contents - arride learning compounds.pdf · 2oh to form aldoximes and ketoximes respectively....

Topic Page No.

Exercise - 1 01 - 13




Answer Key 30 - 33

Contents

CARBONYL COMPOUNDS

Name : ____________________________ Contact No. __________________

A-479 Indra vihar, kotaPh. - 9982433693 (NV Sir) 9462729791(VKP Sir)

Physical & Inorganic By

NV SirB.Tech. IIT Delhi

Organic Chemistry By

VKP SirM.Sc. IT-BHU

Carbonyl Compound_Advanced # 1

PART - I : OBJECTIVE QUESTIONS

* Marked Questions are having more than one correct option.

Section (A) : Nucleophilic addition reactionsA-1. C6H5COOH + CH3MgI ?

(A) C6H5COOMgI (B) CH4 (C) Both A & B (D) none

A-2. + Mg ether

(A) (B) (C) Both (D) None of these

A-3. ?

The product is :

(A) (B) (C) (D) All of these

A-4. The reaction, BrCH2CH2CH2Br + Mg OEt2

produces mainly.(A) CH3CH2CH3 (B) BrMgCH2CH2CH2MgBr

(C) (D) CH3CH = CH2





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A-5.* Point out the incorrect Grignard reaction.

(A)

(B)

(C)

(D)

A-6. Arrange the following compounds in decreasing orders of rate of exchange of O18 with H2O18

(X) CCl3CHO (Y) CH3CHO (Z) CH3COCH3 (W) CF3CHO

(A) W > Z > X > Y (B) W > X > Y > Z (C) W > Y > Z > X (D) W > Z > Y > X

A-7. Which of the following compound has the largest equilibrium constant for the addition of water ?

(A) (B)

(C) (D)

A-8. Acetaldehyde on reaction with sodium hydrogen sulphite produces

(A) (B)

(C) (D)





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A-9. Write the product of following reaction :

22 NHNH

(A) (B) (C) (D)

A-10. Aromatic carbonyl compounds having molecular formula C8H8O react with NH2OH how many oximes can beformed :(A) 8 (B) 10 (C) 12 (D) 6

A-11. The correct order of reactivity of PhMgBr with following compounds will be.(C6H5)2CO, CH3 – CH = O , (CH3)2 C = O (1) (2) (3)

(A) 1 > 2 > 3 (B) 2 > 3 > 1 (C) 3 > 2 > 1 (D) 1 > 3 > 2

A-12. Cyanohydrin formation constant will be highest for ?

(A) O N2 CHO (B) CH – O3 CHO

(C)

CH3

CHONCH3

(D) COCH3

A-13. The cyanohydrin of a carbonyl compound on hydrolysis gives lactic acid. The carbonyl compound is(A) HCHO (B) CH3CHO (C) CH3COCH3 (D) CH3COCH2CH3

A-14. For the given reaction + Mg etherdry A

OH)ii(

CHOCH)i(

3

3 B.

product B is :

(A) (B)

(C) (D)





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A-15.

O||

HCCHCHPh MgBrCHCH)i( 23

OH)ii( 3 (X) ,Cu (Y)

(A) X is 1, 4-addition product ; Y is

O||

CHCHCHCHCPh 32

(B) X is 1, 2-addition product ; Y is

O||

CHCHCCHCHPh 32

(C) X is 1, 4-addition product ; Y is

O||

CHCHCCHCHPh 32

(D) X is 1, 2-addition product ; Y is

O||

CHCHCHCHCPh 32

A-16. Consider the following sequence of reactions :

+ H2NOH Heat A A Heat

SOH 42 B.

The products (A) and (B) are, respectively :

(A) and (B) and

(C) and (D) and

A-17. + Product

(A) (B)

(C) (D)

A-18.* Which of the following correctly indicate(s) the rate.

(A) CH CH3–

–

CN

OH )fastvery(CHOCH3 KCN + HCl –

–

OH

CNMe – – CHMe – – CHMe – – CHMe – – CHMe – – CHMe – – CHMe – – CHMe – – CHMe – – CHMe – – CHMe – – CHMe – – CHMe – – CHMe – – CH

(B) (hydrate))fast(

OCHCH3 H2O/H+ hydrate

(C) Cyanohydrinslow

OH/HCN

C2H5CHOfastMgBrCH3 Adduct formation

(D) All of these





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A-19.* In the given reaction which one of the following statement is/are correct –

(A) Oxime may be E/Z.(B) Amide on hydrolysis gives a mixture acetic acid, benzoic acid, Aniline and methylamine.(C) Preparation of oxime is nucleophilic addition followed by elimination reaction.(D) Oxime and amides are isomers.

A-20.* A compound (A) C5H10O forms a phenyl hydrozone and gives negative tollen's and positive iodoform testcompound can be :

(A) (B)

(C) (D)

A-21. X Y

In the above reaction sequence X & Y are :(A) Identical (B) Homologs (C) Structural isomers (D) Stereoisomer

A-22. A, A is : A A gS :

(A) (B) (C) (D)

A-23. + x + y the organic products x and y are

(A) Enantiomers (B) Diastereomers (C) Metamers (D) achiral molecules

A-24. The product P of the following reaction is

CH3 – COOH P

(A) CH3 – COOH (B) (C) (D)





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A-25. Q.

