Syntheses, Structures and Basicities of 1,2,4,5-Tetrakis(dimethylamino)benzene and 2,3,6,7-Tetrakis(dimethylamino)naphthalene

For comparison to the recently described 2,3,6,7‐tetrakis(dimethylamino)naphthalene (1) the three isomers 2,3, and 4 were synthesized. The basicities of this group of isomers are strongly dependent upon the different mutual orientations of the pairs of dimethylamino substituents: only the isomers 3 and, partially, 4, both with dimethylamino groups in adjacent peri‐positions of the naphthalene, are strong “proton sponges”. For the isomers 1 and 2 with the same number and kind of twofold dimethylamino substituents in neighbouring ortho‐positions, however, no significant basicity increase is observed. To explain this difference between the two groups of isomers it is suggested that in the ortho‐pairs of 1 and 2 the C‐N bonds diverge considerably, leading to an increased N···N distance and consequently to less stable [N···H···N]+ hydrogen bonds in contrast to the parallel C‐N bonds in the peri‐substituted isomers 3 and 4. X‐ray crystal structure analyses of the bases and of some of the salts derived therefrom were solved and are discussed. Cyclic voltammetry indicates that 1 to 4 are strong electron donors, reacting easily to radical cations or dications which with suitable acids have been obtained as salts.

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Isomeric Tetrakis(dimethylamino)naphthalenes: Syntheses, Structure-Dependence of Basicities, Crystal Structures, and Physical Properties

Staab

Kirsch

Barth

et al. 2000

Eur. J. Org. Chem.

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1,8-Bis(tetramethylguanidino)naphthalene (TMGN): A New, Superbasic and Kinetically Active “Proton Sponge”

Raab¹,

Kipke²,

Gschwind³

et al. 2002

Chem. Eur. J.

186

168

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Exclusive β‐Substitution in the Reaction of Octafluoronaphthalene with Secondary Amines

2004

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The reaction between octafluoronaphthalene and dimethylamine, pyrrolidine or piperidine in DMF, dimethyl(ethylene)urea (DMEU) or without solvent leads to the exclusive substitution of β‐fluorine atoms giving naphthalene derivatives with four NR2 groups. This was proved by 19F NMR of the products and a crystal structure determination for 1,4,5,8‐tetrafluoro‐2,3,6,7‐tetrakis(piperidin‐1‐yl)naphthalene. The main feature of the reaction in DMF was a transamidation process. The remaining four fluorine atoms in the synthesised tetraamines could be smoothly replaced by reduction with LiAlH4. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Syntheses, Structures and Basicities of 1,2,4,5-Tetrakis(dimethylamino)benzene and 2,3,6,7-Tetrakis(dimethylamino)naphthalene

Cited by 16 publications

References 13 publications

Isomeric Tetrakis(dimethylamino)naphthalenes: Syntheses, Structure-Dependence of Basicities, Crystal Structures, and Physical Properties

Isomeric Tetrakis(dimethylamino)naphthalenes: Syntheses, Structure-Dependence of Basicities, Crystal Structures, and Physical Properties

1,8-Bis(tetramethylguanidino)naphthalene (TMGN): A New, Superbasic and Kinetically Active “Proton Sponge”

Exclusive β‐Substitution in the Reaction of Octafluoronaphthalene with Secondary Amines

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