21. Aidol condensation ssenco of dilute alkali {ail ‘Two molecules of aldehydes or ketones containing o-hydrogen atom, in, the Prmorketones. Ml NaOH, Ba(OH), etc.] undergo condensation to form Phydroxy aldehydes or B - ° ; tN ° ¢ CoH o I SoD ae Ul a i i -CH-C—H cH, 70 + HGH,—C—H __anmson_, CH, 5 Ha oH is? Cs rasan 2-Butenal L an (Crotonaldehyde) Two molecules of ethan: 8-Hydroxybutanal thanal ss x on cH feel * eee! CH,CH,—C + H—CH— CHO _aixson oH,GH oR G 2 | H H ‘Two molecules of propanal 3-Hydroxy-2-methylpent-2-enal i CH, H I CH,CH,CH =C—C=0 2- Methylpent-2-enal * Please note this reaction. The second molecule joins only from a-carbon atom. 6 ° pH 8 0) 4) CHy 641-0, | -C—CH, __Baiow, cn,-¢-c tos, sig? a0 =-CH—C—CH, I CH, bu, CH, ‘Two molecules of propanone 4-Hydroxy-4- methyl 4-Methylpent-3-en-2-one 2-pentanone (mesityl oxide) (Diacetone alcohol) Formaldehyde and benzaldehyde which do not have a-hydrogen atom do not undergo aldol condensation. aeyer Villiger Oxidation of Ketones Ketones react with peroxy acid to form esters. In this reaction, the oxygen from the peroxy acid is inserted ‘between the carbonyl group and one of the attached carbons of the ketone to give an ester. oxH,c0,08 Oban: ceca, Oates Cyclohexylmethyl Cyclohexylacetate ketone ‘Benzoin condensation ‘Two molecules of aromatic aldehydes (such as benzaldehyde), on heating in the presence of ethanolic KCN get condensed to form benzoin. - GF 6 -C e-k : Ree :@-wo we. Ob to - Benzoin } MODERN'S abe OF CHEMISTAY-XI (CBSE)me a a 1. gouvenult Blane reaction - f gxtors are reduced by sodium in alcohol *ohol to primary aleohols o s H,COOC,H, NEGO, 904 CHOH ee: Ethyl ethanoate (oseseniomenn reaction Biend is reaction involves the decom Position of diazonium f i s mnium Muoroborate to aryl Muorides. N,tCr wae i HBF. BF, it : + Fluroborie, 222K, 2 ‘Acid Smee Benzene diszonium —, : ee Se Benzene aon Fluorobenzene uoroborate Gannizzaro reaction ‘Aldehydes which do not contain Y ny h : any a-hydrogen atom (e.g. benzaldehyde, f,jiation and reduction reaction on treatment with cone, olution fenusticalial oxidised to acid while another molecule is reduced to alcohol. : formaldehyde) undergo self In this reaction, one molecule ie HCHO+HCHO sso, CH,OH = + HCOO-Na* Formaldehyde ‘Methyl aleohot Sod. formate s cHO CHO CH,OH COONa 6:-O— ©: O Benzyl alechol Sod. benzoate ‘Carbylamine reaction When a primary amine (aliphatic or aromatic) is warmed with chloroform and alcoholic ‘ide or carbylamine having extremely offensive smell. CH,CH,NH, + CHCl, + 3KOH © “= CH,CH,NC KOH, it forms an + 3KCl + 3H,0 Ethylamine (ale) Ethylisocyanide NH, NC © + CHCl, +3KOH Ys © +3KC1+3H,0 Aniline oy Phenyl isocyanide densation ee “ Lac ae self eondensation of two molecules of eter containing «-hydrogen in the presence of a strong base ide to form Brketo ester ‘ as sodium ethoxi : ° ° o i 3 oytione_, CH, | on b-o0, H,+ C,H,OH —6-00,H, He CH aH, + CoH CH, C00 Hi, + BOs a Ethylacetoncetate 2 molecules of ester (keto ester) ane reduc aldchydes and ketones: tothecorresponding hydrocarbons with amalgamated