7 ‘th Ubt [sl addition wrth lhtocedestrols ok ov oe nr XQ Ea i = SoSH = Pe +H, a> c= oO +2R We PO~ og. le Nhioacéle| Ee Ke 2s Maycl Us et) Ne? +H ~F2-> Seco gd Sse = J ~s-R® és ~S . + QHeg ci) &® Nek ; as > wh Revi > Ald) A Ms HO “sg Elechobhile . |, 3-dtihlane ar gut 2 . ‘ , x ‘Ly, (owt) I 1p a “Ore Nies Rvor oes Sy aa, : HOH Nu R “eee, Hg? t/HoH/MEPN tle a IS ee R rlL=O R oe C Ketone) Nu additton with No nucleo! hes CAddt Ton — EVionnatin Beate Aldehydes and Ketones veaet uit Several devivetives OF Mts oF tyhe NH~Zlez= ALY Le Arye OH, NHasNHPh, NH GH CNo,), » NHCONH ke form Ci | pina tS) th eon otten Pl a * ; i addiHon bro uch Carkinolamines. Conditions carkin ey lamines < clinic nb rete CER Fens rodu cts , Contatyin Carbon — Sit, wo double ond oO tenine eeogen HAUS NOs Bradys feng? e Imtnes - on? > = Not! DEENA nos kd itd ne “© (oxime) “PNP dea o 2s F-DNP dos. Ke- me) SS 1a eRe, . ones NaNHPDS yo NAP DCeNNHew alls OF C Phen! hydrazene) CSemienezene) Scanned with CamScanner ‘Seaned with anSeanneroP nr A garval mechantsm M>e so oS (% eet ipring can ee hol “db, +/t Pf pane rs atiehyde jie ea | clahe Nyce reaction edu \ oH woth eg ® burisy and Sefarate S77 ~~ SH + fi = tb) Son HT LOH, CCarkinelassine) “Nan 7 OE. 2 NHZ DCENZ N-substthueed Cthete Siler stalline commends" osith Sharh“ mel foints. Tis the yeactio could be andl ei tere erize and identify the aldelyde \ eH 7c = We Reaction with Na, CUnsubstituted toni imines of aldeh hydes axe unstable and belymeyise on Sandtn CH) Hea NHS 3 CHy =NH Fetedl eee | BHcHD "Cot 9 ‘Oma H a ON = i arin CUrotrobh 9 Ne im “Nive A A rad A, Cyelbgtylenisinarne \ 7 EBA WSsIve) ey Ng | Scanned with CamScanner ‘Seaned with anSeanner, Stand {a eS cry cn any Deer sending A cetaldimnine nee fe Nenu HN nw Git) i YP Che cH =| o HM, 5 H. < IN cH-eg Hs & He -cH = - eo acl chs Ha F Gite ~o8 =n tS civ) Hy drobenzamide NH =O +NH,— NN i Hye 7 Non gna een, ee [eto * H De Hshe LN HS CHa SN 4 Diacetoy amine | ed 20 anni ak IN J) aetna, | ee wed é- RS Nip <= Rew = N NR CScht f, } Rep’ =k’ oa | AzSmnethY ie | | yt/re, Senki Cambound 2 es Uy y . RAH + RIN HD Sch SO, Ree RY aL ease — Colsusless Soliction twig) CSchife reagesst) Allehyde [ketene : 2 Schi evi) Be Ror’ wsith 2Zamine CHeBy x | — PTS Relax | Sp * Cree Sao é “enamine i 1 eachon) Cenamine) i & Be, Mec Q OG ge oe 2, & a ~~ Scanned with CamScanner ‘Seaned with anSeanner> Relprek ¥ Yeagk 1 ~ wsith Fite ia ee we N= Cathe arnt ~ chinslt nein - mi C24 Re ve 2° “Trials nao hese Sat ‘ ‘ H Sf tHI a i ee Hy-Po- dae Lic x! Clas pale aig ee g Cite 5 -coe's) wesstoD ectie , way Reaction i (w cHzeoot) ‘Pls! extn, ye a mem ct o=c ly Ph. ar CH, Il ade aes Atusidencni he sree : ki er “Frlbhenylphosthonivm alkylise nln a ye] as oa lide is fnel ob < Ete > eS—Rx& : Re = @ a Be sh el 2 oe Salt yatta way one AS Cie) a ue nets Teoldlel or C+ deb 7 trb- +RC=cKR | ‘ aldehy Joh -r Keteped do rfeve ¢ ohn eblor does nto fe Scanned with CamScanner ‘Seaned with anSeannerEV Y@ © eetlg-eu pra Po CHe > GHgcH= cH, . et C Me Phy +p,-P= 0 RN=c =CRe PRN = CR RAC = Ro ober?) cnabyleres 0 + By —P Phy Lact Introduction of exogyelie Go methy lene rep - WT: Re=o+ PhaP—CH—cH,co0U —> Roc =cHetcod +Ph,fe oO Rv Bey merges TS wpe atree — = + PhaP= €'9)s Legs 7 Exrmation of lage Th: scHce + PhsP : a GiscH=D cn = CHACe i oeEH —Brh, > “4s vinyl halide Ww Phac=O+ He = Piha > Phot =cHn- Ochs bcs. H0 ‘ Pha ch-cho" = Scanned with CamScanner ‘Seaned with anSeanner: re] alg IS] Nucleophilic addi Aion “hy of p-unsatwaGfOl | Ss La ‘bonyl Cos b=cH— fog R= Hove lke vary | ov ecvelky| ay OK or MI er vin Cubebeatle may be ox, P- Un Saticrated “cyanide”, 4B Un caludled Ketone tyo ¢ u ined 6 ma fesynt™ hdd y quino " t eros cy — c-R — > =e — $ He (Ald. u Fie) 4 + q cu L- cH —c-R wo i lectvefeke a4 ee ue te EWG iy Hectafhike eM, cH Secor Conjugation ts Carhen- corbin 4 nutie bone Is Jactivated Lowar 1g GC = og Contrary Beales tule he dition “eee. lion « Adee o “YS only Aradktie Cond}; I- if R Very <4 ae : wt 7 ay TER aN Rasa a Robt oy Ay=ij or ew Li AkHa, w NaBiy © sje) 1 Biyggt edition ot corbeny| cH EL radio] . rg! = Phu BrG oe ween er TCH Hear Mag icin jog THT om ene Ph-cH=e te oat Prep —cum Heme, - £03 oy ee OO bh E Majer] mu: