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Intramolecular Cannizzaro reaction:, It is given by dialdehydes having no, a-hydrogen atoms., Electrophilic substitution reactionns:, Aromatic aldehydes and ketones undergo, electrophilic substitution at the ring, in which the carbonyl group acts as a, deactivating and meta directing group., Distinction between aldehydes and, ketones:, , Reduction:, H/Ni or, , R, , P tor P d R I H O H, , C-0AlH, or NaBH,, R', C = 0 - n - H g / H C, , Clemmensen reduction, , CH,, , C=0 H/Bed P.123 K R', CH,, - NH-NH,/KOH, , CH, , Wolff-Kishner reduction R, , Tests with, |Schiff's, , |Aldehydes, , Ketones, , Pink colour, , No colour, , Fehling's, solution, Tollens, , precipitate, , Red, , |No precipitate, , hydrazine, , well defined, , well defined, , crystals with, , crystals with, , reagent, , Haloform reaction:, , 2NaOH+I, Nal+ NaOI + H,O, RCOCH +3NaOI, RCOONa+, CHIg, , +, , 2NaOHH, , lodoform (yellow ppt.), , (Given by compounds having, , CH,CO, , group or CH,CH(OH)-group)., , Silver mirror |No silver, reagent, mirror, Orange2,4, Orange, or, red, yellow or red, | dinitrophenyl-|yellow, melting points melting points, , Aldol condensation:, 2R- H-E-H, , characteristic characteristic, , of individual, , N0H, , |aldehydes. |ketones., , OH, , CARBOXYLIC ACIDS, , R-CH- H- H-, , General Formula : CH2,0, , Aldol, , a.p-Unsaturated aldehyde, , (aldehydes and ketones having at least, one a-hydrogen), Intramolecular aldol condensation :, It takes place in diketones and give rise too, , cyclic products., aldol, , condensation, , : Aldol, , condensation is carried out between two, , different aldehydes and/or ketones and if, both of them contain a-hydrogen atoms, it, gives a mixture of four products., Cannizzaro reaction:, , HCHO+HCHOCOncNCH,OH+ HCOOK, Formaldehyde, , having, , -COOH group., RCOOH where, R=H or alkyl or aryl., , R-CH-CH=, , Cross, , of individual, , Potassiumn, , Methanol, , tormate, , (aldehydes which do not have an, , a-hydrogen atom), Cross Cannizzaro reaction, , Structure : 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., , ö-H, , CH--H + H-C-Ha]OH, CsHCH,OH + HCOOÑa, Benzyl alcohol, , Nomenclature : The common names end, with the suffix -ic acid' and have been, derived from Latin or Greek names of their, natural sources., In the IUPAC system, aliphatic carboxylic, acids are named by replacing the ending, e, in the name of the corresponding, alkane with -oic acid'. In numbering the, carbon chain, the carboxylic carbon is, numbered one., , Sod. formate, , -C6-H, , Classification:They are classified as mono,, di, tri and polycarboxylic acids depending, upon the number of carboxyl groups present, in a molecule.
