ORGANIC REAGENTS Reagent 7 Function PCI. PBrs, Ply Alcohols into Alkyl halides _ SoCs PClis Alcohols into Alkyl chlorides & HCWV/ZnCl, HBr.HL Cla/Fe or FeCl: _ NaNO; /HCI 0-5°C CuCl.CuBr,CuCN,KLH20, HaPO: Carboxylic acids into Acid Chlorides Alcohols Cl group substituting on Benzene Diazotisation azonium Cholride into Chior Benzene, _ Bromo Benzene, Benzo nitrile, lodo 7 | HBF, or NaBF, z - [9 Na/dry ether Alky] halides into alkanes 10 | NaOH 623/443/368K Chloro benzene to phenol u n of Benzene 12 13 I 14 | CH-CO-CI/AICI, 15 H2SO, /HNO3 16 (CHCO)»O /AICL, © _Acylation of Phenol 17 _H,SO, Sulphonation on Benzene 18 H,O/ H2SO. Aq KOH 19 BH;/H202/OH" Alkenes into alcohols (Anti _ _ Markownikoff product) _ _ 20 NaBH LiAIH(LAH) Aldehydes. ketones, acids i Nito & Cynides . Isocyanides into amines 21 H2/ Ni or Ha/Pd reduction of aldehydes, ketones and | | cynides _ 22 | RMgX/H,0* Aldehydes, ketones into alcohls 23 | O./H" Cumene to phenol 24 Na Alcohol or phenol into Sodium _ alkoxide/Phenoxide 25 (CHCO),0/ CH-CO-Cl O acylation on phenol or N acylation on ee Aneline 26 Conc.H2S0/443K 27___| Conc.H,SO./410K - “28 _ | Secondary alco 29 Tertiary ulcohol into alkeneORGANIC REAGENTS 30 CrOy/KMn0, or K;Cr:0; | oxidation of alcohols into acids in acidic medium 3! Cu /573k dehydrogenation of alcohols gives 1° alcohols into aldehydes and 2° alcohols into ketones & 3” alcohos into alkenes 32 Dil. HNO; Mono nitration of Phenol 33 Conc.HNO; tri nitration of phenol 34 Br; /H,0 tri bromination of phenol 35, Bn /Cso mono bromination of phenol 36 NaOH /CO> Phenol to salicilic acid 37 CHCl; NaOH Phenol to salcilaldehyde 38 | Zn dust Phenol to Benzene 39 NayCrO; /H2SO, or air Phenol to Benzo quinone 40 | Zn/Cr0; 20010 300 aim = | CO & H into methanol 573 673K 41 Tnvertase Sucrose into Glucose or Fructose 42 Zymase Glucose or Fructose into ethanol 43 HI Ether into alcohol & alky! halide Ad pcc alcohol to aldehyde 45 Pd /BaSO,,Hy acid chloride into aldehyde 46 | SnCi/HCV/H;0° Cyanides into aldehydes 47 __| AIH(@-Bu),/HO Cyanides into aldehydes 48 DIBAL-H/H,0 Esters into aldehydes 49 CrOxCl2/H20 Toluene to aldehyde 50. CrO3(CH3CO),0 Toluene into Benzaldehyde St | Clyhv Chlorination on alkyl group of Benzene or alkane 52__| CO, HCl anhydrous AICI; | Benzene to Benzaldehyde 53 (CH3)3Cd acid chloride into ketones 54__ | RMgX/H,0" Cyanides into ketones 55__|HCN Carbonyl compound into cyanohydrin 56 NaHSO; addition to aldehyde and ketone 57__|H:NOH carbonyl compound into oxime 58 _| H:N-NH) carbonyl compound into hydrazone 59 | H.N-NH-Ph carbonyl compound into Phenyl hydrazone 60 2,4DNP carbonyl compound into 2,4 dinitro phyny! hydrazone G1__| H;N-NH-CO-CH; carbonyl compound into semi carbazide 62 ROH/HCI Aldehydes & ketones into hemiacetal and acetal 63 HO-CH;-CH)-OH/HCL Aldehyde or ketone into ethelene glycolORGANIC REAGENTS ketone carbonyl compound into alkane 64 | Zn-Hg/HCl 65 H.N-NH2/KOH ‘carbonyl compound into alkane 66 KMnOWV/OH/7/ K2CrO7 Ketones into mixture of carboxylic acids AH2SQ; or HNOv on prolonged oxidation 67 (Ag(NH4)2.)NO;+NaOH Tollen s test 68 Cu(OH)2 Fehiling s test 69 NaOQH+h Iodoform 70 NaOH or Ba(OH)» aldal condensation 7 Cone KOH or NaOH Cannizaro s