zine Itinvolves the reductionPar CH,COCH, +4H — —onencr Acetone cOcH, zat + 4H ene HET ‘Acetophenone ‘. Coupling reaction 4 carried out in ice cold solution, ©O>-n,c14O)-on Benzene diazonium Phenol chloride ©-x01+ Gm Benzene diazonium Aniline chloride i i i i is obtained by coupling the diazonium fethy] orange which acts as an indicator in the acid alkali titrations is obtaine : ‘pained 5 -dimethyl aniline in the presence of alkali. salt of p-aminosodiumbenzene sulphonate with N, Na,s—{O)—NH, p-Amino sodiumbenzene sulphonate Na0,8-{O)-W,01 + (O)—NicH,), OH 1 Ninety “ysCiaotsation reaction The NH, N © too HE © ae LDiele-Alder Renetion YAO te paiction Betroen 6° Buunsaturated carbonyl com Product is kown as Diels Alde: gun CHM oy CH—CHO 1st + sna CH. C Neu, " 1,8 Butadiene Ae (Conjugated diene) (@,B- unsaturated carbonyl compound) ‘The reaction of diazonium salts with phenols and aromati ara-278 K Hes , =Hich NaNO, /H1C. _Navo,/nicr_, formation of diazonium salt from primary aminein a dilute mineral acid (HCI or H,SO,) and treatment ope cold solution of nitrous acid (NaNO, + dil HCl) at 273-278K. ;pound and a conjugated diene to form an addition + reaction. This reaction is als cH,CH,CH, + 1,0 Propane CH,CH, + H,0 Ethylbenzene fc amines to form azo compounds. The reaction ig ©-n-n—{O)-011 p-Hydroxyazobenzene (Orange dye) -v-n—{O>—NH, ‘p-Amino azobenzene (Yellow dye) wos-O-nea Diazonium salt NaG,8 XO)—N-nLO)—NcHH, ‘Methyl orange cl +2H,0 Benzene diazonium chloride © known as eyclo addition, CH, 7 CH cH CH—CHO l | CH CH, eae 1,2,3,6-Tetrahydro benzaldehyde13. Etard’s reaction ,/_ Tue oxidation of toluene to benzaldehyde with chromyl chloride (CrO,Cl,) dissolved in CCl, o CS 7 ocroHcl, ec ce oe =2E- © ocxowa, ue, G) oer Brown complex Benzaldehyde .| ap. Bsterification reaction / The reaction of alcohols with carboxylic acids in the presence of a few drops of cone. H,SO, to form esters. / ° i cone. H,S0, ; CH,C—OH .+ HOCH,CH, CH,-C_ocH,CH, + H,0 Acetic acid Ethyl aleohet Bthyl acetate It may be noted that if HCI gas is used as a catalyst in the above reaction, the reaction is known as Fischer- Speier esterification, ‘ ‘/Blb's reaction ‘The oxidation of phenol by potassium persulphate (K,S,0,).in alkaline medium to form a mixture of catechol Oo - oT. DO 7 Phenol Catechol iy p-Quinol chaustive alkylation ‘The process of converting an amine (1°,2° or3*)into ts quaternary ammonium salt on treatment with excess dfelky] halide is called exhaustic alkylation. If alkyl halide is methyl halide, the process is called exhaustive st | Sctiyaion. cH H, -S. (cHyH 8S. HN 8. CH) aror Methyl Dimethyl Trimet Fittig’s reaction “: This action is a modification of the Wurt’z reaction. In this reaction two molecules of haloarene combine fh metallic sodium in the presence of anhydrous ether to give diphenyl. (Ofer anes ao) "se +2Nacl ve ‘Two molecules of oe # : 3 chlorobenzene [tinccinrnction esr toed inaney etn withsllum atid Sucived in acetone. * Asus, CH,CH + NaCl 7 ae Snide j Actos, CH,CH,I + NaBr caycrspe, + Nat ist iodide FE Ethyl