Carbonyl group resonance structures

These three conjugation types may correspond to aromaticity or antiaromaticity, in accordance with the Hiickel rule. They can be depicted using the partial resonance structures given in Fig. 4. An additional requirement is that each branch required to participate in cyclic conjugation not contain a formally two-electron heteroatom site (such as -NH-, -O-, etc.) or exocyclic double bonds (such as carbonyl groups). These structural elements are incompatible with Kekule-type canonical structures. Finally, it should be noted that in the case of type C structures macrocyclic conjugation will be preserved, even when one of the a and b branches is not fully conjugated. 

Because the carbon atom attached to the ring is positively polarized a carbonyl group behaves m much the same way as a trifluoromethyl group and destabilizes all the cyclo hexadienyl cation intermediates m electrophilic aromatic substitution reactions Attack at any nng position m benzaldehyde is slower than attack m benzene The intermediates for ortho and para substitution are particularly unstable because each has a resonance structure m which there is a positive charge on the carbon that bears the electron withdrawing substituent The intermediate for meta substitution avoids this unfavorable juxtaposition of positive charges is not as unstable and gives rise to most of the product... 

The resonance effect of the carbonyl group Electron delocalization expressed by resonance between the following Lewis structures causes the negative charge in acetate to be shared equally by both oxygens Electron delocalization of this type IS not available to ethoxide ion... 

The stabilizing role of other functional groups can also be described in resonance terms. Both electron-attracting groups such as carbonyl and cyano and electron-donating groups such as methoxy and dimethylamino have a stabilizing etfect on a radical intermediate at an adjacent carbon. The resonance structures which depict these interactions indicate delocalization of the unpaired electron onto the adjacent substituents ... 

Protonation of the dienyl carbanion formed by reduction of a linear dienone may occur at a carbanion center either p or S to the carbonyl group as is implied by the resonance structures shown below ... 

A hydrogen attached to the a-carbon atom of a p-keto ester is relatively acidic. Typical P-keto esters have values of about 11. Because the a-carbon atom is flanked by two electron-withdrawing carbonyl groups, a carbanion formed at this site is highly stabilized. The electron delocalization in the anion of a p-keto ester is represented by the resonance structures... 

The reaction starts with the nucleophilic addition of a tertiary amine 4 to the alkene 2 bearing an electron-withdrawing group. The zwitterionic intermediate 5 thus formed, has an activated carbon center a to the carbonyl group, as represented by the resonance structure 5a. The activated a-carbon acts as a nucleophilic center in a reaction with the electrophilic carbonyl carbon of the aldehyde or ketone 1 ... 

On reaction with acid, 4-pvrone is protonated on the carbonyl-group oxygen to give a stable cationic product. Using resonance structures and the Hiickel 4n 4- 2 rule, explain why the protonated product is so stable. 

The RAHB effect may be illustrated by the ubiquitous C=0- -H—N hydrogen bond of protein chemistry. As shown in Section 5.2.2, the simplest non-RAHB prototype for such bonding, the formaldehyde-ammonia complex (5.31c), has only a feeble H-bond (1.41 kcalmol-1). However, when the carbonyl and amine moieties are combined in the resonating amide group of, e.g., formamide, with strong contributions of covalent (I) and ionic (II) resonance structures,... 

Another important site of structural variation in cephalosporins is C(3) (Table 5.4.J). Electron-withdrawing substituents at C(3) such as a Cl-atom or a MeO group increase base-catalyzed hydrolysis of cephalosporins by both resonance and inductive effects [92], For cephalosporins carrying 3-methylene-linked substituents with leaving group ability (e.g., acetate, thiol, or pyridine), it has been postulated that a concerted expulsion of the substituent facilitates the nucleophilic attack on the /3-lactam carbonyl group [104][105]. However, there are also arguments for a stepwise process in which the ex-... 

The H- and C-NMR spectroscopic data support the proposed primary structure of poly(Lys-25). The amide carbonyl resonances are particularly informative as these signals are well resolved in the C-NMR spectrum of poly(Lys-25) (Figure 4). An amide carbonyl resonance is observed at 174.9 ppm for poly(Lys-25) that does not appear in the spectrum of poly(Val-Pro-Gly-Val-Gly) [13]. The position and relative intensity of this resonance are consistent with a lysine amide carbonyl group within a peptide bond [14]. Moreover, the resonances of the amide carbonyl groups for other residues in the pentapeptide repeat are split due to the substitution of a lysine residue at position 4 in every fifth pentapeptide in Lys-25. In addition, the absence of splitting in amide carbonyl group of valine in position 4 (174.5 ppm) supports this assignment, as this residue is replaced by lysine in the fifth pentapeptide of the Lys-25 repeat. The presence of other resonances attributable to the lysine residue can be detected in the H- and C-NMR spectra of the Lys-25 polymer at levels commensurate with its... 

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