl)pyridine
• 英文别名: 2-[4-(4-methoxyphenyl)buta-1,3-diynyl]pyridine
• CAS: 22779-13-1
• 化学式: C₁₆H₁₁NO
• 分子量: 233.269
• InChiKey: LWSDOJAYXJLOAS-UHFFFAOYSA-N

物化性质

• 沸点：
  395.8±38.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.49
• 重原子数：
  18.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  22.12
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2-((4-methoxyphenyl)buta-1,3-diyn-1-yl)pyridine 在 sodium hydroxide 、 硫化氢 、 sodium nitrite 作用下， 以 甲醇 、 溶剂黄146 、 乙腈 为溶剂， 反应 15.17h， 生成 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-乙炔基吡啶 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 苄基三甲基氯化铵 copper(I) chloride 、 sodium hydroxide 、 盐酸羟胺 、 乙胺 作用下， 以 甲醇 、 苯 为溶剂， 反应 38.0h， 生成 2-((4-methoxyphenyl)buta-1,3-diyn-1-yl)pyridine
  参考文献：
  名称：

  Novel Synthesis of Unsymmetrical Diarylbutadiynes

  摘要：

  由 6-芳基-3,5-己二烯-2-醇衍生的末端芳基丁二炔，在相转移催化剂存在下与活化的芳基卤化物发生钯催化偶联，生成不对称的二芳基丁二炔，而其他偶联过程不易得到这种二芳基丁二炔。

  DOI：

  10.1055/s-1988-27578

文献信息

• Novel Synthesis of Unsymmetrical Diarylbutadiynes
  作者：Susan Adams Nye、Kevin T. Potts

  DOI：10.1055/s-1988-27578

  日期：——

  Terminal arylbutadiynes, derived from 6-aryl-3,5-hexadin-2-ols, undergo a ready palladium-catalyzed coupling with activated aryl halides in the presence of a phase transfer catalyst to unsymmetrical diarylbutadiynes, not easily available by other coupling procedures.

  由 6-芳基-3,5-己二烯-2-醇衍生的末端芳基丁二炔，在相转移催化剂存在下与活化的芳基卤化物发生钯催化偶联，生成不对称的二芳基丁二炔，而其他偶联过程不易得到这种二芳基丁二炔。
• Iron-Catalyzed Cadiot–Chodkiewicz Coupling with High Selectivity in Water under Air
  作者：Yi-An Liao、Wen-Sheng Peng、Ling-Jun Liu、Ting-You Ye、Jun-Hao Fu、Yi-Tsu Chan、Fu-Yu Tsai

  DOI：10.1021/acs.joc.2c01354

  日期：2022.11.4

  An iron-based catalytic system was developed for the cross-coupling of 1-bromoalkynes with terminal alkynes to selectively generate unsymmetrical 1,3-butadiynes in water under air. It was found that a combination of 1-bromoalkynes derived from less acidic terminal alkynes with more acidic counterparts would greatly enhance yields and selectivity for unsymmetrical 1,3-butadiynes. The reaction was also

  开发了一种铁基催化体系，用于 1-溴炔烃与末端炔烃的交叉偶联，从而在空气中选择性地在水中生成不对称的 1,3-丁二炔。发现由酸性较低的末端炔烃衍生的 1-溴炔烃与酸性较强的对应物的组合将大大提高不对称 1,3-丁二炔的产率和选择性。该反应还适用于通过一锅法偶联1-溴炔烃和三甲基甲硅烷基保护的1,3-丁二炔来合成不对称的1,3,5-己三炔。
• A convenient route to 1,3-diynes using ligand-free Cadiot-Chodkiewicz coupling reaction at room temperature under aerobic conditions
  作者：Sujatha Asha、Sasidharan Anjana、Anns Maria Thomas、Minu Elizabeth Thomas、K. R. Rohit、K. Keerthi Krishnan、Sankuviruthiyil M Ujwaldev、Gopinathan Anilkumar

  DOI：10.1080/00397911.2018.1554142

  日期：2019.1.17

  Abstract In this study, we report a copper-catalyzed ligand-free Cadiot-Chodkiewicz coupling reaction. No additives or ligands are required for this Cu-catalyzed C(sp)-C(sp) coupling reaction of terminal alkynes with alkynyl halides. The low cost of copper catalyst, excellent yield of the products, suppression of side-products and mild reaction conditions are the major advantages of this protocol.

  摘要 在这项研究中，我们报告了铜催化的无配体 Cadiot-Chodkiewicz 偶联反应。这种铜催化的末端炔烃与炔基卤化物的 C(sp)-C(sp) 偶联反应不需要添加剂或配体。铜催化剂成本低、产品收率高、副产物抑制和反应条件温和是该协议的主要优点。图形概要
• (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.