Molecular orbital investigation of various reaction pathways in reaction of ketones with bromoform
Само за регистроване кориснике
2006
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
To elucidate the ring opening, nucleophilic reactions of dihaloepoxides the extensive calculations were done on a model system cyclohexanone-bromoform. In this reaction, the formation of dihaloepoxide is postulated as a key step that determines the distribution and stereochemistry of products. Every reaction scheme involves epoxide as a key intermediate (1). Three major products (2, 3, and 4) can be obtained, in principle, by three different competing reaction pathways. The calculations showed that all the pathways are exothermic. Reaction pathway 1 is most convenient, it does not include any intermediate, and its energy is not much affected by the polarity of the medium. In pathways 2 and 3, the calculations showed the intermediates having a largely carbocationic character on the spiro junction carbon atom. The step in which these intermediates are formed determines the reaction rate. Because of the polarity of intermediates in pathways 2 and 3, the base concentration and polarity of ...solvent determine the balance of reaction pathways and the product yield. (c) 2005 Wiley Periodicals, Inc.
Кључне речи:
MNDO-PM3 / reaction pathway / dihaloepoxides / bromoformИзвор:
International Journal of Quantum Chemistry, 2006, 106, 6, 1323-1329Издавач:
- John Wiley & Sons Inc, Hoboken
DOI: 10.1002/qua.20888
ISSN: 0020-7608
WoS: 000236034600005
Scopus: 2-s2.0-33645704057
Колекције
Институција/група
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Vitnik, ZJ AU - Kiricojevic, VD AU - Ivanović, Milovan AU - Juranić, Ivan O. PY - 2006 UR - https://cherry.chem.bg.ac.rs/handle/123456789/528 AB - To elucidate the ring opening, nucleophilic reactions of dihaloepoxides the extensive calculations were done on a model system cyclohexanone-bromoform. In this reaction, the formation of dihaloepoxide is postulated as a key step that determines the distribution and stereochemistry of products. Every reaction scheme involves epoxide as a key intermediate (1). Three major products (2, 3, and 4) can be obtained, in principle, by three different competing reaction pathways. The calculations showed that all the pathways are exothermic. Reaction pathway 1 is most convenient, it does not include any intermediate, and its energy is not much affected by the polarity of the medium. In pathways 2 and 3, the calculations showed the intermediates having a largely carbocationic character on the spiro junction carbon atom. The step in which these intermediates are formed determines the reaction rate. Because of the polarity of intermediates in pathways 2 and 3, the base concentration and polarity of solvent determine the balance of reaction pathways and the product yield. (c) 2005 Wiley Periodicals, Inc. PB - John Wiley & Sons Inc, Hoboken T2 - International Journal of Quantum Chemistry T1 - Molecular orbital investigation of various reaction pathways in reaction of ketones with bromoform VL - 106 IS - 6 SP - 1323 EP - 1329 DO - 10.1002/qua.20888 ER -
@article{ author = "Vitnik, ZJ and Kiricojevic, VD and Ivanović, Milovan and Juranić, Ivan O.", year = "2006", abstract = "To elucidate the ring opening, nucleophilic reactions of dihaloepoxides the extensive calculations were done on a model system cyclohexanone-bromoform. In this reaction, the formation of dihaloepoxide is postulated as a key step that determines the distribution and stereochemistry of products. Every reaction scheme involves epoxide as a key intermediate (1). Three major products (2, 3, and 4) can be obtained, in principle, by three different competing reaction pathways. The calculations showed that all the pathways are exothermic. Reaction pathway 1 is most convenient, it does not include any intermediate, and its energy is not much affected by the polarity of the medium. In pathways 2 and 3, the calculations showed the intermediates having a largely carbocationic character on the spiro junction carbon atom. The step in which these intermediates are formed determines the reaction rate. Because of the polarity of intermediates in pathways 2 and 3, the base concentration and polarity of solvent determine the balance of reaction pathways and the product yield. (c) 2005 Wiley Periodicals, Inc.", publisher = "John Wiley & Sons Inc, Hoboken", journal = "International Journal of Quantum Chemistry", title = "Molecular orbital investigation of various reaction pathways in reaction of ketones with bromoform", volume = "106", number = "6", pages = "1323-1329", doi = "10.1002/qua.20888" }
Vitnik, Z., Kiricojevic, V., Ivanović, M.,& Juranić, I. O.. (2006). Molecular orbital investigation of various reaction pathways in reaction of ketones with bromoform. in International Journal of Quantum Chemistry John Wiley & Sons Inc, Hoboken., 106(6), 1323-1329. https://doi.org/10.1002/qua.20888
Vitnik Z, Kiricojevic V, Ivanović M, Juranić IO. Molecular orbital investigation of various reaction pathways in reaction of ketones with bromoform. in International Journal of Quantum Chemistry. 2006;106(6):1323-1329. doi:10.1002/qua.20888 .
Vitnik, ZJ, Kiricojevic, VD, Ivanović, Milovan, Juranić, Ivan O., "Molecular orbital investigation of various reaction pathways in reaction of ketones with bromoform" in International Journal of Quantum Chemistry, 106, no. 6 (2006):1323-1329, https://doi.org/10.1002/qua.20888 . .