a\* oy? ey CL4 f -abdieg 7 ; near oq” Ex Arined, Ks ne SH, Active Se cEvclutes) Revit nl, Scanned with CamScanner ‘Seaned with anSeannercree ~ EI Reduction of aldehyde and ketone | sy ow b XO) Roca o Le AH/ether LO HoF ! bt CHO - CNlon-hychronylic ReNe ‘s | Solverst) 4 ; Ha /NE,P2 or B Bem i Lee -) R/S OH NaBits/E+0H peo ov Ti Ctealy Et fon! «Ba He THF LAN doekret SEE ERG Pah “led i Ube also NaBia/ Pree, ov configs * Ha with K-c | NaBhlg +A /: i 2 aBlly FALCG /Aigh dibs can be. taken Fey GI) okt B “edu ace. Na Atty electiv. - + eve Te Bes edict hy Bis /T HF Ph-checn—Ly. * Napiy doesict Tada Tsclated ‘“a— . Ll (@—NO0z be NH25 Metat/Aci4 3 tor tobe Ls O- CEN b clones | Dan +Hee wageh RNa be RNHS* Fn HySO,21 XX c=0 7 ; exebt In 2 | -INo othe: + An+AcOH vy dyJNo other arub ts iz Phecizen veduced - for fea ee Nabily Yell - Sn tHe Cony a Metalfmeid and Nafeien! FY Woco, eter]\ Yeduces only cx0 te elie aig whe Alea) and ARKal metal Na)/exon\_— <~° does redace | | Cbouenal- Baz Ske Treit, Blesinls bond: \e0 Veducek Vy CEN te chanuy : : NER tay cry Scanned with CamScanner ‘Seaned with anSeannerOT ae (i2| ©) MEERWELN - PONNDORE - VERLEY REDUCHy on CMPV Reduclion)(Reverse Of O}fenauer ° en XTdalfon R-c-H Fells—cw — cH, Ae@ity, 9H 3 = a Fr alucho| on (extess) if ~ ° ew +5 R- Cag ; eee) ae Sot eS? oon ) (93) Ree! 4 Equilibrium is shifted 5 | Elis] by distilling acctone opp,” =O Ron Occurs under mild condition , iS Yatid , side veactlont ave neglsible and | the feld 15 hy he Rone 4 4 ' hig 1 ecific ~fey Carbeny.0 grub Othey Lucble gra eee asbery rubs Such ad Noy, Ole Finte bond, ND, eter fredent in the Substrate Yemain Unaffected « If¢ the combsund covtaing two Carbonyl obs, One may be fustecled b acélal formation and the other ts then teduced « ' * Ketones volth high enol covert, e- « Preliketones, | B- Ketoesers Yte. do not give thin YeacHon: anism Y— -- AL Geum a a re ee ponAR bein), Bea” ao \ RM \ dk Ce 1078, UP wee & rm It me Coe Nite Ctesey ee | neo oa H oy Mh Z Ro Cuixed ajeKozide) oe) | ees Ry +k +) | we (2") i Scanned with CamScanner ‘Seaned with anSeannerri for mechanism 7 5 os ize a een A number PF, wnetal alkoxides, have bean uded buck alunirin I ele Sbextde “have been found ta be, the beats AC 0 bon. covalent andhence 1s much less polar. Thus tis ae much less dissociation by zive alkoxide tmeshich Sorne eb revieetic of carbonyl comprunds, specially the “WOLEF ~_LKISHNER REDUCTION. Wner reduction mvolves the conversion OF ny! gress Re) ee and ketones bo methylene he. their hydrazones ae pretence of shang base such ad groubs 9 or aeiace CoHEONa ov NadH.- S ted Naor | (a) > C=O +HQNNH, — > cs = NN Lee he cant ) Jeo} (Solvent | (e) R, C=N+ NHCONH+HZO Cages), (o)-Rs=N—N SUR, tN 8 re N = am Nia (cts), co ents ne, Us)e= NNH, | | ye lox’ or aaeeay | Uslike clemmenten reludin, G5 CHa“ Hs Net | Whe ks Re A wet high molec Det e Soal acacia Subaleatets [> ue Ps =p Oe why eodé — w= N-Hi+HO . fron of Wada [ - OL a DE ans WP eH ea Dene oNp 1 eed n—ot difmine. Sea + ou | Che mefiad is.» es net, Sule fr oh]. ; * Scanned with CamScanner ‘Seaned with anSeannerCE) Clemmensen Reduction Reducken Of Carbonyl aldehydes and Ketones by vf easton gets * Z Zine b vith Amalgamat on haa of hy. Paget Nash fe rrdiiylee Fm is Knsdon-2 ak Clemmensen Caliction ° GH — CO-CHS 2 gee ~o GH CHa CH3 Clemmensey veduclion is easier to than biel Kishney Reduction « nei not eae i aci Sensitive and high molecular mass substrates. \ The eel j om is esbeciall usefi henolic. Ketones’ oy | Ketones having Schon geepy dte and coe aldehydes "ES fected. poste ave. reduced more ea “than Cnydeh « 530°, B- unsaduncted Ketmed , Yeduction “olefiate and iz Nc gvoub Occurs: Mise pee ass net reduc Acid sensitive grubs in substrale ave Mechanism * CNakabayas: alashol, acetal ete] WaKabayasky mechants n) R—c=0 He Sc Bie Pon] R R 4 mo 4 @ Can) | #2 R-c@® ala gon Read c-&) e {ex H B J a R-c ———_- k A 5 7 on doesyit occur at olefinic C*» igted 9 = e< a —C=EC— 4 reduction doew efi =) Reduction Ketones ‘bo Prnacols Bipolar os Sa lat Anion) (,, , PSyn Addn’) Reductior) et qe Ag hete,A R R RY 2 gtr? + 2CH7] cit) H,0 —C—c—R’ Deudfeal) si qk ceueretum ou by Mechanism 2 sys onine” CFinacol) R br oe a wR! Re Re Rak NR