((prop-2-yn-1-yloxy)methylene)dibenzene | 30119-01-8

• 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: ((prop-2-yn-1-yloxy)methylene)dibenzene
• 英文别名: Propargyl diphenylmethyl ether；[phenyl(prop-2-ynoxy)methyl]benzene
• CAS: 30119-01-8
• 化学式: C₁₆H₁₄O
• 分子量: 222.287
• InChiKey: PUAPJXZGNJWLMT-UHFFFAOYSA-N

物化性质

• 沸点：
  122 °C(Press: 1 Torr)
• 密度：
  1.062±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  ((prop-2-yn-1-yloxy)methylene)dibenzene 在 N-溴代丁二酰亚胺(NBS) 、 silver nitrate 作用下， 以 丙酮 为溶剂， 反应 2.0h， 以95%的产率得到{[(3-bromoprop-2-yn-1-yl)oxy]methylene}dibenzene
  参考文献：
  名称：

  Intramolecular [4 + 2] Trapping of a Hexadehydro-Diels–Alder (HDDA) Benzyne by Tethered Arenes

  摘要：

  We report here the efficient, intramolecular trapping in a Diels-Alder (DA) sense of thermally generated benzynes by one of two pendant arene rings. A more electron-rich ring (p-methoxyphenyl) reacted substantially faster than a simple phenyl ring, which was, in turn, slightly more reactive vs a 4-carbomethoxyphenyl ring. Photoinduced di-pi-methane rearrangement of the initial DA adducts gave rise to unusual isomeric polycyclic adducts.

  DOI：

  10.1021/ol5037024
• 作为产物：
  描述：

  二苯甲醇 在 iron(III) chloride 、 18-冠醚-6 、 potassium hydroxide 作用下， 以 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 12.0h， 生成 ((prop-2-yn-1-yloxy)methylene)dibenzene
  参考文献：
  名称：

  使用氯化铁（iii）从2-二苯基甲氧基吡啶实际制备二苯基甲基醚。

  摘要：

  提出了一种由2-二苯基甲氧基吡啶生产二苯甲基（DPM）醚的简便合成方法。通过在催化FeCl3存在下用2-二苯基甲氧基吡啶处理醇，成功高收率地获得了各种DPM醚。该方法是保护各种醇类的实用而有效的合成方法，可用于制备生物活性化合物。

  DOI：

  10.1039/c9ob01093a

文献信息

• Asymmetric “Acetylenic” [3+2] Cycloaddition of Nitrones Catalyzed by Cationic Chiral Pd^II Lewis Acid
  作者：Kazuya Honda、Koichi Mikami

  DOI：10.1002/asia.201801016

  日期：2018.10.4

  Highly enantioselective [3+2] cycloaddition of ynones and nitrones has been developed. Very bulky ligand, DTBM‐SEGPHOS, was used for an effective asymmetric induction over distal reaction centers on the linear ynone dipolarophile and for prevention of PdII catalyst deactivation by coordination of the nitrones. The reaction has wide scope of substrates in both ynones and nitrones.

  已经开发出对映体和硝酮的高度对映选择性的[3 + 2]环加成反应。很大体积的配体DTBM-SEGPHOS用于在线性乙炔双极性亲和体的远端反应中心进行有效的不对称诱导，并通过硝酮的配位防止Pd II催化剂失活。该反应在炔酮和硝酮中具有广泛的底物范围。
• Rapid formation of diphenylmethyl ethers and thioethers using microwave irradiation and protic ionic liquids
  作者：Jarrad M. Altimari、Joshua P. Delaney、Linden Servinis、Jennifer S. Squire、Megan T. Thornton、Simren K. Khosa、Benjamin M. Long、Mark D. Johnstone、Cassandra L. Fleming、Frederick M. Pfeffer、Shane M. Hickey、Matthew P. Wride、Trent D. Ashton、Bronwyn L. Fox、Nolene Byrne、Luke C. Henderson

