TY - JOUR
T1 - Benzocyclobutadienyl anion
T2 - Formation and energetics of an antiaromatic molecule
AU - Broadus, Katherine M.
AU - Kass, Steven R.
PY - 2000/10/6
Y1 - 2000/10/6
N2 - Benzocyclobutadienyl diazirine (2) was synthesized and reacted with hydroxide ion in a Fourier transform mass spectrometer to afford the conjugate base of benzocyclobutadiene (1a). Authentication of the ion structure was carried out by a derivatization experiment (i.e., 1a was converted to benzocyclobutenone enolate, which has previously been studied), and its reactivity was explored. Thermochemical data for benzocyclobutadiene (1) were obtained (ΔH°(acid) (1) = 386 ± 3 kcal mol-1, EA(1r) = 1.8 ± 0.1 eV, and C-H BDE (1) = 114 ± 4 kcal mol-1), compared to MP2 and B3LYP calculations, and contrasted to a series of model compounds. Cyclobutadienyl radical appears to be quite different from benzocyclobutadienyl radical (1r) and worth further exploration.
AB - Benzocyclobutadienyl diazirine (2) was synthesized and reacted with hydroxide ion in a Fourier transform mass spectrometer to afford the conjugate base of benzocyclobutadiene (1a). Authentication of the ion structure was carried out by a derivatization experiment (i.e., 1a was converted to benzocyclobutenone enolate, which has previously been studied), and its reactivity was explored. Thermochemical data for benzocyclobutadiene (1) were obtained (ΔH°(acid) (1) = 386 ± 3 kcal mol-1, EA(1r) = 1.8 ± 0.1 eV, and C-H BDE (1) = 114 ± 4 kcal mol-1), compared to MP2 and B3LYP calculations, and contrasted to a series of model compounds. Cyclobutadienyl radical appears to be quite different from benzocyclobutadienyl radical (1r) and worth further exploration.
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U2 - 10.1021/jo000709o
DO - 10.1021/jo000709o
M3 - Article
AN - SCOPUS:0034613367
SN - 0022-3263
VL - 65
SP - 6566
EP - 6571
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 20
ER -