ee BT SELECTION LEKE RAHENGE YE WADA HN HAMARAGURENTEED itt AYZs DAY 24 TARGET CHAPTER WITH TOPICS Aldehyde Ketone & Carboxylic Acid <0). Chemical Reactions: CO BW * Clemmensen Reduction, Wolff- Kishner Reduction Tollens,Benedict,Fehling, Haloform Oxidation Reaction Reactions Of Alpha Hydrogen YQ AES (7) > Chemical\Reaction: Basic character * Alkylation & Acylation: Benzoylation Reaction * Carbylamine Reaction Da loa lel) * Hinsberg’s Reagent Ce 3 SELECTION LEKE RAHENGE YE WADA HN HAMARAAfter‘studying this Unit; you will be able:to write the-common’ and IUPAC names of ‘aldehydes, ketones and: carboxyll acids: write the structures» of! the: compounds »containing:fimetional. TES groups» namely: carbonyl! and: carboxyl 'groups;. Carbonyl compor unds are of utmost importance to organte describe the: important: methioas» MeMmIstry. They are constituents of fabries, flavourings, plasties of! preparation iandreactions» of; 2 drugs. . these: classes of compounds; lm) . Previous’ Unit; you: have studied organic correlate dance La rhe and compotinds with function; ‘groups containing cartons chiemical eee elaetiy ties oxygen sifiglé bond. In this Unit, we will study about the cde ibe acids: organic: compounds containing carbon-oxygen double 4 : j bond.(+G=0) called carbonyl group, which ts one of the~ See aonatcee most important functional Broups'in organic chemistry: Efiidkitenen . "ES Intaldéhydés,\the: carbonyl 'group, is bonded !to a understands various» factors, -Cubonrund Hydro whilé in the ketones, it ts:bondéd alfecting:thecactdity;ofcarboxylie. ‘© tWocarbon atoms; Thie:carbonyl compounds in which acidssand their’ reactions; catbonof" carbonyl! gheup, ie. bonded to carbon vee : hydrogen and: oxygen':ft hydroxyl imotety: (OH) are~ déscribe- the: uses of aldehydes; f Ketonesand ‘carboxylievaelda: KNOwn as-carboxylic acids\whiledin compounds where, carbon s:attached to:carbor or hydrogen and hitrogen of- Fj ,moletyy ors to. halogens-arecalledlamides-and acyl thalidés»respectivelyy Bstergvandianhydrides-are- derivatives. oficarboxylic.acids; The general.formulas-of! thiese:classes-oficompounds-are given below: oO oO ’ oO ce ra Ash ee ¢ . “Aldéhy\te Ketoner Carboxyldraetd?oO 0 Ao 7 < Or IR Acid anhydride d carboxylic acids are widespreaq In nlaehydes, Kel a oa play an important role in bik and animal {ini ‘aad fragrance and flavour to nature, for ine, They ad FE" eyialdehyde (from meadow ome ‘iin (from vanilla ste nave very pleasant fragrang wpamaldehyde (rom ee Ore = oy CHO cHO Of [ego CO w (as OCH; on wx Goniin.) ‘7Gatioylatdenvde (Ginna: “y harmaceuticals t in many food products and p 2 ue ee these families ‘are manufactured for use as solvy, ah” Gee ac be, aceon « for preparing materials like adhesives: paints, es plastics, fabrics. ete. perfumes. PS abe ram of =O OS 5 a ; atch ot conta 12.1 Momenclatn structure of Carbonyl Group apton>: 121.1 L Aldehydes and ketones Nomenclature ‘Aldehydes and ketones are the simplest and most important carb compounds. ‘There are two systems of nomenclature of aldehydes and ketones (a) Common names a ‘Aldehydes and ketones are often called by their comma nat instead of IUPAC names. The common names of most aldehydes! Gerived from the common names of the corresponding carboy seids Section 12.6.1] by replacing the ending -ic of acid with aldehy ‘At the same time, the riames reflect the Latin