1,2-bis[4-(dimethylamino)phenyl]-1,2-ethanediol | 54322-62-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 1,2-bis[4-(dimethylamino)phenyl]-1,2-ethanediol
• 英文别名: 4,4'-bis-dimethylamino-bibenzyl-α,α'-diol；1,2-Bis-(p-dimethylaminophenyl)ethane-1,2-diol；1,2-bis[4-(dimethylamino)phenyl]ethane-1,2-diol
• CAS: 54322-62-2
• 化学式: C₁₈H₂₄N₂O₂
• 分子量: 300.401
• InChiKey: RHYWTTJMPMTONP-UHFFFAOYSA-N

物化性质

• 熔点：
  178-179 °C
• 沸点：
  491.3±45.0 °C(Predicted)
• 密度：
  1.175±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  46.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,2-bis[4-(dimethylamino)phenyl]-1,2-ethanediol 在 盐酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 甲醇 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 30.0h， 生成 1,1-di(azulen-1-yl)-2,2-bis[4-(dimethylamino)phenyl]ethylene
  参考文献：
  名称：

  Reaction of azulene with 1,2-bis[4-(dimethylamino)phenyl]-1,2-ethanediol in a mixed solvent of methanol and acetonitrile in the presence of hydrochloric acid: a facile one-pot synthesis and properties of new triarylethylenes possessing an azulen-1-yl group

  摘要：

  Reaction of azulene (1) with 1,2-bis[4-(dimethylamino)phenyl]-1,2-ethanediol (2) in a mixed solvent of methanol and acetonitrile in the presence of 36% hydrochloric acid at 60 degrees C for 3 h gives 2-(azulen-1-yl)-1,1-bis[4-(dimethylamino)phenyl] ethylene (3) (8% yield), 1-(azulen-1-yl)-(E)-1,2-bis[4-(dimethylamino)phenyl]ethylene (4) (28% yield), and 1,3-bis{2,2-bis[4-(dimethylamino)phenyl]ethenyl}azulene (5) (9% yield). Besides the above products, this reaction affords 1,1-di(azulen-1-yl)-2,2-bis[4-(dimethylamino)phenyl]ethane (6) (15% yield), a meso form (1R,2S)-1,2-di(azulen-1-yl)-1,2-bis[4-(dimethylamino)phenyl]ethane (7) (6% yield), and the two enantiomeric forms (1R,2R)- and (1S,2S)-1,2-di(azulen-1-yl)-1,2-bis[4-(dimethylamino)phenyl]ethanes (8) (6% yield). Furthermore, addition reaction of 3 with 1 under the same reaction conditions as the above provides 6, in 46% yield, which upon oxidation with DDQ (=2, 3-dichloro-5,6-dicyano-1,4-benzoquinone) in dichloromethane at 25 degrees C for 24 h yields 1,1-di(azulen-1-yl)-2,2-bis[4-(dimethylamino)phenyl]ethylene (9) in 48% yield. Interestingly, reaction of 1,1-bis[4-(dimethylamino)phenyl]-2-(3-guaiazulenyl)ethylene (11) with 1 in a mixed solvent of methanol and acetonitrile in the presence of 36% hydrochloric acid at 60 degrees C for 3 h gives guaiazulene (10) and 3, owing to the replacement of a guaiazulen-3-yl group by an azulen-1-yl group, in 91 and 46% yields together with 5 (19% yield) and 6 (13% yield). Similarly, reactions of 2-(3-guaiazulenyl)-1,1-bis(4-methoxyphenyl)ethylene (12) and 1,1-bis{4-[2-(dimethylamino)ethoxylphenyl}-2-(3-guaiazulenyl)ethylene (13) with 1 under the same reaction conditions as the above provide 10, 2-(azulen-1-yl)-1,1-bis(4-methoxyphenyl)ethylene (16), and 1,3-bis[2,2-bis(4-methoxyphenyl)ethenyl]azulene (17) (93, 34, and 19% yields) from 12 and 10 and 2-(azulen-1-yl)-1,1-bis{4-[2-(dimethylamino)ethoxy]phenyl}ethylene (18) (97 and 58% yields) from 13. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.05.038
• 作为产物：
  描述：

  4-[2-[4-(dimethylamino)phenyl]-1,2-bis(trimethylsilyloxy)ethyl]-N,N-dimethylaniline 在 氢氧化钾 作用下， 以 甲醇 为溶剂， 生成 1,2-bis[4-(dimethylamino)phenyl]-1,2-ethanediol
  参考文献：
  名称：

  Synthesen MIT verbindungen - [R 3 MHgMR 3 UND（R 2 MHg）Ñ（MC，硅，锗，锡）：IX。还原性水飞蓟素羰基verbindungen Mittels双（三甲基甲硅烷基）-que

  摘要：

  芳香醛是由我还原二聚3 SiHgSiMe 3（I），得到双（ø -甲硅烷基）氢化苯偶姻衍生物。1,2-二酮经过1,4-加成反应生成双（O-甲硅烷基）烯二醇，而共轭二羧酸的酯则生成O-甲硅烷基烯酮缩醛：马来酸主要产生C，O-双甲硅烷基衍生物（1,4- ，而富马酸酯和乙烯四羧酸酯主要产生相应的O，O-双甲硅烷基产物（1,6-加成）。1,2-和1,4-醌很容易被（I）转化成相应的双O-甲硅烷基）苯系。

