CBSE CHAPTERWISE SOLVED PAPERS ers ce i iLi CHAPTER 11 Aldehydes, Ketones and Carboxylic Acids [TOPIC 1] Aldehydes and Ketones Depending upon the atoms or group of atoms attached on either side of the carbonyl group, carbonyl compounds are divided into three major classes, i.e. aldehydes, ketones and carboxylic “cide RO RR Ko I ll 9° Aldehyde Ketone Carboxylic acid The compounds, which contain ‘—C—~’ group are called carbonyl compounds. ° Aldehydes and ketones have same molecular formula C,H,0 and are functional isomers of each other. 1.1 Nomenclature The word ‘al’ and ‘one’ replaces the ending ‘e’ of corresponding alkanes while naming the open chain aliphatic aldehydes and ketones, respectively. Common and IUPAC names of some aldehydes and ketones ‘Common name TUPAC name ‘Aldehydes HCHO Formaldehyde Methanal cH, —cHO Acetaldchyde thanal a ‘a-methylbutyraldehyde 2-methylbutanal (iCal Ext —cHO cH, ‘mv-bromobenzaldchyde 3-bromobenzenecarbaldehyde Br272 @chapterwise CBSE Solved Papers : CHEMISTRY Structural formula Common name PAC name Crotonaldehyde But-2-enal Cinnamaldehyde 3-phenylprop-2-enal Ketones cH coc, Acetone Propanone oy 9 cH, Diisopropyl ketone 2, 4-dimethylpentan-3-one cH, —CH—C—cH—cH, 1.2 Structure of the Carbonyl Group The carbonyl carbon atom is sp?-hybridised and forms three sigma (6) bonds. The fourth valence electron of carbon remains in p-orbital where it forms a n-bond by overlapping with p-orbital of an oxygen. It possesses a trigonal coplanar structure with bond angle 120°. The carbon-oxygen double bond is polarised due to higher electronegativity of oxygen relative to carbon. m1 e G le aN AN 1.3 Preparation of Aldehydes and Ketones (i) Controlled oxidation of alcohols in the presence of K,Cr,0, / dil. HS0,, KMnO,/dil. H,SO, or Cu metal at 573 K result in the formation of aldehydes and ketones (ii) Dry distillation of some calcium salts of acid gives simple ketones. (iii) Mixture of calcium salts of formic acid and calcium salts of any other carboxylic acid on dry distillation gives an aldehyde. (iv) Addition of Grignard’s reagents to alkyl or aryl cyanides followed by hydrolysis with dil. acids gives ketones while with HCN, aldehydes are formed. (v) Addition of H,0 on alkynes in presence of H,SO, and HgSO, yields aldehydes (by terminal alkynes) and ketones (by non-terminal alkynes). 1.4 General Properties of Aldehydes and Ketones (4) Boiling points of aldehydes and ketones are higher than hydrocarbons and ethers of comparable molecular masses. (ii) The lower members of aldehydes and ketones are miscible with water in all proportions, because they form hydrogen bond with water. (iii) Aldehydes and ketones generally undergo nucleophilic addition reactions. (iv) Aldehydes are more reactive than ketones toward nucleophiles due to more + Jand steric effects in ketones.CHAPTER 11: Aldehydes, Ketones and Carboxylic Acids 1.5 Chemical Properties of Aldehyde and Ketones (i) Aldehydes and ketones undergo a number of addition reactions due to the presence of polar carbonyl group (the carbonyl carbon bears partial positive charge, thus, undergoes ‘nucleophilic addition reactions). Common nucleophilic addition reactions are : ‘Acetal Cyanobydrins ashes ‘kom eo = Bisulphite addit = phite addition Z85— Carbonyl compounds compounds Nii sm ey uct Se (ii) Aldehydes and ketones also react with ammonia derivatives like: (i) NHOH (hydroxylamine) to give oximes. (ii) NH, NH, (hydrazine) to give hydrazones. 3° alcohols (ii) NH,—-NH— (phenyl hydrazine) to give phenyl hydrazones. (iii) Reaction with 2, 4-DNP can be used to identify the presence of a carbonyl group. (iv) Clemmensen reduction of aldehydes and ketones (Zn-Hg/conc. HCl) gives alkanes. (v) Wolff-Kishner reduction The carbonyl group of aldehydes and ketones is reduced to—CH, group on treatment with 273 hydrazine followed by heating with KOH in ethylene glycol. (vi) Aldehydes give positive Tollen’s test, Fehling’s test, Benedict’s test and Schiff’s test. (vii) Aldehydes can be distinguished from ketones by Tollen’s reagent, Fehling’s solution and Benedict's solution. (viii) Tollen’s reagent is an ammoniacal silver nitrate (AgNO; +NH,OH) solution, It is mild oxidising agent. (ix) Aromatic aldehydes do not reduce Febling’s solution. {x) Iodoform test is given by CH;CO— or CH,CH(OH)— group containing compounds. (xi) Aldol condensation is given by aldehydes ‘and ketones that have a-hydrogen atom in the presence of dilute alkali. It involves carbanion as an intermediate (xii) Cannizzaro reaction is given by those aldehydes which do not have a-hydrogen atom (like C,H,CHO, HCHO) in the presence of concentrated alkali. (xiii) Aromatic aldehydes and ketones undergo electrophilic substitution at the ring. in which the carbonyl group acts as a deactivating and meta-directing group. Uses Formaldehyde is well known as formalin (40%) solution used to preserve biological specimens and to prepare polymeric products. Benzaldehyde is used in perfumary and in dye industries.@ Chapterwise CBSE Solved Papers : CHEMISTRY 274 ®NOOD8H®O + HO"HOFH*O HORN 2009 + OHOFH®D pAyprezuoqonyru-t Sy OOH =n tn 008 O09 HO= 9-H “sag HOODFHO S nr + ( "Ho or ov + ( OHH = HOH agg OHO'HO: § <2 (158 10=X ‘82940 SHO + NOOO —xORN + HOON froamior aeRO [forsee major} jars imam (P1099 —%p Jo aBeanop fa) ere! Ferooan] RSE SRT Wie TIE HOT HOOD + HOOOHON (p10q 29 —19 J0 aBeavop Ag) HOOO*HO.Y+HOOO—¥: [mORESIEpIOS TORTI seuoyey |X potar + 10-00 a Dy amee + nota + Horo +x-3n-a 818 '0%H "a9 4 + sHoME, FOO BEY TH 00 ena cr) a AS F19%O40 + auan|OL, TSAR ooeaTIMT arson ng [SO LS a a (epson na prea] (roqoaye Krewe }—fsepayepiy}! "HN : - 9-0. a om ais, tyo-07 NOH THOMHO TUK, On 7840s, EE om ma FN a OW ae eae 40" ‘HO’ *osva-Pd “H + 1000u or en Se a HO” Nyt HOO weg vests a a TT 10-¥0 ona aai| HotHOW © OHOH wag {X8R TEA souaype jo asmouo70 Ag] PNON 0 Fos H‘os# S joyooye Jo wopyeuadospAyap 4G] an =o ND mam SHA oar WORT Seer Gp OUT wORMP RT FG SRO TR} omeoonn suonovey peormeyy suoreredorg sauojey pue sapAyaply Jo suonoway fes1weYyD pure SuoNEsedald a4) 10) HEYD MOL NOTE In Rosenmund’s reduction, poisoning of Pd with BaSO, prevents reduction of RCHO toR—CH,OH.oD SS EE PREVIOUS YEARS' EXAMINATION QUESTIONS TOPIC 1 (@1Mark Questions 4. Write the IUPAC name of the following: CH, — CH,— CHO aliindia 20180 2. Draw the structure of 3-methylpentanal. 1 2015¢ Write the IUPAC name of the compound CH, —GH— CH — 6 — CH, | OH ° All nda 2014 4. Write the structure of p-methylbenzaldehyde. peihi 2014, pei 2013 5. Give a test to distinguish between propan-2-one and pentan-3-one. all india 2014c 6. Write the IUPAC name of the following compound : CH,— CH— CHO pethizowse CH, rite the IUPAC name of the following mpound : an Oo = All india 2014 8. Write the structure of 3-methylbutanal. Deihi 2013, 2011 Write the structure of 4-chloropentan-2-one. Delhi 2013; all india 2071, 204 10. Rearrange the following compounds in the increasing order of their boiling points. CH,— CHO, CH,—CH,— OH, CH,— CH,— CH, all india 2013 11. Draw the structure of the compound named 4-methylpent-3-en-2-one. Delhi 2013¢; Foreign 2012 12. How will you carry out the following conversion? Ethanol to acetone pelhi 2013 13. Write the IUPAC name of the following : 0 IL CH,—CH,—CH = CH—C—H All nla 2012 14, Give chemical test to distinguish between benzophenone and acetophenone. Delhi 2012 15. Arrange the following compounds in an increasing order of their reactivity in nucleophilic addition reactions: Ethanal, propanal, propanone, butanone. Belhi 2012 16. Illustrate the following reaction giving a suitable example : Cross aldol condensation 17. Give simple tests to distinguish between the following pair of compounds: Pentan-2-one and pentan-3-one Delhi 2012 18. Illustrate the following name reaction giving suitable example : Clemmensen reduction Delhi 2012, 2009, 2008; All India 2011, 2010 19. Write the name of Oho CH= C—CH, | CH, Delhi 2012 Delhi 2011¢; Foreign 2010 20. Write the structure of 3-oxopentanal. Foreign 201, 2009; Delhi 2008 21. Write IUPAC name of the following : CH,CH,—C= 0 Delhi zone 22. Illustrate the name reaction: Wolff-Kishner reduction. all india 2010276 23. Draw the structure of 1-phenyl propan-1-one. Delhi 2010 24, Write IUPAC name of —~C ))-c—cry Il O _ bethi 2010 25. What is Tollen’s reagent? Write one usefulness of this reagent. all india 2010 26. Write the IUPAC name of the following : a I Sen, @ 2 Marks Questions 27. Write the equations involved in the following reactions : (i) Wolff-Kishner reduction. (ii) Etard reaction. pelhi 