12 Aldehydes, Ketones and Carboxylic Topic | __ Aldehydes and Ketones Acids Previous Years’ Examination Questions 4 Mark Questions 7 1 Wie the structire of 3-méthyt butanal. [Delhi 2013] e Write. the > structure. of een rite the: structure © of » pamethylbenzaldehyde ‘molecule. (Delhi 2013] Srrange the téllowing compounds in the “increasing order of their boiling points. -- CH)—CHO, CH;—CH,—OH, ‘ < .Chy—CH,—CHy ye : [AD India 2013} ene the IUPAC name of the following. ee ° cH, cy cH Hoos a (Au India 2012] Give chemical test to-distinguish berween benzophenone and acetophenone. <0" [Delhi 20821 (B)aranse the following compounds. in an incteasing order “of their reactivity. in nucleophilic addition reaétions: ethanal, propanal, propanone, butdnone. (etki 2012) table example. Crosé‘aldol condensation “’ (Delhi 20125 (Delhi 2013} G)itusrace the (ollowing reaction giving Practice the Real questions @ Give’ simple teits to distinguish between the following. pair of. compounds pentan-2-one and pentan-3-one, at, (Wathi 2012} ALO Draw. the molecular structuré. ‘of. the compound 4+methylpent-3-en-2-one. < WRoreiga 2012} I-Braw the structure of Semethy ba Bical thi 20L11 ~. Draw the structure of scahGeponan: -2-one. [All tadia 2011, 2008) Write IUPAC name of |” OCOcH, © en ONS crs, etn z0itey u ‘rite the name of. : cl Hy GH, Oo. CH; vty “(Delhi 2011C: Foreign 2010] i Gite the i of oxo : (Foreign 2011, 20 fhi 2008] 16 Wie sevewure of th htoro-3:methylpentane. : oo TAM ro Draw’? the propan-1-one. structureAldehyde, Ketones and Carboxylic Acids write JUPAC naine of [Dethi Zo10c7 a fo" What is -Tollen’s: reagent? Write oie eae of this reagent. [All India 2020) rite IUPAC name of the following i Cl] CiycHzcaio Dabi2onc1 Write thé IUPAC name of the following. [Al India 2010C) @ a4 New, 22 Witte the structure’ of peri: Raina, a (Foreign 2009] Write, sinitural formula of 1-phenyl TAU India 2009) we Write the IUPAC ame of the following. (Deli 2008C1 cH 5 CH; —C—CH,COCH, OH : eC the TUPAC raine Of the following. {All India 20090] eee ct Ww fe UPAC name of, ct {All India 2009C7 is the IUPAC name of the following tompounde. So CHa He cH ° a ‘etn 2000) 28. Write IUPAC. name. of. the: following ‘compound, OO I 2 ° oan “. (Dethi 2008C}. (write the IUPAC name of the folewing compound. Che FH CO CHC 5 CH; CHS.” mpethé 20077 ~ Name the compotind according to IUPAC sytem CHyCOCH,COCH, >: FAH India 2007, 2008; Foreign 2007] < Complete the reaction . He Rol > a . “fall India 2006C) Write TUPAC nanie of! “CH, CHICH ICH CICHA),COCH, Foren 2 2008) % 2M Questions" “Give simple chemical tests to distinguish between the fallowing pairs of compounds: ot (Dethi 2013]. wy Ethanal and propanal LBénzoic ald and phenol 34, Give 4 plausiblé explariatidt for each one of the following. There” are two. NH," groups in semicarbazide: However only one such group is involved i thé formation of semicarbazones: ‘¢i) Cyclohexanone formscyé rins in. good. yield but rimethyl- cyclohexanone does not! iDethi 2012)Chapterwisé CBSE Solved Papers Chemistry, : ‘Niastrate’ the: following’ naine reactions oe suitable example in each case. \ Se Cmiensen reduction -. iaRell-Volhard-Zelinsky reaction tee - «, (Delhi 2012) Give cheinical tests to distinguish between the following pairs of compounds. [Delhi 2007] Wropatal and propancne (Delhi 2012] (i) Benaaldehyde and benzoic acid 3 ‘Marks Questions. 87. “Complete the following reactions. oH Sa Gomer KOH, pees oe = BryiP if CH,COOH > wal CHO. uNosPhSOe es oe ; “82 Delhi 20137 '98.