i: ABLE OF CONTENT — Topic [_Ascom nes |Hyb. No, = no. of atoms connected (CA) * Lone pair on atom (IP)| Incase oflone ° pairs (or -ve, +ve, iy | radical charge) In & 2 sp | —“ C—H | conjugation. o | “ee Bee _| tmmvoncn } changes from sp? P| HN=3+0 0 HN=2+2 HN=2+0) (00 z g 3 a Py = = 4 : 3 Adjacent p orbitals (sp2 Every Heteroatom, Negative Charge or adjacent double bond cor atoms) are considered as, ° ° conjugated and AF mH CP | electrons can delocalise ° vi in these orbitals leading Cony. pea Conj.p=3 Con.p=4 Conj.p=4 ne me=6 ne=4 to resonance. For eg. Energy Released during combustion. HOC & no. of carbons & 1/Stability ; HOC per CH; ° angle strain HOC order ZN A ZS Chas more mbonds than B and OBA both C, B have more carbon atoms than A Chas 10cH's, B has 7aH's , Ahas 4aH's. OQ Cl seem ‘one Angle strain has major role, Cyclopropanes has the most angle strain with internal angle of 60°. A B c HOC order per CH, |A>B>C) ou — x= = ~ = re = =) = = = ro) e rc) I = c wi FS a os = 3 3 & 3 FA Pa Fey o ra ce} a 2 Fa Py EcHomolysis occurs mainly for non-polar bonds, Heat or light is needed to provide sufficient energy. In Heterolysis bond breaking occurs in the way that one part of the molecule takes both electrons. C-C+Cr CPX Xis Electronegative Group (-1) C-C+CeCxY Vis Electropositive Group (+!) CHa<-CD3<-CT3 < ~CzHs < -CsHy < Cas < (COO- < -O- < -NH-< -CH3 a: > =NR3* >-SRat >NH3" > -NO:> ~SOsH > eT ~CN >-CHO >-COOH >-F >-Cl >-Br >-I > ~OR> -OH > Benzene > Alkene > H Acidity of Carboxylic acids: -| Increases acidity Basicity of Amines: +1 increases basicity Stability of carbocations: +1 increases stability Stability of Carbs -Lincreases stability © Cl— CH, — COOH > CHCOOH (Acidity) (I of cl) @ EtgN > NH (Basicity) (+1 of Et) © (CHs)3C* > CHa* (Stability) (+1 of Me) 1 CH,” > CH3~ (Stability) (—I of Cl) aS Localisation of ¢ electrons of a~ to adjacent Double bond or empty p. Seen in Alkenes, Free radicals, Carbocations Carbocations. SZ a aS Por SS) More e- =. in ring in B due to more a-H's. 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 + Hyperconjugation is stronger than Inductive + No. of a-H's & Stability of Alkenes, Free Radicals, + Bond Length Becomes shorter. cnSonos Both the resonance structures of ozone contributes to form a hybrid and thus Oxygens on sides have similar character. Unsymmettical resonances structures contribute differently governed by rules. Charge on more| © Electronegative NH atom #4: +ve Charge on substituted carbons a GES eres ference botweon the theoretical va expernonal vl (Real Value). Resonance Energy ‘Stabgy Resonance Energy :C >B> A CY ZaAF7 ZZ F7 A B c 2T1 bonds 311 bonds Aromatic structure Rese ean sade) oconce LVF fA A Resonance Energy : © >B> A (more number of pi bonds) Resonance Energy Per ring : A>B > (Stability) AROMATICITY CYCLIC | PLANAR CONJUGATED] Sg vl] w |tn+2)ne-| Areata ww] ~ | anne | antiarematie Maybe | Maybe] Maybe | No RULE Non ariWhen in conjugation (adjacent p orbitals) contribution of re- is Double bond = 2; Carbanion = 2; Carbocation = 0; Heteroatom = 2; Free Radical = 1 Trick socoe Oaegne Cyclopropenyl Cyclopentadieny! Trop Benzene Napthal penpeaany pylium rolle dose anion Cation Pre 2ne- éne-— 10 ne ‘ne- éne- -s6ne-—=s Ge sGre=—m0~ NOTE : In case of Pyrrole, Furan and Thiophene, Lone pair of heteroatoms is involved in the ring, whereas Lone pair of Nitrogen in Pyridine is not involved in the ring. (Lone pair is present in sp plane) ae Stability N Order Ly 7 A Cycle | Cvclopentadieny Non Non Non NA ation ime- |] conitind Planar Conugred Cyto a Anti-aromatic - AA Atulene ADA0 Px NA ‘OH ne one: 6ne- + 2ne- ae 10me- Gne- ére- Bond Rotation Oxygen donates Aromatic in Polar state ‘Oxygen donates in resonance (high Dipole moment) Easier Nitrogen doesn't donateOccurs when