bromide19, Friedel Craft's alkylation the presence of anhyirous AICI form aaeae cnt other avomatie compounds react with aks! halides" he Pe benzene TIDE. Jy! benzene. This reaction involves the addition of allyl (—®) &™ eg CH, “| HCl 1) + CHL —Asveach * Methyl ‘Toluene Benzene chloride : CH,CH, HB: 1) + CH,CH,Br —Asotale a Became Bibel bromide erg benzene cH, CH, CH, © + CHCl _tstdAch_, o™ : Methyl chloride Touene * o-Xylene CH, p-Xylene ‘Thealkylation ofbenzene can also be carried with propene in the presence of phosphoric acid (as the catalyst) when the product formed is isopropyl benzene. © + cHcHecH, HF, O-cuict, Benzene Propene Isopropylbenzene or Cumene 20, Friedel Craft’s acylation Passe end other eromatic compounds react with acid chlorides or anbydridesin the presence of anhydrous IOI, to form ketones, This reaction involves the addition of acyl (RCO-) group. < 4A : COCH, Oo + ° CH,COCI _Atwdatcl,_ + HO Acetyl chloride Benzene Acetophenone COC, HH, © +0,H,COCL AlCl Oo + HCl B Benzoyl chloride jenzene Benzophenone . COCH, + (CH,CO),0 AIC, O Acete anhyrid aaa £3, CH,COON Benzene rae ‘Acetophenone a rearrangement conversion or rearrangement of an aryl este 4 treatment with anhydrous AICI,. aryl ester into o- and p-hydroxy ketone or a mixture of both et : ococH, on © AL, gna, Phenyl ny acetate o-Hydroxyacetophenone CocH, ~. : . ‘i p-Hydroxy acetophenon 1382 = MODERN'S abc OF CHEMISTRY:ey jpriel phthalimide synthesis i is reaction is used to prepare primary amine, mide converted nti yl Breating vith alcohols ek ey aN this reaetion, phthalimide converte give Nealkyl a5, wh soln KOH. The salt is then treated with alkyl pba, which on hydrolysis with dilute hydrochloric acid gives a primary amine as the product. con, CON Crean tote or NK 10 Phthalimide Potassium phthalimide coon co 2 SS Crees + CHANH, 220 ox Go Na Cas Phithalis acid Ethylamine N-Bthylphthalimide a) | gx-Gattermann reaction , ‘Thisis a modification of Sandme : yer's reaction, This involves the reaction of benzene diazonium chloride with - ) cufICl and CuBr to prepare chl lorobenzene and bromobenzene respectively. s NyCI- a ‘ cutie. + Ny i Benzene diazonium ‘Chlorobenzene : chloride a N,tcl- Br na oO can: oO a 4 Benzene diazonium Bromebenzene a chloride 3 4, Gattermann Koch reaction | ,, Benzene is converted to benzaldehyde by passing a mixture of carbon monoxide and hydrochloric acid gas _ inthe presence of anhydrous AICI, and traces of cuprous chloride. : a CO+HCL =——> HCcoc i Forms chloride <4 ‘ » CHO “ oO + HCOC] _Ad,.ceo , + Ha y Formyl ‘ Benzene chloride Benzaldehyde Thisieaction i, thus, a modification tothe Friedel-Craft reaction in which—CHO group is introduced in the yt Bltiotorn react loform reaction yi 1e compounds containing methyl group bonded to carbonyl group i.e. methyl Ketones (CH,CO—) or the é “pounds which can be converted to methyl ketones upon oxidation (eg, | 1g Tenet with aqueous sodium I q niaate and iodine solution and give yellow precipitates of iodoform. This reaction is also called iodoform. | [ion, q NaOH ——> CHI, .