a) Electrochemistry(l)—Electrofysisit is the process of dissociation of an electrolyte when an electric Current is passed through either its molten state or its aqueous solution. 2) Electrolytic cell -an inert container e.g made of glass; anode clectrode (where oxidation takes place) that is positively charged and a cathode(where reduction takes place) which is negatively charged ; they can be inert e.g.Pt or reactive e.g.Au or Cu. 3) Products of electrolysis : > dissociation of the electrolyte into ions takes place and are directed to the oppositely charged electrodes and this depends upon a)nature of electrolyte ; b) type of electrode —~ inert/reactive; c) oxidizing and reducing species present in the electrolytic cell and their electrode potentials: at the cathode species with higher Eves value gets reduced(even if there is a competition between 2 reactions); and at the anode, species with lower E%.g value gets oxidized (even if there is a competition between 2 reactions); and d) Overvoltage/ overpotential ->extra voltage supplied for a kinetically slow electrachemical process to take place which otherwise do not take place at lower voltage); Examples: 1) electrolysis of molten Nac8: —_NaC{l) > Na{l) + C8“(l) . On passage of electric current: atcathode Na*(l) +e” > Na(s) (reduction) atanode:- C8"(l) 9% Cér(g)+ &° (oxidation) Net reaction : Na'(I) + Ce“(l) > Na(s) + % Cea (e) 50, Na(s) is deposisted at cathode and Ces gas is liberated at the anode. 2) electrolysis of aqueous NaC2: 2 sets of reactions are taking place here : NaCe(aq) > Na*(aq) + Ce"(aq) HO >) HY + OW ‘At cathode : Nat and H' move towards the ccthode but H* will get red Wie" 3s "wy, 0.0 Vis higher than that of E'ysyua= -2.71V . So, Ha gas is liberated at the cathode. While at anode: both Ce" ions and OH” ions can get oxidized ; and even though, Evoir/H0x%0, = 1.23V islower than E* ce pice, = #1.36V , itis C8" that will be oxidized and Ce, gasis liberated at the anode . This is because oxidation of water is a kinetically slow reaction and an over voltage is required for it. Oxidation of water is represented as : OH" > 2H,0 + 02 +4e7 Sonet reactionis: 2NaC&-+2H,0 > 2NaOH(aq) + Cex(e) + Hale) 3) electrolysis of dilute sulphuric acid (H,S0s) : (even by using Pt electrode] The 2 competing reactions are: H:S0; > 2H *(aq)+ SO. (aq); - H,0 (I) > H'(eq). + OH"(aq) ‘At cathode : 2H*(aq) +2e” DH, (g) : reduction of H* to Hx(g), takes place. & at anode: 2H,0(l) > 0, +4H"+4e; i.e. oxidation of H:0 to Ostakes place in preference to oxidation SO,* to $0: ie : 2$0?"(aq) > S20s*" (aq) ; as reduction potential for oxidation of water , even with an over voltage, ie. E’oi/#,0.0, =1.23V is lower than E's =1.96V forthe oxidation SO," to S,0,"" . So, net reaction : H,S04 + 2H.0 2 Halg) + O2(g) + SO4* (aq) 4) electrolysis_of concentrated sulphuric acid (H;5Os) at cathode : 2H*(aq) #2e” > He (g) ; Ej-= 0.0V or 0.83V atanode : 2S0."