In the above reaction Q is.

(A) (B) (C) (D)

Section (B) : Name Reaction (Presence of -Hydrogen)

B-1. In which of the following compounds the methylene hydrogens are the most acidic ?(A) CH3COCH2CH3 (B) CH3CH2COOC2H5(C) CH3CH2CH(COOC2H5)2 (D) CH3COCH2CN.

B-2. Which of the following will not undergo aldol condensation ?(A) CH3CHO (B) CH3CH2CHO (C) CD3CHO (D) PhCHO

B-3. (X) is the product of cross aldol condensation between benzaldehyde (C6H5CHO) and acetone What is itsstructure ?

(A) (B) C6H5–CH=C–(CH3)2

(C) C6H5–CO–CH2–C=(CH3)2 (D) None of these

B-4.* The compounds that undergo Aldol condensation is :

(A) (B) (C) (D)

B-5. In the given reaction sequence B is

(A) (B)

(A) (B) (C) (D)

B-6. (A) (B)

The reactant (A) will be :

(A) (B) (C) (D)





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B-7.

3

23

3

CH|CCHOCCHCH|||CHO

O2H,KOH Product (C7H10O) :

(A) (B) (C) (D)

B-8. (X) Identify.

(A) (B) (C) (D)

B-9.

O

+

CHO

/HO Product is :

(A) (B) Ph – CH

O

(C) Ph – CH

OH

(D)

COOH

+

OH

B-10. PhCHO + (CH3CO)2O ,hydrolysis)2(

COONaCH)1( 3 A HBr B

The product B is :(A) PhCH = CHCH2Br (B)

(C) PhCH2 CH(Br) COOH (D) PhCH = CH – COBr

B-11.* Which of the following gives haloform reaction

(A) (B) (C) (D)

B-12.* In which of the following reaction deuterium exchange is not observed ?

(A) (B) (C) (D)





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B-13. OH)ii(

Br/P)i(

2

2 X, X is :

(A) (B) (C) (D)

B-14. In the given reaction

CH3COOH [X], [X] will be

(A) CH3–COOH (B) HOOC–CH2–CH2–COOH

(C) (D)

Section (C) : Name Reaction (without -hydrogen)C-1. Cannizzaro reaction does not take place with

(A) (CH3)3CCHO. (B) (C) (D) CH3CHO.

C-2. In the reaction, (CH3)3CCHO + HCHO heatNaOH A + B.

the products (A) and (B) are respectively :(A) (CH3)3CCH2OH and HCOO– Na+. (B) (CH3)3CCOONa and CH3OH.(C) (CH3)3CCH2OH and CH3OH. (D) (CH3)3COONa and HCOO– Na+.

C-3. + HCHO KOH

(A) + (B)

(A) (B) + CH3OH

(C) (D) Both (A) and (B)





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C-4. In the cannizzaro's reaction the intermediate that will be the best hydride donar ?

(A) (B)

(C) (D)

C-5. Product of following reaction is

+ conc. NaOH heat ?

(A) (B) (C) (D)

C-6. In the given reaction Product is

(A) (B)

(C) (D)

C-7. The suitable reagent for the following reaction is :

(A) LiAlH4 (B) Na / C2H5OH (C) H2 / Ni (D) CH2 = O /





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C-8. Which of the following can be the product/s of following reaction.

NaOH.Conc

(A) I, II, IV (B) III, IV (C) II, V (D) I, V

C-9. What will be the product of the following reaction

HRCO3 ?

(A) (B) Ph

O||

C —CH (C) PhCH(Me)OCOOMe (D) None of these

C-10. 2-Methyhlcyclohexanone is allowed to react with metachloroperbenzoic acid. The major product in the reactionis :

(A) (B) (C) (D)

C-11.

Above conversion can be achieved by(A) NH2–NH2/ NaOH (B) Zn–Hg/HCl(C) LiAlH4 (D) NaBH4.(A) NH2–NH2/ NaOH (B) Zn–Hg/HCl(C) LiAlH4 (D) NaBH4.





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PART - II : MISLLANEOUS QUESTIONSCOMPREHENSIONComprehension #

Aldehydes and Ketones reacts with NH2OH to form Aldoximes and Ketoximes respectively. Configuration ofthese can be determined by Beckmann rearrangement as that group migrates which is anti w.r.t –OH.

R'

RC N

OH

..

R'

RC N

OH2

..

)(II RNC'R

)(OH2

III

OH|

RNC'R

O||

RNHC'R

1. [X] 42SOH OH2 Ph – NH2 +

Identify the configuration of [X] compound :

(A) (B) . (C) (D)

2. Which step is Rate determening step ?(A) I (B) II (C) III (D) IV

3. OHNH2 (A) hydrolysis)2(

SOH)1( 42 (B). The product (B) is :

(A) (B) (C) (D)

MATCH THE COLUMN4. Match Column- I & Column- II.

