1-3.4-tetramethylen-benzol | 1914-36-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: 1-3.4-tetramethylen-benzol
• 英文别名: 1-(Hexin-(5)-yl)3.4-tetramethylen-benzol；6-Hex-5-ynyl-1,2,3,4-tetrahydronaphthalene
• CAS: 1914-36-9
• 化学式: C₁₆H₂₀
• 分子量: 212.335
• InChiKey: XRLALQHWVRZBNK-UHFFFAOYSA-N

物化性质

• 沸点：
  337.8±21.0 °C(Predicted)
• 密度：
  0.970±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  1,7-辛二炔 在 五氯化钼 、 氢化铝 作用下， 以 乙二醇二甲醚 为溶剂， 反应 1.0h， 以89%的产率得到1-3.4-tetramethylen-benzol
  参考文献：
  名称：

  Reduction of Molybdenum(V) Chloride with Various Reducing Metals: Reactivity Correlations with the Descendant Lewis Acids

  摘要：

  来自MoCl5与各种还原金属在DME中制备的低价钼的反应性，依赖于还原金属，对于炔烃的环三聚化反应，其顺序为：Al > Sn, In > Zn, Mg, Li。这个顺序与后续路易斯酸的酸性相对应。

  DOI：

  10.1246/cl.2000.140

文献信息

• Highly Regio- and Stereoselective Cocyclotrimerization and Linear Cotrimerization of α,β-Unsaturated Carbonyl Compounds with Alkynes Catalyzed by Nickel Complexes
  作者：Thota Sambaiah、Lih-Ping Li、Daw-Jen Huang、Cheng-Hong Lin、Dinesh Kumar Rayabarapu、Chien-Hong Cheng

  DOI：10.1021/jo9900580

  日期：1999.5.1

  degrees C affords the corresponding conjugated trienes 17a-c in 82-92% yields. The MS data of 17firmly support an adduct of two molecules of alkyne and a molecule of acrylate. Similarly, the reaction of 15a with octa-1,7-diyne in the presence of Ni(PPh(3))(2)I(2), ZnI(2), and zinc gives triene derivative 21 in 68% yield. NOE and X-ray results indicate that in these trienes the substituents from each alkyne

  环烯酮2-环己烯-1-酮（1a），4,4-二甲基-2-环己烯-1-酮（1b），2-环戊烯-1-酮（1c）和2-环庚烯-1-酮（ 1d）与Ni（PPh（3））（2）I（2），ZnI（2）和Zn粉在62°C下在THF中与octa-1,7-diyne（2）反应，得到[ [2 + 2 + 2]环加成-脱氢产物3a-d的产率为32-80％。对α，β-不饱和内酯5a（5,6-二氢-2H-吡喃-2-酮）进行[2 + 2 + 2]环加成反应，得到2相应的环己二烯产物6（29％）和脱氢产物7（ 39％）。在相似的反应条件下，3-丁烯-2-酮与2和各种取代的庚-1,6-二炔9a-c反应，以68-80％的产率得到[2 + 2 + 2]环加成-脱氢产物11a-d 。二苯乙炔也可与1a-d，5a反应，和2（5H）-呋喃酮（5b），得到相应的[2 + 2 + 2]共环三聚产物13a-d和14a-b。在反应和后处理条件
• Nickel(0)-Catalyzed [2 + 2 + 2 + 2] Cycloadditions of Terminal Diynes for the Synthesis of Substituted Cyclooctatetraenes
  作者：Paul A. Wender、Justin P. Christy

  DOI：10.1021/ja0763044

  日期：2007.11.1

  The Ni(0)-catalyzed [2 + 2 + 2 + 2] cycloadditions of 1,6- and 1,7-diynes are shown to provide an efficient and selective method for the preparation of 1,2,5,6-tetrasubstituted cyclooctatetraenes (COTs). Catalysts and conditions are described that favor in all cases COT formation over competing [2 + 2 + 2] cycloadditions. A hitherto unexplored crossed reaction is also described, providing access to

