Concurrent pathway and unexpected products in the CuAAC reaction of ethyl prop-2-ynyl methylphosphonate with aromatic azides

Pokhodylo, Nazariy T.; Shyyka, Olga Ya.; Tupychak, M.; Slyvka, Yu. I.; Обушак, Н. Д.

doi:10.1007/s10593-019-02467-9

Cited by 11 publications

(6 citation statements)

References 15 publications

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“…The dihedral angle between the tolyl and 1,2,3-triazole rings in the title compound is 32.75 (7) , which is comparable with the corresponding angle in 5-cyclopropyl-1-(3-methoxyphenyl)-1H-1,2,3-triazole-4-carboxylic acid [39.1 (2) ] but lower than in the structure of 5-methyl-1-(4-nitrophenyl)-1H-1,2,3triazol-4-ylphosphonate [45.36 (6) ] (Pokhodylo, Shykka, Goreshnik et al, 2020). Conversely, in the triazoles unsubstituted at the 5-position, [1-(3-bromo-or 4-fluorophenyl)-1H-1,2,3-triazol-4-yl]methyl methylphosphonate, these angle are 22.9 (3) and 15.7 (2) , respectively (Pokhodylo, Shyyka et al, 2019).…”

Section: Structural Commentarymentioning

confidence: 99%

Synthesis, crystal structure and Hirshfeld surface analysis of 5-cyclopropyl-N-(2-hydroxyethyl)-1-(4-methylphenyl)-1H-1,2,3-triazole-4-carboxamide

Pokhodylo¹,

Slyvka²,

Pavlyuk³

2021

Acta Crystallogr E Cryst Commun

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The title compound, C15H18N4O2, was obtained via a two-step synthesis (Dimroth reaction and amidation) for anticancer activity screening and was selected from a 1H-1,2,3-triazole-4-carboxamide library. The cyclopropyl ring is oriented almost perpendicular to the benzene ring [dihedral angle = 87.9 (1)°], while the dihedral angle between the mean plane of the cyclopropyl ring and that of the triazole ring is 55.6 (1)°. In the crystal, the molecules are linked by O—H...O and C—H...N interactions into infinite ribbons propagating in the [001] direction, which are interconnected by weak C—H...O interactions into layers. The intermolecular interactions were characterized via Hirshfeld surface analysis, which indicated that the largest fingerprint contact percentages are H...H (55.5%), N...H/H...N (15.4%), C...H/H...C (13.2%) and O...H/H...O (12.9%).

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Section: Structural Commentarymentioning

confidence: 99%

Synthesis, crystal structure and Hirshfeld surface analysis of 5-cyclopropyl-N-(2-hydroxyethyl)-1-(4-methylphenyl)-1H-1,2,3-triazole-4-carboxamide

Pokhodylo¹,

Slyvka²,

Pavlyuk³

2021

Acta Crystallogr E Cryst Commun

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“…The above angle between the planes is comparable with that for the bulky 5-(2-phenylhydrazineylidene)methyl analogue [73.3 (2) ; Pokhodylo et al, 2018] but is considerably larger than in the structure of 5-cyclopropyl-1-(3-methoxyphenyl)-1H-1,2,3triazole-4-carboxylic acid [39.1 (2) ] in which the cyclopropyl ring is oriented to the triazole ring (Pokhodylo et al, 2017) or in 5-methyl-1-(4-nitrophenyl)-1H-1,2,3-triazol-4-ylphosphon-ate [45.36 (6) ; Pokhodylo et al, 2020]. In selected 5-free triazoles, 1-(3-bromo-or 4-fluorophenyl)-1H-1,2,3-triazol-4yl)methyl methylphosphonates, this angle is 22.9 (3) and 15.7 (2) , respectively (Pokhodylo, Shyyka et al, 2019). Within the cyclopropyl ring in the title compound, the three C-C bond lengths differ by an insignificant amount [C11-C12 = 1.491 (3), C11-C13 = 1.475 (3), C12-C13 = 1.457 (3) Å ].…”