Column- I Column- II(A) RMgI + Acetonitrile ( NCCH3 ) (p) Alkanone

(B) RMgI + Carbon disulphide (q) Ester

(C) RMgI.(1eq) + Ethyl chloroformate (r) 1° Alcohol

(D) RMgI + Oxirane (s) Dithionic acid

5. Match the column

Column I Column II

(A) MeCO(CH2)4COMe

/H)ii(

OH)i( (p)

(B) (CH2)4

OEt (q)

(C) PhCHO + –

3COOCH (r)

OH|

COO—C)Ph( –2

(D) PhCOCOPh OH (s)





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6. Column-I Column-II

(A) (p) 1, 4-addition

(B) (q) Tautomerism

(C) CH3–CH=CH–CH = CH2 (r) AgNO3 / NH4OH

(D) (s) 2, 4 DNP test

ASSERTION / REASONINGDIRECTIONS :

Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.(C) Statement-1 is True, Statement-2 is False.(D) Statement-1 is False, Statement-2 is True.(E) Statement-1 and Statement-2 both are False.

7. Statement-1 : Aldehyde and ketone undergo nucleophilic addition reaction with carbon nucleophile andunderog nucleophilic addition-elimination reaction with nitrogen Nucleophile.Statement-2 : Addition of nucleophile on aldehyde and ketone form tetrahedral intermediate, in case oftetrahedral intermediate of nitrogen nucleophile non bonding electrons are present on nitrogen which causewater molecule to eliminate while in case of carbon and hydrogen nucleophile non bonding electron are notpresent.

8. Statement-1 :

Compound II is more reactive towards nucleophilic addition reaction.Statement-2 : Cyclic ketones are more reactive than acyclic ketone due to less steric hinderance andcompact structure of cyclic ketone.

9. Statement-1 : NaHSO3 is used in seperation and purification of aldehydes.Statements-2 : NaHSO3 is reducing agent.

10. Statement -1 : Dehydration of aldol takes place by the following mechanism.

Statement -2 : It is due to acidity of – H and stability of conjugated double bond

11. Statement-1 : (cinnamaldehyde) fails to undergo aldol condensation

Statement 2: This is due to the fact that cinnamaldehyde does not have acidic – H





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TRUE I FALSE12. Acid or Base catalysed halogenations of Acetaldehyde follows the reactivity order as Cl2 = Br2 = I2

13. Conc. KOH changes Ph–C–C–Ph

O O

to Ph–C–COO

Ph

OH

14. (CH3)2CuLi changes to

FILL IN THE BLANKS15. Fehling solution (A) consists of aquous solution of copper sulphate, while Fehling’s solution ‘B’ consists of

an alkaline solution ............

PART - I : MIXED OBJECTIVE

Single Correct Answer Type1. The reaction CH3 CH = CH—C—CH3 + CH3 MgX

O

H2O yields :

(A)

CH3

OH

CH3 CH = CH—C—CH3 (B)

CH3

CH3 CH2 CH2—C—CH3

OH

(C)

CH3

CH3CH CH = CH2 (D)

CH3

CH3CH CH2 CHO

2. What will be the products in the reaction given below?

CH3COO C2H5 + CH3COCH3 NaOC2H5

H2O

(A)

OCH3

CH3—C = CH—C—OC2H5 (B)

O

CH3—C—CH2—C—CH3

O

(C)

O

CH3—C = CH—C—CH3

CH3

(D)

O

CH3—C—CH2 COO C2 H5





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3. O1. NaOH

2. (X)

(X) is %

(A)

O

(B)

O(C) (D)

4. m-chloro benzaldehyde on reaction with concentrated KOH at room temperature gives(A) potassium m-chlorobenzoate and m-hydroxybenzaldehyde(B) m-hydroxybenzaldehyde and m-chlorobenzyl alcohol(C) m-chlorobenzyl alcohol and m-hydroxybenzyl alcohol(D) potassium m-chlorobenzoate and m-chlorobenzyl alcohol

5. Which of the following will not show aldol condensation?(A) acetaldehyde (B) propanaldehyde (C) benzaldehyde (D) trideuteroacetaldehyde

6. The reagent with which both acetaldehyde and acetone react easily is :(A) Fehling’s reagent (B) Grignard reagent (C) Schiff’s reagent (D) Tollen’s reagent

7. In the Cannizaro reaction given below

2Ph CHO OH– PhCH2OH + PhCOO– , the slowest step is

(A) the attack of OH– at the carbonyl group(B) the transfer of hydride to the carbonyl group(C) the abstraction of proton from the carboxylic acid(D) the deprotonation of PhCH2OH

8. What is the decreasing order of nucleophilic addition in following compounds?CH3 CHO (I), CH3COCH3(II), HCHO(III), C2H5 COCH3 (IV)

(A) (III) > (I) > (II) > (IV) (B) (IV) > (II) > (I) > (III)(C) (I) > (II) > (III) > (IV) (D) (II) > (IV) > (I) > (III)

9. C6H6 + CO + HCl Anhyd. AlCl3 [X] + HClCompound [X], the major product, is :(A) C6H5 CH3 (B) C6H5CH2Cl (C) C6H5CHO (D) C6H5COOH

10. (CH3)2C = CHCOCH3 can be oxidised to (CH3)2C = CHCOOH by(A) chromic acid (B) NaOI (C) Cu at 300°C (D) KMnO4