reaction 72 KMnO, /KOH Toluene/alkyl Benzene into Benzoic Acid 73 H,0/H" Cyanides into carboxylic acids, amides into carboxylic acids, esters into carboxytic acis and alcohols, acid chlorides or anhydrides into carboxylic 74 NaOH ponificaiton of ester, acid into salt of acid 75 NayCO; or NaHCO; Carboxylic acid test 76 P O10 or P205 Dehydration of acids into anhydride, H/cone H,SQx amides into nitriles Caroxylic aci to acid chlorides . SoCs PCls Carboxylic aci 79 NH, heating Carboxylic acids into amides 80 NaOH/CaO Decarboxylation (acids into alkanes) 31 LiAIHy Carboxylic acids into alcohols, amides into amines 82 Ch /red.Ps HVZ reaction 83 Sn /HCI or Fe /HCI, H2/Pd | Reduction of nitro compounds into amines &4 NH; _ Alkyl! halides into amines 85. H,/ Ni or H2/Pd LiAIHy Amides into cyanindes 86 KOH/R-X Phthalamide into amine: 87 NaOH /Br2 Hoffman bromamide, amide into amine with one _C_less 88 KOH.CHCh Amines into Carbyl amines 89 amines into alcohols 90 9o1 92 Aneline into tri bromo aniline 93 Bry CH-CO-Cl Aniline into Bromo Aniline AMCHCO)0ORGANIC REAGENTS 94 | HNOy CH-CO-CI Niwo aniline ACHCO);0 95 | HySO, ‘Sulphonation on aniline 96 | CuCl,CuBr.CuCN.RI,H;0, | Diazonium Cholride into Chior Benzene, HyPO; or CH3-CH>-OH Bromo Benzene, Benzo nitrile, lado Benzene . Phenol,Benzent respectively sapereNAME REACTIONS Acetone 1. | Finkelstein CHiBr + Nal CHyl + NaBr 2. | Swarts CHy8r + Agy. ——————> CHF + AgBr Hy 3. | Friedel-Crafts Anhydrous AICI Alkylation + ayc—a 1 4. | Friedel-Crafts cH ,coct Acvlation Anhydrous AICL 5. Wurtz 4,c—a a—ctH aid . x + 3 ae Hyce——on, + Nad ' 1 6. | Fittig 2Na oO = oO —— ay eter + mei g 7. | Worte-Fitti Na . + a—a, 4, + maa Ory ether oH ou a: | “deme Non nee, cooH aa iH Na on CHCl + Na OH 9. | Reimer-Tiemann ee ae AHO Williamson CH3-Br + CH;-ONa CH 3-0-CH, + NaBr 11) Stephen #c—en ee RCN SnCh FHC ——= Hyc—c4 ann 4yc—cHO12. Etard CHO 13.| Gatterman ~ Koch cornea Anhydrous AICI 5 ° 14,] Rosenmund i Ha reduction Hye er Pd /BaSO, Qo 15.| Clemmensen ll 2n-Hg c > agen reduction Hye oH, Cone. HCI =e 4 1) NH NH 16. Wollff-Kishner il anne? Acasa ; € 2 reduction 4,67 cn, il) KOH / Ethylene glycol ee 17,| Toltens’ test R-CHO+2 [AgiNHih]" + 3 OH R-COO' + 2Ag! + 2H,0+4NHs 18.| Fehling’s test RCHO+2Cu* + 5 OH R-COO' + Cu,0} +3H,0 4 1, / NaOH 19.| fodoform t cit f+ CH COO Na Hye7 Son, OR, Nao! dil NaOH 20.| Aldo! 244ye—co Hg CH tH cho —S occ = cHicHO condensation ‘Cone. NaOH 21,| Cannizzaro HCHO 4 HCHO ~—————_» HCOONa + HC —OH 1) Cl, / Red Phosphorus 22.) Hell-Volhard- 4yC—COOH > cco Zelinsky (HVZ) H,0 4 9 23.| Hoffmann fl Br, bromamide 4y¢——c x, ———_> 4, degradatian NaOH24 7 a Carbylamine R-NH, + CHCl + 3KOH —————™ R.NC + 3 KCl + 31,0 25, Hy nfo Nano, + ailHe! Diozo ane 273-278 K 26 vo cd Sondmeyer. io every or mn 27, nyo q cus Hct Gotterman CO é ems 28 . oH Distinguish By a Single Chemical Test All aldehydes ( R-CHO) give Tollens' Test and produce silver mirror. RCHO + 2 [Ag(NH,),]” + 30H —> RCOO’+ 2Ag L + 2H,0 +4 NH, Tollens' Reagent silver ppt Note: HCOOH(methanoic acid) also gives this test, ketones (RCOR) do not give this test All aldehydes (R-CHO) and ketones(RCOR) give 2,4-DNP test RCOR + 2,4-DNP -> Orange ppt R-CHO + 