cil) 2 NG +27 —-» oot — ce 3 = . Om y Be aE a capt © =e ae bu + +™q C oH), + be omget Scanned with CamScanner ‘Seaned with anSeanner- Oxidation ofa aldelydes and Ketones Aldehydes have Hon carbonyl ger Thus aldehydes Can We easily oxidised pe d not ly by sheng oxidisin agents but “also by mild eee agents 4 ke carboxylic actds Kaving same wubber of C-atoms oO mes Newser alke ov wee ao? R—cm es R= sy TES BeTTifed Gy Ree K, se [siete HSH edgyte cleave re Baie 1804 | tol @a/Hz0 | Ail. ye Cant HND, | Tollew's goog ils £ Csheg O- A‘) Ma Fels ERS Oo" 0 Benedict?s reagent fou! 3 CR=AW phatic) oe ! cold Oxidising “gd R-— coor ta ones & i It ko oxidise further under norma. Ketek ee be oxid ised to wiixture of Ketones can \eletan Cavbouylic acids (each — Le Coates — ten i em vot ae a 2 a Ddvastle certian’ CHG" Cmentimed above) under a tembs cencene HNO, te 507% HNDz ve a ene, jy ab petene 2° With uns mmetrical Ketmes, 4° unsy | between la oC ally. tan-2-me, Cleavage 0 dig . ep a “caobengl carbon peers fre fe“ C Poros RULE): | Scanned with CamScanner ‘Seaned with anSeanner| | L CHO ++ KgCr,0,, +44, (Orange) _ Gwen) 20, Hg SO, + HO PAN Oytky § Og. ~e=0 H- 4 RO > Y GY CF 0 Sey — oH a; TL. Rch2cocH, R44 K,Cr,0,+ 4H SO, a ar + 07 No-4 RCH, COOH + R’eOOH pate) Has Og tN “a > ane . SP RCOOH+A R cHgcootl + Cr, (S04) +Ky SO, +4450 ae v* xt 2 { eA BRCHO + 2KMnOy +420 —3RcooH +2Mnd,+2KoH] |! Town, Mechanism % iaie ya PRED, Sino ca) ie H20_, R— Fah > ag cn on R laigaty on day | Cb) 2 M0; === MnO, + MDZ a : ; R-c-oH 2K M04 + H2d/S “M05 +40 R +1 [[R-cl, -c0- cH RY EU coon tangs ete 1 2. Kine 91S Reoo + Kelconn + avin 2 ee \ + Reta “ES ee MnO, , hydrorylation ce ow “2 Cr | fy ie ; ee Rd feay 8 Te OH OH Rorjeootl + R/CETH Scanned with CamScanner ‘Seaned with anSeanneri wy _s “_z 8 bie BR Gi, eVienination) 6 H CAehydeo enation) . — s-0A+ also affects C anbon— carbon roultifle ‘bonds @ Oxidation with mild oxidising agents Aldchydes ave easiey to oxidise te corresponds carboujlec acids even with wild oxidistng cqeatsn such as broniine wale, Ag” ton, curt tonite Re Cart be oxidised with “such Weak oxidising uts This is due to pretence of H on cerbony| Zabon in aldehyde + 12 ig easy te cleave c—H bed and ge its Converted be @-o-—H° In Ketnes cubeny| C= cbmd hat te be cleaved. “This, difference ak, been gplatte in the fron of highly ‘Zelective tests that distinguish an aldehyde Ketone: te Test ov Silver Mivwoy Test C4] Tollews Réagen famation of TR aa 2 AgN0,,Caq:) + dil ag. NH Solu ion,i-e- page anny © anunoneg) ~ aitey she e) Ag,O +4NH4OH —a[Ag (ny) JOH + 24s ° 3 ON), [0 2! TR, : Corner Es en th KOS + SolucHan “A Ce) Reto +2 [Ag %4),] + 30H" = (six 4 5 Reo ov + 4NH3 +2Ag | +2N,0 RcHO +2bg Canyon Reset Cshini ak: ok ongee ‘ 2 Innby + wy rote |. Re ol-hydaow Ketone, frrmatte ion ,ceme ol-hydvox and “d-Keto ale gee give fosttive test with Tee Lona Braet ts an alkaline ‘th. Fehling’s solution (F.S)+ FiS- a BAS Of capid_ion comblexed voith Rertvote Ion - | Scanned with CamScanner ‘Seaned with anSeannerHj, { wo-en-coo Nay ae + Caan @oebdle Salt) co) FS) ey FS: 6B” nat Fn As mix FeseD and FST in eq ual Volume w [CxS0,42Na0H SaxoW), +NaaSO4] ¢ HH ng) [exloW), 4 Re Na¥ 4 2 NaOH C4oeant vemain ab ot is PER rather jus” ei vedissolve.s‘] ° 6- C4Ne! pee E> Rood + Cu, Cag OF 3 HzO | a-hychoxyKetone gives osifive Fes+ Test.| CBet bot) Ris te a Weaker O-As than TR: So aromatic aldelydes do not yeduce Frese. C31 Test of aldehydes Benedicts Solution +, B+S+ is alkaline colton ef ste ‘lon Cornblexed usith citrate. Ton Rie brebaned by by ot CUSO4's Sodium citrate and Sodium carbonate. In Watev> Citrate im Reet Cu2* in’ Solutio and dvedn't allow Yr deeb blue Solutio. won above, K d ke qe Vedelttiede Bess is a ~ Scanned with CamScanner ‘Seaned with anSeanner+ Na,SO4 + HpcO3 tycusog + Nase bo, +2420 —7 culos (b) : engcoona * oy oO ° Cu(OW), +2 poe eooNa — Aeon a \ ed Oe ee 1c? cH coon ° ° No CHC eodium Citrate Sodium biscitratoosprate CH) a] ohigen eS amend Cn) Be eck B 4+2Hz 0 cosine | caters 2 few(c40r), (nat) +NaotHeD i atgc OONS : RCOONa + Guy OI, ty L cowyeoona i oR iycoona ! acho +2007 + 5OHH pene aE cReA Ue eee “TRF Sy BR Jo net oxidise olefinte bond. \t Re. test is also given by alky| -r