11. Acetaldehyde reacts with phosphorus pentachloride to produce :(A) ethylene chloride (B) ethylidene chloride(C) ethyl chloride (D) trichloroacetaldehyde

12. 2, 3-dimethyl butane-2, 3-diol (pinacol) on treatment with hot dilute H2SO4 yields(A) 3,3-dimethyl butan-2-one (B) 2,3-dimethyl butanal(C) 3-methyl pentan-2-one (D) none of these

13. Ketones can be oxidised to esters by(A) acidic KMnO4 (B) iodoform reaction(C) Baeyer-Villiger oxidation (D) none of the above

14. A compound [A] has the molecular formula C2Cl3OH. It reduces Fehling’s solution and on oxidation gives amonocarboxylic acid [B]. [A] is obtained by the action of Cl2 on ethyl alcohol. [A] is :(A) chloral (B) chloroform (C) chloromethane (D) chloroacetic acid





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More than one choice type15. Which of the following can be used to distinguish between an aldehyde and a ketone?

(A) KMnO4 (acidic) (B) Fehling’s solution(C) Tollen’s reagent (D) 2, 4 - dinitro phenyl hydrazine

16. Which of the following reaction(s) proceed via carbanion intermediate?(A) Cannizzaro reaction (B) Aldol condensation(C) Claisen reaction (D) Perkin reaction

17. Aldols formed by condensation of two molecules of the same or different carbonyl compounds(A) have a carbonyl as well as an alcoholic group(B) are hydroxy carbonyl compounds(C) are unsaturated aldehydes or ketones(D) have an aldehyde and a ketone group

PART - II : SUBJECTIVE QUESTIONS

1. Give the reaction of C2H5MgBr with 2-butanone followed by acid hydrolysis.

2. Bring about the following conversions(i) Acetone to 2-Methylpropane -2-ol.(ii) Ethyl magnesium chloride Propane-1-ol.

3. Predict the product of the following reactions

(a) Methylmagnesium iodide + D2O ?

(b) Isobutylmagnesium iodide + Phenylacetylene ?

4. Draw the organic products you would expect to isolate from the following reactions (after hydrolysis)

(a) + ?

(b) + ?

5. Arrange the following compounds in decreasing order of rate of nucleophilic addition with RMgBr.(I) Ph–CO–CH3 (II) Ph–CHO (III) CH3CHO (IV) CCl3CHO

6. Arrange the following compounds in decreasing orders of rate of addition of HCN.

(a) (b)

(c) (d) CH3CHO

7. Arrange the following compounds in decreasing orders of Keq for hydrate formation.

(a) (b) (c) (d)





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8. Cyclohexanone forms cyanohydrin in good yield but 2,2,6-trimethylcyclohexanone does not. Explain why ?

9. Write the product of following reaction :

(a)

HPhC

O + NaHSO3 (b) C = N

CH3

OHC H2 5

42SOH

(c) + H

10. Write the product of the following reaction

(a) + HO – NH2 H

(b) + NH2 – NH2 H

(c) Ph – CH2 – CH2 – CHO +

(d) + Ph – NH – NH2

11. Show how would you accomplish the following synthesis

(a)

(b)

O||

CH–C–CH–CH–Br 322

O||

CH–C–CH–CH–CHC 322

(c) CH - Br2

O

CH - Ph2

O

12. Predict the product of following aldol condensation reaction :

(a) CH3–CH2–CHO /OH

(b) Ph–CH2–CHO /OH

(c) Ph–CO–CH3 /OH





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13. Predict the products of following cross condensation reaction,

(a)

OCH|||

HC—C—CH|CH

3

3

3

+

O||

H–C–CH3 /OH

(b)

O||

HC–Ph +

O||

H–C–CH–CH 23 /OH

(c)

O||

HC–Ph +

O||

CH–C 3 /OH

14. What is the principal product of the follwoing reaction ?

15. Show which esters would undergo claisen condensation to give the following –ketoester.

(a)

(b)

(c)

16. Predict the product from claisen condensation of the following pair of esters.

(a) + EtO

(b) + EtO

(c) +

/O2H.2

EtO.1

17. Write the components which on crossed claisen condensation could be used to prepare the following esters.

(a) (b) (c)





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18. + CH2 = CH –

O||C – Ph

EtO Product (P) is :

19. Write the product of following reaction,

(a) CH3–CH2–OH KOH/I2 (b) Ph–CH2–CO–CH3 KOH/I2 (c) (Me)3C–CO–CH3 KOH/I2

20. Identify the products in the following disproportionation reaction and also mention rate determining step.

+ +

21.O||

HCCH3 +

O||

HCH OH Product

excess

22. Write the product of the following reaction,

(a)

CHO

OMe

+

CDO

OMe

/OH

(b)

CHO

NO2

+

CHO

/OH

23. Glyoxal (CHOCHO) on being heated with concentrated NaOH forms.

24. +

COOH|CHO

OH)ii(

,NaOH.conc)i(

3 Product is :

25. Write the product of following reaction,

(a) (p) 4LiAlH (q) + (r)

(b)

O

acidPer





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PART - I : IIT-JEE PROBLEMS (PREVIOUS YEARS)

* Marked Questions are having more than one correct option.

