(a) INTRODUCTION Pericyclic i sis definton tates to Key points that characterise a per 0 icyclic reaction Ro ne ; fs cobeared setciion chclanl bonis es ree Teaction. First point is that reaction i on eee en and product bonds are formed at the cane time with T. S. Second Key point in pericyclic reactions involves « cyclic thf of electrons, The : \d the circle. Pericycli for perieyelic means around the c YeHe Word comes from cyclic shift of electrons. Pericyclic reactions thus are characterised by acyclic transition state involving the n-bonds. ‘Some common examples of pericyclic reactions are : i AN +4 O @ XU ‘: Diels-Alder addition SS b> = O (2) Ring closure-ring opening CI = WL =) Ene reaction The energy of activation of pericyclic reactions is supplied by heat (Thermal Induction) or by UV light (Photo Induction). Pericyclic reactions are stereospecific and it is not uncommon that the ‘Wo modes of induction yield products of opposite stereochemistry. Pericyclic reactions can be classified into following categories : () Electrocyclic reactions (i) Cycloaddition reactions (ii) Sigmatropic rearrangements and oe transfer reactions See feat icyeli i inti interrelated. Thes : (ly Activations Peco mee oe elf by thermal energy or by UV light. However, many reactions that require heat are not initiated by light and vice-versa. ® The number of mbonds involved in the reaction, and (681) a(2) The escheat. ca Qh-cm, oe “y YY YD Y * mesg ei vk a dh i et cE rt el se See eee ia SS eae Se see ae a oe see th a eS eee rite een ae FESR Sd pois Ti hy apse owe es Cmseratlo of orb 3 ici pepattcmcerciplonios need upon coer make els. The ey wopag rm’ Acer obi (MO) mth. The Woodvard-Hlfman ra ng incl Mobice GE metbod (cr PO tnt) ae aso ted fo te explants of pee ‘sts Thee four ne ae te te pees for perl easton ee soi nos far oking oe sa roca Hee wll sews tice orn Le MO mod, WoodetHotfonconelaon gam and PMO appx ‘pine pepe ation. n Sone moral hve te my set te minor ae Cn) which Ht neta and pepenlro te pe be io tal te tr men iwi om ve mv oer pe ny son two fl (3) png a ight nl ite ‘slough ete of be anew ef be ow ge le ns See ~_ Lhe en 1, ta et aus pein ido poe i he soe ey i fl nn wie ga. ty kt Care ad Fe 24. can tory ft ese aan a eC [Cr-symmery mes cate yayTe METRY IN ALLYL AND 2.0833, 8 Sedo (eae AOENM. See 7 eerie ae ene... ear se eee ane oo 0" ya O00 0 espe tt Ts ey | roama[ = ee o wal s ‘ie stem as re led Phin ae cathe pu of cers i of CH —ch—i, Amnere | wpepe te pppoe tte Pai at a ( erate eee eens teh of ahve so etapa concn at fr nang ye se faniony. wine eae: When“ senasen nlc syamea aa ‘wth Cyr when (r= ha 0S vel hee te Smmety eel ya esi eg til acne tna fms ctjmoy mul ‘mt inating ee cate pay a __Tabe 122. Symmety eloments inthe sortsSim ean apy nym sem se i A ate ln Fe 7 has “ | u D on | 9070 7 | COROT Ty eA non ato ean a ee tte HOMO gd tt eps en Sey unt ponds nd exc sis ae np DIFFERENCE BETWEEN CONIUGATED OS MOCKS, TOUUGATED POLYENES (OPEN CHAN “ Seo Fe at eon © Tne sas tne see oe met Tm See At oil ‘ei al wey aces) eye aa ©) Xen aie pat athe ese tedeg MO ag MO aar oe GBA Tres oF pemercue REACTIONS gue dan smn ene pn es sin tng woe (err banh ste S—-OR Soscin tn oie alee Cen ts mason frac of new nts cs ch sean: Orel iota renin oo nae “he hc oso nao he map rare rc) 3 etn ig ‘o-oo en eer est Be he S- Dr Pr ‘Me our pe fest ie rep tamer conf whch eo mee sone ete one tical erm ar maon bl meer SS O-5 (EB) etecrmocrcuc REACTIONS : FO METHOD pene ce in id ao a com i re ng lt ee i a neg oes arcs a ade mepee Sear ee Ate ROAM egy, enti voi ahi of a aa wes Sees ‘ewed daring eo eae Roam Pine mmc alowed fen yen” on i ck a de 2 en nok es mage ame bce ate cen ts hws ye ey at “a "loner thane symmetry foes “a ite eit he ar ee te at mat com a pes ae it sec Tce mn ree ct mn woo mo emacs ® Pe a Set rae tte tee ne orn Rott nme of oe sila aa ahr ig emer rae seat mine meee en emermat e Se assuiietteeeencosp aren mache Sp cueeen este sere sie ceeenee teen Een syd STAG Armin ech arm aterector Lee ees fs Satna atamereeee = {BB ovcusaTion oF (tn 2) ~vSTEM Tero cine tema rel ar occ 1281 Thermal . —. 1 sesame ate veniam ym LES Ba EE . hoe | ee ate bs 1254. stereochemistry of Flog Opening ofthe Sytem In which Product Hos sed aneeictors| lowest, — “Tera anton ing pening cn esc of hereon eerie ™ os a somo HO ope an Pe | Tes te hema ttn prety dae mtrefreshing rae ss we 1223 Ring Opening ofthe System In wich Prosuct hes 4+ 2) = Elec ‘erm soreean BO Stent ee n,m a 4? or et ritchie syndy nay ca be Sain en ee “oumeran by cola Sar =" § Srey oot ‘sume on pe of ton Wp fe he ie ees ner eo vl tint ha Tae ee ‘onreLATION DIAGRAM OF ELECTROCYCLIC Reactions orm ht tema ne a re ei ey Spe ond ae Togethers enti n im teeena nero scot Sarena Sac ety wre, rgermvagn Sb At presi un Slee gm emg aC gare cee ae mi soma) mci wos. 86) ym MLC mmo ye peeks ie w alse a cyclo y soning een dng wih tops nga owing te pose tsar ores pu el ta {Scam «avery openings nites eh mama sed SA epee rt — sc eeitc a tee hen iw tht he “onduion etree sae of ae Ooemeonce nt rey Trew one ee eo ei (0 ea mm ty pce in ten el wa lec ego a Nhe aches me a et ‘ml wise ceeds ha ee SP oe eed © Phen anrmie SEF i Stl ef oe het ate en ia cn nh nye pes oes a shy teres pene ra oe viv (0 fi xc sie of eons) see wid oper eed st (Ges any ace tn mains a cacy er ee es ‘eer sated sue "Jef eyabes ke Nous pcan esa? iar esis des ops > wo a sg werenoous 4 Heo0 Se sil TOEULIN FS eat singh meets eloped ue dived leo cy eg he See ee Seng oe roves of ae wy oo ti Te ch Cine 2 nce Ace» ua pom at a) acne macs ommna neinet at gen eg a simone a Cares gh ae aca Sige a A pel os Sa cer tart ye selene oA st es tas ‘Soper eel a pv Partner at Sree nc ee eg ne Wek oy sao oni rps Wal a ene “eh ay doe Mcneela eela mura teee cay, eer CS $e "istry ection af +2) slat iis Ee HS ee Ti my ean ee (@B crctoapomon Reactions: Leer gasas es teatro sa aitcarpead Rem emeee ee | appertatel eee aeres eeere nee nt ws | (Goeemeiea atone etn ene a ree cymes | Rm dey ~ Reereiris Oo o = ‘Sint gn ee A imei Mri cave uy ma ne Mt in ae su three cag an eles lb donyt ot ray wb Ha a OF cone nny igre | ga+ oO ao ae 2 Secon otro by ne | eer fern] Ane [sate [Wea sSohsies S || |e TD son ects died wi em i emai me | meme | Smee | | Remember of actos of chit patting moon me |eomee ne | BESS teteee ‘ech! made eek a 80 8)™ ec Oy, to ening ee Te a seg aes oe a tte eg cwcare Meme de hen by «bis 6 Ht SUE ere cemeemucetante Mohan aeons Tae Sneete ieane it TT acer he he ma agar ce ore seen Pare —_ ‘Tis abion mason th +2 esa mao ‘Tasca abo beeps foe oN 1! SEE OC yk wa ee ecg wo me