1,2-bis[4-(tert-butyl benzoate)]acetylene

• 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: 1,2-bis[4-(tert-butyl benzoate)]acetylene
• 英文别名: 1,2-bis(4-(t-butoxycarbonyl)phenyl)ethyne；di-tert-butyl 4,4'-(ethyne-1,2-diyl)dibenzoate；4,4'-Tolan-dicarboxylic acid di-tert.-butyl ester；tert-butyl 4-[2-[4-[(2-methylpropan-2-yl)oxycarbonyl]phenyl]ethynyl]benzoate
• 化学式: C₂₄H₂₆O₄
• 分子量: 378.468
• InChiKey: BLTPTMRZTSCZER-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  28
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,2-bis[4-(tert-butyl benzoate)]acetylene 、 二氧化碳 在 三乙氧基硅烷 、 [IMesCuF] 、 盐酸 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 水 为溶剂， 反应 4.25h， 以71%的产率得到(E)-2,3-bis[4-[(2-methylpropan-2-yl)oxycarbonyl]phenyl]prop-2-enoic acid
  参考文献：
  名称：

  使用二氧化碳和氢硅烷的铜催化炔烃加氢羧化反应

  摘要：

  解决方法：已开发出在还原性氢化硅烷的存在下使用二氧化碳在铜上进行炔烃的铜催化加氢羧化反应（参见方案）。带有N杂环卡宾配体（例如IMes和Cl 2 IPr）的氟化铜显示出高催化活性。

  DOI：

  10.1002/anie.201006292
• 作为产物：
  描述：

  4-碘苯甲酸叔丁酯 、 三甲基乙炔基硅 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 水 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 苯 为溶剂， 反应 36.0h， 以62%的产率得到1,2-bis[4-(tert-butyl benzoate)]acetylene
  参考文献：
  名称：

  使用二氧化碳和氢硅烷的铜催化炔烃加氢羧化反应

  摘要：

  解决方法：已开发出在还原性氢化硅烷的存在下使用二氧化碳在铜上进行炔烃的铜催化加氢羧化反应（参见方案）。带有N杂环卡宾配体（例如IMes和Cl 2 IPr）的氟化铜显示出高催化活性。

  DOI：

  10.1002/anie.201006292

文献信息

• Sodium silylsilanolate as a precursor of silylcopper species
  作者：Hiroki Yamagishi、Kenshiro Hitoshio、Jun Shimokawa、Hideki Yorimitsu

  DOI：10.1039/d2sc00227b

  日期：——

  Sodium silylsilanolates are demonstrated as useful silylating reagents for copper-catalysed hydrosilylation of unsaturated bonds via the formation of reactive silylcopper species that can deliver a series of silyl groups.

  硅酸钠硅醇盐被证明是铜催化的不饱和键氢硅化反应中有用的硅基化试剂，通过形成反应性硅基铜物种，可以提供一系列硅基团。
• Bifunctional stilbene compounds containing at least one Z-configurated
  申请人：Bayer Aktiengesellschaft

  公开号：US05068300A1

  公开（公告）日：1991-11-26

  New Z-stilbene compounds and a process for their preparation are disclosed wherein the compounds correspond to the following formulae: ##STR1##

  本发明涉及新的Z-苯乙烯化合物及其制备方法，其中化合物对应于以下公式：##STR1##
• Catalytic C−C/C−H Bond Activation Relay for Synthesis of Fluorescent Naphthoquinolizinium Salts
  作者：Jan Ulč、Jaroslav Jacko、Ivana Císařová、Lubomír Pospíšil、David Nečas、Martin Kotora

  DOI：10.1002/ejoc.202300153

  日期：——

  A sequential catalytic C−C/C−H bond activation relay starting from 1-azabiphenylene via intermediate benzo[h]quinolines allows short syntheses of various 5,6,10,11-tetrasubstituted naphtho[2,1,8-ija]quinolizinium salts bearing various types of substituents. The salts exhibit strong fluorescence (up to >99 %) ranging from 420–600 nm.