1. An alkene A (C16H16) on ozonolysis gives only one product B (C8H8O). Compound B on reaction with NaOH/I2 yields sodium benzoate. Compound B reacts with KOH/NH2NH2 yielding a hydrocarbon C. (C8H10). Writethe structure of compound B and C based on this information two isomeric structures can be proposed foralkene A. Write their structures and identify the isomer which on catalytic hydrogenation (H2/Pd-C) gives aracemic mixture. [JEE 2001, 5/100]

2. A mixture of benzaldehyde and formaldehyde on heating with aqueous NaOH solution gives :(A) Benzyl alcohol and sodium formate (B) Sodium benzoate and methyl alcohol(C) Sodium benzoate and sodium formate (D) Benzyl alcohol and methyl alcohol [JEE 2001, 1/35]

3. 1-Propanol and 2-Propanol can be best distinguished by [JEE 2001, 1/35](A) oxidation with alkaline KMnO4 followed by reaction with Fehling solution(B) oxidation with acidic dichromate followed by reaction with Fehling solution(C) oxidation by heating with copper followed by reaction with Fehling solution(D) oxidation with concentrated H2SO4 followed by reaction with Fehling solution

4. Compound 'A’ (molecular formula C3H8O) is treated with acidified potassium dichromate to form a product 'B'(mol. Formula C3H6O). 'B' forms a shining silver mirror on warming with ammonical AgNO3 . 'B' when treatedwith an aqueous solution of H2NCONHNH2. HCl & sodium acetate gives a product 'C'. Identify the structure of'C’. [JEE 2002, 3/90]

(A) CH3CH2CH = NNHCONH2 (B) 23

3

CONHNHNCCH|CH

(C) CH3 – CH = N.NH – CONH2 (D) CH3CH2CH = NCONHNH2

5. Compound A of molecular formula C9H7O2Cl exists in ketoform and predominantly in enolic form ‘B’. Onoxidation with KMnO4, ‘A’ gives m-chlorobenzoic acid. Identify ‘A’ and ‘B’. [JEE 2003, 2/60]

6. OH/H)ii(

C100/NaOH)i(

2

Major Product is [JEE 2003, 3/84]

(A) (B)

(C) (D)





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7. In the following reaction [JEE 2005, 3/84]

heatCOONaCH3 , X can be :

(A)

Br|

HOCCH||O

2 (B) HOCCH||||OO

(C) HOCCH||O

3 (D) O)COCH( 23

8. In conversion of 2-butanone to propanoic acid which reagent is used. [JEE 2005, 3/84]

(A) NaOH, NaI / (B) Fehling solution (C) NaOH, I2 / (D) Tollen's reagent

9. Cyclohexene on ozonolysis followed by reaction with zinc dust and water gives compound E. Compound Eon further treatment with aqueous KOH yields compound F. Compound F is : [JEE 2007, 3/162]

(A) CHO (B) CHO (C) COOH (D) CO H2

CO H2

10. Match the compounds/ions in Column I with their properties/reactions in Column II. [JEE 2007, 8/162]Column I Column II

(A) C6H5CHO (p) gives precipitate with 2,4 dinitrophenylhydrazine.

(B) CH3C CH (q) gives precipitate with AgNO3 .

(C) CN– (r) is a nucleophile.

(D) – (s) is involved in cyanohydrin formation.

11. In the following reaction sequence, the correct structures of E, F and G are [JEE 2008, 3/163]

[E] [F] + [G]

(*implies 13C labelled carbon)

(A) E = F = G = CHI3 (B) E = F = G = CHI3

(C) E = F = G = *CHI3 (D) E = F = G = CH3





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Passage for questions 12 to 14A tetriary alcohol H upon acid catalysed dehydration gives a product I. Ozonolysis of I leads to compoundsJ and K. Compound J upon reaction with KOH gives benzyl alcohol and compound L, whereas K on reactionwith KOH gives only M.

M =

12. Compound H is formed by the reaction of : [JEE 2008, 4/163]

(A) + PhMgBr (B) + PhCH2MgBr

(C) + PhCH2MgBr (D) +

13. The structure of compound I is [JEE 2008, 4/163]

(A) (B) (C) (D)

14. The structure of compounds J, K and L respecitvely, are : [JEE 2008, 4/163](A) PhCOCH3, PhCH2COCH3 and PhCH2COO–K+ (B) PhCHO, PhCH2CHO and PhCOO–K+

(C) PhCOCH3, PhCH2CHO and CH3COO–K+ (D) PhCHO, PhCOCH3 and PhCOO–K+

Passage for questions 15 to 17A carbonyl compound P, which gives positive iodoform test, undergoes reaction with MeMgBr followed bydehydration to give an olefin Q. Ozonolysis of Q leads to a dicarbonyl compound R, which undergoesintramolecular aldol reaction to give predominantly S.

