WORK BOOK- Exercise in Chemistry

Work Book (Phase − V) Subjective: Board Type Questions 1.

Assign d, l and meso character to the following COOH (i) (ii)

COOH

H

OH

H

H

OH

HO

COOH COOH

(iii)

OH H COOH COOH

(iv)

HO

H

HO

HO

H

H

COOH

H OH COOH

2.

Write structure of (2Z, 4E)  3  ethyl  2, 4  hexadiene.

3.

Biological reduction of pyruvic acid gives (+) lactic acid, represented by Fischer projection shown. Assign R/S configuration. COOH

H3C

C

COOH

Biological reduction

HO

O

CH3

(pyruvic acid) 4. 5.

( ) lactic acid

Assign R and S configuration to the products when cyclopentene reacts with (a) cold KMnO4 (b) Br2 water Identify the product of the following reaction with proper configuration.

Br

CH3 OH H

H 6.

H

2

SN  →

In the following molecules indicate presence of a centre of chirality with an asterisk (*). CH3 Br (a) (b) Cl

CH3

7.

Are the following compounds chiral – enatiomers or achiral-Identical mirror images?

H

H C

C

H

H

and

H

CH3

C

C

H3C

H

8.

Give the aldol condensation product of CH3CH = CHCHO.

9.

Arrange the following in increasing extent of hydration. O

O

CHO

CHO Br

Br

10.

Explain the reason for the stability of choral hydrate.

11.

What is the product of the following reaction? O

?

(C6H5)3P = C(CH3)2

12.

In which of the following compounds would you except intramolecular H bonding to occur (a) o – nitro phenol (b) o – hydroxybenzoic acid (c) o – fluoro phenol (d) methyl salicylate (oil of winter green)

13.

Outline steps of the following conversion NH2

Br

Br

Br

14.

Convert (a) acetylene into n-butyl alcohol. (b) propane into 1 – propanol, 2 – propanol and allyl alcohol.

15.

An organic compound with molecular formula C10H18O contains no double or triple bonds. It reacts with hydrochloric acid to give dichloride as shown Cl H3C

Cl

CH3

CH3

Deduce the structure of the organic compound.

16.

Would it be possible to form di-t-butyl ether from dehydration of t-butyl alcohol?

17.

Suggest reaction conditions for the following conversion OH

O COOH

O H3C

18.

Predict the most acidic hydrogen in the following compounds. O O (a) (b)

H

(c)

N

O

(d) O

O

19.

Which of the following compounds would be expected to decarboxylate when heated? O O O (a) (b) OH HO

OH

O

O

(c)

O

(d)

O

O

HO

20.

Saponification of esters of optically active alcohols proceeds with retention of configuration. Explain.

O

21.

NaOBr, ∆ 2− − H2N C NH2 → N2 + CO3 + Br + H2O Calculate volume of N2 gas obtained at NTP from 1mL of body fluid containing 6 µg of urea.

22.

Barbituric acid is formed when diethyl malonate reacts with urea. What is the type of isomerism shown by it?

23.

Convert CH3COOH into (CH3)2NH.

24.

Arrange the following in increasing basic nature. N N H Piperidine (I)

N

N Pyridine (II)

Imidazole (III)

True and False

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25.

Tertiary alcohols are more reactive towards halogen acids than secondary alcohols.

26.

2-Pentanol or 3- pentanol on treatment with HCl gives both 2-chloropentane and 3chloropentane.

27.

Terminal Gem-dihalides on hydrolysis yield aldehydes.

28.

m-Chlorobromobenzene is an isomer of m-bromochlorobenzene.

29.

Aldehydes react with alcohols in presence of dry HCl gas to form acetals.

30.

Aldehyde group is m-directing and deactivates the benzene ring towards further electrophilic substitution reactions.

31.

Bromination of propionic acid with bromine in presence of small amount of red phosphorus gives β − bromopropionic acid.

32.

Acid chlorides react with aromatic hydrocarbons in presence of anhydrous AlCl3 to form aromatic ketones.

Fill in the Blanks 33.

A mixture of phenol and phthalic anhydride when heated with conc. H2SO4 forms…………..which is used as an ……in acid-base titrations.

