Part - III NAMED REACTIONS in Organic Chemistry BALZ-SCHIEMANN REACTION ‘When arenediazonium chloride is treated with fluoroboric acid, arene diazonium fluoroborate is precipitated which on heating decomposes to yield aryl fluoride. AYN} CI- + HBF, ——» Ar— Ny BrRy “ Ar—F + BF, +No Fluoroborie acid FINKELSTEIN REACTION Alky! iodides are often prepared by the reaction of alkyl chlorides/ bromides with Nal in dry acetone. This reaction is known as Finkelstein reaction. R-X+Nal ——+R-I+NaX (X= Cl, Br) Note: This reaction in forward direction can be favored by precipitating NaX formed in dry acetone (according to Le Chatelier’s principle). SANDMEYER REACTION The Cl, Br and CN nucleophiles can easily be introduced in the benzene ring of benzene diazonium salt in the presence of Cu(1) ion. This reaction is called Sandmeyer reaction. COMICS wepe ny CoB Arar Ns CuCNINNS AeN ) Ny GATTERMAN REACTION, Chlorine or bromine can be introduced in the benzene ring by treating the benzene diazonium salt solution with corresponding halogen acid in the presence of copper powder. This is referred as Gatterman reaction, eM act Ny CuN LOo Ming Aer + Ns+ uN ‘The yield in Sandmeyer reaction is found to be better than GattermannSWARTS REACTION Heating an alkyl chloride/bromide in the presence of a metallic fluoride such as AgE, HgaFz, CoF; or SbF, gives alkyl fluorides. The reaction is termed as Swarts reaction. H,C- X + AgF___»H,C - F + AgX (X= Cl, Br) Note: Finkelstein Reaction and Swarts Reactions are known as halogen exchange reaction. WURTZ REACTION Alkyl halides react with sodium in dry ether to give hydrocarbons containing double the number of carbon atoms present in the halide. This reaction is known. as Wurtz reaction. dry etner CH,Br + 2Na + BrCH;~"""S CH, - CH + 2NaBr Bromoethane Ethane CcHsBr + 2Na + Broly e4H1 — Colts Bromoethane n- Butane WURTZ-FITTIG REACTION A mixture of an alkyl halide and aryl halide gives an alkylarene when treated with sodium in dry ether and is called Wurtz-Fittig reaction. x R CO va ses EE (CT + os FITTIG REACTION Aryl halides also give analogous compounds when treated with sodium in dry ether, in which two aryl groups are joined together. It is called Fittig reaction. x 2 + ne CTT) +28 FRIEDEL-CRAFTS ALKYLATION REACTION When benzene is treated with an alkyl halide in the presence of anhydrous aluminum chloride, alkylbenzene is formed.CH, @: crc: Maat, Cen Toluene 03,75) Cath, + cy,c) Sas Cr: Hel Ethytbenzene cl cl cl Anhyd. AICI, CH, +cH,cl ———> 1-Chloro-2-methylbenzene (inor) 1-Chloro-4-methylbenzene (Major) OCH, oct, ocn, Anhyd. AICI cH, }+cH,c) SWRA. + cs, 2-Methoxy- toluene toluene (Minor) (Major) Note: Aromatic carboxylic acids do not undergo Friedel-Crafts reaction because the carboxyl group is deactivating and the catalyst aluminum chloride (Lewis acid) gets bonded to the earboxyl group. FRIEDEL-CRAFTS ACYLATION REACTION The reaction of benzene with an acyl halide or acid anhydride in the presence of Lewis acids (AIC) yields acyl benzene. cocn, +CH,COcI —_— oO +HCl Acetylchloride Acetophenone 03.77 cocn, + (CH,CO),0 =~ & Acetic anhydride ¥ CH,COOH2-Chlornacetophenone (Mino 4-Chloraacetophenone (@tajon cn, och, cocH, + en.coct Anh. AICI, i cocn 2-Methoxy- 4-Methoxy- acetophenone acetophenone (Miner) (Major REIMER-TIEMANN REACTION On treating phenol with chloroform in the presence of sodium hydroxide, a -CHO group is introduced at ortho position of benzene ring resulting in salicylaldehyde. This reaction is known as Reimer - Tiemann reaction. on Ona’ on CHL, CHO yy CHO 4] Nao, ns Salicylaldehyde Intermediate KOLBE'S REACTION Phenol with sodium hydroxide gives sodium phenoxide ion which with carbon dioxide in acidic medium results in hydroxybenzoic acid (salicylic acid). This is known as Kolbe's reaction. ou