TABLE OF CONTENT Topic Pz Reactive Intermediates IES 15-17 Srey Practical Organic Chemistry | 13 | Important Line Maps for Exam @ o% ey & Es Ransuo EV 10N =e> iS 3 J = a = co) = F < s ea S = cd c wi FI a co) 3 Incase oflone iy 5 pairs (or-ve, +ve, é radical charge) in} oa re] conjugation. ( O 7 The hybridisation |) J 5 changes from sp tosp*. ‘Adjacent p orbitals (sp2 Every Heteroatom, Negative Charge or adjacent double bond contributes 2 7 e- ‘electrons can delocalise in these orbitals leading Conj. p= 4 to resonance. For eg. Energy Released during combustion. HOC & no. of carbons & 1/Stability ; HOC per CH, & angle strain HOC order (~~ Chas more m bonds than B and <—— both C, B have more carbon come than AED Chas 10aH's, B has 7aH's ,Ahas 4aH's. A>B>C_ Thus, Cis most stable. ‘Angle strain has major role, Cyclopropanes has lA ‘the most angle strain with internal angle of 60°. Thus, Highest HOC per CH, A B c HOC order per CH, A>B>C_ Gem sued[Homolysis occurs mainly for non-polar bonds, HYPERCONJUGATION 5 Heat or light is needed to provide sufficient energy. ers bearer Lei bond (9 InHeterolysis bond breaking occurs inthe way that one || {2 sdlacent Double bond ex erp P part of the molecule takes both electrons. =e [ Mopeebamat tal} srbocations 1.a-C should be sp* 2.a-C should contains at-least 1H No. of Hyper conj. structures. = No. of a-H's +1 Suni ‘+ Hyperconjugation is stronger than Inductive C-C-C+C>»X X is Electronegative Group (-l) + No.of a-H's & Stability of Alkenes, Free Radicals, €-C-CxCxY Vis Electropositive Group (+1) soho z 7 CHs<-CD3<-CTs < -CaHls < ~CsHHy < -CaHy < + Bond Length Becomes shorter. x COO- < -O- < -NH- < -CH>- STs NF," > -NRat >-SRet >NH3" > -NO2> -SO3H > “CN >-CHO >-COOH >-F >-Cl >-Br>-I> ® ® @ : |-OR> ~OH > Benzene > Alkene > H CHOON Sa-H's 6a-H's 9a-H's Hoo H Stability of carbocations: +1 increases stability — Stability of Carbanions: -1 increases stability © ClCH, — COOH > CH5COOH (Acidity) (—! of Cl) © EtgN > NHs (Basicity) (+1 of Et) More e- density ‘© (CH;)3C* > CH,* (Stability) (+ of Me) in ring in B due je Cl— CH,” > CH” (Stability) (~1 of Cl) x to more a-H's.SES Both the resonance structures of ozone contributes to form a hybrid and thus Oxygens on sides have similar character. Unsymmetrical resonances structures contribute differently governed by rules. Bo - 0% nob. a a nse are better #2: Octet <— ~S8, Completion gives stability © Electronegative NH atom #4: 4ve Charge on more substituted carbons Geers Energy difference between the theoretical value and the experimental value (Real Value). Resonance Energy & Stability Resonance Energy :C >B >A ZZ Z~7~7 A B c 2M bonds 311 bonds Aromatic structure GSN rea ads) B A c Resonance Energy : © >B> A (more number of pi bonds) Resonance Energy Per ring: A>B>C (Stability) rT on wT = vile] we [ent2)ne- | Ait wile uu 4n ne- Anti Aromatic Maybe | Maybe | Maybe | NO RULE SONRERIE oypee senone Aecne $reopentadeny| TePyiom prc furan Cation Gree ne t0ne- > = -_ NOTE : In case of Pyrrole, Furan and Thiophene, Lone pair of heteroatoms is involved in the ring, whereas Lone iIved in the ring. (Lone pair is present in sp” plane) butadiene cation 4ne~ 4re- ‘4ne- Anti-aromatic - AA ae ry Gace Ge 10ne- Nitrogen doesn't donate as in resonance _(tigh Dipole moment) acc 8 Ogead Pyridine Bond Rotation Oxygen donates Aromatic in Polar state (Oxygen donates éne- Stability Order