bis-4-(1-N,N-dimethylaminonaphthyl)methane | 98659-68-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: bis-4-(1-N,N-dimethylaminonaphthyl)methane
• 英文别名: 1,1'-bis(dimethylamino)-4,4'-dinaphthylmethane；4,4'-methylenebis[1-(dimethylamino)naphthalene]；4,4'-methylenebis(N,N-dimethylnaphthalen-1-amine)；bis-(4-dimethylamino-[1]naphthyl)-methane；Bis-(4-dimethylamino-[1]naphthyl)-methan；4-[[4-(dimethylamino)naphthalen-1-yl]methyl]-N,N-dimethylnaphthalen-1-amine
• CAS: 98659-68-8
• 化学式: C₂₅H₂₆N₂
• 分子量: 354.495
• InChiKey: POFGIQIMKUQEIN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bis-4-(1-N,N-dimethylaminonaphthyl)methane 、 四氯苯醌 在 溶剂黄146 作用下， 生成 Bis-(4-dimethylamino-[1]naphthyl)-methanol
  参考文献：
  名称：

  十八。萘系列研究。第二部分。甲基-α-萘胺的二芳基和三芳基甲烷衍生物

  摘要：

  DOI：

  10.1039/jr9310000118
• 作为产物：
  描述：

  1-dimethylamino-4-piperidinomethylnaphthalene 在 氢氧化钾 作用下， 以 水 、 丙酮 为溶剂， 反应 1.25h， 生成 bis-4-(1-N,N-dimethylaminonaphthyl)methane
  参考文献：
  名称：

  摘要：

  Aminomethylation of 1,8-bis(dimethylamino) naphthalene ("proton sponge") afforded a series of its 4-dialkylaminomethyl-substituted derivatives. An attempt to introduce the second peri-dialkylaminomethyl group unexpectedly led to the formation of salts with the 2,2-dialkyl-6,7-bis(dimethylamino)-2-azonia-2,3-dihydrophenalene cation. The structure of one of these salts was established by X-ray diffraction analysis. Treatment of 1,8-bis(dimethylamino)-4-piperidinomethylnaphthale ne with iodomethane gave a spiro compound rather than the expected N-[4,5-bis(dimethylamino)-1-naphthylmethyl]-N-methylpiperidinium iodide. This spiro, compound was generated through cyclodimerization of the 1-naphthylmethyl carbocations. These transformations provide evidence that "proton sponge"-derived Mannich bases quaternized at the dialkylaminomethyl group are unstable and undergo the spontaneous transformation into the resonance-stabilized 4,5-bis(dimethylamino)-1-naphthylmethyl carbocation. By contrast, 4-dialkylamino-1 -dimethylaminomethylnaphthalenes gave methoiodides, which are stable under standard conditions. The latter compounds undergo the nucleophilic substitution of the NR3 group typical of such salts.

  DOI：

  10.1023/a:1022477205623

文献信息

• Cu(ii)-catalyzed C–H (SP3) oxidation and C–N cleavage: base-switched methylenation and formylation using tetramethylethylenediamine as a carbon source
  作者：Lei Zhang、Chen Peng、Dan Zhao、Yue Wang、Hai-Jian Fu、Qi Shen、Jian-Xin Li

  DOI：10.1039/c2cc32009f

  日期：——

  Base-switched methylenation and formylation using tetramethylethylenediamine (TMEDA) as a carbon source have been achieved under mild conditions, catalyzed by CuCl(2), with atmospheric oxygen as oxidant. Bisindolylmethanes, diphenylmethanes and 3-formylindoles were synthesized with excellent regioselectivity and good yield.

  使用四甲基乙二胺（TMEDA）作为碳源的碱转换的甲基化和甲酰化反应已在温和的条件下实现，由CuCl（2）催化，大气中的氧气作为氧化剂。合成了双吲哚甲烷，二苯基甲烷和3-甲酰基吲哚，具有良好的区域选择性和良好的收率。
• Electrophilic fluorination of N,N-dimethylaniline, N,N-dimethylnaphthalen-1-amine and 1,8-bis(dimethylamino)naphthalene with N–F reagents
  作者：Vladimir I. Sorokin、Alexander F. Pozharskii、Valery A. Ozeryanskii

  DOI：10.1016/j.jfluchem.2013.06.017

  日期：2013.10

  Reaction of N,N-dimethylaniline, N,N-dimethylnaphthalen-1-amine and 1,8-bis(dimethylamino)naphthalene (proton sponge) with 1-chloromethyl-4-fluorodiazonia-bicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor) and N-fluorobenzenesulfonimide (NFSI) has been studied under various conditions. Unlike the proton sponge, which is fluorinated rather selectively at the ortho-position to NMe2 group, producing