ONa ou ‘NaOH, 100, ‘COOH wir 2-Hydroxybenzole acid (Salicylic acid) ROSENMUND REDUCTION Acyl chloride (acid chloride) is hydrogenated over catalyst, palladium on barium sulphate. This reaction is called Rosenmund reduction. cio r Oo 1, TESS Benzoyl chloride DerwaldehydeSTEPHEN REACTION Nitriles are reduced to corresponding imine with stannous chloride in the presence of hydrochloric acid, which on hydrolysis give corresponding aldehyde. ‘This reaction is called Stephen reaction. RCN + SnCl, + HCl ——> rcH = nH So rcHo ETARD REACTION Chromyl chloride oxidizes methyl group to a chromium complex, which on hydrolysis gives corresponding benzaldehyde. This reaction is called Etard reaction. en, . emocrouicn, exo CY + co CF =. CF Toluene Chromium complex Denzaldehyde GATTERMAN - KOCH REACTION When benzene or its derivative is treated with carbon monoxide and hydrogen chloride in the presence of anhydrous aluminum chloride or cuprous chloride, it gives benzaldehyde or substituted benzaldehyde. This reaction is known ‘as Gatterman-Koch reaction. CHO co. uct oer _,, ‘Auhyd. ACL /Eucr Benzene Benzaldehyde CLEMMENSEN REDUCTION The carbonyl group of aldehydes and ketones is reduced to CH group on treatment with zinc- amalgam and concentrated hydrochloric acid. This is known as Clemmensen reduction, tu-He SN, oa Dell + 10 (Clemmensen reduction) WOLFF KIRSHNER REDUCTION The carbonyl group of aldehydes and ketones is reduced to CHs group on treatment with hydrazine followed by heating with sodium or potassium hydroxide in high boiling solvent such as ethylene glycol. This is known Wolff Kishner reduction. \ NUNHL Noy \ , (=O Tio DOSNNIL, lk +N, (WolT-Kishner rdueiTOLLENS’ TEST On warming an aldehyde with freshly prepared ammoniacal silver nitrate solution (Tollens’ reagent), a bright silver mirror is produced due to the formation of silver metal. The aldehydes are oxidized to corresponding carboxylate anion. The reaction occurs in alkaline medium. RCHO + 2[Ag(NHy):]* + 30H —» RCOO+ 2Ag + 2H.0 + 4NHy FEHLING’S TEST Febling reagent comprises of two solutions, Febling solution A and Fehling solution B. Fehling solution A is aqueous copper sulphate and Fehling solution B is alkaline sodium potassium tartarate (Rochelle salt). ‘These two solutions are mixed in equal amounts before test. On heating an aldehyde with Febling’s reagent, a reddish-brown precipitate is obtained. Aldehydes are oxidized to corresponding carboxylate anion. Aromatic aldehydes do not respond to this test. R-CHO + 2Cu* + 50H—»RCOO + Cu.0 + 3H:0 Red-brown ppt ALDOL REACTION Aldehydes and ketones having at least one a-hydrogen undergo a reaction in the presence of dilute alkali as catalyst to form -hydroxy aldehydes (aldol) or B- hydroxy ketones (Ketol), respectively. This is known as Aldol reaction, The name aldol is derived from the names of the two functional groups, aldehyde and alcohol, present in the products. ALDOL CONDENSATION The aldol and ketol readily lose water to give a,f-unsaturated carbonyl compounds which are aldol condensation products and the reaction is called Aldol condensation. dil, NaOH, 2CH,-cho ——= CH-CH-cl,-cHo =4> cH.-ct |=CH-CHO (Aldo) product) CH, cH, vaio, | I 2CH,-CO-CH, ——+ cHeece 1,co-ci, <4-> CH,-C=CH-CO-CH, Propanone r on 4-Methylpent-3-en-2-one IKetod (aldol condensation 4-Hydroxy-4-methylpentan-2-one product)CROSS ALDOL CONDENSATION When aldol condensation is carried out between two different aldehydes and / or ketones, it is called cross aldol condensation. If both of them contain a-hydrogen atoms, it gives a mixture of four products. CHsCHO, aon + = CHyCH=CH-CHO + CHsCH:-CH=C-CHO CH;CH.CHO 2.4 But-2-enal CH; + CH;-CH=C-CHO + CH,CH:-CH=CHCHO CHs 2-Methylbut-2-enal Pent-2-enal CANNIZZARO REACTION Aldehydes which do not have an a-hydrogen