A NA éne-Due to steric repulsion by group at ortho position, -sp” group 5) bec (5) becomes non planar and Hr) resonance will be inhibited. This ( > < 3) is Steric Inhibition of Resonance. Z « 5) SIR applied by all bulky groups ED except On, H, OR, NHZ, Pete More Stable due to delocalisation _ More Basic due to Nitrogen being ° of Charge in ring. Other one is out _out of plane and not contributing L on all sp? Groups of plane. Thus, cannot delocalise Lone pair in Ring, Rime, Kime, Zz Essen 1.Compounds wi 2.Compounds with available d-orbitals PFs, '3.Multiple bonds with dissimilar electronegat 4,Sextet of electrons Cartienes 5.All Simple Cations Na, Ag’ Mig, ete incomplete octet BF, AlCl, etc. [aos 1.Molecules with lone pair fils, Ha, R-OM, py ete 2. Unsaturated Hydrocarbons R,C=CR,,RC=AC 3. Multiple bonds with dissimilar electronegat 4.All Simple Anions Cl, OH, SH, Br ete Cl, Sn, ete vity 0-0-0 6 ity + C- CHARGE + A-ATOM ‘+ R- RESONANCE. + DI- DIPOLE INDUCTION More positive charge, |] Along Group & Period |] Resonating Conj. bases ae More Acidity Acidity Increases have stronger acids Ne > H,0*>H;0>OH- || CH, Alkenes (sp") > AlkSTRUCTURAL ISOMERISM * Chain isomerism Arrangement of carbon chain is different + Position isomerism Position of Functional. ~~-\_-0! oN. group is different criropropane —_ho-butane iLO Ester CCarbonylic acid + Functional isomerism Different Func, groups + Metamerism =o Different alkyl gps LO on two sides of functional groups er + Tautomerism © Interconvertible structures that are different in terms of the relative position of one atomic nucleus is generally the hydrogen © Need to have ana-H for inter-convertibility Keto is more stable but in some cases, enol concentr Oe 0 is higher. E.g. More stable due to aromaticity in case of phenol. Enol is also higher due to intramolecular H-Bonding Order. of Enol-Content : B-diketo > Ket-aldehyde> B-Aldehyde > Di-ester > Ketone > aldehyde oo + Arises due to hindered bond rotation. * Restricted site must have different groups. CH,Chiral Center : A Center with 4 different atoms connected. WamMlctS Sch SSSI) Chiral Molecule ; A Molecule with Non superimposable mirror image. (NO Plane of symmetry or center of symmetry) Achiral Molecule : A Molecule with Superimposable mirror images. (Either POS or COS or both Present) Chiral Centers : 3 Stereocenter : No. of Chiral Centers + 2 for every Gl exhibited Stereocenters : 4 * Chiral Molecule rotates plane polarized light Roa ee by an angle a (Optically active molecule) + Prioritise the connecting atoms according to their + Observed rotation a may vary 7 atomic numbers as 1,2,3,4. with concentration and length, so [a], = —— ‘+ Draw a curved arrow from 1+2-*3 keeping the we define specific rotation [a] as Ixc 4th priority group on dash. arrow rotates arrow rotates [a] mixture of + &- Clockwise: . 77.3, Anticlockwise: S| ale seuss + Rotation of PPL on Right : Dextrorotatory (+ or d) 1 : + Rotation of PPL on Left : Levorotatory (- or!) AE Hfeurve La Optical purity = x 100 [@]pure isomer (+/:) Priority Order: 5 5 1 > Br> Cl > SO3H > SH > F > OR > OH > NO.