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Mg. ether Carboxylic acid +2Na + CICH:CH2R S28» [RCHsCH2CH2CHs Alkane Br alc. KOH —+© RCHBr — CH:Br KBr -2H:0 Alkyne Aldehyde Jarboxylic acid GI O- Aryl halide _ NaOH _ Gil. HCL HCl ~ (622K. 30am K, 300 atm (Ona = (Q)-on Sod. phenoxide Phenol ©-« lSndecio O LCh + INHs+ OKO 24O)- NH: +0nCh 10 Aryl amine |_cucn | Pyridine 475K O-en+ CuBr Cyanobenzene |__Mgether Oy- MaBr Pheny! magnesium bromide | Shi dry ether (Oy i+ LiBr Phenyl lithium Cl — CH;+2N: eee (Ochs + 2Nacl Toluene 2H = = +2HCI Ni-Al NaOH ©) Benzene Ch — ©- a+ a Opn + No:—{O)- on NO2 o - nitrophenol p-nitrophenol Conc. H2SO: OH 288 - 293 K SO;H 2 - hydroxy benzene sulphonic acid Cone. H2SO4 373K Hs0;—{O)- On 4 - hydroxy benzene sulphonic acid Phenol move Veactions :-) Cone. HNOs + NO, #82 +o, {Of-on+ 3H:0 NO; 2. 4. 6 - trinitrophenol (Picric acid) |__ cise Anhyd. AICls Paya aes® OX-0F oH iwc {O)- on o- aa p-cresol NaOH (CH\CO~O a aor Tan (Q-0H se (Q)-ococHs+ CHsCOOH COz, 4-7 atm Cone. HiSOs . Kolbe's reaction COOH COOH Salicylic acid Aspirin |__3HiNi__ Ni ( )-on Cyclohexanol OH |} —2 +0 ={_)=0+ 0 Cro: : = p - benzoquinonc © CHCh,NaOH Phenol rane © ge OH Reimer Ticmann reaction CHO Salicylaldehyde CCli.NaOH 340 K HCI _———— OH Reimer Tiemann Or reaction COOH Salicylic acid — HS _+((©)-0), Fe+3HC! Ferric phenoxide fe ile (O)-N=N ©)-OH + HCl NaOH p - Hydroxy azobenzene avo ky lic atid. Yeactions Or HI/Red P NH>/Ni Quinolino NH:— NH: + KOH ~* glycol RCH: CHO Aldehyde PCls or PCh or SOCIz . . RCH2 COOH | RCH2COCI | Acid chloride Carboxylic ncid [Nee NHs ™|RCH:CONH:| Acid amide ROH | RCH:COOR' Bu/KOH Conc. H:SO« eas. Hoffmann Bromamide reaction CaO + NaOH/ A [RoH:CHs RCH2 NH Alkane Amine LiAIHs or B2Hs RCH2CH20H Alcohol Clemmensen Reduction Zn(Hg) + HCl > | RCH2CH; Or Wolff Kishner Reduction Alkane 4RI RCH;NH; |————»|_ R:CHNI Amine Tetra alkeyl ammonium iodide RCOCI RCH: NHCOR' Amide 0 \I Z A RCH:NH—C—R' RCOOH ae Carbarylic scid ie) o @-ccl i RCH:NH— C—O) Amido RCHO —————= RCH= N Scluft's base CHCh + 3KOH(ale.) aan | = = RCH: NC | +3KCI+3H;0 Carbylamine reaction Isovyanide HNO» > | RCH: OH Alocohol S=C=S/A Dithioalky! exrbamie Alkyl ocid isothiocyanate Oo ll ca) ci—c—cl [o Il R—CH:—NH—C—NH—CH:—R Sym. disubstituted area a ®| RCH2NHOH alk. KMnO« fl, jk—c R—CH:NOz Aydroxy) amine Nitroso compound Noto compound 1. Aldol condensation Two molecules of aldehydes or ketones having a-hydrogen condense together in presence of base [dil. NaOH, Na,CO,, Ba(OH),] to form 6-hydroxyaldehyde or B-hydroxyketone respectively which are collectively known as aldol. O lI a dil. NaOH CH;— C—H + H— CH;—CHO Acetaldehyde OH | | CH,—CH—CH,—CHO 3-Hydroxybutanal (®-Hydroxybutanal or aldol) 2. Birch Reduction In case of disubstituted alkynes reduction with sodium in lig. ammonia gives trans-alkene predominantly. This type of reduction is known as Birch-reduction. CH H Ss Na/lig NH, CH;, CH, - C=C -CH, ———+—» Bo Nees, frarts - But-2-ene 3. Beckmann Rearrangement Oximes on treatment with