2017 28. Write the reactions involved in the following reactions: () Clemmensen reduction (ii) Cannizzaro reaction peihi 207 29. How are the following conversions carried out? (i) Propene to propan-2-0l. (i) Ethyl chloride to ethanal. Foreign 2018 30. Complete the following reactions: @ 2H—C— Hom KOH oO CHO aC) 31. Give a possible explanation for each one of the following : (i) There are two —NH, groups in semicarbazide, However, only one such group is involved in the formation of semicarbazones. Gi) Cyclohexanone forms cyanohydrins in good yield but 2,2,6-trimethy! cyclohexanone does not. delhi 2012 @ Chapterwise CBSE Solved Papers : CHEMISTRY 32. Explain the mechanism of a nucleophilic attack on the carbonyl group of an aldehyde or a ketone. Foreign 2010 @ 3 Marks Questions 33, Write the equations involved in the following reactions: (j) Stephen reaction. (i) Wolff-Kishner reaction (iii) Etard reaction. Foreign 2018 34. How will you bring about the following conversions? (i) Propanone to propane. (i) Benzoyl chloride to benzaldehyde. Gi) Ethanal to but-2-enal. pethi 2013 35. Write the structures of the main products of following reactions : a C catzcoct M8, Hg®* 280, (i) H,C—C= cH — CH; (9 cr0xch : > ii) cpmor > belhizon2 NO) 36. (i) Describe the mechanism of the addition of Grignard’s reagent to the carbonyl group of a compound to form an adduct which on hydrolysis yield an alcohol. (i) Draw the structure of the following compounds: (@) 3-methylbutanal (b) p-nitropropiophenone Foreign 2012 37. (i) Ilustrate the following reaction giving suitable chemical equations: Cannizzaro reaction (ii) How would you bring about the following conversions? Write the complete equations in each case. (@) Ethanal to 3-hydroxybutanal () Benzaldehyde to benzophenone Foreign 2012CHAPTER 11: Aldehydes, Ketones and Carboxylic Acids (@ 5 Marks Questions 38. (i) Draw the structures of the following derivatives: (a) Propanone oxime (b) Semicarbazone of CH,CHO (ii) How will you convert ethanal into the following compounds? Give the chemical equations involved: (a) CH, — CH, () CH; —CH— CH, — CHO HH (©) CH,CH, OH alt india 20150 (i) Deseribe : (a) Aldol condensation 39. (©) Cannizzaro reaction (i) Describe a chemical test to distinguish between (a) ethanal and propanal (b) benzaldehyde and acetophenone () propan-2-one and pentan-3-one Foreign 2014 (i) An organic compound with molecular formula Cy H,,O forms 2,4-DNP derivative, reduces Tollen's reagent and undergoes Cannizzaro reaction. On vigorous oxidation, it gives 1, 2-benzenedicarboxylic acid. Identify the compound (i) Give the chemical tests to distinguish between (a) propanol and propanone (b) benzaldehyde and acetophenone Arrange the following compounds in an increasing order of their property as indicated : Acetaldehyde, acetone, methyl tert- butyl ketone (reactivity towards HCN). Allindia 2012 (@ An organic compound A(CjH,O) on treatment with copper at 573 K gives B. B does not reduce Fehling’s solution but gives a yellow ppt. of compound C with I, / NaOH. Deduce the structures of A, B, and C. 40. a1. 277 (ii) Predict the products of the following reactions : @) Opa (OQ)-coans > Anh w) ee aaron, ‘Achy 2 Delhi zone (i) Identify A, Band C in the following sequence of reactions: CO Catig Mac CH,CHO—> A wn 42. br a Peroxide c (ii) Predict the structures of products formed when benzaldehyde is treated with (a) cone. NaOH (b) HNO, / H,S0, (at 273 -383 K) Delhi gone 43, A ketone A(C,H,O) which undergoes a haloform reaction gives compound Bon reduction. Bon heating with sulphuric acid gives a compound C which forms mono-ozonide D. D on hydrolysis with zine dust gives only E. Identify A, B,C, D and E. Write the reactions involved. ‘eth 20100 cone, HyS0,, ces @ Explanations 4. CH, —CH,—CHo Propanal CH, o I 2. CH; —CH,—CH—CH, —cHO 3-methylpentanal o NOTE ‘al’ represents —CHO group and ‘pent represents chain of five C-atoms, Boa 21 3. CH, aa a —CcHy OH TUPAC name 4-hydroxypentan-2-one o278 CHO cHy p-methylbenzaldehyde {pameans para and ath postion vor aldehyde group © 5. Pentan-2-one and pentan-3-one can be distinguished by iodoform test. On heating with NaOH +1, or [NaOt], propan-2-one being a methyl ketone forms yellow pt of iodoform, whereas pentan-3-one does not, 9 cn, bere snc — CH,COGNat + CHI, L +2NaOH Iodoform (yellow prt ° | exxcu, —b— cuca, Ls No yellow ppt ofiodoform Ap 6. dx, 2x bio cH, 2-methylpropan-t-al o 2-hydronpbensaldehyde 0 8. Hy,C—CH—CH, —CHO cH, 3-methylbutanat 0 ° 5 4 3 all p 9. dpa —CcH, —"C—CH, a ‘4 chloropentan-2-0ne o 11. 12. 13. 14. 15. @ Chapterwise CBSE Solved Papers : CHEMIstay CH, —CHO and CHy—CH,— Clty, CH CHO possess higher boiling point than CH1,CH,cy, because CH , CHO possess dipole-dipole interactions which are stronger than van der Waals’ forces of attraction existing in CH, Ci Hence, the order of thei cH, —CH, —CH,< CH, —CHO < CH, —CH,—on © or The structure is, cy Fcc, cH, 0 4methylpent-3-en-2-0ne o Ethanol to acetone 0 CH,OH+KMn0, 4 cHyCHO+CH)MgBr—, CH,CH CH, OH OMgar 101 " CHSC CH OL CHACH CH] "its | kmno, ° 0 ° iy —CH,— CH=CH CH Pent-2-en-I-al ny Benzophenone (C,H,COC,) and acetophenone (CdH,COCH,) can be distinguished by iodoform {eSt. Acetophenone, being a methyl ketone on treatment with; / NaOH [or NaOI] undergoes iodoform reaction to give a yellow ppt. of iodoform. On the other hand, benzophenone des not give this test. CAH,COCH, + 3NaOI —+ CACOONa ‘etpenene + cuit + 2Na0H Tato Siete cascocga, 04 No vellow ppt. of Teniopinone—, i0doform : a Reactivity depends on two factrs: steric ete ar | electronic elfect Lesser the steric hindrance, higher | isthe reactivity 10, | Boling point is related to attractive forces, Songer the attractive force, higher is the bolling point. Ethanol, i. CH; —CH,—OH undergoes extensive intermolecular hydrogen bonding, therefore, its boiling point is highest among all the given compounds. In contrast, among ‘On moving from ethanal to butanone, + I-effect and steric hindrance of alkyl group increases due to Which the electron density on the carbon atom of the carbonyl group progressively increases and hence, attack by nucleophile becomes slower and slower. Thus, the reactivity increases in the order as Butanone< propanone < propanal Hyc~ Acetone 279 He C= NNH, tO 7 sxienewvt HC cH,—cH, —cH, +N, Propane o fa 23. ‘o_n,—cH, 1-phenypropan-I-one o ya 24, F. 3 4-uorophenyethanone o 25. It is ammoniacal silver nitrate (AgNO, + NH,OH) solution. It is used to test the presence of aldehyde group as it is a mild oxidising agent. a ° a, dl 26. 1 3CHy KA 2-chlorophenylthanone a. 27. (i) Wolff-Kishner Reduction Refer to solution 22. o (ii) Etard Reaction Toluene reacts with chromyl chloride in presence of CS, followed by hydrolysis produces benzaldehyde. Hy GHOCOHCI) CHO cy tot, + C10, > Chromyt Toluene chloride Choma O. complex o 28, (i) Clemmensen reduction Refer to solution 18, (ii) Cannizzaro reaction Aldehydes which do not have a-H atoms undergo self oxidatio and reduction reaction on treatment with conc, alkali. This reaction is known as Cannizzaro reaction. In this reaction, one molecule of aldehyde is reduced to alcohol while another molecule is oxidised to salt of carboxylic acid.280 © + cone. KOH Formaldehyde Mt 5 a O Nox > nAc-on + Id u Potassium Ato he (J ctt0 + one soon #5 Benzaldehyde y ‘Bensylatcoho Sodium benzoate o 29. (i) CH,—cH = cH, U2" repens os | ch,—cu—cH, roan 20 o (ii) CH; —cH,—c1 2", ‘a tie cH;—CH,— on 21» cH,—cHO » Beare Ethanal o 30. (i) 2H—c—H Loe KOH § Hoe —OH + HCOOK* i a NOTE iis n example of anna escton, a Ho cHo / ore «ay 273-283 K No: ae enhrbesacyde Benzaldehyd in wey 31. (0 Lone pair of electrons involved in conjugation with >CO group (i) +Heffect due to methy| groups, steric hindrance, ___makes a carbonyl compound less recive. (i) Although semicarbazide has two —NH, groups but gne of them which is directly attached to C= 0 group is involved in resonance a shown below: 32. @ Chopterwise CBSE Solved Papers : CHEMISTRY oly | . HENAN ney tie Semicatbaeide HNC SNH NAD Therefore, the electron density on —NH group involved in the resonance decteases. As a result, it cannot act as a nucleophile. in contrast, the Jone pair of electrons on the other —NH, group is not involved in resonance, thus, it can act as a nucleophile and can attack carbonyl carbon atoms of aldehydes and ketones to produce semicarbazones. o (ii) Cyclohexanone forms cyanohydrin according to the following equation: oO HO CN aa, Cyclohexanone cyanotydin ‘As in cyclohexanone, there is no_ steric hindrance, therefore the nucleophile CN" can casily attack the carbonyl carbon. However, in case of 2,2,6-trimethylcyclohexanone, the presence of three methyl groups at c-positions offer steric hindrance and as a result, CN" cannot attack effectively. For this reason, it does not form a cyanohydrin. 