( List of Important Name Reactions ] 1. 2,4-DNP or DNPH test Reactions: ‘When carbonyl compound (Aldehyde and Ketone) is treated with 2,4 dinitrophenylhydrazine, yellow ppt of carbonyl 2.4-dinitrophenylhydrazone is formed. This test is used to distinguish carbonyl from other class of organic compound, os cm pom te = oan me 0 Aldehyde or Ketone 2,4-DNP 2, Aldol condensation ‘Two molecules of aldehyde or ketone containing « hydrogen (aromatic or aliphatic) condense in presence dilute alkali to give § — hydroxyl aldehyde or ketone. An aldol condensation between two different aldehydes or ketones is called mixed or cross aldol condensation. OF 9 g g dil, NaOH a -C- CH + -€- CHy-H | > ¢- CH,-C- CH 3. Anti-markovnikov's Reaction: Peroxide effect or Kharasch effect : “When HBr is added to an unsymmetrical alkene in presence of organic peroxides ( R-O-O-R ), the reaction takes place opposite to the Markovnikoy's rule ie, the H atom of HBr joins with that double bonded carbon atom which contains lesser number of hydrogen atoms” Organic peroxide (R-0-0-R) CH;-CH=CH, + HBr ————————> CH, -CH)- CH, i Propene Br 1-bromopropane It may be noted that only HBr shows peroxide effect. HF, HCI, and HI do not show peroxide effect even in the presence of peroxides. 4, Baeyer's reagent test reactions: Cold, dilute alkaline solution of KMnO. is known as Baeyer’s reagent ‘When ethene is treated with dilute alkaline solution of KMnOs, glycol is formed. The pink color of KMnOs gets decolorized. 2KMnO, +2KOH ——* 2K MnO, +H30 +[0] cold, dil, KMaO, / KOH CH=CH) + 1,0 +[0) SE cH, - CH, ot Ethene OH OH Glycol 5. Benzoin condensation ‘When benzaldehyde is heated with alcoholic KCN, 2 molecules of benzaldehyde condensed together to form a hydroxyl ketone called benzoin. Benzaldeyde Benzaldshyde Benzsin 1|Page © Jay Prakash Paudel || Department of Chemistry6. Cannizzaro's Reaction ‘Two molecules of aldehydes (aliphatic or aromatic) which does not have a hydrogens undergoes self-oxidation or reduction in presence of cone. NaOH to form alcohol and sodium salt of carboxylic acid. HCHO + HCHO +NaQH ~=————> CH, OH + HCOONa methanal methanal methanol sodium formate 0 co cooNe Benzakshyde Renzy aot! Sou benzoate 7. Carbylamine Reactio: When a primary aliphatic or aromatic amine is warmed with chloroform and alcoholic KOH solution, an isocyanide or carbylamine (-NC) is formed. This compound is identified with its offensive smell. R-NHb + CHCl + 3KOH (ale.) R-N*C + 3KCI+2H,0 (1° amine) Alkyl carbylamine (CH CH - NH + CHCl + 3KOH (alc.) + CHsCH2 -N == C +3KCI + 3H20 Ethanamine Ethyl isoeyanide He Nec Aniline Phenyl isoeyanide This reaction is used as the test for primary amine, Secondary and tertiary amines don't show this test. 8. Clemmensen's Reaction Aldehyde or ketone reacts with zinc amalgam and cone. HCI to give alkane. 