° How will’ you bring. about the’ following conypaions? ori inane to propane... = Bey chloride to benzaldehyde. (fy) Ethanat to but-2-enat {Delhi 2613) om the structures of the main produ of following reactions: Asi PAICI; 00 -+Gu,coci HEME — ae gt H,80, ) HC—Ceac—H “nego, 5 oa : <2 (Doth 20121 Whe Geib the mechanism ofthe dltton of Grightrd reagent to the'carbony| group of a compound: to: form:an-adduct which on hydrolysis yield an alcohol. . 4) (i) An organic’ compound wit formula Hig" forms i Brow the © structuré.of. the. illowiig compedtnds. F-methylbutarial p-nitropropiophenone - (Foreign 2012] Aiffastrate the following reactions: giving: suitaple chemical equations fr each. ‘Cannizzaro reaction (By Fletl-Volhard-Zetinsky reaction’: roe would you, bring. “about © thé following.“ conversions? ”.. Write © the complete equations in each case. Ethanal to 3-hycroxybutanal Benzaldehycte to berzoplicnione (Foreign 2012] ® An organic ompound A contains 69. 77% carbon, 11.63% hydrogen and rest oxygen: The molecular mass of the compound is 86. -does not reduce: Tollen’s reagent but forms an addition compound with sodium’. hydrogen sulphite- and gives positive iodoform test. On vigorous oxidation, it gives’ ethahoic acid and propanoic’ acids. Derive the'structure of compound A: «FAW India 2009; Delhi 2008, 2009; Foreign 2008; 2008] nnizzaro reaction: Rosenmund reduction. Estetification réaction. _ FAIL India 2007; Delhi 2006CE 5 Marks Questions : 4ae-DHow ‘will you convert the following? " (aire ypanone to propan-2-o| (-Ethanat to 2hyalioxy | repanoie acid oS @-Toluene to benzoic aci : WiGive. Simple ch istinguish between. 20 res an-2-one and pientan:3-one. or eanal ‘ind propanal “Sets equation for derivative, reduces: Tollen’s: reagent and undergoes Carinizzaro’s reactioi On - vigorous: oxidation, «it gives. 1, 2-benzenedicarboxylic acid, Identify: thé compound.Aldehyde; Ketones and Carboxylic Acids (Q)-Give the: chemical tests. to: distinguish benyedh.. iosianol and propanone ibs Senzaldehyde and acetoghenoné () ‘Arratge the following compounds in an creasing order: of their property: a$ indicated : ‘Acetaldehivde,~ - “acetone, methyl - tem-butyl’ ketone. (reactivity towards [All India 2012) a : 46, (“An organic compound A (CyHsO) on treatment with copper at 573K gives B. B-does not reduce Fehling’s solution but gives a yellow ppt. of compound with l, /NaOH. Deduce the structures of A,B, andC, redict the products of the following reactions : (Melhi 2012C) fa) Overs + Orne . | Athy ib) Or Case, oO OH" 293K ATs (ij Identify ‘A, B and Cin: the: followitig 2 sequence of reactions + 6 CaCl | “QO, CH,CHO HBr: : “oS iReroxide “bir Peedcn the structures of “products formed when berizaldehyde is treated witl 8 . pri Reo Os FING} 7 H2504 (at 273K-383K) ‘A ketone A (CHg0) which undergoes a haloform: reaction’ gives’ compourid 8 on reducti Heating with sulphuric acid. “ives. a. “compatind - C. Which forms mono-ozonide’D. D on’ hydra zine dust gives only . identi and E, Write the reactions involved. s : (Dethi 20100} G)o How will you prepare the following compounds starting with benzene? (a) Benzaldehyde (b) Acetopienone (i, How.-will you. bring ® about the following conversions? {a} Propanone to propene. (b} Ethanol to 3-hydroxy butanal. (©) Bénzaldehyde to benzophenone. »» [Foreign 2010, 2009) @) An organic compound A on treatment with acetic acid: in the: presence of sulphuric acid- produces. anester-3.