or Greek term fort original source of the acid or aldehyde. The location of the substitt im the carbon chain is indicated by Greek letters a, B, 7, 5, ete. o-carbon being the one directly linked to the aldehyde group! carbon the next, and so on. For example CHO X rr fl com Ca y\ B @ Acetaldehyde Benzaldehyde CF Bromobutyraldehyte ine at NS‘The common names of ketones are derived by naming two ally! or aryl qroups bonded to the earbony! group. ‘The locations of substituents are Indicated by Greek letters, 07, ff’ and 0 on beginning with the carbon atoms next to the carbony! group, Indicated as ao’, Some ketones have historical the simplest dimethyl ketone ts called acetone. Alkyl pheny! ketones are usually named by adding the name of acyl group 46 prefix (o the word phenone, For example oO O Acetone Acetophenone es Benzophenone Proptop! REE (b) IUPAC names ‘The IUPAC names of open chain aliphatic aldehydes and ketones are derived from the names of the corresponding alkanes by replacing the ending ~e with -al and -one respectively. In case of aldehydes the longest carbon chain 1s numbered starting from the t carbon of-the aldehyde group while In case of ketones the ‘ numbering begins from the end nearer to the carbonyl group. The substituents are prefixed in alphabetlcal order along with numerals indicating thelr positions in the carbon chain. The same applies to cyclic ketones, where the carbonyl carbon is numbered one. When q the aldehyde group 1s attached to a ring, the suffix carbaldehyde 1s added after the full name of the cycloalkane. The numbering of the ring carbon atoms start from the carbon atom attached to the aldehyde group. The name of the simplest aromatic aldehyde carrying the aldehyde group on a ‘benzene ring Is benzenecarbaldehyde, However, the common name benzaldehyde is also accepted by IUPAC. Other aromatic aldehydes are hence named as substituted benzaldehydes. ° Br CH, CH-C-H CHs-CH-CH, CH-CH-cH-b—H Ethanal 4-Bromo-3-methylheptanal ‘CH; 3-Methylcyclopentanone ° i CH,—CH,—CH=CH—C-H © )-cuo EB Htonasd OR cance, i int-2-enal Ht Cyclohexanecarbaldehyde L-Phenylpropan-1-one id Carboxylic Acidsg ;—C—-H G9 oR H,C—CH;— C— CH;—C— CHJ—CH~C~G 3-Oxopentanal' 24-Dimethytpeny ch, CHO = ‘ OHC- CH CH= CH; CHo cHO 0, Propane=1/2,3-trlcarbaldehiyde 4-Nitrobenzenecarbaldehydé: (7, sro giveddentical-treatment to allay ie es hia groups: the compound 1s named as soya benzaldehyde é given.in Tablé-1221! Aldehydes HCHO CH,CHO (CHJ,CHCHO “Cn CH.CH(OCHJCHO > CH,CH,OH,CH,CHO CHscHCHO> =| Ce on Bri Ketones* CH;COCH,CH;CH} (CH3,CHCOGH(CH,),| 1 OS | (CHJ;0=CHOOGH;, Table: 12:1: Commomand? IUPAC. Names: of! Some: Aldehydes: and:Keton, ‘Common’ name Formaldehyde: Acetaldehyde: Isobutyraldehyde ‘-Methyléyclohexanecarbaldehyde a-Methoxypropionaldehyde: Valeraldehyde: Acroléin’: Phthaldehydec m-Bromobenzaldéhyde: Methyl n-propyl Ketone. Ditsopropyl ‘ketone o-Méthyléycléhexanone~ Mésityl toxide: The.common and IUPAC names:ofisome:aldehydes: ‘and keton 3-Methyleyclohexanecarbalde 2:Methoxypropanal Pentans Prop-2enali Benzene*1}2-dicarbaldehyde! 