Steric Modification of the Intramolecular Hydrogen Bond in 2-(Methylimino-phenyl-methyl)-phenols

Filarowski, Aleksander; Koll, A.; Głowiak, Tadeusz

doi:10.1007/pl00010288

Cited by 5 publications

(1 citation statement)

References 14 publications

(22 reference statements)

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“…Some of these structures may adopt N…O distances as short as 2.46 Å and, in some of these cases, the shortening produces a DW modification of the H-bond potential as, for instance, in 2-(methylimino(phenyl)methyl)-phenol (FUBWII; Fig. (11b)) [66] where both molecules of the double asymmetric unit display N…O distances of 2.488 and 2.496 Å associated with a disordered H-bond proton.…”

Section: Sterically Hindered 2-(1-alkyliminoalkyl)phenols (Class Ii')mentioning

confidence: 98%

Crystal Chemistry and Prototropic Tautomerism in 2-(1-Iminoalkyl)- phenols (or naphthols) and 2-Diazenyl-phenols (or naphthols)

Bertolasi¹,

Gilli

2009

COC

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This review reports a systematic investigation, carried out on the Cambridge Crystallographic Database (CSD), on the structural features of iminoalkyl-phenols (or naphthols) as well as azo-phenols (or naphthols). All these compounds form N-H…O/O-H…N intramolecular hydrogen bonds assisted by resonance (RAHB) in tautomeric equilibrium which can be finely tuned by the substituents. Accordingly, they can present reversible proton transfer leading to interesting properties such as thermochromism and photochromism. The phenol derivatives 2-(1-aryliminoalkyl)phenols and 2-arylazophenols display the predominance of the O-H…N form. Furthermore, they display the following features: i) strongly electron-donating substituents in p-position on the N-phenyl group shorten the N…O contact distance but not enough to produce the O-H…N to O-H…N/N-H…O transition; ii) such a transition can be however induced by strongly electron-withdrawing substituents at the phenol ring which increase the phenol acidity; iii) very similar effects are determined by intermolecular hydrogen-bonded O-H…O contacts with the phenolic oxygen which, stabilizing the N-H…O bond produce the O-H…N to O-H…N/N-H…O transition and, sometimes, the complete proton transfer to the pure N-H…O form. The naphthol derivatives (1-(1-aryliminoalkyl-2-naphthols and 1-arylazo-2-naphthols) display the most interesting situation of two roughly isoenergetic O-H…N/N-H…O tautomers which can be tuned by modifying the Nsubstituent, the effects of substitution at the N-phenyl moiety being by far the most extensively studied. The structures of variously aryl-substituted 1-(1-aryliminoalkyl)-2-naphthols, though collected only at room temperature, indicate that almost all of them are tautomeric equilibria, even if full information on proton populations and dynamic or static nature of the proton disorder are not available. Conversely, the structures of a series of aryl-substituted 1-arylazo-2-naphthols have been recently determined at variable temperature showing that strongly electron-attracting substituents stabilize the pure N-H…O form, while substituents with increasing electron-donating properties transform the system into a dynamic, or static, N-H…O O-H…N tautomeric equilibrium in the solid with an ever increasing population of the O-H…N azoenol tautomer.

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Section: Sterically Hindered 2-(1-alkyliminoalkyl)phenols (Class Ii')mentioning

confidence: 98%

Crystal Chemistry and Prototropic Tautomerism in 2-(1-Iminoalkyl)- phenols (or naphthols) and 2-Diazenyl-phenols (or naphthols)

Bertolasi¹,

Gilli

2009

COC

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Characterisation of the PT-form of o-hydroxy acylaromatic Schiff bases by NMR spectroscopy and DFT calculations

Hansen¹,

Filarowski²

2004

Journal of Molecular Structure

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Matrix-isolation FT-IR studies and theoretical calculations of the vibrational properties of 4-methyl-2′-hydroxy-4′-ethyloxyazobenzene

et al. 2003

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Steric Modification of the Intramolecular Hydrogen Bond in 2-(Methylimino-phenyl-methyl)-phenols

Cited by 5 publications

References 14 publications

Crystal Chemistry and Prototropic Tautomerism in 2-(1-Iminoalkyl)- phenols (or naphthols) and 2-Diazenyl-phenols (or naphthols)

Crystal Chemistry and Prototropic Tautomerism in 2-(1-Iminoalkyl)- phenols (or naphthols) and 2-Diazenyl-phenols (or naphthols)

Characterisation of the PT-form of o-hydroxy acylaromatic Schiff bases by NMR spectroscopy and DFT calculations

Matrix-isolation FT-IR studies and theoretical calculations of the vibrational properties of 4-methyl-2′-hydroxy-4′-ethyloxyazobenzene

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