(aq)> S:0e* (aq); Ered = 1.96V Net reaction: — HzSOs (I) > H2(g) + $206" (aq)® 5) electrolysis of ag. Salt solutions containing F~,C€~, Br”, I” results in liberation of C@2 (q), 8r,(q), and |; (q) are liberated at the cnode but not F,(e) 87V is higher than that of E“ow-y4,0,0, =1-23V with overpotential, 36V, Ea, =1.09V & E\yar =0.54V are lower than that of 23. 6) electrolysis of CuSO, solution using Pt electrode_: CuSO,(aq) > Cu*(aq) + S0,-(aq) & —H20(I) > HY (aq) + OH(aq) are two competing reactions. At cathode : Cu**(aq) +2e7 > Cus) 5 at anode: Net reacn. H20(I) > 02 + 4H" + 4e (oxidation of H:0) CuSO. + 2H20 2Cu + 02 +4H* +250,2" Thus Cu is deposited at cathode and 0; is liberated at anode. 7) electrolysis of CuSO, solution using Cu electrode: CuSO,(aq) > Cu*(aq) + S0."(aq): #20 (I) > Ht (aq) + OFT(aq) At anode, oxidation of Cu metal: Cut E°on 0,0 =1.23V At cathode, reduction of Cu* ions from the electrolytic solution takes place, Cu**(aq) + 22° Culs) ; since E*cwjeu=0.34V_ is more than that for reduction of H* ions LeE aan = 0.0V ‘Thus Cu dissolves at anode and Cu is deposited at cathode. (s) > Cu**(aq) + 2e" ; since E“cusycu = 0.34V is less than 8)electrolysis of AgNO; solution using Aq electrode AgNOs(aa) > Ag*(aq) + NOs" (aq #20 (I) > HY (aq) + OHaq) At anode, oxidation of Ag meiaic Agis} > ABYagPHe pute E EFownoo, =1.23V . At cathode, reduction of Agtions from the electrolytic solution takes place,Ag*(aq) +e” ->.Ag(s) ; Since E"»gr/ag = 0.80V is more than that for reduction of H* ions i.e.E"2in, = 0.0V Thus Ag dissolves at anode and Ag is deposited at cathode. 9) electrolysis of AqNO; solution using Ptelectrode_: AgNOs (aq) > Ag*(aq) +NOs"(aq) & H,0\(I) > H* (aq) + OH"(aq) are two competing reactions. At cathode :4 Ag*(aq) +4e” > 4Ag(s) ; at anode: 2H20(I) > 02 + 4H* + 4e” (oxidation of H20) Net reacn. 4 AgNOs (aq )+ 2H:0> 4Ag + 0, +4H* +4NO3" ‘Thus Ag is deposited at cathode ,as E°sg-ag = 0.80V is higher than that E*2u4, =0.0V and O;is liberated at anode,since "seq for oxidation of NOs” is higher than that for oxidation of water i.e. E°on/H,0,0, =1.23V . 10) electrolysis of CuC@, solution using Pt electrode_: “ Cucealaq) > Cu*(aq) + 2Ce“(aq) ; : & H,0 (I) > H* (aq) + OH" (aq) are two competing reactions. At cathode : Cu**(aq) +2e” > Cu(s) ; . at anode: 2C@"(aq) > Ce2(g); E°ce,/2ce-=1.36V_ is lower than E°owjx,0,.0, =1.23V ; for: H,0(l) > 02 + 4H? + 4e (oxidation of Hz0) which requires an overpotential. Net reaction: CuC@,(aq) + 2H:0(I) > 2Cu(s) +Cea(g) sited at cathode and Cé, is liberated at anode. &XU Organic Chemistry Conversions Road Map * RCH,CH,CH,OH H HCHO eee RCHCH; ~"—7—=—+|_(1° alcohol) RCHO [R CH;CH,—CH—OH fo “| @ateonon ___, [R— CH,CH2MgBr] econ” RF (Me, dry ether! Grignard reagent RCH,CH | oti 2 | (3%atcohol) |_©02___ -RCH,CH,COOH RCH,CH2Br Dy __ /RCHACH{CH{CHLR . alkyl halide [* 2 Na + BrCH CHAR e+ Ene (Wurtz reaction} -2NaBr aie lac Kou NaNHgiKNH [Roa CH] 3|8 R CHBr—CHABr —Fsic. KOH |_Allyne 2 IS [29 KOH Fe GHCH,on |Sw573 KF GH,CHO aldehyde Terri [Acidic KMnO, faik. KMn0, comida af Fluoroalkane ik CHZCOOH| fRCH{CH,NH, 1° amine ken [FR CH{CHZCN | H20/H" ff CH,CH,COOH]. Cyanide Carboxylic acid Agen [RCH,CHANC ]|__HaINi/Pd__ RCHjCH,—NH—CH, Isocyanide__ [or LIAIH,/ether (2° amine)iia Naot, SILKE! (7) (Phenol) (Dons