aryl hydrox [amine [o-hydrony Ketered having at leat one at a eae RB, BRIFS [Ageo}talse gelectively oxidices aldehydes te ched without affecting othey oxidcable reaps | The Hoalofomm Reaction | Methyl Ketones and acétaldenydedhe only aldehyde) [ov any other ‘strucheres ohich, under yeactign condition ca” qet converted “wrto Mend ay shuckwe suitable te give this Yeaction | when heated sebavately vith an excess of & halogen Cc22,8%2 7 X2) an Cen Cexcess) wroduce Tae arene i chloy o| ov todofon and Salt of ee cel Ea f; | Carbon atom less than Starting carbonyh : cop oun as ae is Kon as haloferm Bf the "prods: ~ alform is produend ak ome Scanned with CamScanner ‘Seaned with anSeanner™ Sie files (20) FR C-ONat CHXs +2NaX+3H,0 4 ° Pee - R-¢-—CHs +3x,+4Na0H CR= Halkyb cycloalkyl, alkeny | «ary |) OH Gwatly|cartinols) [A Lechols having “etructwe Uke @- = CHa [R= Same as above] also Give haloform Yeactn. H Such alechols get converted (oxidised) first te aldehyde ice havi agaist romping. ] i R—6 chy +4%_+ CNaOH Se Reod Na \ 4 cHXs ¢ + BNaxt+ 5H20 Haloform yeaction is a Valuable method to spithesise carborylic acids+ Mechanism 3— ob HEB) (2 yoeere ti] i OW ® R- e He LR CH He gi Ha Resonate, stabilised Core wie enolate 7 a @ Move acidic . ao Pili, 65 | Te & unless ated Cow) =% by additionah u eleetion ~ atthractin web Roe — Na Vike. ~€0,-co0R, ENO, x and -CN ak ctycockcooGts ; CRepeat an | be OH” io gaged, |? Xo Gecmtes rb ea ava oH of ZS u {- OHT ql R-C-CX3 eT | R-c—CHX, tas LRefest as fe I’ wol/+ e pu eX%s — Re ffexae Tada": ent] be p P= wp ESM Sx Eos Re (Redo » Stab) [Rote exchange] o ‘Scanned with CamScanner ‘Seaned with anSeannercavbanten fll 4 is well H asl fa Ket ne of the Yare SY rere instances voheve cavbanion tw as Seavin walk ak 7 stabilised by Aisbey sal of tts -ve chavge Da three -L GF X & by a-ovbital yeAonance of X des and Ketones do wat cadletee Suey OF” Eixaciad ton) [simple Aldely H- and Ro (alkyl anion ov an OH and hence AY lanton CXa oe better because N ave yuch stinger bases very poor leaving aps: swihalometh ig a Weakey bAce than HO” Dane leaving gmp than ot, H7 and R~ pues, avd CHBr., ote colunlcs Liquide and E 1s ‘immiscible With, solverit (water) an Pinas abbery as sebavate layer, CHT a is Ansoluble, a yellow chayacterl stic fongent te,meb- Ug? and havin Breer, "TG easily Wewtified se Smell- Tus CHT, '§ Fev TAD Yeabon, iodo form yeactin is usec d a tart ke identify methyl Ketones and methy| ¥ carbinols: This is Known oF test] \ [Gots OH is only P alechol giving +e Todoferm feat. fer HCH O(and its Todo derivatives) at ” ” a No other aldehyde » tats tesk7] er 2 alechols that do vot Bie cxiateed and ae en heater, rf with ra and Ailute Naok a They yleld Aq 1980 plays and Ketones respectively ait do not fmm fodoAurm= = pa gpayr 4NAOH 2? HB" + 4 Nak +4420 fe No ais tpt ENO FA 4+ 6Nart on ¥ 6N20] [In a halo: yeactin, C= i; =c and c=c b if present in the molecule, vemain nant? | TZ With Xe 5 base may be Kon a Got), and may rad Pe 2 en by Ge(ODa LHypeiodile} TL Xo with DH- is actually In follows Si bei : Xo + 2Na0H SZ ae es = NadX +°Nax +H Lpwring purificati cacti 4 eo. fication f water cots is produ a relat YE gy i ossess CH3CHOH — ons Scanned with CamScanner ‘Seaned with anSeanneree + BNad ore aa RANGEMENT OxEDATION a grup from @® BAEYER- gree Ress BAEYER — aus It Te an examble of rig vation OF Cc to electon-deficient oe Reactim ‘mvolves conversion Coxice lation) of Ketones -to esters by tearing Ketones, worth | b¢ Tre Such ad id, pn chlovoperkenze\e fewncetie acta, 2 fevbenzote, act (bei plucvonete acids fermonosulfhurt acid MEDS b ce act yp Ci wOoH aan RS R- é- ek Ave converted bo t 2 oR tC cooH La ctones vith Cyclic Keten acing expansion” = Ay eswoot_, os Thus ovevall yeaction is insertion Lace oO ogee a Letween carbory| carbo and th adjacent carbon in ketone + teh are inert under the conaxtions schverts wo . ahs, chotce of colvevst dekends on eolubttity © eattants- Commonly se. colvets 4¥e a: \actal acetic acid and’ CHES Reactim is zalysed by acids- “the reaction is not wi successfull with alde' lee Aathet aldehydes Ae px tse WwW pipes iki 2 ao 2 mal ae fo Fatates by pager cA have been © ‘ntgraction oF aryh a ‘ Ae n Ketone 4 EW