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: |
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 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Jha, Sanjiv K [VerfasserIn] |
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| Links: |
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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): |
OLC1981752692 |
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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 |
| 264 | 1 | |c 2016 | |
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| 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. | ||
| 540 | |a Nutzungsrecht: © Author(s) | ||
| 700 | 1 | |a Brown, Katie |4 oth | |
| 700 | 1 | |a Todde, Guido |4 oth | |
| 700 | 1 | |a Subramanian, Gopinath |4 oth | |
| 773 | 0 | 8 | |i Enthalten in |t The journal of chemical physics |d Melville, NY : AIP, 1933 |g 145(2016), 7 |w (DE-627)129079049 |w (DE-600)3113-6 |w (DE-576)014411660 |x 0021-9606 |7 nnns |
| 773 | 1 | 8 | |g volume:145 |g year:2016 |g number:7 |
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| 856 | 4 | 2 | |u http://dx.doi.org/10.1063/1.4960955 |
| 856 | 4 | 2 | |u http://www.ncbi.nlm.nih.gov/pubmed/27544105 |
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