afer studying this Unit, you will be able to ite the common and Tupac ies of aldehydes, ketones and carboxylic acids; write the structures of the compounds containing functional groups namely carbonyl and carboxyl groups; describe the important methods of preparation and reactions of these classes of com, : correlate physical properties and chemical reactions of aldehydes, ketones and carboxylic acids, with their structures: explain the mechanism of a few selected reactions of aldehydes and ketones; understand various factors affecting the acidity of carboxylic acids and their reactions; describe the uses of aldehydes, ketones and carboxylic acids. Carbonyl compounds are of utmost importance to organic chemistry. They are constituents af fabrics, flavourings, plastics and drugs. In the previous Unit, you have studied organic compounds with functional groups containing carbon- oxygen single bond. In this Unit, we will study about the organic compounds containing carbon-oxygen double bond (>C=0) called carbonyl group, which is one of the most important functional groups in organic chemistry. In aldehydes, the carbonyl group is bonded to a carbon and hydrogen while in the ketones, it is bonded to two carbon atoms. The carbonyl compounds in which carbon of carbonyl group is bonded to carbon or hydrogen and oxygen of hydroxyl moiety (-OH) are known as carboxylic acids, while in compounds where carbon is attached to carbon or hydrogen and nitrogen of -NH, moiety or to halogens are called amides and acyl halides respectively. Esters and anhydrides are derivatives of carboxylic acids. The general formulas of these classes of compounds are given below: oO Oo a: KX aoe x on Aldehyde Ketone Carboxylic acid oO Il lI YN i . Nu, Acyl halide; X = (Halogen) “Amide{ i i oe iC or iC o ‘* Ester Actd anhydride etones and carboxylic acids are ay an Important role in bioch, feganc and flavour to nature, for a) CHO CH= con OH ‘OCH, OH Vanillin Salicylaldehyde Cinnamaldehyde ‘They are used in many food products and pharmaceuticals to aq, id flavours, Some of these families are manufactured for use as Solvents (Le., acetone) and for preparing materials like adhesives, paints, Tesing, perfumes, plastics, fabrics, etc. 12.1 Nomenclature and Structure of Carbonyl Group 12.1.1 oA Aldehydes and ketones Nomenclature ‘Aldehydes and ketones are the simplest and most important carbonyl compounds. ‘There are two systems of nomenclature of aldehydes and ketones, Common names Aldehydes and ketones are often called by their common names instead of IUPAC names. The common names of most aldehydes are derived from the common names of the corresponding carboxylic acids [Section 12.6. 1] by replacing the ending -ic of acid with aldehyde, At the same time, the names reflect the Latin or Greek term for the original source of the acid or aldehyde. The location of the substituent in the carbon chain is indicated by Greek letters a, B, 7, 8, etc. The a-carbon being the one directly linked to the aldehyde group, B- carbon the next, and so on. For example ir CHO P f CH,CHO H,C—CH —CH,—C—H y p a Acetaldehyde Benzaldehyde B-Bromobutyraldehyde Chemistry 358The common names of ketones are derived by naming two alkyl sunty! Soups bonded to the carbonyl group. The locations of Substituents are indicated by Greek letters, a a’, B B’ and so on Peginning with the carbon atoms next to the carbonyl group. indicated as aq’, Some ketones have historical common names, the stmplest dimethyl ketone is called acetone. Alkyl phenyl etones are usually named by adding the name of acyl group as Prefix to the word Phenone. For example es i i ° ll g Cc c CH c CH,C-cH, Co cu, (oF x Co oO Abetome Asetovnenone Proplophenone eee ee names The IUPAC names of open chain aliphatic aldehydes and ketones are derived from the names of the corresponding alkanes by Teplacing the ending ~e with -al and -one respectively. In case of aldehydes the longest carbon chain is numbered starting from.the _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 alphabetical order along with numerals indicating their positions in the carbon chain, The same applies to cyclic ketones, wheré the carbonyl carbon is numbered one. When the aldehyde roup is 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 be hyde. However, the common name ., Other aromatic aldehydes are hence named as substituted benzaldehydes. ° I 2 nets 29 CH-C-H — CHy-CH>-CH, CH-CH-CH;-C-H : Ethanal 4-Bromo-3-methylheptanal ‘CH; 3-Methylcyclopentanone 0 I 0 oud CH,—CH,—CH=CH—C-H i -CH;-CH, Pent-2-enal Cyclohexanecarbaldehyde A Phenyipropan-1-fae) : Aldehydes, Ketones and Carboxylic Acidsy % 6 / ‘) q : GH i OH, Hc-cH,— CCH CI CH,~ CH C-CH~ cy, 3-Oxopentanal 24-Dimethylpentan sy, CHO ol CH GH— CHF CHO | CHO 0, pine 2.3tearbaldeyde A 4-Nitrobenzenecarbaldehyde — [yote: "To give dential tesiment to all aj ety) or groupe, the compound 8 NAMEG 28 shoyy 7% : 4-Nitrobenzaldehyde The common and IUPAC names of some aldehydes and ketone * given in Table 12.1. : . tt Table 12.1: Common and IUPAC Names of Some Aldehydes and Ketone, pu Jem Sooty Cord ret MCU Aldehydes : HCHO Formaldehyde | Methanal CHCHO Acetaldehyde ___-| Ethanal | i), CHCHO Isobutyraldehyde 2-Methylpropanal | HX HO ‘y-Methyleyclohexanecarbaldehyde | 3-Methylcyclohexanecarbaldehyge CH,CH(OCH,)CHO | o-Methoxypropionaldehyde —_| 2-Methoxypropanal isCH,CH,CH,CHO | Valeraldehyde Pentanal Pti=CHCHO | Acrolein Prop-2-enal i CHO | AL | Phthaldehyde Benzene-1,2-dicarbaldehyde ‘CHO HO 3-Bromobenzenecarbaldehyde or m-Bromobenzaldehyde 3-Bromobenzaldehyde Br Ketones CH,COCH,CH,CH,: | Methyl n-propyl ketone Pentan-2-one (CH,),CHCOCH(CH,),| Diisopropyl ketone 2,4-Dimethylpentan-3-one oO Ch a-Methyleyclohexanone 2-Methylcyclohexanone 1H ‘Hg),C=CHCOCHg —_ w 4-Methylpent-3-en-2-one \ J Lo ____Chemistry 98601 / Us 4 . & Uensw2 structure Theo yo of the bora ran Carbon atom is sp’-hybridised and forms thee ae “ four a Carbonyl and forms a pitt Valence electron of carbon remains i ae ne Jectron pairs. Thus, oxygen atom also has two non bonding ¢ same plane ean carbon and the three atoms attached to it He in the and the n-electron cloud is above and below this plane. bond Angles are approximately 120° as expected of a trigonal coplanar structure (Figure 12.1). | Group In addition, ™-bond with oxygen by overlap with p-or! Fist 2.1 Orbital diagram for the formation of carbonyl group The carbon-oxygen double bond is polarised due to higher clectronegativity of oxygen relative to carbon. Hence, the carbonyl 0 Q- Carbon is an electrophilic (Lewis acid), and carbonyl I —— | oxygen, a nucleophilic (Lewis base) centre. Carbonyl A ce e substantial dipole moments a a . e larity of the carbony! / 7 \ is expl ‘on Re ee involving a neutral a (B) (A) and a dipolar (B) structures as shown. Intext Questions e structures of the following compounds. -Methoxypropionaldehyde 3-Hydroxybutanal 5 iydroxycyclopentane carbaldehyde 2 -Oxopentanal -sec. butyl ketone CAA riirietoptcomne 12.2 Preparation of Aldehydes Some important methods for the preparation of aldehydes and ketones are as follows: . By oxidation of alcohols of Aldehydes and ketones are generally prepared by oxidation of primary aehyees \d secondary alcohols, respectively (Unit 11, Class XII). an Ketones . By dehydrogenation of alcohols This method is suitable f and is of industrial application. In this method alcohol vapours are passed over heavy metal catalysts (AGIORCu))Primary and secondary alcohols give ea and ketones, respectively (Unit 11, Class XI). ~ Fro idrocarbons y ozonolysis of alkenes: As we know, ozonolysis of alkenes followed by reaction with zinc dust and water gives aldehydes, ,86h, Aldehydes, Ketones and Carboxylic Acids12.2.2 Preparation of Aldehydes ding on the syp, ketones or a mixture of both depent ids {tern of the alkene (Unit 13, ee tut By hydration of alkynes: Addition of water to ethy preanace of H,SO, and HgSO, gives acetaldehyde, : alkynes give ketones In this reaction (Unit 13, Class x,t, ~ From acyl chloride (acid chloride) ted. Acyl chloride (acid chloride) is hydrogenat t, on barium sulphate. This reaction is call rt 0 il CHO i : ‘ak, CO Pd-BaSO, Benzoyl chloride Benzaldehyde From nitriles and esters “ Nitriles are reduced to corresponding ine vith stannous choy in the presence of hydrochloric acid, which on hydrolysis ide corresponding aldehyde. Bre HO RCN + SnCl, + HCl ——> RCH = NH ——>RCHO This reaction is called) Stephen reaction. Alternatively, nitriles b diisobutylaluminium hydrid fo imines followed hydrolysis to aldehydes: Y 1. AIH(-Bu), RCN: te R-CHO 1. AIH(-Bu), CH, — CH-CH-CH,CH,-cN-" 5 CH, — CH=CH-CH,CH,-c1jp 24,0 Simla, esters arab reduced lddhydes with DIBAL i 0 1, DIBALJ a II CHCH),— C— OCH, FEE crea), — 0-1 A From hydrocarbons Chemistry Aromatic aldehydes (benzaldehyde and its derivatives) are prepared from aromatic hydrocarbons by the following methods: By oxidation of methylbenzene Strong oxidising agents oxidise toluene and its derivatives to benzoic acids. However, it is possible to stop the oxidation at the aldehyde stage with suit ts methods are used for purpose. ee, Chromyl chloride oxidises methyl complex, which on hydrolysis Gives corresponding benzaldehyde.CHO ch, ‘or + Cro,c1, CS, some ae, _H0', Toluene penzaldehyde Chromium complex mes Feaction is = Ise ubstituted toluene of chromic oxide (CrO,): Toluene oie si ting with chromic 4s converted Oxide in acetic anhy e Be iiene diacetate can f a hydrolysed to corresponding benzaldehyde with aqueous CHO cH, : (I + 2+ ter: coy aaa, ce. no’, (CY \ : A Benzaldehyde <$8By stab chain ctvortnaion (followed by rudy 3 zal chloride, which m Co CL,/hw CHC1, HO co: ae 373 K . ‘ Toluene Banal chloride Benzaldehyde \ peor When benzene or its derivative is treated with carbon monoxide and hydrogen chloride in the presence of anhydrous aluminium chloride or cpros chon gives benzaldehyde or substituted benzaldehyde. : -CHO CO, HCl ‘Anhyd. AICI,/CuCl Benzene Benzaldehyde Ths reaction is known &1GRHERSAKOGH Teuton. 12.2.3 Preparatic From acyl chlorides of Ketones Treatment of acyl chlorides with dialkylcadmium, prepared by the reaction of cadmium chloride with Grignard reagent, gives ketones. 2R—Mg—X + CdCl—>RCd + 2MgQCl ada ao + R,Cd ——> 2R—C—R + CdCl, 9863, Aldehydes, Ketones and Carboxylic Acids™ From nitriles ‘Treating a nitrile with Grignard reagent followed by hydro. tone. aketone. pier H,O° Zo — oH, ~ 7° CH, — CH, — = N + CHyMgBr—S22> CH,CH, -¢ \ CH \ 2D! i Pep mo, From benzene or substituted benzenes ‘When benzene or substituted benzene is treated with acid the presence of anhydrous aluminium chloride, i afor y corresponding ketone. This reaction is known as the acylation reaction. oO Il A, O: smba ma, CY Give names, of the reagents to. bring about the following | formations: lexan-1-ol to hexanal lohexanol to cyclohexanone p-Fluorotoluene to Ethanenitrile to ethanal luorobenzaldehyde ‘Allyl alcohol to propenal 97 ut 2-ne to ethanal (@ C,H,NH‘Cr0,CIPCC) (i) Anhydrous CrO, (ii) CrO, in the presence (iv) Diisobuty)}aluminium of acetic anhydride/ hydride (DIBAL-H) 1. CrO,Cl, 2. HOH (vi)_0,/H,0-2n dust = ‘2 Write the structures of products of the following reactions; AQ "0 a An sci PRE 9 ACE 1H, we H,c-c=c-H _Hé", H,S0, Me 1.Cr0,Cl, 2.H,0* No, Chemistry 364hysical Th 23 Ply ove slcal properties of aldehydes and ketones are described as Properties “lows, “Oe a aempetr.saTar a Ma } Th 's and Ketones are liquid or Solid at room temperature. | yan Points of aldehydes and ketones are higher than | Weak maha’ ad ethers of comparable