2,4-DNP—> Orange ppt Aldehydes and ketones having CH,CO- (keto methyl) group give lodoform Test. Alcohols having CH,CH- OH group also give lodoform Test. CH,CHO +31, +4NaOH — CHI, 4 + HCOONa +3Nal +3H,0 Yellow ppt The following compounds give lodoform Test: ethanol (C,H,OH), propan-2-ol (CH,CH(OH)CH,), ethanal{CH,CHO), propanone(CH,COCH,), butanone (CH,COCH,CH,) pentan-2-one (CH,COCH, CH,CH,), acetophenone ( PhCOCH, ) All carboxylic acids (R-COOH) give Bicarbonate Test RCOOH + NaHCO, > RCOONa + CO, T + H,0 effervescence Phenol gives FeCl, Test CH,OH + FeCl, -> (C,H,O),Fe + 3 HC (neutral) (violet color)10. 11. 12. All primary amines (R/Ar -NH,) give Carbyl Amine Test RNH, + CHCI, + KOH(ale) » RNC + KCI+ HO offensive smell Aniline gives Azo Dye Test ( Only for aromatic amines) GH,NH, +NaNO,+HCl + CH.NCI; then add B-naphthol orange dye Alt alcohols (ROH) give Na-metal test ROH + Na +> RONa+ H, bubbles Far esters (RCOOR) : Hydrolyses first. Then see the products ( acid & alcohol) and givea test to identify them, All alkenes (C=C) and alkynes (C=C) decolorizes Br, — water from red to colourless Lucas Test to distinguish primary, secondary and tertiary alcohols Lucas reagent: ZnCl /HCI 3¢-alcohol + Lucas reagent —+ immediate turbidity 2'-alcohol + Lucas reagent — turbidity after sometime 1-alcohol + Lucas reagent — no turbiditySCHEME ~ 1: Conversions related to alkyl halides RCH:CH;OH | 1° alcohol Ri Hee OH) 2° alcohol R I R-CH3— 5 —OH| 3° alcohol R" RCH:COOH| Carboxylic acid RCH:CHiCI]+ 2Na + CICH:CH:R Seer Mg. ether Alkyt halide Alkane R ke. KOH ae ROW fecH= cH: | 22» Rupr CHB a Alkene 2,0 Alkyne ay. KOH a RcH:CH.OH] FF¥> RcH:CHO] Aldehyde Alcohol Uy [eto RCH:CH:NH3 RCH:COOH | Carboxylic acid ~ HCI Alkyl amine‘onversions related to aryl halides ca Aryl halide — NOH »., dil, HCI [623 K. 300 atm Oro: ©)-on Sod. phenoxide Phenol eee o OES +2 Op nn +cuct +H:0 Aryl amine cca K Ores 1CuRe Cyanobenzene Mg ether O- MgBr Phenyl magnesium bromide eet O} Lit Libr Pheny! lithium — CHI Joe, crt, + ana Toluene naa Se + 2HCI Ni-Al NaOH Benzene [Ce Qra ‘ Oa cl o-dichlorobenzene —_p - dichlorobenzene HLSO., Bene Qua + Hs0. Op onasito Sod. phenoxide |» ()+20 Benzene NH; ‘Aahyd. 20h. a the eK | Aniline CHNCOCI or |_cHicoro Op ococi, AS > AIGA. on + HicocO)-on | Pyndine =HeL oo o- phenyl acetate P- phenyl acetate ee O)-on + Br-O)-on Br o-bromo phenol ——_p- bromo phenol Br | 382 __, py. O+ 3HtBr ‘Br 2, 4, 6-tribromophenol [A HINGD rou +No{O)-on @-nitrophenal p-nitrophenol Cone. | Conc. H:80. am Opon SOH 2+ hydroxy benzene sulphonic acid [ cone. 1:80. ak Hs0:O)- ou 4+ hydroxy benzene euinhonie eciA-u Cone. HNO: + 0: is _eno: OH 3:0 ‘NOs 2,4, 6 - trinitrophenol (Picric acid) Anhyd. ACh [aaa nies ® OL On + he Op-on o-cresol p-cresol |__ Non (CH\CO).0 5 : [eos Tam” Ol-O# E> Oy ococts+cricoow ise! ‘COOH (COOH Salicylic acid Aspirin 3H2,Ni O- OH Cyclohicxanol Ou [2 —+ 0 = )e0-.0 Cra p-benzoquinone CHC NaOH Phenol 340 K HCI Q oH Reimer Tiemann reaction CHO Salicylaldchyde CChNaOH |_ 340K HC freon OX i Reimer Tiemann ‘COOH Salicylic acid FeCl, ( ) (O—O) Fe+ suet 3 Ferric phenoxide NCI Q-" O-n=n-O- on + er p+ Hydroxy azobenzeneSCHEME — VI: Conversion related to aldehydes Aldehyde