3-Bromobenzenecarbaldehy, ors 8-Bromobenzaldehyde~ Pentan=2-one: 2.4:Dimethylpentan-3-one> 2:Methyleyclohexanone: 43Méthylpent:3en-2-one* Chemistry: 5860;R Sek NAR S cP —a- , A~ Le 4211.28trecture ‘The carbonyl carbon:atom is-sp'-hybridised-and forms Ge ‘sigma (6) ~s 6f.the ‘bonds. ‘The fourth. valence electron of carbon-remains in its; p-orbital «Carbonyl and forms a-7-borid.with oxygen by overlap with: p-orbital of an oxygen. Jn addition, the oxygen atom also has two non bonding electron pairs. Eis: the carbonyl carbon and the three atoms attached to It le in the c Plane and the:n-electron cloud is above and below this plane. The ond angles are approximately: 120°.as structure (Figure!12! : The carbon-oxygen double’ bond clectronegativity of oxygen rela x we ESL 12:1 \Write the structures of the following compounds. (i). a-Methoxypropionaldehyde (ii) 3*Hydroxybutanal | \Gti):2-Hydroxyeyclopentane carbaldchyde’ (iv) '4-Oxopentanal : _ (v): Di-sec. butyl ketone (vi) :4+Fluoroacetophenone 2'Preparation of fildehydes‘Some important methods'for the preparation of-aldehydes and Ke andiketones:are:as follows: _, traded} otk -By[oxidation of alcohols "Aldehydes andiketones are generally prepared by oxidation of primary »and.secondary.alcohols; respectively (Unit 11; Class XI), ‘dehydrogenation:of alco! passed over heavy sts (Ag or‘ Cu}.\Primary..and secondary alcohols give pectively (Unit 11; Class XII). a followed by reaction with zinc dust and.water gives aldehydes, a & Aldehydes, Ketones and Carboxylic Actd a xylic Acids Rc ¥ WO yyv 2. From nitriles and esters Nitlles are reduced to corresponding imine with g ae in the presence of hydrochloric acid, tangy 7 corresponding aldehyde. Which on yas \O“ i oS > ced : 2S ketones or a mixture of both q, CO pattern of the alkene (Unit 13, cinching a (i) By hydration of alkynes: Addition ore Ly ,-presence_o ; ti ou ' eR eZ AN 1 12.2.2 Prepligiiti\ NoFrom acyl chloride (acid chlor, v of ea! Acyl chloride (acid chloride) is hydrogenat, ed Tt Aldehydes on barium sulphate. This reaction jg calleg wi! wh Ua on Se SAA WOUS CHEAAL RCN ¥SnCl, + HCl | —— RCH = NH This reaction is called”St x Alternatively, nitriles are Coctectively tie diisobutylaluminium hydride! (DIB, to imine a hydrolysis to aldehydes: ‘ ok A. Sacks @sduad “cs take RCN —2:AIK(-Bu), x) #0 =, >RCHO LQALY Oh — SS RCHO - 2. i, 1. AIH(i-Bu), cHy Hed)-cr.c CN] = cu,—edhere Ys 1 CNp SB Ayanups q prrore'e Similarly, esters are also reduced to aldehydes with DIY ‘ oO oO AY) pdAWyy ll 1. DIBAL-H boy CAICH.— OG Hy SIE cacy, —E- - From hydrocarbons Aromatic aldehydes (benzaldehyde and its dervaes tf m aromatic hydrocarbons by the following methods: By oxidation of\methylbenzend) sett Strong oxidising agents oxidise toluene and ey benzoic acids. However, it is possible to stop th the aldehyde stage with suitable reagents that aise Hing, f0.aN intermediate that is difficult (0 0 following methods are used for this ee yore? (a) Use of chromyl chloride (CrO,Cl,): which on methyl group ts + esomioe: coo to a chromium complex. gives corresponding benzaldehyde. Chemistry 162)Toluene sz) Chromium complex Benzaldehyde is reaction is calldyeifard reaction) ; 0) Ustips hors oxide (CxO. Toluene or substituted toluene heen is converted to benzylidene diacetate on treating with chromic oxide in acetic anhydride. The benzylidene diacetate can be hydrolysed to corresponding benzaldehyde with aqueous acid. ~CH(OCOCH,), CHO (CH,CO),0 273283K,, oe HON Benzaldshyde % CHy, (i) By side chain chlorination followed by hydrolysis Side chain chlorination of toluene gives benzal chloride, which i on hydrolysis gives berizaldehyde. This is 4{gommercial