P

,SOH.3OH,H.2

MeMgBr.1

42

2

Q OH,Zn.2

O.1

2

3 R

.2OH.1 S

15. The structure of the carbonyl compound P is : [JEE 2009, 4/160]

(A) (B) (C) (D)





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16. The structures of the products Q and R, respectively, are : [JEE 2009, 4/160]

(A) , (B) ,

(C) , (D) ,

17. The structure of the product S is : [JEE 2009, 4/160]

(A) (B) (C) (D)

18. Match each of the compounds given in Column I with the reaction(s), that they can undergo, given incolumn II. [JEE-2009, 8/160]

Column I Column II

(A) (p) Nucleophilic substitution

(B) (q) Elimination

(C) (r) Nucleophilic addition

(D) (s) Esterification with acetic anhydride

(t) Dehydrogenation

19. In the scheme given below, the total number of intramolecular aldol condensation products formed from 'Y' is:[JEE 2010, 3/163]

O2H,Zn.2

3O.1 Y heat.2

)aq(NaOH.1





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Passage for questions 20 to 22

Two aliphatic aldehydes P and Q react in the presence of aqueous K2CO3 to give compound R, which upontreatment with HCN provides compound S. On acidification and heating, S gives the product shown below :

20. The compounds P and Q respectively are : [JEE 2010, 3/163]

(A) and

(B) and

(C) and

(D) and

21. The compound R is : [JEE 2010, 3/163]

(A) (B)

(C) (D)





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22. The compound S is : [JEE 2010, 3/163]

(A) (B)

(C) (D)

23. Match the reaction in column I with appropriate types of steps/reactive intermediate involved in these reac-tions as given in column II [JEE 2011, 8/160]

Column-I Column-II

(A) (p) Nucleophilic substitution

(B) (q) Electrophilic substitution

(C) (r) Dehydration

(D) (s) Nucleophilic addition

(t) Carbanion





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24. The number of aldol reaction(s) that occurs in the given transformation is- [JEE 2012, 3/136]

CH3CHO + 4HCHO NaOH.aq.conc

OHOH

OH OH

(A) 1 (B) 2 (C) 3 (D) 4

25. The major product H of the given reaction sequence is [JEE 2012, 3/136]

CH3 – CH2 – CO – CH3 CN G

Heat

SOH%95 42

(A) CH3 CH C COOH

CH3

(B) CH3 CH C CN

CH3

(C) CH3 CH2 C COOH

CH3

CH3

(D) CH3 CH C CO

CH3

NH2

Paragraph for questions 26 and 27In the following reaction sequence, the compound J is an intermediate.

3 2

3

(CH CO) OCH COONa J

2

23

(i) H , Pd / C

( ii) SOCl( iii) anhyd. AlCl

K

J (C9H8O2) gives effervescence on treatment with NaHCO3 and a positive Baeyer’s test.

26. The compound K is [JEE 2012, 3/136]

(A) (B)

O O

(C)

O

(D) O

27. The compound is [JEE 2012, 3/136]

(A)

HO

(B)

H

(C)

CH3O

(D)

HH

H





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28. With reference to the scheme given, which of the given statement(s) about T, U, V and W is(are) correct ?[JEE 2012, 4/136]

O

O

CH3T

LiAlH4

U (CH3CO)2Oexcess

CrO3/H

V W

(A) T is soluble in hot aqueous NaOH(B) U is optically active(C) Molecular formula of W is C10H18O4

(D) V gives effervescence on treatment with aqueous NaHCO3

29. After completion of the reactions (I and II), the organic compound(s) in the reaction mixture is(are) :

Reaction I :

Reaction II :

[JEE_Advanced_2013-P-2](A) Reaction I : P and Reaction II : P(B) Reaction I : U, acetone and Reaction II : Q, acetone(C) Reaction I : T, U, acetone and Reaction II : P(D) Reaction I : R, acetone and Reaction II : S, acetone

PART - II : AIEEE PROBLEMS (PREVIOUS YEARS)

1. On vigorous oxidation by permangnate solution (CH3)2C = CHCH2CHO gives [AIEEE-2002]i j esaxusV foy; u ds } kj k r hoz vkWDl hdj .k dj us i j ; kSfxd (CH3)2C = CHCH2CHO fuEu esa l s dkSul k ; kSfxd nsr k gS \

[AIEEE-2002]

(1) (CH3)2CO and OHCCH2CHO (2)

OHOH||

CHOCHCHC)CH( 223

(3) (CH3)2CO and OHCCH2COOH (4) (CH3)2CO and CH2(COOH)2





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2. Which one of the following is reduced with Zn, Hg and HCl acid to give the corresponding hydrocarbon?[AIEEE-2004]

(1) Ethyl acetate (2) Butan-2-one (3) Acetamide (4) Acetic acid

3. Which one of the following undergoes reaction with 50% sodium hydroxide solution to give the correspondingalcohol and acid ? [AIEEE-2004](1) Phenol (2) Benzoic acid (3) Butanal (4) Benzaldehyde

4. The best reagent to convert pent-3-en-2-ol into pent-3-ene-2-one is [AIEEE-2005](1) Pyridinium chloro-chromate (2) Chromic anhydride in glacial acetic acid(3) Acidic dichromate (4) Acidic permanganate

5. The reaction [AIEEE-2005]

R – C + NuX Nu

O O- R – C + X-

is fastest when X is :(1) OCOR (2) OC2H5 (3) NH2 (4) Cl

6. The decreasing order of the ratio of HCN addition to compounds A to D is [AIEEE-2006](a) HCHO (b) CH3COCH3 (c) PhCOCH3 (d) PhCOPh(1) d > b > c > a (2) d > c > b > a (3) c > d > b > a (4) a > b > c > d