electrons move towards ot away from a substituent in conjugation with m bonds QRRARE X is a Substituent with Lone. Pair donating in the chain (+M) ROR, sz Y=Z is a Substituent without Lone Pair accepting electron pair (-M) -O- > -NH; > -NHR > -OR> (& -NHCoR > -ocoR > -Ph > -F >-Cl>-Br>-1 NO; > -CN > -CHO >-C=0 > COOCOR > -COOR > COOH > -CONH: Mesomeric is stronger than Inductive and Hyper conjugation. =M Increases Acidity and Stability of Carbanion +M Increases Basicity and Stability of Carbocation. + Mesomeric effect only operates with Conjugation (Adjacent p orbitals) ic effect doesn't operate on the meta position of the benzene ring jhest acid jon in Benzene Carboxylic acids have (Ortho Etfect co0H COOH > C NO, Nop Ortho Effect -Meffect -1 Effect (meta) ae Geos Halogens do not show mesomeric NH NH NHp effect to much extent. Thus, Only -1 OCH Poor overlap with 2p > > CI orbitals of carbon. Thus, Halogens are OH NO, far Otho para directing +Meffect -Metfect Ortho Effect But Deseivatore S8_ +Metfect +H effect <—— Stobility e e No, F -leffect -Moffect -leffect | <— Stability —HDue to steric repulsion by group at ortho position, -sp? group becomes non planar and resonance will be inhibited. This is Steric Inhibition of Resonance. SIR applied by all bulky groups except OH, H, OR, NH2, Fete. Baccus ‘SIR applied on all sp? Groups Gsaenss 1.Compounds with incomplete octet BF; ACs, et 2.Compounds with available d-orbitals PF, Sal, SnCl, etc 3. Multiple bonds with dissimilar electronegativity 0=C-0 4 Sextet of electrons Carbenes o 5.All Simple Cations Na*, Ag’, Mg‘, H* etc (ners More Stable due to delocalisation of Charge in ing. Other one is out of plane. Thus, cannot delocalise time, fie, More Basic due to Nitrogen being out of plane and not contributing Lone pair in 1.Molecules with lone pair is a0, R-OM, py etc. 2. Unsaturated Hydrocarbons A:C=CR.,AC=AC 3. Multiple bonds with dissimilar electronegativity 9-9 4.All Simple Anions C-, OH SH-.Br- ete (ines + A-ATOM ‘Along Group & Period Acidity Increases, (CH, H,0 > OH- + R-RESONANCE Resonating Conj. bases have stronger acids Ethanol < Phenol Phenoxide is stable + DI- DIPOLE INDUCTION coon t 4 More acidic due to stronger -I of F + O-ORBITALS CCE eo Terminal Alkynes (sp) > Alkenes (sp*) > Alkanes (sp°)= 2 es i = =) 4 Sa een + Chain isomerism Arrangement of carbon ~~ chain is different Keto is more stable than enol due to + Position isomerism ci Position of Functional, ~~-\_-l oN group is different 1-chloropropane —“Inesbutne Enol is also wa higher due to pa Go + Functional oO OH intramolecular — isomerism pe L —_y H-Bonding Different Func. © 6 ' + B-diketo > Ket- rues = carbonyl sid Order. of Enol-Content : B-diketo > Ket-aldehyde> B-Aldehyde > Di pier tetetee GEOMETRICAL ISOMERISM ferent alkyl gps AN . ~ ‘ontwo sides of 8 + Arises due tohindered oy, ‘ functional 1s Ester Carboxylic acid bond rotation. een + Restricted site must have oo, + Tautomerism different groups. © Interconvertible structures ee that are different in terms yer Re CH of the relative position of 1 Wa . one atomic nucleus which on is generally the hydrogen © Need to have an a-H for inter-convertibility aot stronger bond but in some cases, enol concentration is higher. E.g. ° OH More stable due ~ to aromaticity in = case of phenol, ister > Ketone > aldehydeChiral Center : A Center with 4 different atoms connected. Chiral Molecul image. (NO Plane of symmetry or center of symmetry) Achiral Molecule : A Molecule with Superimposable mirror images. (Either POS or COS or both Present) ‘A Molecule with Non superimposable mirror Stereocenter : No. of Chiral Centers + 2 for every Gl exhibited (yertlen Mel sour stasis ‘OH Chiral Centers : 3 Stereocenters : 4 Chiral Molecule rotates plane polarized light by an angle « (Optically