Infrared spectra and X-ray structure of (tetrazol-5-yl)acetic acid

Pagacz-Kostrzewa, Magdalena; Jesariew, Dominik; Podruczna, M.; Wierzejewska, Maria

doi:10.1016/j.saa.2013.01.086

Cited by 14 publications

(11 citation statements)

References 40 publications

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“…In a previous X-ray structural study of TAA, it was demonstrated that this molecule in the crystals adopts solely the 1H-tautomeric form. 38 However, the present work clearly shows that monomers of TAA frozen in a cryogenic matrix assume both 1H-and 2H-tautomeric forms. The monomeric molecules arrive to the matrix support from the compound vapor obtained during the sublimation process.…”

Section: Mechanistic Discussion Of Tautomerization Of Taamentioning

confidence: 49%

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Tetrazole acetic acid: Tautomers, conformers, and isomerization

Araujo-Andrade

Reva

Fausto

2014

The Journal of Chemical Physics

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Monomers of (tetrazol-5-yl)-acetic acid (TAA) were obtained by sublimation of the crystalline compound and the resulting vapors were isolated in cryogenic nitrogen matrices at 13 K. The conformational and tautomeric composition of TAA in the matrix was characterized by infrared spectroscopy and vibrational calculations carried out at the B3LYP/6-311++G(d,p) level. TAA may adopt two tautomeric modifications, 1H- and 2H-, depending on the position of the annular hydrogen atom. Two-dimensional potential energy surfaces (PESs) of TAA were theoretically calculated at the MP2/6-311++G(d,p) level, for each tautomer. Four and six symmetry-unique minima were located on these PESs, for 1H- and 2H-TAA, respectively. The energetics of the detected minima was subsequently refined by calculations at the QCISD level. Two 1H- and three 2H-conformers fall within the 0-8 kJ mol(-1) energy range and should be appreciably populated at the sublimation temperature (∼330 K). Observation of only one conformer for each tautomer (1ccc and 2pcc) is explained in terms of calculated barriers to conformational rearrangements. All conformers with the cis O=COH moiety are separated by low barriers (less than 10 kJ mol(-1)) and collapse to the most stable 1ccc (1H-) and 2pcc (2H-) forms during deposition of the matrix. On the trans O=COH surfaces, the relative energies are very high (between 12 and 27 kJ mol(-1)). The trans forms are not thermally populated at the sublimation conditions and were not detected in matrices. One high-energy form in each tautomer, 1cct (1H-) and 2pct (2H-), was found to differ from the most stable form only by rotation of the OH group and separated from other forms by high barriers. This opened a perspective for their stabilization in a matrix. 1cct and 2pct were generated in the matrices selectively by means of narrow-band near-infrared (NIR) irradiations of the samples at 6920 and 6937 cm(-1), where the first OH stretching overtone vibrations of 1ccc and 2pcc occur. The reverse transformations could be induced by irradiations at 7010 and 7030 cm(-1), transforming 1cct and 2pct back to 1ccc and 2pcc, also selectively. Besides the NIR-induced transformations, the photogenerated 1cct and 2pct forms also decay in N2 matrices back to 1ccc and 2pcc spontaneously, with characteristic decay times of hours (1H) and tens of minutes (2H). The decay mechanism is rationalized in terms of the proton tunneling. In crystals, TAA exists exclusively as 1H-tautomer. By contrast, the tautomeric composition of the matrix-isolated monomers was found to consist of both 1H- and 2H-tautomers, in comparable amounts. A mechanistic discussion of the tautomerization process occurring during sublimation, accounting also for the observed minor decomposition of TAA leading to CO2 and 5-methyl-tetrazole, is proposed.

