GEOMETRICAL ISOMERISM IN β-NITROSTYRENES: PREFERRED CONFORMATIONS OF (E)- AND (Z)- 1-(4-METHYLTHIOPHENYL)-2-NITROBUTENES
Condensation of 4-methylthiobenzaldehyde with 1-nitropropane unexpectedly afforded separable amounts of both (E)- and (Z)-1-(4-methylthiophenyl)-2-nitrobutene. The ¹H and 13C NMR spectra allowed the unequivocal assignment of all signals and their correlation with the preferred conformations adopted...
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Sociedad Chilena de Química
2004
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oai:scielo:S0717-970720040003000132006-03-21GEOMETRICAL ISOMERISM IN β-NITROSTYRENES: PREFERRED CONFORMATIONS OF (E)- AND (Z)- 1-(4-METHYLTHIOPHENYL)-2-NITROBUTENESHURTADO-GUZMÁN,CLAUDIOITURRIAGA-VÁSQUEZ,PATRICIOZAPATA-TORRES,GERALDCASSELS,BRUCE K -nitrostyrene geometrical isomers preferred conformations NMR studies RHF/6-311G(d,p) calculations Condensation of 4-methylthiobenzaldehyde with 1-nitropropane unexpectedly afforded separable amounts of both (E)- and (Z)-1-(4-methylthiophenyl)-2-nitrobutene. The ¹H and 13C NMR spectra allowed the unequivocal assignment of all signals and their correlation with the preferred conformations adopted by these compounds as determined by NOESY experiments. Hartree Fock theory optimizations at the 6-311G(d,p) level were carried out for the stereoisomeric 4-methylthionitroethene, -nitropropene, and -nitrobutene pairs, and the relative energy differences between isomers were calculated in order to estimate approximate E/Z equilibrium constants. These energy differences decrease with the increasing number of side chain carbon atoms, explaining the possibility of separating (E)- and (Z)-nitrobutenes and the failure to isolate the (Z) isomers of the lower homologues under the usual thermodynamically controlled reaction conditionsinfo:eu-repo/semantics/openAccessSociedad Chilena de QuímicaJournal of the Chilean Chemical Society v.49 n.3 20042004-09-01text/htmlhttp://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072004000300013en10.4067/S0717-97072004000300013 |
| institution |
Scielo Chile |
| collection |
Scielo Chile |
| language |
English |
| topic |
-nitrostyrene geometrical isomers preferred conformations NMR studies RHF/6-311G(d,p) calculations |
| spellingShingle |
-nitrostyrene geometrical isomers preferred conformations NMR studies RHF/6-311G(d,p) calculations HURTADO-GUZMÁN,CLAUDIO ITURRIAGA-VÁSQUEZ,PATRICIO ZAPATA-TORRES,GERALD CASSELS,BRUCE K GEOMETRICAL ISOMERISM IN β-NITROSTYRENES: PREFERRED CONFORMATIONS OF (E)- AND (Z)- 1-(4-METHYLTHIOPHENYL)-2-NITROBUTENES |
| description |
Condensation of 4-methylthiobenzaldehyde with 1-nitropropane unexpectedly afforded separable amounts of both (E)- and (Z)-1-(4-methylthiophenyl)-2-nitrobutene. The ¹H and 13C NMR spectra allowed the unequivocal assignment of all signals and their correlation with the preferred conformations adopted by these compounds as determined by NOESY experiments. Hartree Fock theory optimizations at the 6-311G(d,p) level were carried out for the stereoisomeric 4-methylthionitroethene, -nitropropene, and -nitrobutene pairs, and the relative energy differences between isomers were calculated in order to estimate approximate E/Z equilibrium constants. These energy differences decrease with the increasing number of side chain carbon atoms, explaining the possibility of separating (E)- and (Z)-nitrobutenes and the failure to isolate the (Z) isomers of the lower homologues under the usual thermodynamically controlled reaction conditions |
| author |
HURTADO-GUZMÁN,CLAUDIO ITURRIAGA-VÁSQUEZ,PATRICIO ZAPATA-TORRES,GERALD CASSELS,BRUCE K |
| author_facet |
HURTADO-GUZMÁN,CLAUDIO ITURRIAGA-VÁSQUEZ,PATRICIO ZAPATA-TORRES,GERALD CASSELS,BRUCE K |
| author_sort |
HURTADO-GUZMÁN,CLAUDIO |
| title |
GEOMETRICAL ISOMERISM IN β-NITROSTYRENES: PREFERRED CONFORMATIONS OF (E)- AND (Z)- 1-(4-METHYLTHIOPHENYL)-2-NITROBUTENES |
| title_short |
GEOMETRICAL ISOMERISM IN β-NITROSTYRENES: PREFERRED CONFORMATIONS OF (E)- AND (Z)- 1-(4-METHYLTHIOPHENYL)-2-NITROBUTENES |
| title_full |
GEOMETRICAL ISOMERISM IN β-NITROSTYRENES: PREFERRED CONFORMATIONS OF (E)- AND (Z)- 1-(4-METHYLTHIOPHENYL)-2-NITROBUTENES |
| title_fullStr |
GEOMETRICAL ISOMERISM IN β-NITROSTYRENES: PREFERRED CONFORMATIONS OF (E)- AND (Z)- 1-(4-METHYLTHIOPHENYL)-2-NITROBUTENES |
| title_full_unstemmed |
GEOMETRICAL ISOMERISM IN β-NITROSTYRENES: PREFERRED CONFORMATIONS OF (E)- AND (Z)- 1-(4-METHYLTHIOPHENYL)-2-NITROBUTENES |
| title_sort |
geometrical isomerism in β-nitrostyrenes: preferred conformations of (e)- and (z)- 1-(4-methylthiophenyl)-2-nitrobutenes |
| publisher |
Sociedad Chilena de Química |
| publishDate |
2004 |
| url |
http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072004000300013 |
| work_keys_str_mv |
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| _version_ |
1718445341665132544 |