molecular masses. It 1s due to | dipole cheat 88sociation in aldehydes and ketones arising out of the of alcoh ree interactions, Also, their boiling points are lower than those hydro sO Snllar molecular masses due to absence of intermolecular gan bonding, The following compounds of molecular masses 58 60 are ranked in order of increasing boiling points. rcs) Poca n-Butane Methoxyethane Propanal Acetone Propan-1-ol aldehydes and ketones sucl re miscible with water fons, However, the solubility of aldehydes and ketones decreases rapidly on increasing the length of alkyl chain. All aldehydes and ketones are fairly soluble in organic solvents like benzene, ether, hanol, le h our becomes Arrange the following compounds in the increasing order of-their boiling points: a CHCH,CH,CHO. CH,CH,CH,CH,OH, H,C,-O-C,H,, CH,€4,CH,CH, The molecular masses of these compounds are in the range of 72 to 74. Since only butan-1-ol molecules are associated due to extensive intermolecular hydrogen bonding, therefore, the boiling point of butan-1-ol would be the highest. Butanal is more polar than ethoxyethane. Therefore, the intermolecular dipole-dipole attraction is stronger in the former. n-Pentane molecules have only weak van der Waals forces. Hence increasing order of boiling points of the given compounds is as follows: CH,CH,CH,CH, < H,C,-O-C,H, < CH,CH,CH,CHO < CH,CH,CH,CH,OH 8G Aldehydes, Ketones and Carboxylic Acids‘arrange the following heir bolling points. ct CHO, CH,CH,OH: CH,OCH, CH,CH,CH, f estion compounds in increasing ong er ve es both possess the carbony! fy, 124 Chemis Since aldehydes and keton mits 7 Rent group, they undergo similar chemical reac ny ———__Raations _ Tetrahedral intermediate Ptg.12.2: Nucleophilic Chemistry 9866; * 1, Nucleophilic addition reactions Contrary to ele’ Unit 13 Class XI), the aldehydes an addjtion reactions. a0 Mecasism of nucleophile addtton reactions le_12.3 Would you expect benzaldehyde to be more reactive or less reactive in nucleophilic addition reactions than propanal? Explain your answer. Solution The carbon atom of the carbonyl group of benzaldehyde is less + electrophilic than carbon atom of the carbonyl group present in @ o propanal. The polarity of the carbonyl | group is reduced in benzaldehyde due i H to resonance as shown below and —_— hence it is less reactive than propanal. dition reactions observed in al ctrophilic adi d ketones undergo uke My, attacks the electrophilic carbon atom of hil the outer go from a direction approximate erpeniin Pt ON} theplne oth brialsed oy eg aren ig 1g ate = PrOte, intermediate capty; Thy proton from the r, res medium to eve electrically neutral prog The net result is auilton Nu’ and H’ across carbon oxygen double by le as shown in Fig. 129! Addition product ‘on carbonyl carbon Reactivity Aldehydes are generally more reactive than ketones j ORE an : ” nucleophilic addition reactions due reasons. Sterically, the presence of two relatively tay substituents in ketones hinders the approach of nucleophiRe @arbony! carbon than in aldehydes having only one sith substituent. Electronically, aldehydes are more reactive than ketones because two alkyl groups reduce the electrop] a the carbonyl carbon more effectively than in former.AG Some important examples of nucleophilic addition and HCN + on nucleophilic additjon-elimination reactions: == :CN+ H,0 ‘Addition of hydrogen cyanide (HCN): Aldehydes and ketones react with hydrogen cyanide (HCN) toylel i adie é Therefore, it is catalyses generated cyanide ton (CN) phile readily adds to 0 NZ J SS N yy a base Ve a £0 + ):CN SZ Saas being a stronger nucleo, Ht ~ CN Tetrahedral carbonyl compounds to yield corresponding eS ON intermediate cyanohydrin. OH Cyanohydrins are synthetic Cyanohydrin Addition of sodium hydrogensulphite: Sodium dehydes and hydrogensulphite adds to al ketones to form the addition products. O° + NaHSO, een o/ 0504 proton tans /080.N8 noe position t Nona 7 Non T a the_right_hand a addition side or most [es an the left for mos' ketones due to steric reasons, The hydrogensulphite adaition compound “and can be converted back to the original carbonyl compound by treating it with dilute acid or alkali. Therefore, these are useful ition of Grignard reagents: (refer Unit 11, Class XI). “erator of alcohols: Aldehydes react with one equivalent of monohydric alcohol in the presence ofr og core to yield alkonyalcobel intermediate, known as hemiacetals, which er Teact with one more molecule Oa [cohol to give a gem-dialkoxy compound Knowi 2s ROH OR’ oR’ aes own in the HCl gas. a ROH — reaction. RCHO === |R-CH —— RH + HO H Eee a Ketones react with ‘OH ‘OR’ ethylene glycol under Hemiacetal Acetal similar conditions to form cyclic products known as ethylene . protonates the oxygen of HCI gas R/O —CH, the carbonyl compounds ———— | + HO and therefore, increases — R” \o—CH, the elec icity of the : Ethylene glycol ketal carb Rv CH,OH eG Aldehydes, Ketones and Carboxylic Acids VA: 1. Acetals an the nucleophilic attack of ethylene glyco! d are Tiydi sed with ‘aqueous mineral acids to i corresponding aldehydes and ketones respectively, id $ : Nucleophil Addition of ammonia and its dertvatives: es, g ain ammonia and its dervaives HAN ad 0 the a dehydes and ketones. The reaction 1s reye, group of aldehydes al Linens ra The _equiltbee® \ favours the pr a 70 + Ne |\ 1" | can + 0 Tormation due tora due tort \ 7 dehydration of te NHz intermediate to a le >CENZ. mt Z= Alkyl, aryl, OH, NH,, CoHgNH, NHCONHh, etc. a Table 12. Some N-Substituted Derivatives of Aldehydes and Ketones (>C=N-2) i. Orr rons a Coa Product name PCr tae ty Amine Hydroxylamine Hydrazine Phenylhydrazine Phenylhydrazone 2,4 Dinitrophenyl- hydrazone * Reduction to alcohols: Aldehydes and ketones are reduced to primary