H, KMnO, Wollf Kishner Reduct NIT - NH:+ KOH + glycol Clemmensen Reduction Zn (Hy) > HCL or IN RCH2COOH cone HSOu RCH CHO] —S—> RCH = CH Alcohol ron RrcHcx.ci] Ale! halide “te RCH2CH:NH3IA Ikyne amine RC=CH Alkyne AlkaneSCHEME — VI: Conversion related to carboxylic acids PClsor PCh or SOCh RCH: COOH RCH2COCI | Acid chloride Carboxylic acid: RCH: CONH: Acid amide ROH Br — 2} KOH Conc. H2804 Hoffmann Bromamide reaction Ester CaO + NaOH/ A RCH: NH2 Alkane Amine LiAIHy or B2He Alcohol Clemmensen Reduction Zn(Hg) + HCL Or Wolff Kishner Reduction NH2~ NH: + KOH + glycol Or HI/Red P Alkane NH:/Ni Quinoline AldehydeSCHEME —~ VII: Conversion related to alkyl amines RCH: NH: R'COOH Carboxylic acid ‘Schit?'s base CHCh+ 3KOH(ale.) ‘Carbylamine reaction RCH:NC_|+ 3KCI~ 31:0 Tsoeyanide HNO; RCH:OH ‘Alocobol s I RCH:NH— C—SH| Dithvoalkyt carbasme aaa a tsothiocyanate ° «lt o ci-c—c 1 NH—C—NH—CH3—R| ‘Symmm, disubstinuted area (e) RCH:NHOH [o] alk. KMnOs Hydro? amineSCHEME — VIII: Conversion related to aryl amines #:0/4 NaNO: + HCI — ArNH: be fa cl Rel C Biszontum amine Chloride Phenol Cyanobenzene lodobenzene Fluorobenzene Bromobenzene Chlorobenzene Nitrobenzene Benzene =N—O>—R" zodye Thiophenol ASCENDING SERIES (1) By Wurtz Reaction R-X+2Na+x—-R—Dorelet, pk + aNux Dry ether R-X+2Na+X-R SE R_ Rs 2NaX (2) By Using CyanideRed P+ KCN RI ROH RCHOH alkatine KMnOu {o] RCH2NH2 RCOOH Br/KOH RCONE: « Nia Hoffmann bromamide degradation (2) Decarboxylation reaction Clyho RCH:c} —“E KOH, rH RCHs alkaline KMnO. RH [0] CaQ + NaOH NaOH RCOONa <—————- RCOOHLR-Clvs R—-Br vs R—1(R walkyl or aryl) { SNe. |" Test R-a R-1 a) | Dil Rc BNO, Aycl 1 gl AgNO: {White ppt) (Pale yellow ppt) (Yellow ppt b) | NH,OH | abosepm > hg. NM above ppt + tq. NH or ‘above ppt? hig. NEL or test ofagc) | or SILOM siaise | Stow j men | ee (ee IL Ethylidene chloride (Geminal) vs Ethylene Dichtoride (Vicinal) cH nC | Cle CH eh wane ame on cn. Yellow ppt SNo.| Test ee {Ethylidene chloride) Byline scbleride: | a) | AgKOI test De ll (Hydrolysis) | CH. CH 898 Jott ay AKON, (ydraiysisy a f al ge cn ee ou qe Ho, oy ” aoa OH OH 2s cc: So NHNH: 10 ON NH No: NO: 2.4 dimtro phen! Iyderine 2,4 dinirophenyl hydrazine No reactionHL CHCl; vs CHyCVCCL/CH;OH 7 cack CHLCUCCL/CHOH a) | Carbylamine @ | @ ten RNH: = 3KOH + CHCh (Y amine | (aq) No reaction RANG © OKC + LO nyt ride TV. CH; - CH: — OH (Alcohol) vs CHs— O — CHs (Ether) [SNo. [Test _CH,- CH, -OH I CH-0-CHy a) | Na metal test @ we | lon ct Om Na eet ae ond | | | b) | fodoform test T © (for alcotiolx CHENOI « «XL0IT ah Ae cams: “ having TICOONa + SNal = S1L0° fesstoom Clls-CH- OH) | v. OH ge CH) -CH:-CH:-OH ys CH ad CH vs CH ¢ CH vs I r cS (scot) on (sent) (seo) OH (Phenol) SNo. | Test yan abc] eh cay i cH ow on bee at dan slecol ¢PhcnatVier | ENG a F © » er fe an bon ‘Test I CHCH-CHA col nafs, on [ee CWCH CHINO: Ts Jeo sare, ome ct g se | ak gH a ou Sow so, salroo irae Ast : {ne « rom ‘ an eat Bes 8 Bla Rel Colton ‘ o Oh Peso (es Wine Colesaratian Mamartion ven | Cotutess MI. va OH a) LOFT {oy cHLON Test | [Litmus Test | Tums tlue Litmus to red | @ @o Cn @ [Neutral FeCl | on 0 | test ; fet { I | ‘ Ferrie Phone + ICL (vtoet ppp©) | Indoform Test @ ] ] @ (0) pro-am