o-Ethynyltoluene-d1 | 928044-70-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: o-Ethynyltoluene-d1
• 英文别名: o-Tolylacetylen；2-ethynyl-d1-toluene；DCC(o-Tol)；1-(2-Deuterioethynyl)-2-methylbenzene
• CAS: 928044-70-6
• 化学式: C₉H₈
• 分子量: 117.155
• InChiKey: MYBSUWNEMXUTAX-MICDWDOJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-(4-methylbenzensulfonyl)-4-phenyl-1H-1,2,3-triazole 、 o-Ethynyltoluene-d1 在 辛酸铑 、 silver trifluoroacetate 作用下， 以 正己烷 为溶剂， 反应 12.0h， 生成
  参考文献：
  名称：

  Rh 催化 N-Tosyl-1,2,3-Triazoles 与末端炔烃的环化反应

  摘要：

  报道了具有末端炔烃的 1,2,3-三唑的第一次环化成吡咯。该反应在 Rh 2 (oct) 4 /AgOCOCF 3二元催化剂体系的存在下进行，提供了一种以良好到极好的产率获得 1,2,4-三取代吡咯的直接方法。

  DOI：

  10.1021/ol2014347
• 作为产物：
  描述：

  2-乙炔基甲苯 在 正丁基锂 、 氘代甲醇 作用下， 以 正己烷 为溶剂， 反应 0.5h， 生成 o-Ethynyltoluene-d1
  参考文献：
  名称：

  Rh 催化 N-Tosyl-1,2,3-Triazoles 与末端炔烃的环化反应

  摘要：

  报道了具有末端炔烃的 1,2,3-三唑的第一次环化成吡咯。该反应在 Rh 2 (oct) 4 /AgOCOCF 3二元催化剂体系的存在下进行，提供了一种以良好到极好的产率获得 1,2,4-三取代吡咯的直接方法。

  DOI：

  10.1021/ol2014347

文献信息

• Ultraviolet Photochemistry of Diacetylene:  Reactions with Benzene and Toluene
  作者：Allison G. Robinson、Paul R. Winter、Christopher Ramos、Timothy S. Zwier

  DOI：10.1021/jp001427v

  日期：2000.11.1

  The reactions of metastable diacetylene with benzene and toluene are explored using a molecular beam pump−probe time-of-flight mass spectrometer. Diacetylene is laser-excited to the 210610 band of the 1Δu ← X1Σ+g transition, whereupon rapid intersystem crossing occurs to the lowest triplet states. The triplet state diacetylene then reacts with either benzene or toluene as the gas mixture traverses

  使用分子束泵-探针飞行时间质谱仪探索了亚稳态联乙炔与苯和甲苯的反应。联乙炔被激光激发到 1Δu ← X1Σ+g 跃迁的 210610 波段，因此系统间快速交叉发生到最低的三重态。当气体混合物穿过短反应管（~20 μs）时，三重态联乙炔与苯或甲苯反应。当气体混合物膨胀到飞行时间质谱仪的离子源区域时，反应被淬火，在该区域使用真空紫外 (VUV) 光电离或共振双光子电离 (R2PI) 检测初级光产物。联乙炔与苯反应的主要产物分子式为 C8H6 和 C10H6，并使用 R2PI 光谱鉴定为苯乙炔和苯二乙炔。亚稳态二乙炔与甲苯反应的主要产物是C9H8和C11H8。C9H8 产物被确认为 o-、m-、...的混合物
• Dimerization of Alkynes Promoted by a Pincer-Ligated Iridium Complex. C−C Reductive Elimination Inhibited by Steric Crowding
  作者：Rajshekhar Ghosh、Xiawei Zhang、Patrick Achord、Thomas J. Emge、Karsten Krogh-Jespersen、Alan S. Goldman

  DOI：10.1021/ja0647194

  日期：2007.1.1

  The pincer-ligated species (PCP)Ir (PCP = kappa(3)-C6H3-2,6-((CH2PBu2)-Bu-t)(2)) is found to promote dimerization of phenylacetylene to give the enyne complex (PCP)Ir(trans-1,4-phenyl-but-3-ene-1-yne). The mechanism of this reaction is found to proceed through three steps: (i) addition of the alkynyl C-H bond to iridium, (ii) insertion of a second phenylacetylene molecule into the resulting Ir-H bond, and (iii) vinyl-acetylide reductive elimination. Each of these steps has been investigated, by both experimental and computational (DFT) methods, to yield unexpected conclusions of general interest. (i) The product of alkynyl C-H addition, (PCP)Ir(CCPh)(H) (3), has been isolated and, in accord with experimental observations, is calculated to be 29 kcal/mol more stable than the analogous product of benzene C-H addition. (ii) Insertion of a second PhCCH molecule into the Ir-H bond of 3 proceeds rapidly, but with a 1,2-orientation. This orientation gives (PCP)Ir(CCPh)(CPhCH2) (4) which would yield the 1,3-diphenyl-enyne if it were to undergo C-C elimination; however, the insertion is reversible, which represents the first example, to our knowledge, of simple beta-H elimination from a vinyl group to give a terminal hydride. The 2,1-insertion product (PCP)Ir(CCPh)(CHCHPh) (6) forms more slowly, but unlike the 1,2 insertion product it undergoes C-C elimination to give the observed enyne. (iii) The failure of 4 to undergo C-C elimination is found to be general for (PCP)Ir(CCPh)(vinyl) complexes in which the vinyl group has an alpha-substituent. Thus, although C-C elimination relieves crowding, the reaction is inhibited by increased crowding. Density-functional theory (DFT) calculations support this surprising conclusion and offer a clear explanation. Alkynyl-vinyl bond formation in the C-C elimination transition state involves the vinyl group pi-system; this requires that the vinyl group must rotate (around the Ir-C bond) by ca. 90 degrees to achieve an appropriate orientation. This rotation is severely inhibited by steric crowding, particularly when the vinyl group bears an alpha-substituent.
• Rh-Catalyzed Transannulation of <i>N</i>-Tosyl-1,2,3-Triazoles with Terminal Alkynes
  作者：Buddhadeb Chattopadhyay、Vladimir Gevorgyan

  DOI：10.1021/ol2014347

  日期：2011.7.15

  The first transannulation of 1,2,3-triazoles with terminal alkynes into pyrroles is reported. The reaction proceeds in the presence of a Rh2(oct)4/AgOCOCF3 binary catalyst system providing a straightforward approach to 1,2,4-trisubstituted pyrroles in good to excellent yields.

  报道了具有末端炔烃的 1,2,3-三唑的第一次环化成吡咯。该反应在 Rh 2 (oct) 4 /AgOCOCF 3二元催化剂体系的存在下进行，提供了一种以良好到极好的产率获得 1,2,4-三取代吡咯的直接方法。
• Creating Dynamic Nanospaces in Solution by Cationic Cages as Multirole Catalytic Platform for Unconventional C(sp)−H Activation Beyond Enzyme Mimics
  作者：Kang Li、Kai Wu、Yu‐Lin Lu、Jing Guo、Peng Hu、Cheng‐Yong Su

  DOI：10.1002/anie.202114070

  日期：2022.1.26

  The generation of permeable porous-cage nanospaces in solution by a highly charged cationic [Pd6(RuL3)8]28+ cage for multirole and multi-way supramolecular catalysis is reported.

  报道了通过高电荷阳离子[Pd 6 (RuL 3 ) 8 ] 28+笼在溶液中生成可渗透的多孔笼纳米空间，用于多角色和多向超分子催化。