active molecule) + Observed rotation a may vary a with concentration and length, so [a]} = we define specific rotation [a] as + Rotation of PPL on Right : Dextrorotatory (+ or d) + Rotation of PPL on Left : Levorotatory (- or!) [a] mixture of + & Ixe Optical purity = x 100 [@lpure isomer (+/-) if a Chiral Molecule rotates the Plane Polarised light = by +30°, it's non superimposable mirror image will rotate the PPL by -30°, The Two are Enantiomers. Equal amounts of enantiomers will | create racemic SS \\. mixture (optically inactive) OH * Prioritise the connecting atoms according to their atomic numbers as 1,2,3,4. + Draw a curved arrow from 1+2-*3 keeping the {ath priority group on dash. If curve If curve arrow rotates arrow rotates Clockwise: R 7.4 Anticlockwise: S 1> Br> Cl > SO3H > SH > F > OR > OH > NO;> NRe > COOR > COOH > RCOR > RCHO > ROH > CN > Ph>T>D>H ° S-Configuratio: Examples 2) Ho Wo “CH1.Mark a line in between Alkene and Prioritise the right-handed and left-handed atoms as 1,2 according to atomic numbers. 2.if Priority 1 lay on same side, Configuration: Z 3.1f laying on opposite side, Configuration: E TRICK VIA R/S METHOD AP), on, Diasteroomers oH —=-- KA) (s) ” op . Enantiom Enantomers (s) hon (9), OH a : ) AR) "ee «+ fall the configuration changes on going from one stereoisomer to other relationship is enantiomers. + Ifeither one or all except one configuration changes, Configuration: Z _ Configuratior ~J 7 EB Atleast Two chiral centers are required for PA iastereomers z i= NHe = Not Mirror # a Images. = Ej Compounds with Plane or Center of Symmetry coon Optically Inactive ‘cooH ™ =o eo Chiral Centers: . oa meso-tartaricacid |. coon Molecule: Molecules with POS: without POS n = number of Chiral Centers neven or odd nodd neven 2 a pet 4.204 d/\ forms d/l Meso. to meso forms| Total forms en formes: re]4 4 Torsional Strait in na Strain due to repulsion All the conformations dihedral angle of electrons between Staggered we a and eclipsed are called " 8 Van der Waals Strain ‘SKEW conformations least stable mast stable Strain due to bulky Eclipsed Staggered alkyl Ha peer + Stability order : Antiperiplanar > Gauche > _ = = Anticlinical > Syn Periplanar oe 4 + Gauche becomes more stable in case of A B c oO * H-bonding involvement. staggered eclipsed staggered eclipsed e.g. 2-Fluoroethanol, gauche is more stable ‘anti antictinel gauche synperiplanar f q ‘Chair | —_ Half Chair 4Hybridisation : sp’ or sp_@, Bond Angle : 120° Diamagnetic : 6e~ system SSS jgehead carbocations are not stable due to non planarity e @ D Unstable Carbocations BEE) Dancing Resonance Aromaticity yo O- = Hyperconjugation Resonance === Unstable sp carbocations == Carbocations also stabilised by + effects :+M >+H>+1 ” REACTIVE INTERMEDIATES Ring expansion happens when angle strain is relieved by moving from a smaller ring to bigg membered most stable| _o[AREA — Hybridisation : sp -sp? when in conjugation C system : 8e~ negative ‘Stability order: 1° Benzyl > 1° Allyl > Methyl > 1° Alkyl > 2° Alkyl > 3° Alkyl Stabllised by : - Effects like -M > -H > -I Factors : Aromaticity > Resonance > Back bonding > S-character > Inductive Hybridisation : sp rately sp° (CF!) System : 7e- neutral [__ (CARBENES) J Hybridisation : sp* or sp System: 6e" neutral | e- deficient species SCR, Triplet > Singlet Stal 2.Nucleophilic additior 2.Nucleophilic Substit. Other Reactions : Ell | FREE RADICAL, Stability order : t-butyl >1° Benzyl 1° Allyl > 3° Alkyl > 2° Alkyl > 1° Alkyl Free radicals are formed mostly using Sunlight which generates neutral 5 ree fe po tom Me es nies e singlet test 2, sp sp ‘Seen in Alkenes and Alkynes CHy=CH, + X—Y ——m CH,—CH, Seen in Aldehydes and Ketones ia 3. Radical addition (Eg. Anti-Markonikov effect) doce x oY 1.Electrophilic Substitution : Seen in Aromatics. Seen in Carboxylic acid derivatives 3. Radical substitution : Seen in Alkanes (or Alkyl halides) Stabilised by : + Effects like +M > +H > +1 Factors : Resonance > Hyperconjugation > Inductive ies with odd electrons via homolysis ee B+ A—CH,——> A+ B—CHy mination Reactions and Rearrangement Reactions Discussed Later Usually seen with CarbocationsNCS TT VS Te) Say CENTS Ee LUSK OSL ce 2) SLO) Wiican) Fi formed which Roan form symm. alkanes or-x Say R + Free Radical Intermediate (Can undergo ‘combination or disproportionation) + Methyl Cannot be formed + RAD R-Br> R-CI>R-F + IFR = Ph, Reagent : Na; Fittig Reaction © Reagent : Cu; Ulmann Reaction © Reagent : Zn; Frankland Reaction ersten 5 2R-COONa —> R—»> R—R At Anode na * Carbanion formed — 1H + Rate of Rxn o carbanion R—COONa 804 RH statbilty. Electron withdrawing ii, Cao ‘ groups increases Rate REACTION WITH GRIGNARD | ‘Acidic H’ can come from H:0, ROH, RSH, RCOOH, RSO3H, RNHz, Phenol, Ph-H add iseac ea iceans > Pt/Pd/Raney Ni/Ru can HoINi \a/ BN ON also be used + Ha comes from same side + Hydrogenation is used in both Alkenes and Alkynes + Rate of Hydrogenation & 1/Steric Crowding ReMax Acme ‘+ COz at Anode and H: at Cathode + Methyl Cannot be formed + pH increases due to NaOH formation + Formate lon forms only Hz [eoney HOUSE | Reagent BOILING POINT ORDER GENERAL ORGANIC COMP. + BP cIntermolecular forces © Ionic Bond > H-Bonding > Dipole-Dipole > Vander waals, + BP o HX +R’ opogation 1X" HR, eS . Pr tion 2. R + XX ——» X-R+ X ropogation2 R“+ XX + Inlast step, different radicals combine to form neutral species, TERMINATION step. + Reactivity Series : F, > Cl > Br2 >I. CI'is more reactive less selective, Br is less | teactive more selective. Selectivity is decided by free radical stability. AROMATISATION REACTIONS i. with AlOs/ Cr:Os, V205/ 4 \ ee ee ii, with Pd/C or Se Gee with ater 7 ner (CHs)sCH > (CHs)3COH Cath, 74 OW, + CH, — CH, + C,H, +Cl * Follows Free radical mechanism, + Rate of Pyrolysis e Molecular WeightBes : . a + Reactivity & Electron richness of alken Soe ° X¢ of] ° x x + More subs. alkenes are more reactive. oy SO OO + 4M, +H, +1 effects increases e- density. e tich alkene Carbocation or Bridge carbocation Syn or Anti Addition of Y-_* Anti addition with bridged carbocation Crane Loe een uicold 1.BH, 1. Hg(OAe),, H,0 — Hy —CH=CHe7 NaBH, ONC HO, NaOH an on ou A i = inanar~ 1.Syn Addition, Anti-Markonikov Addi 2.NO carbocation Rearragement 3.Terminal Alkynes form Aldehydes; Others form Ketones Gonna 1.Hg@Ac),,H,0 © 2. NaBH, ON 41.Syn + Anti Addition, Markonikov Addition 2.-OR gets attached to Carbon, in case solvent is ROH, 3.1n Alkynes except acetylene, always ketone is formed. CONOSannn nes ‘+ Monosubstituted Carbon, Zn/Me:S: Aldehyde + Monosubstituted Carbon, H:02 : Carboxylic Acid + Disubstituted Carbon with either : Ketone Os ‘0 20 Os ot te _—— 0 Zn/MezS W202 ‘+ Intermediate. is the ozonide formation + Reductive workup breaks ozonide to carbonyl 4 1:9; i ‘2.H,0 oF HD, CHO O% + + Reductive Ozonolysis gives diketones °°? + Oxidative give acids Terminal alkynes give CO>HYDROCARBONS - Alkenes and Alkynes ec ued alk. KOH [Dehydrohalogenation Dehydration of alcohol or Hydration of Alkene (Markonikov) H*/H,0 Zn \Vicinal Dihalides to Alkenes Hs, Pd/BaSO,|Lindlars : Alkynes to Cis Alkenes Na/Liq NHs [Birch : Alkynes to Trans Alkenes [Dehydrohalogenation or asa base NaNHz ior terminal Alkynes [Anti Addition of X and X/OH X2/CCle OF | leophile (X/OH) attacks more Xa/¥:0 | substituted carbon. x. _|Matkonikov addition of Hx (Stable carbocation is priority) HBr, ROOR |Anti-Markonikov addition of HBr NBS [allylic Bromination Br Por-acid |Forms epoxides with Alkene +-BuOk — KMn0,; 080, |Cis Diols formation tba remover tee hindoed proton HOT KMn04Trick for