on VIL. HCHO vs CH»CHO ‘SNo. Test HCHO CH,CHO a) | Todoform test és ° WN (EN C= AN@O = My —e OH ‘ation “MCOONa - 381-3150 HCHO - SNH, —= (aN. o | a ia | ws Liquor Weramethiene HQ -Ni— etl, cars Ammonia Test ermine Aktion prodast, (uroropees vin. i i ener # ew enw ()-LLO) @ cnc @ (6)-e f ; 5 \ I 4 @ -€- ah ow HE CH cn. CHG Cew [Tadatorm S So test © Sy —*CHhd - HCOONa oF Ciellony ° 2 3Nal + Il ee, cH GCHy on CHI Na+ 3H0+ CHLCHCOON oF CH.COONe or Kop tom b) | Tolten’s reagent @ @ @ 8 famm. silver CHCHO + any nitrate) AABN) +381 — BAgINth n+ cucod? - @ sof NHP > 2agh + wast + HO + 3NHL ©) | Fehting’s seis eS 8 8 & (copper sulphate + ancnio+ ‘Oxidation is sodiem NCO » NaOH very difficult Potassium 1 tartarate } ‘0 eancoo? + 2 NP cao so ted ppon court i i win @ anton @ @ [SNe] Test 3 ; oii coon 1 Con cH, -€- on K-. | a) Tallen’s test e @ @ e HCOOH ABO 00s 0+ zn b) Fehilng" 5 @ 9 Solution @ test fe | NaHCO oy @ @ | atest HCOOH + NaltCO. —sHc00N. + 0 + Ot ink Etlervescence —crco0Ns + 10+ COt uy Eo CGUTE NAC,3(0) - ren © 3 Vise ppt ot fem phenowe ©) | Carbylamine G ic) test R-Nis + 3KOH © ~ (amine) (ag) CHG RNY + SKOH + CHC allt 9) Laat poeard (amine) | (Paget wvelingy KCI + HO. = + 3keI- 0 Phayt Isocyanide {__tets lings @ | AwDye Text | Azo dye formedis | nN © we tte [KOM aS eee ~ removed from solution a ¢o)- on Ong — tL R-Nifivs R:NH vs RN SNo. Test R-NE RNA RN (1° amine) (2° amine)3) | Carbyfamine | RON: + CHER = 3KOR @ Test J ea RNC +IKC + H:0 ally! inocyanide {Pungsxt smsting) by) | Nitrous Acid NW HO WO RN Hew So Test ROW -Nt- HO ee acts - eatin lh amine Reston of straes ‘eth ue) ~ Phenol Sete Grae low c) Hinsberg’s Test (Hinsberg’s Reagent is a mixture of (i Benzene sulphony! — 6) (#) KOH, and { (ai) HCL Neat itensene salphonamide ‘insane wasn YON Ho, MA eatino, (Water Soluble) t —4 a =o | Neen ete Jw keNner “Tratkyammonium chloride (Soluble m HCIR-CONtE we RON SNo. Test 9 R-~NH; R A a a) | Litmus Test No response to litmus Red litmus changes to Blue b) | Carbylamine test 3 6 ? RENE + CHC + IKOHI (aq) > RNC + IKCH+ SLO Mist tocyanite XIII. RNO; vs RONO SNo. Test R—NOz RONO a) Reduction BNO; + OH —* RNH: + 214.0, RONO + oH —+ ROH + NH) > 10 (SHC b) | NaOH Form's soluble sodium salt Readily hydrolysed to give corresponding alcohol and soxlium nitri RONO + NsOH —+ ROH XIV. RCN ys RNC SNo. Test R-NO: RONO a) | Solubility in Soluble Tasoluble water by | Reduction RENAN — RCHENTE RNa — RNG followed by iomne 4 nitrous acid: Jo, Ji80: treatment: ROH -Nt- HO Evolaiun ofromoac R-N-N-0 +180 cis win tone° k-can 22. Reon, RONTe + HOES oe RNH: + HCOOH mo ome Fomve sc HN + RCOOH Carboxylic mid a) No effeat Alkyl eyanide is formed© Hydrolysis HCN He RcoR wf uN + RCOOH Cathoxyhic Heating ‘No effect ‘Alkyl cyanide is formed10 11 12 13 ORGANIC CHEMISTRY CONCEPT BASED QUESTION & ANSWER Bond enthalpy decreases as : CH,-F >CH,-Cl > CH,-Br >CH,-| Because C-X bond length increases from F to! due to greater size Phenol can not be converted into chlorobenzene by using HCl Because C-O bond in phenol has partial double bond character and OH gr is attached to sp carbon Thiony! chloride Is preferred to convert ROH into RCI Because the side products are gases and the