+ HCOONa + SNal + SH ye cues a ose —> oesCH,CH(OH)CH, + 41,+ 6NeOH ——> CHI, + CH,COONa + 5Nal + 51,0 ‘2Propanol CH,COCH, + 31, +4 Propanone HH ——> CHI, + CH,COONa + SNal + 3H,0 CH,CH,COONa + 8Nal + 3H,0 CH,COCH,CH, + 31, +4Na0H ——> CHI, + -Butanone g reaction is commonly used to distinguish between methyl ketones or methyl carbinols from other kefofips and aleohols. {ell Vohlard Zelinsky reaction ‘ The aliphatic carboxylic acids containing a-hydrogen react with Cl, or Br, in the: eect it i al sie ‘fred phosphorus togive a-haloacids, With excess of halogen, all the a-hydrogen atoms ofthe aliphatic carboxylic acids are replaced by halogen atoms. cH,coon —?, c,coon +? ai,cHcoon —8#?> Cl,CCOOH Acetic acid | Dichloroacetic ‘Triehloro acetic cl acid acid Monochloro acetic acid By. P CH,CH,COOH 432» CH,CHBrCOOH —“tis, > CH,CBr,COOH Propionic acid ‘a-Bromopropionie 4, ecdibromo propionic acid acid ‘The o-halogen in the reaction can be replaced by ather groups such as OH, —CN, —NH,, —COOH, ete. by suitable reagents. _/* Hofmann bromamide reaction ‘The amides can be converted into primary amines containing one carbon atom less than the original amid by heating with a mixture of Br, in the presence of NaOH or KOH. This reaction is also called Hofmann’ degradation reaction. CH,CONH,+Br,+4KOH ——+ CH,NH,+ K,CO,+2KBr+2H,0 Acetamide Methyl amine C,H,CONH, +Br,+4KOH ——> _,H,NH, + K,CO, + 2KBr + 2H,0 Benzamide ‘Aniline ‘The reaction is very useful to convert a higher member in a family to its next lower member. 28, Hofmann elimination reaction This is the pyrolysis of quaternary ammonium hydroxide which contains one alkyl group other than meth A ‘to give alkene. CH, E \ CH,—N—C,H,| OH —HSt. + CH,= CH, +H,0 1 cH, cH, Ao Mofmann mustard oil reaction ‘When amixtureofprimary amine carbon disulphide andmercuricchlordeisheated, alkylisothioyan with'a characteristic smell of mustard ol is formed, 1 s I Hest CH,CH,NH, + Heh, CH,CH,-NH—C_SH Tee, CHCHN = =S+HgS + 2HG Carbon disulphide Dithioethylearbonie acid Ethyl isothiocyanate . (Mustard oil) 580. Hunsdiecker reaction 7 / Alkyl halides are prepared by decomposing the silver salts of carboxylic acids dissolved in CCI, by bromity or chlorine. CH,COOAg + Br, Ch, CH,Br + CO, + AgBr Silver acetate ‘Methyl bromide a +_MODERNS abe OF CHENISTRY-M (CBSECH,COOAg | Hydroboration reaction meee ai. 4 The {5 qhis reaction involves addition i Thi rea Dy aaaltion of water to a double bond oppasite to that of MarkownikofT reaction. The jon takes pl addition of bor Fj nscion tal ama By zis ” of borane (BE,) followed by hydrolysis to aleohol. = , Is 2 —tHt> (CH,CH,CH,),B 10, 3cH,CH,CH,OH es (oni. or OH, CH = CH, —O Ri. THF, 8CH,CH,CH,OH 2, Kolbe’s electrolysis reaction A, The electrolysis of sodium or potassium salt ofa carboxylic acid in aqueous solution, gives alkane, alkene or as the product dependin; ie ack alkyne as the Broduet depending upon the nature ofthe carboxylic acid used. (® Ethane is prepared by the electrolysis of aqueous potassium acetate. 