electrop! ‘add. stereochemistry to alker 1.CSM : Cis alkene - Syn Addition - Meso Product 2.TSR : Trans alkene - Syn Addition - Racemic Product is alkene - Anti Addition - Racemic Product 'AM : Trans alkene ~ Anti Addition - Meso Product Hydrolysis of Carbides + CaC; + 2H;0 + Ca(OH), + CoH2 (Acetylene) + MguCs + 4H,0 > 2Mg(OH): + C3Hs (Propyne) + Be,C + 4H,0 — 28e(OH), + CH, (Methane) * AliC3 + 12H:0 *3CH, + 4AI(OH)3 (Methane) Reaction with Red Hot Fe CH — Ill CH ‘CH,—COOK CH, CH—COOK I — il i ‘CH,—COOK CH, CH—COOK Potassium Succinate __ GENES Potassium Maleate NT OME OCR OPN Cae Tbe CLUES Nu" Intermedia escort karet ed ‘© Electron Deficiency of Carbon \ effects increases reactivity ° ° ° > > cao, Se of Sons PCC | 1" alcohol > Aldehyde ; 2° Alcohol ~ Ketone CuorZnO _|1*alcohol-> Aldehyde ; 2° Alcohol -> Ketone Se0; __|Gives 1,2-Dicarbonyls from Ketones HEN [Forms Oyanohydrin with Aldehyde, Ketones LAI, _ |Reduces carbonyl species, Nitrles, Epoxides etc NaBH, [1° alcohol ~ Aldehyde ; 2° Alcohol « Ketone [Reduces carbonyl to CH: (Clemmenson) Reduces carbonyl to CH: (Wolff Kishner) 17Br NaBH 1:80, br “Nou fe nO Nae HAZ Dehydration Br NaN VO ag testi Cuor Lal 1.Hg(OAe), HO. UC eS EL SSUES — ch —— Hyon SCR [ cHy— Fomation of Imine Intermediate cHy—CHO OTHER REACTIONS FOR AROMATIC ALDEHYDES 1.Etards Reaction : Toluene to Benzaldehyde using CrO;Cl,/CCl, followed by hydrolysis 2.Gattermann Koch Reaction : Benzene to Benzaldehyde using CO* HC! in presence of AICls 3.Gattermann Reaction : Benzene to Benzaldehyde using HCN + HCI + AICI, followed by hydrolysis 4, Using CrOz/CH3(CO;)0 : Toluene to Benzaldehyde ° io) + BaSO, reduces activity of Pd, Hp, Pd-BaSOg AA *+ Poisons like Quinoline-S, ci ” Xylene is added RIEMER TIEMANN REACTION OH CHO Jeet > JA ee R, “Dy carbene TS omepS SS Sas GENS eel Br Mor a Bry ether a A Followed by | © ‘Acetals are formed by hydrolysis alcohols and can be used as protecting {groups in organic chemistry UTC ccc) iC Cee DES CONE Phenyl Hydrazine | Phenyl Hydrazone| + Cyclic Acetals (On treatment of Grignard : RMgX, 2,4-Dinitrophenyl 2,4-Dinitropheny! hydrazine hydrazone Aldehydes + 2° Alcohol (except HCHO) Ketones ~ 3°Alcohol ‘Semicarbazide ‘Semicarbazone NH,OH Hydroxylamine NH,NHp Hydrazine NH,NH-GgHg Phenyl Hydrazine ° NHNH, Done using cso ot, —— CHj-COOH + H-COOH = KCr,0; and 2,4- Heat Dinitrophenyl ep No, Yctazine + CH,-COOH NO, 2 COOH . Brady's Reagent m9]— Aldehyde wv VY (Aliphatic)| ‘Only Ethanal Keon ‘Only Methyl lonly a-hydroxy 5 ‘Only Methyl ketones methyl ketones| x Ketones Formaldehyde wv x ‘Acetaldehyde XIxIXIN|x, ASIN) SIS Benzaldehyde x x | Acetophenone x x Va Benzophenone x x x Tollen's Test 2[Ag(NH3).]"OH- ‘Aldehyde to Carboxylic acid Silver Mirror Formed cenedict's test Cu(Citrate).* ‘Aldehyde to Carboxylic acid Brick red ppt of Cuz0 ‘A: CuSO,.5H;0 ehling' Aldehyde to Carboxylic acid ux Fohling's Test is: Rochelle's Sait jehyde to Carboxylic aci Red ppt of Cuz0 odoform Test NaOH, lz Methy| Ketone to Carboxylic acid Yellow ppt of CHlsEnolates - The part to study name Reactions Ease of Abstraction of H varies as following oe oO °o 0 ° ° JENOLATE #H, H, Seow J A Ok ry ° we ‘NaOH A et saw, ° ° dil.NaOH 4 Ais 2eq.Acetaldehyde hydroxy carbonyl a, unsaturated carbonyl + a-H's should be available for aldol to take place. + Two carbonyls (ald. or ket.) form 4 diff. products (Crossed Aldol) Intramolecular aldol Reaction + Conjugated carbonyl is stable ° ° OH oF I SL. Nao vl H aon a So alle, ae di. NaOH “Aldehydes without «-H's H + Rate determining step in cannizaro is Hydride Transfer. 