9 HBC CHS cy CH; > No cyanohyarin formation 2.2,6-trimethyleyclohexanone o Mechanism of a nucleophilic attack on carbonyl carbon A nucleophile attacks the electrophilic carbon atom of the polar carbonyl group from a direction approximately perpendicular to the plane of sp?-hybridised orbitals of carbonyl carbon. The hybridisation of carbon changes from sp? to sp* and a tetrahedral intermediate is produced. This intermediate immediately accepts a proton from the reaction medium to give electrically neutral product,CHAPTER 11; Aldehydes, Ketones and Carboxylic Acids 281 35. () Friedel-Crafts reaction (acylation), |e. introduction of acy! group in benzene ing (i Hycration of propyne, ie. adation of water to propyne and tautomerisation. (i) Etard’s reaction (aldehyde is formed, i.e. — CH o {group is converted into — CHO group). = ae a Ae + |e * rast’ | 74] — “Anhydrous: of No® | (aidan | 67 Non oy CO +CH,cocL > + HCl COC6Hs of proton) Teurahedsal ‘Addition product ae intermediate ae . ba. 33. (i) Stephen Reaction Gi) HC Cm CAH + HO R—CN+ SnCl, + HCI . nt | mo" automaton, ROHS NH—M RHO gy | cy, —— cx, cu, ten, . Propi-en-2-0l Acetone (ii) Wolf-Kishner Reaction Refer to solutions 22. een © (ii) Btard Reaction Refer to solution 27 (i). cH, CH(OCrC1OH)2 34, (i) Conversion of Propanone to Propane an cit, —¢—on, Steen eon i ati) + He G F cest.tt ston propangne NaH KOM * Bre No, No, cHO cH, —cH, —cH, Propane o {&) Conversion of Benzoyl Chloride to Benzaldchyde ° ° Il ] NO2 ca cH p-nitrobenzaldehyde © paseo 36. (i) Alcohols are produced by the addition reaction of eon, Grignard’s reagents with the carbonyl group of nowt sana aldehydes and ketones, Benzoyi chloride "10" penpatgchyde «y -=«,_=«s Mechanism ‘Step The first step of the reaction is the (iii) Conversion of Ethanal to but-2-enal nucleophilic addition of Grignard’ reagent to ach cH —euson the carbonyl group to form an adduct. ‘hana eondenation Nou oH Sond + Rmx ‘CH, —CH— CH, —CHO No o- hie ‘>hydroxybutanat A Oo Mg—x A pcH,—cH cH—cHO R pdduer nal o o282 @ Chapterwise CBSE Solved Papers : CHEMISTRY Step Il Hydrolysis of the adduct yields an alcohol N , 1,0 * Yee tee fe nom R re“ o (ii) (a) 3-methylbutanal cH, ° I H,C—’cH —CH, —'C—H aay (b) p-nitropropiophenone ? ow{~ fore a) 37. (i) Refer to solution 28(ii) (ii) (a) Ethanal to 3-hydroxybutanal Dil. Na0H, ‘aldol condensation) 2CH;—CHO Ethanal 4 x 2 CH, —CH —CH,—CHO on shydroxybutanal” (1) (b) Benzaldehyde to benzophenone ies or oO fame o. ewmee (CS acylation) Benzophenone o 38. (i) (a) Propanone oxime The structure of propanone oxime is: cH,—¢ =N—OH cH, o NOTE tis formed when propanone reacts with hydroxylamine Be 0+H,—N— OH Hydroxyamine 82 OF =n on cH, Propanone oxime (b) Semicarbazone of CH,CHO The structure of semicarbazone of CH, CHO is i CH,—CH = N—NH—C—NH, NOTE itis formed when CH CHO reacts with semicarbazide 9° Ic WDC OF HAN NH CN, Semicarbaxide 24 cHy CH= N—NH—C NH, ‘Semicarbazone (ii) (a) Ethanal, (CH,CHO) to CH) —CH cH,CHO —#445 CH, — CH, +H.0 Clemmensen reduction o (b) Ethanal,(CHCHO) to cx, — exter, cH on 20H, cHO BLO, cH, —CH—CHt,— CHO condensation | on 0 (¢) Bthanal ClCH 0 CH,CH,OH cHcHo 2 scHcHoH 1. (i) (a) Aldol condensation In this reaction two ‘molecules of an aldehyde or ketone condense in presence of dilute alkali (dil NaOH, Ba(OH), etc.) to form a B-hydroxy aldehyde or aB-hydroxy ketone respectively. These B-hydroxy aldehydes or ketones are collectively called aldols and the reaction is called aldol condensation. The reaction is based on acidity ofa-hydrogen of aldehydes and ketones. o 0+ H—CH,cHODL MOH, 1H Ethanal thanal 7 Sas—4— Ch H 2 yd butanal (All) (b) Cannizzaro reaction Refer to solution 28 (ii) oCHAPTER 11: Aldehydes, Ketones and Carboxylic Acids 283 (ii) (a) Ethanal and propanal Both can be distinguished by iodoform test, Ethanal 0 contains CH — C — group, therefore, it undergoes iodoform reaction and gives yellow precipitate of CHI. While propanal does not give this test. o oO CH, —C— H+ 3NaoI—*> tina "+> cH, COO a+ 2NaOHFCH yaw rH crt, ‘oles + 2Ag 1 cHo reagent Silver mirror CoHs + Conc. NaOH ————> (Cannizzaro| reaction) cooNa CH,OH CoH CoHs +284 CHO Hs Ak MnO COOH COOH Benzene-1, 2- dicarboxylic acid (ii) (a) Propanone, because of the presence of —COCH, group when treated with NaOH and 1, gives yellow crystals of iodoform. CH,COCH, + 4 NaOH + 31, —> cui, 1+ cH,COONa + 3Nal + 31,0 Intom In contrast, propanol (CH,CH{CH,OH) does not contain CH. EH group, sot does not give on iodoform test o (b) Refer to solution 39 (ii) (b). o (iii) The reactivity towards HCN addition decreases as the +T-effect of alkyl groups increases as they tend to increase the density of electrophilic carbonyl carbon and makes nucleophilic attack by CN” difficult. Further, the presence of large number of alkyl groups causes steric hindrance to the nucleophilic attack by CN at carbonyl carbon. Hence, reactivity increases as: Methyl ‘-butyl Ketone < acetone < acetaldehyde i.e. [CH,COC(CH,),}< (CH,COCH,) < (CH,CHO) (Reactivity towards HCN) o 41. (i) Compound B gives a yellow ppt. with I; /NaOH, i.e. positive iodoform test and not reduce Fehling’s solution, it means that it contains —COCH, (methyl ketone) group, and is a ketone. Moreover, B is obtained by the oxidation of A, thus A must be a 2° alcohol. (As only 2° alcohol give ketones on oxidation with Cu at 573 K), Hence, the structure of compound Ais REA CH, on Comparing with the given molecular formula gives R=CH,, Thus, compound 4 is CH, CHCH, oH Propan-2-ol The reactions are as follows cH, cHcH, — ae on ao 3 4) Acetone (a) Acetone Stet No reaction ‘oll @ @ Chopterwise CBSE Solved Papers : CHEMISTRY CH,COCH, + 31,+ 4NaoH —> CH,COONa+ 3Nal+ CHIL +319 Iodofeem 0 ‘Thus, A=CH,CH(OH)CH, 0 B= CH,COCH, a C=CHI, di) (a 1] _ aldo condensation =| O- cH=cH—< I Benzalacetophenone © {0r 1.3-diphenylprop-2-en-1-one} » And » Oenpea ° CoH, |-phenylpropan-1-one 42. (i) CHcHO SW OMgcl ay 0 cH,—cH—cn, | ——> Hy —CH— Gt, S059 CH,CH. | W804 HCR, ‘But-2ene i (8) 4) Peroxide HGH GH—cH, HOB 2-bromobutane ey (axt=3) i (a) 2 cHo Se Nason envaldetyde (Cannizearo'sreection) ©r CHZOH +( @) COONa* Benzyl alcohol sodium ber zoate (b) ON: Conc. NO + ‘Cone. F350, 273383K o CHO: CHO Benzaliehyde am-nitrobenzaldehyde(CHAPTER 11: Aldehydes, Ketones and Carboxylic Acids 43. Since, A gives haloform test, it must contain —COCH, group. Thus, its possible formula is CH,COCH,. Since, Aon reduction gives B which on heating with sulphuric acid gives C that forms ‘mono-ozonide (i.e. undergoes ozonolysis) this suggests that Cis alkene which is formed by dehydration of alcohol. Hence, Bis alcohol. ‘Therefore, C:HsCOCH, on reduction gives butan-2-ol (4) which on dehydration gives but-2-ene (C). Ozonolysis of but-2-ene gives only acetaldehyde (E). The reactions involved are: tH cucocu,cH, —“_, a Al Buta cH,— CH —CH&H, anol one. #38041 ets, “#20 OH 8) one 0 285 CH,—cH =cH—cH, 5 (C) But-2enc o ct, Seat, sano Doo (D) eee acugHo (&) Acetaldehyde (A) gives iodoform reaction as CH,COCH.CH, + 31, + 4NSOH —> cat, + ¢3H,COGNa + 3Nal +30 «y [TOPIC 2] Carboxylic Acids 1. The carbon compounds containing “—C€— OH" group (— COOH) are known tI ° Structure Commenname TUPAC name CH,CH,CH,COOH Butyricacid —Butanoie acid as carboxylic acids. The carboxyl group, (CH,),CHCOOH —sobutyric acid 2- methylpropanoie consists of a carbonyl group attached to a acid hydroxyl group, hence it is named as carboxyl. HOOC-COOH ‘Oxalic acid ‘Ethanedioic acid ° ° aan il il Qe coon — Bewwesetseeensetotie ni cog C_O—H (Benzoic acid) Cartons] Hydroxy Carbo 2. The general formula of carboxylic acid is CyH2,02- 3. Higher aliphatic acids are also known as fatty acids. 2.1 Nomenclature Aliphatic carboxylic acids are named by replacing the ending ~e in the name of the corresponding alkane with —oic acid. Names and structures of some carboxylic acids Structure Common name 1UPAC name HCOOH Formic a Methanoic acid cH,coon Acetic acid Ethanoic acid Propionic acid _Propanoic acid 2+ phenylethanoic acid on Phenylacetic acid 2.2 Structure of Carboxyl Group In carboxylic acids, the bonds to the carboxyl carbon lie in one plane and are separated by about 120°. The carboxylic carbon is less electrophilic than carbonyl carbon because of the possible resonance structure. - Got \o—H \286 2.3 Preparation of Carboxylic Acids Carboxylic acids can be prepared by (i) oxidation of 1° alcohols and aldehydes. (ii) oxidation of alkyl benzenes. iii) hydrolysis of alkyl cyanides and amides. (iv) carbonation of Grignard’s reagent. (v) hydrolysis of acyl halides and anhydrides. (vi) Aromatic carboxylic acids are prepared by side chain oxidation of alkyl benzenes. 