product can be obtained as pure 3 alcohol easily can be converted into alkyl halide Because 3” carbocations are stable Benzene is converted into lodobenzene in presence of oxidizing agent like HNO, or HIO, CH, + |,/Fe 45 C,H,| + HI Because HNO, or HIO, oxidises HI and prevent backward reaction ROH is converted into RI by using KI inpresence of H,PO, not H,SO, H,SO, converts Kl into HI and than into |, B.pt. of alkyl halides (RX) is higher than hydrocarbons Because R-X is polar so there is dipole dipole attraction B.pt: RI>R-Br>R-Cl>R-F Because molecular mass decreases so van der Waals force decreases fram Ri to RF B.pt: CH,-CH,-CH,-CH,-Br > CH,-CH,-CH(Br)-CH,> (CH,)CBr Because as the branching Increases surface area decreases so van der Waals force of attraction decreases p-dichloro benzene has higher m.pt than ortho and metaisomer Because p-dichloro benzene has symmetrical structure so it fits well in the crystal lattice Alkyl halide (RX) with KCN gives alkyl cyanide (RCN) where as with AgCN it gives isocyanide(RNC) KCN is ionic and CN is ambident nucleophile but it link thraugh C because C-C bond is more stable than C-N. In the other hand AgCN Is covalent and links through N only 5,2 reactivity : CH,-X > CH,CH,-X>CH,-CH(X)-CH,> (CH,),C-X (1'>2°>3") Due to steric hindrance nucleophile can not approach easily. In $,2 path release of X and linking of Nu take place simultaneously 5,1 reactivity : CH,-X < CH,CH,-X < CH,-CH(X)-CH,< (CH,),C-x (1°<2%3°) Because 5,1 path involves formation of carbocation intermediate. And stability of carbocation isin the order ; CH,"R-Br >R-Cl>R-F Because as the size of halogen increases C-X bond becomes weaker Aryl halides ( C.H,-X) are less reactive than alkyl halides(R-X) towards nucleophilic substitution Because in aryl halide C-X bond has partial double bond character and X is attached to sp’ C. there is also the repulsion between Nu- and benzene ring which iselectron rich Chloroform is stored in dark coloured bottle as closed and completely filled Because in air and light it converts into poisonous phosgene gas(COCI,) In many countries DDT has been banned now Because of its slow metabolism and it has toxic effect on aquatic animals Cyclohexyl chloride has greater dipole moment than chloro benzene Alkyl halides are immiscible in water although they are polar In water there is intermolecular H-bonding but there is less attraction between R-X and H,O Grignard reagent(RMgx) should be prepared in. anhydrous condition Because RMgxX reacts with water and gives corresponding alkane Alkyl halides undergo substitution when treated with aq KOH but in presence of alc KOH elimination takes place Alcohol + KOH produces RO” which is a strong base so it extract _H” and elimination takes place C-O-H bond angle in alcohol is less than regular tetrahedral angle Due to Ip-Ip repulsion In phenol the C-O bond length is less Due to i) partial double bond character ii) O is attached to sp’ carbon In ether the R-O-R bond angle is greater Due to repulsion between two bulkier R group To convert acid into alcohol LiAIH, is not used Because itis expensive so : RCOOH —RCOOR' then ester is reduced into RCH.OH by using H,/Pd b.pt of