An Acyclic Trialkylamine Virtually Planar at Nitrogen. Some Chemical Consequences of Nitrogen Planarity

Y Jie; P Livant; H Li; M Yang; W Zhu; V Cammarata; P Almond; T Sullens; Y Qin; Eric Bakker

doi:10.1021/jo100628v

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An Acyclic Trialkylamine Virtually Planar at Nitrogen. Some Chemical Consequences of Nitrogen Planarity

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An Acyclic Trialkylamine Virtually Planar at Nitrogen. Some Chemical Consequences of Nitrogen Planarity

Y Jie, P Livant, H Li, M Yang, W Zhu, V Cammarata, P Almond, T Sullens, Y Qin and Eric Bakker

Journal of Organic Chemistry, Vol.75(13), pp.4472-4479

2010

DOI: https://doi.org/10.1021/jo100628v

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Abstract

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The synthesis of the exceedingly congested amine tris(1,3-dihydroxy-2-propyl)amine, 9, was achieved in 47− 51% overall yield. The nitrogen atom of 9 is virtually planar; it is 0.082 Å out of the plane defined by the three attached carbons. The corresponding out-of-plane measurement is 0.282 Å for triisopropylamine and ca. 0.4 Å for uncongested trialkylamines. The N−C bonds of 9 are quite short, despite the steric congestion. The conjugate acid of 9 (viz., 9H+) is very strong: pKa = 3.08 (cf. Et3NH+ pKa = 10.7). Comparison with suitable model compounds suggests 9 is less basic than predicted by ca. 1.5 pKa units. The structure of 9H+Cl− was determined by X-ray crystallography. Here too, the nitrogen is severely flattened relative to ordinary ammonium cations. In 9H+Cl−, the proton on the nitrogen of 9H+ forms three intramolecular hydrogen bonds to hydroxyl groups, i.e., a so-called trifurcated hydrogen bond. The NH···O lengths in 9H+ are slightly shorter than comparable trifurcated hydrogen bonds. Cyclic voltammetry (CV) on 9 finds E1/2ox is 0.88 V, which is consistent with the inductive effect of the 1,3-dihydroxy-2-propyl groups attached to nitrogen. It is also observed that the electrochemical oxidation of 9 is reversible on the CV time scale. The 15N NMR chemical shift of the essentially planar nitrogen atom of 9 is discussed.

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Title: An Acyclic Trialkylamine Virtually Planar at Nitrogen. Some Chemical Consequences of Nitrogen Planarity
Authors: Y Jie (Author)
P Livant (Author)
H Li (Author)
M Yang (Author)
W Zhu (Author)
V Cammarata (Author)
P Almond (Author)
T Sullens (Author)
Y Qin (Author)
Eric Bakker (Author)
Publication details: Journal of Organic Chemistry, Vol.75(13), pp.4472-4479
Publisher: American Chemical Society
Date published: 2010
DOI: 10.1021/jo100628v
ISSN: 0022-3263
Organisation Unit: University of the Sunshine Coast, Queensland
Language: English
Record Identifier: 99450308102621
Output Type: Journal article

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