Section: Structural Commentarymentioning

confidence: 99%

Synthesis, crystal structure and Hirshfeld surface analysis of N-(4-chlorophenyl)-5-cyclopropyl-1-(4-methoxyphenyl)-1H-1,2,3-triazole-4-carboxamide

2020

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The title compound, C19H17ClN4O2, was obtained via a two-step synthesis involving the enol-mediated click Dimroth reaction of 4-azidoanisole with methyl 3-cyclopropyl-3-oxopropanoate leading to the 5-cyclopropyl-1-(4-methoxyphenyl)-1H-1,2,3-triazole-4-carboxylic acid and subsequent acid amidation with 4-chloroaniline by 1,1′-carbonyldiimidazole (CDI). It crystallizes in space group P21/n, with one molecule in the asymmetric unit. In the extended structure, two molecules arranged in a near coplanar fashion relative to the triazole ring planes are interconnected by N—H...N and C—H...N hydrogen bonds into a homodimer. The formation of dimers is a consequence of the above interaction and the edge-to-face stacking of aromatic rings, which are turned by 58.0 (3)° relative to each other. The dimers are linked by C—H...O interactions into ribbons. DFT calculations demonstrate that the frontier molecular orbitals are well separated in energy and the HOMO is largely localized on the 4-chlorophenyl amide motif while the LUMO is associated with aryltriazole grouping. A Hirshfeld surface analysis was performed to further analyse the intermolecular interactions.

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“…У попередніх працях ми дослідили широкий спектр реакцій купрумкаталітичного 1,3-диполярного циклоприєднання, зокрема, вивчили особливості реакції стерично утруднених азидів [6], знайшли деякі обмеження таких реакцій у випадку низькомолекулярних азидів та азидів, що містять гетероциклічні замісники [7], відкрили приклади, коли реакція відбувається не тільки без утворення "класичних" продуктів циклоприєднання -1,2,3-триазолів, а йде іншим маршрутом, унаслідок чого одержали акриламіди [8]. В CuAAC-реакціях застосовували каркасні азиди [9], азиди, здатні хелатувати мідний каталізатор [10], а також досліджували нові типи каталізаторів -π-комплекси міді [11].…”

Section: вступunclassified

“…Таблиця 1 Азиди 1a-g Під час вибору умов проведення CuAAC-реакції, керуючись отриманими результатами наших попередніх праць [6][7][8][9][10][11][12], ми зупинились на каталітичній системі СuI/NEt3 як одній з найефективніших та толерантній до широкого кола замісників.…”

Section: результати досліджень та їх обговоренняunclassified

Synthesis of 1-substituted-4-(methylsulphonylmethyl)-1H-1,2,3-triazoles by the CuAAC reaction

Tupychak¹,

Pokhodylo²,

Obushak³

2021

Visnyk Lviv Univ. Ser. Chem.

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Concurrent pathway and unexpected products in the CuAAC reaction of ethyl prop-2-ynyl methylphosphonate with aromatic azides

Cited by 11 publications

References 15 publications

Synthesis, crystal structure and Hirshfeld surface analysis of 5-cyclopropyl-N-(2-hydroxyethyl)-1-(4-methylphenyl)-1H-1,2,3-triazole-4-carboxamide

Synthesis, crystal structure and Hirshfeld surface analysis of 5-cyclopropyl-N-(2-hydroxyethyl)-1-(4-methylphenyl)-1H-1,2,3-triazole-4-carboxamide

Synthesis, crystal structure and Hirshfeld surface analysis of N-(4-chlorophenyl)-5-cyclopropyl-1-(4-methoxyphenyl)-1H-1,2,3-triazole-4-carboxamide

Synthesis of 1-substituted-4-(methylsulphonylmethyl)-1H-1,2,3-triazoles by the CuAAC reaction

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