  DOI：

  10.1016/s0022-328x(00)90077-9

文献信息

• Novel and efficient Ni-mediated pinacol coupling of carbonyl compounds
  作者：Lei Shi、Chun-An Fan、Yong-Qiang Tu、Min Wang、Fu-Min Zhang

  DOI：10.1016/j.tet.2004.01.073

  日期：2004.3

  It was firstly found that the Rieke Ni generated in situ was able to promote the pinacol coupling of various carbonyls efficiently. Based on this information, another catalytically effective, cheaper and more convenient NiCl2(Cat.)/Mg/TMSCl system was designed and developed further successfully. The interesting single-electron transfer (SET) mechanisms for the coupling reactions were proposed. Additionally

  首先发现原位生成的Rieke Ni能够有效地促进各种羰基的频哪醇偶联。基于此信息，设计并成功开发了另一种具有催化作用，更便宜，更方便的NiCl 2（Cat。）/ Mg / TMSCl系统。提出了有趣的偶联反应单电子转移（SET）机理。另外，还根据提出的机理解释了dl /内消旋非对映选择性和一些累加效应。
• Some organic reactions promoted by samarium diiodide
  作者：J. Souppe、L. Danon、J.L. Namy、H.B. Kagan

  DOI：10.1016/0022-328x(83)85053-0

  日期：1983.7

  Various homoallylic alcohols and homobenzylic alcohols were prepared by the reaction between aldehydes and allylic or benzylic halides in the presence of samarium diiodide. This iodide is also a very good reagent for formation of pinacols from aldehydes or ketones. The reactions are especially fast and selective in the case of substituted benzaldehydes. The reactivities of various nitrogen functional

  在二碘化sa存在下，醛与烯丙基或苄基卤化物之间的反应可制得各种均烯丙基醇和均苄基醇。该碘化物也是从醛或酮形成石aco醇的非常好的试剂。在取代的苯甲醛的情况下，该反应特别快速和选择性。还检查了各种氮官能团（亚胺，肟，硝基，偶氮，氰基）对SmI 2的反应性。
• A Convenient Synthesis of Unsymmetrical Pinacols by Coupling of Structurally Similar Aromatic Aldehydes Mediated by Low-Valent Titanium
  作者：Xin-Fang Duan、Jian-Xia Feng、Guo-Fu Zi、Zhan-Bin Zhang

  DOI：10.1055/s-0028-1083264

  日期：2009.1

  pinacol-type couplings between two structurally similar aromatic aldehydes promoted by low-valent titanium generated unsymmetrical pinacols in moderate to good isolated yields in an erythro/threo ratio of up to 91:9. This synthetic methodology significantly extends the scope of the cross pinacol-type couplings. pinacol - pinacol-type coupling - cross coupling - McMurry­ coupling - low-valent titanium

  低价钛促进的两个结构相似的芳族醛之间的一锅，选择性交叉频哪醇型偶联以中等至良好的分离产率生成不对称的频哪醇，其赤/苏比率高达91：9。这种合成方法大大扩展了交叉频哪醇型偶联剂的范围。 频哪醇-频哪醇型偶联剂-交叉偶联剂-McMurry偶联剂-低价钛
• Alkylative Reduction of Titanium(IV) Isopropoxide with EtMgBr: Convenient Method for the Generation of Subvalent Titanium Alkoxide Reagents and their Reactivity in Pinacol Coupling Reactions
  作者：Oleg G. Kulinkovich、Evgenii A. Matiushenkov、Nikolai A. Sokolov

  DOI：10.1055/s-2003-43370

  日期：——

  products from the reaction of Ti(IV) isopropoxide with ethylmagnesium bromide in diethyl ether evidences the formation of subvalent titanium isopropoxide species in various oxidation states depending on relative amounts of the reactants. Reaction of titanium(IV) isopropoxide with one equivalent of the Grignard reagent gives presumably titanium(III) isopropoxide. The latter is generated as a result

  Ti(IV) 异丙醇与乙基溴化镁在乙醚中反应的气态产物的组成表明，根据反应物的相对量，形成了各种氧化态的亚价异丙醇钛物种。异丙醇钛 (IV) 与一当量的格氏试剂反应，推测可能生成异丙醇钛 (III)。后者是由于起始 Ti(IV) 物质和钛 (II) 异丙醇-乙烯络合物的歧化而产生的，后者是从二乙基钛 (IV) 异丙醇中挤出乙烷的结果。通过这种方式制备的异丙醇钛 (III) 以良好的收率将醛和芳香酮转化为相应的频哪醇。
• Tehrani, Mohsen Mazaheri; Asghari, Jila, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2006, vol. 45, # 1, p. 332 - 334
  作者：Tehrani, Mohsen Mazaheri、Asghari, Jila

  DOI：——

  日期：——