  DOI：10.1016/j.tetlet.2012.02.011

  日期：2012.4

  Using microwave irradiation and protic ionic liquids (pIL) as co-solvent and catalyst for the synthesis of several diphenylmethyl ethers was achieved. The desired ethers were isolated simply by filtration through a silica plug to remove the pIL and proceeded in high yields (60–98%). These reactions were extremely rapid (10–30 min) and occurred under mild conditions (80 °C). This protocol was also successfully

  使用微波辐射和质子离子液体（pIL）作为助溶剂和催化剂，合成了几种二苯甲基醚。只需通过硅胶塞过滤除去所需的pIL，即可分离出所需的醚，并以高收率（60-98％）进行。这些反应非常迅速（10–30分钟），并且在温和的条件下（80°C）发生。该方案也成功地应用于硫醚的合成。
• Cyclopropanation of Benzene Rings by Oxidatively Generated α-Oxo Gold Carbene: One-Pot Access to Tetrahydropyranone-Fused Cycloheptatrienes from Propargyl Benzyl Ethers
  作者：Kegong Ji、Liming Zhang

  DOI：10.1002/adsc.201701322

  日期：2018.2.15

  carbenes are for the first time demonstrated in a Buchner reaction, in which readily available propargyl benzyl ethers are converted in one-pot to tetrahydropyranone-fused cycloheptatrienes via sequential oxidative gold catalysis and base-promoted isomerization. Additional examples of arene cyclopropanations without fragmentation of the cyclopropane ring are also realized.

  在Buchner反应中首次证明了由氧化生成的α-氧代金卡宾对苯环的环丙烷化，其中易于获得的炔丙基苄基醚通过顺序氧化金催化作用，一锅转化为四氢吡喃酮稠合的环庚烯，并经碱促进异构化。还实现了芳烃环丙烷化而没有环丙烷环断裂的其他实例。
• Enantioselective Palladium‐Catalyzed Hydrophosphinylation of Allenes with Phosphine Oxides: Access to Chiral Allylic Phosphine Oxides
  作者：Zhiping Yang、Jun (Joelle) Wang

  DOI：10.1002/anie.202112285

  日期：2021.12.20

  A highly efficient, versatile and atom-economic protocol to chiral allylic phosphine oxides is demonstrated via palladium-catalyzed asymmetric hydrophosphinylation of allenes with phosphine oxides. A family of chiral allylic phosphine oxides with a diverse range of functional groups were obtained in high yield (up to 99 %) and enantioselectivities (up to 99 % ee).

  通过钯催化的丙二烯与氧化膦的不对称氢膦酰化，证明了一种高效、通用和原子经济的手性烯丙基氧化膦方案。以高产率（高达 99%）和对映选择性（高达 99% ee）获得了一系列具有多种官能团的手性烯丙基氧化膦。
• Bis(amidate)bis(amido) Titanium Complex: A Regioselective Intermolecular Alkyne Hydroamination Catalyst
  作者：Jacky C.-H. Yim、Jason A. Bexrud、Rashidat O. Ayinla、David C. Leitch、Laurel L. Schafer

  DOI：10.1021/jo402668q

  日期：2014.3.7

  o) titanium precatalyst for the anti-Markovnikov hydroamination of alkynes is reported. Hydroamination of terminal and internal alkynes with primary alkylamines, arylamines, and hydrazines is promoted by 5–10 mol % of Ti catalyst. Various functional groups are tolerated including esters, protected alcohols, and imines. The in situ generated complex shows comparable catalytic activity, demonstrating

  报道了一种有效且选择性的双（氨基酸酯）双（酰胺基）钛预催化剂，用于炔烃的抗马尔科夫尼科夫加氢胺化反应。5-10 mol％的Ti催化剂促进了末端和内部炔烃与伯烷基胺，芳基胺和肼的氨化反应。容许各种官能团，包括酯，保护的醇和亚胺。原位生成的复合物显示出可比的催化活性，证明了其在台式应用中的合成多功能性。描述了该催化剂在合成氨基醇中的应用和一锅法在吲哚合成中的应用。提出了一种机制建议，要求限制营业额的质子分解，以合理化所观察到的区域选择性。