act eae wstcation ctaes’ aa “ae ao Bcc eock is very € 2 5 U Bed heaving got ffective ab BSC coo ts a [fer mechanism, See 'PNo: —> alta Scanned with CamScanner ‘Seaned with anSeannerACS ISN LETTE " SELENIUM DIOXIDE, $00, SJ Oxidation ley Se Oz SELENIUM DIOXIDE, SeO, Selenium dioxide is an important oxidizing agent, specific forthe oxidation of reactive methylene and methyl ‘groups. Preparation IUis prepared by the direct oxidation of metallic selenium. ‘Selenium burns with a blue flame in air producing Selenium divyide. The oxidation is catalyeed by nitrogen peroxides’ > Ar) obsolete maria ae NOgc=] { Se + O2lei—» Seog Wis a white crystaline soli, dissolves in water forming selenious acid (H,Se0,) and is highly toxic. The } feagert, in general, oxidizes active methylene and methyl groups to Ketonle and aldehydic groups { respectively. | eel (ie 9 | Q so 22. 2 Q | ong E— SO. 8B, Boy, SH Pct | Double bonds, triple bonds and aromatic rings may also activate the methylene group. The reaction is usually carried out in acetic acid or acetic anhydride at a temperature between 100°C-140°C. Alcohol or dioxan may also be used as diluents. Uses Besides oxidation of the active methylene and methyl groups, the reagent has been employed for allylic oy hydroxylation, allylic oxidation, dehydrogenation and as a catalyst in some reactions. i { weactions 1 1. Oxidation of reactive methyl and methylene groups Ege Follow axezin gendval, Knoumn ox (a) CHyCHO- Se ‘CHE CHO. Giyoxal ~ \ A» Riley yeackfori| 800; (CHsCOcHs > cHycocHo Methyityoxal $02 ()CoHsCOCHy — = ceHsCOCHO ‘Acetophenone Phenyatyoxal Se; (H2C(C00C Hee ——* O=6(2006Hsi, Diethyl malonate Disthst mesvoxalate S00; (@)CHscHacocHs —— CHyCH,COCHO + CHyCocOCHs Butsnone Eyl Dincaty majo (sino) \ CettsCOCH2 CgHs +Se0, © Cesc RECGNs Desoxben zoin +Se +H Scanned with CamScanner ‘Seaned with anSeanner(24] 28 REACTIONS, REARRANGEMENTS AND REAGENTS: si CL, tte lompnionig Mt carooat | (h) Activated ring methylene groups are also oxidized to carbonyl groups, OC So Cyeeeranone Gye e-de | ‘Mechanism | The oxidation is carried out in aqueous acetic acid medium and hence the actual reagent is sole acid, H,Se0,. The mechanism is stil not clearly known. It is suggested that the reaction proceeds by the attack of selenious acid on the enol form of the substrate to yield selenate ester which climinates water and selenium to give the product. 4 140 5. i bolt, fa is ‘ seat ener | \ 2. Allylic hydroxylation and oxidation The methylene or methyl group «to the most highly substituted end of / the couble bond is hydroxylated according to the order of preference of oxidation CH, » GH, » CH groups, | ail i Lieve t-butylhydro~ | Here SeO, ery-cHizb—cHy ——"» cHty-cH26-cHtzoH beroxt de “is rnay be taken Belin 2onsene 2M 2Atanenolet used ab jn glactal cataly ot] o { CH, Hs, CS Singy q ae 284] enor anon 8 eny-cind tapn-om a) j i 2 det 2-pentene SMathy-S-paniter 2 gis S40 ¢r0H ! (icity -E=cn-city-cHy Ee chhyE=CH chy ~CHly ' 2Mhetinf-2-pentene DAdethyA-2-pentenl-! % Fi) in eycloaluenes, the ring methylene group at c-position to the double bond is oxidized to ketlonic group. { ° a= oO Cyethorwm = 2.0 enasane-\one Scanned with CamScanner ‘Seaned with anSeannerSN ers ee 239 SELENIUM DIOXIDE. S00, sition to the substituted When the eyeloalkene is substituted on the double bond, the methyione group at u-position to the substitut cr = OF | [Aiyleyrohexene —seHydroxy akyleyclohexane long with allylic migration of the oxidized to primary aleoholic groups al {v) Terminal double bonds are | double bond. Se02 CHy-GHp-CHp-CH=CH, ——> CHy~CH2~CH=CH-CH20H Penteno-t 2-Pentonol-t 3. Dehydrogenation Selenium dioxice has been used for dehydrogenation at elevated temperature. S002 ()ceHs-oh20H ZT CeHs-CHO S002 (2ckycooh => GH»-COOH ¢H2-COOH Suseinie acid ¥ S002 (icHy-CO-cHy-CH2-CO-CHy —g—~ CHs—CO~CH=CH=CO-CHs Hexan-2. 6-dione SHexene-2. 5 dione | | (™Hse-covet $602 £1000-GH Hgc-coor, HC-cooet Ethyl euesinate thy fumarate 4. Asa catalyst It catalyses the frans-hydroxylation of some unsaturated compounds by hydrogen peroxide. on (HG~COOH _ 10s | H--COoH e t HE-CooH “S20, H-E-COOH gy cgynte Am a OK ¥ Maleic acid DL-Tariaric aid ca, #2 cets) : } r ‘ (9 Hs —(CHa)y—CH=CH—(CHa)y—COOH N22 = Hy ~(CHahy—CH(oH) ~CH(OH)—(CHa}y—COOH ‘ Oleic acid nica 9. 