Furan serves as a diene in dielsalder reactions with electrondeficient dienophiles such as ethyl e3. The bromination of benzene, for example, is an aromatic substitution because a hydrogen of benzene the aromatic compound that undergoes substitution is replaced by another group bromine. Heterocyclic compound heterocyclic compound nucleophilic ring closure. Step 3 loss of a proton from the carbocation to give a new aromatic compound. Electrophilic aromatic substitution furan, thiophene, and pyrrole, like benzene and naphthalene, undergo electrophilic aromatic substitution reactions. Furan and furan derivatives bearing methoxy, methyl, or formyl groups at their 2 or 3positions were investigated with maleimide and maleimide derivatives bearing nmethyl, nallyl, and nphenyl substituents. Pyrrole undergoes readily electrophilic substitution reactions, for example.
Structure and pharmacological activities the electrophilic substitution reactions of furan take place preferably in 2position. Substrate and positional selectivity in electrophilic substitution reactions in pyrrole, furan, thiophene, and selenophene derivatives and related benzoannelated. Pdf substitution reactions of tetrahydrofuran in crthf. Xray crystal structures of crbipyoh2cl3 and hpynh2crbipycl4.
In case of reactivity order you have to see first how much stability is lost due to attaining of the t. Ki or br2 acoh nbs n h socl2 ether x nch32 o h hcl etoh n h nch32 etoh acona n h coch3 ch3co2o 200 250 c. Electrophilic aromatic substitution of furan favors addition to the 2position because the intermediate cation is more stable than addition to the 3position. Data on the relative reactivities substrate selectivity of fivemembered heterocycles in electrophilic substitution reactions and positional selectivity. Therefore, the apparent electrophilic ipsosubstitution was the net result. The chloroform extract was studies on some electrophilic substitution reactions in the furan series 3329 filtered to remove the cu powder and washed successively with in hc1 3 x 50 ml and water 100 ml and finally with nahco, aq until neutral to litmus.
Partial rate factors relative rate of electrophilic aromatic substitution compared to benzene electron rich aromatic rings are more nucleophlic. Reactions of five membered heterocycles electrophilic aromatic substitution 7 the substitution in the five membered heterocycles is regioselective to the aposition. It has a role as a carcinogenic agent, a hepatotoxic agent and a maillard reaction product. The simplest member of the furan family is furan itself, a colourless, volatile, and somewhat toxic liquid that boils at 31. Preparation and reactions of heterocyclic compounds ii. Thiophene is the most aromatic in character and undergoes the slowest reaction.
Chemistry of heterocyclic compounds 1982, 18 5, 448455. This chapter discusses certain features of the substrate and positional selectivities in electrophilic substitution reactions of derivatives of pyrrole, furan, thiophene, and selenophene, along with the corresponding benzannulated systems. Electrophilic substitution reactions of pyrroles, furans and thiophenes metallation of fivemembered heteroaromatics and use the of directing groups strategies for accomplishing regiocontrol during electrophilic substitution indoles comparison of electronic structure and reactivity of indoles to that of pyrroles. Electrophilic aromatic substitution reaction is easy and is preferred at. There is a clear preference for substitution at the 2position. Pdf microwave assisted synthesis of substituted furan2. As an example here is the general pattern for the electrophilic aromatic substitution reactivity of furan, complete with the 3 important resonance structures that justify the reactivity of the 2position. We have performed nucleophilic substitution reactions of arylthio, heteroarylthio, and arylsulfonyl group at the furan ring. These compounds are more reactive compared to benzene. Furan, any of a class of organic compounds of the heterocyclic aromatic series characterized by a ring structure composed of one oxygen atom and four carbon atoms. Furan is a source of 1,4dicarbonyls in organic synthesis o meo ome h h o h o r. Electrophilic aromatic substitution of furan favor. The effects of furan and maleimide substitution on the dynamic reversibility of their dielsalder reactivity have been investigated computationally and by 1 h nmr spectroscopy.
Electrophilic substitution reactions of pyrroles, furans and thiophenes. Therefore, the apparent electrophilic ipso substitution was the net result. The effects of furan and maleimide substitution on the dynamic reversibility of their dielsalder reactivity have been investigated computationally and by 1h nmr spectroscopy. In the electrophilic aromatic substitution eas of pyrrole, why is the alpha position preferred over the beta position so much. Actually 3,4furan reacts very well with dieneophiles.
Some additional reactions, such as oxidation and desulfurization, are due to the presence of sulfur and are thus confined to thiophenes. Comparison with furan, thiophene, and benzene rings in piperidinodenitration. The extremely important vitamin c ascorbic acid is formally a 1,2,3trihydroxyfuran, but assumes a tautomeric lactone form. Regioselectivity in electrophilic substitution of pyrrole. Substitution reactions of tetrahydrofuran in crthf3cl3 with mono and bidentate ndonor ligands. Due to its aromaticity, furan s behavior is quite dissimilar to that of the more typical heterocyclic ethers such as tetrahydrofuran. To prepare compounds containing one heteroatom, an openchain hydrocarbon derivative containing two halogen element atomsspecifically, chlorine, bromine br, or iodine ieither as halides in which the halogen atoms are attached directly to the hydrocarbon chain or as acyl halides in which the halogen atoms. Furan, being less aromatic, undergoes substitution as well as addition reactions. Thiophene prefers reactions with electrophilic reagents.