atom, undergo self-oxidation and reduction (disproportionation) reaction on treatment with concentrated alkali. In. this reaction, one molecule of the aldehyde is reduced to alcohol while another is oxidized to carboxylic acid salt. u H ‘ fo) C=0 + Yc=0 + Cone. KOH ——> H—C—OH + HC 7 7 1 \ H H H ‘OK Formaldehyde Methanol Potassium formate 2 € pene + Cone. NaOH ——> Oprenion + Creo Benzaldehyde Benzyl alcohol Sodium benzoate KOLBE ELECTROLYSIS An aqueous solution of sodium or potassium salt of a carboxylic acid on electrolysis gives alkane containing even number of carbon atoms.lt is decarboxylation reaction. The reaction is known as Kolbe electrolysis. 2CH,COO'Na’+ 2H,O Sodium acetate [Electroiyss (CH3-CHs + 2CO2 + H2 + 2NaOHHELL-VOLHARD-ZELINSKY (HVZ) REACTION Carboxylic acids having an a-hydrogen are halogenated at the a-position on treatment with chlorine or bromine in the presence of small amount of red phosphorus to give a-halocarboxylic acids. The reaction is known as Hell- Volhard-Zelinsky reaction. R-CH,— Coon a eetesPheNS R _ CH - COOH Gi) HO | x X=Cl, Br «-Halocarboxylic acid GABRIEL PHTHALIMIDE SYNTHESIS Gabriel synthesis is used for the preparation of pure primary amines. Phthalimide on treatment with ethanolic potassium hydroxide forms potassium salt of phthalimide which on heating with alkyl halide followed by alkaline hydrolysis produces the corresponding primary amine. ° ° © ! ! J ‘ Noe ke N CL nn SO Cr se BN NR c i. of IL 8 ° ° Paid Alpine 3 i oo “: 7 (amie) IL Il g g Note: Aromatic primary amines cannot be prepared by this method because aryl halides do not undergo nucleophilic substitution with the anion formed by phthalimide. HOFFMANN BROMAMIDE DEGRADATION REACTION An amide with bromine in an aqueous or ethanolic solution of sodium hydroxide gives primary amines. In this degradation reaction, migration of an alkyl or aryl group takes place from carbonyl carbon of the amide to the nitrogen atom. The amine so formed contains one carbon less than that present in the amide. oO Il R-C—NHz+ Br: + 4NaQH —+ R ~ NH, + Na;CO, + 2NaBr + 2H,0CARBYLAMINE REACTION Aliphatic and aromatic primary amines on heating with chloroform and ethanolic potassium hydroxide form isocyanides or carbylamines which are foul smelling substances. This reaction is known as carbylamines reaction or isocyanide test. R-NH2 + CHCl, + 3KOH “S R-NC+3KC1+ 3.0 Note: Secondary and tertiary amines do not show this reaction and is used asa test for primary amines. HINSBERG’S TEST Benzenesulphony] chloride (CcH;S0.Cl), which is also known as Hinsberg's reagent, reacts with primary and secondary amines to form sulphonamides. (a) The reaction of benzenesulphonyl chloride with primary amine yields N- ethylbenzenesulphonyl amide. The hydrogen attached to nitrogen in sulphonamide is strongly acidic due to the presence of strong electron withdrawing sulphonyl group. Hence, itis soluble in alkali. oO oO o i" a4 G “folate 1 (b)_In the reaction with secondary amine, N, N-diethyl- benzenesulphonamide is formed. Since N, N-diethylbenzene sulphonamide does not contain any hydrogen atom attached to nitrogen atom, it is not acidic and hence insoluble in alkali. i) q Ora + H-N-CH,—> Hf 4 D-b-s-cms HCL 1 1 o cu, oO Cn, (©) Tertiary amines do not reaet with benzenesulphonyl chloride. Note: This test is used for the distinction of primary, secondary and tertiary amines and also for the separation of a mixture of amines. However, these days benzenesulphonyl chloride is replaced by p-toluenesulphonyl chloride. COUPLING REACTIONS Benzene diazonium chloride reaets with phenol in which the phenol molecule at its para position is coupled with the diazonium salt to form p-hydroxyazobenzene. This type of reaction is known as coupling reaction. pattydroyazmtenrene (orang dye)