10-Dihydroxystearic acd 4 ‘* ceis) - Scanned with CamScanner ‘Seaned with anSeannerfechanism : Ro CHOo- RR! + Ri- EH 0-H - Ae the leaving groub debartuve and migrartin rroup anal ave. concerted, migracti er R’ migrates voit velention oF confi guration: C hy acy cit euhe ich mtarate must be 2 | Bear vinylic * Hewever migration OF Palky | aot may be by bh Ione by using Be —egert vv BR—H2O as yeagevit] LBVeR may be breught abact with W205 and base in Some casesy Migratory Wrude ovdey t— an of (> Palkyl> —CHs | Mr fo alky| a7 ali 2 i cy, ‘ Vrrol X i Cr | OY) po ree > a rT | -anisy! p-toly | © By Mnds/en=t Aldehydes -fo esters ciy nD, /ehi AA HO CONAN eee Hs — CHS CH —C Cien,o4 Scanned with CamScanner ‘Seaned with anSeannerTigres sation Reactions, Other Ralatec| © DP .. oo i ue te -I effect —C— grey iar eaadier. of Caaeledier -c7 rot ts acidic: There A- acidte Cthan othe! A-n attached be sl? cooone aldehydes and KetoneX exWibit_ elorengl,-laulor | yoonance and y—Hvert cy ratte Henre ote mM fisvn Je] ty ade sey Ca HOT me yo: a < 6 <= ew CHeN AO as feronance eiabilized envlate tov oe Tobe cacle and enplates beta ove good nucleophiles » chobliles cuch ab halogen alky| halide ke give of- Substite woduds: Enols land enviateA,* also qve yucleoplilic addition: Tae condensation yoachien | { ® Adi cattalyced hhalogenation : i In tne of acid, aldelyeles aad Ketone’ having dH react wrth \ralogens Cc2o By sh2) be fern d-halogenated pooduets One ov more AH CAN be vreflaced Aefevdinrg fon amount of halogen i 4.0 i i + 4, mmole) Hey cect 6-4" APC’ cu Ea ++ See5 “He 5 coescH? BA CO , Cexiess) enemy peg ctefef halegensation | ne- Sosit 1s bosdible : bose menohalgenation Bge-c ws] [ele halegte). They veact wiin ele ; cH, © clower ‘than reackion «t - Scanned with CamScanner ‘Seaned with anSeannerch @ Bare beomsted halo: enatio : LAbeady cliccasced + Mechantcm. A-Brempacelane haloge CWith successive addition &| foster than tre le difficn wate (Sy. @ Deuterium exchange veaction is brmited as wae bake Yeblace, by D- vrevions she + Oktain if mere 4 4 2, merchaloge nated blued ia nected product is 0 Devieviun exchange 6H . (ea! “Ww YD en a 7 "Hi 4 ode rome cuss éne CHa “~ cu ° CA) 3 aaa) i CH, c ty ~ » caen [et By a 70 Chaat) GS ooo cae & ° CHa By The halofern Yeact Tr. b iT steb bets haleing each next Stel Ler none d-H 6 eect tained] reaction by acid CD) Cop). Tn both casey all AA 12 D a 1 R- e-chy- Rk es R-c— q-R Bo D i P20 iS Roc cH R yr Tf A- carbo Ketone ts chivah and has oly one “deity then such type ef Ketmne und ‘in prebence of Hh er CHT, 9 ul g-e 3 + Ha —H ——=_ > fos H ae aks R-é—cpd,—R megs. ies a CRacemic Mi pate) Scanned with CamScanner ‘Seaned with anSeanner\221 dol Condensation and Related React tens (@) Kale of Aldol veactien = K (AA[ 1 Laie rw : Very fiel clef is De ge. Ordev Kinelich on relot Limolecular, 4a aldol ‘hiow* ; “ fate nt 2 “Whe veactian frre 4 el C Mechantem of acid cataly ced aldol condensation t ( oy i -cu, = yen o I oH Hy, CCE ren sie Ay and cus ete cls » waa) cus TH —————. — om Colon —> y —! Clys—— CO GH cm Hs ¢ a H Hs Velone cavbaniens ane better —Wy oO nucleophiles ° Ha than I 4 aldehyde Cyc ch a 6 ee cat banions Mexsity| oxide Why 2 = vik e po 3 as —_ 4 — Basie a” ee chart Ge cnos © Fees ae Scanned with CamScanner ‘Seaned with anSeannerWO @ Reversibility of aldol addition Sem acel | When aldol addition produc She based, 1 reverts | thet We Me—c mal oy) Me — © on I. Me— ey ot a 5 Ph ii Ph—CHH + nc-Cc=EN Eto” EtOH Ph eno th SCR CEN- to an eqs consists largely (95 /) of aceiwmne* called yew aldd reaction: y W clg- c— Me ve Ch wy ot [20 | qe is healed est Rbvium mbelute Lk 1s ° OQ ul ZH yg Me cow! . * cus coh Casy) © Dire cred aldol +x ustth Lithium enolel “We use of Vitatum enolate of a Ketme as ene Comboneri! and aldehyde -v Kebme ab othey is “the most effective metho. prepare a single erosed bre 4 "A. 5 This ig call Aivected aldol yeact{n: Scanned with CamScanner ‘Seaned with anSeanner1a) a Stable caybanion nucleophile could be obtained am . C1) Aldelyde ov Kelme pave) at leat one d-H Cli) Esteve having at le + one a- Cit) Anhydride haging at least ane