1 ibibo lar + Carboxylate can be taken out with acidic workup = CH, Gand oe Election ~ PPhg=CH, teglle + PPhg=O | oitewing song Phosphorous Vlides R so Pree oo Phosphorous Vi -Mgroups H : HESS on Ring contraction with benzil benzilic acid) bh OH on rearangement Ae Acidic workup PP 1, } Se O° Acidic workup (J 9 a-Hydroxy carboxylic acids Haloform reaction is given by compounds having ° OH Acetaldehyde AL ate show pao acon CHs CH a cH workup HO Imethy\ Ketone Carboxylic acid ——_lodoform‘Nu \ °) AAS A = LG Tendency C1 > ~COCHs > -OCHs > -NHz + Reactivity: Acyl Chloride > Anhydride > Ester > Amide, + R-C=O group is known as acyl group. ° co, 2 80h 8 Jorp—woBr} £02. cry Con ——e cHy—C—c1 : [ene 3 ° LAH oy city~b-00'4 coco SAM ry 8-1 Jeroune 6 cr, —b—on OH DIBAL-H : cH, OCH SR —N2e CHyCH.-OH Jprinoe : Clg —C=N F208 CHy—C—NH i iH oy Bon ° CHiN: cH, Coch, Tollens, oy, cy CHty—C—OH \CrO,, H+, Acotone| Gones Reagent) ice kau 11° alcohol > Carboxylic Acid l2° Aleohol Ketone 1 alcohol or aldehyde Carboxylic Acid KMnO« oF K:C1207]>» alcohol -» Ketone RMgX with CO; [Formation of Carboxylic Acid PCls, PCls, SOCI, [Coverts OH of acid to Chlorine DIBAL-H__ [Esters to Aldehydes; Nitriles to Aldehydes POs [Acid to Anhydride; Amide to Nitrile Esters to Alcohols (Bouveaul CHiN, _|A&Y! Chloride to a-Chloroketone |Carboxylic acids to Esters Hydrolysis of Acid Derivatives can be done easily for acid chloride, Slowly for esters in acidic medium or basic medium and only with strong heating with amides 4)209.89, 0 nok ‘OH with a C-Br bond. —_ B-keto ester Claisen cond. is just aldol of esters with a leaving group Br2/P CH bond on the a-carbon Replaced Br bu _, R—Br cl, ‘O-Agt Silver salt of fatty acids Alky!Bromide | Intermediate involved in the reaction. COOH KMn0, Benzylic-H is a — requirement for] the reaction Essen REACTION WITH NaHCO2 + On reaction with NaHCOs, Carboxylic acid releases carboxylate ion, CO2 and water. + Phenols do not react with NaHCOs With leaving group R__ involved, Reaction happens twice and end product is a Tertiary alcoholNucleophilic Substitution Reaction at Saturated Carbon : C-X + Nu- —> C-Nu + x- Weak Nu- (neutral) SN' (Unimolecular) | SN? (Biomolecular) First order Second order K{Substrate] k{substrate][Nu-] Carbocation Stability| Steric Hinderance driven driven 3° >2°>>1° 19>2°>>.3° Strong Nu- (-vely charged) Polar Protic solvent Polar Aprotic Solvent Retention + Inversion Inversion Only Electron Releasing Group increases rate Electron Withdrawing Group increases rate Energy Brn coordinate “\ Fon coordinate Energy Good Leaving Gp. Good Leaving Gp. (EES Forms Racemic mixture both (Gand) Nu x Vv Stept %@ _ awd Nu + Nu Mg 7 Ny 7 owning Undergoes Inversion (d converts tol orltod) HH HH Hy || (pis Se Nu Ve > wl’ Nu “ansition state Polar Protic Solvents : H connected directly to Electronegative Element. Eg : Water, Formic Acid, Acetic Acid, Ammonia, Methanol, HF. Polar Aprotic Solvents : H not connected directly to En. Element. Eg ‘Acetone, Ethyl Acetate, DMSO, DMF, HMPA, THF, Crown Ethers ieee eae Charge | Increases with -ve charge OH->H20 Along period | Dec. with Electronegativity |CHy- > NHz- > OH-> F- Down the Increases in Polar Protic b> Br >ch>F Group | Decreases in Polar Aprotic |r HCl : Br~ is a better leaving group Better the acid, better the Leaving Group. T.OH >> E10! Form Conjugate acid of the leaving group, « cH,COOH > CH,OH : CHsCOO- or OAC is better LG Trick Tis one of the best LG Other Fluorides _ <8 of Alcohol fee 1 see SE. Nal KCN Agen] __KNO; ‘AgNO, | Molt a0 Dry]Ag:0 R-NC R-ONO R-NO, R-OH = R-O-R Rel R-CN ( 4° Alcohol R-X prone eens 2° Alcohol 3° / Benzylic / Allylic Alcohol Turbidity No Turbidity Appears ( SN2) Turbidity after 5 minutes (SN1) Immediate white ppt (SN1)| JEE Other Reactions to convert Alcohol to Haloalkanes but with different Mechanisms Reagent ction Mecha Stereochemistry HX (X=Cl, Br, 1) R-OH + HX > R-X + HO. Carbocation formation (SN1) | _ Inversion + Retention Red P/Br: or PBrs R-OH + PBr > R-Br + H,0 ‘SN2 