7. In the following sequence of reactions, [AIEEE-2007, 3/120]

CH3CH2OH 2P A EtherMg B HCHO C OH2 D. The compound ‘D’ is is

(1) n-propyl alcohol (2) propanal (3) butanal (4) n-butyl alcohol

8. In the following sequence of reactions, the alkene affords the compound 'B' [AIEEE-2008, 3/105]

BACHCHCHCHZn

OHO33

23 .The compound B is

(1) CH3COCH3 (2) CH3CH2COCH3 (3) CH3CHO (4) CH3CH2CHO

9. In Cannizzaro reaction given below [AIEEE-2009, 4/144]

2Ph CHO

HO: PhCH2OH + PhCO2

..

the slowest step is :(1) the transfer of hydride to the carbonyl group (2) the abstraction of proton from the carboxylic group

(3) the deprotonation of PhCH2OH (4) the attack of : HO

at the carboxyl group

10. How many chiral compounds are possible on monochlorination of 2 - methyl butane ?[AIEEE-2012, 4/120]

(1) 8 (2) 2 (3) 4 (4) 6

11. 2-Hexyne gives trans - 2 - Hexene on treatment with : [AIEEE-2012, 4/120](1) Pt/H2 (2) Li/NH3 (3) Pd/BaSO4 (4) LiAlH4

12. In the given transformation, which of the following is the most appropriate reagent ? [AIEEE-2012, 4/120]

(1) NH2 NH2, (2) Zn – Hg/HCl (3) Na, Liq. HCl (4) NaBH4





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NCERT QUESTIONS

1. What is meant by the following terms ? Give an example of the reaction in each case.(i) Cyanohydrin (ii) Acetal (iii) Semicarbazone (iv) Aldol(v) Hemiacetal (vi) Oxime (vii) Ketal (vii) Imine(ix) 2,4-DNP-derivative (x) Schiff’s base

2. Draw structures of the following derivatives.(i) The 2,4-dinitrophenylhydrazone of benzaldehyde(ii) Cyclopropanone oxime(iii) Acetaldehydedimethylacetal(iv) The semicarbazone of cyclobutanone(v) The ethylene ketal of hexan-3-one(vi) The methyl hemiacetal of formaldehyde

3. Predict the products formed when cyclohexanecarbaldehyde reacts with following reagents.(i) PhMgBr and then H3O

+ (ii) Tollens’ reagent(iii) Semicarbazide and weak acid (iv) Excess ethanol and acid(v) Zinc amalgam and dilute hydrochloric acid

4. Which of the following compounds would undergo aldol condensation, which the Cannizzaro reaction andwhich neither? Write the structures of the expected products of aldol condensation and Cannizzaro reaction.(i) Methanal (ii) 2-Methylpentanal (iii) Benzaldehyde(iv) Benzophenone (v) Cyclohexanone (vi) 1-Phenylpropanone(vii) Phenylacetaldehyde (viii) Butan-1-ol (ix) 2,2-Dimethylbutanal

5. How will you convert ethanal into the following compounds?(i) Butane-1,3-diol (ii) But-2-enal (iii) But-2-enoic acid

6. Write structural formulas and names of four possible aldol condensation products from propanal and butanal.In each case, indicate which aldehyde acts as nucleophile and which as electrophile.

7. An organic compound with the molecular formula C9H10O forms 2,4-DNP derivative, reduces Tollens’ reagentand undergoes Cannizzaro reaction. On vigorous oxidation, it gives 1,2-benzenedicarboxylic acid. Identifythe compound.

8. An organic compound (A) (molecular formula C8H16O2) was hydrolysed with dilute sulphuric acid to give acarboxylic acid (B) and an alcohol (C). Oxidation of (C) with chromic acid produced (B). (C) on dehydrationgives but-1-ene. Write equations for the reactions involved.

9. Give simple chemical tests to distinguish between the following pairs of compounds.(i) Propanal and Propanone (ii) Acetophenone and Benzophenone(iii) Phenol and Benzoic acid (iv) Benzoic acid and Ethyl benzoate(v) Pentan-2-one and Pentan-3-one (vi) Benzaldehyde and Acetophenone(vii) Ethanal and Propanal

10. Describe the following:(i) Acetylation (ii) Cannizzaro reaction(iii) Cross aldol condensation (iv) Decarboxylation





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11. Complete each synthesis by giving missing starting material, reagent or products :

(i) (ii)

(iii) (iv)

(v) (vi)

(vii) (viii)

(ix)

12. Give plausible explanation for each of the following :(i) Cyclohexanone forms cyanohydrin in good yield but 2,2,6-trimethylcyclohexanone does not.(ii) There are two –NH2 groups in semicarbazide. However, only one is involved in the formation ofsemicarbazones.





