Pyrrole Carboxylic Acid Esters

The electrophilic substitution of these stable compounds has been much studied the meto-directing effect of a 2-ester overcomes the normally dominant pyrrole tendency for a-substitution.  

An ester group can also activate a side-chain alkyl for halogenation, and such pyrrolyl-alkyl halides have been nsed extensively in synthesis. Cerinm(IV) triflate in methanol can be used for the analogous introduction of methoxide onto an alkyl side-chain. The rates of alkaline hydrolysis of a- and P-esters are markedly different, the former being faster than the latter. 

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Pyrrole Carboxylic Acids and Esters. The acids are considerably less stable than benzoic acid and often decarboxylate readily on heating. However, electron-withdrawing substituents tend to stabilize them toward decarboxylation. The pyrrole esters are important synthetically because they stabilize the ring and may also act as protecting groups. Thus, the esters can be utilized synthetically and then hydrolyzed to the acid, which can be decarboxylated by heating. Often P-esters are hydrolyzed more easily than the a-esters. 

Pyrrole-2-carboxylic acid esters, from pyrrol-2-yl trichloromethyl ketone, 51, 102 PYRROLE—2-CARBOXYLIC ACID,... 

Pyrrole-2-carboxylic acid esters have been prepared from ethyl chloroformate and pyrrolylmagnesium bromide1 2 or pyrrolyllithium,3 by hydrolysis and decarboxylation of dimethyl pyrrole-1,2-dicarboxylate followed by re-esterification of the 2-acid4 and by oxidation of pyrrole-2-carboxaldehyde followed by esterification with diazomethane.4... 

In terms of A -substitution, Hartwig reported improved conditions for the Pd(0) catalyzed N-arylation of indoles and pyrrole <99JOC5575>. It was found that when commercially available P(<-Bu)3 was employed as ligand and cesium carbonate as base, the reaction between indoles 95 and unhindered aryl bromides 96 or chlorides occurred under milder conditions than the Pd(OAc)2/DPPF system previously reported yielding the A/-arylated products 97. Alternatively, it has been found that pyrrole- and indole-2-carboxylic acid esters can be selectively 7V-arylated with phenylboronic acids in the presence of cupric acetate and either tiiethylamine or pyridine <99T12757>. 

Figure 16 Principal mass spectrometric fragmentations for pyrrole carboxylic acids and esters...

Food, flavors consist of numerous compounds, none of which alone is characteristic of specific food. Classes of compounds which emcompass food flavors are - hydrocarbons (aliphatic, ali-cyclic, aromatic) carbonyls (aldehydes, ketones) carboxylic acids, esters, imides, anhydrides alcohols, phenols, ethers alkylamines, alkylimines aliphatic sulfur compounds (thiols, mono-, di- and tri-sulfides) nitrogen heterocyclics (pyrroles, pyrazines, pyridines) sulfur heterocylics (thiophenes, thiazoles, trithiolane, thialidine) and oxygen-heterocyclics (lactone, pyrone, furan). Discussion will be limited to striking developments in heterocyclics. 

The reaction of cyclohexenamides with nucleophiles such as water, alcohols, or thiols, produced carboxylic acid, esters, or thioesters. Reaction with acetylenic dipolarophiles in acidic conditions produced highly functionalized pyrroles via a complex mechanism, implying as intermediates 1,3-dipoles and bycyclic cycloaddition products. Reaction of cyclohexenamides containing protected hydroxylic functions with AcCl/MeOH produced < -lactones, while cyclohexenamides, bearing in Ri an o-aminophenyl group, easily cyclized to 1, 4-benzodiazepine-2, 5-diones. 

As in the furan series, the loss of an OH or an -OR group is very favored in pyrrole carboxylic acids and esters, (53)->[51]. The presence of an N—H group in a-pyrrole carboxylic esters causes also the elimination of an ROH fragment,41 (53)->[54]. 

Nearly 1000 compounds have so far been identified in the volatile constituents of meat from beef, chicken, mutton and pork (6). The largest number of volatiles has been determined in beef and these were representative of most classes of organic compounds. Hydrocarbons, alcohols, aldehydes, ketones, carboxylic acids, esters, lactones, ethers, sulfur and halogenated compounds as well as different classes of heterocyclic substances (Figure 1) namely furans, pyrldlnes, pyrazines, pyrroles, oxazol(in)es, thiazol(in)es, thiophenes were present in cooked meat flavor volatiles as shown in Table I. Many of these compounds are unimportant to the flavor of meat and some may have been artifacts (16). 

The most famous of the many alkaloids isolated so far is without any doubt batrachotoxin and its derivatives. Batrachotoxin has a LD50 of 2 ug per kg body weight (mouse, i.m.), thus being the most toxic nonprotein substance at all. Because of its special pharmacologic activity to keep open irreversably the sodium channels of nerve cells it has become an important tool in the studies of sodium channels. Chemically the batrachotoxins are esters of a 20-hydroxy steroid, batrachotoxinin A, with different pyrrol carboxylic acids. Although the activities of the different batrachotoxins is qualitatively the same, it differs quantitatively according to the acid part of the molecule (refs. 14, 15). 

Potassium tert-butanol Pyrrole-2-carboxylic acid esters from tosylglycine esters via 3-hydroxypyrrolidine- and J -pyrroline-carboxylic acid esters... 

Pyrrole-2-carboxylic acid esters. 2-Methyl-3-ethoxyacrolein added dropwise with stirring to N-benzylglycine ethyl ester under N2, heated at 100° for 2 h, treated with NaOEt in ethanol, and refluxed for 2 h product. Y 48%. F.e.s. G.H. Walizei, E. Breitmaier, Synthesis 1989, 337-40. 

Diazabicyclo[ 5.4.0 Jundec- 7-ene Pyrroles from 1,1-nitroethylene derivs. PyrroIe-2-carboxylic acid esters... 

Volatile components constitute about 0.1% of roasted coffee by weight Cojfea species, Rubiaceae), and more than 200 substances have been shown in green coffee. More than 800 compounds are known to make up the aroma of roasted coffee. Of these, only about 60 compounds have a significant role in the coffee aroma. Especially typical are a large number of heterocyclic compounds, mainly furans, pyrroles, indoles, pyridines, quinolines, pyrazines, quinoxalines, thiophenes, thiazoles and oxazoles, which arise in caramehsation and the MaiUard reaction during coffee roasting. In addition to heterocyclic products, other important volatiles are also some aliphatic compounds (hydrocarbons, alcohols, carbonyl compounds, carboxylic acids, esters, aliphatic sulfur and nitrogen compounds), alicyclic compounds (especially ketones) and aromatic compounds (hydrocarbons, alcohols, phenols, carbonyl compounds and esters). 

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