A DFT study of the hydrolysis of hydantoin
Abstract Density functional theory (DFT) calculations were made on the hydrolysis of hydantoin (2,4‐imidazolidinedione). In the neutral hydrolysis, reacting systems composed of hydantoin and (H 2 O) n with n = 1+3, 2+3, 3+3, and 4+3 were adopted. Three water molecules (“+3”) participate in the in‐pl...
Published in: | International Journal of Chemical Kinetics |
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crwiley:10.1002/kin.21312 2024-06-02T08:05:13+00:00 A DFT study of the hydrolysis of hydantoin Yamabe, Shinichi Tsuchida, Noriko Yamazaki, Shoko 2019 http://dx.doi.org/10.1002/kin.21312 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fkin.21312 https://onlinelibrary.wiley.com/doi/pdf/10.1002/kin.21312 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/kin.21312 en eng Wiley http://onlinelibrary.wiley.com/termsAndConditions#vor International Journal of Chemical Kinetics volume 51, issue 11, page 831-839 ISSN 0538-8066 1097-4601 journal-article 2019 crwiley https://doi.org/10.1002/kin.21312 2024-05-03T10:59:38Z Abstract Density functional theory (DFT) calculations were made on the hydrolysis of hydantoin (2,4‐imidazolidinedione). In the neutral hydrolysis, reacting systems composed of hydantoin and (H 2 O) n with n = 1+3, 2+3, 3+3, and 4+3 were adopted. Three water molecules (“+3”) participate in the in‐plane hydrogen‐bond circuit, and the n –3 = 1, 2, 3 or 4 water cluster works for the out‐of‐plane nucleophilic attack onto the carbonyl carbon of hydantoin. Transition states (TSs) involving bond interchanges prompted by proton transfers were determined. The reaction path with n = 3+3 containing N ‐carbamoyl glycine, N ‐carboxy glycine and three tetrahedral intermediates was found to be most likely. In the acid‐catalyzed hydrolysis, a reacting system composed of hydantoin and H 3 O + (H 2 O) 7 was employed. Ten TSs and nine intermediates were obtained. N ‐carbamoyl glycine and N ‐carboxy glycine were confirmed to be detectable stable species. The product consists of glycine, carbonic acid (not CO 2 ), NH 4 + , and (H 2 O) 5 . It has the exothermic energy, whereas the product in the neutral hydrolysis is of the endothermic one for all n values. For both neutral ( n = 3+3) and acid‐catalyzed hydrolyses, the rate‐determining steps were calculated to be for formation of the tetrahedral intermediate, HOOC‐CH 2 ‐NH‐C(OH) 2 NH 2 . The pattern of proton transfers along hydrogen bonds was carefully investigated. Article in Journal/Newspaper Carbonic acid Wiley Online Library International Journal of Chemical Kinetics 51 11 831 839 |
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Abstract Density functional theory (DFT) calculations were made on the hydrolysis of hydantoin (2,4‐imidazolidinedione). In the neutral hydrolysis, reacting systems composed of hydantoin and (H 2 O) n with n = 1+3, 2+3, 3+3, and 4+3 were adopted. Three water molecules (“+3”) participate in the in‐plane hydrogen‐bond circuit, and the n –3 = 1, 2, 3 or 4 water cluster works for the out‐of‐plane nucleophilic attack onto the carbonyl carbon of hydantoin. Transition states (TSs) involving bond interchanges prompted by proton transfers were determined. The reaction path with n = 3+3 containing N ‐carbamoyl glycine, N ‐carboxy glycine and three tetrahedral intermediates was found to be most likely. In the acid‐catalyzed hydrolysis, a reacting system composed of hydantoin and H 3 O + (H 2 O) 7 was employed. Ten TSs and nine intermediates were obtained. N ‐carbamoyl glycine and N ‐carboxy glycine were confirmed to be detectable stable species. The product consists of glycine, carbonic acid (not CO 2 ), NH 4 + , and (H 2 O) 5 . It has the exothermic energy, whereas the product in the neutral hydrolysis is of the endothermic one for all n values. For both neutral ( n = 3+3) and acid‐catalyzed hydrolyses, the rate‐determining steps were calculated to be for formation of the tetrahedral intermediate, HOOC‐CH 2 ‐NH‐C(OH) 2 NH 2 . The pattern of proton transfers along hydrogen bonds was carefully investigated. |
format |
Article in Journal/Newspaper |
author |
Yamabe, Shinichi Tsuchida, Noriko Yamazaki, Shoko |
spellingShingle |
Yamabe, Shinichi Tsuchida, Noriko Yamazaki, Shoko A DFT study of the hydrolysis of hydantoin |
author_facet |
Yamabe, Shinichi Tsuchida, Noriko Yamazaki, Shoko |
author_sort |
Yamabe, Shinichi |
title |
A DFT study of the hydrolysis of hydantoin |
title_short |
A DFT study of the hydrolysis of hydantoin |
title_full |
A DFT study of the hydrolysis of hydantoin |
title_fullStr |
A DFT study of the hydrolysis of hydantoin |
title_full_unstemmed |
A DFT study of the hydrolysis of hydantoin |
title_sort |
dft study of the hydrolysis of hydantoin |
publisher |
Wiley |
publishDate |
2019 |
url |
http://dx.doi.org/10.1002/kin.21312 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fkin.21312 https://onlinelibrary.wiley.com/doi/pdf/10.1002/kin.21312 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/kin.21312 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
International Journal of Chemical Kinetics volume 51, issue 11, page 831-839 ISSN 0538-8066 1097-4601 |
op_rights |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
op_doi |
https://doi.org/10.1002/kin.21312 |
container_title |
International Journal of Chemical Kinetics |
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51 |
container_issue |
11 |
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831 |
op_container_end_page |
839 |
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1800749999352446976 |