2.4 Properties of Carboxylic Acids Carboxylic acids are weak acids, they give H* ions on ionisation. But they are stronger acids than phenols and alcohols, due to greater stability of, carboxylate ion by two equivalent resonance structure in which the negative charge is at more electronegative oxygen atom. The acidity of carboxylic acids are effected by substituents which i directly attached with carboxylic carbon. Electron withdrawing groups increase the acidity of carboxylic acids while electron donating groups decrease the acidity of carboxylic acids. Carboxylic acids has higher boiling points than aldehydes and ketones of comparable masses. This is due to intermolecular hydrogen bonding. NOTE Benzoic acid has lesser acidic strength than formic acid 2.4 Reactions of Carboxylic Acids 1. Reactions Involving Cleavage of O—H Bond (i) Carboxylic acids react with active metals like Na, K, Ca, Mg, Zn, etc, to form respective salts with evolution of H, gas. (ii) They neutralise alkalies forming salts. (ii) They react with weaker bases such as carbonates and bicarbonates producing CO, gas, @ Chapterwise CBSE Solved Papers : CHEMISTRY of C —OH Bond (i) Formation of anhydrides When carboxylic acids are heated in presence of strong dehydrating agent such as P,O, or conc. H,S0, acid anhydrides are formed. (ii) Formation of ester When carboxylic acids are heated with alcohols or phenols in presence of a mineral acid such as conc, HSO, or HCI gas, esters are formed, This reaction is known as esterification, (iii) Formation of acid chlorides They react with SOCI,,PCI, or PCI, to form acid chlorides by replacement of —OH group by Cl atom, (iv) Formation of amides They react with Ni, to give ammonium salt which on further heating at high temperature give amides 3. Reactions Involving — COOH Group (1) Carboxylic acids are reduced to 1° alcohols by LiAIH, or with B3Hg, (ii) They lose CO, to form hydrocarbons when their sodium salts are heated with sodalime (NaOH + CaO) in the ratio (3 : 1). This is known as decarboxylation. (iii) Alkali metal salts of carboxylic acid also undergo decarboxylation on electrolysis of their aqueous solutions and form hydrocarbons having twice the number of carbon atoms present in the alkyl group of the acid. The reaction is known as Kolbe electrolysis. (iv) Carboxylic acid having an a-hydrogen are halogenated at the a-position with Cl, or Br in presence of small amount of red phosphorous to give a-halocarboxylic acids. The reaction is known as Hell- Volhard Zelinsky reaction. Test to Distinguish between a Phenol and a Carboxylic acid Sodium bicarbonate test Carboxylic acids when treated with NaHCO, solution gives brisk effervescence due to evolution of Ci gas whereas phenol doesn’t give this test. CH,COOH + NaHCO, —+CH,COONa +H,0+ CO,287 Aldehydes, Ketones and Carboxylic Acids CHAPTER 11 (ii) Ferrie chloride test Carboxylic acids give coloured ppt. when treated with neutral FeCl, solution whereas phenol give a violet coloured complex with FeCl, solution, 3CH,COOH+ FeCl, —> (CH,COO), Fe+ 3HCI (uff colored ppt) (Cyrene ect eqocayba436r (i) The main use of carboxylic acids are in industries, in the manufacture of soaps, Uses (ii) Esters are used in perfumery industries and sodium benzoate is used as a preservative. <énos8 Sunsonp-ui st dnos8 HOOD fuonbrax uonninsqns Sydon29ra poonpoxd are (HoooxHDy) sppe ansxoqre>oeu-D ‘snuoydsoud jo aouasoxd a ut ag 130 tus parean st (HOOD"HO#) nsoupAy-n pum pe a Axoqre> [uonbeax Aysun7-preUiOA- (PH ued woqesoxpéq] arp tt suon>ear wormansans panpoud axe [S1SA012919 5 2410% OFD/HON (ey) Sourqy L + 1fesexqe snospéquy soya e se dnoz3 HOOD — 01 9nd (o®(oou)] sapupaaue pre ssonpord iH 20 vFOFa th wonespAyoa Zanooy sont Stmeoq to woTye paonpoud SUPHNQODW 1S 1--— HN (DIM (ape Woe) KODE pos pue Sa “xa MUM peonposd st (2152) OOD¥-— HO. HIM ddnox8 HO — 01 ang, poreurua st wafoxpAy pue paonposd st eOOOW aes (EN) sTeI9uH KpUMA 1 ) paonposd st 910m pte eX OODY es (“ODHEN) sayeuoqie> uaSosphy pur (HORN) SOTeATE HAN H ayqeaoeydas 01 ang. suopeay [e>qw94D (HooDw) sppe skxoqresouow stom = 08H ow HN a GO 0 ox Fomexet Tea pao fons 08H Ton aTeNY¢ oar useuog Hoy HOHE uoperedarg Proy s114xoqreoou0yy Jo suorovay TworMONS pue uoHEIEdarg 94} 105 WEYD MOLL NOTE Carboxylate ions have more acidic strength than phenoxide ion due to delocalisation of lone pair of elections over mare electronegative two oxygen atoms,288 2.5 Derivatives of Carboxylic Acids @Chapterwise CBSE Solved Papers : CHEMISTRY Esters, acid chlorides, amides and acid anhydrides are the derivatives of carboxylic acids. Some important reaction of its derivatives are as follows: Chemical Reactions of Acid Chlorides SoH + RCOOR’ (Schotten-Baumann reaction) Hyd, BaS04 (Rosenmund reaction) RCHO RCOCI SeH/NC , CH,COR Ken N30 RCOCN °>RCOCOOH 2-oxoalkanoic acid Chemical Reactions of Acid Amides 720s ps RCN NaNO, + HCI RCOOH RCONH, BrsKOH, (Hofmann bromamide reaction) | HANS RCH)NH) Lw&0" _, COOH + NEY -RNH, Chemical Reactions of Esters *2H_, RCOONa + R'OH (saponification) RCOOR’ | ++ rconn, + ROH sate RCH,OH + ROH or Na-GOH Chemical Reactions of Anhydrides *S_. Rcoor’ + RCOOH (RCO),0 SoHINCN © .HSCOR + RCOOH Caigntty RCONHG3Hs + RCOOHPREVIOUS YEARS’ EXAMINATION QUESTIONS TOPIC 2 (@1Mark Questions 1, Write the IUPAC name of the compound CH, —CH — CH,—COOH . attindio 2014 OH 2. Write the structure of 2-hydroxybenzoic acid. oel 3. Complete the following reaction: Bry P CH,COOH——> _pethi zorse 4. Give chemical tests to distinguish between phenol and benzoic acid. Dethi zor 2010 5. Illustrate the following reaction giving a suitable example : Decarboxylation Delhi 2012 6. Draw the structure of the following compound : Hexane-1, 6-dioic acid. Foreign 2012 7. Illustrate the following name reaction giving suitable example; Hell-Volhard-Zelinsky reaction. Delhi 2012; Foreign 2012 8. How would you complete the following conversion? Write the complete equation. Benzoic acid to m-nitrobenzyl alcohol. 9.2012 9. Write IUPAC name of CH,—C= C—CH= cH—f—OH ° eth zone. 10. Write IUPAC name of COOH Br Cl allindia 200 41. Write IUPAC name of OCOCH; HC CHs Delhi zone 12. How will you convert benzoic acid to benzaldehyde? peihi 2010 @ 2 Marks Questions 13. Write the reactions involved in the following: (i) Hell-Volhard Zelinsky reaction (ii) Decarboxylation reaction belhi 2077 14, Although phenoxide ion has more number of resonating structures than carboxylate ion, carboxylic acid is a stronger acid than phenol. Give two reasons. Delhi 2013 45. How will you carry out the following conversions? (i Acetylene to acetic acid (ii) Toluene to m-nitrobenzoie acid Dethi 20130 16. Arrange the following compounds in an increasing order of their property as indicated: (i) Benzoic acid, 3,4-dinitrobenzoic acid, 4-methoxybenzoic acid (acidic strength) (ii) CH,CH,CH(Br)COOH, CH,CH(Br)CH,COOH, (CH,),CHCOOH (acidic strength) Ail indi 2012 @ 3 Marks Questions 17. How are the following conversions carried out? () Ethyl cyanide to ethanoic acid Gi) Butan-1-ol to butanoie acid (iii) Benzoic acid to m-bromobenzoic acid ethi 20120290 @ Chopterwise CBSE Solved Papers : CHEMISTRY 18. An organic compound A (molecular formula C,H<02) was hydrolysed with dilute sulphuric acid to give a carboxylic acid Band an alcohol C. Oxidation of C with chromic acid also produced B, On dehydration C gives but-1-ene. Write the equations for the reactions involved. 7. Hell-Vothard-Zelinsky (11VZ) Reaction Carboxyli- acids having a-hydrogen atom are halogenated at the a-position on treatment wit chlorine or bromine in the presence of small amount of red phosphorus to give a-halocarboxyli¢ acids, The reaction is known as Hell-Volhard Zelinsky reaction. R—cH,—coon 472 Ne horus [Foreign 2010; Dethi 2010 ee —— #41 — coon i x @ Explanations chabeaic ai a ec gy 1, _ —CH,—COOoH 8. Benzole acid to m-nitrobenzyl alcohol OH COOH COOH > ptonbuana © — cone NOY $04 ‘NO; 6 ‘OH poke acid menitrobenzoic acid 2 si J CH20H 2. + o 2-yonybenzte act ane a m0 3. cucoon "5 en, — coon " _ Aci | ‘m-nitrobenzy alcohol Br © tt tomosctie ae NOTE. This reaction is an example of Hell:Volhard-Zelinsky reaction. 