@ IMPORTANT NAME OF REACTIONS & 1. Aldol Condensation. When two molecules of aldehydes or ketones containing a-hydrogen (atleast one) react with dil NaOH undergo condensation to form § hydroxyaldehydes or ketones. OH dil NaOH | a 2CH,CHO 4——* CH,CHCH,CHO —He#, CH,CH=CHCHO But-2-enal Ethanal 3-Hydroxy butanal (Aldol condensation (Aldol) product) OH HN dil NaOH CH,CHO + HCH,CHO —““*S"> CH,CHCH,CHO Ethanal Ethanal (3 Hydroxy butanal) Aldol 2. Balz-Schiemann reaction. This reaction involves the decomposition of diazoniun fluoroborate to aryl fluorides. + x 4 es NeNCI N,BF, F 78K + HBR, 27278 a Heat a Benzene diazonium ——_-Fluoroboric Benzene diazonium Fluoro chloride acid fluoroborate benzene 3. Cross aldol condensation. Aldol condensation of a mixture of two different aldehyde: or ketones, each containing an a-hydrogen, gives a mixture of four products. dil NaOH . CH,CHO + CH,CH,CHO ——“—+ Different products obtained as below Ethanal Propanal Self aldol condensation products HH ; f Hi @ CH,CHO +CH,CcHO #184, o4,.¢HCH,CHO “> cH,CH=CHCHO a Sto? CHa Ethanal ——_Ethanal 3-Hydroxy butanal f But-2-enalOW OH, (i) CH,CH,CHO + CHCH, cry Naot Propanal Propanat >» CH,CH,CH bono A Mydroxy 2methyl pontanal Heat > 1,0 Cross aldol condensation products OHCH, (ii) CH,CHO + CH,CH,CHO SMH, oy bs cue BHydroxy, d-methy! butanal § B Het, CH,CH=CHCHO 2 2Methylbut-2-enal Ethanal Propanal OH (iv) CH,CH,CHO ai NaOH, t ‘0! CH,CH,CHO + CH,CHO S™OH, oH cH.CHCH,CHO Propanal Ethanal 3-Hydroxy pentanal —, cH,cH,cH=cHcHO “HO pent-2-enal 4. Carbylamine reaction. When a primary amine (aliphatic or aromatic) is heated with chloroform and ethanolic KOH, it forms an isocyanide or carbylamine having offensive smell, CH,NH, + CHCl, + 3KOH (Ale) Us CH,N 20 + 3KCI + 3H,0 Methyl. Methanamine Chloroform isocyanide NH, N=C + CHCl, + 3KOH (Alc) Het, + 8KCl + 3H,0 Aniline Chloroform pan ining - hen treated 5 2 ction, Aldehyde not containing an o-hydrogen atom, w 4 Racca alkali, one molecule gives an alcohol and another molecule gives corresponding carboxylic acid or corresponding carboxylic salt.HCHO + HCHO —=™8_, CH,OH + HCOONa, um formate ‘Methyl Formaldchydo moe CH,CHO + C5H,CHO —2@™20H_, C,H,CH,OH + CoH,COONa Benzaldehyde Renzaldehyde Benzyl alcohol Sadium benzoate 6. Coupling reaction. When diazonium salt reacts with phenol or aromiate amine to give azo compounds. The coupling with phenol takes place in mildly alkaline medium, while in case of amines it occurs in acidic medium. + a 273-278 KIOH ‘ 23-278 KOH, N= NGI + HoH Gaeiy Benzenediazonium Phenol chloride «p> 7 n{_)-oH +HCI +H,0 P-hydroxyazobenzene (orange dye) + = 273-278 K/H" a —w_wa Cp =NGl + HK pnt, Gaaso ‘line Benzenediazonium chloride P-amino azobenzene (yellow dye) 7. Clemmensen reduction. When carbonyl group of aldehydes or ketones is reduced to CH, group on react with zinc amalgam and conc. HCI, it is referred as clemmensen reduction. CH,COCH, + 4(H] —20/He+Cone HCl, OH CH CH, + H,O Acetone ‘Propane Zn/Hg + Cone. 1 ( p-eoct + af] —ZnlHle* Cone C1, Cpremcry + HO Acetophenone Ethyl benzene primary aromatic amine is treated With cold solution of nitrous acid in the presence of dil. mineral acia at (273-278 K), arenediazonium salts are formed. NaNO, +HCl—> HNO, +Nacl Nitrous