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Section: Mechanistic Discussion Of Tautomerization Of Taamentioning

confidence: 49%

“…The structure of TAA in the solid state has been recently studied by Pagacz-Kostrzewa et al 38 The combination of infrared spectroscopy, X-ray diffraction and theoretical calculations led to the conclusion that, in the solid state, TAA exists exclusively as the 1H-tautomer.…”

Section: Introductionmentioning

confidence: 99%

Tetrazole acetic acid: Tautomers, conformers, and isomerization

Araujo-Andrade

Reva

Fausto

2014

The Journal of Chemical Physics

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“…2H tautomerization equilibrium takes place, even when high energy barrier are predicted for the unimolecular tautomerization process [31,32]. In the present case, tautomeric equilibrium is precluded by substitution of the hydrogen atom from the tetrazole ring, but substitution at both 1-and 2-positions can in principle take place during the synthesis procedure.…”

Section: Tautomerism and Conformational Landscapementioning

confidence: 68%

“…In both structures, the tetrazole and phenyl groups are co-planar, the -C(O)O-ester group oriented perpendicular to this plane. Contrary to this conformational behavior, it is worth noting that for (tetrazol-5-yl)acetic acid, the -C(O)O-group is nearly co-planar with the tetrazole ring [31]. It is plausible that the C@OÁ Á ÁH-N intramolecular hydrogen bond between the carboxylic group and the 1-H tetrazole moiety favors the planar conformation.…”

Section: Tautomerism and Conformational Landscapementioning

confidence: 95%

A combined experimental and theoretical study of the tautomeric and conformational properties of (5-phenyl-tetrazol-2-yl)-acetic acid methyl ester

Saeed

Qasim

Hussain

et al. 2015

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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The tautomeric and conformational properties of a new tetrazole derivative are studied in a combined approach that includes the analysis of the experimental vibrational data together with theoretical calculation methods, especially in terms of natural bond orbital (NBO) population analysis. Moreover, the molecular and crystal structure was determined by single crystal X-ray diffraction. The compound crystallized as the 2-tautomeric form, monoclinic space group P21/c with Z=4, a=10.0630(14), b=8.2879(11), c=12.8375(18) Å, β=105.546(3)°, V=1031.5(2) Å(3). The tetrazole and phenyl rings are coplanar with the acetate group oriented perpendicular to the plane. The NBO analysis showed that delocalizing interactions of the lpp(N2) lone pair orbital contributes to a strong resonance interactions with both adjacent π(∗)(N3N4) and π(∗)(N1C5) antibonding orbitals of the tetrazole group.

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14] There are several biologically active molecules that contain the tetrazole functionality. 1,2 One reason for their popularity in pharmaceuticals is their ability to serve as carboxylic acid bioisosteres due to the similar acidity of the free N-H [3][4][5] functionality and also because of their better metabolic resistance. As of December 2015, Drugbank reported 24 Federal Drug Administration (FDA) approved drugs containing either the 1H-or the 2H-tetrazole substituent.…”

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confidence: 99%

The synthesis of [1‐¹⁴C]2‐(1H‐tetrazol‐5‐yl)acetic acid

Maxwell

Tran

2016

Labelled Comp Radiopharmac

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Tetrazoles are a common heterocyclic functionality in many biologically active molecules. [1- C]2-(1H-Tetrazol-5-yl)acetic acid was required as an intermediate in the synthesis of a development candidate as part of a discovery phase program to complete metabolic profiling studies. [1- C]2-(1H-Tetrazol-5-yl)acetic acid was prepared in 4 steps overall and in 3 radiochemical steps from K CN in an overall 32% radiochemical yield.

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Infrared spectra and X-ray structure of (tetrazol-5-yl)acetic acid

Cited by 14 publications

References 40 publications

Tetrazole acetic acid: Tautomers, conformers, and isomerization

Tetrazole acetic acid: Tautomers, conformers, and isomerization

A combined experimental and theoretical study of the tautomeric and conformational properties of (5-phenyl-tetrazol-2-yl)-acetic acid methyl ester

The synthesis of [1‐¹⁴C]2‐(1H‐tetrazol‐5‐yl)acetic acid

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Infrared spectra and X-ray structure of (tetrazol-5-yl)acetic acid

Cited by 14 publications

References 40 publications

Tetrazole acetic acid: Tautomers, conformers, and isomerization

Tetrazole acetic acid: Tautomers, conformers, and isomerization

A combined experimental and theoretical study of the tautomeric and conformational properties of (5-phenyl-tetrazol-2-yl)-acetic acid methyl ester

The synthesis of [1‐14C]2‐(1H‐tetrazol‐5‐yl)acetic acid

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The synthesis of [1‐¹⁴C]2‐(1H‐tetrazol‐5‐yl)acetic acid