2CH,COOK ——+ 2CH,coo-+ 2K* Pot, acetate (Anode) (Cathode) Atanode: 2CH,COO~ _-2* ,2CH,CO0-—— CH,CH, + 2C0, Ethane At Cathode Both K* and H* ions (obtained by the electrolysis of water) will be formed but H’* ions are preferentially discharged due to the lesser discharge potential of hydrogen. 2H? +2e- ——» 2HorH, i) Ethene can be obtained by the electrolysis of aqueous solution of the potassium salt of succinic acid. CH,COOK CH,COO- I Bieta, | ya CH,COOK CH,COO- Pot succinate (Anode) (Cathode) At anode : $H,c00~ gucoo > =200, | : CH,COo- CH,COO CH, ; _ Ethene At cathode : 2H* +2e- ——> 2HorH, (iii)Ethyne can also be obtained by the electrolysis of aqueous solution of potassium maleate. CHCOOK CHCOO— I Elects, | + 2K CHCOOK CHCOO- Pot, maleate (Anode) (Cathode) ‘ CHCOO- _,- CHCOO__5¢9,_ CH | At anode : i) so ah el cHCOO- cHcoo cH \ Ethyne ‘At cathode : 2H*+2e- ——> 2H or Hy 38. Kolbe’ idt reaction : Fecanet anes reacts with CO, under pressure (6-7 atm) at 400K to form sodium salicylate which upon “ification with HCl gives salicylic acid. ONa OCOONa oe ou, i COONa 2, or [O}+co, =i ae ue Sodium 2-Hydroxy benzoie acid Sod. phenate re salieylate alieylic acid) pvesaces| 7) pete+34, Knoevenagel reaction Sheree ile hides ana Aldehydes react with compounds containing active methylene group in the presence of organic a form a, frunsaturated acids. CH,CHO+CH(COOH), —HSi> CH,CH= HCOOH + CO, + H,0 Acetaldehyde Malonie acid Crotonie acid C,H,CHO + CHCOOH), —HSi CjH,CH=CHCOOH + CO, + H,0 Benzaldehyde Malonie acid Cinnamie acid 85, Liberman nitroso reaction a Both aliphatic and aromatic secondary amines react with nitrous acid (NaNO, + dil HCI togivenitrosoamines which are generally yellow oily compounds and are insoluble in mineral acid R,NH+HONO = —> N-N=O +H,0 Danie NDitipinitrosonmise (CH), NH+HONO . ——+ (C,H,),N-N=0 +H,0 Diethylamine N-Diethylnitrosoamine “ ‘The nitrosoamine on warming with a erystal of phenol and a few drops of concentrated sulphuric acid gives ‘green solution which upon treatment with aqueous alkali solution changes to deep blue. This reaction is used a8 a test fo distinguish secondary amines from primary and tertiary amines. 86. Lederer - Mannasse reaction Phenol condenses with aliphatic or aromatic aldehydes in the o- and p-positions. For example, phenol undergoes condensation with formalin (40% aqueous formaldehyde) at low temperature to form p-hydroxy benzyl alcohol. OH OH. OH 7 © + mew aan, O ur Gre CH,OH o-hydroxybenzyl p-hydroxybenzyl alcohol alcohol Anis reaction is the basis of preparation of bakelite. ra Mendius reaction The alkyl or aryl cyanide is reduced to. a primary amine with nascent hydrogen produced by the action sodium amalgam and alcohol. CHCN +4H _NvCHOH | CH CHE, Methyl Ethyl amine cyanide CN CH,NH, Phenyleyanide Benzylamine 438. Oxymercuration and Demercuration of alkenes yy Alkenes react with mercuric acetate in a mixture of THF a ind water to sive (hydroxyalkyl) me /compound, involving addition of -OH and -HgOAc to the double b ydroxyalkyl) ond. This is called Oxym ion. /f NeBl, reduces - HgOAc and replaces with hydrogen. This is demercuration eo coe CH,(CH,),CH=CH, #0, CH,(CHL), Fa fe r— Pent-l-ene OB Hy0Ac Ou Pentan-2-o] : ca oH cH, oH entan-2-ol ith HgOAC Nai TF o> - Methyl cyclopentene Methyl eyclopentanol MODERN'S abe OF CHEMISTRY-XI (COS.