ee BT SELECTION LEKE RAHENGE YE WADA HN HAMARAGURENTEED !!! AY DAY 23 TARGET CHAPTER WITH TOPICS ~7—~ Aldehyde Ketone & Carboxylic Acid <0) Introduction « IUPAC Nomenclature « Structure of carbonyl Group « Preparation Of Aldehyde & Ketone e Physical Properties eZ Nines uO) ¢ Introduction « IUPAC Nomenclature e Structure of Amine e Preparation Of Amine « Physical Properties 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; OH “(Cinnam $ ‘vanillin, ‘Salicylaldehyde Cinné wre “y harmaceuticals t in many food products and p 2 ue ee these families ‘are manufactured for use as solvy, goh” Gee ap be, acetone « for preparing materials like adhesives: paints, es plastics, fabrics. ete. perfumes. PS abe ram of =O OS 5 a ° etch oh conta 12.1 Momenclatn structure of Carbonyl Group option: 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 wsESL 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 : 32S 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\MoFrom acyl chloride (acid chior; v of ea! Acyl chloride (acid chloride) is hydrogenat, ed Tt Aldehydes on barium sulphate. This reaction jg calleg wi! a 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 groupie esoioe: co to a chromium complex. gives corresponding benzaldehyde. Chemistry 162)a : - CH(OCrO! CHC we + Cro,cl, C5 Co : -_ Ho, ( Toluene poco nd R,Cd + 2Mg(X)Cl xy Ye) dae ft Red 9 2R —E—R + Cach, Ge-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) BS a eSLiOn their bolling points. CH,CHO, CH,CH,OH, CH,OCH,, CH,CH,CH, Tao apace a 12.4 Chemical Since aldehydes and Ketones both possess the carbonyl jy Reactions &TOUP: they undergo similar chemical reactions. CACLION, 1. Nucleophilic addition reactions Contrary to electrophilic addition reactions observed in Unit 13, Class X), the aldehydes and ketones undergo nucy addition reactions. (@ Mechanism of nucleophilic addition reactions Anucleophile attacks the electrophilic carbon atom of ty, carbonyl group from a direction approximately perpengig, the plane ors" hybridised orbitals of carbonyl carbon (Fig) ‘The hybridisation of carbon changes from sp” to sp” in this slow ||step 1 and a tetrahedral alkoxide intermediate is produced, intermediate captu proton from the re medium to give electrically neutral py The net result is addi Nu” and H° acrog carbén oxygen doubk as shown in Fig. 122 Tetrahedral intermediate Addition product Fig.12.2: Nucleophilic attack on carbonyl carbon (i) Reactivity Aldehydes are generally more reactive than ketoz nucleophilic addition reactions due to steric and elet reasons. Sterically, the presence of two relatively! substituents in ketones hinders the approach of nuclesit carbonyl carbon than in aldehydes having only ont substituent. Electroriically, aldehydes are more reactit ketones because two alkyl groups reduce the(lectro the carbonyl carbon more effectively than in former. id you expect benzaldehyde to be more reactive or less reactive nucleophilic addition reactions thah propanal3 Explain your anst Solution The carbon atom of the carbonyl group of benzaldehyde Is IS electrophilic than carbon atom of the carbonyl group preset! o propanal. ‘The polarity of the carbo group is reduced in benzaldehyde S to resonance as shown below hence it is less reactive than prop* Ss Sg =o.—