process] © Os" 6 ° 300at™ (enzatéehyded 1 coceo,c1 ©-x fest pate, ())en BW (O) NH, (Oy-200r Cel, Hy Benzonitrite (Benzamide) (Benzoie acid) (HY M50" Crotueney 1 © i Etard reaction a 7 Paes ‘ Alo ZO rngrecion q eon Cra uae! 8021 )_coons N= sen ClyiAnh Fels Qe . (O)- fe 1 edichlacbentene pdichirabensene ncn, | HeS04 leone) AY, ) O oO ee ans pa - Oh Op w10-{O)-2 vo ete o-chleronitrbenzene Lcuscunc oe Ox + 04-(O)-e city PeNTeuene ochleretstuene Cone. Haiti | R—CH;CHy FF COOgH, CHAR] nS0vs [Rooneon_| * (alkane) 'RCHCOOH. 443 K (alkene) (Dehydration — + [rcs -—ch | AIkKino, 02%: #280] f° COOH a er RCH2CHO Cw573K _| R—CH,—CH,OH| HSOa_ | RCH,CH,0CH;CH2! aldehyde ["or PCC orCrOs) (alcohol) 413K (ether) or lk, KMAOs | K2Cr203/HsS04 (cxidation) FOH,COOH PCls__,[RCH,—CH,Cl]_NHs , [ACHACHANHA] carbonic acid (alkyl hatide)|-HOI"{ 1° amine Note}. Lo * R RR ~\ cro, aS f Hon. 2241" Sono Acigitied, | B/E aleoton R/ ketene | RZ Rsinon Kian, "| RCO} + CH:COOHdil. HCI CH,CHOH—CH,(2"alcohol) / LAI NaBH, [ecusecheects ef GMs 3 eduction CH3—-C=CHCOCH, «9 CH, —C_—CH,COCH «tll. NaOH 1 Za (Hg) + Holor = GHz-OH emethyl-pe oo Ichiy—C—cH,| NHe—NH KOH CO! Ly oy Sen-2one OH uf Ketol R =H,0 ] CH Ai) Rig . | | I (i) NH. 7 CH —-C—OH CH,—CH—NH, J 1,07 : Hac | OCH, ‘sopropyl amine Hi) HeINE : H (3° alcohel) Hye? “Sodu, (2° amine) tKetal) Goch, | —_oH _. + CHI. I 1p (Haloform) Yellow ppt. oO COCH,CHN (CHs)2 Acetophenone HCHO + (CH), NH Mannich | reaction quia, CHOH—CH, O co (2* alcoho!) NH. aD NHy 2,R CH,CONH, ROH *——RCH;COOR Pr Amide (Ester) ROH BrJKOH + 5 Hofmann cone. HO, So bromamide (esterification) € ae reaction SHI RCH,CH2NH, Hs *Regpa7SK] NH,OH ICH.NH2 moras Red P7873 K] R CHCOOH t—FRo 7 R CH,COONH, (Amine) (Reduction) } Carboxylic acid af ammonium carboxylate g Nee 2 RCH,COOAg wea RCH —8r RCH,CH,OH 3 Hunediecker Bromeatkane (Wieahol) g reaction 4 bn st id *— Rewcoon 18244, g ccooH RCH, CCH CH=CHCOOH Benzoyl chlocie Tenzin ibe ore’ s ew oh de cinnanie act pe y /° CH==CHCOOH c CN cH,co,0F4=NOH Oo + CH COOH 3 Qe Che, Q P-nitrobenzaldehyde * Benronitriie. Cinnamic acid newene —— ARAERMELELI aay Schiff’s base 2 + RCH, NHC—R’+h’ COOH CH atnes \ 4 ?" Acid amide o ©, WL (i) UAIH gether Ct KMnO \ 9 u R—CH, NHCH, sho) ee A Res tenes (2° amine) RH @ tex | RCH,NH, |_# CoCr i (alkane) MERIC Amine __J”Acylation’ RCH Ht fete 4 HONO} | N-substituted amide ICHCIy3KOH R—OH i RCHNC | 4 axci +3H,0 (Alcohol) cartydmine L_lseevanide reaction HyNuPs = or RCH,NH, + HCOOH, =J | LiAlH,/ether RCH NI (1° amine) aan (Formic acid)Appendix Vil y (a IMPORTANT NAME OF REACTIONS & / 1. /Aldol Condensation, When two molecules of aldehydes -or ketones containing / ochydrogen on react with dil NaOH undergo condensation to form$-hydroxyaldehydes / or ketones. «dil Nagi 2CH,CHO' === Ch, —CH—Cll,-CHO#Y, CH, —CH=CH—CHO bn. But2enal Ethanad Bydroxyboten (Alda endensation (Ala) provet) ou | vy / CHLCHO + HcH,cHo 2%", cH, —CH_CH, —cHO / ~All bsrorybotanad 2. Cross aldol condensation. Aldol condensationof a mixture of two different lde- » J hyde or ketones, each containing an chydrogen, gives a mixture of four