-perkin's reaction Penni $9 aldehyde on heating with acetic anhydride in the presence of sodium acetate, and the hydrolysis product obtained gives a, Brunsaturated ser lcinnamic acid, O,H,CH = 0 + H,CHCQ ‘i C,H,CH: co cxi,coone bai CH,COO Ba a = CHCOOH + CH! 0 SB 70 > CiH,CH a CH,CO” cH,co Cinnamic ‘Acetic anhydride 440, Rosenmund’s reaction Acid chlorides are converted to corresponding aldch, ing through a hot solution of the acid ehloridein ly poisoned with sulphur or quinoline), ion is carried out des by catalytic reduction. The reaction is earris the presence of palladium deposited over barium sulphate ° t ° a CH,—C—cl 4 HA, PAS, CH CH + HCI Acetyl chloride Acetaldehyde ° : ° i ll CoHs—C—Ol +H, —PABSSO. CHy.—C-H + HO Benzaldehyde imer Tiemann reaction Phenols react with chloroform in the Presence of aqueous alkali at 340K, The hydrolysis of the resulting Product gives 2-hydroxybenzaldehyde (salicylaldehyde), OH ONa ONa OH vat Cl Cl ‘ OscH0, 3g Gy 38-6 HOH), — nor HO ‘ Phenol (Unstable) Hydroxy ~ benzaldehyde (Salicylaldehyde) _[nthis reaction, a small amount of p-hydroxy benzaldehyde is also formed. ‘Itinstead of chloroform, carbon tetrachloride is used, salicylic acid is formed, OH ONa ONa on OB Ose Grom Fem Salicylic acid small amount of p-hydroxy benzoic acid will also be formed, batier and Sendern’s reaction jaa turated hydrocarbons are reduced to saturated hydrocarbons with hydrogen in the presence of Raney 8 catalyst at 473—573. : CH,=CH, +H, iii? CH,—CH, Ethene Ethane CHeCH+2H, —yatst? CH,—CH, et Ethane® _ 48, Sandmeyer's reaction enzene, eyanobenzene on treatment ith Benzene diazonium chloride is converted to chlorobenzene, bromob CuCVHCI, CuBr/HBr and CuCN/KCN respectively. 44, Schiemann reaction Fluorobenzene is prepared from benzene N,cr Che's Benzene diazonium chloride Chlorobenzene NiCr | Br Nior cN CuCn N, O = Os re diazonium chloride by treating with fluoroboric acid and heati the product formed. ,C1 N,BF, F HBF, Fusraben acid © Heat O REESE ar Benzene diazonium Benzene diazonium Fluorobenzene chloride fluoroborate AB, Sehotten Baumann reaction ‘The reaction involves the benzoylation of phenol, primary or secondary amine with benzoyl chloride in yresence of aqueous sodium hydroxide. OH OCOC,H, © + CHcoc =, + HO Benzoyl chloride Phenol Phenyl benzoate NH, NHCOC,H, © + -CjHcocl = =—% > + Hel Benzoyl chloride Aniline Stephen's reaction e partial reduction of alkyl or aryl cyanides to the corresponding aldehydes with a suspension of anhydn SnCl, in ether saturated with HCI at room temperature followed by hydrolysis. SnCl, +2HCl ——> SnCl, + 2H] ‘Nascent CH,—C =N+2(H)+2HCl ——> CH,CH = NHHCI H,0 Bo), CH, NH, v m5 Methyl cyanide Acetaldoxime hydrochloride retaness 4 C,H;—C=N+2(H]+2HCl — C,H,CH = NH HCI HOG). CH. : CH Cl Phat une Eaaiddeaisbpdrodiide >" “Git oheeanigtealdehyde to an a-amino acid with one more carbon