2-benzoyl-1,8-bis(dimethylamino)naphthalene | 936500-49-1

• 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: 2-benzoyl-1,8-bis(dimethylamino)naphthalene
• 英文别名: [1,8-Bis(dimethylamino)naphthalen-2-yl]-phenylmethanone
• CAS: 936500-49-1
• 化学式: C₂₁H₂₂N₂O
• 分子量: 318.418
• InChiKey: DHSNNHRZIGKZEU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 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：

  2-benzoyl-1,8-bis(dimethylamino)naphthalene 在 lithium aluminium tetrahydride 作用下， 反应 12.0h， 以71%的产率得到1,8-bis(dimethylamino)-2-(α-hydroxybenzyl)naphthalene
  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：

  1,8-bis(dimethylamino)-2-(imino(phenyl)methyl)naphthalene 在 盐酸 、 水 作用下， 反应 1.0h， 以99%的产率得到2-benzoyl-1,8-bis(dimethylamino)naphthalene
  参考文献：
  名称：

  1,8-双（二​​甲基氨基）萘的邻甲酮亚胺：质子海绵部分的合成，水解稳定性和碱度转移至氨基官能团

  摘要：

  摘要 已经获得了一系列的1,8-双（二​​甲基氨基）萘的2-酮亚胺和2,7-二亚胺（质子海绵，DMAN），并通过酸性水解转化为相应的酮。对基于DMAN的亚胺的结构和光谱性质的研究得出的结论是，它们不同寻常的水解稳定性是由多种不同因素的综合作用产生的，其中最重要的是邻二甲基氨基的强电子给体作用。 已经获得了一系列的1,8-双（二​​甲基氨基）萘的2-酮亚胺和2,7-二亚胺（质子海绵，DMAN），并通过酸性水解转化为相应的酮。对基于DMAN的亚胺的结构和光谱性质的研究得出的结论是，它们不同寻常的水解稳定性是由多种不同因素的综合作用产生的，其中最重要的是邻二甲基氨基的强电子给体作用。

  DOI：

  10.1055/s-0034-1379008

文献信息

• Reaction of 2-trifluoroacetyl-1,8-Bis(dimethylamino)naphthalene with strong organic bases: Deprotonation of 1-NMe2 group resulting in the formation of Benzo[g]indole derivatives versus nucleophilic addition to C O group
  作者：Alexander S. Antonov、Svetlana G. Kachalkina、Alexander F. Pozharskii、Gennady S. Borodkin、Aleksander Filarowski

  DOI：10.1016/j.tet.2017.05.013

  日期：2017.6

  8-bis(dimethylamino)naphthalenes via treatment with 2-lithium-1,8-bis(dimethylamino)naphthalene producing the corresponding benzo[g]indole derivatives, was examined with different alkyl- and aryllithium compounds as well as with LDA. It was found that the highest yields of benzo[g]indoles (up to 70%) are obtained with aryllithium reagents when they contain NMe2 group in ortho-position to the carbanionic centre

  通过用2-锂-1,8-双（二​​甲基氨基）萘处理产生相应的苯并[ g ]吲哚的新方法来封闭2-三氟乙酰基和2-乙氧基羰基-1,8-双（二​​甲基氨基）萘中的吡咯环用不同的烷基锂和芳基锂化合物以及LDA检查了它们的衍生物。发现当芳基锂试剂在碳负离子中心的邻位含有NMe 2基团时，使用芳基锂试剂可获得最高产率的苯并[ g ]吲哚（高达70％）。在所有其他情况下，由于碳通常通过分子间加成而形成无环醇。O组非常占优势。在2-锂-N，N-二甲基苯胺的情况下，通过反应过渡态的特定结构说明了底物中N-Me基团去质子化的显着促进，然后是吡咯环化。
• Out-Basicity of 1,8-bis(dimethylamino)naphthalene: the experimental and theoretical challenge
  作者：Valery A. Ozeryanskii、Alexander F. Pozharskii、Alexander S. Antonov、Alexander Filarowski

  DOI：10.1039/c3ob41986j

  日期：——

  group might chelate either the proton sponge 1-NMe2 group or another basic center (N,N-dimethylaniline) of known basicity; (2) measuring the basicity of naphtho[1,8-b,c]diazabicyclo[3.3.3]undecane considered to be a close analogue of the proton sponge capable exclusively of out-protonation; (3) X-ray, spectral and DFT studies of structure, energy and stereodynamics of compounds obtained, including their

  讨论了1,8-双（二​​甲基氨基）萘（质子海绵）非常规两步质子化的可能性。不同于一般公认机制，涉及质子的相对缓慢直接渗入之间的裂口围-NMe 2个基团，它由快速添加质子给的出-inverted NME 2组的随后较慢旋转传递质子进入氮间隙，产生稳定的螯合阳离子。在该工作中采用了以下方法：（1）在特殊设计的醇中形成竞争性氢键，其中OH基团可能会螯合质子海绵1-NMe 2基团或另一个碱性中心（N，已知碱度的N-二甲基苯胺）；（2）测量萘的碱度[1,8- b，c ^ ]二氮杂双环[3.3.3]十一烷被认为是能够排他的质子海绵的密切类似物出-protonation; （3）对所得化合物（包括其构象异构体）的结构，能量和立体动力学进行X射线，光谱和DFT研究。首次报道了氮原子完全平坦的有机碱的p K a值。最终的结论是，传统的和非传统的质子海绵质子化的两种途径都以平行的方式起作用，而比例仍未确定。估
• 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.
• ortho-Ketimines of 1,8-Bis(dimethylamino)naphthalene: Synthesis, Hydrolytic Stability and Transfer of Basicity from Proton Sponge Moiety to the Imino Function
  作者：Alexander Pozharskii、Alexander Antonov、Vladimir Mikshiev、Valery Ozeryanskii

  DOI：10.1055/s-0034-1379008

  日期：——

  important of which is a strong electron-donor effect of peri-dimethylamino groups. A series of 2-ketimines and 2,7-diketimines of 1,8-bis(dimethylamino)naphthalene (proton sponge, DMAN) have been obtained and converted into the corresponding ketones via acidic hydrolysis. Investigation of structural and spectral properties of DMAN-based imines led to the conclusion that their unusual hydrolytic stability results

  摘要 已经获得了一系列的1,8-双（二​​甲基氨基）萘的2-酮亚胺和2,7-二亚胺（质子海绵，DMAN），并通过酸性水解转化为相应的酮。对基于DMAN的亚胺的结构和光谱性质的研究得出的结论是，它们不同寻常的水解稳定性是由多种不同因素的综合作用产生的，其中最重要的是邻二甲基氨基的强电子给体作用。 已经获得了一系列的1,8-双（二​​甲基氨基）萘的2-酮亚胺和2,7-二亚胺（质子海绵，DMAN），并通过酸性水解转化为相应的酮。对基于DMAN的亚胺的结构和光谱性质的研究得出的结论是，它们不同寻常的水解稳定性是由多种不同因素的综合作用产生的，其中最重要的是邻二甲基氨基的强电子给体作用。
• 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
  作者：Alexander F. Pozharskii、Alexander V. Degtyarev、Oksana V. Ryabtsova、Valery A. Ozeryanskii、Mikhail E. Kletskii、Zoya A. Starikova、Lucjan Sobczyk、Alexander Filarowski

  DOI：10.1021/jo062667v

  日期：2007.4.1

  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.