and secondary alcohols respectively by sodium borohydride (NaBH,) or lithium aluminium hydride (LiAIH,) as ll as by catalytic hydrogenation (Unit 11, Class XII). Reditction to hydrocarbons: The carbonyl group of aldehydes and ketones is reduced to CH, group on treatment with zinc- an hydrochloric _aci Chemistry 368,redu 7 ection} or with hyd heatiny swith sodas “Ssitum hyd ent s Sexo Zu My “wer mn + HO (Clemmensen reduction) = _NH,NH. e=0 a> » =n, —Koti/ethylene glycol > i, +N, heat A exteaton (Wolff-Kishner rduction) Tollens Aldehydes differ from ketones in thelr oxidation reactions. Aldehydes (ng41-1918) was a are easily oxdIsed To Carboxylic acids on treatment common pressor of Chemistry GNilising agents like nitric acid, potassium permanganate, potassit Pre University Of dichromate, etc. Even mild oxidising agents, mainly Tollens reagent Gottingen. Germany. Fehlings' reagent also oxidise aldehydes. RcHO Ol, p.cooH Ketones are i ditions, i.e., generally oxidised under vigorous conditions, iron Oxidising agents and at elevated temperatures. Thetr oxidavir" acta te bon-carbon borid cleavage to afford a mixture of ‘carboxylic 's having lesser number of carbon atoms than the parent ketone. | 2 3 R-CH,—C_cH,R —Ol_, R.cOOH + R-CH,COOH 8 (By cleavage of C,-C, bond) + RCH,CQOH + R-COOH (By cleavage of C,-C, bond) The mild oxidising agents given below are used to distinguish aldehydes from ketones: (i Tollens’ test: On warming an aldehyde with freshly prepared ammoniacal silver nitrate solution (Tollens’ reagent) luced due to the formation of silver me! The aldehydes are oxidised to corresponding xylate anion. The reaction occurs cE RCHO + 2[Ag(NH,),]’ + 30H——>RCOO + 2Ag +2H,O + 4NH, Fehling's test: Fehling reagent comprise: Ss 4 and Fehling solution(B)) and'I mixed On heating an aldehyde with Fehling’s reage! precipitate is obtained. Aldehydes are oxidised : aldehyde: R-CHO + 2Cu* + 50H ——> RCOO + Cu,0 + 3H,O -Red-brown ppt 1869, Aldehydes, Ketones and Carboxylic Acids“oxidation of methyl ketones bY haloform react wn Adele a ketones having at least one methyl et linked to the carbonyl carbon atom (methyl keton’? are oxidised by sodium hypohalite to sodium salts corresponding carboyyi! acids having one ¢; atom less than that 0 0 REL _ cr Mts r-! Na + CHX, (X=Cl Br.) : carbonyl compound, mK HCH, HCH, methyl soup rertes Moy, Me PK on + CHC ts oxta Z : ul ; eM : \ ee bond 9 ? in the molecule: odium hypoiodite is also used for Iodoform reaction with s' of CH,CO group H(OH) group which produces CH;CO groy, on oxidation. organic compound (A) with molecular formula C,H,O forms an orange-red precipitate with 2,4-DNP reagent and’ gives yellow precipitate on heating with jodine in the presence of sodium hydroxide, It neither reduces Tollens’ or Fehlings’ reagent, nor does it decolourise bromine water or Baeyer's reagent. On drastic oxidation with chromic acid, it gives a carboxylic acid (B) having molecular formula C,H,0,, Identify the compounds (A) and (B) and explain the reactions involved. Solution (A) forms 2,4-DNP derivative. Therefore, its an aldehyde or a ketone, Since it does not reduce Tollens’ or Fehling reagent, (A) must be a ketone, (a) responds to fodoform test. Therefore, it should be a methyl Ketone ‘The molecular formula of (A) indicates high degree of unsaturation, yet it does not decolourise bromine water or Baeyer's reagent, This indicates the presence of unsaturation due to an aromatio ring. + d (B), being an oxidation product of a ketone should bea acid, The molecular formula of (B) indicates that it should nd compound (A) should, therefore, be a be benzoic acid a monosubstituted aromatic methyl ketone. The molect rm (A) indicates that it should be phenyl! methyl ketone Reactions are as follows: Compount carboxylic CHO 2, 4-Dinitrophenylhydrazine 2, 4-DNP derivative Chemistry BOsCHO, COOH Cc il I HG cro, CO Nao ‘C—ONa + CHI, 8) i (a) Reactions due to a-hydrogen Acidity of -hydrogens of aldehydes and ketones: The aldehydes and ketones Undergo a number of reactions due to the acidic nature of o-hydrogen, t The acidity of o-hydrogen atoms of carbonyl compounds is due © the strong electron withdrawing effect of the carbonyl group and Tesonance Stabilisation of the conjugate base. oO iL & stp e- = ab HOB MO ait Condensation: Aldehydes and ketones hat 30 a reaction in the presence as Cal lyst to form B-hy aldehydes (aldol) or B-hy droxy =a : tet), rape Tas Seat reo 2CH-CHo SLNaOH CH CH-CH,-CHO I> CH,-CH-CH-CHO Ethanal OH But-2-enal 3-Hydroxybutanal (Aldol condensation (aldo) product) cH, CH, 2CH,-CO-cH, 2 OF-6 1400-08, > c,b-cx.c0-0, 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,-unsaturated carbonyl compounds which are aldol condensation products and the reaction is called Aldol condensat (Bid Aldehydes, Ketones and Caroxylie Acids: “ aldol condensation j, Cross aldol condensation: When on 8 ‘out between two different aldehydes by jo het, tt cy aldo! condensation. If both atom it gives q mixture: of a products. This 1s Delow by aldo! reaction of a mixture of ethanal and Prope CH,CHO 1. NaOH CH,-CH=CH-CHO + CH.CH,CH6-crg + 2 A But-2-enal CH, CH,CH,CHO a Jecules of ethanal 2-Methylpent-2- ee from two molecules, of propanal simple or self aldol products * CH CH=C-CHO + CH,CH,CH=CHCHO CH, ‘2-Methylbut-2-enal - Pent-2-enal from one molecule of ethanal and one molecule of propana| cross aldol products Ketones can also be used as one component in the cross aldo} reactions. t CHO + C-CH, —OH_» (CH=CH-C: § 293 K 1, 3-Diphenylprop-2-en-1-one jor product) . Other reactions ‘Cannizzaro reaction: Aldehydes which do not have an a-hydrogen atom, undergo self oxidation and reduction eabpeitendtin rnc ‘on heating cea is Teaction, one molecule of the aldehyde is reduced to alcohol while another is oxidised to carboxylic acid salt. H, H, u 9 \ \ A | a No=o + Yo=0 + Cone, KOH > H—C—O8 + HC | H H | Nox | H i | Formaldehyde Methanol Potassium formate | AC)-c10 +Cone. NaH A> reson + Gro Benzaldehyde Benzyl alcohol Sodium benzoate Chemistrynemophite tones Uubstitution reaction: At tic aldehydes and ke! un lon: Aromat Pe © electrophilic substitution at the ring in which the carbonyl Acts as a deactivating and meta-directing group. ON, CHO tINO,/H,SO, ‘CHO > 0 “3285 K Benzaldehyde mNitrobenzaldehyde Arrange the followin, '8 Compounds in in their reactivity in ball addition reactions, creasing order of s al, Propanal, fr } Propanone, Butanone. HieConsdeece. Tolualdehyde, p-Nitrobenzaldehyde, Acetophenone. Pred “r steric effect and electronic effect. 