2-[(But-2-yn-1-yloxy)methyl]-1-(2-{2-[(but-2-yn-1-yloxy)methyl]phenyl}ethyn-1-yl)naphthalene | 207673-33-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-[(But-2-yn-1-yloxy)methyl]-1-(2-{2-[(but-2-yn-1-yloxy)methyl]phenyl}ethyn-1-yl)naphthalene
• 英文别名: 2-(But-2-ynoxymethyl)-1-[2-[2-(but-2-ynoxymethyl)phenyl]ethynyl]naphthalene
• CAS: 207673-33-4
• 化学式: C₂₈H₂₄O₂
• 分子量: 392.497
• InChiKey: QPMZOWLIZPQSOZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-[(But-2-yn-1-yloxy)methyl]-1-(2-{2-[(but-2-yn-1-yloxy)methyl]phenyl}ethyn-1-yl)naphthalene 在 carbon monoxide,cobalt,cyclopenta-1,3-diene 三苯基膦 作用下， 以 癸烷 为溶剂， 反应 2.0h， 以80%的产率得到4,5-dimethyl-1,3,6,8-tetrahydrobenzo[c]naphtho[1'',2'':5',6']oxepino[3',4':5,6]benzo[3]oxepin
  参考文献：
  名称：

  A Novel Strategy for the Synthesis of Molecules with Helical Chirality. Intramolecular [2 + 2 + 2] Cycloisomerization of Triynes under Cobalt Catalysis

  摘要：

  A straightforward synthetic approach to a new das's of molecules with helical chirality has been developed involving an intramolecular [2 + 2 + 2] cycloisomerization of triynes under CpCo(CO)(2)/ PPh3 catalysis. The cyclization reaction is promoted by visible light irradiation. Starting from 1,2-diarylacetylenes with two terminal or methyl-substituted tethered acetylene moieties (1a,b,4, 5, and 7), the target products (8a,b, 11, 12, and 14) are obtained in 64-89% yield. The triynes bearing terminal trimethylsilyl groups (Ic, 2, and 3) are less reactive and afford the products (8c, 9a,b, and 10) in 23-71% yield. The ability of the trimethylsilylated derivatives to cycloisomerize strongly depends on the tether length. The cyclized products (8-14) with five, six, and seven ortho-fused rings structurally resemble classical helicenes. Several representatives (8b, 11, 12, and 14) have been resolved into enantiomers by HPLC on a chiral column. Thus, the methodology exhibits a considerable versatility and allows the preparation of a variety of helical objects.

  DOI：

  10.1021/jo9801263
• 作为产物：
  描述：

  methyl 1-[2-(2-methoxycarbonylphenyl)-1-ethynyl]-2-naphthoate 在 三溴化磷 、 sodium hydride 、 红铝 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 5.33h， 生成 2-[(But-2-yn-1-yloxy)methyl]-1-(2-{2-[(but-2-yn-1-yloxy)methyl]phenyl}ethyn-1-yl)naphthalene
  参考文献：
  名称：

  Synthesis of Aromatic Triynes as Precursors to Helicene Derivatives

  摘要：

  已经开发出一种通用且多功能的合成方法，用于制备芳香三炔作为螺环衍生物的前体。利用一组简单的工具，在整个反应序列中成功制备了包含苯基乙炔基苯、1-(苯基乙炔基)萘和1-(1-萘基乙炔基)-萘基的三炔，收率良好至优良。该方法允许在中心二芳基乙炔基和附加的乙炔单元之间构建各种类型的连接点，以获得通用公式 R-C≡C-CH₂-X-CH₂-Ar-C≡C-Ar'-CH₂-X-CH₂-C≡C-R 或 R-C≡C-CH₂CH₂-Ar-C≡C-Ar'-CH₂CH₂-C≡C-R（R = H、CH₃、TMS 或 TIPS；X = O、NTs 或 C(CO₂CH₃)₂；Ar/Ar' = 2-苯基或2-萘基）。

  DOI：

  10.1135/cccc20000577

文献信息

• Synthesis of Aromatic Triynes as Precursors to Helicene Derivatives
  作者：Irena G. Stará、Adrian Kollárovič、Filip Teplý、Ivo Starý、David Šaman、Pavel Fiedler

  DOI：10.1135/cccc20000577

  日期：——

  A general and versatile synthetic approach to a broad series of aromatic triynes as precursors to helicene derivatives has been developed. Employing a set of simple tools, triynes comprising the (phenylethynyl)benzene, 1-(phenylethynyl)naphthalene, and 1-(1-naphthylethynyl)- naphthalene moiety have been prepared in good to excellent yields throughout the whole reaction sequence. The methodology allows constructing various types of a junction between the central diarylacetylene moiety and the attached acetylene units to get the target triynes of general formula R-C≡C-CH₂-X-CH₂-Ar-C≡C-Ar'-CH₂-X-CH₂-C≡C-R or R-C≡C-CH₂CH₂-Ar-C≡C-Ar'-CH₂CH₂-C≡C-R (R = H, CH₃, TMS, or TIPS; X = O, NTs, or C(CO₂CH₃)₂; Ar/Ar' = 2-phenylene or 2-naphthylene).

  已经开发出一种通用且多功能的合成方法，用于制备芳香三炔作为螺环衍生物的前体。利用一组简单的工具，在整个反应序列中成功制备了包含苯基乙炔基苯、1-(苯基乙炔基)萘和1-(1-萘基乙炔基)-萘基的三炔，收率良好至优良。该方法允许在中心二芳基乙炔基和附加的乙炔单元之间构建各种类型的连接点，以获得通用公式 R-C≡C-CH₂-X-CH₂-Ar-C≡C-Ar'-CH₂-X-CH₂-C≡C-R 或 R-C≡C-CH₂CH₂-Ar-C≡C-Ar'-CH₂CH₂-C≡C-R（R = H、CH₃、TMS 或 TIPS；X = O、NTs 或 C(CO₂CH₃)₂；Ar/Ar' = 2-苯基或2-萘基）。
• A Novel Strategy for the Synthesis of Molecules with Helical Chirality. Intramolecular [2 + 2 + 2] Cycloisomerization of Triynes under Cobalt Catalysis
  作者：Irena G. Stará、Ivo Starý、Adrian Kollárovič、Filip Teplý、David Šaman、Miloš Tichý

  DOI：10.1021/jo9801263

  日期：1998.6.1

  A straightforward synthetic approach to a new das's of molecules with helical chirality has been developed involving an intramolecular [2 + 2 + 2] cycloisomerization of triynes under CpCo(CO)(2)/ PPh3 catalysis. The cyclization reaction is promoted by visible light irradiation. Starting from 1,2-diarylacetylenes with two terminal or methyl-substituted tethered acetylene moieties (1a,b,4, 5, and 7), the target products (8a,b, 11, 12, and 14) are obtained in 64-89% yield. The triynes bearing terminal trimethylsilyl groups (Ic, 2, and 3) are less reactive and afford the products (8c, 9a,b, and 10) in 23-71% yield. The ability of the trimethylsilylated derivatives to cycloisomerize strongly depends on the tether length. The cyclized products (8-14) with five, six, and seven ortho-fused rings structurally resemble classical helicenes. Several representatives (8b, 11, 12, and 14) have been resolved into enantiomers by HPLC on a chiral column. Thus, the methodology exhibits a considerable versatility and allows the preparation of a variety of helical objects.