catalyst such as conc. H,SO,, SOCI,, PCI,, etc. undergo rearrangement to form substituted amides. Reaction is known as ‘Beckmann rearrangement. C CH, O / (i) Conc. H,SQ, i C ————> CH,— C—NHC,H, (ii) HyO OH syn-Acetophenone oxime 4. Balz-Schiemann’s reaction This is the method to prepare fluorobenzene from benzene diazonium salt by first converting it to benzene diazonium tetrafluoroborate. + N=NCI N=NBF, F HBF, A “Ha ——t +N, + BF, Acetanilide 5. Clemmensen Reduction In this method, aldehydes and ketones are reduced with £n - Hg amalgam and conc. HCl. CH,CHO + 4H-2-HEEC, CH, - CH, +H;0 CH,COCH, + 4H “~—H8EO, Cy, - CH, - CH, + H,0 6. Corey-House synthesis In this reaction, an alkyl halide (1°, 2° or 3°) is first converted into lithium dialkyl copper and then reacted with another alkyl halide (preferably 1°) to give corresponding alkane. 2R-X—*2R-Li Sh> R,Culi + Lil Alkyl halide Lithium dialkyl cuprate R,CuLi+ R°’—X ——* R—R’+ RCu+ LiX 7. Cope elimination Tertiary amines are not oxidised by KMnO,. Their oxidation is carried out with Caros acid or ozone or hydrogen peroxide to form amine oxide. HO, or O, Hees RN —Taap-? BNO 3° Amine Amine- N-oxide Tertiary amine oxide containing a B-hydrogen atom forms an alkene. This reaction is called Cope reaction or Cope elimination. 8 f seis oa Ta Mal + CH, | R’CH;CH, — . + N—OH RCH =CH, we CH,CH,R’ 8. Carbylamine Reaction Primary amines both aliphatic and aromatic on heating with chloroform and alcoholic solution of potassium hydroxide form isocyanides or carbylamines which have an extremely unpleasant odour. CjH.NH, + CHCI, + 3KOH (alc.) on Ethylamine Chloroform C,H;N==C + 3KCI + 3H,O Ethyl isocyanide AS za CH Kk) | ~ T ins q CH, CH, ‘cH, Sen/ Buta-1,3-diene — Ethylene Cyclohexene 14. Etard Reaction Aromatic hydrocarbons on treatment with mild oxidising agents such as rata chloride CrO,Cl, yield aldehydes, CHO CrO,c I; ——______# Toluene Benzaldehyde 15. Frankland Reaction This is similar to Wurtz reaction with the difference that instead of sodium, zinc is used here in inert solvent. R{X+Zn+X]R —*R-R+ZnX, Dialkyl zinc compounds react with tertiary alkyl halides to give hydrocarbons with quaternary carbon atoms only. (CH,),2n + (CH,),CCl ——® (CH,),C + CH,ZnCl 16. Finkelstein reaction lodoalkanes can be conveniently prepared by treating alkyl chloride or bromides with sodium iodide in acetone or methanol, This is known as Finkelstein reaction. CH,Cl + Nal So", CH,I + NaCl 17. Friedel-Crafts Reaction Simple aromatic hydrocarbons can be converted to substituted hydrocarbons by reaction with alkyl halide in presence of Lewis acid like AICI, or FeCl,, etc. CH,CH, ©) + CH,CH,Cl ——> “ + HCl Ethyl benzene 18. Fries Rearrangement Phenyl esters on heating with anhydrous AICI, undergo Fries rearrangement in which acyl group (acetyl, benzoyl, etc.) migrates from phenolic oxygen to ortho or para position of benzene ring resulting in the formation of mixture of o- and p-hydroxyketone. OCOCH “ COC,H rn (O) sa ashes AICI, oo” Cols Phenyl benzoate