> NRz Ifa Chiral Molecule rotates the Plane Polarised light by +30°, it's non superimposable mirror image will eed ee ee ae. rotate the PPL by ~30°, The Two are Enantiomers. Fala a) : Equal amounts of 8, om OH enantiomers will ! create racemic othe Oe oe mixture (optically |] "4%: oe inactive) 2 | ENANTIOMERISENV ss1 se) ict 1.Mark a line in between Alkene and Prioritise the right-handed and left-handed atoms as 1,2 according to atomic numbers. If Priority 1 lay on same side, Configuration: Z Sith + Two Isomers which are not mirror images of one ing on opposite side, Configuration: 1 1 1. 2 2 2 2 1 Configuration: Z Configuration: E another are called diastereomers. + At least Two chiral centers are required for diastereomers. Saas ‘with Plane or Center of Symmetry Optically Inactive ‘coon on feos camcmur ae oH ot meso-Tartaric Acid coon * Hall the configuration changes on going from one stereoisomer to other relationship is enantiomers. * If either one or all except one configuration changes, the relationship is diastereomers. DI CSc ey TRICK VIA R/S METHOD ‘Molecules en EOS Molecules with POS” neven or odd neven nodd 2 ot ant 4 2(3)-1 d/\forms d/l Meso nomeso forms| Tetalforms | a”, Mee g4 sk "SOY" dihedral angie 4 HOO 4 Torsional Strain Strain due to repulsion All the conformations of electrons between Staggered and eclipsed are called oS 4 Van der Waals Strain least stable most stable Strain due to bulky ‘SKEW conformations Eclipsed Staggered groups like alkyl etn ba fey Hs 6. Stability order : Antiperiplanar > Gauche > —_ — — Anticlinical > Syn Periplanar H 1H #. H H 4 Oh ° 4 ‘+ Gauche becomes more stable in case of A B c D ‘+ H-bonding involvement. seovered sclrees race scipsed _9.g. 2-Fluoroethancl, gauche is more stable nt antielinal auche synperiplenar ererseusSTABILITY ORDER “SO Le AN CS Dancing Resonance Aromaticity — ~ Bridgehead carbocations are not stable due to non planarity ° ° Y a A - Hyperconjugation Resonance =~ Unstable sp carbocations ~~ —<—— Carbocations also stabilised by + effects :+M >+H>+1 Dancing Resonance > Aromaticity > Equivalent Resonance > Resonance > Hyperconj. > Inductive > S-character RING EXPANSION Ring expansion happens when angle strain is relieved by moving from a smaller ting to bigger. SixHYDROCARBONS - ALKANES Preparation (Simplest UST rd Tlomed which | CRAAESTEST + Carbanion formed in form symm. i.NaQH * Rate of Rxn cx cay 2R-X Nae RR eee R—COONA ji Gag * RH stably. lecvon snc 9'OUps increases Rate "9 > Free Radical Intermediate (Can undergo combination or disproportionation) Acidic H’ ca ‘+ Methyl Cannot be formed —— idie H* can come froma, +R see R-CI> R-F R—Mgx Aci py ROH, RSH, RCCOH, RSOH,, + If R= Ph, Reagent : Na; Fittig Reaction RNHz, Phenol, Ph-H © Reagent : Cu; Ulmann Reaction ETE © Reagent : Zn; Frankland Reaction FUP ae ‘ J Holi NN, iso be used Sse sas —> + He-comes from same side 2R-COONa —> R—> R—R + Hydrogenation is used in both Alkenes and Alkynes ‘At Anode + Rate of Hydrogenation & 1/Steric Crowding REACTION WITH GRIGNARD * CO; at Anode and H2 at Cathode ‘+ Methyl Cannot be formed + pH increases due to NaOH formation + BP c H-Bonding > Dipole-Dipole > Vander waals + BP o Cl > Bra > + Cf'is more reactive less selective, Br is less reactive more selective. Selectivity is decided by free radical stability ae CLES wih alch7Hr CGO ii, with Pd/C or Se O-O ¢ CH, + O2 > CH30H CH, + 02> HCHO) 2CH3CHs + 30; + 2CH3;COOH + 2H20 (CH3)sCH > (CH3);COH 773K. CH, t— CH, + CH, ‘> CH, + CH,+Cl «Follows Fee radical meshanism. * + Rate of Pyrolysis Molecular WeightElectrophilic Addition Reactions To Alkenes and Alkynes - Important Ea Ne a7, : ¢ 7 Reactivity & Electron richness of alkene xf : A A + More subs. alkenes are more reactive. ee ee eG eee + Anti addition with bridged car e-tichalkene _Carbocation or Bridge carbocation Syn or Anti Addition of ¥- ROI uio meso CyMvene aioe anna) 1. Hg(OAc),, HzO E CH OA OO oy — cH oe CHy—CH=CH-7 NaBH, CHy: . cH, 210, NaOH 1 OH OH ° 1.BHy “\y" 1. Hg(OAc)2, HzO Ok 2.02, NaOH u 2. NaBH; 1. Syn + Anti Addition, Markonikov Addition 2.