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Product distribution of tricyclopentadiene from cycloaddition of dicyclopentadiene and cyclopentadiene: A theoretical and experimental study
- Source :
-
Fuel . Sep2010, Vol. 89 Issue 9, p2522-2527. 6p. - Publication Year :
- 2010
-
Abstract
- Abstract: Tricyclopentadiene (TCPD), product of dicyclopentadiene (DCPD)/cyclopentadiene (CPD) cycloaddition, is a promising candidate as high-energy–density fuel. Thermal [4+2] cycloaddition of DCPD and CPD was simulated using M05-2X/6-311G(d,p) to predict the product distribution. There are four concerted but slightly asynchronous pathways leading to four adducts for endo-DCPD/CPD and exo-DCPD/CPD additions, respectively. The pathways connecting endo-adduct are kinetically preferred compared with those connecting exo-adduct. NB-adducts show higher stability than corresponding CP-adducts. Moreover, exo-isomers are more stable for CP-adducts, but the tendency is inverse for NB-adducts. The predicted product preference is NB-endo>CP-endo>CP-exo>NB-exo. Experiment shows product composition of NB-endo:CP-endo=7.32:1 and NB-endo:CP-endo:CP-exo=3.79:1:0.1 for thermal endo-DCPD/CPD and exo-DCPD/CPD additions, respectively, consistent with the predicted result. However, catalytic reaction gives completely different distribution, in which [4+2] NB-exo and CP-exo, along with at least 21.6% [2+2] adducts, are formed. [Copyright &y& Elsevier]
Details
- Language :
- English
- ISSN :
- 00162361
- Volume :
- 89
- Issue :
- 9
- Database :
- Academic Search Index
- Journal :
- Fuel
- Publication Type :
- Academic Journal
- Accession number :
- 51295326
- Full Text :
- https://doi.org/10.1016/j.fuel.2009.11.020