5 ict the products of the following reactions! 0 HK HO—NH, Ht, ve ; on CY + NH—NH 4-10 9 Ut R-CH=CH-CHO + NH,-G.NH-NH, = 0 HL uo >) ‘CH, it + CH,CH,NH, > 12.5 Uses of In chemical industry aldehydes and ketones are used as solvents, Aldehydes starting materials and reagents for the s3 ands Ketones Formaldehyde is well known in), urea-formaldehyde~glueS-and other polymeric products. ‘Acetaldehyde is used primarily as a starting material in the manufacture of acetic acid, ethyl acetate, vinyl acetate, polymers and drugs. Benzaldehyde is used in perfumery and in dye industries. Acetone and ethyl methyl ketone are common industrial solvents. a aldehydes and ketone: le, vanillin, i, Aldehydes, Ketones and Carboxylic AcidsFe va Carboxylic Acids Carbon compounds containing a carboxy! functional group, ~COOK called carboxylic acids. The carboxyl group, consists of a carbony, art attached to a hydraxyl group, hence Its name carborylCarboryi aa may be aliphatic (RCOOH) or aromatic (ArCOOH) depen b 8 On the alkyl or aryl, attached to carboxylic carbon. Large number of carboxy? acids are found in nature. Some hig her members of aliphatic cars, "te acids (C,, - Cj) known as fa acids, occu n nate a8 2 sie att glycerol. Carboxylle acids serve as starting material for severay oe important organic compounds such as anhydrides, esters, acid Chong amides, etc. , 12.6 Nomenclature and Structure of Carboxy! Group 12.6.1 St re amongst th He compou Nomenclature oa carboxylic acids ox Tage numberof them are known t common names. The common names end with the suffix -ic acig ang have been derived from Latin or Greek names of their natural For example, formic acid (HCOOH) was first obtained from Fans, (Latin: formica means ant), acetic acid (CH;COOH) from vinegar atin, acetum, means vinegar), butyric acid (CH;CH,CH,COOH) from Fanci butter (Latin: butyrum, means butter). In the IUPAC system, aliphatic carboxylic acids are nameq by replacing the ending -e in the name of the corresponding alkane With. olc acid. In numbering the carbon chain, the carboxylic carbon j, numbered one. For naming compounds containing more than one carboxyl group, the alkyl chain leaving carboxyl groups is n and the number of carboxyl groups is indicated by adding the multiplicative prefix, dicarboxylic acid, tricarboxylic aca, etc. to the name of parent alkyl chain. The position of -COOH groups are indicated by the arabic numeral before the multiplicative prefix. Some of the carboxylic acids along with their common and IUPAC names are listed in Table 19,3, able 12.3 Names and Structures of Some Carboxylic Acids Seataotcy Common name bo LL HCOOH Formic acid | Methanoic acid CH,COOH Acetic acid | Ethanoic acid CH,CH,COOH Propionic acid Propanoe ald CH,CH,CH,COOH Butyric acid | Butanoic acid (CH),CHCOOH . . butyric acid © | 2-Methylpropanote acid HOOC-COOH | oxalic acid Ethanedioic acid HOOC -CH,-COOH am |) Malonic acid Propanedioic acid HOOC -(CH,),-COOH Succinte acid Butanedioie acid HOOC -(CH,),-COOH ~ Glutaric acid | Pentanedioic acid HOge(CH,),-COoH | Adiptc acia Hexanediote acid fe Aaah mmc Propane-1, 2, a) }\cqpgarbalteaed?) ) tiarbonic acid) Chemistry 3745COOH 7 Benzote acid Renzenecarboxylic act H,COOH (Benzolc acid) CH, Phenylacette acid 2-Phenylethanoic acid COOH 5 Phthalic acid Benzene-1, 2-dicarboxylic acid Tn carboxylic acids structure e 1987 ecarboxyl and are ven 71% the bonds to the carboxyl carbon He in one plan Grow arated by ab a carbon is less electroph y about 120°. The carboxylic 8 | : Tae c than carbonyl carbon because of th e Stucture shown below: Give the IUPAC names of th ‘A MP € following compounds: Pu CH,CH,COOH WP eaestrcecet CH, HO 12.7 Methods of Some important methods of preparation of carboxylic acids are as follows. Preparation From primary alcohols and aldehydes of Carboxylic Primary alcohols are readily oxidised to carboxylic acids with common Acids oxidising agents such as potassium permanganate (KMnO,) in neutral, acidic or alkaline media otassi ate (K.Cr,0,) CrO,-H,SO, CHLICH.CH. Ol res reagent CFs(C#3.COOH 1-Decanol Decanoic acid (8%) Aldehydes, Ketones and Carboxylic AcidsCarboxylic acids are also prepared from aldehydes by they, Use {ld oxidising agents (Section 12.4). i. ee alkylbenzenes Aromatic carboxylic acids can be prepared by vigorous Oxiday alkyl benzenes withiehromtvate or acidic or alkaline pots! o, permanganate. The entire side chain is oxidised to the carboxy} gth of the side chain. Pri groupsa xr Suitably substituted alkenes are also oxid with these oxidising reagents (refer Unit 13, Class xD. OOK CHS vino-KOH HO" ‘COOH Heat Benzoic acid CH,CH,CH, CO HLACH.CHs seveno KOH COOK COOH “a Benzoic acid ~ From nitriles and amides Nitriles are hydrolysed to amides and then to acids in the presence o, H’ or OHas catalyst. Mild reaction conditions are used to stop the reaction at the amide stage. ii or OH tt a or OH RCN HOOK, Be Gh. fo? R-CNH, = ZA» RCOOH CH,CONH, ae, CH,COOH + NH, Ethanamide Ethanoic acid CO! INH, HY 3 c (OOH #0, : az i