Resonance furan

The ethanolie filtrate can be concentrated to 10-15 ml. under reduced pressure to obtain 0.3 g. (7%) of crude product, m.p. 187-202°. Unchanged starting material, if present, is concentrated in this second fraction and may be detected by the furan resonance at 8 5.85 in the proton magnetic resonance spectrum or by a sharp infrared absorption... 

The regioselectivity of substitution in furan is explained using a resonance descrip tion When the electrophile attacks C 2 the positive charge is shared by three atoms C 3 C 5 and O... 

Pyrrole has a planar, pentagonal (C2 ) stmcture and is aromatic in that it has a sextet of electrons. It is isoelectronic with the cyclopentadienyl anion. The TT-electrons are delocalized throughout the ring system, thus pyrrole is best characterized as a resonance hybrid, with contributing stmctures (1 5). These stmctures explain its lack of basicity (which is less than that of pyridine), its unexpectedly high acidity, and its pronounced aromatic character. The resonance energy which has been estimated at about 100 kj/mol (23.9 kcal/mol) is intermediate between that of furan and thiophene, or about two-thirds that of benzene (5). 

One of the more useful predicative applications of the relatively crude Hiickel method has been to illustrate quantitatively the effect of benzenoid annelation on the resonance energies of furan and thiophene. The results are summarized in Figure 1. As expected, thiophenes are more stable than the corresponding furans and 3,4-fusion results in less stable compounds than 2,3-fusion (77CR(C)(285)42l). 

In summary, all estimates of resonance energies indicate a decrease in aromaticity in the sequence benzene > thiophene > pyrrole > furan. Similar sequences are also found for the benzo[6] and dibenzo analogues. A somewhat different sequence is found for the benzo[c] fused heterocycles with isoindole > benzo[c]thiophene > benzo[c]furan. As would be anticipated, the resonance energies for the benzo[c] heterocycles are substantially lower than those for their benzo[6] isomers. 

The heteroaromatic compounds can be divided into two broad groups, called n-excessive and n-deficient, depending on whether the heteroatom acts as an electron donor or an electron acceptor. Furan, pyrrole, thiophene, and other heterocyclics incorporating an oxygen, nitrogen, or sulfur atom that contributes two n electrons are in the rr-exeessive group. This classification is suggested by resonance structures and confirmed by various MO methods. ... 

Types i and ii are the most important. An essential difference between them is that in type i both tautomers can be aromatic [e.g., pyrid-2-one (16) and 2-hydroxypyridine (17) both satisfy the criteria for aromaticity and have large resonance energies], whereas in type ii at least one tautomer, that corresponding to 3, is nonaromatic [e.g., 3-hydroxyfuran (18) is aromatic, but furan-3-one (19) is not]. In... 

Infrared and nuclear magnetic resonance spectral evidence led Kendall and Hajos to conclude that furan-3,4-dione (37) exists as such, which is surprising since cyclic a-diketones with five-membered rings are usually monoenolized. The 2,5-dicarbethoxy derivative 38 was earlier stated to exist in the dihydroxy form. ... 

The amino form is usually much more favored in the equilibrium between amino and imino forms than is the hydroxy form in the corresponding keto-enol equilibrium. Grab and XJtzinger suggest that in the case of a-amino- and a-hydroxy-pyrroles, structure 89 increases the mesomeric stabilization and thus offsets the loss of pyrrole resonance energy, but the increase due to structure 90 is not sufficient to offset this loss. Similar reasoning may apply to furans and... 

The allylic-type furylic radical 6 is resonance stabilized to such a degree that its reactivity in promoting propagation by adding onto another furan ring is minimal. The fate of these radicals will simply be to couple with another radical present in the reaction medium (primary or secondary) or to disproportionate to regenerate the furan character of the ring26. ... 

The resonance energy of 0.93 v.e. for furane, C4H4O, arises from the same structures as for pyrrole. 

Furan, Pyrrole, and Thiophene.-—The carbon-heteroatom distances found in furan, pyrrole, and thiophene correspond to 5 = = 5%, 12 = = 6%, and 17 = = 10% double-bond character, respectively. Resonance of the normal structure I with structures of the types II and III (X = O, NH, S) is assumed to be responsible for this double-bond character, while excited structures characteristic... 

Values of Resonance Energy of Derivatives of Furan and Pyrrole... 

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