° A- on mild ‘oxidation gives C. C with 50%: KOH followed .by acidification with: dil., HCI generates A and D. D with PCI. followed by » Feaction. with. ammonia gives: £ £ on dehydration: produces, hydrocyanic acid. Identify the compounds A, 8, C, D and E. [Delhi 2009C} Identify A,B,C, D and € in the following ‘ sequence of reactions. - Ch NaOH: |. GHsCOcT As cHeh SS gc Hg /AICI SIAC oe {Delhi 20090} () Complete ‘the “following. reaction statements" by’ givirig™ the missing starting material, reagent or product as required : CH,CH, ) KMAO; . KOH, heat: Gi) Ocscribe the following reaction {a} Cannizzaro reaction: > (bY Cross aldol condensation {Delhi 2008]Chapterwise CBSE Solved Papers Chemistry i) How. would you. account for the following? (@) Aldehydes ate mote: reactive than ketones towards nucleophiles, (b). The boiling points of aldehydes and ketones are lower than that of the corresponding acids. {C). The aldehydes and ketones undergo a number of addition reactions. ii). Give.*chemical tests to distinguish between yb {a) acetaldehyde and benzaldehyde. {b) propanone and propanol. {Delhi 2008] 84. An organic “compound A (CsH,O} is resistant té oxidation but forms compound. 8 (CHO) on reduction. B reacts with HBr to form the compound C. € with Mg forms Grignard reagent D which reacts with A to. form a product which on hydrolysis gives €. Identify A to E. [AIL Indian 2008C] 5B. Identify’ A to E in the following ‘series of reactions, [AU India 20080} CatOH). stil ae 2 ¢ Dist = CaCO; inte ued E ai se Hy FH CH Br: Step-by-Step Solutions 3 | 4 Roe By yc f= CHa CHO, CHy” os 3-methy! butanat oO {Note al. represents. CHO group and. “but répresents chain of four C atoms.) g 2 CHy CH — Ca — — CH a a” CHO. 3. CHy p-mothylbenzaldehyde {p means 4th position." = w 4. CH; — CHy = CHy.< CHy —CHO < CH) CH) + OH cry cH, - oH 5 6. This is because in case of alcohol, the forces of attraction are strong H-bonding while in case of hydrocarbons, these are weak van der Waals’ forces. i CHy-~CHy—CH=CH—C—H po a sag Pont.2-e0-1-af a Benzophenone ©-. (CgHsCOCgH5) "and acetophenone.” (CgHsCOCH,).- can’ be = distinguished by fodoform test. . ‘Acetophenone, belhg’a’ methyl ketone “oA treatment with Ip/NaOH lindergoes iodoform reaction to give a yellow ppt. of iodoform. On « “the other hard, benzopherione does riot give this ‘test. CeHsCOCH, +3NaOl —> C,HsCOONa ‘Acetophenone + CHL + 2NaOH lodoform CeHsCOC gH; 2 No yellow ppt. of Benzophenone fodoform @)Aldehyde, Ketones and Carboxylic Acids 7. Butancne< propanone < propanal < ethanat o 8. Cross aldol condensation" When’ aldot condensation is carried out between two different aldehydes and/or ketones, itis cafled ¢r055 aldol. condensation. If both of them Contain c-hydrogen atoms, it gives a mixture of four products. (1/2) CH;CHO + CH,CH,CHO a ao HCHO + CH;CH,CH=C—CHO -enal I CH; | 2methyipent-2-enal +CH,—CH =F—cHO : CHy 2-rmethylbut-2-enal * + CH;CHy—CH=CHCHO Pent-2-enai : (v2 Pentan-2-one... and. pentan-3-one-. can be. distinguished by iodoform test. (1/2) Pentan-2-one’ is a rhethyl ketone: ‘Thus, it “responds: to this test. But pentan-3-one not being ‘a: methyl ketone doesnot respond to this test: ° if CHyCH,CH2— C—CH3+ 3NaOi + Pentan-2-one, CH,CH,CH,COONa + CHIL. +2NaQH iam bua locator Sodiurmbowscate (velow BDU e CH CH) — C—CH,CHy + NaOl 5 Pentae-done : No yellow ppt. of fodéform “ay ae 10. HjC—C—CH=C—Ch,. a aM i. CH eh CH,—CHO chy -methyibutanal 12. HEF CHE CH o ° ct A-chloropentane2-one 13. 3, 5-dimethylphenyl ethanoate, a 14. 4-methylpent-3-en-2-one. a) 18. HyC—H,C— Ga cHO o ° . 3-oxopentanal 16. cH CH— cH CH, — CH, {cl CH, a ° I 1 CCH cH; a 18. Atuoroacetophenone or” 1-4 -fluorophenyl) ethanone. @ 19. is “ammoniacal.:. silver." nitrate (AgNO; +NHOH) solution. It is used to test the presence of aldehyde group as itis. a mild. oxidising agent. a 20. 