Benzamide Benzoic acid 6 fae Grignard reagents Grignard reagents react with carbon dioxi form salts of carboxylic acids which in turn give correspon’ nxylic acids after acidification with mineral acid. 4 RMgX + 0=c=0 PES R_ Nomex’ ‘As we know, the Grignard reagents and nitriles can be prepared from alkyl halides (refer Unit 10, Class XI). The above methods 40°, RCOOH Chemistry 226,ding (3 and 5 Into correspon an ou are useful for converting alkyl hae tate that present in Ic acids having one carbon atom more ae halides (ascending the series). * From acyl halides and anhydrides Acid chlorides whe ‘carboxylic acids or more n hydrolysed with water give’ readily hydrolysed wit nor caus base to give carboxylate ions which on ride the aedlltcatlorl provide corres| boxylic acids. Anhydrides on ponding carboxy! other hand are hydrolysed to corresponding acid(s) with water. H,0 RCOOH + Cl ROC! _ Lo SH/HO_, coo + G1 2 RCOOH (C,H,C0),0 —2:2_, 2 c,H,cOOH Benzole anhydride Benzoic acid C.HCoOcocH, —2-> ¢,H,COOH + CH,COOH Benzoie ethanote Benzoic acid -—-—Bthanoic acid anhydride \ A From esters Acidic hydrolysis of esters gives directly carboxylic acids while basic hydrolysis gives carboxylates, which on acidification give Corresponding carboxylic acids. : COOH HO ‘on + C,H,OH Ethyl benzoate Benzoic acid CH,CH,CH,C0OC,H, —“2L= cH,CH,CH,COONa + C,H,OH Ethyl butanoate [po CH,CH,CH,COOH Butanoic acid Write chemical reactions to affect the following transformatior Butan-1-ol to butanoic acid enzyl alcohol to phenylethanoic acid -Nitrobromobenzene to 3-nitrobenzoic acid Cia -Methylacetophenone to benzene-1,4-dicarboxylic acid ig clohexene to hexane-1,6-dioic acid festa to butanoic acid. (BiH_Aldehydes, Ketones and Carboxylic AcidsCr0,-H,S0, Solution cHyeH,cH,c! Mee eageal? CH,CH,CH,COOH, Butan-1-ol Butanoie acid KCN w cyicH,01| 2 G,H,CH,Br ——— CH.CH,C1 Benzyl aleohol Benayl bromide Benzyl cyanide Ajko | | C\H.CH,COOH, Phenylethanoteacg | ° Se Bt Cre ie Tay io PS ‘oh | 3-Nitrobromobenzene q | ‘OH ON 3 ltrobenzoe ag rs) FS © eee: ane bau rod 4-Methylacetophenone Dipotasstum benzene- ieee Lop Aen, Teephitaecy "0 a Cel Hexane-1, 6-diole acid (Adipic acid) () CH,CH,CH,CHO = CH,CH,CH,COOH Butanal Butanoie acid tophenone Chemistry 38; "‘are wax Tl d to e solids and ar’ oe low volatility, Carboxyl! couuds than aldehydes, ketones 271° 49 more aden ble molecular masses. This 18 er lation of carboxylic acid m b intermolecular hydrogen Ponding. The b, co ; broken completely even in the aporre vapour phase ing mber 0! T carboxylic acids are practically insoluble the increased hydrophobic interaction in of en bonding of ( 1 CoH with H,0 are classified as follows: The reaction of carboxylic acids Acidity javolving Reactions with metals and alkalles cleavage Of The carb oxylic acids like alcohols evolve hydrogen 0-H Bond :netals and form salts with alkalies similar to phenols. Howeor: phenols they react with weaker bases_such_as_carbonates “ hydrogencarbonates To evolve carbon dioxide. This reaction is Se detect the presence of car 1ip In an organic compounc. 2R-COOH + 2Na——>2R-COONa’. + He Sodium carboxylate ctropositive with ele P a R-COOH + NaOQH——>R-COONa’ + H,0 R-COOH + NaHCO, ——>R-COONa’ + H,O + CO, Carboxylic acids dissociate in water to give resonance stabilised carboxylate anions and hydronium ton. , le Peon” RG + HO === HO’ +/R-C eee =R OH to Bi Aldehydes, Ketones and_ Carboxylic Acidsco a > Cr cot aS | —__ ____Shemistry i Se + 01 {H,0] {RcooH] [ J equilibrium constant th of an acid is generally in, eae y the above reaction: : | 7 and Kis the acid digg, where Koy | y » constant. For convenience, the stren its pK, value rather than Its K, value. [ pk.=- leek, | rach “i here a8 pK, of" hrloric acid is -7.0, wi P ‘The pK, of hydrochlo! ic tic acid), benzoic acid eile aa SDB. 1orand 76; respelvel ee ee sre ver the acid (the Better its ag q ‘Smaller the pK,, the stronger donor). Strong ee have pK, values < 1, the acids with PK yt between 1 and 5 are considered to be moderately strong acids, “es elds have pK, values between 5 and 15, and extremely wea th have pK, values >15. cd, Carboxylic acids are weaker than mineral acids, but they are g acids than alcohols and many simple phenols (pK, is ~16 for eth and 10 for phenol). In fact, carboxylic acids are amongst the most, ave studied so far. You already Im, oO ic compounds you hi phenols are more acidi¢ than alcohols. The higher acidity of _ acids as compared to phenols can be understood similarly. The conju. base of carboxylic acid, a carboxylate ion, is stabilised by two equiy, as resonance structures in which the negative charge 1s at the mor electronegative oxygen atom. ‘The conjugate base of phenol, a phe te {on, hias non-equivalent resonance structures in which the negative is at the less electronegative carbon atom. Therefore, resonance phenoxide ion isnot as important as itis in carboxylate ion. Further i negative charge is, alee ‘over two electronegative oxygen. atoms in carboxylate ion whereas itis less effectively delocalised over one atom and less electronegative carbon atoms in phenoxide ion (Unit 1), Class XII). Thus, the carboxylate ion is more stabilised than phenoxide ion, so carboxylic acids are more acidic than phenols. Effect of substituents on the acidity .of carboxyl : Substituents may affect the stability of the ha ae also affect the acidity of the carboxylic acids. Electron withdrawin groups increase the acidity of carboxylic acids by stabilising ie conjugate base through delocalisation of the negative charge by inductive and/or resonance effects. Conversely, electron donating groups decrease the acidity by destabilising the conjugate base. Electron withdrawing group (EWG) _Electron donating group (EDC) stabilises the carboxylate anion destabilises