Regioselective Carbon–Carbon Bond Formation Reactions between TCNE or TCNQ and a Quinonoid Ring

Braunstein, Pierre; Siri, Olivier; Taquet, Jean‐philippe; Yang, Qing-Zheng

doi:10.1002/anie.200502574

Cited by 24 publications

(17 citation statements)

References 72 publications

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“…In particular, benzoquinonemonoimines have been found to display unique properties in various areas such as color, [34] organic, [35,36] supramolecular, [37] coordination, and organometallic chemistry [37][38][39][40][41][42][43][44] and homogeneous catalysis. [39,43,45] The first member of a new family of 12π-electron quinone-based zwitterions (1, R = tBu) was reported in 2002.…”

Section: Introductionmentioning

confidence: 99%

Reactions of Amines with Zwitterionic Quinoneimines: Synthesis of New Anionic and Zwitterionic Quinonoids

et al. 2009

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Following the discovery of an unprecedented transamination reaction between primary alkylamines and a quinonoid molecule of the type [C6H2([pb2]NHCH2R)2([pb2]O)2] (1), obtained from commercially available diaminoresorcinol·2HCl, we have extended this method to the use of primary arylamines, and found that, in contrast, secondary amines led to a different outcome. Whereas functionalized molecules of type 1, which are best described as 6π + 6π zwitterions, were obtained with aniline or 4‐methoxyaniline, no transmination was observed with tBuNH2 in ethanol. In water, however, a reaction took place, but it afforded instead salt 6a, which resulted from hydrolysis of the imine group and deprotonation. Under similar conditions, secondary amines led to comparable results. The cations associated with the anionic quinonoid are readily exchanged in the presence of a primary amine. Whereas for the transamination reaction basic amines react under mild conditions, slightly harsher conditions are needed for less basic amines such as piperidine, diisopropylamine, or diethylamine. Transamination reactions were also performed with bis(methylamino) quinoneimine 4c, which is more soluble in organic solvents than 3. This led to the first examples of quinonoidal zwitterions functionalized with different alkyl groups on the nitrogen atoms. A number of compounds were characterized by X‐ray diffraction, which allowed a better understanding of their electronic situation, and in many cases, the presence of multiple hydrogen‐bond donors and acceptors results in crystal packings dominated by these interactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Introductionmentioning

confidence: 99%

Reactions of Amines with Zwitterionic Quinoneimines: Synthesis of New Anionic and Zwitterionic Quinonoids

et al. 2009

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“…53 The critical layer thickness at the onset of island formation cannot be ascertained from our measurements here, but the very large substrate signal evident in the XPS data is indicative of the formation of a very thin (1-3 nm) molecular overlayer before island growth is initiated. The crystal packing of the TCNQ-derived p-benzoquinonemonoimine zwitterion 4, first described in prior work, [46][47][48] presents multiple opportunities for strong hydrogen bonding, as illustrated in Fig. 8.…”

Section: Resultsmentioning

confidence: 94%

“…1 2 as the C-substituent. [46][47][48] Graphene was grown on copper foil by Chemical Vapor Deposition (CVD) at 1000 uC, at the pressure of 1.4 Torr for 30 min using the gas mixture of C 2 H 2 (1.4 sccm) and H 2 (2 sccm). The zwitterions were deposited on clean gold and graphene substrates from a CH 2 Cl 2 solution, as noted in prior work.…”

Section: Experimental Methodsmentioning

confidence: 99%

Adsorption of TCNQH-functionalized quinonoid zwitterions on gold and graphene: evidence for dominant intermolecular interactions

et al. 2013

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“…Organic compounds containing a quinonoid fragment are of great interest because of their intrinsic properties and their numerous applications in chemistry, physical chemistry and biology. In particular, benzoquinonemonoimines have been found to display unique properties in various areas such as coloring, 27 organic, 28,29 supramolecular, 30 coordination, organometallic chemistry 30,31,38,39 and homogeneous catalysis. [32][33][34][35][36][37] Previous studies have shown that the reactions between alkylamines or arylamines and benzoquinone gave a trans-dialkylaminobenzoquinone or trans-diarylamino-benzoquinone and monoarylamino products.…”

Section: Introductionmentioning

confidence: 99%

Accessibility of Zwitterionic Compounds From Primary Amines and 2,5-Dihydroxy-1,4-Benzoquinone

Tamboura

Lo²,

Kaihil³

et al. 2019

ECB

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Following the discovery of an unprecedented transamination reaction between primary alkylamines and a quinonoid molecule of the type C6H2(NHCH2R)2(=O)2 (I), obtained from commercially available diaminoresorcinol.2HCl, we have extended this method to the use of primary arylamines and found that, in contrast, secondary amines led to a different outcome. Whereas functionalized molecules of type I, which are best described as 6π +6π zwitterions, were obtained with aniline or 4-methoxyaniline, no transamination was observed with tBuNH2 in ethanol. However, a reaction which afforded salt 2-methylpropan-2-aminium 4-(methylamino)-3,6-dioxocyclohexa-1,4-dien-1olate (2b) took place in water and resulted from hydrolysis of the imine group and deprotonation of 5-hydroxy-2-(methylamino)-4-(methylimino)-cyclohexa-2,5-dienone (1a). Under similar conditions, secondary amines led to comparable results. The cations associated with the anionic quinonoid are readily exchanged in the presence of a primary amine. Whereas for the transamination reaction, basic amines react under mild conditions, slightly harsher conditions are needed for less basic amines such as piperidine, diisopropylamine, or diethylamine. Transamination reactions were also performed with 5-hydroxy-2-(methylamino)-4-(methylimino)-cyclohexa-2,5-dienone (1a), which is more soluble in organic solvents than 2-amino-5-hydroxy-4-iminocyclohexa-2,5-dienone (compound I) This led to the first examples of quinonoidal zwitterions functionalized with different alkyl groups on the nitrogen atoms. A number of compounds were characterized by X-ray diffraction, which allowed a better understanding of their electronic situation, and in many cases, the presence of multiple hydrogen-bond donors and acceptors results in crystal packings dominated by these interactions.

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Regioselective Carbon–Carbon Bond Formation Reactions between TCNE or TCNQ and a Quinonoid Ring

Cited by 24 publications

References 72 publications

Reactions of Amines with Zwitterionic Quinoneimines: Synthesis of New Anionic and Zwitterionic Quinonoids

Reactions of Amines with Zwitterionic Quinoneimines: Synthesis of New Anionic and Zwitterionic Quinonoids

Adsorption of TCNQH-functionalized quinonoid zwitterions on gold and graphene: evidence for dominant intermolecular interactions

Accessibility of Zwitterionic Compounds From Primary Amines and 2,5-Dihydroxy-1,4-Benzoquinone

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