7 Heterocyclic Compounds 1 INTRODUCTION ‘clig or ring compounds which are made up ageeral, we have studied so far the cy fay of carbon ams, such compounds are called homocyclic compounds. Where siose eyelic oF FINE ‘zompound in which one or more of the ring carbon atoms tereplaced by other atoms are called Heterocyclic Compounds. The non-carbon stomsin such rings are known as hetero atoms. ‘The most common hetero atoms are nitrogen (N), oxygen (0), OF sulphur (S), however other hetero atoms such as boron (8), phosphorous (P), or silicon (Si) are also found in some heterocyclic rings. There are a number of heterocyclic rings compounds which can be easily opened and that do not posses any aromatic properties, e.g., ethylene oxide or epoxide, ‘re not considered to be heterocyclic compounds. or six-membered heterocyclic rings ye and S-lactones etc. These a Trterocyeles are those compounds with five: veh me sable, contain conjugated double bonds ‘and exhibit aromatic character ‘The heterocyclic compounds are very important class of compounds found everywhere and specially in the biological world. Penicin (antbite) o a) Hoon 8h, 5 TO tron CH,— OH | e CICHs thamine | tems 8) 159101 10N [AND NOMENCLATURE Me \y classified on the basis of number and x) also, on the ring npounds are refered by well established os remmon names of some of the important five and six cx wg compound ae given below: Sowe-dy Cato” He Do Ls c\ Soci, Y e Chiorophy vie is (Green poment catalyst | ‘cephconyatcsa} on AY \ Kd N. cH Ne Note 4 or ‘cune H Shy wr Aro CO ohm Quine crc, ee! Jature of heterocyclic compounds is 28 Cte fig method of nomenclature o! \ spe systematic meth AG follows: derived by concn, te compounds ae tom \_ Nery yee sph". oh ee econ, “st phorus, “phospt He trogen, "az" silicon, te pretest 7 AL? re used. for examples: dioxa, 4 ore sr more diferent eter atoms 2 the heteroatom 0 act oat Sao and heme are ty i ‘are present in tne blood {No important heterocyclic compounds which mak? Fulphur and nitouen a of teach erlifeto plants and animals, Many heer heterocyles prese shzymes and coen: ‘Most importantly, sing ranging fm 3 acid which on polymeri ra) 35, (Pen) 10, e¢ (dees) take compounds particularly tothe ee on Few of | ty one ster 0% ‘membered heterocyel important ones vet a8 cate ot Heh tee being manufactured amount Ny Sesseantsing ©) The ving is always numbered 19 YE the lowest numbers possible. If the‘Rings Containing nitrogen Sizo [Unsaturated | Saturated 3 he ine 4 =e ate eB =o eine 8. ne z one o = A enna i = (0) These are express 12 by prefing “perhyero" to ho name of The cars SOA Examples: oi co Ci . a2 FIVE-MEMBERED HETEROCYCLIC COMPOUNDS Furan, pyrrole and thiophene are o ypounds containing a single heter iplest five membered heterocylc mie the structure ofthese caps mgt sh chanctr ic pom ofa furan), an amine (in pyrrol Zi bes nd experimental aoe ig. 44. Ovetap of uohyb Po structure of these het these molecul valence bond theory w! the following contributing structures. Q— Ty be 163 rable aromatic character as evident-by The jc substitutiONTERCtions such as nit ce st ‘and 29 kcal/mole for thiopene which is less put is much larger in magnitude than that of “rnese facts clearly demonstrate that aromatic analogy with benzene and wean say thatthe ir properties. ture of these heterocyelic molecule, gen, is sp? hybrid and containing an try Each tom is aud above 2 te seen in terms of jridof (xing m bonds or= 8 also red as resonance Ht erocycles €8" les are conside ; O-8 located at he onote hat partion, 5 eure may ofthesecomponnds ne stailizationensre 5 eeeLarge numbers of evidences are avi structure of furan, pyrrole these compounds are interm bond lengths for (C — C) carbon. (C—5) carbon-sulphur bond and (C— evidence comes from compe those of suitabl ay be rationalized by considering