Furan and furan derivatives bearing methoxy, methyl, or formyl groups at their 2 or 3positions were investigated with maleimide and maleimide derivatives bearing n. A substituent x is said to be activating if the rate of electrophilic. Try the following multiple choice questions to test your knowledge of this chapter. Baran group meeting furans and thiophenes 091504 furans. The 5membered ring heterocycles furan, pyrrole, thiophene are. Typical electrophilic aromayic substition reactions of benzene organic chemistry ii 10. This report is an extension of our previous papers on the preparation. Hence a compound with higher electron density will be more susce. General the aromatic furan system is a familiar motif in many natural products, occurring widely in secondary plant metabolites.
Studies on some electrophilic substitution reactions in the. An expedient route to substituted furans via olefin cross. Additions and ringopening reactions are less important than with furan, and substitution reactions are dominant. Electrophilic aromatic substitution of heteroaromatics. Rate and regioselectivity in electrophilic aromatic substitution the nature of a substituent already present on the benzene ring affects the rate and regioselectivity relative position of electrophilic aromatic substitution. Feb 23, 2018 pyrrole, thiophene, and furan gives electrophilic aromatic substitution reaction. Furan is a heterocyclic organic compound, consisting of a fivemembered aromatic ring with four carbon atoms and one oxygen. Hydrogenation of furans affords sequentially dihydrofurans and tetrahydrofurans. Reactivity in this case depends on how readily an electrophile attacks the compound. Mechanism of the reaction of aldehydes of the furan series with secondary amines in methanol. Heterocyclic compound nucleophilic ring closure britannica. The periodic table, physical constants and relative atomic masses needed for these problems are given on the inside covers of chemistry, fourth edition by c.
Substituent effects on the reversibility of furanmaleimide. Electrophiles majorly attack on 2 nd position rather than 3 rd position in these heterocyclic compounds. Substrate and positional selectivity in electrophilic. Lets try to predict the ring carbon at which substitution occurs in these compounds by examining the carbocation intermediates involved in the substitution reactions. It is considerably more reactive than benzene in electrophilic substitution reactions. Notice that either of the oxygens can accept the electron pair.
The evolution ceased by this time and the mixture was extracted with chloroform 50 ml. The equilibrium reactions of furan and six 2,5dialkyl derivatives with fumaronitrile were investigated under standard conditions 3. Chemical compounds containing such rings are also referred to as furans. Ethers will often form complexes with molecules that have vacant orbitals, enabling unstable molecules to be used as reagents. It is considerably more reactive than benzene in electrophilic substitution reactions, due to. The relative reactivity of thiophene and furan can be shown by the following. Nitration is the usual way that nitro groups are introduced into aromatic rings. It enables compounds, with various substituents, to be obtained.
On account of its high reactivity very mild reagents are required as compared to other compounds. Furan serves as a diene in dielsalder reactions with electrondeficient dienophiles such as ethyl e3nitroacrylate. Kjmol1 the chemistry of furan is not only that of electrophilic substitution but. Studies on some electrophilic substitution reactions in. Pyrrole and furan react under very mild conditions. Positional selectivity in reactions of pyrrole and its n. Reactions of protonated furans the hydrolysis or alcoholysis of furans involves nucleophilic addition of water or an alcohol to an initially formed cation, giving rise to open chain 1,4 dicarbonyl compounds or derivatives 11. The 5 membered heterocycles react in a similar way. Pfs can be employed in other da reactions with strong dieneophiles like maleic anhydride. Pyrrole, thiophene, and furan gives electrophilic aromatic substitution reaction. Why is furan more reactive than pyrrole towards electrophilic. Draw the mechanism arrows for the friedelcrafts acylation of furan. Pdf substrate and positional selectivity in electrophilic substitution. Cyclic ethers naming these heterocyclic compounds depends on the ring size and.
All activating group donate electrons through inductive effects andor resonance. Microwave assisted synthesis of substituted furan2carboxaldehydes and their reactions article pdf available in journal of saudi chemical society 144. Electrondonating groups stabilize the carbocation intermediate of electrophilic aromatic substitution. Furan is a monocyclic heteroarene with a structure consisting of a 5membered ring containing four carbons and one oxygen, with formula c4h4o. The reactivity and positional selectivity of electrophilic substitution reactions of pyrrole, furan, and thiophene was studied quantitatively 30 years ago. Electrophilic substitution in pyrrole reactivity and. Electrophilic aromatic substitution halogenation of benzene is one of many electrophilic aromatic substitution reactions. However, when the apositions are occupied, the bposition becomes the target for substitution. Introduction overview the module deals with the concept of aromaticity and aromatic compounds. I do not think that furan is more reactive than pyrrole for electrophilic substitution reactions. Reactions of pyrrole require careful evaluation, since nprotonation destroys its aromatic character. The electronegativity order,is,s pyrrole furan increasing tendancy to react as dienes in dielsalder reactions and to undergo electrophilic addition cf.
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