-OR gets attached to Carbon, in case solvent is ROH 3.In Alkynes except acetylene, always ketone is formed. 1.Syn Addition, Anti-Markonikov Addition 2.NO carbocation Rearragement 3.Terminal Alkynes form Aldehydes; Others form Ketones CNeaancey CONOeannn nes oo + “Monosubstituted Carbon, Zn/MeS: Aldehyde vos nou + Monosubsttut a LO > ch 00 Monosubstituted Carbon, H:0; : Carboxylic Acid Cty 4 tom chee o —— 1 Cy * SRDorED, oO" co + Reductive Ozonolysis gives diketones + Reductive workup breaks ozonide to carbonyl + Oxidative give acids. Terminal alkynes give COHYDROCARBONS - Alkenes and Alkynes LINE MAP 2 Bre = ae i= NAS, SL cc Br ry é nt NY th —— Ci cpee eu ka alk. KOH |Dehydrohalogenation Dehydration of alcohol or Hydration of Alkene (Markonikov) (/H20 Zn Vicinal Dihalides to Alkenes Pd/BaSO, a set a Ha, Pd/BaSO,|Lindlars : Alkynes to Cis Alkenes ‘Na/Liq NH; [Birch : Alkynes to Trans Alkenes Dehydrohalogenation or as a base NaNHs [for terminal lkynes [anti Addition of x and X/OW — INucleophile (X/OH) attacks more X2/H20 | substituted carbon. HX. |Markonikov addition of Hx (Stable [carbocation is priority) HBr, ROOR | Anti-Markonikov addition of HBr t-Budk, Bully Base remover NBS [Allylic Bromination Per-acid Forms epoxides with Alkene KMn0,; 080, |Cis Di Is formation less hindered proton HOT KMn04 |works like oxidative OzonolysisTrick for electrophilic add. stereochemistry to alkenes | [ Hydrolysis of Carbides 1.€SM : Gis alkene - Syn Addition - Meso Product + CaCy + 2H,0 ~ Ca(OH): + C22 (Acetylene) ‘Syn Addition - Racemic Product + MgzCs + 4H,0 — 2Mg(OH), + CsHs (Propyne) ition ~ Racemic Product + Be;C + 4H,O > 2Be(OH), + CH, (Methane) + AUCs + 1220 +3CHs + 4Al(OH); (Methane) CH2 CH—COOK CH 1 — ill CH—COOK CH Potassium Maleate Reaction with Red Hot Fe 3CHy—-HC=CH——> (Aromatisation) NEC SECC Um uae Pont eee UL > Proton 1° alcohol > Aldehyde ; 2° Alcohol ~* Ketone on Pec ‘CuorZno sohol > Aldehyde ; 2° Alcohol -* Ketone SeO: [Gives 1,2-Dicarbonyls from Keto Forms Cyanohydrin with Aldehyde, Ketones HCN LIAIH, [Reduces carbonyl species, Nitriles, Epoxides ete. NaBH, _|1° alcohol ~ Aldehyde ; 2° Alcohol + Ketone [Reduces carbonyl to CH: (Clemmenson) Reduces carbonyl to CH; (Wolff Kishner)NaBH, 1800 OF pamachan ae Zn-Ha Cuor LAIHe 1. Hg(OAc)s, HO “OGRE Yes 2.NaBHe UT GE SET CL Evora eosin tol) ‘snc i + BaSO, reduces activity of Pd, CHy—CN SACP» | CHy—CH==NH, | * Poisons like Quinoline-S, Fomation of Imine {no Xylene is added oly i OTHER REACTIONS FOR AROMATIC ALDEHYDES 1. Etards Reaction : Toluene to Benzaldehyde using CrO,Ch/CCl. followed by hydrolysis 2.Gattermann Koch Rea Benzene to Benzaldehyde using CO+ HC! in presence of AICI; 8.Gattermann Reaction : Benzene to Benzaldehyde using HCN + HCI + AICI, followed by hydrolysis ET] carbene Intermediate : 4, Using CrO2/CH,(CO,)0 : Toluene to BenzaldehydeGeass REACTION WITH ALCOHOL CSREES ‘Acetals are formed by ‘alcohols and canbe OF OR used as protecting groups in organic chemistry Acetal On