atom. Hs PHAN ne Gg pacocH Acetaldehyde NH, NH, eealanine 48, Transesterification (a-Amino acid) When an ester is treated with e the presence of a base such as the as catalysts, a new ester and a ne ‘Xcess of another alcohol (other than one from which ester is formed) in corresponding sodium or potassium alkoxide or an acid (H,SO, or HC) w alcohol is formed. e R-C~or'+ RX HY, WeONa ane Ester ‘OH AELRONA, ~-R-C- OR" + ROH ne Reflux CH,Co0C + C,H,OH _#' GH,ONe_ — CH,COOC,H, + C,H,OH i n-Butylacetate lux n-Butyl alcohol 49, Ulmann reaction a sone a een Bs Todobenzene is heated with copper powder in a sealed tube forming diphenyl. if OQHTrasioO) — + 2Cut , Todobenzene Diphenyl Tischenko reaction All aldehydes can be made to undergo Cannizzaro's reaction with aluminium ethoxide. Under these conditions the acid and the alcohol combine to form ester and the reaction is known as Tischenko - reaction : : 2CH,CHO —AWGiIy: , CH,COOC,H, Acetaldehyde Ethyl acetate - 61. Wittig reaction ; : ; °™ Aldehydes and Ketones react with phosphoranes (or phosphorous ylides) to give alkenes and triphenyl Phosphine oxide. cucu, CH,CH,CH,CHO + (C,H); P - Butanal > CH,CH,CH,CH = ¢ ~ CH, ~ CH, +, cH, (C.H,),PO ‘3-Methylhept-3-ene a oO 0+ (C,H), P CH, =—— CR cH, + CHiy.PO Methylene cyclohexane Cyclohexanone : Wiliams ised to prepare both symmetrical and unsymmetrical ethers by treating alkyl halide with is react ther sodium alkoxide or sodium phenoxide. ON + cHC,H, + NaBr SE an” sol on Habeas Bronomethane Sod. ethoxide on Hi, + NoBi Gate, Sime eso tietas nee rom Sod, ethoxi thane Bromoe' : ae = oo i Ethoxybenzene CHC ye Sod: Phenoxide Chloroetha Be CH, + ee, eagle, > Sa Sinnoethane Sod te buttion of alkyl aryl ethers because oftheir low reactivity d for the prep Aryl halides cannot be use"53. Wurtz reaction : Z Alkyl] halides react with metallic sodium in the presence of anhydrous ether to form alkanes. This reaction hs used for the preparation of higher alkanes. For example, CH,Br +2Na+CH,Br ——> CH,CH,+2NaBr Bromomethane Ethane C,H,Br + 2Na+C,H,Br ——> .CH,CH,CH,CH, + 2NaBr Bromoethane Butane Ifwe start with different alkyl halides, then a mixture of alkanes will be formed. For example, if we start with CH] and C,Hgl, a mixture of ethane, propane and butane will be formed. a CH,+2Na + ICH, —— > CH,CH, + 2Nal Methy! iodide Ethane CH,CH,I = + 2Na+ICH,CH, ——> CH,CH,CH,CH, + 2Nal Ethyl iodide Butane CH,CH © +2Na+ICH, © —> CH,CH,CH, + 2Nal Ethyl iodide: Propane 54. Wartz Fittig reaction Haloalkanes react with haloarenes in the presence of sodium and anhydrous ether to form alkyl benzenes. ©HaF eran, —> ©O)-cu,+2Nacr Chlorobenzene Toluene ©-# ¥Bicu,cx, —+ (O)—CH,CH, + 2NaBr Bromobenzene Ethyl benzene 5. Wolff-Kishner reduction ‘The reduction is done by heating the carbonyl compound with a mixture of hydrazine and KOH in the //f presence of ethylene glycol. It is called Wolff-Kishner reduction. CH,CH = 0 NN CH,CH = NNH; _KOH_, CH,CH, +N, Acetaldehyde Hydrazone Ethane CH,—C=0 SN, CH,—P-NNH, —KOH_, CH,CH,CH, +N, ; Hy cH, cet » Proper ] ‘Acetone Hydrazone