tt nd beat: An ami MO METHOD ere fc ecto 1 x, het ms be hag cep ees pra te STrivinitsslorimaaber Lt pee be des eens mace Sevan he demphie Geconpenen) ss Orca meee ‘heros wil be fcc oe’ (tout se wil bes alec deze ects int HOMO Te compen sits elcns io fom new bond The ml atid ase ee ae ee chez em bil ct nn ta ‘Sets HOMO sd te oe component edie LUM fr ne Seance "eave oe serbia hese ras so neg ya ll new 9 "2101 +2] Cycloadatons Thermal Indice: Whe yl sinks a rmsd ein rae ye taint ps ft pd HOMO oe ce nd styl tale, we conse oy i ert ct ing och pase of he vpn i a Ti et he te LIN Bown se HOMO an LUMO of two een mac ny oar [23] scm Sopris ota eco fr tg + era nae 2 ots ‘tote afm fren aconarr rasa won rs sma | oma i 1 a ran nn Proton + 2 osnson ans Se eewnenaerapanmemssemstonnes! | yn ox cna ete are ne ee | paps et baltic HOMO ne ee ‘ a on ne oo aa | there rn il yaney fen Frayer alowed ‘rmmny Say HOMO He | Dei Seca =. (“Hs wet = hg.oe ste MA ny, 12102-4421 cytonaton Reacons Pett neta pen na a en Tho onsite io, HOMO ey, (wii) a i rp a | ‘Datos em gn epee eae toss ra a same fet coHomo wii a ae oe > 0 ee tiie an fie HOMOLUMO ti of em of rs ara ers ei es nram: Wsdec candi ienremoneeery Sat ie BS tan in LO MOMO Ny heh as ‘ur noche cmd phot eel ai, Seale Compounds rom Diele-Alder Reactions "dau an Sear dens iy cia i Ar cn SESE ie SNe ec ate B nn acre nf meno Ps ‘Sse rests ws ms ap DE pe BAe oacy p28 AM em, O-tp = By PSK Time ne ey gc tn i oe ‘Seen dnd rey om be cee do Saad yc (id conne amin DIAGRAMS OF CYCLOADOMION REACTION ‘to mcd cyhdcic macon whch x apf. Con be {S\dlocoldion of yee mens pu ws pong eae erly ma en i et eee eee eee Se70 i i Wl es as wa oa 2, ty et tnt a Nowe th moe wl bs he yon wl enya he ey teen ti ‘We can am cnt he il ee ag at re hi we mat i yey a he wal ieee fr pe Mating nbd pee ‘En daeov re 125A) an hen re pe een ce = Wrox ———_______ » 2) Ts te oe ec essed te et beSesel Mee ones ia of cpt es mn 5 antes, Sembanien of Ue lo SSando, Sh a ae hm an Tehshinten at Fea amt Fg, 1220 by cee eae cat ti a ee ne Siese te tis fe stove iron, oo ga 1221) my eS macay eos ina A 0 a aa nit Sn in ie Ae tiie apa wc gre (7 gn cee se a tan, ia nsequently, the combination of two gromnd sae ethylene: ‘Sisco rn te ans pus oe rae ater eer (9 Arcus eee Sar oe mtn, * is process i symmetry tc aswore aston ‘Ascender intone SA wo ote concn dngae a 7 & Senate «= be dane by following sep: - >} See ens | ‘backward and forward reaction aed ™ Q-8 Hy ye sei) pect in ay wc nis ene wet Sel) td a * ‘monn en ume cca ely ae © eae ea mean hee meee oh Guest crake et pata ine ae ee Ree . . eal eg a SE at tev ft ah 7 (©) Hy ay ener ene minis eg Se wm, ne Sr hl ene ie eae tT ey SELES UM Ra Mee oe ye SS Toten pe ah i men Cae er “s s SOU SuM ae renee Fore conesannne Scottie anna © bata See Sk ti et i Poi) teu dpc ce yy 7) Cenarion inoue escent eal SSS | uy z ‘nian ao he tne anes.) cmeneief@h cS nc Sa ey mn a v8} cmc wo sec ped ih ep ta of oe " s 7 a Vievi —olale Ske esemn ma < fm =a Tew Pa 28 caatn gn ft eran nSse aioe aye (Ui noe tn rs te re ee 8 Visayan te arn todoonce ot ty, Some pel, ptr spc ae gen in Toe 27 ‘Tate 127 TW pc no re en 788 Nye ng lary of 1, 3-poar ey 218, Situ oe L.Sper ycana Te So al Dense Epi aM SIE a of ata cd, a saa ee eke: [Nwieowse | m D— Umm ea Sem Seca eile ain — 99 = 0 09 — | 9 = 6 ( a a O 0 = — Suppose 1 digo is dinzomethane (Ctfy—ie=N ts HOMO wl te ys a = Sto plac ene (Cyc) ISLUMOYSSome of he ie a tle compane He sre anne igh me ses iol ester Oot he bye es xe ye eae ‘Sede th ane tof ne iin ets, SE St Ss (Focus in on We peers fhe dpi’ Same ans common Ty Spa como ae sno ee sae ows CO Be tS be ~ ep sslaooron oF KeTENES Dee ee men mieten a fo in Fs i eT Ne oe oS a cad ce. o Gad Cie 7 oreo euler fe sti i epic Ts to sy Se Foe enon cain a ery ede. TACT Ti ctdoaatooe w pouchemenecin mb apts on iy aloe ten eagle ne, a ‘has eae tr ir htc ow name oe . azo i ht mo eco apc ach te gh i na ‘pteitme fhe ken. Making he eso lowe ini et 5 shined at tegen Thr he on spe ein, D24] 1230 gs tne ‘The hoi he an aan ond + coon ncn ‘The FMO semen sors tt hen nn teen C1 C1 ve ay ‘omens ete LM eesweO)a HOMO o 123 d QOL 0 te bind beneen C2 nd C2" devel my fom eatin of HOMO by tee tom owt ois anos te al ane] n MO eee 12 Sean dl OO an represented flows ia Hw * ns ro tyehpimoe — no we no caospee H nt {BB cretoTRontc REACTIONS oa SEES SINEST nim Ee ref ONS » oe — Cenev oo Si Oni as ae Pree lr ont eg tin ee tt a fm cylin or bien hype Ts aon ta ts Sag cs Ren ema shod En 6action of stares win So, cmt ecu wate = Seenm = son Omer, Semaine ten an aan Fr ay stytccaten 28: wee ema ging pap Hn wth YE mY see en mmter smarese -¢ bog jer ont fomrheeeereranerieten tnd gman enema Le ema ii st FENG AGED) le eect, RS enna ie Ce vr = wm tt en es ay ‘se atte ir | GES Da aN On “| QA = eS a Pe Se ci ne rai ton. ee nett wn pra. eye 220 aris whe mising mor ep bonded tg its ac nd ome ge. “3 seman ernest ia which cen mp nde ape a ‘et een be poe | Bo “DDL mn mn ny i ene ate ven i ome ten eo Ne Mo hawcyororsourrone ns REARRANGEMENT : FO METHOD Ma Coser vig reason™ ye a | eS gw mt im in| cee ee tow rm at Sateen Sinden flea tcp een | Sonn pidaerncmagoaen eee ln ve cp toe gt 9 Ma (ean) Te pon sent ar erp etn. Ta scp ‘Sep 3] smatopexuagenet oa ng 8s ot bene, ae ‘As sow fra cn cl) be wien gb mony ged hat he} egg her path the Sl ete (3) a we sede Se CS PP acai A cond sage spc fi acon cos fom phen expat, Me Seen enantio > mei op he tn ty ma c= fost lh 1213 (31 Syma Perengeart Neca tse oil prc noma erectus ance why | ‘etc hi a nem mg ch 3 i Gh.—cimcD; 4 emer -cHD, Yr Se taming ins wa ty in otc i ue to unlr Romany stele inge ene en ce oo ahs sari pe ‘ ‘he seam oa . i Tecmo, SEM, meen, aye pre-e ease tl ca i na Q 9 9 we Wo inns eeeroenreemeeencem: Se eet Soir aaa On O fF 6-008 ea a ‘ane of migrn. Fore syne ond 3 Sema Sige78 cee 0 = i SoS a eae aN ho = oY See Perr Serene Na ee haba pin re 1.3m site ke yc ie pc of Y Up tl ae a Ce Cray SP en i tee in ape ‘ee we cr pr IMO es ma i rn {Fiche noe now pce HOME e123. 90 0. mee (> soo" * y q Tensions} aptacopc manage ota caey nab menial fof eo 0 ¢ Poe r £P-@p46 0068 rere, Yet sar cometh ed sts a | ae cei Pe In cer cen yen Se a gt 4st rt es ays nt ii Spe tment se pom st ion nice tinea | Se gen tr samatepe ara weno tw ano hg th yy HOM te era 0 ‘ce mipnn Gey aa ‘sia Fig 1238 doen tw | ae crea aca of mk Gael a gm st | ti Sane mt cr gga rep Se cataa eee pets Brssen cay seer See an 9 SOMA ere en tg ey To St et 2 oe ae ale 128, Stcton le [18 wc ping ea eon ol eof cee hf Dercc terete ea otees rains Ly ERE Ik, some nr 16 rh mpg maton omer sicuarnonc