Mechanism Inversion of Halogen PCls R-OH + PCl, > R-Br + HzO ‘SN2 Mechanism Inversion of Halogen SOCK (Darzens) | R-OH+SOCI>R-Cl+S0,! +HC! | SNi mechanism (HIGH YIELD) Retention SOCI, + pyridine | R-OH+SOCI,>R-Cl+ 50, /+HCI ‘SN2 Mechanism Inversion of Halogen s - Goverened by + Haloarenes do not undergo substitution reactions due to partial double bond character except two mechanisms Ki {as Ph-I Cu/HCL phe Ph-Br. + It is not possible to form a carbocation on Ph-Cl benzene but Nz is an excellent leaving SNES Eee group resulting in SNyAr mechanism. Ph-Br + Other mechanism : SNzAr (discussed in Ph-H Ph-F GERSON eae)Costa Et (Unimolecular) | 2 (Biomolecular) First order Second order KSubstrate] k{substrate](Base] Carbocation Stability Antiperipl driven rearrangement Weak base + Heat or | Strong bases like alc, Dehydration using | KOH, NaNH2, EtO- in H2s04 EtOH, t-BuOK. his is @ SN* mechanism (alkoxide nu-) ~vmary, Secondary Alkyl halide can be used, alkyl halides result in formation of alkenes via E2. coseds via protonation ‘owed by SN2/SN1 reaction I-25 nucleophileRING OPENING OF EPOXIDES In Acidic Medium, epo» site due to formation of carbocation OH ‘OCH, CHO" CHONG: Uae In Basic Medium, Epoxide open from less hindered site (SN? mechanism) Crs 4° Alcohol — aldehyde | pehyarogenation 2° Alcohol > Ketone 3° Alcohol + Alkene } Dehydration of alcohol je open from more substituted OH = OH Pinacole , € L t. _ANOIP)s : Ry Re Aw. a ‘The Meerwein-Ponndort—Verley (wey eduction ‘The reversed oxidation is called the Oppenauer oxidation. Bannon a Carbocation intermediate is involved. Proton helps OH become a good leaving group. In Unsymmetrical diols, More electron rich group migrates first. reversible, Nu + The rate-determining step is attack of the aromatic ting by the nucleophile, which disrupts aromaticity. Electron-withdrawing groups on 0,p position to LG., help to stabilize the -ve charge. * Ar-F> Ar-Cl > Ar-Br > Ar-I, Since it makes the carbon site of attack more electropositive.o- STEP 2 : Attack of berizene on Electrophile a H <>\) Ve" N72 Delocalised Intermediate STEP 3 : Regain of Aromaticity oo as Name [Reagent] Lewis Acid | E+ -OH, -OR, -NH2, Nitation | HNO, | 1:50, | Now | | Activating groups | -NRs and other __ | +MGroups ‘Chlorination | Cl |FeChorAIch] ch | —— S8)<¢H10/=COOH; Domination | Br |FeByorAl6y| Gr | |Deactivating Groups| Halogens.__| -COOR and other -M FC Alkylation] R-X AIX R Groves: = —<] _ “Friedal Craft Alkylation proceeds via formation of carbocation © Aeylation |R-CO-X|_AIXs _|R-C'FO| which undergo rearrangement for stability fonation | SO; 1:50, | SO3H | — Halogens are the only deactivating and ortho para directing gp. OCH, a NOx Ss HNO, a ae | MajorOH Picrie Acid is one of the most acidic cl O-Nat NO2 Oz phenols (more acidic than acetic acid) NaOH OH Ol CS; is. anon polar — HH Br medium and ionisation is not faciliated in it. OH Phenols are very Br feactive due to+M er effect of OH and thus on reaction with Br. Reaction Br doesn't stop & CO of 7 a ou : y |e coon CEZEED i ook SJ8 FG OCOCH; oO; a \ COOH oO ‘Also shown by Anilin Oo Aspirin byHOFFMANN | EUAN ACAD Helps in detection of KL Br NAOH NH, primary amines which ~~ NH CHCl, KOH give offensive smel Primary Amide Primary Amine a of isocyanide. CUS Carbamate 0 yy A. Noo eo tree NH pa N, Ny, R—NH2 |] nore: alkyl halide should always be in excess else quatenary Reyltalde ——ocyanata A Urea amines will be formed. Sosa TT * Aniline on treatment with Brz 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 NaOH, ; nH, +Sodim Pthalatel | $5 B°>2°>1° B°>2°>1° 3°>2°>1° Aqueous| 2">1°>3° >3°>1° g°>2°>1° soni, Primary AminePRACTICAL ORGANIC CHEMISTRY ©+Cu0 > co, Excess CO; makes the solution colourless due to | CO2 turns lime water milky _ {formation of Ca(HCOs)2 