alcohal{ROH) is higher than alkane(RH), ether{R-O-R), alkyl halide(R-X) and ary! halide(Ar-X) Due to inter molecular H-bonding in R-O-H. b.pt: n-butyl alcohol > sec. butyl alcohol > tert. Butyl alcohol Because as the branching increases surface area decreases so van der Waals force of TaN ae eles28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 Alcohols are highly miscible in water Que to H-bonding with water Acidity of alcohol : R-CH,-OH > R,CH-OH > R,C-OH Because as the R gr increases +! effect increases so alkoxide ion becomes less stable Alcohol is weaker acid than water Because R-O" is less stable than HO Phenol (Ph-OH) is acidic in nature Because phenoxide ion( Ph-O") is resonance stabilized. Acidity: nitro phenol > phenol > methyl phenal Because -NO, group is electron withdrawing it further increases the stability of phenoxide ion where as-CH, groupis electron donating it destabilizes phenoxide ion Esterification is carried out in presence of small amount of conc. H,SO, Because it absorbs the water produced and accelerate the forward reaction. RICOCI +R-OH > R'COOR+ HCI. Pyridine is used in this reaction Itis to remove HC! produced and to prevent the backward reaction Tert. Alcohols are easier to dehydrate Because the intermediate tert. carbo cationis stable. -OH group in benzene ring is ortho and para directing for electrophilic substitution Oue to +R effect it increases the electron density at ortho and para positions ‘o-nitro phenol is steam volatile( low b.pt) but p-nitro phenol is not In o-nitro phenol there is intra molecular H-bonding. But in p-nitro phenol there is inter molecular H-bonding so molecules get associated and hence it has comparatively higher b.pt Phenol with aq bromine gives 2,4,6-tribromo pheno! but in non polar medium mono substitution takes place CuSO, and pyridine are mixed with ethanol used for industrial purpose To prevent its misuse. CuSO, gives colour pyridine gives smell Ethers ( R-O-R) are potar Ethers are soluble in water Due to H-bond with water and ether Aldehydes (R-CHO) and ketones (R-CO-R) have higher b.pt than hydrocarbon and ether Because they are polar so there is dipole-dipole attraction in aldehyde and ketones Lower aldehydes and ketones are miscible with water Because they form hydrogen bond with water45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 Aldehydes (R-CHO) are more reactive than ketones (R-CO-R) in nucleophilic addition In ketone the two alkyl groups ( R) have +1 effect so they reduce the electrophilicity co carbonyl carbon. Also there is steric hindrance in ketone Benzaldehyde ( C,H,CHO ) is less reactive than propanal ( CH,CH,CHO ) Due to resonance the electrophilicity of carbonyl carbon is less in benzaldehyde NaHSO, is used for separation of aldehydes It forms a soluble compound with aldehyde which on hydrolysis give back the aldehyde ‘a-H of aldehyde and ketone is acidic in nature Because the corresponding carbanion is resonance stabilized Carboxylic acids ( R-COOH ) do not give nucleophilic addition reaction like RCHO & RCOR although it has >C=O due to resonance the carbonyl carbon looses its electrophilicity Carboxylic acids have higher b.pt than aldehyde, ketones and