34.

Phenol on treatment with bromine water gives……..but with bromine in CS2, it mainly gives……….

35.

Chloropicrin is formed by the action of ……on chloroform.

36.

Alkyl halide with……….Ag2O gives alcohol and ………………Ag2O gives ether.

37.

The reaction of acetyl chloride with diethylcadmium followed by hydrolysis gives………..

38.

The structure of the intermediate product formed by the oxidation of toluene with CrO3 and acetic anhydride, whose hydrolysis gives benzaldehyde, is…………

39.

Oxidation of o-xylene with alkaline KMnO4 gives…………

40.

Hell-Volhard-Zelinsky reaction involves the replacement of an ……….atom from the alkyl group of a monocarboxylic acid by a ……atom.

IIT Level Question 41.

Comment on the chirality of the following molecules H H (a) (b) H

C Cl

C

C

C Cl

Cl

CH3 C

C CH3

42.

For each of the following additions, predict the regiochemistry of each adduct and determine whether the product mixture is optically active. If not, determine whether the inactivity results from the absence of chiral centres, the formation of equal amounts of enantiomers or formation of a meso compound. (a) (b) DCl

43.

D3O

Comment upon the nature of products in the following. H (a) OH

SOCl 2

H

CH3

CH2CH3

(b) H3C

Br

CH3CH2OH SN1

CH2CH2CH3

44.

Identify A to E in the following O B

DIBAH H2O

C

OCH3

LiAlH 4 H2 O

A

KMnO4 H

C PCl5

B

45.

E

D

Identify products in the following reaction OH (a) () SO2 Cl2 ∆  → A   →C C6 H5 NMe2 ( ii) HCl → B  i KOH

CO 2 Et

NO2

(b)

NH4HS H2 O  → D  → E  →F NaNO , H SO , 00 C 2

2

4

NO2

OH

(c) Bu

Bu ( i) PbO 2 , C6H6  →G ( ii) Br2 

Bu

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46.

Identify A, B and C. H

H

TsCl A

Pyridine CH3

NaBr

B

OH

PBr 3

C

Identify A, B and C. 47.

What is wrong in these reactions? O (a) H C 3

CH3OH

CH3O

OH

H3C

OCH3

(b)

H2SO 4 OH 48.

Identify the products (a) Conc. KMnO 4  → A ∆, H O + 3

CH2

(b)

+

CO2 H3 O Hbr Mg Ether  → B  →  →  →C

+

H3 O CO2 HBr, peroxide Mg Ether  →  →  →  →D

49.

Explain the difference in the following observation 5 N NaOH

CHCH O

CR O

50.

CHCH

CHCH3

OH

CHCH3 di. NaOH

CH

CHCHCH3 OH

The pKa values for the amino acid cysteine are 1.8, 8.3 and 10.8. Assign these pKa values to the functional groups in cysteine and draw the structure of the molecule in aq. Solution at pH 1, 5, 9.

Objective: Multiple choice questions with single correct options

COOH

1.

H

Configuration at C1 and C2 atoms are:

OH

HO

H COOH (A) d and d (C) R and R 2.

(B) l and l (D) R and S

H

CH3

CH3

H

CH3

H

H

CH3

(A)

(B)

A and B are (A) achiral identical mirror images (C) geometrical isomers (each separately) 3.

(B) chiral enantiomers (D) racemic mixture

Which of the following compounds are enantiomers? CH3 (A) (B) CH3 H

OH

HO

H

and

HO H

OH

HO

OH CH3

CH3 H

OH

HO

H

and

H

(D) OH

H

H

H

HO

HO

OH

CH3 OH

H

H

and

HO

Meso – tartaric acid is optically inactive due to the presence of (A) two chiral carbon atoms (B) molecular unsymmetry (C) molecular symmetry (D) external compensation

5.

Which of the following compounds can occur in enantiomeric forms? H H (A) (B)

H

(C)

H

6.

COOH

COOH

(D)

COOH

H CH3

4.