suits S\ | iia ee ermine Seana ahs aoema 1040 ORM Cay, ‘Ts rt ald. sigan amet HE RE 3.3. elon we soe Tetris, Sty cnn pte he ra, Sh = C4 Eee Shes EO unemntemuamianents SS — sot se ca cn ue ms wetness San aS 4-4-4 \ we wa ‘Te mtn sein py se hag ne fo Sa ‘Para ane rte He anes aS ame oT SS LI-S~-£9 ‘re ‘Te mot adc eu f elas pr eefmc ann t ving se ply Scaled caren Te mt cet co es tae Somes Dee moet Se ud ee ‘Sastre ata an rc rea ea nn op ie Cope arate he miso ey ‘Asis oe mei he ree tes wy is ean a ‘ui ema res Secon red el wa hr oe Sinctnwole 2 hope ote ocney toe een ase renee oe ee DESHI Sm na rata ete a e609) ston iy, 241 aed ec einen te seta two tet bog 184 mere caret in te poz Vg he an po om he on wee LUMO and LUMO wil me pha HOMO TR 1) 12 hrcchamiey of ope rang senna tet a et Sega ne areas eee me mee Se eanasia, ‘shore el ssh chi mie pt fe ‘i pei i ew ee og a a ae a cin in anton ues CLAISEN REARRANGEMENT {hse ernment ste map aman ich 8 UKE Te ge gman erage ccs when nl ee an wil sae. The oa ‘erearanpenn olen , ‘ese Cae marten 0 pai. Te ft ah Seno rats. on anion é oy = A K pew ‘te pn tiie a i ‘asco ongen aig sigma bad a ali eto of ely gop. Tes ep ‘eatin i simple on ro ue weet, ChE— ocr Intiseacioe a op nies wih is coimedbyaemeil al et 0. OR me water Om r K I I ‘a, AN och, ee ood NAT SE ao mtg cas cen opuartnanentenee ° fe pep TL 9 eer cee ne cee see meer es Shi es tei LS Seen ot pe LY os, Ly ‘Ths eg dole oad onl fuse Eee SG] Sonate Rearangenens ‘sehen $B ore oss enon wscuumoreIeNCENS (Cees, 3] sigmatpic ramangenest™ —— ————___ semen nt : Yemen | "ewes =[MODIFIED AND DEGENERATE COPE REARRANGEMENT AND FLUXIONAL MOLECULES sd (opener open ofsoners i Se ae ec oe rere nytt an CR Ty seo Se i i se gy et ‘ets Cope emngme ee tmacam pse eon Tt arty me 1S Se ce Ce one ee ‘Gnd Sv rio Cpe py ey TSE Depend Sy wep ere Cae marge tm epee och ea oa papi NS at ‘ie 9.3 demaopcmamngmen inbtee apynecone nel se Q-G-C--- - secre ay Vet ‘cic Huo ee moka hn vee, ty ST tg Si Ma om pan rnc - Ba OF Og ese a Sc nl mas se ee cat soe =< (ga onours ansren nexcToNs Ere roves ict es fe ec en mie se 8 Ee oa vue azine The snr wal noms oey ieee SESS Bact es wr one eo : ‘pe REACTIONS 5 NTT sue ema cin hs rw ehnge n ae lta ym ei co Saloni oC tt a tse sie le eee mse ey SAL, a fo ete = cy ee SSR ne? sehr ptr tee a emt clr bade mm > CA onIheeratin tension pido srt nh rin se tel 9 sc i em Sen, en | siete Than si ene (5 SEH Sat sr en anna mn ie Sram in Ta desl ci PHA Seba Dettmann campo op nme Tn Da Al Dra tees a k= ti Si shen etoe a pics bt wo ees Hm ect Ths gt sme of it pati i em De 8TH trier eopea inet Arn an ° CO mee og ; : YoY ey COs hp seam , ty Faust mary en econ canbe aed Lvis ail ete prec Levi ‘Scat reason ped unr mie cons Asay iconceed hts bid with ty auinion as, CH iy i A “a * bacon, BE by * fc esses Dh * ke Di Aer aie ai isso eile tn. Pen see! pena ote 7 Qe 0s a Q u | As mend eater at nope ned be ee ose drives, Heel ane ne deca | cA Mm ao * ° Th Ob en (je aoa” ma o &y 1 % { ¢ 0 t ol . Siglo haa) coe eon fas st poi te ss of exe amp a asf ire mene ig ajuadson n, pi ey pray MY a a & ‘er ition of 1 8 iene ples + ell fe prio ein es ince ent [Ky_Prosiems with Sowuti 1. Give pda wh serch ee tine conc ay “LO+r) Om om ig aioe “O- eee a © Cpe tide sie © Ora bt, om «efit tet “Cyne cee 2 a.