acidie NH, aO + HNO, + HCI Anilin ~ 7 J + 2H,0 Benzenedinzonium chloride g, Etard reaction. When toluene reacts with chromyl chloride (€r0,G1,) in CCL, or CS, to give benzaldehyde, it is called Btard reaction, CH, 4 CH(OCrOHCL, Cc + Cro,cl, —O% cy (OCrOHCh)s 4, ‘Toluene Chromium complex Benzaldehyde 10. Finkelstein reaction. Alkyl iodide propared by the reaction of alkyl chloride/bromide with Nal in dry acetone, CHO Acetone R—X+Nal ——“, R-14NaX (X= Cl, Br) Acetone CH,CH,Cl + Nal ““"", ciy,0H,1 + NaCl Chloro ethane Todoethane 11. Fittig reaction. When aryl halide is treated with sodium in dry ether, it gives analogous compounds. 2€ ra #8Ne. oe +2NaCl Chlorobenzene Biphenyl or Diphenyl 12, Friedel-crafts reaction. Aromatic compounds like benzene, chlorobenzene, toluene etc., react with alkyl halide, acid chloride and anhydride in presence of Anhydrous AICI, to form electrophilic substitution products. « Friedel-craft alkylation reaction cl ol cl CH, Anhyd. AICI, a iy CHCl es CY + QO Chlorobenzene Methyl chloride 1-Chloro-2-methyl benzene CH, (minor) 1-Chloro-4 methyl benzene (major) * Friedel-crafts aceylation reaction a a cl Anhyd. AIC, OCH, + CH,cod ===> + acetyl chloride COCH, 2-Chloroacetophenone _4-Chloroacetophenone Chlorobenzene ia (@najor)imide i into potassium salt 1. Garbriel phthalimide synthesis. Phthalimide is converted ant polesstal ne ” treating with ale. KOH, then heated with alkyl halide to vial 4 eae which is hydrolysed to phthalic acid and a primary amin‘ KOH. co ea oN Sco" coon Phthalimide iL _tomn'_, Ge + OHNH, Hydrolysis ‘COOH Ethylamine Bites 14. Gattermann-Koch synthesis. When a mixture of CO and HCl gas is passed through benzene at 323 K in presence of a catalyst consisting of anhydrous AICI, and a smal} amount of CuCl, benzaldehyde is formed. CHO CO, HCL —— Anhy AICI/CuCl Benzene Benzaldehyde 15. Gattermann reaction. In this reaction benzene diazonium chloride is treated with copper powder and halogen acid to form aryl halides. Cp nor WHC Cl + Ny Heat Benzenediazonium Chlorobenzene chloride ( pence ae Cp +N, Benzene diazonium Bromobenzene chloride 16. Hell Volhard Zelinsky reaction Carboxylic acids having an c-position are halogenated of the a-position on treatment with chlorine or bromine in the presence of small amount of redphosphorus to give a-halocarbo: xylic acids, a ClJRed P a iF &x,coon 25" 5 ciéu,coon Set? 4 Saar? CL.CHCoon Dichloroacetie acid Acetic acid Chioroacetie acia ClyRed P Tha, ChCcoon ‘Trichloro acetic acidHottnsnn deyradation of amides. T: TY AIING eontesningy, on WAN Nhe preserve tf jy Hftonau HWeomunide » QiVONATO OFT DEEY Hinide boa i welll OW Heb Wit inixture of fh Hath Binnie renetinn, SHChON oF HOU ACONE LS 1 thny Alcon te wnyrannnnnnenteles 7 CCH eAbinntninw jon nn \ . NH, | \| Wy AKON > f J + Wir + Y, Hiouenunlele jh Thuvediocker venetion, Ally ha carboxylic elds dissolved tn GG) 0, + THO Aniline lide re prepared by decomposing the I, hy bromine or chlorine, ce OU COOAK 4 Bry + CH,Br + CO, + AgBr Hilvor nootate Methyl bromide 1p. lodoform renction, All compounds containing the group CHCH,OH, CH.COCH, won treated with haloyon nnd exec a allall fometnelooeme CH CH,OH 4 44,4 6NnOM ——5 CHI, +HCOONa + 5Nal + 5H,O thanal VoAchorin (yellom ou CHy—CH—CH, 4,41, + NAOH ——+ CHI, + CH,COONa + 5Nal + 53,0 Propane2-ol CH,COCH, + 31, +4NaOH ——> CHI, + CH,COONa + 3Nal + 3H,0 Acetone 20, Kolbe's reaction. Sodium phenoxide reacts with CO, under pressure (4~7) atmospheric prossure at 400 K to form sodium salicylate which upon acidification with HCl gives salicyclic acid, On ONa ONe OH COOH coon NaOH, i 4-1 atm Hydrolysis _ + CO, OK? ae Phenol, Sodium Salieyclic acid phonoxide. 