the carboxylate and strengthens the acid anion and weakens the acid»s In Increasing acidity order 1s Ing acids are arranged in order of Incrbasing acidity >CC] COOH CHICI,CooH > NO,CH,COOH > NC-CH,COOH > FCH,CooH > (continue) BrcH,coon HCOOH CICHLCH,COOH? C.H,COo) (continue ) CH,CH,COOH —e Direct ata rh acid Tnereae tment of groups such as phenyl or vinyl to the carboxyie the decrease corresponding carboxylic acid, contrary to ected due to reson effect shown below: ° WeSMG 5, no¥eXc ‘OH H \on This is to which, igre of greater electronegativity of sp’ hybridised carbon withdray xyl carbon is attached. The presence of electron group on the phenyl of tic carboxylic acid increases the phenyl of aromatic oxy] eir acidity while electron donating groups decrease their acidity. COOH COOH COOH Hy No, 4-Methoxy Benzole acid 4-Nitrobenzoic benzoic acid acid (pK,= 4.46) (pK, = 4.19) (pK, = 3.41) 12.9.2 Reactions AO Formation of anhydride ae yxylic acids on heating with mineral acids such as H,SO, or with C-OH Bond give ee anhydride. 00 c - \. EY sc é % Ho-G + HRC GP Cth ‘OH HO’ ‘0 Ethanote acid Ethanoie anhydride on Carboxylic acids are esterified with alcohols or phenols in the p1 ce of a mineral acid such as concentrated H,SO, or HCl gas as a cast Hw RCOOH + ROH=——RCOOR + H,O Aldehydes, Ketones and Carboxylic Acids© of esterification of lo aclds: The esterification of carbo, ‘apids with alcohols Is a kind Protonation of Vl carbonyl oxygen activates the carbonyl group is nucleophilic addition or “is alcohol. Proven transfer in the tetrahedral Intermediate converts the hydrony, ge Into -OH, group, which, being a better leaving group, is eliminated as neutral Foy, molecule, The protonated ester so formed finally loses a proton to give the cater o . ¢ Oy OH J HW V/ R-OH fe re ——= pb ian ae OH OH ‘OH H ' Carb ic acid Tetrahedral intermediate oR OR Sox Protonated ester _& Reactions with PCl,, PCL, and SOCl, The hydroxyl group of carboxylic acids, behaves like that of; Alco and is easily replaced by chlorine atom on treating with PCI, Pq) ls SOc! referred a rod escape the reactlon mixture making i Purification of the products easier. Lhe RCOOH + PC —» RCOC] + POCI,+ HC 3RCOOH + PC, —* SRCOCI + H,PO, RCOOH + SOC —> RCOC] + SO, + HC AR Reaction with ammonia Carboxylic acids react with ammonia to give ammonium salt which on further heating at high temperature give amides. For example: * -+ CH,COOH + NH,. => CH,COONH, > CH,CONH, Ammonium acetate Acetamide -+ COOH ‘ COONH, CONH, Chemistry 58825COOH CONH * COONH + ‘coon NH, = A o “2H,0 .CONH + 'COONHL Ammontum phthalate (oe Phevatamide Strong “NH, heating 12.93 Rae ue Reduction COOH Carboxylic acids are reduced to primary alcohols by lithium wi um hydride or better with diboran: 5 ictionall groups | etc. Sodium borof yaride does not reduce the LAIN, /ether_or Bits (i) HO" _Decarboxytation Carboxylic acids lose carbon dioxide to form hydrocarbons when thelt salts are heated with sodalime'( Oi oe The reaction is known as decarboxylation. R-COONa NACHE CAO, per + Na,CO, Heat Alkali metal salts of carboxylic acidgalsjandengp carbon on electrolysis of their aqueous solutions anc form hydrocarbons having twice the number of carbon atoms present in the allyl group of the acid. ‘reaction is known. a§Kolbe electrolysis (Unit 13, Class XI). 12.9.4 © Halogenation RCooH i) Lialii/ether_or Be. p.ciOH Substitution Carboxylic acids having an a-hydrogen are halogenated at the Reactions in the a-position on treatment with chlorine or bromine in the presence of Hydrocarbon Part Bios = acids. The (Red phosphi ~ RcH,-coon —2/Re phosphor R-CH-COOH . (i) HO x X=Cl, Br a.- Halocarboxylic acid 1883, Aldehydes, Ketones and Carboxylle Acidsisi - rom 7 is ajectrophilic substitution Pe le acids undergo elec Aromatic carboxylic ¢ eal nwhich the carboxyl group acts group. They howeve ib e the carboxyl x SOOH COOH COOH Br,/FeBr, Cone. HNO, + ol Oo — —__ Cone. H,S0, NO, ~oounail m-Nitrobenzole acid ae % Intext_ Question f 12.8 Which ac e str 12.8 Which acid of each pair shown here would you expect to onger? (u) CH,FCO,H or CH,CICO,H (i) CH,CO,H or CH,FCO,H (itl) CH,FCH,CH,CO,H or CH,CHFCH,CO,H & FC <<} COOH or H.C x} COOH ibber, textile, dyeing, leather and elect no : Methante acids wsed in ruber te Fo nega i od i il industries. Ethanoic Carbone Hexanedioic acid is used in the. manufacture of nylon-6, 1 Acids jum enzoate is used as a food preserae Higher fatty acids are used for the ‘manufacture of soaps and det y sania cosaisnsisansieena are some of the important classes of wands containing carbonyl group. These are highly polar molecules. Therefore, they boil at higher temperatures than the hydrocarbons and weakly lar compounds such as ethers ‘of comparable molecular masses. The lower Frembers xe more soluble in water because they form hydrogen bonds with water. ‘The higher members, because of large size of hydrophobic. chain of carbon atoms, are insoluble in water but soluble in common organic solvents. Aldehydes are prepared by dehydrogenation or controlled oxidation of primary alcohols and Controlled or selective reduction of acyl halides. Aromatic aldehydes may also be prepared by oxidation of (i) methylbenzene with chromyl chloride or CrO, in the presence of acetic anhydride, (ii) formylation of arenes with carbon monoxide and hydrochloric acid in the presence of anhydrous aluminium chloride, and (iii) cuprous chloride or by hydrolysis of benzal chloride. Ketones are prepared by oxidation of secondary alcohols and hydration of alkynes. Ketones are also prepared by reaction of acyl chloride with dialkylcadmium. A good method for the preparation of aromatic ketones is the Friedel-Crafts acylation of aromatic hydrocarbons with acyl chlorides or anhydrides. Both aldehydes and