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0BJECTIVE TYPE QUESTIONS, , Multiple Choice Questions(MCQs), 1., , Ketones (R-Ë-R) can be obtained in one, , (Z) are, , step by (where R and R' are alkyl groups), (a) hydrolysis of esters, (b) oxidation of primary alcohols, (c) oxidation of secondary alcohols, (d) reaction of alkyl halides with alcohols., 2., , test. Compound (Z) does not give Fehling's test, but give iodoform test. Compounds (X), (Y) and, Y, , X, , Z, , (a) CsH,COCH, , CH,CHO, , CHcOCH, , (b) CH-CH=c-CH,, , CH,CHO, , CH,COCH, , CH, , Aldehydes other than formaldehyde react, , with Grignard's reagent to give addition products, which on hydrolysis give, (a) tertiary alcohols, (b) secondary alcohols, (c) primary alcohols, (d) carboxylic acids., , (c) CH,CH,CH=CH2, , CH,CHCHO HCHO, , (d) CH,-CH-CH--CH, CH,CHo, , CH,CHO, , 7., , A compound (X) with a molecular formula, CgH00 gives a positive 2,4-DNP test but a, negative Tollen's test. On oxidation it gives a, , 3. Which of the following compounds will, , carboxylic acid (Y) with a molecular formula, , undergo Cannizzaro reaction?, (a) CH,CHO, (b) CHCOCHg, (c) CgH,CHO, (d) CgH,CH,CHO, , CgH 02.Potassium salt of (Y) undergoes Kolbe's, , 4., , (a) pentan-3-one, propanoic acid, butane, , reaction and gives a hydrocarbon (Z). (X), (Y, and (Z) respectively are, , Propanal on treatment with dilute sodium, , (b) pentanal, pentanoic acid, octane, (c) 2-methylbutanone, butanoic acid, hexane, , hydroxide gives, (a), (b), (c), (d), , CH,CH,CH,CH,CH,CHO, CH,CH,CH(OH)CH,CH,CHO, CH,CH,CH(OH)CH(CH,)CHO, CH,CH,coOH, , ., , Various, , products formed, , on, , (d) 2, 2-dimethylpropanone, propanoic acid,, hexane, 8., oxidation of, , Incorrect?, , (a) FeClg is used in the detection of phenols., (b) Fehling solution is used in the detection of, , 2,5-dimethylhexan-3-one are, , (i) CH-CH-COOH, , glucose., (c) Tollens' reagent is used in the detection of, unsaturation., (d) NaHSOg is used in the detection of carbonyl, compounds., , CH, (i) CH-CH-CH-CoOH, , CH, (ii) CH,COOH, , 9. Which of the following compounds will, give a coloured crystalline compound with, , (iv) HCOOH, , NHNH,, , (a) (i) and (ii), , (b) (i), (ii) and (ii), (c) (i), (Gii), (ii) and (iv) (d) (ii) and (iv), 6., , Alkene (X), , Which of the following statements is, , (C5H1o), , on, , ozonolysis gives, , NO,, a, , ON, , mixture oftwo compounds (Y) and (Z). Compound, , (a) CH,COCI, , (, , (c) CHCOCH, , gives positive Fehling's test and iodoform, , (b) CH,CO0C,H,, (d) CH,CONH2
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10. Which of the, , following reagents, , are, , not, , (c), , correctly matched with the reaction?, (a) CH,CH=CHCHO CH,CH=CHCOOH, Ammonical AgNO,, , (b) CH,CH=CHCH0, (c) R-COOH, , CH,CH=CHCHOH, , R-CH,OH:NaBH,, , (d) CH,CH,COCI, , HPt, , Ha, Pa/BaSO, 11. In the following reaction, product (P) is, , (b) RCH, (d) RCH,OH, , following will, , not, , condensation?, (a) Phenyl acetaldehyde, , give aldol, , is the most reactive, , (a) CHCH,CH,CH,- -H, , (d) CH,-C-CH-CH, , 18. The correct order of increasing acidic, , 13. Which of the following statements is correct, regarding formic acid?, (a) It is a reducing agent., (b) It is a weaker acid than acetic acid., (c) It is an oxidising agent., , (d) When its calcium salt is heated, it forms, acetone., , (a), , following, , CH, , (d) 1-Phenylpropanone, , and acetone is, , 17. Which of the, , 2,4, 6-Trinitrobenzoic