treatment of Grignard : RMgX, ‘Aldehydes —* 2*Alcohol (except HCHO) Ketones + 3*Alcohol NHLOH Hydroxylamine NH,NHp Hydrazine NH,NH-GgHs Phony! Hydrazine NHNH, Done using K:CrnOy 24 and Heat Dinitrophenyl hydrazi CHj ——» CH3-COOH + CHs-COOH od Brady's Reagent2 \ Tolen's Test. 2[Ag(NH,),};OH- : Aldehyde to Carboxylic acid Silver Mirror Formed Benedict's test CulCitrate),~ Aldehyde to Carboxylic acid Brick red ppt of CuO a A: CuSO,SHZO0 ae aca Febog'sTest | rea Aldehyde to Carboxylic acid Red ppt of Cu,0 ‘edctonm Test] NaOH, [ Metin Ketone to Carbomytic acid | Yellow ppt of CH,uw V Aliphatic)| Vlaliphatic)| Only Ethanal uw Only Methyl wv bales, vw Ketone x jonly a-hydroxy yi Only Methyl “2 methyl ketones, ~ Ketones {$$$ — rer —__ + — 4 Formaldehyde ye vw wv x postadehyde | wu wv wu tenaldehyde |W x Me ‘eetophenone | x x Beraophenone | x x | ee | ; Tollen's Test ‘2[Ag(NH;)2}"OH- Aldehyde to Carboxylic acid Silver Mirror Formed Benedict's test | Cu(Citrate).* Aldehyde to Carboxylic acid Brick red ppt of Cuz0 Fehling's Test ie : Sera ‘Aldehyde to Carboxylic acid Red ppt of Cuz0 jodoform Test| NaOH, | Methyl Ketone to Carboxylic acid Yellow ppt of CHlsas following eine of Abstraction fH varies a5 flowing —— ° o ° o 0 ACID BASE |ENOLATE i i 20q. Acetaldehyde -—-Behydroxy carbonyl «,B unsaturated carbonyl | + a@-H!'s should be available for aldol to take place. + Two carbonyls (ald. or ket.) form 4 diff. products (Crossed Aldo!) NNIZARO ° > CRS =, 5 ee Ge R’ HR 1H R’ H R oO: ‘ ‘Aldehydes without a-H's = Rate determining step in cannizaro is Hydride Transfer. + Carboxylate can be taken out with acidic workup GandG' are Electron withdrawing =M groupsrs rae Ring contraction with benzil benzilic acid m OH: fesiaigienit on ph OH : C on oe e 0 0 7h ‘Acidic workup "" >, Acidic workup ° a-Hydroxy carboxylic acids ai O CH 4 CH=CH x onX, suomi CH;COONa CCinnamie Acid Acetic pasa ° o} I = A} ~~ workup” No; B-hydroxyester Haloform reaction is given by compounds having OH = Acetaldehyde oO pee AQ thoston CH chy haloform reaction D)_Methyl Ketone° " . SOCk (CHy—C—OH——» CHy—C—cl DIBAL-H ° LialHs . Ha cy —o—00H1, OMe CHE cHyow [eroune 6 ° sty —P—or SOM cr —5-00.8, Hae CHyCH,-OH caH.OH | KMino, ° ° CHy—C=N F205 _cH,—C- Nea oy, —E—OH DIBAL-H ° ° Tollens, gy, Con HENS cHy—c—ocH, cH,—C-H + LG Tendency = ~Cl > -COCHs > -OCH, > -NH, + Reactivity: Acyl Chloride > Anhydride > Ester > Amide. + R-C=0 group is known as acyl group. leohol -» Carboxylic Acid |2° Alcohol -» Ketone 1° alcohol or aldehyde» Carboxylic Acid 12" Alcohol -* Ketone RMgX with CO; [Formation of Carboxylic Acid PCls, PCls, SOCIz |Coverts OH of acid to Chlorine DIBAL-H_ _ [Esters to Aldehydes; Nitrles to Aldehydes P03 [Acid to Anhydride; Amide to Nitrile . ED evento ‘Alcohols (Bouveault-Blanc) [Acyl Chloride to a-Chloroketone Cte [Carboxylic acids to Esters Hydrolysis of Acid Derivatives can be done easily for acid Ichloride, Slowly for esters in acidic medium or basic, medium and only with strong heating with amides BjImportant Name Reactions for Carboxyl ‘CLAISEN CONDENSATION fo) oO won I awe J ON B-keto ester ust aldol of esters with a leaving group Gia) Cin rogaine as =. : f ra ‘oH chibond on the a-carbon Replaced with a C-Br bond. REACTION WITH NaHCO3 1 7~~on = On reaction with NaHCOs, Carboxylic on acid releases carboxylate ion, CO2 and r water. carboxylic acid : ‘Backward reaction in basic