9. CH—G= C—CH = cH c—on 4. Phenol and benzoic acid can be distinguished by ferric chloride test. Phenol reacts with neutral Hex-2en-4- ic acid w FeCl, to form ferric phenoxide complex giving violet colouration. ay COOH 6C,H,OH+ FeCl, —+ [Fe(OCgH),)” + 6H" + 3Cl" But benzo‘c acid reacts with neutral FeCl, to give a buff coloured precipitate of ferric benzoate. (1/2) o Seyt{COOH# Feely > fegtsCOO} Fee 3Hel NOTE Naming willbe doen alphabetical manne Tarot eran (Buff coloured ppt.) OCOCHs 5. Decarboxylation refers to the reaction in which yy, A carboxylic acids lose carbon dioxide to form . 6 hydrocarbons when their sodium salt are heated x 3 with sodalime, e.g. 2) CH” “J CHs eee 3, 5-dimethyiphenylethanoate ' cugooia “mesa ca waco, : Sodium Methane 12, |Benzaldehyde 1s easily obtained from benzoyl thanante i) chloride, so convert benzolc acid into benzoyl chloride 6 Hexane-1, 6-dioic acid HOOC — (CH,), — COOH o and then do Rosenmund’s reduction.CHAPTER 11: Aldehydes, Ketones and Carboxylic Acids coon cocl O90 ttenzoni chlor cn vie? corquinoling o 13, (i) Hell-Volhard-Zelinsky reaction Reler to solution 7. {ji) Decarboxylation reaction Refer to solution 5. (0) (in soxialime, the ratio of NaOH and CaO is 3: 1.) 14, Comparative effectiveness of delocalisaton of negative charge is responsible for the acidic strength. ‘A resonating structure having negative charge on | more electronegative atom, is more stable (i) Phenoxide ion has non-equivalent resonance structures in which the negative charge is at the less electronegative carbon atom whereas in case of carboxylate ion, the ion is stabilised by equivalent resonance structures, in which negative charge is ‘on more electronegative atom. o Resonance structures of carboxylate ion (ii) In. carboxylate ion, the negative charge is delocalised over two electronegative oxygen atoms, whereas in phenoxide ion the negative charge is less effectively delocalised over one ‘oxygen atom and less electronegative carbon atoms. Thus, the carboxylate is more stabilised than phenoxid 291 carboxylic acids are more acidic than, o oF Carboxylate jon Phenoxide ion 15, (i) Acetylene to acetic acid Ce fet on Taytomerisaion . Sj} cus co =, curcoon Acct HS” Acc aunt ( (ii) Toluene to m-nitrobenzoic acid coon O BBenzoic acid cooH Nitration Gnc HNOYHSSO, NO2 imenitrobenzoke acid o 16, Presence of electron withdrawing group increases the acidity, whereas presence of electron releasing groups decreases the acicity Since, electron releasing group decreases the acidic strength, therefore, 4-methoxybenzoic acid a weaker acid than benzoic acid. Further, since, electron withdrawing groups increase the acidic strength, therefore presence of two electron. withdrawing groups in 3, 4-dinitrobenzoic acid makes it a stronger acid Therefore, increasing order of acidic strength is COOH = COOH COOH NO; OCH; NO. 4-methoxy Benroic 3,4-dinitrobenzoic acid benzoic acid acid a) (ii) The + Leffect decreases while —F-elteet inereavey the acidic strength of carboxylic acids, Theretore,292 (CH,),CHCOOH is weaker acid than other two acids: containing a chain of three C-atoms because isopropyl group, (CH,),CH-exerts greater +reffect. As we know, -I-effect decreases with distance, therefore CH,CH.CH@NCOOH is a stronger acid than CH,CH(B)CH,COOH. Thus, {he overall acidic strength increases in the order. (CH, ,CHCOOH < CH CHBNCH,COOH coe 17. (i) cH eN 2 Y cH coon MU nex ™2 cuoon ne caHjon —AIERIIOL CH COOH L ot weneneren pn ON a eaERooH COOH COOH wy Ou ©. — A ae 12. [0 Esterpodiesacabonicacand accion | robes (ii) Ester A has 8 carbon atoms, calculate number | oC some set ang ae (i) Guess the alcohol and acid according to the «given reactions () Now guess the ester. |_™ Write all the related equations. | Compound C on dehydration gives but-1-ene (CH,CH,CH= CH,), so it must be butan-1-ol When subjected to oxidation ¢ gives butanoic acid B.Thus, compound Ais, CH,CH,CH,COOCH CHCH,CH, ‘The reactions involved are as follows CHCH.CHCoocH,CH CH cH, 82, « CH,CHCHCOOH + CH,CH,CH,CH,OH (8) © o CHCH.CH,CH,on £2 cH,cH CH COOH a or oy CH,CHCH, CH,0n 5 cH CH CH = City Ch soe Dut-oene o @ Chapterwise CBSE Solved Papers : CHEMISTRY ee MISCELLANEOUS QUESTIONS (@ 1Mark Questions 1. An aromatic organic compound ‘A’ with molecular formula CJH,0 gives positive DNP and iodoform tests. It neither reduces Tollens’ reagent nor does it decolourise bromine water. Write the structure of ‘A’. AlLindia 2018 2. Draw the structure of 2-methybutanal. Delhi 20160 @ 2 Marks Questions 3. How do you convert the following? () Ethanal to propanone (ii) Toluene to benzoic acid 4. Account for the following (i) Aromatic carboxylic acids do not undergo Friedel-Crafts reaction. (ii) pK, value of 4-nitrobenzoic acid is lower than that of benzoic acid. Delhi 2018 5. Write the reagents required in the following reactions : @ CH, =CH—CH,OH—, CH, =CH—CHO Gi) CH,—CooH—, cH, —conn, Dethi 2015 6. Arrange the following compounds in the increasing order of their property as indicated. () CH,COCH,, CH,COCH,, CH,CHO (reactivity towards nucleophilic addition reaction) (ii) Cl—CH,—COOH, F—CH,—COOH, CH, —COOH (acidic character) All india 2005CHAPTER 11: Aldehydes, Ketones and Carboxylic Acids 293 7, Name the reagents used in the following reactions, (i) CHy— CO— CH, 5 CH,—CH—CH, on (ii) CH; CH, —CH, CyHs —COOK* pat 2015 8. Give reasons: a (i) chloroacetie acid is stronger than acetie acid (ji) pH of reaction should be carefully controlled while preparing ammonia derivatives of carbonyl compounds. beth 20136 9. Give simple chemical tests to distinguish between the following pairs of compounds: ()) Ethanal and propanal. (i) Benzoic acid and phenol. oethi 201 10. Give chemical tests to distinguish between the following pairs of compounds: (i) Propanal and propanone. (ii) Benzaldehyde and benzoic acid. ‘oeihi 2012 41, Predict the products, oO KMno, ae, wo Gi) tT ‘CHy z ors + CHjCH NH, 5 All india 2016 12. Give chemical tests to distinguish between () ethanol and propanol, (ii) benzoic acid and ethyl benzoate. ath 2010 @ 3 Marks Questions 13. Write structures of compounds A and Bin each of the following reactions CH,CH, KMnO,—KOH, 1,0" —aA 0 B ou ee (ii) ie aa Z Delhi 2019 14,N—NII— CON, B A, Band C are three non-cyelie funetional isomers of n carbonyl compound with molecular formula CH,O. Isomers A and C give positive Tollens’ test whereas isomer 3 does not give Tollens’ test, but gives positive iodoform test, Isomers A and Bon reduction with Zn(Hg)/cone. HCl give the same product D. (i) Write the structures of A, B,C and D. (ii) Out of A, Band C isomers, which one is least reactive towards addition of HCN? pet 2018 Write the structures of the main products in the following reactions ° cry coc Hy Sy 0 j CH,=CH, + H,0"> (ii) oF OCH, ii) +HI———> Write structures of compounds A, Band C in each of the following reaction () CiH,Br—Metostor_ COW a 10" Bora Gi) CHYCN—OSHCMEL, 4_DuNwoH Gyno" B—*> C pelnizov Do the following conversions in not more than two step: (i) Benzoic acid to benzaldehyde. (ii) Ethyl benzene to benzoic acid. (iii) Propanone to propene, pethi 2077294 18. Predict the products of the following reactions: Ne, @ oe te oo CH, (io KMaoy KOH (ii) CH; —CH, 2 wnt COOH Bry/PeBry Gi) ‘All india 2015 19. Predict the products of the following reactions: ) Cr,—c-=0 Me, » | i KOWGyeoL CH, (ii) CH, —CO—CH, 2, 24.2 NeoWCx0_, » (ii) CH,COONa Mg 2 20. How do you convert the following? (i) Benzoic acid to benzaldehyde. i) Ethyne to ethanal. (iii) Acetic acid to methane. Foreign 2018 21. Two moles of organic compound A on treatment with a strong base gives two compounds B and C. Compound B on dehydrogenation with Cu gives A while acidification of C yields carboxylic acid D with molecular formula of CH,05. Identify the compounds A, B, C and D and write all chemical reactions involved. pelhi 2013 An organic compound (A) which has characteristic odour, on treatment with NaOH forms two compounds (B) and (C). Compound (B) has the molecular formula C)H,O which on oxidation with CrO, gives back compound (A). Compound (C) is the sodium salt of the acid. Compound (C) when heated with soda lime yields an aromatic hydrocarbon (D). Deduce the structures of (A),(B), (C) and (D). Write chemical equations for all reaction taking place, allindla 20vac, 20126 22 23. An organic compound (A) with molecular formula CyH,0 forms an orange red @ Chopterwise CBSE Solved Papers + CHEMISTRY precipitate with 2, 4-DNP reagent and gives yellow precipitate on heating with I, and NaOH. It neither reduce Tollens’ reagent nor Fehling’s reagent, nor does it decolourise