1-phenyl propan-t-one m 21, 2-chloro phenyl ethanone a 22, HyC—-H,C—HC = CH—CHO® Pent-2-ental a Op-pormoi-cnay, 0 a 24, 4 hydroxy—4-methylpentan-2-one- a 25, 2, 5-dimethylhexan-3-one. wo 26. Ethyl-4-chloro benzoate. ao 27. 4-chloropentan-2-one. a. 28, 4, #-dihydroxybenzophenone. w 2, A-dimethylpentan-3-one ay 30, Pentan-2, 4-dione, lenChapterwise CBSE Solved Papers Chemistry. Anhyd, AIC HCI SU. CyHy + RCOCE 82, 3,3,54 timethylhoxan 2-one. a 33. {) Distinguishing test between cthanal and propanal lodoform test ‘Ethanal’ because of the presence of CH,CO—skeleton gives iodoform test whereas propanal due to the absence of such a skeleton does not, (1) CH;CHO + ANIOH+31p—> cH Ethanal (Yellow ppt. Or todoform Acetaldehyde + HCOONa + 3Nal +3H,0 Sodium formate. Sodium: iodide’ CH;CH,CHO + 4NaOH + 31, —-»No reaction Prepanal © Gi) Distinguishing test between benzoic acid ..and phenol . sats Sodium bicarbonate (NaHCO ) test. 1), Benzoie acid when treated with NaHCO; gives effervescence due to the evolution of (CO gas, whereas..phenol: being weak acidic does not give this reaction. COOH ~ © COONa oO “snaico, —- (C) Oo Sodium Bengals brcrbonate Sedum “os, Benoate + H,O'+ CO;t Brisk effervescence: OH ENEHCO, —“* No ‘reaction Phenol 84. (i). Semicarbazide’ “undergoes. fesonance . involving only. one of the. two —NH2 groups which is attached directly to the carbonyl-carbon atom: o | RR NH o | HN ESN of Pay Therefore, the electron density on —NHy group involved in the resonance also decreases. As a result, it cannot act as a nucleophile. Since, the “other —NHy group is not involved in resonance; it can act a§ a nucleophile and can attack carbonyl carbon atoms of aldehydes and ketones to produce semicarbazones. (1). (i) Cyclohexananes form —cyanohydrins according to the following equation: c OH. CN O*O Cyclohexanorie ‘Cyanohydris, In this-case, the nucleophile CN” can easily attack without any steric hindrance. However, in aie of 2,2,6-Irimethylcyclohexanone, . °° methyt ‘grOups at a-positions offer steric hindrance and as a result, CN" cannot attack effectively. oO HyC CHy . CHy 2,2,6-trimethyteyciohexanone «wy Forthis reason, itdoes not form a cyanohydrin. 85, (i) Clemmensen reduction’ The carbonyl ‘group of aldehiydes and ketones is reduced to CH) group on treatment with zincamalgam - and concentrated hydrochloric acid, This is known as Clemmensen teduction. >c=o a Sch, +H,0 moAldehyde, Ketonés and Carboxylic Acids (ii), Hell-Volhard-Zelinsky (HVZ) reaction Carboxylic, acids. having’ an:‘a-hydrogen atom are halogenated at the a-position on treatment with chlorine or bromine in the * presence’ - of smatl” amount» of red phosphorus: to give achalacarboxylic acids.” The’ reaction’ is” known as Hetl-Volhard-Zelinsky reaction. (2 X,-Red phosphorus R—CH,—COOH tiH,o R=GHCCOOH x a-balocarboxylic acid (ech Bn a 86. (i) On: adding Tollen’s ceagent to each of them, propanal gives silver mircor whereas propanone will not react. a (ii) On adding NaHCO, solution, to each of tham, “berizaldehyde’ will not react whereas benzoic ‘acid will’ give brisk effervescence due to COs. . wm 9%. © MEH ACOTEKON 0. Formaldebyde H--C—OH + HCOOK I Potassiuns H formate. Methanal- Iris an example of Cannizzaro reaction.