ketones can be prepared by ozonolysis of alkenes. Aldehydes and ketones undergo nucleophilic addition reactions onto the carbonyl group with a number of nucleophiles such as, HCN, NaHSO,, alcohols (or diols), ketones and carboxylic acids _ Chemistry 384,f g 5 z 2 5 i 2 g Zz Gnard reagents, The a hydrogens In aldehydes and » aldehydes and ketones. having at least one a-hydrogen, undergo Aldol Condensation in the Presence of a base to give a-hydroxyaldehydes undergo Can, Waroxyketones(ketol), respectively, Aldehydes having na a-hydrogen and ketones Mizzaro reaction in the presence of concentrated alkall, Aldehydes The carbonyl grou ar ete.tleools with NaBH, LAAM I. by catalytic hydrayenation by Clemmeny! SOUP of altchyetes an ean be reduced to a methylene yr) E z 2 2 Z 8 Presence of red phosphorus (Hein Methanal, ethanal, Propanone, benzaldehy benzo! ¢ acid are highly useful compounds in indie, sormis ee, acete ald and benal terms ? Give erie lowing ve.an example of the reaction in ohydrin AT acetal smicarbazone idol lemiacetal e Imine “2+ DNP-deratv iin : 122 Ni the following compounds accordit "AC system of nomenclature: CH(CH,)CH,CH,CHO. CH,COCH(C;HJCH,CH,CI .CH=CHCHO Ci ‘OCH,COCH, CB.CH(CHJCH,C(CH,),COCH, “pat ehayceet coe Wwip~OHCC,H,.CHO-p 12.3 e structures of the following compounds, / pcos ome (ethylbenzaldehyde Methylpent-3-en-2-one chloropentan-2-one Sere hr acid P.p'-Dihydroxybenzophenone Hex-2-en-4-ynoie acid Write the IUPAC names of the following ketones and aldehydes. Wherever var give also common names. ,CO(CH,),CH, )241,CH,CHBrCH,CH(CH,)CHO (CH;(CH,);CHO Ph-CH=CH-CHO CHO A mncorn Drgw structures: of the following derivatives. '2,4-dinitrophenylhydrazone of benzaldehyde ‘Cyclopropanone oxime ) AGetaldehydedimethylacetal 1 semicarbazone of cyclobutanone wae ethylene ketal of hexan-3-one Sone methyl hemiacetal of formaldehyde 1885 Aldehydes, Ketones and Carboxylic AcidsNe en cyetohexanecarbaldenyde Feacta ny, " 6 Predict the products formed ; following reagents PY lens’ reagent 1 HO" ‘excess ethanol ang aerg pase and ther 7 micarbazide and weak acl ‘| . yarocntoric ac Zine amalgam and dilute hydrochl te go al crenata : e structures of the exneh "*Pecteg 1a “whie ving compounds Wo yhich of the flowing, COMP ger? Wate the struct Cannizzaro Feat (ut) Benzaldehyde the Cannizzaro reaction i i products of aldol condensalle al /Methylpentan a 1 pensopbenone zMeecanane AM Sy roPanong Phenylacetaldehyde (yf Butan-1-o! compounds? vibutangy How, will you convert ethanal to the ua But 2-en0e _ aa ie of four possible sid, condenag . fh ease, indicate which ald lon 32.0 Write structural formulas and RANT acy products from propanal, a a ae inde. ts hile and whic! sctrop! Acts as nucleophile and Wi ular formula CHO forms 2A-DNP deta and undergoes reaction. On VIgOTOUS Oxidation’ ‘gives. 1,2-benzenedicarboxylle ‘acid. Identify the ‘compound. ‘An organic compound (A) (molecular form we ae ity dilute iphuric acid to give a carboxy! . of (0) sith chromic acid produced (B). {C) on dehydration gives but-1.en0 Write equations for the reactions involved. tte propa 8 ne as 12 Arrange the following compounds in increasing order Pp : (py Acetaldehyde, Acetone. ‘Di-tert-butyl ketone, Methyl tert-butyl Ketone (CH,),CHCOOH, "(reactivity towards HCN) H,CH(Br)CH,COOH, Si gascxcuite71c008. al CH,CH,CH,COOH (acid strength) benzoic acid, 3,4-Dinitrobenzoic acid, ) Benzoic acid, “4-Nitrol id (acid strength) 4-Methoxybenzoic acl simple chemical tests to distinguish between the following pairs of com, ane and Propanone ‘Acetophenone and Benzophenone jenol and Benzoic acid sngoic acid and Ethyl benzoate ‘tan-2-one and Pentan-3-one J nzaldehyde and Acetophenone thanal and Propanal \ds from benzene? You may use How will you prepare the following compount any inorganic reagent and any organic reagent having not more than one yn. atom jethy! benzoate Nitrobenzoic acid itrobenzolc acid Phenylacetic acid Nitrobenzaldehyde. you bring about the following oe in not more than two steps? panone to Propene ic ‘acid to Benzaldehyde ‘thanol to 3-Hydroxybutanal énzene to m-Nitroacetophenone nzaldehyde to Benzophenone Bromobenzene to 1-Phenylethanol nzaldehyde to 3-Phenylpropan- 1" Idehyde to a-Hydroxyphenylacetic acid ‘Benzoic acid to m- Nitrobenzy! alcohol 7 be the following: tylation 2 canta reac tion ‘Cross aldol condensation yr ecarboxylation Chemistyf! comniss sch athe by @iving missing starting material, reagent or products OOH : ; : ZA a, oO soc, ‘OH, heat coon heat 9 HANCONHNH, t i concn icon, | HQ CO vO te oy” NaN / HC : ao ‘COOH a CCH A ye ti “a a.Naon SRY x.c00x,c00c8, H cCHCH.cHo A Aon a. Aro ae (Cex (00, ve (i) Z-H,0 2( no ys Giye"Plausible explanation for each of the following: f Cyclotn enone forms cyanohydrin in good yield but 2,2,6-trimethyleyclo- jone does not, er are two -NH, groups in semicarbazide. However, only one is involved . the formation of semicarbazones, “pif During the preparation of esters from a carboxylic acid and an alcohol in the presence of an acid catalyst, the water or the ester should be removed as soon as it is formed. An organic compound contains 69.77% carbon, 11.63% hydrogen and rest oxygen. The molecular mass of the compound is 86. It does not reduce Tollens’ reagent but forms an addition compound with sodium hydrogensulphite and give positive iodoform test. On vigorous oxidation it gives ethanoic and propanoic acid. Write e possible structure of the compound. ; Althor ‘ide ion has more number of resonating structures than | late ion, carboxylic acid is a stronger acid than phenol. Why? | Answers to Some Intext Questions 121 CHO 9 () H,C-CH-C-H (iv) cr enzcu-cHo i I hg Hes (i) HJC-CH-CH,-C-H (v) CH,CH,CH-C-CH-CH,CH, ° Os w) F bc, ‘OH 1BBiq_ Aldehydes, Ketones and Carboxylic Acids