bromine water or Bacyer's reagent. On drastic oxidation with chromic acid, it gives a carboxylic acid (B) having molecular formula C;H,O». Identify the compounds (A) and (B) and explain the reactions involved. Delhi 2012 24, An organic compound with molecular formula CyH;o0 does uot reduce Tollens’ reagent but forms an addition compound with sodium hydrogen sulphite and gives a positive iodoform test. On vigorous oxidation, it gives ethanoic acid and propanoic acid. Identify the compound and write all chemical equations for the reactions. all india 20120 25. A compound A(C;H,O) on oxidation by PCC gave B, which on treatment with aqueous alkali and subsequent heating furnished C. Bon oxidation by KMnO,, forms a monobasic carboxylic acid with molar mass 60 g mol~', Deduce the structures of A, B and C. all india zone 26. Describe how the following conversions can be brought about? (i) Cyclohexanol to cyclohexan-1-one. (i) Ethyl benzene to benzoic acid. (iii) Bromobenzene to benzoic acid. All india 2010; Delhi 2008 27. Complete the following reactions CHO cs (ii) (CgHgCH,),Ca + 2CH,COCL—> CH, ( BryRed Py (iii), CH, —CH—COOH FG Delhi 2019 28. Write chemical equations for the following reactions pelhi 2019CHAPTER 11: Aldehydes, Ketones and Carboxylic Acids 295 (i) Propanone is treated with dilute (ii) Give simple chemical tests to Ba(OH), distinguish between the following (ii) Acetophenone is treated with pairs of compounds : Zn(HgyCone. HCL (a) Ethanal and propanal (iii) Benzoyl chloride is hydrogenated in (b) Pentan-2-one and pentan-3-one presence of Pd/ BaSO,. ‘Li 32. (i) Write structure of the product(s) (5 Marks Questions formed : ee ed phoaphore a 29. (a) Carry out th: f lowing conversions OF ae eee (i) pnitrotoluene to 2-bromobenzoic acid (&) CgH,cOC]l "+, (ii) Propanoic acid to acetic acid Cone. KOH (b) An alkene with molecular formula _, ORHCHO CsHjo on ozonolysis gives a mixture of (ii) How will you bring the following two compounds, Band C. Compound conversions in not more than two Beives positive Febling test and also steps : reacts with iodine and NaOH (a) Propanone to propene solution. Compound C does not give Fehling solution test but forms iodoform. Identify the compounds (&) Benzyl chloride to phenyl ethanoic acid All india 2 ‘A, Band C. alindia 2018 33. (i) Write the product(s) in the following a reactions 30. (a) Carry out the following conversions : 0 (j) Benzoic acid to aniline ® oy +HCN—? (ii) Bromomethane to ethanol Coon (b) Write the structure of major © + NaOH 29 2 product(s) in the following : a (@DIBAL-# (a) H.N—NH,_ (c) CH; —CH = CH—CN ——~—? () CHy—CH,—C—H Fon, ayaa (© CH, HO 0 (i) Give simple chemical tests to cH, distinguish between the following I ca pairs of compounds : Gi) CHy—C—CHO (@) Butanal and butan-2-one CH. (b) Benzoic acid and phenol All india 2017 fcon 34. (i) Write the chemical equations for the reaction involved in Cannizzaro : on reaction, Gi ot, ‘linda 2018 Gi) Draw the structure of semicarbazone of ethanol. 31. (i) Give reasons : (iii) Why pK, of FK— CH, — COOH is (a) HCHO is more reactive than __ lower than that Cl —CH, —COOH ? CH, —CHO towards addition of HCN. (iv) Write the product in the following () pK, of O,N—CH,—COOH is lower oe ioe than that of CH; —COOH. CH, —CH = CH— CH,CN———5 Tio (¥) How can you distinguish between propanal and propanone? oaihi2016 (© Alpha hydrogen of aldehydes and ketones is acidic in nature.296 35. Write the structures of A, B,C, D and in the following reactions. CHACOCL - Zn-Hg/Cone. HCI CoHe Anhyd. AICI, oo Nal KMnO-KOIL A, 6 (ii) Hy" z DIE ote eth 2016 (i) Write the structures of A and Bin the following reactions: 140-011 (@) CHcocl 2FEB4 4 B (b) CHMgBr 92, 48, p «nor (ii) Distinguish between (a) C,Hs— COCH, and G,H,—CHO (b) CHy—COOH and HCOOH (iii) Arrange the following in increasing order of their boiling points. CH,CHO,CH,COOH, CH,CH,OH. Allindia 2016 37. (i) Write the chemical reaction involved in Wolff-Kishner reduction. (ii) Arrange the following in the increasing order of thir reactivity towards nucleophilic addition reaction. CyH,—COCH,, CH, —CHO, CH,COCH, (ii) Why carboxylic acid does not give reactions of carbonyl group? (iv) Write the product in the following reaction: (e-bay -Alt CHCH,CH = CH—CH,CN ———> Gio (v) Aand Bare two functional isomers of compound C,H,0. On heating with NaOH and I, isomer B forms yellow precipitate of iodoform whereas isomer A does not form any precipitate. Write the formula of A and B. allindia 2016 38. Write products in the following (i) (a) 2CH,CHO PMO © ~— cocHy tole HG @ Chopterwise caSE Solved Papers : CHEMISTRY (ii) Give simple teat to dintinguish the following pairs of compounds, (a) Ethanal and propanal (b) Benzaldehyde and acetophenone. (c) Benzoic acid and ethyl benzoate, Delhi 2o16¢ (i) Complete the following equations, @) CHO 39. () cH,coon Hs, re meiysr wo (ii) Distinguish between (a) CH,COOH and OH O (b) Cif, — CHO and CH, — ff —CH, AlLindla 20166 o 40. (i) What is meant by the following terms? Give example of the reaction in each case. (a) Aldol (b) Semicarbazone (ii) Complete the following: CH,COOH ccoos tate () CH, —CH = cH—cn 2 © CHO Cone, HNO + H,S0y, All india 20160 (i) Draw the structures of the followin (a) p-methylbenzaldehyde (b) 4-methylpent-3-en-2-one (ii) Give chemical tests to distinguish between the following pairs of compounds : a1. (a) Benzoie acid and ethyl benzoate (b) Benzaldehyde and acetophenone (© Phenol and benzoic acid All india 20150CHAPTER 11: Aldehydes, Ketones and Carboxylic Acids 297 42. (i) Describe the following by giving (a) Wolff-Kishnor reduction chemical equations: (b) Aldol condensation (©) Cannizzaro reaction All (a) Decarboxylation reaction (b) Friedel-Crafts reaction 46, (i) Write the products formed when Gi) How will you bring about the CH,CHO ronets with the following following conversions ? Toagenta : (a) Benzoic acid to benzaldehyde (a) HCN () HyN—OH (b) Benzene to m-nitroacetophenone (©) CH,CHO in the prosence of dilute (©) Ethanol to 3-hydroxybutanal lee F (i) Give simple chemical tests to Setht20%se distinguish betwoon the following 43. (i) Describe the following reactions. pairs of compounds: (a) Acetylation _(b) Aldol condensation (a) Benzoic acid and phenol () Propanal and propanone (ii) Write the main product in the AlLIndla 2014; beth! 20130 following equations : (a) CH, —C—CH, “ML, 2 47. (i) Account for the following : (a) CL— CHCOOH is a stronger acid oO than CH,COOH. CHO (b) Carboxylic acids do not give reactions of carbonyl group o HNO4I:S04 (ii) Write the chemical equations to a illustrate the following name reactions. (9 c,—coon—Z, 2 (@) Rosenumund reduction Delhi 20156 (b) Cannizzaro’s reaction 44. (i) Write the products of the following (ii) Out of CH,CH, — CO— CH, — CHy reactions: and CH,CH, — CH, — CO— CH,, which gives iodoform test? pelhi 2018 (@) (re +H,N—OH+S 48. (i) Account for the following : (a) CH,CHO is more reactive than (b) 2C,H,CHO+ cone. NaOH —> CH,COCH, towards reaction with HCN, aye (©) CH,COOH (6) There are two — NH, groups in (ii) Give simple chemical tests to semicarbazide (H;NNHCONH,). distinguish between the following However, only one is involved in the pairs of compounds: formation of semicarbazone. (a) Benzaldehyde and benzoic acid Gi) Write the chemical equation to (&) Propanal and propanone bamiguie illustrate each of the following name a reactions : 45. (i) Account for the following: (a) Rosenmund reduction (a) CH,CHOis more reactive than (b) Hell-Volhard-Zelinsky reaction CH,COCH; towards reaction with (© Cannizzaro reaction Forelgn 2014 HCN (b) Carboxylic acid is a stronger acid than phenol following compounds : (ii) Write the chemical equations to (a) CHyCO(CH,),CH, illustrate the following name (b) Ph— CH= CH— CHO. reactions: 49. (i) Write the IUPAC names of the298 @ Chapterwise case Solved Papers : CHEMISTRY Gi) Describe the following conversions in ( F—CH,—COOH not more than two steps : GOH (a) Ethanol to 3-hydroxybutanal or Cl_CH,— CF (©) Benzoic acid to m-nitrobenzyl alcohol On (©) Propanone to propene Delhi 2 50. (i) Draw the structures of the following Seen ) or CH,COOH pethi 2012 (a) 4-chloropentan-2-one i " Hl ie) uiaoeraiephseaae 54. 