(1) BrP CH;COOH 3° CH) COOH Acetic see] acid S Br: i broioacetic acid It is, an example of Hell-Volhard-Zelinsky reaction. oS mM CHO CHO «i HNOyHSOs i 273-283K NO} Benzatdehyde mnitrobenizaldchyde 38._: (it Conversion of propanone to propane | (1) Clemmensen reduction CH, ~C—CHy fi Zale + HC! oO or Wolff-Kishner reduction Prapanone NH,—NH3 + KOH+ glycol CH; — CH — CHy Propane (ii Conversion of benzoyl’ chloride to benzaldehyde w ° 9 I il cc C+H Benzoyl chtdride Benzaldehyde (iii) Conversion of ethanal to but-2-enal. HCHO —DILNZOH_,* Ethanal - aldol condensation OH I CHy—CH —CH)—CHO 3-hydroxybutanal a [-n,9. CHy—CH=CH-—CHO' (1) But-2enal 39.40) C SCcH,coct Aiea Ah Sy COCSHs + HCl Benzophienare aM Gil HyC-C=C-H+H,0 =— OH Y oO ijn mcr Talomeriatin cry cry “Prop-l-en-2-ol sTAcetone 4) Aunstable) Le)Chapterwise CBSE Solved Papers Chemistry » CHOCChOH)] Gai) S21Ch, NOz NO2 CHO H,0" NOz Parasiobenzaldehyde o 40. {i) Alcohols are produced by the’ addition reaction of Grignard reagents with the carbonyl group of aldehydes and ketones. Mechanism |. Step 1 The first step of the reaction is the nucleophilic addition of Grignard reagent to the carbonyl group to form an adduct DeQo-' * Oo Revie ~ Pres “ | adduct 7 (8) Step 1. Hyolysis ofthe adduct yields an alcohol. Pro be H oth DE-OH asisionnx R a Gi) (@)_3-methylbutanal . ‘ii oO i HyC—CH—CH,—C-H° (0) p-nitropropiophenone t wk tern : iz) (2 41, f(a) Cannizzaro reactionAldehydes which do not have an echydrogen atom, undergo self oxidation. and reduction (dispropartionation) reaction on treatment with concentrated alkali. This reaction is known as Cannizzare reaction. In this reaction, one molecule of the aldehyde is reduced to alcohol while another i oxidised to salt of carboxylic acid, e.g., K 2 Scmo + Coné. KOH, Ah” Formaldehyde i — HO i om a Potassium fone ay ay Methanol, (b) -Refer ans. 35 (i). Gi) (@) Ethanal (o 3-hydroxybutanal Oil, NaOH, => ‘(sldot condensation} a Rey CH) FH CH CHO (3) OH, 3-hydroxybutanal (b) Benzaldehyde to benzophenone CHO | COOH “twos o “aie =o coc Cr hp ee 25° _ 2CH;—CHO Ethanal acylation! () Find ‘the “empirical” formula of the 2 compound and then derive molecular formula (i) Carbonyk compounds react with NaHSO,. (ii) Aldehydes give positive Tollen’s test and meth! Ketone gives iodoform test. C=69.77%; H=11.63% © =100~ (69,77 + 11.63) = 18.6%Aldehyde; Ketones and Carboxylic Acids. c 77, | j 58 5 & ne | j 163 10 ° v6 | coup ft Empirical formula wher compound =H (1) Empirical formula mass =5x12 41014 1x 16 286 é 86 1.Motecular forniuta = (C3H,q0), . = CsHg0> wo Since, it does not give Tollen’s test but gives Positive iodoform test, it isa methyl ketone ie., fave =COCH; group. Since, on oxidation it gives ethanoic acid and propanoic acid, it is pentan-2-one. ~, 10) CHE —cHicHech ° Ales Propanone CHyCOOH + CH,CH,COOH A= pentan-2-one a )) Caninizzaro’s reaction Refer ans. 4¥(ita). — a (i) Rosenmund’s reduction Pal, BaS05, chy —C—cl+ I+ Hy ——— cli CHO i Ethanal 3° Ehanoyl chloride. : + HCl a) (iii) Esterification reaction RCOOH +ROH == RCOOR +H,0 Acid Alcohol’ Ester, [e3) 44, (i) (a} Propanone to propan-2-ol 0 9 . OH ll LAlHs CHy—C-—CHy 5 CHj— CHCH, Propanene Reduction Propana2~ol (6) Ethanal to 2-hydroxy propanoic acid BOK Hse in HZ NAN " enyds eyanohyrin 2H, + Hel it an wn ra ~~ COOH z -hydroxy propancie acid’ (1) (©) Toluene to benzoic acid C= O+HCN > CHy OOH KC} H2S0s (oxidation) Toluene Benzoic acid ~ aw 4ii) (a). Pentan-2-one’ and pentan-3-one pentan-2-one résporids positively towards jodoform test whereas -" pentan-3-one (CH;COCH;) due to the absence of this Broup dees Rot. chy bo diy Guy Gey Pentan-2-one + 3Na0l CH + + coychicri,codNa +2NaOH Yellow pat : @ (b} Refer ans 33¢i) a 4) (@) Carbonyl compounds react with 6. 2.4.DNP- {0) Aldehydes (CHO grotip’ containing compaunds) reduce Tollen's reagent. {@) Aldehydes having. lack of aH atom undergo Cannizzaro's reaction. (d} Oxidation at successive places shows: the presence of two groups at 1, Places. Gi) (a) Jodoform test (0) Tollen's reagent, iodatorm fest (ii) Reactivity decreases as. the: number of electron donating groups increases. NaOH, 12