A mechanochemical study of the effects of compression on a Diels-Alder reaction
We examine the effects of compressive external forces on the mechanisms of the parent Diels-Alder (DA) reaction between butadiene and ethylene. Reaction pathways and transition states were calculated using the nudged elastic band method within a mechanochemical framework at the CASSCF(6,6)/6-31G**, as well as the B3LYP/6-311++G** levels of theory. Our results suggest that compressive hydrostatic pressure lowers the energy barrier for the parent DA reaction while suppressing the undesirable side reaction, thereby leading to a direct increase in the yield of cyclohexene. Compressive pressure also increases the exothermicity of the parent DA reaction, which would lead to increased temperatures in a reaction vessel and thereby indirectly increase the yield of cyclohexene. Our estimates indicate that the compression used in our study corresponds to a range of 68 MPa-1410 MPa.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2016 |
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| Erschienen: |
2016 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:145 |
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| Enthalten in: |
The Journal of chemical physics - 145(2016), 7 vom: 21. Aug., Seite 074307 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Jha, Sanjiv K [VerfasserIn] |
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| Anmerkungen: |
Date Completed 10.01.2017 Date Revised 11.01.2017 published: Print Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1063/1.4960955 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM263605957 |
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| 100 | 1 | |a Jha, Sanjiv K |e verfasserin |4 aut | |
| 245 | 1 | 2 | |a A mechanochemical study of the effects of compression on a Diels-Alder reaction |
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| 500 | |a Date Completed 10.01.2017 | ||
| 500 | |a Date Revised 11.01.2017 | ||
| 500 | |a published: Print | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a We examine the effects of compressive external forces on the mechanisms of the parent Diels-Alder (DA) reaction between butadiene and ethylene. Reaction pathways and transition states were calculated using the nudged elastic band method within a mechanochemical framework at the CASSCF(6,6)/6-31G**, as well as the B3LYP/6-311++G** levels of theory. Our results suggest that compressive hydrostatic pressure lowers the energy barrier for the parent DA reaction while suppressing the undesirable side reaction, thereby leading to a direct increase in the yield of cyclohexene. Compressive pressure also increases the exothermicity of the parent DA reaction, which would lead to increased temperatures in a reaction vessel and thereby indirectly increase the yield of cyclohexene. Our estimates indicate that the compression used in our study corresponds to a range of 68 MPa-1410 MPa | ||
| 650 | 4 | |a Journal Article | |
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| 700 | 1 | |a Todde, Guido |e verfasserin |4 aut | |
| 700 | 1 | |a Subramanian, Gopinath |e verfasserin |4 aut | |
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