1,8-bis(dimethylamino)-2-formylnaphthalene | 936500-48-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1,8-bis(dimethylamino)-2-formylnaphthalene
• 英文别名: 2-formyl-1,8-bis(dimethylamino)naphthalene；1,8-Bis(dimethylamino)-naphthalene-2-carbaldehyde；1,8-bis(dimethylamino)naphthalene-2-carbaldehyde
• CAS: 936500-48-0
• 化学式: C₁₅H₁₈N₂O
• 分子量: 242.321
• InChiKey: YZEHJDHMIYAMRL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  23.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,8-bis(dimethylamino)-2-formylnaphthalene 在 lithium aluminium tetrahydride 作用下， 反应 12.0h， 以90%的产率得到1,8-bis(dimethylamino)-2-hydroxymethylnaphthalene
  参考文献：
  名称：

  2-α-Hydroxyalkyl- and 2,7-Di(α-hydroxyalkyl)-1,8-bis(dimethylamino)naphthalenes:  Stabilization of Nonconventional In/Out Conformers of “Proton Sponges” via N···H−O Intramolecular Hydrogen Bonding. A Remarkable Kind of Tandem Nitrogen Inversion

  摘要：

  A regular set of 2-(alpha-hydroxymethyl)- and 2,7-di(alpha-hydroxymethyl)-1,8-bis(dimethylamino)naphthalenes has been prepared. Their X-ray, NMR, and IR studies have demonstrated that in tertiary mono-alcohols the orientation of free nitrogen electron pairs in crystals and solution corresponds to nonconventional in/out conformers stabilized by O-H center dot center dot center dot N intramolecular hydrogen bonding. For tertiary 2,7-dialcohols, the superimposed equilibrating in/out-out/in nitrogen invertomers are observed in solution. Unlike this, primary and secondary mono- and dialcohols commonly exist in the in/in form, which is typical for the parent proton sponge and the majority of its derivatives.

  DOI：

  10.1021/jo062667v
• 作为产物：
  描述：

  2,7-dibromo-1,8-bis(dimethylamino)naphthalene 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 生成 1,8-bis(dimethylamino)-2-formylnaphthalene
  参考文献：
  名称：

  2-α-Hydroxyalkyl- and 2,7-Di(α-hydroxyalkyl)-1,8-bis(dimethylamino)naphthalenes:  Stabilization of Nonconventional In/Out Conformers of “Proton Sponges” via N···H−O Intramolecular Hydrogen Bonding. A Remarkable Kind of Tandem Nitrogen Inversion

  摘要：

  A regular set of 2-(alpha-hydroxymethyl)- and 2,7-di(alpha-hydroxymethyl)-1,8-bis(dimethylamino)naphthalenes has been prepared. Their X-ray, NMR, and IR studies have demonstrated that in tertiary mono-alcohols the orientation of free nitrogen electron pairs in crystals and solution corresponds to nonconventional in/out conformers stabilized by O-H center dot center dot center dot N intramolecular hydrogen bonding. For tertiary 2,7-dialcohols, the superimposed equilibrating in/out-out/in nitrogen invertomers are observed in solution. Unlike this, primary and secondary mono- and dialcohols commonly exist in the in/in form, which is typical for the parent proton sponge and the majority of its derivatives.

  DOI：

  10.1021/jo062667v

文献信息

• H-Bond-Assisted Intramolecular Nucleophilic Displacement of the 1-NMe₂ Group in 1,8-Bis(dimethylamino)naphthalenes as a Route to Multinuclear Heterocyclic Compounds and Strained Naphthalene Derivatives
  作者：Maria A. Povalyakhina、Alexander S. Antonov、Olga V. Dyablo、Valery A. Ozeryanskii、Alexander F. Pozharskii

  DOI：10.1021/jo201171z

  日期：2011.9.2

  It has been shown that azomethines, hydrazones, and oximes derived from 2(7)-carbonyl derivatives of 1,8-bis(dimethylamino)naphthalene can undergo acid-catalyzed heterocyclization leading to a nucleophilic displacement of the 1-NMe2 group. The process is believed to be directly connected with the proton sponge nature of the substrates, in which 1-NMe2, being a poor leaving group, is preliminary activated

  已经表明，衍生自1，8-双（二​​甲基氨基）萘的2（7）-羰基衍生物的偶氮甲碱，和肟可以进行酸催化的杂环化作用，从而导致1-NMe 2基团的亲核取代。据信该方法与底物的质子海绵性质直接相关，其中作为不良离去基团的1-NMe 2通过形成螯合的质子化形式而被初步活化。已经以中等至高产率制备了许多难以接近的苯并[ g ]吲唑，苯并[ g ]喹唑啉，萘[2，1- d ]异恶唑和8-二甲基氨基-1-萘酚的衍生物。
• Naphthalene proton sponges as hydride donors: diverse appearances of the tert-amino-effect
  作者：Alexander F. Pozharskii、Maria A. Povalyakhina、Alexander V. Degtyarev、Oxana V. Ryabtsova、Valery A. Ozeryanskii、Olga V. Dyablo、Anna V. Tkachuk、Olga N. Kazheva、Anatolii N. Chekhlov、Oleg A. Dyachenko