H 5 C2

H

HO

CH3

COOH

H CH3

CH3

CH3

CH3

and

HO

CH3

CH3

CH3

(C)

H

H

CH3

CH3

H

COOH

Ethylene glycol reacts with excess of PCl5 to give (A) 1, 1 – dichloroethane (B) 1, 2 – dichloroethane (C) 1, 1, 1 – trichloroethane (D) 2, 2 – dichloroethane

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7. Br2 , CCl4 H  → [ F]  → C 4H 8Br 2 −H2 O +

H3C

OH

How many structures of F are possible? (A) 2 (C) 6 8.

(B) 5 (D) 3

HOOC

OH O 2N 2 moles NaNH2 C

A

CH

OH

The product A will be OOC (A)

OOC

(B)

OH

OH

O 2N

O 2N

C

CH

C

O

(C)

C

OH

HOOC

(D)

HOOC

O O 2N

OH O 2N

C

CH

C

O

C

O

O

9. H3C

CH

CH3

PBr3

Mg / ether  → (X)  →

(Y)

OH

The final product is (A)

10. 11.

O

∆

(B)

OH (C)

H 2O

(D)

O None of the above

During dehydration of alcohols to alkanes by heating with conc. H2SO4, the initial step is (A) formation of an ester (B) protonation of alcohol molecule (C) formation of carbocation (D) elimination of water The correct acidic order of the following is

OH

OH

CH3 (II)

(III)

OH

(I)

NO2

(A) I > II > III (C) II > III > I

(B) III > I > II (D) I > III > II

12.

What is formed when glycerol reacts with HIO4? (A) 2 formic acid molecules and one formaldehyde molecule (B) 2 formaldehyde and one formic acid molecule (C) 3 formic acid molecules (D) 3 formaldehyde molecules

13.

Phenol is heated with phthalic anhydride in presence of conc. H2SO4. The product gives pink colour with alkali. The product is (A) phenolphthalein (B) bakelite (C) salicylic acid (D) fluorescein

14.

The reaction of

with RMgX leads to the formation of

O (A) RCHOHR (C) R2CHCH2OH 15.

(B) RCHOHCH3 (D) RCH2CH2OH

In the following compounds

OH

NO2

H3C

(I)

OH O 2N

OH (II)

OH (IV)

(III)

The order of acidity is (A) III > IV > I > II (C) II > I > III > IV

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

16.

An organic compound ‘X’ on treatment with acidified K2Cr2O7 gives a compound ‘Y’ which reacts with I2 and sodium carbonate to form triiodomethane. The compound ‘X’ is (A) CH3OH (B) CH3COCH3 (C) CH3CHO (D) CH3CHOHCH3

17.

In the reaction of phenol with CHCl3 and aqueous NaOH at 70°C (343K ), the electrophile attacking the ring is (A) CHCl3 (B) •CHCl2 (C) :CCl2 (D) COCl2

18.

The compound which gives most stable carbonium ion on dehydration is (A) (B )

OH (C)

19.

OH (D)

OH

OH

An ether is more volatile than alcohol having the same molecular formula. This is due to

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(A) (B) (C) (D) 20.

intermolecular hydrogen bonding in alcohols dipolar character of ether alcohols having resonance structure intermolecular hydrogen bonding in ethers O

Me C

Me X

CH2

CH

Me

Me

CH2 OH

X could be (A) LiAlH4 (C) LiAlH4/BF3 21.

(B) NaBH4 (D) NaH

CH2OH

O

NaBH4

C O

(A)

O

A is

A

CH3

CH2OH

HO

(B)

CH2OH

CH2OH

(C)

CH2OH

HO

CH2OH

O

(D)

CH2OH

HO

C O

O

CH3 CH3

22. H3C

C

C

OH

OH CH3 CH3

(A) H3C

CH3

C

C

H

H3C

C CH3

C

P

P is

CH3 CH3

(B) CH3

CH3 O

(C)

23.