9 e Zn - Hg / conc. HCL + ary Acs /eone HO cH, +H,0 alkane 9. Coupling Reaction: Benzenediazonium chloride coupled with aniline or phenol at low temperature to give azo dye. « 2|Page © Jay Prakash Paudel || Department of Chemistry10. Decarboxylation: When aliphatic or aromatic carboxylic acid or sodium salt of carboxylic acid is heated with soda ( NaOH ) and. Lime (CaO ), alkane is formed by the removal of COO group. Thus formed alkane contains one less carbon than parent. CaO R-COONa + NaOH —= R-H + Na,CO; CaO R-COOH + NaOH a R-H + Na,CO; + H,0 co (Sodium enzo) (Benson 11. Decarbonylation Reacti When amide is warmed with bromine and aq. NaOH or aq. KOH solution about 70°C, amine with one less carbon will be formed as compared to the parent compound. This reaction involves the removal of carbonyl (>C =0) group from the amide and hence is also called Decarbonylation reaction. 9 70°C CH;-C-NH; +Bry+4KOH —[—— CH,-NH, + 2KBr+K,CO, + 2H,0 Ethanamide Methanamine 12, Dehydrohalogenation Reaction: ‘When haloalkane is heated with ale. KOH or NaOH, alkene is formed as a result of elimination of hydrogen and halogen 13. Diazotization Reactions: Aniline reacts with nitrous acid (NaNO: + HCI at ice cold condition to give benzene diazonium chloride. This, reaction is called diazotization reaction. Nitrous acid being unstable and is prepared in situ by the reaction of NaNO» and HCI. At higher temperature phenol is formed thus, temperature should not be exceeds the 5°C, NE Niwa NaNO + HCL + HNO; —— +2H20 + NaCl = o-5PC ° Aniline Benveneinzonim chloride 14, Dow's Process Reactions: When chlorobenzene is heated with ag. NaOH under high temperature and pressure, sodium phenoxide is formed which on acidification gives phenol. a ona 330 300m +2 NAOH (ag) + NaCl + HO. Chlocobenzene Sovtum phenoxide 3|Page © Jay Prakash Paudel || Department of ChemistryNa o ow os Ose sunt) oO 7 O anon i rnd 15, Esterification Reaction: ‘When alcohol is heated with carboxylic acid, in presence of conc. H»SOs ester is formed. conc. HzS05 ll R= 2—c_o— re +H,0 Alkylalkanoate water (Ester) cone. H5$0, I OCH cy ETO 4, Co orto + 10 Ethanoic acid Ethanol Ethyl ethanoate water Esters have fruity smell, so this reaction can be used to test the presence of acid or alcohol. Therefore this reaction is also called esterification test. 16, Fehling's Reagent Test Reactions The alkaline aqueous solution of CuSO. containing some Rochelle salt (ic. sodium potassium tartrate) is called Fehling’s solution. The solution is prepared by mixing equal parts of alkaline solution of Rochelle salt (Fehling’s solution A) to aqueous CuSO; solution (Fehling’s solution B) COONa H—¢—on 2.Na0| —+ at Hon * 2 NaOH] + Cuso, i 4 NaySO,+2H,0 copper sulphate (Eehling solution A) cook doicn: alkaline solution of Rochelle Salt (Felling solution B) Deep blue colored complex (Pehling’s Solution) Fehling’s solution Test: The test reaction in which aldehyde reduces the cupric (Cu’*) ions of Fehling solution into cuprous (Cu’) ie. cuprous oxide (Cu,0) which is obtained as brick red ppt and respective aldehyde itself gets oxidized to carboxylic acid is called Fehling’s solution test Only aliphatic aldehyde (like formaldehyde, acetaldehyde etc.) gives positive Fehling’s solution test but aromatic aldehyde and ketones do not give the Fehling solution test 4|Page © Jay Prakash Paudel || Department of Chemistry9 9 ° “ R—C—H + 2Cu'* 40H —» R—C—on + COV + 2H,0 Alkanal Alkanoic acid ticked Pt 17. Fermentation Reaction ‘The process of decomposition of complex organic compounds into simpler ones in presence of enzyme produced. by yeast as catalyst is called fermentation, Fermentation