o-Hydroxy benzophenone COC, Hs p-Hydroxy benzophenone 19. Gabriel phthalimide synthesis Phthalimide on reaction with caustic potash forms potassium phthalimide which on treatment with alkyl halide gives N-alkyl phthalimide. This N-alkyl phthalimide on hydrolysis with hydrochloric acid yields primary amines. co OL “| KOHGak) > NH 2a co~ ’ NK co~ aHl Phthalimide Potassium phthalimide |)" COOH cor C,H + HHO 0 COME ELS-cn Ethyl amine COOH co” Phthalic acid N-Ethyvi phthalimide 20, Gattermann-Koch reaction Benzene on reaction with a mixture of CO + HCI in presence of AICI, forms benzaldehyde. 21. Hydroboration-Oxidation Alkenes react with diborane to give alkyl boranes which on oxidation with hydrogen peroxide in presence of hydroxide forms alcohol. H B R - CH=CH, —+ R- CH, - CH, - BH, lecu=cu, (RCH,CH,),B A =C% (RCH,CH,),BH Trialkyl borane 3H,0/0H ae 3RCH,CH, - OH + B(OH), Alcohol Boric acid 22. Hunsdiecker reaction This reaction involves the treatment of silver salt of carboxylic acid with bromine in refluxing CCl, to yield alkyl bromide with one carbon atom less than the original acid used. cd, CH,CH,COOAg + Br, —» CH,CH,Br + CO,+ AgBr 23. Hofmann Mustard oil Reaction This reaction is given by aliphatic and aromatic primary amines only, hence it can be used as a test for primary amines. C,H;-NH—-H +$>=C=$ Ethylamine (1") Carbon disulphide | S HgCl, I C)H;,N=C=S + HgS + 2HC1<— C,H.NH—C—SH Ethyl isothiocyanate Dithiwethvicarbamic acid Alkyl isothiocyanates have a characteristic unpleasant smell of mustard oil. Hence, this reaction is known as Hofmann mustard oil reaction. 24. Haloform reaction Methyl ketones on oxidation with sodium hypohalite (NaOX i.e. NaOH + X;) yield haloform along with sodium salt of carboxylic acid with one carbon atom less than the starting ketone. RN ge C=O + 2HCOONH, or 2HCONH, R g’ > CHNHCHO + CO, + NH, + H,0 30 Meerwein-Ponndorf-Verley reduction In this reaction, ketones are reduced to secondary alcohols on heating with iso-propyl alcohol in presence of catalyst aluminium isopropoxide. In the reaction iso-propyl alcohol gets oxidised to — R (CH,) CHO R ” CH; Ketone iso -propyl alcohol R CH, CH—OH + C=O ~, on? ? alcohol Acetone 31. Ozonolysis Ozone on passing through a solution of alkenes in an inert solvent like CCL, or CHC], at low temperature oxidises the alkene to a cyclic product called ozonide which is unstable and on reduction with reducing agents like zinc and water or hydrogen in presence of palladium gives aldehydes and/ or ketone depending upon structure of alkene, ie¢., >C — part of the alkene gets converted to >C =O. Pc=c<+ oe => 2>c=0 O46 32. Oppenauer’s oxidation In this reaction, secondary alcohols are oxidised to ketones in a good yield using aluminium tert- butoxide in excess of acetone. a) R II _>CH—OH + CH,—C—CH, Re i aoe [(CHy),CO),Al OH | c= O + CH;—CH—CH, Ketone lso- propyl alcohol 33. Oxo process In this process, an alkene on heating with water gas (CO + H,) under pressure in the presence of catalyst cobalt carbonyl hydride [CoH(CO),) yields aldeh Sc=c< +c0+4,———> —~C—¢~cHO 100°C, Pressure | | 34. Perkin condensation It is a condensation reaction in which an aromatic aldehyde condenses with aliphatic acid anhydride in presence of sodium salt of same acid to give a condensate which upon hydrolysis yields o:,f-unsaturated acid. ae co HCH—C~ CH,COONa C.H.