acid, , (c) CH,CH-C-CH,CH, , (b) 2-Methylpentanal, (c) Benzaldehyde, , 14. The condensation, , 0,NNO., , (b) CH,CH,CH,-C-CH,, , R--Cl Pd/BaSo2So,P, , 12. Which of the, , COOH, , (d), , isomer?, , CH,CH,CHO, , (a) RCHO, (c) RCOOH, , PhCH,CH2COOH: 3-Phenylpropanoic acid, NO, , product, , of, , benzaldehyde, , strength is, (a) Phenol < Ethanol < Chloroacetic acid <, Acetic acid, (b) Ethanol < Phenol < Chloroacetic acid <, Acetic acid, , (c) Ethanol < Phenol < Acetic acid < Chloroacetic, acid, , (d) Chloroacetic acid < Acetie acid < Phenol <, Ethanol, 19. To, , CH,CH=C(CH3),, , differentiate between pentan-2-one, , and, , pentan-3-one a test is carried out. Which of the, following is the correct answer?, (a) Pentan-2-one will give silver mirror test, , (b) CH,CH,-C-CH=CH2, , (b) Pentan-2-one will give iodoform test., (c) Pentan-3-one will give iodoform test, (d) None of these., , (c) CH- -CH=CH-CH,, , 20. What, , (d) CHs-CH=CH-C-CH3, , happens, , when, , a, , carboxylic acid is, , to give nucleophilic addition?, , treated with lithium aluminium, (a) Aldehyde is formed., (b) Primary alcohol is formed., , (a) FCH2CHO, , (b) CICH,CHO, , (c) BrCH,CHO, , (c) Ketone is formed., , (d) ICH,CHO, , 15. Which among the following is most reactive, , 16. Which of the following IUPAC, correctly matched?, , names, , CH, (a), , (b), , coOH:3-Cyclopentylpropanoic acid, (CH,),C=CHCOOH :3-Methylbut-2-enoic acid, , hydride?, , (d) Grignard reagent is formed., is not, , 21. Which of the, , following will, , not, , reaction?, , (a) Propanoic acid, , (b) Ethanoic acid, (c) 2-Methylpropanic acid, (d) 2,2-Dimethylpropanoic acid, , undergo HVZ
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(c) CHCH,CHO + CH,CHO, , (A) +CH,OH, , (d) 2CH,CH,CHO, , (C)+ HOH, , (B) + (C), , (B) + (D), , 55. Addition of water to alkynes occurs in acidic, , medium and in the presence of Hg* ions as a, catalyst. Which of the following products will be, , B), (B) +CalOH)2, , Caleium salt + H,0, , formed on addition of water to but-1-yne under, , dry distillation CH,coCH3, , these conditions?, (A), , (C), , (B), , (Acetone), (D), , (a) CH-CH-CH,-C-H, , (a) (CH,Co%0 CH,coOH CH,cooc,H,, (b) CH,CoCi HCOOH, CH,COOCH, , (b) CH-CH,- -CH, , (c) CH,coOH CH,OH, CH,COOCH, (d) CHaNH2, CH COOH CH,coOCHg, , (c) CH-CH-C-OH, , +, , CH,OH, , CH,OH, CH,OH, CaH,OH, , 61. Compound (X) with molecular formula, CgHO is treated with acidified potassium, dichromate to form a product (Y) with molecular, , CO2, , (d) CH-C-OH+H-C-H, , formula CgH,O. (Y) does not forma shining silver, , 56. An organic compound (X) with molecular, , mirror on warming with ammoniacal AgNO., , CgH100, formula, Tollen's tests., , gives positive 2,4-DNP and, , aqueous solution of, treated with, when, NH2CONHNH2. HCl and sodium acetate to give, , reaction and on, , vigorous oxidation it gives, , It undergoes Cannizzaro, , an, , a, , product (Z, , he structure of (Z) is, , 1,4-benzenedicarboxylic acid. Compound (X) is, , (a) CH,CH,CH= NNHCONH,, , (a) benzaldehyde, , (b) (CH,),C=NNHCONH,, , (b) o-methylbenzaldehyde, (c) p-ethylbenzaldehyde, (d) 2, 2-dimethylhexanal, , (c) (CH),C=NCONHNH,, , 57. R-CH=CH-CHO+NH--NHNH,, , (d) CH,CH,CH=NCONHNH,, , X, , X) in the above reaction is, , OH, (a) R-CH=CH-H-NH,CONHNH, , 62. Aldehydes and ketones are isomers as, they have same general formula but different, functional groups. Both these functional groups, can be distinguished by various tests., , A compound with molecular formula