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Exercise # 1PART - I

A-1. (C) A-2. (B) A-3. (A) A-4. (C) A-5.* (ABD) A-6. (B) A-7. (C)A-8. (D) A-9. (A) A-10. (B) A-11. (B) A-12. (A) A-13. (B) A-14. (B)A-15. (B) A-16. (D) A-17. (A) A-18.* (AC) A-19.* (ABCD) A-20.* (AD)A-21. (B) A-22. (A) A-23. (B) A-24. (B) A-25. (B) B-1. (D) B-2. (D)B-3. (A) B-4.* (ABD) B-5. (B) B-6. (B) B-7. (C) B-8. (C) B-9. (B)B-10. (B) B-11.* (ABC) B-12.* (AC) B-13. (D) B-14. (A) C-1. (D) C-2. (A)C-3. (A) C-4. (C) C-5. (C) C-6. (B) C-7. (D) C-8. (C) C-9. (A)C-10. (C) C-11. (B)

PART - II1. (A) 2. (B) 3. (A) 4. (A) - (p) ; (B) - (s) ; (C) - (q) ; (D) - (r)5. (A) - q ; (B) - p ; (C) - s ; (D) - r 6. (A) - p, q, s ; (B) - p, q, r, s ; (C) - p ; (D) - q, r, s7. (A) 8. (A) 9. (B) 10. (A) 11. (A) 12. True13. True 14. False 15. Sodium potassium tarterate


1. (D) 2. (B) 3. (A) 4. (D) 5. (C) 6. (B) 7. (B)8. (A) 9. (C) 10. (B) 11. (B) 12. (A) 13. (C) 14. (A)15. (BC) 16. (BCD) 17. (AB)

PART - II

1. CH3—

O||C —CH2—CH3

OH)2(

MgBrHC)i(

3

52 OH|

HC—C—CH|

HC

523

52

3-Methylpentan-3-ol

2. (i) OH2 +

(ii) OH2 CH3CH2CH2OH +

3. (a) CH3 – D + (b)

3

33

CH|

CHCHCH +

4. (a) (b)

5. IV > III > II > I 6. d > b > c > a 7. c > b > a > d





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8. Cyanohydrin is formed by nucleophilic attack on carbonyl group (C=O), 2, 2, 6-trimethylcyclohexanone hasmore steric crowding and three methyl groups in tri methyl cyclohexanone which nearly neutralise thepositive charge on carbon hence CN– nucleophile does not react with 2,2,6-trimethylcyclohexanone.

9. (a)

OH|

NaSOCHPh 3 ; (b)

O||

NHCHCHC 352 ; (c) 18

33

O||

CHCCH ; (d)

10. (a) (b)

(c) (d) Ph – C – Ph||N – NH – Ph

11. (a)

H

OHCH|

OHCH

2

2

H)ii(

LiAlH)i( 4

(b)

O||

CH–C–CH–CH–Br 322

H

OHCH|

OHCH

2

2

Br – CH – CH C – CH2 32 –

OO

H)ii(

NaCCH)i(

O||

CH–C–CH–CH–CHC 322

(c) CH - Br2

O

H

OHCH|

OHCH

2

2 CH –Br2

OO OH)ii(

PhMgBr)i(

2

CH - Ph2

O

12. (a)

3

23

CH|

CHO–CCH–CH–CH (b)

Ph|

CHO–CCH–CH–Ph 2 (c) Ph–CO–CH=CPh

CH3

13. (a)

OCH|||

HC–CHCHCCH|CH

3

3

3

; (b)

3CH|

HCCCHPh||O

; (c) O||CCHCHPh





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14.

15. (a) CH3CH2CH2COOEt ; (b) PhCH2COOCH3 ; (c) (CH3)2CHCH2COOEt

16. (a) (b) (c) CH3CH2COOH

17. (a)

O||

OCHCCHPh 32 +

O||

ORCH (b) +

O||

OCHCCHPh 32

(c)

O||

ORCPh +

O||

HOCCCHCH 5223

18.

19. (a) CHI3 + HCOONa (b) CHI3 + PhCH2COONa (c) CHI3 + (Me)3C–COONa

20. (P) = (Q) = D–CH2–OH 21.OHCH

|OHCHCCHHO

|OHCH

2

22

2

+ HCOO–Na+

22. (a) +

CH–OH

D

OMe

(b) +

CH –OH2

23. HO – CH2 – COONa. 24. +

25. (a) (p) , (q) , (r) CH3 – CH2 – CH2OH

(b)

OO





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1. A = or

B =

O||

CHCHC 356 C = C6H5 – CH2 – CH3

Trans isomer give racemic mixture.

2. (A) 3. (C) 4. (A)

5.

6. (B)

7. (D) 8. (C) 9. (A) 10. (A) – (p, q, s) ; (B) – (q) ; (C) – (q, r, s) ; (D) – (q, r)11. (C) 12. (B) 13. (A) 14. (D) 15. (B) 16. (A) 17. (B)18. (A) - p, q, t ; (B) - p, s, t ; (C) - r, s ; (D) - p 19. 1 20. (B) 21. (A)22. (D) 23. (A) r,s,t (B) p,s (C) r,s (D) q,r 24. (C) 25. (A) 26. (C)27. (A) 28. (AC) 29. (C)

PART - II1. (4) 2. (2) 3. (4) 4. (1) 5. (4) 6. (4) 7. (1)8. (3) 9. (1) 10. (3) 11. (2) 12. (1)

contents - arride learning compounds.pdf · 2oh to form aldoximes and ketoximes respectively....

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