products, cH,cHo. +-cH,cHcHO 2" pitterent product obtained as below Ethanal Propsnal Sélf aldol condensation products OH a ‘ansoy, pe @) CH,CHO+CH,CHO ——> CH,CH—CH,CHO aro CH;-CH=CH—CHO ‘Ethanol hydroxy butanal But-2-enal HH a = NaOH - (i) CH CH,CHO + cH,cH,CHO SOF ; Cy-Ci—C-—CHo Propanal . fe, “wales x 3-hydroxy, 2-methyl pentanal _ GH,Chl-—CH=f-H0 cH 2-methyl pent-2-enal 543,3 saa eXamAitin Chemistry, | Cross aldol condensation products on CH, ~CH—E~cHO: erie ait NaOH, wary CHG ae Cs~CH=CH-CHO CH, 2emethyl, but2enal On i I G0) CH,cH,cHo + CH,CHo #1 Na0H, CH,—CH,—CH—CH,—CHO- * CH,—CH,—CH=CcH—CHo Pent-2-enal 5. Benzoin reaction. When two inolecules of aromatic aldehydes undergo condensation on heating with ethanolic KCN, to formbenzoins. —° po 8. amine reaction, When a primary am loroform and ilcoholic KON, it forms \réffensive smell 1 (aliphatic or aromatic) is warmed n isoeyanide or carbylamine having CH,NI, + CHCI, + SKOH ——s CHAN C4 3KCI + 311,0 Methyl Methanamine ehtoreforss ree Nun, c ‘ 4 CHC), + 3kon Bet, + 3KCl + 3H,0 Lf (le) brik: Sh Phenyl ~ inecyanide ‘6: Cannizzaro reaction. Aldchyde not containing an a-hydrogen atom, when ts with concentrated alkali, then one molecule gives an alcohol and another mol Eives corresponding carboxylic acid or corresponding carboxylic salt.dix VII 545 HHO + HeHo 2201, CH,OH + HCOONa Pormetaetyae HOH + eeStonete meta CcHsCHO + C,H,CHO 825 C,H,CH,OH + CgH,COONa Beosaldchyde Bentyi lech Soin berate Coupling reaction. When diazunium salt react with phenel or aromatic amine to ssiypizo compounds. The coupling with phenol takes place in mildly alkaline medium, le in case of amines it occurs in acidic medium. A. n-{)-0H +HCI+H,0 : : Pbrdonrzabensne (eng ds) ain Ker i Nena + Beneenediezonium Aniline ‘hlorde if wa Cp wp ‘+ Her HO amino azobenzene (yellow dye) 7. Etard reaction. When toluene reaet with chromyl chloride (CrO,Cl,) in CCl, or CS, to give benzaldehyde is called Etard reaction. se CH, = CH(OCrOHCI), 4, 4* CHO re Cr + Cr0,Cl, 5 0", (og Mig ae Toluene Chromium complex Bonaaldchyde is iy 8. Diazotisation reaction. When a cold solution of primary aromatic amine is treated | | de ‘with cold solution of nitrous acid in the presence of dil. mineral acid at (273-278 K), soe \ \ arenediagonium salts are formed. Ei mea NaNO, +HCl——> HNO, + NaCl i * wizous cid NH; > . N=NcT + HNO, + Hol 228K, |}! + 2H,0 iline Benzenediazonium chlorideea oe qectate, phenyl benzoate ete. on hea? 9. Fries rearrangement. Phenyl esters (phenyl : tr ‘a solvent undergoes a rearrangemen, Ang with anhydrous AICL, in pfesence of CS, and a mixture of o- and p-hydroxyketones is obtained. ne OCOC,H, on 7 A i COCs Any All, CS : o-Mydroxy = cnphonohe coc, pityaress 7 bineebbonone 19° Garbriel phthalimide synthesis. Phthalimide is converted into potassium salt by / treating with alc, KOH, then heated with alkyl halide to yield an N-alkylphthalimide “which is hydrolysed te phthalic acid and a primary amine by heating with HCl or KOH. Co. co. co. ore eng i CIC yn soit, Cie. = CIC yon, co : cow : cot ' coon nem + omen coon } co.nei CHO. / ‘Any AICI /Cur : Bonzaldehyde 12, Hoffmann bromamide reaction or Hoffmann degradation of amides. ‘The —% conversion of a primary amide to a primary amine containing one carbon less than the original on heating with a mixture of Br, in the presence of NaOH or KOH is called Hoffinann bromamide reaction. ee “" CH,CH,CONH, + Br, + 4KOH Yt, CHLCH,NH, + 2KBr + K,CO, + 21,0 sispassed thr 4 AIC], and a! reais bionte /18. Liebermann Nitroso reaction. Both aliphatic and aromatic 2* amines react with a nitrous acid to give yellow coloured oily N-nitrosoamines. oes R D>wm + now-0 eso +n,0 R R Zramine + NonitroaliylamineAppendix Vil ~ 14. Rosenmund 4 tildechydes is ¢ Ay reaction, Catalytic roy alled Rosenmund reduot CH,COCI + H, —Pwss0, ating sytem ‘duction of acid chloride tion, CH,CHO + Hel Acetyl chloride Acetaldchyde 15. Transesterification. When an ester with exci base such as the corres R—C—oR" + R—OH Il ‘aleohol Reflux’ I new alcoho} oO oO ee igor eae oO oO I lomon 2 i CH,—C—ocH, + CH;-—C—0C,H, + CH\OH Parheta® * SaHQOH “catetaneaes GOH 16. Gdttermann reaction. In this reaction ben: zene diazonium chloride is treated with /®pper powder and a halogen acid to form a ww iryl halides. (De anor, 2, (pon Benzenediazonium Chiorobenzene chloride ¢ 17. Todoform reaction. All compounds containing the group CH,CH,OH, CH,COcH, ™ en treated with halogen and excess of alkali forms haloforine sonenmrone CHCH,On + 41; + stag ——s a + HCOQNa+ 5Nal ¥ 51,0 Custe ety 4 hep ae CH,CHOHOH, + 41, +6NaOH —> CH, + CHCOONa + 5Nal+s 5H,0 J CHi,CooH, + SI, + 4NaQH ——> cyl, + CH,COQNa + 3Nal + 9HLO 1 HO) -nGr &n,coon S28", cde,coon 2", o 8coon ~ ClyReaP, c,ccoon | aby. AlCl, alkyl and acyl benzene 17, Fries rearrangement | phen! esters anhyd. AlCl, CS, ©» and pehydroxyketones \}4E Gabriel phthalimide phthalimide KOH(ale,) followed by C,H,1| aralkyl and aliphatic ‘synthesis followed by H,O/H* primary amines 19, Gattormann reaction CeH.Necr Cu powder + HCI halovenzene 3 [20 Gattermann-Kotch reaction | C,H, + CO + HCL anhy, AIC, aromatic aldehyde & “EAL. Grignard synthesis alkyl or ary! halides Mg + dry ether Grignard reagents 5 32, Haloform resetion CH,CHO, methyl ketone, CH,CH,OH, | NaOH/X, or NaOX, haloform 3 (test for-COCH, group) RCHOCH, 3 i, Hell-Volhard-Zelinsky carboxslic acid having a-hydrogen atom| Bryred P Gchatogerated carboxplic fi reaction | ee:Appendix Vill _ ee iON FOR DISTINGUISHING ‘ANIC COMPOUNDS 64 ny] ketones and all alcohols 1 SOME IMPORTANT REACT! BETWEEN PAIRS OF ORG: 1. Todoform test for ethanol acetaldehyde, all net ning CHy-CH—EroUP. . . on 4 GNa0H Heat Clit + HCOONa + 5Nal + 5H,O Yellow me Citly! + CH,COONa + SNal + SH,0 CH,CH,O1 + 41, RL ER TA IPTG LTE City —CH—CH, + 41, + 6NaOH ~ ou CH,—COCH, + 31, + NaOH _Heat, qul,! + CH,COONa + 3Hal + 3H,0 CH,CHO + 31, + 4NaOH Heat, ciil,) + HCOONa + 3Nal + 3H,0 SR ROC 2. FeCl, test for phenol / 30,H1gOH + FeCl, —— (Cell, 0),Fe + HCL vilet eslour / Phenol ~ / g. Fehling solution test for aldehyde and formic acid RCHO+ 26u** + 60H ——> RCO” + Cu,0 1431,0 | - ey i HCOOH (formic acid also reduce with Fehling solution) p 4. Tollen solution test