6) Give chemical tests to distinguish ween (ii) Give tests to distinguish between the following pairs of compounds : (a) Ethanal and propanal (®) Phenol and benzoic acid (©) Benzaldehyde and acetophenone (a) propanal and propanone () benzaldehyde and acetophenone Gi) How would you obtain (a) butanoic acid from butanol? (©) benzoic acid from ethyl benzene? all india 20r4¢ 51. () Draw the structures of the following Belt gont Foreign 201: All india 2008 compounds : 55. (i) Describe the following giving linked (a) 4-chloropentan-2-one chemical equations : () But-2-en-1-al (a) Cannizzaro reaction Gi) Write the producti) i ] the following : (b) Decarboxylation all india 2010; Delhi 2008 (ii) Complete the following chemical (@) CH, — COOH" ? equations : AIH, (b) CH, — CHO——*? CH,CH, Lact © ay OH ener? ° reign 2014 (a) 52. (i) How will you convert the following: (a) Propanone to propan-2-ol? (b) Ethanal to 2-hydroxypropanoic acid? w (©) Toluene to benzoic acid? COOH (ii) Give simple chemical tests to (© CgHsCONH, —2—> distinguish between Fast Delhi 2011, 2008; Foreign 201) (a) pentan-2-one and pentan-3-one Sethi 20m, 20 20m . rt 56. (i) Illustrate the following name reaction. 53. () Predict the products Cannigsare’s reaction (a) CH,COCH, > (Gi) How would you obtain Pa: BasO, (a) butanoie acid from butanol? (©) CH,COCI + Hy " (b) benzoic acid from ethyl benzene? COOH ‘all india 201; Delhi 2008, BryfPeBry 57. (i) Give chemical tests to distinguish between the followin, (a) Benzoie acid and ethyl benzoate (ii) Which acid of each pair shown here (b) Benzaldehyde and acetophenone would you expect to be stronger acid? (ii) Complete the following : ©CHAPTER 11: Aldehydes, Ketones and Carboxylic Acids COOH pm OC" COOH 6) catgcHto —HNCONEN ‘6 wOna One ‘AlLindio 207; Foreign 2010 58, (i) Identify A, Band C in the sequence COOH Or + NHj=2A “498 COOH RC (ii) Predict the products of the following reactions : Pa-BaS0, delhi zone 59. (i) Illustrate the following name reactions : Hell-Volhard-Zelinsky reaction (ii) How are the following conversions carried out? (a) Ethyl cyanide to ethanoie acid (b) Butan-1-ol to butanoic acid (©) Methyl benzene to benzoic acid all india 2010 60. Identify A to E in the following reaction : COOH conc. HNO3+ (NaBH, ‘cone. H80y (H30" ls Hy/Pa,Ba804 S0Ck_, py _HoPi +S or quinoline sock, Dethi 2010 299 61. An organic compound Aon treatment with ethyl alcohol gives a carboxylic acid Band compound C. Hydrolysis of C under acidified conditions gives Band D. Oxidation of D with KMnO, also gives B. B on heating with Ca(OH), gives E having molecular formula C,H,0.£ does not give Tollen’s test and does not reduce Fehling’s solution but forms a 2,4-dinitrophenylhydrazone. Identify ‘A,B,C, D and E, allindia 20100 @ Explanations Given, molecular formula = CH,0, which gives positive DNP and iodoform test and it neither reduces Tollen’s reagent nor decolourise bromine water which means it has one carbonyl ‘one —CH, group is directly Also, degree of unsaturation = (cH,— ‘Therefore, structure of (4) is o aoe 2k 2. CH, —CH,—CH —CHO j CH ‘2m! utara o 3. (i) Ethanal to propanone CHy—CHO H orcngtne CHa, | DEH a, So OH han GRO” oH O} ‘Oxidation CH,COCH, Propanone (4) (ii) Toluene to benzoic acid CH, COOH Kno, ‘Toluene Benzoie acid300 J. (i) Due to presence of strong —COOH group, aromatic carboxylic acids not undergo for Friedel-Crafts reaction. o (ii) Aswe know, more be the value of K,, more is the acidic strength of compound and PK, =~ logik,] ie. Therefore, pK, « More is the value of pk,, lower be the acidic nature of carboxylic acid and vice-versa. ‘The groups which shows (-) -effect, if present in benzoic acid are stronger acids than that show (+) Feffect or has no group. As, nitro-group (—NO,) show (-) L-effect, thus has lower pK, value than that of benzoic acid. o 5. (i) CH, —cH—cH,on EE sen, —cH—cHO Here, PCC is Pyridinium chlorochromate, a 1 : 2 complex of chromium trioxide pyridine (CrO,- 2C,H,N). It only oxidises — OH group and not the double bond, o (ii) Hy — Coon —M#2"_, cH, —cONH, 6. (i) The increasing order of their reactivity towards nucleophilic addition reaction is HCN. HAC, pe=0< "c= o0< | yc=0 HC HC W ‘On moving from ° ° cu cio = ett, cH, cyt, tc, +Leffect, ie. electron donating effect of alky! group increases which increases the electron density on C-atom of carbonyl group, and in C4H,COCH, phenyl group get resonance stabilised, makes it stable. Due to this reason itis. less reactive towards nucleophilic addition as the attack of nucleophile becomes lower. Further, steric effects of methyl and phenyl groups around carbonyl carbon atom makes the attack of nucleophile on carbonyl carbon difficult, o (ii) The correct increasing order of their acidic character is : 9° a oo CH,—C—OH < CH, — @ Chapterwise CBSE Solved Papers : CHEMISTRY F-being more electronegative clement produces sgreater-I-effect than Cl-atom due to which F-atom withdraw electrons from O—H bond and thereby making O—H bond weaker and hence, facilitates the release of H* ion from O—H bond, Hence, FCH COOH is stronger acid than CICH,COOH and CH,COOH. In CH COOH, due to +-effect of methyl group, electron density in O—H bond increases. As a result, release of H ions from acetic acid becomes more difficult. o ° oH Natit 7. (i) CHy—C — CH, “5 cH,—CH—cH, (y (Gi) Cs — CH, — CH, “M8O4= gH dls — COOK? pn 8. (i) Clis an electron withdrawing group, thus, increases the acidity of carboxylic acid by stabilising the conjugate base through delocalisation of the negative charge by inductive effect. While in acetic acid no such group is present which stabilises the conjugate base. That’s why, chloroacetic acid because of the presence of electron withdrawing group is more acidic than acetic acid (where no such group is present), o (ii) If the medium is too acidic, the ammonia derivatives being basic in nature will form their respective ammonium salts. Due to the absence of lone pair of electrons on the nitrogen atom, these ammonium. salts will no longer be nucleophilic and hence, the reaction will not occur. However, if the medium is slightly acidic, the protonation of the carbonyl group will not, ‘occur. This in turn will not increase the electron deficiency (or+ve charge) on the carbon atom of the carbonyl group and hence, weak nucleophiles like ammonia derivatives will not be able to react. Hence, the reaction will not occur. Therefore, to carry out such reactions, an optimum value of pH isneeded. Hence, pH should be controlled in such reactions, ao 9. | () lodoform test Given by CH{CO — © | or CH,CH(OH)— group containing compounds. {i Sodium bicarbonate test Given by COOH group containing compounds. 7 (i) Distinguishing test between ethanal and propanal Todoform test Ethanal because of the presence of CH,CO— skeleton gives positive iodoform test whereas propanal due to the absence of such a skeleton does not gives such test. oCHAPTER 11; Aldehydes, Ketones and Carboxylic Acids CH,CHO + 4NaOH +31, CHT, tania (Yetow ppt) tnt sre + HCOONa sottomtemate Sig * 2 whe CH,CH,CHO +4NaOH + 31, —> No reaction Propanal (ii) Distinguishing test between benzoic acid and phenol o Refer to solution 4 of Topic 2. 10. (i) Propanal and propanone ‘These compounds can be distinguished by using Tollen’s test. Propanal being an aldehyde reduces Tollen’s reagent to shining silver mirror and propanone being a ketone does not. CH,CHLHO+ 2[Ag(NH,),I" + 30H Propanal—Tollens reagent —CHCH £00" + 2AgL Propandate on Silver mirror + 4NH,+2H.0 CH,COCH, —™* No silver mirror Propanone’ += (ii) Benzaldehyde and benzoic acid Both can be distinguished by using sodium bicarbonate (NaHCO,) test. Benzoic acid being an acid reacts with NaHCO, solution {0 produce brisk effervescence due to evolution of CO, gas while benzaldehyde does not. C4H,COOH+ NaHCO, —> Benaoie acid o CHCOONa+C0, 1 +H, CJH{CHO. + NaHCO, —>+ No effervescence Benzaldehyde (due to evolution of CO; gas) : ‘COOH me) inn, Cone Hexane-1,6-di acid o + CH,CH,NH,—"> on —CH,—CH; cH 7 o (ii) ll ° 301 12, (i) Ethanol reacts with, / NaOH to give yellow ppt. of iodoform but propanol does not react with 1, /NaOH, con 21, cHcHo CHJCHO +31, + 4NaOH— HCOONa ane + CHI, L + 3Nal + 31,0 won 'eifom CHCH,CH OH 2+", No reaction Troaaol o (ii) Benzoic acid produces brisk effervescence with NaHCO, solution while ethyl benzoate docs not. C{i,COOH + NaHCO, —> Sec ot C4H,COONa+ H,0 + co, T C41LOOCH, + NaHCO, —> Noreaction ‘Edyiberte cH,cH, cookt coon -.O=-O-O 5 WK) on ° (in| a ns N—NH—CONH, a 3 om 14, (i) The possible functional isomers of carbonyl compound with molecular formula, C,H,0 are cH, (CH, —CH—CHO, CH,CH,CH,CHO, ° | cH,CH,—C—cH, (a) Isomers (4) and (C) gives positive Tollen's test, thus they must be aldehydes, RCHO + 2{Ag(NH,),I* 4 RCOO Aldehyde Tolle’ reagent + 2agl Siver mirror CH, —CH —CHO and CH,CH,CH,CHO +2804 4NH,T cH,302 (@Chopterwise CBSE Solved Papers : CHEMISTRY (b) Isomer (B) does not give Tollen’s test, but gives positive fodoform test, thus it must be a ketone with ° 1 CHC — group. RcocH, “4 RcOONa+ CHX, [Y=Cl, Br, 1] o (c) Isomers (A) and (B) on reduction with Zn(Hg) / conc. HCI give same product (D) cH, cH, ties el ol cH, —L—cHo + apy 2B", cH orc 0 Cay CH,—CH,—CH,—CHO + 4[H] CH) —CH,—CH, —CH, + HO. zy ro) CH CH,COCH, + 4H] ZENE HE, CH CHCH,CH, + 1,0 6 (0) So, the structures of (A), (B), (C) and (D) are : Zn-Hig/cone. HCI cH, CH,CHCH,CHO, CH,CHCOCH, CH,CH—CHO, CH,CH,CHCH, “4 ) 0 D) o (ii) The isomer (B) is least reactive towards addition of HCN. Since, aldehydes are more reactive towards nucleophilic addition reactions than ketones due to inductive and steric effects. a 15. 