CH2OH

CH2

H3C

C

CH3

O CH3 H

(D) CH3

C

H3C

C

C

CH3

CH3 OH

A compound X of molecular formula C4H10O is soluble in conc. H2SO4. It does not react with sodium metal but is cleaved by HI to give CH 3I and an alcohol Y which gives iodoform. ‘X’ may be (A) C2H5OC2H5 (B) CH3OCH2CH2CH3 H3C O CH CH3 (C) C2H5CHOHCH3 (D) CH3

CH3

24. H3C

C

H

18 H2O

CH2

A is

A

O

(A)

(B) 18

OH

OH HO18

HO

(C)

(D)

18

OH

OH HO

HO

25.

18

Which one is not cyclic ether? O (A)

(B)

O (C)

O O

(D) O

O

O

O

26.

H

A is (A)

A

OH

CH2OH

(B)

CH3

CH3 OH

OH

CH2OH

(C)

CH3

(D)

CH3

CH3

27. Oxalic acid

OH

O

A

O

O O

conc. H2 SO4 Hence, A  → B; B is

(A)

O

(C)

O O

OH

(B)

O O

O

CH2

(D)

None

OH

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28. CH3

O CH3OH

CH3OH

CH3O

H2SO4

[A] [B]

A and B are (A)

(B) H

OH3C

(C)

CH3 OH

H

CH3

HO

H3CO

(D)

OCH3 H3C H

H

and

OCH3

CH3

H3CO

OH

H

and

OH CH3 H

OH

H

and

CH3

H3CO

H H3CO

O

29.

C

HgSO 4 / H2SO 4

CH

O

(A)

A

O

(B) C

CH2CHO

CH3

O O

(C)

OH

(D)

CH2CHO

COOH

30.

What are A, B and C in the following? O

Raney Ni, H 2

B

Pt, 1 mol H 2

A

NaBH4, CH 3OH

C O

(A)

in all cases

OH

(b)

in all cases

OH

(C)

in all cases

(D)

O A:

OH

OH B:

C:

CH3

HO

and OH

OCH3

CH3 OH

O

31.

1. KBrO, ∆ 2. H + 3. ∆

→

COCH3

A

CH3

A is (A)

O

O

(B) COOH

CH3

CH3

(C)

COOH

COOH

(D)

CH3

OH

OH

32.

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

33.

The end product ‘C’ in the following sequence of chemical reactions is CaCO3 NH2 OH ∆ CH3 COOH  → A  → B  →C (A) acetaldehyde oxime (C) methyl nitrate

34.

(B) formaldehyde oxime (D) acetoxime

In cannizzaro reaction given below: −

OH 2PhCHO  → PhCH2OH + PhCO 2−

the slowest step is − (A) the attack of OH at the carbonyl group (B) transfer of hydride ion to carbonyl group (C) abstraction of proton form carboxylic acid (D) deprotonation of Ph  CH2OH 35.

Reduction with aluminium isopropoxide in excess of isopropyl alcohol is called MPV reduction. What will be the final product when cyclohex-2-enone is selectively reduced by MPV reduction? (A) cyclohexanol (B) cyclohex-2-enol (C) cyclohexanone (D) benzene

36.

Which of the following reagents convert C6H5COCHO to C6H5CHOHCOOH? (A) aq. NaOH (B) Acidic Na2SO3 (C) Na2CrO4/H2SO4 (D) NaNO2/HCl

37.

The enol form of acetone, after treatment with D2O, gives C CH2 O (A) H3C (B)

(C)

H2C

OD C OH

CH2D

D3 C

C OD

CD3

D2 C

C

CD3

(D)

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38.

Reduction of

can be carried out with C

O

to

CH2

(A) catalytic reduction (C) Wolff-Kishner reduction 39.

(B) Na/C2H5OH (D) LiAlH4

Identify the compounds A and B in the following reaction sequence H O NaCN → A  →B ( CH3 ) 2 C = O  HCl Heat (A) A = CH3 COOH B = ( CH3CO ) 2 O (B) A = ( CH3 ) 2 C ( OH) CN B = ( CH3 ) 2 C ( OH) COOH 3

+

(C) A = CH3 CHO B = CH3COOH (D) ( CH3 ) 2 C ( OH) CN B = ( CH3 ) 2 C = O 40.

Which of the following has the most acidic hydrogen? (A) 3-hexanone (B) 2, 4 – hexanedione (C) 2, 5 – hexanedione (D) 2, 3 – hexanedione

41.