for aldehyde ROHO + td) J" 4 3017 ——» RCOO-+ 2Ag! +2H,0 + 4NH, Silver mirror = < RCOOH + NaHCO, ——>, RCOONa + CO,1 + H,0 6. Isocyanide test for 1* aromatic and’ aliphatic amine, RNU,+ CHCl, +3K0H—>° -RNG_ + 3KC1+ 3H,0 “a , Isocyanide 2 terre nmeliog ArNHly+ CHCl, + 3KOH ——> AINC + SKC1 + 31,0 554 H I 5. NalICO, test for carboxylic acid| : } | + Ji tictiana bromemide reaction lteter seen H, PaBaSO, S, slene 1 Sabatier Senderans réaction Raney Ni, 200-300°C ‘unsaturated hydrecarbon ondmeyer reaction catytacr (CuCVEO! or CuBertB er CuCNIKCN, heat (42, sehotten-Baemann reaction | pena ran Stephen reduction C,r,coC1 SnOlJHCL 6. | aligteaniae 35, Transesterfleation fester « aleotiot | 6“0nmann rection 53 Wiliamtoneynhess heat alkyl halide + ine oF leshal) + | NaOH | heat | phenoxide [3p Mouekiviner reaction | alchodes and ketones NH,NH,, KOH, glyeol 0. Warts reaction alk halider - Nalty eth Wares Fitting reation aks hatige “ary halide primary amine alkyl or ary! bromide alkane, alkene & alkyne salicylic acid primary amine salieylaldohyde aldehyde alkane hhalo or eyancbenzene benzolyated product aldehyde fnew ester and a new | aeonot Alpenyl other hydrocarbons alkanes alkyl benzeneest for alkyl halide, cyclohalo compounds and ArCH,X. 7. Silver nitrate t RX +KOH (Aq) —> R-OH+ KX a: KX +AgNO,——> AgX ! + KINO, if AgKis = White ppt(chloro) _* Pale yellow ppt(Bromo) « Yellow ppt(Iodo) DISTINGUISHING BETWEEN PAIRS OF COMPOUNDS & ae i DISTINGUISHING BETWEEN PAS 4, Chloroethane and Bromoethane Chloroethane (C,H,C)) Bromocthane (C;H,Br) ‘AgNO, test : C,H,C1+ KOH(A) — C,H,OH | CHsBr + KOH(Ag) > CzH50H + KBr +KCl KC} + AgNO, — AgCl! + KNO, | KBr + AgNO, ———> AgBr! + KNOs white pot Pale yellow ppt Chlorocyelohexaie and chloro benzene cl on cl A + Ket 7] + KOH (Aq) —— No ppt 4+ KOH (Aq). KC1+ AgNO, —— AgCll + KNO, White ppt a Benzyl chloride Chlorober [Benzyl chloride (C, ‘AgNO, test - Cl CHOW cl Cro 80 Csr} Ceo som KCI + AgNO, —> AgCH! + KNO, White ppteXanrkit in Chemisty a 4. Ethanol and Methiunol Ethanol (C,0,0H) 1(CH,OH) Jodo form tos! Meat + CHIyL + HCOONa Yellow pt + 5Nal + 5H,0 CHOU ~~~» No yellow pnt ©,11,011 + 41, +6 NaOH 5. 2-Propanol and 1-Propanol —— - ______} 1-Propanol CH,CH,CH, 2-Propanol Cli,CH(OINCH, { Jodoform test CHy—CH=—CH, +41, + NAOH ies, | cu,cH,cu,ou—— OH No yellow ppt. : Cll, L + CHCOONa + 5Nal + 51,0 i zelow mt i tecaeeh 6. Phenol and Ethanol Ethanol (C,1,01) Phenol + FeCl, test to S0,Q01s Fect, ——» \CH,O1 » Pec}, ——+ i = (Gyn,onke + a11c1 No vioot colour Draeremtcet G,H,0H ——sNoyettow ppt | CH,CH,011+ 41+ onaomt A, CHI; L+HCOONa+ ica 5Nal + 5H,0. 7. Acctaldehyde and Benzaldehyde Acetaldehyde (CH,CHO) Benzaldehyde (C,11,CHO) + | +todoform test Hest ‘CH,CHO + 31, + 4NaOH —> C,H,CHO + I,+ 4NaOH —» i t f ‘ CHI, | + HCOONa + 3Nal + 3H,0| No yellow ppt lejos :10. de and Acetone Acetald hyde (CH,CHO) + Fehling’s solution teat CH,CHO 4 2602" 4 5011 —— CH,C00 4 Cuol He ppt 31,0 + Tollen’s reagent test CH,CHO + 21Ag(NH,),}* + 301 ——> CH, COO + 21,0 + f+ ee onc (CH,COCH,) CH,COCH, 4 Febling solution ——~ No red ppt CH,COGH, + Tollen’s reagent » No silver