7 ° CH,—C—OCH, cHy—c_ocH, V (i) i a CCH, (CH=CH, + H,0 «Ci oS © OCH; on on «OQ + CH o a Maer coon coal cane ns Oo wscon o a o Ps ettest pals ref Mg Soil) eum re wo on cHcHo PHN, cH,—CH—CH,— CHO -8s CH,— CH =CH—CHO Wnyor tay 3) 0 Accaldehyde S-hydroxy butanal bu Penal a oeCHAPTER 11: Aldehydes, Ketones and Carboxylic Acids 17. (i) Benzolc acid to benzaldehyde Refer to solution 12 of topic 2. (ii) Ethyl benzene to benzoic acid cucu, cook coon weno ae, a ty benzene reussan benzote ens oc (iii) Propanone to propene ° cone: H,S04 (CH, —C—CH, + NaBH, —> CH,CHCH; "5 CH, =CHCH, Propanone 1 rope on Propan-2-01 HC nity, HC 1B GD HLCS at Nc N—NH, 4,0 HC” HC! Fropanone 2-propanone hydrazone ai) cH, COOK ay ye COOH a (MnO /KOH Cr cya el, a a ‘Toluene Potassium: ‘Benenkc acta Tense (iii) COOH ‘COOH ce OF “tryed, ae Bromma? venste sao sm-omobencole acid m9. (i) ae co (i) NHy— NH i jethylene glycol » CH; — ae De N — NH, ti KoWerhylene glycol Son, HC C Propane This is an example of Wolff-Kishner reduction. (ii) C4, —Co—CH, "2, c1,coGNat + CHT, L Yt This is an example of haloform reaction. (iil) CH,COOHa “ONES, CH, —H + Na,Co, Mahane This is an example of decarboxylation. 20, (i) Benzoic acid to benzaldehyde Refer to solution 12 of Topic 2. (ii) Ethyne to ethanal on ° Peers dot = cr, —temesain y oy, Ethyne’ AH 504 / E504 (Unstable) Ethanal 303 o o o o o o o o o o304 @Chopterwise CBSE Solved Papers : CHEMISTRY (ili) Acetic acid to methane CH,COOH —M24cH,COGNa MUG, CH, + NacOs ‘ceicacid “M20 Sad acetate a Methane o 21. Since, the molecular formula of D is CH,O,, thus, 2 is HCOOH (formic acid). D is obtained by the acidification of C, so, C is sodium formate (HCOONa). ‘Thus, A must be formaldehyde (as it undergoes Cannizzaro reaction with a strong base) and B must be methyl alcohol as on dehydrogenation with Cu, B gives back A. The reaction involved are as follows: aos ait 2HCHO CH,OH + HCOONa (ee ¢ Formaldehyde Methanol Sodin formate cutaeny. | aceieation arogenatin) HCHO HCOOH ormadehyde ——‘ermlc acl Zi > a Thus, A = Formaldehyde (HCHO) 2) B=Methanol(CH;OH) —_, (wa) C= Sodium formate (HCOONa) v2) D = Formic acid (HCOOH) 2) 22. Compound ‘4’ has characteristic odour that means it can be benzaldehyde, which undergo cannizzaro reaction with NaOH to give alcohol and sodium salt of acid. Compound ‘B’ can be alcohol as it contain only ‘one oxygen atom which on oxidation gives back compound ‘A’. Compound ‘C’ can be sodium salt of benzoic acid which on heating with sodalime yields aromatic compound ‘D’, which may be benzene. Reaction involved are given below Ss CgHisCHOMS C,11,CH,OH + CeHjCOONA J? Cele +NazCO3 (Ay (B) (cy Cc (D) By Sod sat of naen arma j GO @ 23. Organic compound (A) react with 2, 4-DNP reagent and forms, 2, 4-DNP derivative, therefore it is an aldehyde or a ketone. As A does not reduce Tollen’s or fehling reagent. So, it must be a ketone. It also give iodoform test. ° Hence, it has CHy—C—group. A form carboxylic acid B on oxidation. From molecular formula C;H,0, we can say that it should be benzoic acid. Compound A should, therefore, a monosubstituted aromatic methyl ketone. ° Non I NOs oy c No, “Non, H,0 2 +iNnN No, i (A) 2, 4-DNP reagent 2.4-DNP derivative. 9 l — on + cH} = coon {0} (B) Benzo acid @CHAPTER 11: Aldehydes, Ketones and Carboxylic Acids 305 24, Given organic compound CyHt0 does not reduce Tollen’s reagent, soit is not an aldehyde but the formation of addition compound with sodium hydrogen sulphite indicates itis a carbonyl compound. Its also given 0 that it gives positive fodoform test so it should contain —C—CH, group. So It must be a ketone. The possible structure may be ° I i cH, —C—CH,—CH.CH, CH, —C—cH—cn, 1 cuy Further given compound on oxidation gives ethanoic and propanoic acid and which is possible when the compound is | 01 CH, —¢—CHt CH, CH ——+ CH,COOH + cn cH,coom thanoe acid pane acid ° 25. Monobasic carboxylic acid = RCOOH, Given that, molar mass of RCOON = 60 gmol! ie. x 412416 +1641= 60; x=15 Thus, R = —CH, (molar mass 15) and the acid is CH COON. Since, the acid is obtained by the oxidation of aldehyde, so B is an aldehyde, i.e. CH,CHO and A is CH,CH,OH as it gives B on oxidation by PCC. Cis an alkene as itis formed by subsequent heating of aldehyde (B) with aqueous alkali. Thus, the involved reactions are as follows ° ° eH, —cH, — OH cH, —C — 1 2 cH, Con A = (sera wee ° ou sam") co 2H, —C— HOCH, — CH— CH, —¢ —H 5 cH, — cH ZH CH conden : @ 26. (i) OH 9 Site? o Cydobexanel Cyeohexan-1-0ne (i COOK coon 2Hs iasno, . “RoW “0 hear” 10 EthyTbenzene Potassium benzoate Benzo acid o (iii) Br cook COOH O = O Tie" 0 o Bromobenzene —Potassiumbenzoate Benzo acdo (ii) (CH,CH) Cd + 2H COC i — CHSCH,—C—CH, + CUCL, (ny cu, | (Bea Reary (ii) CH, —CH—CooH os —F—cooH Br o 28. |) Propanone is treated with dilute Ba(OH), Dit Blot, | 2CH,COCH;———— cH, — ¢ —cH,—co—cH, retin | oH eo —*> cHy—c=cH—C—cH, +H,0 4 methyl pent -3-en-2- one (Aldol condensation product) (ii) Acetophenone is treated with “meg HL & =. (ili) Benzoyl chloride when ee in presence of Pd/BaSO, coc ony © © Benaoyl Benaidehyde ehlode o This reaction is known as Rosenmund reduction. @ Chapterwise CBSE Solved Papers : CHEMISTRY 29. (a) (i) p-nitrotoluene to 2-bromobenzoic acid cH, be palrlvne Hy ee NaNO Ph OnyPOs ome cooH 2-bromobenzole acid om (ii) Propanolc acid to acetic acid Step (1) CH,CH, —COOH + NaOH —> CHjCH,COONa+ H,0 Step (II) CH, —CH, —COONa NaOH + 2, cH, + Naco, SP? cxscoon (Oxidation) (Acetic acid) om (b) Given alkene = C,H, which on ozonolysis gives (B) which gives positive Fehling test, means last carbon is bonded with double bond with next C-atom, Also, compound (B) reacts with iodine and NaOH, means it has —CH, group bonded with —CO-group. Thus structure of alkene is Hsc—¢ =¢—CH, Step (I) CH, cH H (CHL) ta | ozonolysis cif 0+ O— Fe cH, 4 . 8 (o) (Acetone) —_(Acetaldehyde) @CHAPTER 11: Aldehydes, Ketones and Carboxylic Acids. 30. (0) (i) Benzole act to aniline sre OO CON Ni a 7 () oO) (li) Bromoethane to ethanol KO (aq) CMs, Hiraimoeth jucture of major product () cH, —eny ws cil, ch, —cH, Propan nnn cu (iy CH, —¢ —cHo Sone NaOHt, | cu, A (city) COONS + 1,0 or " | 4n—c—n NC —C—O—Na + 1,0 Wen coott ooNa! 2 & 7 307 91. (i). (a) HCHO Is more reactive than CH y CHO, towards addition af HEN because 1 HCHO, we have no alkyl group, directly bhond to carbonyl ( yC—=0 J romp whieh olfers (+)F-effect and decreases the reactivity of carbonyl group, whereas. 1, CHO has one alkyl group (—CH) dircetly bonded with carbonyl group. (b) Strength of acidic nature of a.com measured by inductive effect (1) of the along with o Jom or group of atoms pre COON group. (-YF-ellect increases the Idic nature whereas, (+)/-elfect decreases the acidie nature, o Also, pk, = ~ loglkKy} ile, K, «acidic nature of a carboxylic act and pk, « 1 Le. Ky Higher be the pk, value of a carboxylic acid, lower Is [tS acidic strength and vice-versa, o (c) The carbon atom next to carbonyl group is o called a-carbon atom and hydrog attached 1 a-carbon atom are called achydrogens, Due {0 strong electron withdrawing effet of carbonyl group. the a-carbon atom becomes electron deficient, Which in tum, withdraws electrons from Cy —H bond, As a result, the electron density in C,—H bond decreases and , O-H atom becomes weakly held which can be easily abstracted by strong bases forming enolate ion which are stabilised by resonance. Thus, strong electron withdrawing effect of carbonyl group and resonance o stabilisation of the conjugate base are responsible for the acidity of a-hydrogen atoms of aldchydes and ketones. (ii) (a) Ethanal and propanal Ethanal gives iodoform test whereas propanal (CH,CH,CHO) does not. hen CHCHO + 3NaOl aot Tear + HCOONa + 2NaOH () (b) Pentan-2-one and pentan-3-one Pentan-2-one gives iodoform test whereas a pentan-3-one (CjH,COC.H,) does not