which of the mn is most stable and consequently having ‘consider the attack of an electropile at ty of oxygen than in furan is in opposite dire ae or ae energy transition state, Lt these compounds. and 3 position of a pha oft OM rormal dipole moments of C — X bond \ ® 2 E £ ‘we where X = O,NH, $; &° = Electrophile ance structures, itis clear that attack Of Dipole Mome r Since the eleetronega nts due to Delocalization. wt the above 10500 aw the hetero atoms are inthe ord due to extra stabilization caused bythe cot sin ‘nectanes Therefore, the transition sat Yeading (0 trated by means of lower energy. The same can be as shown below: reels dona a Thiophene > Pytrole > Fur an lis order can be te exon by the ‘atom increase, th ° ie oye ie |i Kealinle | 20 Keatinte Fig. 7.1. Energy a os.7.4 FURAN 74.1 Methods of Preparation 7.4.1.1 From Mucic Acid 7.4.1.2 From Furoic Acia Furan can be conveniently prepared by the presence of copper powder 7.4.1.3 From Furtural Furan can also be prepare: spared by the catalytic decomposition of furfural in steam in {he presence of an oxide catalyst. One EE Sean 7.4.1.4 Paal-Knorr Synthesis rt ao ®, oo ~, ' general method for synthesizing furan d » 4-diketone compounds in the presence ot acid (80), phosphorus pentoxide (2,0, R es, =e decarboxy! zine chlor Oc 'ves by de hydrating enoiable, eagents like sulphuric ide (ZnCl, ee. following mechanism, rs 2 BS re ON, Cos ‘woe : \ cH— cH rt PR! Ve! \, POA Ag AA aOR Clg Lene tate thylacetoacet ‘When its two molecules 744.5 pou ‘be prepared from et eae is formed which on derivatives can iodine, diacetosuccini aie Fusan sence o 3, 4ediarboxyli a react i the pre methyl furan3, wae wih sulphuric acid gives 2, Sd methyl Ww AoOHCOOCHH AO oy, CHyCOCH,COOC;Hs ———> Ch ° 1 + cy —G— cH —co0csHs © ICH COOC Hs, | ons coon' city —¢ CH COOC He I ng ane secatents ret ion of Stone wa fete enter inthe presence of Pie is is known as Fiest-Benary Synthesis;Orang, ny, ° tcl! 1 ° 100 —CH—C— cH, —Pridne roy lig @ sco ° Hong, W008 o) Ht ° 6 “Ei S Ncs0d fon ee we cH WL, Heo Loy ‘a-chloroketone Hye NSH ‘0 . “ reco—t t Pye Hscz00, SS Sco e- Z \ = / | He POR - ¢ ty ee wo \, © Il Here chy IS ° proceed using acetylene dicarboxylic ester. _000H, < + Gi ten, € \, ‘coc, Hoe, ot EE —& we co00, =" 8 We No coc a 169 con® rl com lal Method or from Aldopentose (Carbohydrate) yer yaad | Be oy Pe ai nes yt AOC yield fa. ie | 2 Ho | wittes Ho ; 1 to 10 v c—on I 9 ‘OH 4 —— H-C-H to 8 SER a> & i aE tei 4,08 HOH HoH 7.4.2 Physical Properties id whieh bs 23 ‘ etm is sig se asus ofa Furan is a o% Which resem Aissolves in most of organic 7.4.3 Chemical Properties - As already discussed that furan behaves a8 an aroma compo i fon reaction predominaaly a Be is observed that W not so stable as compared structures carry unlike charges which structures, Lnscurifuran is an important sy 2-chilorome x by iodine or bot sp can be easily replace OM 2% 2, OV.My, ‘The eyclo addi this reaction isnot moan, than furan and does n . Morons 7.4.3.3 Reduction Furan on « ion with raney nickel yie which is an important industrial solvent, Raney CY + my tm, ) Tatydcheon Ids tetrahydrofuran hp, | 7.4.3.4 Reaction with Carbene Tgoes cyclo-addition reactions with carbene t0 yield cyclopropane derivatives, a ‘oO . oO” ‘generated in a variety of . Fn Creo pepe erates 7.4.3.5 Ring Cleavage or Opening Reaction Furan on treatment with dilute acetic aci yield 1, 4-dicarbonyl compounds whi Fy, csomne," AD. BF id, may undergo ri How "ve © R oo HOPS pee cy nds pout ated with methanol and hydroe arcate io com not acid, furan undergoes so, whe ming the dicetal of sucinaldehyde fe, oes pe io 1 oo + cmon * a cid cH cH vw ore aan (Oe Com sr eenaa forms unstable salt on treatment with lymerize to produce a brown resin or of resorance, The prot reases. due ce yields polymeric product by attack