  DOI：10.1039/c0ob00899k

  日期：——

  It has been shown that the 1-NMe2 group in the 2-substituted 1,8-bis(dimethylamino)naphthalenes (proton sponges) can intramolecularly donate a hydride ion to an appropriate electron-accepting ortho-substituent such as diarylcarbenium ion, β,β′-dicyanovinyl or methyleneiminium group. This produces the 1-N+(Me)CH2 functionality and triggers a number of further transformations (tert-amino effect) including

  已经表明， 1-NMe 2 2-取代的1,8-双（二​​甲基氨基）萘（质子海绵）中的基团可以分子内捐赠 氢化物离子形成合适的电子接受原位取代基，例如二芳基碳鎓离子，β，β'-二氰基乙烯基或亚甲基亚胺基。这将产生1-N +（Me）CH 2功能，并触发许多进一步的转换（叔氨基包括效果）围-cyclization，邻-cyclization或水解的脱甲基化。在每种特定情况下，反应过程由反应混合物中存在的邻位取代基和最有效的亲核试剂的性质决定。对于2,7-二取代的1,8-双（二​​甲基氨基）萘，两种串联叔氨基 双方共同参与的影响 围-NMe 2组已注册。结论是，质子海绵通常在叔氨基反应比相应的单二甲基氨基芳烃高。这归因既质子海绵的更高的电子供体的能力和明显缩短电℃之间的距离α在-原子邻位-取代和氢 最接近的原子 NMe 2团体。观察到的大多数转化都以高产到高收率进行，可用于制备苯并[ h ]喹啉，
• tert-Amino effect in naphthalene proton sponges: a novel approach to benzo[h]quinoline and quino[7,8:7’,8’]quinoline derivatives
  作者：Maria A. Povalyakhina、Alexander F. Pozharskii、Olga V. Dyablo、Valery A. Ozeryanskii、Oksana V. Ryabtsova

  DOI：10.1016/j.mencom.2010.01.014

  日期：2010.1

  aphthalenes with strong –M substituents in the β-positions of vinyl groups have been shown to undergo a tert-amino-type rearrangement providing a new and facile route to benzo[h]quinoline and quino[7,8:7’,8’]quinoline derivatives.

  在乙烯基的β-位具有强–M取代基的2-乙烯基-和2,7-二乙烯基-1,8-双（二​​甲基氨基）萘已显示可进行叔氨基型重排，提供了一种新的且简便的方法苯并[h]喹啉和喹[7,8：7'，8']喹啉衍生物的合成方法。
• Ring lithiation of 1,8-bis(dimethylamino)naphthalene: another side of the ‘proton sponge coin’
  作者：Alexander S. Antonov、Alexander F. Pozharskii、Valery A. Ozeryanskii、Aleksander Filarowski、Kyrill Yu. Suponitsky、Peter M. Tolstoy、Mikhail A. Vovk

  DOI：10.1039/c5dt02482j

  日期：——

  It has been found that 1,8-bis(dimethylamino)naphthalene (DMAN), unlike N,N-dimethylaniline, undergoes ring metallation in the n-BuLi–TMEDA–Et2O system with a low selectivity and in poor total yields. The situation is significantly improved in the t-BuLi–TMEDA–n-hexane system when 3- and 4-lithium derivatives become the only reaction products obtained in good yields. The formation of 3-Li-DMAN is especially

  已经发现，与N，N-二甲基苯胺不同，1,8-双（二​​甲基氨基）萘（DMAN）在n -BuLi–TMEDA–Et 2 O系统中以低选择性和低总收率进行环金属化。的情况是在显著改善吨正丁基锂- TMEDA- ñ -己烷系统当3-和4-锂衍生物成为以良好产率获得的唯一的反应产物。3-Li-DMAN的形成是特别期望的，因为迄今为止还没有直接的DMAN亚功能化方法。DMAN锂衍生物的相对稳定性和结构已借助X射线和多核NMR测量以及DFT计算得到了检验。
• 1,8,1′,8′-Tetrakis(dimethylamino)-2,2′-dinaphthylmethanols: Double <i>In/Out</i> Proton Sponges with Low-Barrier Hydrogen-Bond Switching
  作者：Alexander F. Pozharskii、Alexander V. Degtyarev、Valery A. Ozeryanskii、Oksana V. Ryabtsova、Zoya A. Starikova、Gennadii S. Borodkin

  DOI：10.1021/jo100384s

  日期：2010.7.16

  Previously unknown bis[1,8-bis(dimethylamino)naphth-2-yl]phenylmethanol (5) and bis[1,8-bis(dimethylamino)naphth-2-yl]methanol (6) have been obtained and studied by combination of X-ray, NMR, and IR techniques at variable temperature. It has been established that both proton sponge units in the solid tertiary alcohol 5 exist in nonconventional in/out form, one of which is fixed by intramolecular O-H center dot center dot center dot N hydrogen bonding. In solution, a fast interconversion of two isoenergetic hydrogen chelates occurs which can be frozen below 183 K. Unlike this, the secondary alcohol 6 in the solid at 100 K adopts the in/out-in/in conformation and at 293 K demonstrates a kind of dynamic behavior which can be described as temperature-driven dimer-induced rechelation. In solution under ambient conditions 6 exists as an equilibrating mixture of chelated and unchelated monomeric forms in a similar to 1:1.8 molar ratio.