CgH10 has, two isomers P and Q which undergo ozonolysis, to give two functional isomers (R and S) with, , formula, CgH,0., , OJcH, R+ HCHO,, HCHO,, (i)Zn/H,07R+, s, HCHO, (i) +, Zn/H,0, , (b) R-CH=CH-CH==N-NH--NH,, (c)R-CH=NH,CONH,, (d) R-CH=CH-CH-NH,COCH=NHNH,, , Which of the given options can not be correct for, , OH, , 58. Which of the following will not yield acetic, acid on strong oxidation?, (a) Butanone, (b) Propanone, (c) Ethyl ethanoate, (d) Ethanol, , K and S?, I., , IfPis 4-vinyl toluene then R gives Cannizzaro, reaction but not haloform reaction., , II. If Qis 4-vinyl toluene then S gives haloform, , 59. Which of the following compounds does not, , reaction but not Cannizzaro., III. IfQis 2-phenylpropene then Sgives halotorm, , react with NaHSOg?, (a) HCHO, , (b) CHCOCH, , IV. If P is 2-phenylpropene then R gives both, , (c) CHCOCH, , (d) CH,CHO, , reaction but not Cannizzaro., , 60. Study the following reactions and mark the, appropriate choice., , Cannizzaro and haloform reaction., , (a) I and II only, (c) II and III only, , (b) I and III only, (d) II and IV only
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CHO, , COOH, , [O, , 56. (c), , J, (Gives haloform reaction,, COOH, , C,Hs, , M.F CgH,0), , 14-Benzenedicarboxylic acid, , 63., , (b), , N Derivative, , (B), , (A), , CsH1o0, 57., , (6):, , R-CH=CH-CHO+, , H,N-C-NHNH2, , Haloform t e s t, , H, , -ve, , R-CH=CH-CH=N-NH- --NH,, , 58. (c): CH,COOCH, will not give acetic acid on oxidation., 59. (b): Aromatic ketones are less reactive than aliphatic, ketones which in turn are less reactive than aldehyde. Hence,, , formed, , A g miror test, , -ve, , Ince (5) on reaction with 2,4-DNP forms a derivative, it, , implies that (8) has >c=0 group., , (B) gives-ve Tollens' test, hence it is not an aldehyde, but it, is a ketone., , acetophenone does not react with NaHS0, , (B) gives -ve haloform test, thus it is not a methy! ketone., , 60., , (8) is formed from the oxidation of (A), thus (A) is a 2°alcohol,, , (a):, , (CH,cO),o+C.H,OH, , CH,COOH +CH,COOC,Hs, (B), , (4), , CH,COOC H, + HOH, , (D), , (B), , CH,cOOH, , OH, , 2CH,COOH +Ca(OH)5, , and (B) is CH-CH2-C-CH-CH3, =0n-Hg/, >-CH,, HCI, , (B), , (D), , (A) is CHy-CH-CH-CH2-CH3, , CH,COOH +C,H,OH, , (C), , C.HOH, , (C), , and among the given options,, , aldehyde, , (CH,COo),Ca + H,0, , (B), , alkanes, , ketones, , dry distillation, , 64. (): Ortho-effect says that all the 0-substituted benzoic, acids are stronger acids than benzoic acid, so the correct order, , CH,COCH, (Acetone), , IS, , 61., , (b): CH--OH, , CH-C=0, CH, , H, , CH, (X), , COOH, , COOH, , COOH, , (ortho-effect, , (ortho-effect), , ÇOOH, , (, , NH,CONHNH,HCI, CH,COONa, , NO,, , pronounced due, , (R effect of to H-bonding in, , -NO, group) carboxylate, , (CH),C=NNHCONH,, (2, , ion), , Thus, Order ll given is incorrect as in this ortho-effect is not, considered., , 62. (d): H , c O ) 0 0 / C H , G ,, (i) Zn/H,O, (P), 4-Vinyltoluene, , CHO, , Order I and Il are correct., , 65. (c): Carboxylic acids do not undergo Friedel Craft's, reaction because carboxyl group is deactivating and gets, bonded to the catalyst in Friedel Craft's, , reaction, , CHO+H- -H, , (R), (Gives Cannizzaro reaction,, , 66. (a): A undergoes lodoform reaction hence contains a, methyl ketone. So the structure of A is, , M.E. = CgH0), , Ci O,/CH,Cl, CH, (Q), , (i) Zn/H,O, , CH-CH-C-CH3, (Butan-2-one), , A (butan-2-one) on reduction gives butan-2-ol (B).