  从 1-azabiphenylene 开始通过中间体苯并 [ h ] 喹啉的顺序催化 C−C/C−H 键激活中继允许短合成各种 5,6,10,11-四取代萘并[2,1,8- ija ]喹啉鎓带有各种类型取代基的盐。这些盐在 420–600 nm 范围内表现出强烈的荧光（高达 >99%）。
• 10.1039/d4ob00724g
  作者：Huai, Menglin、Chen, Long、Dong, Wei、Wang, Weijie、Qin, Zhen、Dai, Kaifeng、Li, Yuan、Zhang, Xiulian、Tao, Chuanzhou

  DOI：10.1039/d4ob00724g

  日期：——

  A copper-catalyzed syn-hydrocarbonization of internal alkynes with N,N-dimethylformamide dimethylacetal and silanes has been disclosed that offers an efficient and expedient access to (E)-α,β-unsaturated aldehydes. This highly selective process, which can be performed at gram-scale, enjoys operational simplicity, as well as syngas-free conditions.

  已经公开了铜催化的内炔与N , N-二甲基甲酰胺二甲基缩醛和硅烷的顺式烃化，其提供了有效且方便地获得( E )-α,β-不饱和醛的方法。这种高度选择性的过程可以在克级进行，操作简单，并且无需合成气。
• Synthetic, Mechanistic, and Computational Investigations of Nitrile-Alkyne Cross-Metathesis
  作者：Andrea M. Geyer、Eric S. Wiedner、J. Brannon Gary、Robyn L. Gdula、Nicola C. Kuhlmann、Marc J. A. Johnson、Barry D. Dunietz、Jeff W. Kampf

  DOI：10.1021/ja800020w

  日期：2008.7.1

  The terminal nitride complexes NW(OC(CF3)(2)Me)(3)(DME) (1-DME), [Li(DME)(2)][NW(OC(CF3)(2)Me)(4)] (2), and [NW(OCMe2CF3)(3)](3) (3) were prepared in good yield by salt elimination from [NWCl3](4). X-ray structures revealed that 1-DME and 2 are monomeric in the solid state. All three complexes catalyze the cross-metathesis of 3-hexyne with assorted nitriles to form propionitrile and the corresponding alkyne. Propylidyne and substituted benzylidyne complexes RCW(OC(CF3)(2)Me)(3) were isolated in good yield upon reaction of 1-DME with 3-hexyne or 1-aryl-1-butyne. The corresponding reactions failed for 3. Instead, EtCW(OC(CF3)Me-2)(3) (6) was prepared via the reaction of W-2(OC(CF3)Me-2)(6) with 3-hexyne at 95 degrees C. Benzylidyne complexes of the form ArCW(OC(CF3)Me-2)(3) (Ar = aryl) then were prepared by treatment of 6 with the appropriate symmetrical alkyne ArCCAr. Three coupled cycles for the interconversion of 1-DME with the corresponding propylidyne and benzylidyne complexes via [2 + 2] cycloaddition-cycloreversion were examined for reversibility. Stoichiometric reactions revealed that both nitrile-alkyne cross-metathesis (NACM) cycles as well as the alkyne cross-metathesis (ACM) cycle operated reversibly in this system. With catalyst 3, depending on the aryl group used, at least one step in one of the NACM cycles was irreversible. In general, catalyst 1-DME afforded more rapid reaction than did 3 under comparable conditions. However, 3 displayed a slightly improved tolerance of polar functional groups than did 1-DME. For both 11-DME and 3, ACM is more rapid than NACM under typical conditions. Alkyne polymerization (AP) is a competing reaction with both 1-DME and 3. It can be suppressed but not entirely eliminated via manipulation of the catalyst concentration. As AP selectively removes 3-hexyne from the system, tandem NACM-ACM-AP can be used to prepare symmetrically substituted alkynes with good selectivity, including an arylene-ethynylene macrocycle. Alternatively, unsymmetrical alkynes of the form EtCCR (R variable) can be prepared with good selectivity via the reaction of RCN with excess 3-hexyne under conditions that suppress AP. DFT calculations support a [2 + 2) cycloaddition-cycloreversion mechanism analogous to that of alkyne metathesis. The barrier to azametalacyciobutadiene ring formation/breakup is greater than that for the corresponding metalacyclobutadiene. Two distinct high-energy azametalacyclobutadiene intermediates were found. These adopted a distorted square pyramidal geometry with significant bond localization.