method of manufacture of benzaldehyde. CH, a co Lown, cuyhw ‘CHC CHO Tae k ‘Toluene [Benzal chtorid@) Benzaldehyde (it - ode s dg When benzene or its derivative is treat eee carbo, monoxide and hydrogen chloride in the presence of anhydropé aluminium chloride or cuprous chloride, it gives benzaldehyde or, substituted benzaldehyde. Benzaldehyde action, 12.2.3 Preparation 1, From acyl chlorides KSIMS 29 EF 5 of Ketones ‘Treatment of acyl chlorides with dialkylcadmium, prepared by the reaction of cadmium chloride with Grignard reagent, gives ketones. 2R—Mg— + CdCl—>RCd + 2Mg{xXCl ee ey eK ROR fi RCd —> 2R—C—R + CdCl, ae Benzene This reaction is known as!-2,-From nitriles ‘Treating a nitrile with Grignard reagent followed by twec ‘a ketone. MgBr—S5 > CH,CH, — Sen. 3G we ‘CH; CH, — CH, — + Propi ‘y Chey 3. :From:benzene'or substituted benzenes ‘ When benzene or substituted benzene is treated.with aciq “the presence of -anhydrous.aluminium: chloride, it ns corresponding’ ketone. ‘This: reaction is:kmown as:Frieqo | = sacylation reaction. Give ‘names cof the «reagents -to ‘bring sabout : *the i ss <€yclohexanol to cyelohex y(t) ‘Bthanenttrile to-ethanal (vi) :But-2-ene:to ethanal 2) C,H.NH*CrO,CHPCC) -(d) “Anhydrous Cro, (ii). CrO,in the presence sy) : (DiisobutylJaluminium -ofiaceticanhydride/ “hydride (DIBAL-H) 1. CrO,Cl, 2: HOH PCC “(vi) Bisulphite addition ‘he mien haga ey, a ‘erreaain the left for most ketones due to steric reasons. The hydrogensulphite addition 4% compound is water soluble and can be converted back to the =x original carbonyl compound by treating itwith dilute mineral G3 ’\ acid oralkali. Therefore) these are useful for se and purification of aldehydes me (c) Addition of Grignard reagents: (refer Unit 11, Class XII). (a) Addition of alcohols: Aldehydes react with one equivalent of monohydric alcohol in the presence of dry hydrogen chloride to yield alkoxyalcohol intermediaty, known as hemiacctals, which further’ react with one more molecule-of alcohol to f give a gem-dialkoxy compound known as acetal as shown in the reaction. Ketones react with ethylene glycol under similar conditions to form. cyclic products known as R CH,OH Hel R,_/0—CH, bony] comp MS gas, 7 I therefore,/incteases ‘0 ———— C: + HO here RO _ te OH dil. HCI Rr” No—cu, tlie electrophilicity of the carbonyl carbon facilitating Ethylene glycol ketalthe nucleophilic attabkof ethylene glycolAceta,, ' emineral cagig shydrolysed «with naqueous nat & ve " are eondingaldehydes eae revpectiy =o + Moe ‘ammonia and its derivatives: ‘Nuclegp), wee oe ia anid its derivatives! H,N-Z:add to the oe up of aldehydes and ketones. ‘The reaction ts ae vand catalyse RICK ew - ne tae £ favours: the oH >\c= ‘ formation dy Sexo + HNZ =| So% C=NZ+ 1,0“ fongonde % oNnna intermediaty >C-N-Z. °Z-= Alkyl, aryl, OH, NH, CeHgNH,‘NHCONH,, etc. ‘Table 12.2: Some N-Substituted Derivatives of Aldehydes and Ketones (>C= Z Groce erect ‘Amine } \ j bstitutec x Hydroxylamine Hydrazine: Hydrazone Phenylhydrazine Phenylhyd 2;4-Dinitrophenyl- £24 Dinitrop hydra, hydrazone Ww \Semicaibazide ‘Semicarban — ‘Reduction “(Reduction to alcohols: Aldehydes and? ‘primary :and’ssecondary > 13 w (869) Aldehydes; Ketoneskand Carbo: Setded CON)Sind (4) with, molecular formula_C,H,O forms ange-red precipitate with 2,4-DNP reagent and gives ely cipitate on heating with iodine in the presence