medium is called saponification ‘+ Phenols do not react with NaHCO; With leaving group involved, Reaction happens twice and en product is a Tertiary alcoholOWeas ees PUN esea _NaQEt_, AL Lo None cael Pr= Be ‘Silver salt of fatty acids Alle! Bromide Free Radical Intermediate involved in the reaction. HVZREACTION, Cod a edsencsen ' Br,/P eh ; < Benzylic-H is a| ‘ci bond on ones Replaced > requirement for nets Br bond. the reaction 5 ESTERIFICATION REACTION WITH NaHCO AA “~ou (On reaction with NaHCOs, Carboxylic ‘OH = acid releases carboxylate ion, CO; and Ccarboryfic acid " water. ; Backward reaction in basic medium is called saponification Phenols do not react with N8HCOs With leaving group involved, Reaction happens twice and end product is a Tertiary alcoholWeak Nu- (neutral) 'SN' (Unimolecular) | SN? (Biomolecular) First order ‘Second order k{[Substrate] k{substrate][Nu-] ‘Carbocation Stability] Steric Hinderance driven driven ge >2°>>1° 12>29>>3° ‘Strong Nu- (-vely charged) ax ‘Undergoes tavern ff converts Foor tod) nH H re ie Steet, | Nu yas _ w—K ni = Polar Protic Solvents : H connected directly to Electronegative Group increases rate Polar Protic solvent | Polar Aprotic Solvent | |Element. Eg : Water, Formic Acid, Acetic Acid, Ammonia, Methanol, HF, Retention + Inversion] _ Inversion Only Polar Aprotic Solvents : H not connected directly to En. Element. Eg Tlectron Releasing | Electron Withdrawing | |Acetone, Ethyl Acetate, DMSO, DMF, HMPA, THF, Crown Ethers. Group increases rate Eneigy ‘coordinate Energy ~ xn coordinate Good Leaving Gp. ‘Good Leaving Gp. Charge Increases with -ve charge OH->H20 ‘Along period | Dec. with Electronegativity |CHs" > NH," > OH->F| Downthe | IncreasesinPolarProtic | >Br>Ch>F Group Decreases in Polar Aprotic F HCI: Br- is a better leavi arsed ofthe leaving group, . rz HCI: Bria better leaving group - CHON'cHcOO- sroAcisbeveris TPLIC|s better the Leaving Group. 1301 >> EtOH ; OTs- is one of the best LG 6 SOT ec ae eeee Not Possible due to Ce Cc) ened Aras Nal KCN ‘AgcN] _KNOz] AgNO,| __Moist[Ag:O Dry] Ag.0 RoI R-CN RNC R-ONO R-NO, R-OH = R-O-R 1° Alcohol 2° Alcohol 3° / Benzylic / Allylic Alcohol No Turbidity Appears (SN2) | Turbidity after 5 minutes (SN1) | Immediate white ppt (SN1)eek uae es Reagent Reaction ‘Mechanism HX (X=CI, Br, 1) R-OH + HX > R-X + HzO Carbocation formation (SN1) Red P/Brz oF PBrs R-OH + Br > R-Br + HO ‘SN2 Mechanism Pls R-OH + PCls— R-Br + HO 'SN2 Mechanism SOCh (Darzens) | R-OH+SOCI>R-Cl+ 50. ' +HCI | SNi mechanism (HIGH YIELD) ‘SOCI + pyridine | R-OH+SOCIR-CI+ 50. 1+ HCI ‘SN2 Mechanism s - Goverened by + Haloarenes do not undergo substitution reactions due to partial double bond character except two mechanisms Ls Ph-t ta e (ae Ph-cl _NaNOp, HCl GATTERMANN REACTION Ph-Br + Itis not possible to form a carbocation on Ph-cl benzene but Nz is an excellent leaving So ES group resulting in SN,Ar mechanism. Ph-Br * Other mechanism : SN2Ar (discussed in Ph-H Nucleophilic Substitution in aromatics) Ph-F GXERSSTTaohese |. isis SN? mechanism (alkoxide nu-) pea Secondary Alkyt halide can be used. sy hades recut in formation of alkenes via E2. + CH;CH,OHills) seta edna CHO «OH In Acidic Medium, a ‘open from more substituted te due to formation of carbocation ° OH OCH, CHO" Z~ cor” > In Basic Medium, Epoxide open from less hindered site (SN? mechanism) Cans Alcohol Aldehyde |. pehydrogenat 