H+ CuO H,0 5 2 Ir Iphate is blue in colour lcusoa+sH20 > cusoa.sHz0| _vdrated Copper sup Nitrogen (N) NaCN + Fe? —> [Fe(CN)e] Fes[Fe(CN)Js.xH2O Prussian Blue Scan to know about preparation of the sodium fusion extract NaCN formed Adding Fe”, Fea[Fe(CN)<}s.xH20 + NH2-NH2 doesn't give this test First Sodium Extract boiled with HNO; ‘On Adding Ammonium Hydroxide Halogen (X) + NaCl + AgNO; — AgCl (white ppt) + AgCl Dissolves Naxformed | * NaBr+ AgNOs—> AgBr(pale yellow) | + AgBr partially dissolves + Nal + AgNO; — Agi (Yellow) + Agl doesn't dissolve in NH«Cl Sulphur (S) NaS + Lead Acetate — Black ppt of PbS.2CHzCOONa Na:S formed NazS + Nas{Fe(NO)(CN)s] ~* Nas{Fe(NOS)(CN)s] Thionitroprusside (Violet) S&N together NaSCN + FeCl, > [Fe(SCN)]* [Fe(SCN)}* has Blood Red Colour ‘Solution boiled with nitric acid and then ‘Ammonium Phosphomolybdate Phosphorous (P) treated with Ammonium molybdate (NH,)sPMo,20 is yellow in colour_ i TEST FOR DIFFERENT FUNCTIONAL GROUPS: ALCOHOL Sodium Alkoxide is formed and H; Released Given By all alcohols ALREADY DISCUSSED Orange Red Colour Cr® to Green Colour Cr+ Test for 1°, 2° Alcohol Alcohol + P/lz + AgNO + NaNO2/HCI+KOH | 1°: Red colour ; 2° : Blue Colour Yellow colour of Ceric Amm. Nitrate, Test for 1°, 2° Alcohol, (NH,),Ce(NO3). changes to Red to colourless Slow for 3° alcohols OH CHs ° ° lodine goes from +HI0, ———_» +HIO, +7 oxidation state ‘CHs H to +5 Oxidation OH ‘CH3 state ALDEHYDE AND KETONES - All Tests Already Discussed TESTS FOR UNSATURATION AULSIINIHD JINVDYO WIILIWHd Red Brown Colour of Bromine Disappears | — Given by Alkenes and Alkynes Given by Alkenes, Alkynes, Aldehyde| Purple Colour of KMnO, Disappears = i PHENOLS Gives black/brown ppt with Ceric ammonium NitratePRACTICAL ORGANIC CHEMISTRY “KMnO, Test _ [Reduces potassium permanganate solution and undergo oxidation 0 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 Nitrous Acid Test ee + RNH,+HONO— ROH+H;0+Nz | + Nitrogen gas seen in form of bubbles + RINH+HONO > R:N-NO+H,O | + Yellow Oily Nitrosamine + RsN + HONO ~RsNH‘ONO- + Soluble Nitrite salts [Aniline on Reaction with NaNO; + HCl forms Diazonium which on reaction with ‘Azo-DyeTest |. sothan-2-ol gives Azo dye (Searlet Red in Colour) Libermann Nitroso. R2NH + HONO — R2N-NO Nitrosamines when heated with Phenol and conc. H2SOx is test” - added, Green colour is formed which turns Blue with an alkali. (Only 2° amines) Benzene OL Chloride nH, __N-Alkylbenzenesulfonamide ‘Compound formed is soluble in alkali Cp R2NH N,N - Dialkylbenzenesulfonamide Compound formed is insoluble in alkali No Reaction |_Carbylamine Test CHsCHaNH2 + CHCl + SKOH > CHsCHNC (Offensive smell of isocyanide with 1°) » THEEND &EXECS CH,-Cl “ > CH3—CHy iz > CHy—CHpBr 20H, CHy—CH,OH 4250s, CHp=CH, 170°C Wurtz reaction Br,|ccl, Br Br 1 i Hg(OAch, #20 ——— — =0°_NaNHs yo=cH LYaNH: cH-CH ii. NaBHa “SNa Reaction HO=C ° * ‘o NaOH ° © fexermind Cdl © ‘4Ataton CN a! SOcl, \ lay y in CHIg Ne ——— ee Ne AAA a SA, UoH jH7H:0 ‘;C-—OH OS—P"on COOH O Intramolacular Bast SO pace Ot a H EtOH AaC, + HO ——> Ca(OH), Isopropyl! tee Red hot Chloride _ nich, of ir NCI NH, HNO: NaNO, Zn a “Het O “Dust rer 22.) [ron | CHO ee CH=PPh, a) co+Hel coos C Jem Hg Cs en Os0 ach “ , a | “ach ‘Clemmonson — Propoxide gr Her ~™-=3008 7 ~ v No ie 7~_OH pee ° S203 Le OH: ane(ENG ES e aan eareieee acecclhcad “i G Carbocation. ae Ring Expansion aks Dua Cw OH Carbocation formation Alkyl Shitt Ring formation a fo ° \ oe RMgBr, Cy feo 1,2addition Zoe { ~ Clonde Addition of Her A Fp; De ree Enolate attack on Pr via SN2 me. ‘Br ‘gilman reagent 1,A addition Product (1?) Gilman Reagent is a soft reagent (Due to copper) which Low Temp favours Kinetic Product, attacks soft site i.e. C=C forming an enolate which is a Nu- High Temp. Favours Thermodynamic Product