process is widely used to manufacture ethyl alcohol from carbohydrates. Preparation of ethyl alcohol from sugar ( Suerose ) Invertase €yH0}, +H, CrHi205. + CeHi295, Sucrose or surat Glucose Frutove CeHi0, —22™SE > 9¢,H,0H + 2C0, Glucose / Fructose Ethanol 18. Fittig Reaction: When aryl halide is heated with sodium in presence of dry ether biphenyl is formed, f i Dry eer Ok ca aC) =-O-O) ms ‘Gioeibamsene CCorobenzene Biphenyl 19, Friedel- Craft's acylation The process of introducing an acyl group into benzene ring in presence of Lewis acid is called Fridel Crafts acylation, When benzene is heated with acid halides or acid anhydride in presence of Lewis acid like AIX; or FeXs, acyl benzene (Aromatic ketone) is formed, ° I bac, AlCl +cH,-é-q) —AS + HL Ethanoyl chloride Benzene (Acetyl chide) scp 9 2 ben, # cE) atch Sp A + cH,cooH WZ meg Ethan i eam ‘Acetophenone Ethanoic anhydride non ‘Acetic anhydride) 20, Friedel-Craft's alkylation The process of introducing an alkyl group into benzene ring in presence of Lewis acid is called Fridel Crafts alkylation. When benzene is heated with alkyl halides in presence of Lewis acid like AIX: or FeXs, alkyl benzene is formed, 5|Page © Jay Prakash Paudel || Department of ChemistryHy AICI, + cH,-c)} —AS—> + HEL Chloromethane Benzene Methyl benzene (Toluene) 21. Gattermann- Koch aldehyde synthesis reaction When benzene is treated with mixture of CO and HCI in presence of anhydrous AICI: under pressure, benzaldehyde is formed. This reaction is called Gattermann ~ Koch reaction. ‘CHO anhydrous AIC, +CO+HCL —— + HCl Presure Benzene Benzaldehyde 22, Gattermann Reaction: When benzene diazonium chloride is heated with Cu in presence of HCI or HBr, chlorobenzene or bromobenzene is formed. cy cu + HCl ————+ +Ny+HCI No 23. Grignard’s Reactions ( synthesis of alcohol and carboxylic acids) Alkyl magnesium halide (RMgX) or aryl magnesium halide (ArMgX) are commonly known as Grignard Reagents. They are prepared by reacting alkyl halide or aryl halide with magnesium metal in presence dry ether. dry ether R—x + Mg RMg-X Alkyl halide Alkyl magnesium halide (Grignard Reagent) Applications 6|Page © Jay Prakash Paudel || Department of Chemistry10. ku “MeOIX alkane Nay R “MEHDX ” attane RX px. ane Mex: Alkane cor #0 Pomme > R-COOMEX a R-COOH Mey dry ether Akition poder 8X Carboxptc acid Rox RM x Allg aide Atkyl agnosie lide (Grignard Reagent) HO. | HCHO. e-croMex 0 ch-081 Methanal Addition product SOX primary alcohol cnc a ms R-CHON -ettongx — 20 Tata "jis bar MEOH” cgay Akal carcocn, HO Sr Popmae —~ "OMS gama —~ F408 Adin poet erin Aloha 24, Hoffmann's Ammonolysis When haloalkane is heated with alcoholic NH; in sealed tube , primary amine is formed. HY se A Rx INH, «= RN, + IK \ Haloalkane alc. ammonia alkanamine (excess) sek be A CHs—CH)——8r + NH; (ale) cH; —cH,—NH, + HBr ~7 (excess) Bromoethane Ethanamine Note: If haloalkane is used in excess then mixtures of primary, secondary, tertiary amines and quaternary salts are formed, 25. Hoffmann's Bromamide Reaction When amide is warmed with bromine and aq. NaOH or aq. KOH solution about 70°C, amine with one less carbon will be formed as compared to the parent compound. Such reaction is called Hoffmann’s bromamide reaction or Hoffmann’s hypobromide reaction. This reaction involves the the removal of carbonyl (>C =O) group from the amide and hence is also called Decarbonylation reaction. This reaction is used to shorten the number of carbon chain. 