—CH='0 4.74 5 Benzaldehyde ‘ a -H,0, D O | Acetic anhydride i H,O ce Hydrolysis a , CH,;—C ~ 6 CH,COOH + G,H;—CH=CH—COOH Acetic acid Cinnamice acid 35. Reimer-Tiemann reaction Concentrated solution of CHCl, reacts with phenol in presence of alc. KOH to yield salicylaldehyde. OH OH KOH (ale.) ———_+ dil, HCI CHO + CHCl, Salicylaldehyde 36. Reformatsky reaction It involves the reaction of zinc and o-halogenated ester, which add to carbonyl compound to yield (}-hydroxy ester. f? of Fn H O/nBr | H,0 CH,—C—CH,COOG,H.<— CHy—¢—CH,COOCH | CH, CH; Ethyl-3-hydroxy-3-methyl butanoate 37. Rosenmund’s reduction Acid chlorides are reduced to aldehydes by palladised barium sulphate partially poisoned with sulphur or quinoline. (—COCI is reduced to —CHO) O O II Pd/BaSOy4 | R—C—Cl + H, ————— R—C—H + HC] = § or quinoline 38. Sandmeyer’s reaction In this reaction Diazonium salttract with CuX/HX and respective halide is formed. Cl + N=NCI CuClV/HCl +N O Br CuBr/HBr +N. 39. Schotten-Baumann reaction bo 45. Williamson’s synthesis Metal alkoxides on treatment with alkyl halides yield ethers. The reaction is known as W ao synthesis. RO-— Na* +X—R’ oe O=— R’ + NaX Ether 46. Wacker process Alkenes are directly oxidised by the catalyst palladium chloride-cupric chloride (PdCl,-CuCl,) in the presence of air or oxygen. PdCl,-CuCl, CH,—CH, +r 50; aa CH;—CHO Ethene : Ethanal 47. Wolff-Kishner Reduction In this method, aldehydes and ketones are reduced with hydrazine (NH,-NH,) and KOH. © CH; NH, —NH, | R—C=CH,-—"— + R =C = NNE KOH/glycol or C-H.ONa R—CH,—CH, +N, 48. Wurtz Reaction In this reaction, ether solution of alkyl halide is treated with sodium to form alkane. R—X+2Na+X—-R DUS, np p+ 2NaX 49. Wittig Reaction It is an important reaction to change a carbonyl compound into alkene by treating carbonyl compound with a ylide. Ylides are the species which in their ground state have negative carbon adjacent to a positive heteroatom like P, As, Sb, etc. For example, phosphorus ylide, Ph,P - ~CHR. R‘CH=O+ PhP - CHR 3% R‘CH= CHR + Ph,PO 50. Wohler’s reaction Acetylene is prepared by action of water on calcium carbide. This method is used for laboratory as well as industrial preparation. CaC, + 2H,O —» CH = CH + Ca(OH), 51. Wurtz-Fittig Reaction When a mixture of aryl halide and alkyl halide reacts with sodium metal in dry ether, substituted arenes are obtained. Dry ether (O)-as 2Na vac =.(Q)- CH, + 2NaCl Alcoholic Group Ceric ammonium nitrate test : 2ROH + [(NH4)2Ce(NO3),] —~> |Ce( NO; iR OH >] +2NH NO; Pink « rréed comur: Sodium test : 2ROH + 2Na——> 2RONa + H)/ Ester test : RCOOH + 2R’OH ———5 2RCOOR’ + H,O Xanthate test : ROH + KOH » ROK + H,O ROK + CS, —> RO—C™ 