even than alcohols There is extensive inter molecular H-bonding in carboxylic acid(RCOOH). Even in vapour phase it exists as dimer Carboxylic acids are miscible in water Due to H-bonding with water R-COOH is acidic in nature Because the conjugate base R-COO (carboxylate ion) is stable due to resonance Acidic Strength : Cl-CH,-COOH > CH,-COOH > CH,CH,-COOH Because Cl has -| effect which stabilizes the conjugate base and ethyl gr has +1 effect In amines the C-N-H/C bond angle is less than 109.5° Due to Ip-bp repulsion For reduction of nitro compounds into amines Fe/HCl is preferred instead of Sn/HC! Because Fe + HCI a FeCl,. on hydrolysis FeCl, gives HCI. So just small quantity of HC! is required to initiate the reaction To convert alkyl halide(R-X) into amines (R-NH,) ammonolysis is not suitable Because on ammonolysis a mixture of pri, sec, tert and quaternary amine will be produced Aniline on expasure to air and light turns into coloured Due to atmospheric oxidation Lower amines are soluble in water Due to H-bonding with water. In case of higher amine alky! group is larger which is hydrophobic Amines (R-NH,) are less soluble than alcohols (R-OH) In alcohol the H-bonding with water is stronger because O is more electronegative than N Amines (R-NH,) are lower boiling than alcohols (R-OH) In alcohol the inter molecular H-bonding is stronger because O is more electronegative than N60 Order of b.pt: primary amine > sec. amine > tert. amine The no of N-H bond decreases so extent of H-bonding also decreases In gaseous phase the order os basic strength : 3°-amine > 2°-amine > 1°-amine > NH3 Due to +1 effect of alkyl groups the electron density on N increases. So 3° is strongest as it has 3 alkyl groups In aqueous state the base strength order : (C,H,),NH > (C,H,),N > C,H,NH,> NH, (2°>3°> 1°> NH,) : (CH,),NH > CHNH,>(CH,),N>NH, — (2°> 1°> 3° NH,) In aqueous state +I effect, steric effect and solvation effect interplay. So the order is nat regular R-NH, is stronger base than NH, Due to +! effect of alkyl group electron density on N increases in R-NH, Aniline ( C,H,-NH,) is weaker base than NH, and R-NH, \n aniline the lone pair of electron of N is involved in resonance. So it is less available. Base strength : p-methoxy aniline > aniline > p-nitro aniline Methoxy group (-OCH,) has +R effect where as -NO, group has -R effect so electron density in the first case increases but in the second case it decreases. Acylation of aniline is carried out in presence of pyridine Pyridine removes HC! produced and favours forward reaction -NH, group in benzene ring is ortho -para directing for electrphilic substitution Due to +R effect it increases the electron density at ortho and para position Bromination of aniline gives 2,4,6-tribromo aniline Because -NH, group activates benzene ring by +R effect. So for mono substitution -NH, group is acylated. Nitration of aniline gives unusual meta-nitro aniline although -NH, group is ortho-para directing In presence of acid -NH, is converted into -NH,’ which Is meta directing Aniline does not undergo Friedel Craft reaction Aniline is base and reacts with anhydrous AICI, so N becomes positive which deactivates benzene ring.