  Ni(0)-催化的 1,6- 和 1,7-二炔的 [2 + 2 + 2 + 2] 环加成为制备 1,2,5,6-四取代物提供了一种有效且选择性的方法环辛四烯 (COT)。所描述的催化剂和条件在所有情况下都比竞争性 [2 + 2 + 2] 环加成更有利于 COT 的形成。还描述了迄今为止未探索的交叉反应，提供对非对称 COT 的访问。
• From stoichiometry to catalysis: electroreductive coupling of alkynes and carbon dioxide with nickel-bipyridine complexes. Magnesium ions as the key for catalysis
  作者：Sylvie Derien、Elisabet Dunach、Jacques Perichon

  DOI：10.1021/ja00022a037

  日期：1991.10

  The incorporation of carbon dioxide into nonactivated alkynes catalyzed by electrogenerated nickel-bipyridine complexes affords alpha,beta-unsaturated acids in moderate to good yields. The electrocarboxylation reaction was undertaken on a preparative scale in the presence of a sacrificial magnesium anode: the formation of acids from alkynes is stoichiometric with respect to the nickel complex if performed in a two-compartment cell but can be made catalytic in a single-compartment cell. An intermediate nickelacycle was isolated from the reaction with 4-octyne. The cleavage of this metallacycle by magnesium ions is the key step to explain catalysis.
• Activation of carbon dioxide: nickel-catalyzed electrochemical carboxylation of diynes
  作者：Sylvie Derien、Jean Claude Clinet、Elisabet Dunach、Jacques Perichon

  DOI：10.1021/jo00061a038

  日期：1993.4

  The simultaneous activation of carbon dioxide and diynes by electrogenerated LNi(0) complexes (L = bpy, pentamethyldiethylenetriamine: PMDTA) enables the selective incorporation of one molecule of CO2 into the unsaturated systems and the preparative-scale electrosyntheses of carboxylic acids. A series of nonconjugated diynes afforded selectively linear or cyclic adducts depending on the ligand. Diynes bearing both a terminal and an internal triple bond gave exclusive CO2 incorporation into the terminal alkynyl group, regioselectively at the 2-position. The electrocarboxylation of 1,3-diynes with the Ni-PMDTA catalytic system yielded, regio- and stereoselectively, (E)-2-vinylidene-3-yne carboxylic acids in one step. The electrosyntheses were carried out in single-compartment cells fitted with a consumable magnesium anode, and utilized a catalytic amount of an air-stable Ni(II) complex as the catalyst precursor. Cyclic voltammetry studies revealed that both carbon dioxide and the diynes are able to coordinate to LNi(0)-generated species in DMF.
• Ruthenium-mediated cyclotrimerization of alkynes utilizing the cationic complex [RuCp(CH3CN)3]PF6
  作者：Eva Rüba、Roland Schmid、Karl Kirchner、Maria José Calhorda

  DOI：10.1016/s0022-328x(03)00783-6

  日期：2003.10

  The substitutionally labile cationic complex [RuCp(CH3CN)(3)](+) (as the PF6- salt) was tested with respect to its ability to catalyze the cyclotrimerization of terminal alkynes and diynes to afford benzene derivatives. Whereas [RuCp(CH3CN)(3)](+) is in fact promoting the catalytic cyclotrimerization of alkynes, the formation of stable and inert sandwich complexes of the type [RuCp(eta(6)- arene)](+) deactivates the catalyst and thus quenches the catalytic cycle. All new sandwich complexes were isolated and characterized spectroscopically. A proposal for a plausible catalytic cycle including possible degradation pathways of the catalyst is presented based on DFT calculations. As key intermediates several novel carbene complexes have been identified including metallacyclo-pentatriene and metallaheptatetraene species. (C) 2003 Elsevier B.V. All rights reserved.