21, Mendius reaction. The reduction of alkyl and aryl cyanides to primary amines with nascent hydrogen is known as Mendius reaction, CH,C = N + 4(H] —SuSHthO, CH,CH,NH, Methyl nitrile Ethanamine =N CH,NH, y NalO,H,0H + 4{q]) —~+— Bonzylamine Bonzenonitrilephenol reacts with chloroform in presence of 22, Riemer-Tiemann reaction. When phenol reacts Wi CNT roduces 2 hydroxy. aq. sodium or potassium hydroxide benzaldehyde. 1H ONa® Qa’ 8 s CHC, + aq CHC! CHO pyarotysig AO NaOH co NaOH ae Salicyldeh Phenol Intermediate Ne 23, Rosenmund reaction. Catalytic reduction of acid chlorides to the corresponding aldehydes is called Rosenmund reduction. CH,COCI + H, —P#B80_, CH,CHO + HCI Boiling xylene Acetyl chloride Acetaldehyde 24. Sandmeyer reaction. Benzene diazonium chloride on treatment with CuCV/HCl, CuBr/HBr or CuCN/KCN produces chlorobenzene, bromobenzene, benzonitrile respectively. cl CuCvHCL Heat as Chlorobenzene meso Br N=NCL CuBr/HBr —|__CuBrHBr Heat +N Bromobenzene Benzene diazonium CN chloride CuCN/KCN in Heat 2 Benzene nitrile 25. Stephen reaction or Stephen reduction. Alkyl or aryl cyanide reduces to th corresponding aldehydes with a suspension of anhydrous stannous chloride in ethe saturated with HCl at room temperature followed by hydrolysis, SnCl, + 2 HCL ——_, SnCl, + 2[H] SnCl, +HCL ¥ CH,CN + 2fH] EC, oy cH=NH HC 22°, CH,CHO + NH,Cl ‘Methyl eyanide Acetaldehyde SnCl, + HCL HO" C,H,CN + 2(H) ——*—> C,H, CH=NH —*> C,H,CHO + NH,Cl Ethyl cyanide PropanalVe i q __ swarts reaction. The synth 1 $6 “yl chloride/bromide in the une 559 or SbF. alkyl fluoride i Y" {luoride is best, accomplished by heating ce of a metallic fluoride such as A, CoF, id F, Hg,F, 8 Agl’, Hg,F,, CoP, CHSBr + AgF —__, oy F + Ags: ili ‘ a + AgBr gx, Williamson synthesis. Alkyl hatides n i to form ether. This react act with s ion is called Willen sodium alkoxide or sodium phenoxide synthesis, CH,I RX + R’ONa —, RoR’ + Nax +CH, Methyl Saige 7 CHsCH,ONa ——, CH,OCH,CH, +Nal ‘Methoxy ethane ONa ocn, + CH —> a + Nal Sodium phenoxide Methoxy benzene (Anisole) 98. Wolff-Kishner reduction. Aldehydes and ketones reduce to their corresponding hydrocarbons on heating them with hydrazine and KOH. CH,CH=0 —“M2, [CH,CH = NNH,] Kiel + CH,CHs + N, ‘Acetaldehyde -H,0 453-473 K ‘Ethane CH, CH, | NH,NH, lee KOH/glyeol pce (pe? —H,0 C=NNE2 “G55479K oa Ethyl benzene Acetophenone i i dium in dry ether to give hydrocarbon tion. Alkyl halides react with so b t e are hing double Be aber of carbon atoms present in the halide. Dry ether oRx + 2Na ———> B-R + 2N0K Dry ether CH,CI + 2Na + CCH, CH,CH, + 2NaCl Ethane Chloromethane ; ee A ‘art reaction. A mixture of an alkyl halide and aryl halide gives © alkyl a ena ait sodium in presence of dry ether. “arene CH, cl Dry ether NaCl + aNa + CICHe oe a aN Chloromethane ‘Toluene Chlorobenzene