of sod 1 hydroxide, It neither reduces Tollens’ or Fehlings’ reagent, nor | it decolourise bromine water or Baeyer's reagent. On drastic oxidat with chromic acid, it gives a Carboxylic ‘acid (B) having mol i formula C,H,0,, Identify the compounds (A) and (B) and explain 1 reactions involved. * (8) forms 2,4-DNP derivative. Therefore, it is an aldehyde or a ke ‘Since it does not reduce Tollens' or Fehling reagent, (A) must be a {A) responds io iodoform test. Therefore, it should be a methyl ‘The molecular formula of (A) indicates high degree of unsaturation, it does not decolourise bromine water or Baeyer's reagent. This in the presence of unsaturation due to an aromatic ring. 7 Compound (B), being an oxidation product of a ketone should bei carboxylic acid. The molecular formula of (B) indicates that it shoul be benzoic acid and compound (A) should, therefore, bet monosubstituted aromatic methyl ketone. The molecular formula (A) indicates that it should be phenyl methyl ketone (acetophenont Reactions are as follows: a i i ON ee ’ ON Co “cr + se 27) no, 24S sg @ a 5 oO CHO 2, 4-Dinitrophenylhydrazine 2, 4-DNP derivative Chemistry ,370) -c- E 9° f : cooH 1 ° I HCrO. on wo on + CHI, a 4. Reactions due to a-hyd, teas drogen Orr des and ketones) The aldehydes RETOres reactions due to the acidic nature of a-hydrogen. The acidity of a-hydrogen atoms of carbonyl compounds is due to the strong electron withdrawing effect of the carbonyl group and resonance stabilisation of the conjugate base, Idehydes and ketones having at least one gO a reaction in the ‘presence of dilute alkall rm B-hydroxy aldehydes (aldol) or B-hydroxy respectively. This is known as Aldol reaction. drogen undei as catalyst to fo ketones (ketol), A 2 CH SCH a CH CH-CH,-CHO io” CH-CH=CH-cHo “~Efhanal Ay But-2-enal OnE (chon oatsuds a 3-Hydroxybutanal (dol co: no A paleo) roduc aa ies - Sat i 2CH,-CO-CH, van CHy€-CH,CO-CH, x CH,-C=CH-CO-CH, Propanone OH 4-Methylpent-3-en-2-one (Ketol) (Aldol condensation + 4-Hydroxy-4-methylpentan-2-one product) The name aldol is derived from the names of the two functional groups, aldehyde and alcohol, present in the products. The aldol and ketol readily lose water to give a,B-unsaturated carbonyl compounds which are aldol condensation products and the reaction Is called Aldol condensation. Though ketones give ketols (compounds containing a keto and alcohol groups), the general name aldol condensation still applies to the reactions \ of ketones due to their similarity with aldehydes, we yn 18k) Aldehydes, Ketones and Carboxylic Acids| aldéticondénsations: Whien’aldél condénsa, | mening andi/ orietonce ie eros idol condensation. [fboth of lim contain g, ey sige pam SbspuriprodaeesTh = patcenal fiethanal! 24Méthylpent-2%eng) fromitwomolecules, ofipropanal’' two moléculés:of simpléorself'aldol products» L a Os CH}CH=C-CHO? +* CH;CH}CH=CHCHO, 9 pa dy 2-Meéthylbut-2-enal | Pént-2-enal! | fromrones amoléculé-of ¢thanal‘and one:molecule-of propang ea —aalieanaes -4 Ketones canalso be-used 4s one-component inthe cross reactions. a AS y Oe OP Om 4 2 a ‘one moléculé:of ‘thie -aldéhyde=is*rediicé alcohol whilé:anothier is oxidised ‘to: carboxylic: acid salt: i were m p peso * eo. onc, KOH)—S->» HC oH + HL? H Hf A . Nok = Formaldehyde: Méthanol: Potassium form 2 Creve: NaoH:—4->» «pe OH! + Cr Benzaldchyde- Benzyl alcohol Chemistry ;372)