a civ) Nitvoalkane u ¢ iat - i” CV) Cyanide n ae a = Al, eH of ¥ 4 could be carrie ae i oe eae cay lO werke well), ” ALDOL CONDENSATION HSI ‘Adenyder having a-hydrogenis) undergo tell-condensation on warming with dilute or irid base to give fptyaroxy aldehydes. called aido's (sidetyde ~ aiconal). This reaction is known as aids! condensation ‘Atypical example is the reaction of acetalsehyde win base under mild condition. e el CHyCHO + CH:CHC mmm CHACHHONICH: CHO. * peat ‘Various basic veagents such a5 civic sodiuis hycroxide, aquesus sikel carbonate. kali metal alkoxides, e., may de used, The reaction is nat favourable for ketones. r ‘ausos condensation has road scape. can occur between. si i i i Scanned with CamScanner ‘Seaned with anSeanner‘ALDOL CONDENSATION * () Wo identical or different aldehydes, (i) So identical or different ketones and (Hi) an aldehyde and a ketone. When the condens 10d aldol condensation, sation is between two diferent carbonyl compounds, tis called cro: Mechanism Th be tin xray oso aba ta ba bv ta eevee acide {fom the aldehyde by the base. In the second step the enolate anion attacks the carbonyl carbon ol the second ‘molecule of the aldehyde to form an alaoxide ion. The latter then takes up a proton tromn the s aldol in the thitd step, qi ren Bt + noecayee wo + - 2 re 8 CHEF Enyeno wm coy Thus, the overall reaction is an addition of enolate anion to the carbonyl double bond, [Recall that Michael feaction involves addition to an activated carbon-carbon double bond.) Usually aldol as such ts not isolated, © g., acetaldo! is isolated as a cycte hemiace cm,-cht-on Na Deuht me Leta ane Crchsdeniace tre celal: | rill rernaie Aldo! is isolated under reasonable mild condition, |. using aqueous K,CO, as base. as on The reaction between two Ketones isnot very successtl. The equilibrium is not favourable andes far to thes —- lot. HyCMIOHIEH;CHO + CHCHO —* CH e E 2eHACOCH, CH -C(OH)—CHy-CO-CHy “This is because the carbonyl carbon of ketone is less positive (due 16 +1 etfect) and more sterically hindered Telative to aldehydes. This reduces the nucleophilic attack on the carbonyl carbon. However, itis possible to repare Giacetone alcoho! in reasonable good yield by boling acetone with solid Ba(OH)}, in a specially doses aprsrats. ("in Soxhlet Hrirnble. rough ushich hot acetene is i ereolate * Soxniet features of aldol condensation ANSI 5 Ee tees. used “for dehydrated to a, B-unsaturated compounds on heating alone ot with acid or base, CO extraction of a. Solid by a hat sched Me, aldol product accumulates Wy the Thus vemaink cut oF any chante. ‘Scanned with CamScanner ‘Seaned with anSeannerSeen pal ALDOL CONDENSATION a c 2. CHOW CMO sHtyOH “ CiyCHO- (Teves) CH,0H 10H GHyont ° oe conn es Aldo! condensation between two different ketones Due to poor reactivity of carbonyl carbons (+1 ‘owding) of Katonos, a poor yield is oblainad and so it is raraly attempted. Gil) Crossed aldol condensation between an aldehyde and a ketone (2) When an aldehyde and a ketone both having «a-hydrogons are condonsod, two products are obtained. This is because ketones are pot carbanion accoptors and 80 cannot undorgo soll-condensatlon. Aldehydes being more reactive than ketones act as ‘catbanion acceptors and the ketones provide the carbanions. ° OH, CHyCHO + CHsCOCHy S==* CHy-CH(OH)—CHz—COCHs 4-Hydroxypentan-2-one(crossed product) ° on CH3CHO + CH3CHO <== CHy-CH(OH)—CH2—CHO ‘Aeataldol (normal produc!) Usually, tho crossed product is the predominant product. The formation of acetaldol can be minimized by slowly adding the aldehyde to the mixture of ketone and the catalyst base. (b) When the addition is between a ketone and an aldehyde with no a-hydrogen, only one product is obtained. This Is because the ketones are less reactive and cannot undergo sell-condensation and the ion which is slower than aldol condensation. Hence the ketone aldehyde does not undergo Cannizaro reaction provides the Carbanfon and the aldehyde acts as the carbanion acceptor. Thus, ° OH () CeHgCHO + CHxCOCH, === CeHs—CH=CH-CO-CHs Benzylidencacetone 2 @ CgHCHO + cHycOceHs —~+ cgts~CH=CH~CO~Cels ‘ Benzylideneacetophenone 2 @) cHycocHs + HoHO ~C+ cly-co-cly-CH20H ma 4 4-Hydroxybutanone-2 