mirror Benzaldchyde and Acetone _ Benzaldehyde (C,H,CHO) +Tollen’s reagent test - C,H,CHO + 2/Ag(NH,),]* + 30H" ——+ C,H,COO-+ 2H,0 + 2Ag 1 + 4NH, silver + Iodoform test C,H,CHO + 31, + 4NaQH > No yellow ppt ‘Acetone (CH,COCH,) CH,COCH, + Tollen’s reagent ——> 9°, No silver mirror CH,COCH, + 31, + 4NaOH. > CHI, | + GH,COONa + 3Nal +3H,0 yellow pk ‘Sad-nentate Acetophenone and Benzophenone ‘Acetophenone (C,H,COCH,) ‘Benzophenone (C,H,COC,H,) * Iodoform test C,H,COCH, + 31, + 4NaOH —— > C,H,COONa + CHI, 1 we "etalon + 3Nal + 3H,0 C,1,COC,H, + 31, + 4NaOH ——> No yellow ppt 11. Phenol and Acetic acid : : Phenol (C,H,0H) Acetic acid (CH,;COOH) + FeCl, test 3C}H,OH + FeCl, —> (C,H,0),Fe + 3HCI Violet colour CH,COOH + FeCl, —— No violet colourpendix Xt = Synthetic pathways . . &- Reagents and conditions for specific functional group changes a (a) Alkane derivatives (aliphatic compounds) d| —H —c1 alkylehloride [+ Clysunlight =H Br alkyl bromide [+ BrJsunlight Nonca” DeHcHe | atkane HAN or HyPus25 K Br Br re =G—E—. | 1, 2 attr alkane] » Bryce . HoBr ft ‘ \ 7 11 peaey EF | Bromo stkane |e HBr or HBr Cans H OW Nc=ot ll SON eH 6— |-Aest + (cone. 11,80, (ii) warm water —Br,~ Cl,or-1 | —on ‘Aleohol + NaOH(agVKOM(agVAgOH(aq) alkyl halide —cN Cynide + KCN ‘ —NH, Amine + @Nn, —ococn, | Bster + CH,COOAg —MgBr | Grignard Reagent |+ Mg turnings in dry ether COOH . | carboxylic acid J+ (a) (i) KCN i) hydrolysivyH* —OH —a ‘Alkyl chloride + PCI, or SOCI, or HCMgVZnCly E Alcohol —Br Alkyl Bromide + PBr, or HBr(aq) or (NaBr/H,SO,) iW a: Ally] Iodide + red Pil, | —ONg | Sod. Alkoxide + Na as —OCOR __|-ester + RCOOHH,SO,(ag) as catalyst SER | Sen ; | yeecg Pome, aaa + Excess cone. H,SO fheat or Al,0,/350°C| , Alcohol : |) —cH,0n —CHO ‘Aldehyde + Cw/400°C (Redu.) or K,Cr,0,/F1"(a9) H|__4° alcohol (oxia) Re} oS No . “ | > CHOH Po=0 | Ketone + Cw/400°C (Redu.) or K,Cr,0/H"(aq) A |_~_2° alcohol (oxidation)‘oXanvkit in Chori ction condit into CHO a aaa = _e ” Aldehyde nae Carboxylic + Oxid, K,Cr,0//1"(ay) or KMn | CHOI Aleohel «Null water or HJNidheat or __|_-enonen + HCN we 7 | ae ~ peo " Meohol «= Nalily + water or HLJNisheat ketone No DeOHen | Addi = TCN ncn —coon —GOoNe | Sod. sat acid | = NaOiHlag) or Na,CO, or NAN Carboxylic acid —cCooR Ester + ROWH,SO, catalyst —cocl ‘Acetoyl chloride | * PCI, or SOCl, —CH,On 1° Alcohot + LiAlll, in (C,l}),0 —cocl —cooH Garboxylicacid | + H,0 —COOAr Ester | = Aron ‘Acetoyl chloride | —COOCOR | Anhydride = RCOO"Na* —cH,oH | 1° Alcohol + LIAIH, in (CyH,)20 —COOR —COOH + ROK + He(ayaydrolysis —COONa' + ROH + NAOH(egMhydrolysis -ester —CH,OK + ROW «= LiAIH, in (CyH1,),0 (6) Aromatic compounds ‘To convert into Teagents and conditions © —Cl «C1, + halogen carrier (AICI, or Fe —Br «+ Br, + halogen carrier (AIBr or Fe —No, « cone. HNO,/fcone. 