Transformation of 2,2-Di(3-nitro-4-chlorophenyl)-1,1,1-trichloroethane in the Alkali–Amide Solvent Medium

E. A. Guzov; Гузов Е. А.; M. B. Kuzhin; Кужин М. Б.; M. P. Baranova; Баранова М. П.; V. N. Kazin; Казин В. Н.

Transformation of 2,2-Di(3-nitro-4-chlorophenyl)-1,1,1-trichloroethane in the Alkali–Amide Solvent Medium

Авторлар: Guzov E.A.¹, Kuzhin M.B.¹, Baranova M.P.¹, Kazin V.N.¹
Мекемелер:
1. P. G. Demidov Yaroslavl State University
Шығарылым: Том 94, № 2 (2024)
Беттер: 185-193
Бөлім: Articles
URL: https://transsyst.ru/0044-460X/article/view/667172
ID: 667172

Дәйексөз келтіру

Толық мәтін

Ашық рұқсат
Рұқсат жабық

Рұқсат берілді
Рұқсат жабық

Тек жазылушылар үшін

Аннотация
Толық мәтін
Авторлар туралы
Әдебиет тізімі
Қосымша файлдар
Статистика

Аннотация

A quantum chemical analysis of the transformation pathways of 2,2-di(3-nitro-4-chlorophenyl)-1,1,1-trichloroethane in NaOH–DMF, involving competing reagents, was performed. For each reaction, spatial structures were modeled and the energy parameters of the pre-reaction, activated and post-reaction complexes were calculated. As a result of the analysis of the thermodynamic parameters of the reactions, the most energetically favorable scheme for the transformation of 2,2-di(3-nitro-4-chlorophenyl)-1,1,1-trichloroethane into 2,2-di(3-nitro-4-N,N-dimethylaminophenyl)-1,1-dichloroethene was proposed. The mechanisms of the occurring reactions were established.

Негізгі сөздер

2,2-di(3-nitro-4-chlorophenyl)-1,1,1-trichloroethane, alkaline hydrolysis of DMF, anionic complex, density functional method, mechanisms of dehydrochlorination and nucleophilic substitution reactions

Толық мәтін

Авторлар туралы

E. Guzov

P. G. Demidov Yaroslavl State University

Email: kaz@uniyar.ac.ru
Ресей, Yaroslavl, 150003

M. Kuzhin

P. G. Demidov Yaroslavl State University

Email: kaz@uniyar.ac.ru
Ресей, Yaroslavl, 150003

M. Baranova

P. G. Demidov Yaroslavl State University

Email: kaz@uniyar.ac.ru
Ресей, Yaroslavl, 150003

V. Kazin

P. G. Demidov Yaroslavl State University

Хат алмасуға жауапты Автор.
Email: kaz@uniyar.ac.ru
Ресей, Yaroslavl, 150003

Әдебиет тізімі

Varghese J.J., Mushrif S.H. // React. Chem. Eng. 2019. Vol. 4. N 2. P. 165. doi: 10.1039/C8RE00226F.
Solvents as reagents in organic synthesis: Reactions and applications / Ed. X.-F. Wu. Wiley-VHC, 2017. Р. 199. doi: 10.1002/9783527805624
Muzart J. // Tetrahedron. 2009. Vol. 65. N 40. P. 8313. doi: 10.1016/j.tet.2009.06.091.
Ding S., Jiao N. // Angew. Chem. Int. Ed. 2012. Vol. 51. N 37. Р. 9226. doi: 10.1002/anie.201200859
Pliego J.R., Jr. // Chem. Phys. 2004. Vol. 306. N 1–3. Р. 273. doi: 10.1016/j.chemphys.2004.07.041
Stanovnik B., Svete J. // Chem. Rev. 2004. Vol. 104. N 5. Р. 2433. doi: 10.1021/cr020093y
Agarwal A., Chauhan P.M.S. // Synth. Commun. 2004. Vol. 34. N 16. Р. 2925. doi: 10.1081/SCC-200026634
Garcia J., Sorrentino J., Diller E.J., Chapman D., Woydziak Z.R. // Synth. Commun. 2016. Vol. 46. N 5. Р. 475. doi: 10.1080/00397911.2016.1147051
Ando S., Tsuzaki M., Ishizuka T. // J. Org. Chem. 2020. Vol. 85. N 17. Р. 11181. doi: 10.1021/acs.joc.0c01250
Сибриков С.Г., Казин В.Н., Копейкин В.В., Миронов Г.С., Орлова Т.Н. // ЖОрХ. 1991. Т. 27. Вып. 2. С. 382.
Казин В.Н., Сибриков С.Г., Кужин М.Б., Казина Е.Г., Митрофанова Г.П., Гробов А.М. Пат. RU 2522570 (2014).
Казин В.Н., Сибриков С.Г., Плисс Е.М., Казина Е.Г., Тихонов И.В., Митрофанова Г.П. Пат. RU 2522551 (2014) // Б. И. 2014. № 18.
Казин В.Н., Сибриков С.Г., Кужин М.Б., Митрофанова Г.П., Казина Е.Г., Сирик А.В. Пат. RU 2522553 (2014) // Б. И. 2014. № 18.
Гузов Е.А., Кужин М.Б., Копыткова М.П., Сибриков С.Г., Казин В.Н. // ЖOX. 2021. Т. 91. № 3. С. 404; Guzov E.A., Kuzhin M.B., Kopitkova M.P., Sibrikov S.G., Kazin V.N. // Russ. J. Gen. Chem. 2021. Vol. 91 N 3. P. 373. doi: 10.1134/S1070363221030051
Granovsky A.A. Firefly version 8.2. http://classic.chem.msu.su/gran/firefly/index.html
Marenich A.V., Cramer C.J., Truhlar D.G. // Phys. Chem. (B). 2009. Vol. 113. N 18. P. 6378. doi: 10.1021/jp810292n
Chemcraft – графическое программное обеспечение для визуализации квантово-химических расчетов. Версия 1.8, сборка 654. https://www.chemcraftprog.com

Қосымша файлдар

Әрекет

1. JATS XML

Жүктеу

2. Fig. 1. Energy profile and dynamics of changes in the interatomic distance (H6–C1, C2–Cl4) of the reaction of dehydrochlorination of 2,2-di(3-nitro-4-chlorophenyl)-1,1,1-trichloroethane with dimethylaminomethanediol carbanion (O-attack). Spatial structures of the pre-reaction (1), activated (2) and post-reaction complexes (3). The charge on the atoms according to Mulliken (A. E.) is given in italics.

Жүктеу (265KB)

Метадеректер

3. Fig. 2. Energy profile and dynamics of changes in the interatomic distance (C1–N3, C1–Cl2) of the nucleophilic substitution reaction of the chlorine atom in the interaction of 2,2-di(3-nitro-4-chlorophenyl)-1,1,1-trichloroethane with carbanion N,N- dimethylaminomethanediol (N-attack). Spatial structures of the pre-reaction (1), activated (2) and post- reaction complexes (3). The charge on the atoms according to Mulliken (A. E.) is given in italics.