Scanned with CamScanner ‘Seaned with anSeanner2 HEACHIONS, HEARANGEMENTS| ADI AE AGES sod by hydroxymethyl group to give (HOCH, )6 CO CCH OM Dehydration of aldols ato compovanes i th ace oD Aldols can bo easily dehydrated 10 «4 {F tana rong fon simple hoating. [Alley native Woy te wee Mee + ye. wut at cant) ae ws Tia est cata gen Age ek | oy 7 AL gs Wi a]ne on 2, Aho AP (* cyt pono HE cio He cny-citsci-CHo ( i : eit = As iy i ue F te Ue, Applications rk JL Ah csienonyentetigcio ~F* eaiyeM=eeaNeer10o——— cahyorcHicaHyCHyOn tyne ) ‘he intermodiate{+ionone require! forthe synthesis of vitamin Ais prepared by the condonsation of cltral wth acetone and subsequent treatmont with born thao, it ° ° { 70H _crscochs a AA ‘ _£racocs on cny Se ‘ caMsone not 4 Citrat ‘yelonone. frlonono : (iv) Aldol condensation i also etfected in he presence of acid. Acetone with dry hydrochloric acid gas slowly ‘ives mesiyl oxide and phorone. boy Hag criscoctts ; en,cocns 7AM expsczcncocts HEE ry,cacH-co-cH=Cte Meaty oxte Protone ie ‘Mesitylene is obtained on distling acetone with sulphuric acid. i eh 4) Aisol condensation of iycoladohytie gives monosaccharides.) —a I Scanned with CamScanner ‘Seaned with anSeannerALLYLIC REARRANGEMENT 83 NaOH 3CHZOHCHO ———> Cons Glycolaldehyde formose (V)) Pyridine and quinoline having methyl groups at positions -2 and ~4 undergo aldol type of condensation oe aldehydes. The process forms the basis for the preparation of an important class of dyes, e.g., cyanine lyes (photographic sensitisers). < Piperidine | FS 1 © vo Mei Mer @-Picoline B-Dialkylamino Cyanine dye methiodide benzaldehyde (vil) A number of compounds which have acidic C-H bonds undergo aldol-type condensation with aldehydes and ketones to produce valuable synthetic intermediates. Thus, condensation cf acetylene with aldehydes or ketones gives acetylenic alcohol, a valuable commercial product. CugC2 HH —— HOH2C—C=C-CH20H 2-Butyne-1, 4-diol. 2CH20 + HOS The process is known as ethynylation. Pentaerythritol (see above) is a valuable chemical. It is a medicine for heart trouble. Its nitroderivative, penterythrito! tetra nitrate (PENT) is a valuable explosive. It is also used as a surface-coating agent. Reactions closely related te aldol condensation are: Perkin, Claisen, Knoevenagel, Dieckmann, Doebner, etc. Scanned with CamScanner ‘earned with CamscanerAldehydes ant Ketones 37 E.Other Reactions oe {77.35 The Perkin Reaction Nv vtes unter » sonatcnsatin with ahiphatic aid anhydrides having at least two cehydrogens waned ihe aliphatic acid anhydrides having at least two echydrog fed the Rees Receatce Sextiuum satt of the acid te form fbaryLcp-unsaturated acids. The reaction tea nektive. For example, bercaktehyle om heating with acetic anhydride in the presence *yelscinnamicavit (tor mechanism pleasesee answer toproblem I in tl ah ° eS Non (E major, Z minor) oo BBE ONAN BE gue KE 5 i cerichwte Avticanhytie (Ema. Zina) A Acetic acid ‘OH 17.7.36 The Knoevenagel Reaction oematic aldehydes when heated with malonic acid in the presence of pyridine gives B-arylafeunsaturated For example, benzaldehyde on heating with malonic acid in the presence of pyridine yields cinnamic The reaction is known as Knoevenagel reaction. Aliphatic aldehydes also undergo this reaction. ridin, het CR ICGHSCH=C(COOHg| PAL cyiHJCH=CHCOOH + COs CHxCHO + CHYCOOH): Benzaldehyde —Malonic acid Cinnamic acid (E major, Z minor) 17.7.37 The Cannizzaro Reaction \dehydes that do not possess «chydrogen undergo self-oxidation-reduction (disproportionation) on heat+ with concentrated alkali. One molecule of the aldehyde is reduced to a primary alcohol at the expense of oxidation of another molecule to a carboxylate salt. For example, 2HCHO) + NaOH P@. CHOH + HCOONa Formaldehyde Methyl alcohol Sodium formate } 2C4HsCHO + NaOH CQHSCHZOH + CyHlsCOONa Benzaldehyde Benzyl alcohol Soxtium benzoate Orv OX OSCR EO oO ~cH;0n * 0 COONa o Furan-2-carbaldehyde ‘(Furfural) ‘urfuryl alcohol) (Soxtium furoate) However, there are a few exceptions. For example, isobutyraldehyde, although possesses an alpha hydro- ryDmethanol Sodium furan-2-carboxylate ‘gen, undergoes Cannizzaro reaction. Scanned with CamScanner ‘Seaned with anSeanner