Esters, conjugated => carboxylic acids

Rule of thumb The stability of molecular ions roughly decreases in the following order aromatic compounds > conjugated alkenes > alkenes > alicyclic compounds > carbonyl compounds > linear alkanes > ethers > esters > amines > carboxylic acids > alcohols > branched alkanes. [81]... 

The most common procedure is ozonolysis at -78 °C (P.S. Bailey, 1978) in methanol or methylene chloride in the presence of dimethyl sulfide or pyridine, which reduce the intermediate ozonides to aldehydes. Unsubstituted cydohexene derivatives give 1,6-dialdehydes, enol ethers or esters yield carboxylic acid derivatives. Oxygen-substituted C—C bonds in cyclohexene derivatives, which may also be obtained by Birch reduction of alkoxyarenes (see p. 103f.), are often more rapidly oxidized than non-substituted bonds (E.J. Corey, 1968 D G. Stork, 1968 A,B). Catechol derivatives may also be directly cleaved to afford conjugated hexa-dienedioic acid derivatives (R.B. Woodward, 1963). Highly regioselective cleavage of the more electron-rich double bond is achieved in the ozonization of dienes (W. KnOll, 1975). 

The extremely stable and general sp conformation of esters and carboxylic acids (3a) is one of the remarkable features of stereochemistry. It was observed uniformly2 in all other molecules with the group O—C=0 and also with their heteroatom analogues with S, Se or Te. In contrast with the rigid conformation, the conjugation in the ester molecule, expressed by the formulas 69, is relatively weak and can be just detected in the dipole moment values164. 

Alkynes from halides also alkynes from alkynes Esters from alcohols also esters from carboxylic acids Alkyls from alkenes (Conjugate Reduction)... 

Aromatic compounds > conjugated alkenes > alicyclic compounds > organic sulfides > unbranched hydrocarbons > mercaptans > ketones > amines > esters > ethers > carboxylic acids > branched hydrocarbons > alcohols... 

Salts and esters of carboxylic acids are called carboxylates. When a carboxyl group is deprotonated, its conjugate base, a carboxylate anion is formed. Carboxylate ions are resonance stabilized and this increased stability makes carboxylic acids more acidic than alcohols. Carboxylic acids can be seen as reduced or alkylated forms of the Lewis acid carbon dioxide under some circumstances they can be decarboxylated to yield carbon dioxide. 

Figure 5 shows the spectrum of isobutyl methyl ketone. The position of the carbonyl, while suiting a ketone, is also consistent with conjugated ester and carboxylic acid, but other characteristic bands from these two groups are not present. 

Figure 16 Conjugation of an amine and a carboxylic acid via the (V-hydroxysuccinimide (NHS)-activated ester method. NHS esters may be isolated and characterized and are stable to long term storage as the powder. Alternatively, the NHS esters may be used immediately upon formation without isolation. Details of the reaction are given in Table 4...

After successful installation of the first two stereocenters, our attention was focused on elaboration of the terminal alkene in 64 (Scheme 6.9). Treatment with disiamylborane followed by oxidative workup afforded primary alcohol 65 in good yield (70-85 %). A side product containing a mixture of two diastereomers (66) was also observed and resulted from conjugate addition of the alkoxide formed during basic workup onto the unsaturated ester. Maintaining the temperature at 0 °C by a slow, dropwise quench during the oxidative workup was necessary to minimize the amount of the undesired cyclization product (66). Subsequent oxidation of the primary alcohol 65 using Dess-Martin periodinane [28] and a Pinnick oxidation afforded carboxylic acid 67 [29]. 

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