8 70°C —C-NH, + Br +4KOH —y——>- NH, + 2KBr+K3CO; +2H,0 amide amine 8 70°C CH; -C-NH; + Br, +4KOH —>——* CH; - NH) + 2KBr + K,CO; + 2H, Ethanamide Methanamine 7|Page © Jay Prakash Paudel || Department of Chemistryg G-nn Benzamide Asiline 26. Iodoform test Reaction Alcohol containing ct—S— group when heated with ag. NaOH and Is , at around 70°C, yellow ppt of iodoform (CHI) with characteristics hospital smell is obtained. LyNaOH cucron OS cfs coxa + at + 14,0 ‘Ethanol Todoform Sodium formate (1° aleohol) (yellow ppt) Aldehyde or ketone containing CHsCO - group on reaction with excess iodine in presence of NaOH to give yellow precipitate of iodoform with characteristics hospital smell is called iodoform reaction. fi CH;—C—H +NaOH +1, ———» CHI,} + HCOONa +Nal + 1,0 Ethanal 4 Jodoform 27. Markovnikov's Reaction: “ When unsymmetrical polar reagent is added to unsymmetrical carbon — carbon multiple bond (i.e. double or triple bond ), the negative part of the reagent goes to that double or triple bonded carbon atom which consists of lesser number of hydrogen atoms and positive part to that double or triple bonded carbon atom having greater ‘number of hydrogen atoms” ——~4+—> cH- CH-CH; (Major product) x a CH;-CH=CH, + HX —| (2-halopropane) LS< > cH,-cu,-cH, (Minor product) - 1 x (1-halopropane) CH;-CH=CH, + HBr ——* CH;-CH-CH, Br Propene 2-bromopropane 28, Mendins Reduction : When nitrile is reduced by using Na / CH— CH OH, primary amine is formed. Na/ C)Hs OH R-CN + [H] ———S—* R-CH,-NH, Nitrile 1° amine 8|Page © Jay Prakash Paudel || Department of Chemistry29. Oxo Process Reaction: Alkene reacts with water gas (CO + Hp ) in presence of dicobalt octacarbonyl [ (Co(CO)s)2] asa catalyst under high temperature and pressure to give aldehyde having one more carbon than alkene, Aldehyde on catalytic hydrogenation give primary alcohol. [Co(CO)s]> HyNi CH, =CH, + CO +H; eae (CH - CH; - CHO. = CH - CH, - CH) - OH igh temperature Ethene Water gas, & Propanal Propanol (Alkene) High pressure (Aldehyde) (Primary alcohol) 30. Ozonolysis reaction When alkene is treated with ozone an addition product called ozonid is formed which on treated with water in dehyde or presence of zinc dust, two molecules of carbonyl compounds are formed ( carbonyl compound: ketone ) 2 0 + O=CL + HO; Aldehydes or ketones 31. Perkin condensation ‘When an aromatic aldehyde is heated with anhydride of an aliphatic carboxylic acid (containing a hydrogen) in presence of sociium salt of the same acid as catalyst, a, B unsaturated acid is formed. oH ; 1C00H cuucooxs + Do — Supe + cH.cooHt omg $ venice sci aSytide cima ed 32. Reimer-Tiemann Reaction : ‘When CHC! is heated with phenol in presence of aqueous NaOH or KOH solution followed by acidification, salicyladehyde ( ortho-hydroxybenzaldehyde) is formed. OH oH CHO (60-703 + CHCl + NaOH gy) + NaCl +120 Phenol o-hydroxybenzaldehyde (salicylaldehyde) 33. Rosenmund Reduction ‘When acid halide is heated with hydrogen in presence of Pd with BaSOs ,aldehyde ( aliphatic or aromatic ) is, formed. a I —é-x +H, PASBSO,L Oy 4 Ha Acid halide ’ aldehyde 9|Page © Jay Prakash Paudel || Department of Chemistry34. Sand Meyer's Reaction: When benzene diazonium chloride is heated with CusCl or CusBr2 in presence of corresponding halogen acid (HCL or HBr ), chlorobenzene or bromobenzene is formed. cr +e). ———_> +Ni+HCL a 35. Saponification Reactions Fats and oils are triesters of glycerol with long chain fatty acids (Triglycerides). Long chain fatty acids may be Oleic acid (CHs (CH2)}CH=CH (CH:);COOH]}, palmitic acid [CHs (CH2):COOH] ete When these triglycerides are hydrolyzed in presence of strong alkali like NaOH or KOH then sodium or potassium salt of long chain fatty acid (Soap) and glycerol are formed. This reaction is commonly called saponification reaction. ° I CHO ° a 4 3NWOH —A——> J, 9, 4 3 R—C—ONe Sodium Salt oflong Chain fatty acid CH. oH co Glycerol Oil or Fat righyceride) For Example, R = C,H (From Palmitie acid) 36. Stephen's Reduction When nitrile is treated with SnCl, and HCI followed by acidic hydrolysis aldehyde is formed. ° SnCl/ HCL H,0/H* i R-CN + [H] ——“—=+ R-cH=NH ——> R-C-H Aldehyde Nitrile s Tollens's Reagent Test Reactions: Ammoniacal silver nitrate solution (Diammine silver (I) hydroxide) is called Tollen’s Reagent & is prepared by following process: AgNO: + NaOH > AgOH + NaNO: AgOH> Ag:0 + H.0 ‘Ag.O + 4NH,OH > 2[Ag (NHs)2] OH + 3H:0 Diammine Silver (I) hydroxide or Tollen’s reagent Tollen’s Test or Silver mirror Test: ‘The test reaction in which aldehyde reduces the Tollen’s reagent into free metallic silver which is deposited around the inner wall of reaction tube (test tube) and aldehyde itself gets oxidized to carboxylic acid is called Tollen’s test or Silver mirror test. Only aliphatic aldehydes (like formaldehyde, acetaldehyde etc.) & aromatic aldehyde (like Benzaldehyde) gives positive Tollen’s test whereas ketones do not give this test. ° ° ‘ ° R—C—H 4 [Ag(NH3)I0H—* R—C—oOH 4 _ ahs ant + HO Alkanal (Tollen's Reagent) alkanoic acid silver mirror 10|Page © Jay Prakash Paudel || Department of Chemistry38. Williamson's Synthesis / Williamson's Etherification When primary haloalkane is treated with sodium alkoxide, ether is formed. Both symmetrical as well as ‘unsymmetical ether can be prepared by this method. -R ————> R-0-R + NaX Sodium —Haloalkane Ether alkoxide CH;-CH;-ONa + CH;-CH,-Cl ———» CHs- CH) - 0 - CH) -CH3 + NaCl Sodiumethoxide Chloroethane Ethoxy ethane CH - CH; - 0 Na + CH; -Cl ———* CH -CH)-O0-CHs + NaCl Sodiumethoxide | Chloromethane Methoxyethane 39, Wolff - Kishner Reaction ‘When aldehyde or ketone is heated with hydrazine ( HaN-NHb) and a strong base (NaOH) at 200°C alkane is formed, ° eg any NEENHA/NOOH cay. sino 200° alkane 40, Wurtz Reaction When haloalkane is heated with sodium in presence of dry ether, symmetrical alkane is formed. RX +2Nat+ x: Haloalkane i dry ether CHy—rer + 2Na+ Bri —CHy CHy—CHz + 2NaBr Bromo methane Bromo methane Ethane hy Cy CHs— CH 2,3-dimethylbutane \—cHy + 2NaBr 41, Wurtz-Fittig Reaction: ‘When aryl halide and alkyl halide is heated with sodium in presence of dry ether aromatic alkane is formed. Chiorobenzene Tolwene 11|Page © Jay Prakash Paudel || Department of Chemistry