  的反应Ñ，Ñ二甲基苯胺，Ñ，Ñ -dimethylnaphthalen -1-胺和1,8-双（二甲基氨基）萘（质子海绵）与1-氯甲基-4- fluorodiazonia -二环[2.2.2]辛烷二（四氟硼酸盐）（Selectfluor）和N-氟苯磺酰亚胺（NFSI）已在各种条件下进行了研究。与质子海绵不同，质子海绵在NMe 2基团的邻位上选择性地氟化，以中等收率生成2-氟衍生物，而另外两种胺与Selectfluor和NFSI反应，具有很强的去污能力，并形成了相应的联芳基的复杂混合物，联芳基甲烷和N-去甲基化的产品。还少量形成了2-氟和4-氟衍生物，其中主要是前一种异构体。使用NFSI–ZrCl 4系统可导致芳香环的竞争性氯化反应。
• Novel Mannich-type nucleophilic substitution reaction with tertiary aromatic amines
  作者：Hiroyasu Takahashi、Nobuyuki Kashiwa、Yuichi Hashimoto、Kazuo Nagasawa

  DOI：10.1016/s0040-4039(02)00447-1

  日期：2002.4

  A novel formaldehyde-mediated condensation reaction of N,N-dialkyl aromatic amines and resonance-stabilized carbon nucleophiles is described. A condensation reaction between N,N-dimethylaniline (4) and ethyl acetoacetate (8) in the presence of formaldehyde in acetic acid took place to give 2-(4-dimethylaminobenzyl)-3-oxo butyric acid ethyl ester (9) together with the dimerization product 7 in 73 and

  描述了N，N-二烷基芳族胺与共振稳定的碳亲核试剂的新的甲醛介导的缩合反应。N，N-二甲基苯胺（4）与乙酰乙酸乙酯（8）在甲醛存在下于乙酸中发生缩合反应，得到2-（4-二甲基氨基苄基）-3-氧代丁酸乙酯（9）和二聚产物7的产率分别为73％和21％。该缩合反应进一步用于合成4-取代的二烷基苯胺衍生物。
• Deoxygenative CO₂ conversions with triphenylborane and phenylsilane in the presence of secondary amines or nitrogen-containing aromatics
  作者：Takumi Murata、Mahoko Hiyoshi、Shinsuke Maekawa、Yuta Saiki、Manussada Ratanasak、Jun-ya Hasegawa、Tadashi Ema

  DOI：10.1039/d1gc04599g

  日期：——

  BPh3 catalyzed the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO2 (1 atm) and PhSiH3 without solvent at 30–40 °C. A cascade reaction from 1-methyl-2-oxindole to 3,3′-methylenebis(1-methylindole) via 1-methylindole also proceeded.

  BPh 3在CO 2 (1 atm) 和PhSiH 3存在下，在无溶剂条件下催化仲胺的N-甲基化和N，N-二甲基苯胺或1-甲基吲哚的C-亚甲基化（芳环之间形成亚甲基桥）30–40 °C。1-甲基-2-羟吲哚通过1-甲基吲哚到3,3'-亚甲基双(1-甲基吲哚)的级联反应也进行了。
• Copper(ii)-catalyzed C–H (sp3) oxidation and C–N cleavage: synthesis of methylene-bridged compounds using TMEDA as a carbon source in water
  作者：Dan Zhao、Yue Wang、Min-Xue Zhu、Qi Shen、Lei Zhang、Yun Du、Jian-Xin Li

  DOI：10.1039/c3ra40695d

  日期：——

  A green, simple, and efficient protocol for the selective methylenation via CuCl2/oxygen-mediated C–H (sp3) oxidation and C–N cleavage using tetramethylethylenediamine (TMEDA) as a carbon source has been developed. The reactions were achieved in green solvent water under atmospheric conditions. The protocol exhibited a broad substrate scope including indoles, anilines, pyrroles and 1,3-dicarbonyls. Furthermore, two key intermediates of the reaction were successfully identified and the mechanism was explored.

  以四甲基乙二胺（TMEDA）为碳源，通过 CuCl2/氧气介导的 CâH (sp3) 氧化和 CâN 裂解进行选择性亚甲基化的绿色、简单而高效的方案已经开发出来。反应在大气条件下的绿色溶剂水中进行。该方案的底物范围很广，包括吲哚、苯胺、吡咯和 1,3-二羰基。此外，还成功鉴定了反应的两个关键中间体，并探索了反应机理。