11,50, at appro Rk ‘= RCVanhydrous Al,Cl, —SO,H «+ Reflux with cone, or fuming HySC : O- —MgBr * Mg turnings in anhydrous ether (Opie [OH +» (0, (ii) aqueous acid : *s-CH,OH + (@ HCHO (ii) Hydrolysis/A* > COOH: + (@CO, Gi) Hydrolysis/H* ©-m —O-Na* : + NaOH(cgV/623 K —ocoR * RCOCI or (RCO),0 —0COAr + ArCOCUNaOH(aq)hatic Con’ Road Map Ati i Aikene [Akane > Y % y Ww Alii hatide| Mi ¥ = Grignard les § Reagent Ig x y . J Alcohol y we t cia , a Ester ~ 4} ' iE NHs HNO, 7 q a F “Aleohet Seana balige 1f “20 eg) ——ecntoenmnnsera may u Seti Mi ese Bee, Road Map for Aromati / Conversions 1 eXam-kit in Chenfistry— on,on cant a & ~ do [] Qeitetion 5 Oxitetion omn, SN Panay, a & [ Hivdreiysia > | GHC Coen Ol ev yay | CH,OH Ay soe C7 ‘OOH Ke Ciertaeane Rem | Htydetyit sate Bena ride eect peice von etncton 0, CH; $0, one 2 Bensivnine Bons aba Ay ania 15,0, ott i i Ray ee) O CO) O el pak Benzene coor No, MH, nei A ana, (>) some, A) _| S wanes > I Se ten iunhccene ina en ad ee He, ‘ Nnow (00H Z a Phenyl hydroeyt Dimtbyleitine Phang iocyanida| emcee ae 575 Road Map for Aromatic Conversions I Ho cry Z> comnar ex,cunny, —— CH,CH,NH, em cnc CH,CH,CH,NH, Propan amine ya, tuo, Jase: Fi CH,CH,CH,OH : CH,CH,OH Propanol “acy Ethyl alcohol KOH (aq) CH,CH,CH.MeBr 7 +c1/Sunlight CHCH,CH,Cl_ _CH,CH,oH Bthyl aleobo! 600,97 [es CH,CHO Acetaldehyde NH; (0) CHMeBr- iy HOnyfr HCH, cucu-nn, © co I on. OH Propan-2-0l: HNO, CH,CH=CH—CHO . Crotonaldehydé oH, 0H on Hest on -#H,O Bthan-t,.-diol Aldehyde cH,CHO Acetaidehyde v | Oxidation K,Cr,0,/0" [| CH,COONH, Sod. acetate CH,CONH, CH.NH, cH,ct Methylamine Methyl chloride (K,Cr,0,/1) HCHO ——— . OH —_cH,CHO. cH,CN Acetaldehyde Methyl cyanide e Reduction _{ Oxidation 4(H]| Reduction + \— cu,coon caren, Aeeticacia anamine La | son HNO, ve CH,COONa cu,cHi,on Sodium acetate Eibanol : | erscoa & Oxidation | . CH,COOH = vss, J5cr,0,1 Acetic acid chLCO™, a CH,CHO Oxidation | | _H.OH CH,CO Aesteldohyde EBOHE ‘Acetic Anhydride| 580 CHANH,, Methyl amine HNO, cH,OH Methyl aleohol POI, ¥ CH,CI Methyl chloride KCN ‘CHCN Methyl cyanide foun) CH,CH,NH, Ethyl amine (Wurtz Reaction) Na | Ether CH,—CH, Buhane Brshy ¥. CH,—CH,Br Ethyl bromide INH, CH,CH,NH,, Ethyl amine tn) “CHJCN’ <—— Cynomethane Amine CHMeBr KCN CH,Ni Ethyl amine Lino, HOH Ethyl aleohol cH,cHO Acetaldehyde CH,COOH Acetic acid PC), vi CH,COCI Acetyl chloride na ¥ cH,CONH, Acetamide ¥ CH,NH, Methanamine HNO, ¥ cHOH Methanol PO, ¥ CH,CI Chlorométhane Oxidation, K,Cr,0/H" ¥ Oxidation K,Cr,0,1" ¥ NB, CH,COONH, ‘Amm. acetate 7,0, | Heat Br, + KOH —— NH,581 — important Conversion Chart ay eto) 25000, Cilly 1,0 tagno tH cH,cH,on 204 1, LES, a> nee sccbitne “Dir TSO HSO,AOG? catebyte Sole fe -citcH,01 § : Taine Cote a bd 2H) CHCHCI, —CH,CH(OHCN cH,coon ROH x HSE HCH, Dayle ete etl eyanohyann Ketlesesd Resets ‘kane 2 Soantine oy cHcHoMcoon =O cii,cocr Is ‘acest chide Tikes = CHCONH, —CHACHO.——_cu,cicoon ‘Retaide’ ——AscUbBehyde Meco teed re, es 2am a ro ken cH cHch.on ‘ rctiglonioe Sapa se pee. Joare, ‘axes Cacti , ouon cneng crete, Merhylolshd Enbyte a0 nine cn i “ ney nero a yor cho cu,ch,cw Ieoprapytaeoet Fomsldiye ghey nn Jor mo a uicdon —_cit,e1, coon vormicaed”“Tropieniesed oct, cH, on, cute cH,oH cu. cnc. Py, aon | I 1 Ge gr Te me 28 ron SE ap Guin > pm cH, oe Hn cu.on dua cue Vrpstene Prope 2: trmepropane Ghee! Gieila.n Dithle actin Anca imi ‘ icon ; Jvc : v ener oN cH,-CH-cH, Shee cH, CL pheneide cua