2° Alcohol + Ketone } etctogenmtion 3° Alcohol > Alkene } Dehydration of alcohol NO ENE OH OH c pt ok + Carbocation intermediate is involved. + Proton helps OH become a good leaving group. + In Unsymmetrical diols, More electron rich group rates first. MEERWEIN PONDORF VARLEY / OPPENEAUR AWOIPr), : ° OH ‘le Ayr KA A, Re Ry Re ‘The Meerwein-Ponndorf-Verley (MPV) reduction is reversible ‘The reversed oxidation is called the Oppenauer oxidation. + The rate-determining step is attack of the aromatic ring by the nucleophile, which disrupts aromaticity. * Electron-withdrawing groups on 0,p position to NO, —L.G., help to stabilize the -ve charg + Ar-F> Ar-Cl > Ar-Br> Ar-l, Since it makes the carbon site of attack more electropositive.E @e Z AW 4 "+l + — CY NaH 8 | He sip2: Attack of benzene on Electropl =~ — Delocalised Intermediate Reagent| Lewis Acid STEP 3 : Regain of Aromat ik |-OH, -OR, -NH, Activating groups | -NR2 and other Waotion | HNO | Hao. | Now |] OO" cues =e Giiination | Ch [FeCkor Alc] ck | [>——— ian ae, oe. Bomination | Br |FeBrsorAlBr,| Br | |Deactivating Groups| Halogens ~COOR and other -M. Groups Fc. Alkylation| R-X AIX R = *Friedal Craft Alkylation proceeds via formation of carbocation REREERER|R-CO-K| ADs [RCO] - hich undergo rearrangement for stability. Sulfation | SOs H:SO. | SO3H Halogens are the only deactivating and ortho para directing gp. Es. ‘OCHs a NO C O00 NO. Major oe a .==. Rate of E+ subs. -.Picric Acid the most acidic NOd phenols (more than acetic acid) CS2 is a non polar nd faciliated init Phenols are very Br Feactive due to +m of OH and ‘thus on reaction doesn't stop COOH OCOCH, COOH Breland Also shown by AiliCARBYLAMINE RE/ Helps in detection of primary amines which CHCl, KOH give offensive smell na of isocyani broom _ Nis “nm NOTE : Alky| halide should always be in excess else quatenary amines will be formed. 0 & A> n-nco 1:0, 2, oss Yi, sap ride Lorin Urea + Aniline on treatment with Br: leads to tribrominated product. For Monobromination, Aniline is converted into acetanilide first via shotten baumen reaction. + Nitration of aniline (+M group) leads to 47% formation of meta-nitroaniline as a product, due to protonation of NH. + Any group on ortho position of aniline will reduce its basicity due to ortho effect. = a Gas se>2%>t° B°>2°>1° se>2°>1° | i Aqueous| — 2°>1°>3° 2e>3°>1° Be>2%>1°PRACTICAL ORGANIC CHEMISTRY ©+Cu0 > CO, [Excess CO, makes the solution colourless due to UebeigsTestforS | co, tums lime water milky |formation of Ca(HCO;)2 + Gu0> HO ates Ce pte sk eases sti20| Hydrated Copper sulphate is blue in colour NaCN formed Cais ” NaCN + Fe [Fe(CN}I™ Adding Fe”, Fea[Fe(CN)c]s.xHz0 Fes[Fe(CN)xJs-xH,0 Prussian Blue NH2-NH2 doesn't give this test Halogen (x) NaX formed First Sodium Extract boiled with HNO3 + NaCl + AgNO; > AgCl (white ppt) + NaBr+ AgNO3—> AgBr (pale yellow) + Nal + AgNO3— Agl (Yellow) ‘On Adding Ammonium Hydroxide AgCI Dissolves ‘AgBr partially dissolves ‘Agl doesn't dissolve in NH«CI Sulphur (8) NaiS formed Na,S + Lead Acetate > Black ppt of PbS.2CH;COONa NapS + Na2{Fe(NO)(CN)s] — Nas[Fe(NOS)(CN)s] Thionitroprusside (Violet) S&N together NaSCN + FeCl; > [Fe(SCN)}* [Fe(SCN)}* has Blood Red Colour Phosphorous (P) Solution boiled with nitric acid and then treated with Ammonium molybdate Scan to know about preparation of the sodium fusion extract ‘Ammonium Phosphomolybdate (NH,)sPMo10.w is yellow in colourTest | Sodium Alkoxide is fo Na Metal med and Hz Released Given By all alcohols ‘pas Reagent Test ALREADY DISCUSSED one's Oxidation | Orange Red Colour Cr* to Green Colour CP Test for 1°, 2° Alcohol victor Meyer's test Alcohol + P/I, + AgNO; + NaNO2/HCI + KOH 1°: Red colour ; 2° : Blue Colour Yellow colour of Ceric Amm. Nit | |. Nitrate, Test for 1°, | CAN test (NHi)-Ce(NOs)s changes to Red to colourless Slow for OF Hs ° ° i : lodine goes from Peiodic Acid test |. +HIO, — Kh +HI03 +7 oxidation state Given by Dols CH 4 10 +5 Oxidation OH Scr, state ALDEHYDE AND KETONES - A\\ Tests Already Discussed TESTS FOR UNSATURATION Minch, Red Brown Colour of Bromine Disappears | Given by Alkenes and Alkynes [Given by Alkenes, Alkynes, Aldehyde| Saeyers test Purple Colour of KMinO, Disappears USERS [ PHENOLS BY cantest Gives black/brown ppt with Ceric ammonium Nitrate AULSIINIHS SINVONO TWILLIWHdPRACTICAL ORGANIC CHEMISTRY KMnO, Test [Reduces potassium permanganate solution and undergo oxidation to quinones. FeCl, Test Forms Violet Colour Complex with FeCl, Bromine Water 2,4,6tribromophenol is formed which is white in colour (Brown disappears) AMINES AND THEIR SALTS ‘+ RNH;+HONO > ROH+H;0+N2 — | * Nitrogen gas seen in form of bubbles Nitrous Acid Test | + R:NH +HONO -> R,N-NO +H20 + Yellow Oily Nitrosamine + RsN + HONO R3NH*ONO- ‘+ Soluble Nitrite salts Dye Test _|Altline on Reaction with NaNO3 + HCl forms Diazonium which on reaction with INapthan-2-ol gives Azo dye (Scarlet Red in Colour) Libermann Nitroso R2NH + HONO — R;N-NO Nitrosamines when heated with Phenol and conc. H2SO. is. test ladded, Green colour is formed which turns Blue with an alkali. (Only 2° amines) Benzene Sulfonyl Chloride Ri, __ N-Alkyibenzenesulfonamide ° ‘Compound formed is soluble in alkali M R.NH NN - Dialkylbenzenesulfonamide Hinscerg Test Cp al ‘Compound formed is insoluble in alkali ° BIN, No Reaction Carbylamine Test ICHsCH.NH, + CHCl, + SKOH > CHCHaNC (Offensive smell of isocyanide with 1°) - THE END a : ESerna CH,-Cl = CH—CHg a CH,—CH,Br N20H, cH,—CH,OH H:SOcy CHy=CHp eee Br,|CCl, Br Br 1 i. Hg(OAc)2, H2O —— —-° NaNH: yee, NaNH: oy CH - — a cs paNaNEiz, ii. NaBH, No “sna Resction HC—C =F eq. HC=CH CHa e Br cl NaBH, sat i Aeaor AAW siti. ROH DUA [sai Oa Enantiomer Os CHg H,02 AgCl aig KMnO, —— ae he a — Pas sundsatecker = SO,H H OH Moti, © psu Oleum NaOH rsome Acetic iTSn, HEI hydride Shotten Baumen Malet NH» NH=COCH, PARACETAMOLCEs Kolbe's GHy-COONa =" » CHy-CH, Bn” Chor i.CO, TS _, CHy—CH,MgBr oh es 2Eq. i CHsMgBr ~% CHOH, H+ 2 sore AU ii. i7H.01 Sania qt Estorification ° SLY cmon, CHONa HY, BOn i" NaOH Please. annizaro, Pinacolone OH OH Rosenmund CQ Aldo! O ° oO y SOocl, D Hz,Pd_ yy _NaOH ” aor a Pre ESO \ a NS OH Ox¢_—on . Intramolecular + AA esterification ‘HIsopropyl an Red hot Chloride Cac, +H,0 > Ca(OH), HHC==CH; EOS Je aa NoCI NH2 OH H,0 ‘Nano: 2 Op ‘Cnes CH=PPh, i. Pha Acotone| iv Base” waical ‘ieee GE Zn- zocHst “AC Ose och aut OH Propoxide Br ~_HBr_ aA *ROOR H.0 OH PCC DAs SS so.” “Yt Bonlie(OSS Sea eau eared fo 1 hy mee cu ce dX Oh addition Fo ‘chloride | Ose “Ast tom Enolate attack on Pr via SN2 ‘ton of Hr Faia dA Br 1,4 addition Product (TP) cin ieee isa soft reagent (Due to copper) which Low Temp favours Kinetic Product, ates sot site. C=C forming an enolate which is a Nu- High Temp. Favours Thermodynamic Product