A mixture of benzaldehyde and formaldehyde on heating with aq. 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

42.

CHO

OHC

()  → ( ii) H+ / H O i NaOH /1000 C 2

CHO OHC

Major product is (A)

HOOC COOH

(B)

COOH HOOC O

(C)

OH HOOC

COOH HO OH HO

(D)

O

OH

O

HO

O

43.

Compound ‘A’ (molecular formula C3H8O is treated with acidified potassium dichromate to form a product ‘B’ (molecular formula C3H6O). ‘B’ forms a shining silver mirror on warming with ammonical silver nitrate. ‘B’ when treated with an aq. solution of NH2CONHNH2.HCl and sodium acetate gives a product ‘C’. Identify the structure of ‘C’. NNHCONH2 (B) H3C C NNHCONH2 (A) H3CH2CHC

(C)

44.

H3 C

C

NCONHNH2

(D)

CH3 H2CH3CHC

HCONHNH2

CH3 Which of the following compounds would have the smallest value for pKa?

(A) CHF2CH2CH2COOH (C) CH2FCHFCH2COOH 45.

(B) CH3CH2CF2COOH (D) CH3CF2CH2COOH

When CH2 = CH  COOH is reduced with LiAlH4, the compound obtained will be O O (A) (B)

H

OH OH

(C)

(D)

O OH

46.

Identify the correct order of boiling points of the following compounds:O

O

H

OH (II)

(I)

(A) I > II > III (C) I > III > II 47.

OH (III)

(B) III > I > II (D) III > II > I

The major product obtained when Br2 / Fe is treated with O HN H3 C

CH3 is

O

(A)

O

(B)

HN

HN H3 C

H3 C

CH3

CH3

Br

Br O

(C) H3 C

O

(D)

HN

HN CH3

H3 C

CH3

Br

Br 48.

An ester (A) with molecular formula C9H10O2 was treated with excess of CH3MgBr and the complex so formed was treated with H2SO4 to give an olefin (B). Ozonolysis of (B) gave a ketone with molecular formula C8H8O which shows positive iodoform test. The structure of (A) is: (A) C6H5COOC2H5 (B) CH3COCH2COC6H5 (C) p – CH3O – C6H4 – COCH3 (D) C6H5COOC6H5

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49.

O

CH3COOOH  → P. P is

O

(A)

O

(B)

O O

O O

(C)

HO

O

50.

O

(D)

OH

X and Y in the following reaction sequence are:O P2 O5 X ←  R ∆

Br2 NH2  →Y − OH

C

(A) R – CN, RCH2NH2 (C) RCN, RNH2

(B) RNH2, RCN (D) RCN, RCH2NH2

Multiple choice questions with more than one option correct 51.

1 – propanol and 2 – propanol can be best distinguished by (A) oxidation with 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 KMnO4 followed by reaction with Tollen’s solution

52.

Which of the following statements are correct? (A) CrO3.H2SO4 in acetone oxidizes 2° alcohols to ketones (B) Jones reagent which is chromic acid in aqueous acetone solution oxidizes 1° alcohol to aldehyde and 2° alcohol to ketone but does not effect double bond. (C) chromic acid oxidizes 1° alcohols to carboxylic acid. (D) the formation of cyanohydrin from a ketone is an example of electrophilic addition

53.

O

CH 2CH

CH2

∆

Product is (A)

(C)

?

OH

(B)

CH2CH OH

OR

CH2 CH

CH2

(D)

OH

CH2

* H2 C

54.

CH

* CH2

CH

CH2

CH2

How much bromine is needed to produce tribromophenol from one mole of phenol?

(A) 3.0 mole (C) 240 g 55.

(B) 1.5 mol (D) 480 g

Which of the product expected in the following reaction? CH3

Cl NaNH2  → NH 3

(A)

CH3

(B)

CH3

NH2 NH2

(C)

CH3

(D)

None of these

NH2

56.

Which of the following reactions depict the nuclophilic substitution of C2H5Br? (A) C2H5Br + C2 H5 SNa → C2 H5 SC2 H5 + NaBr (B) C2H5Br + 2H → C 2H6 + HBr (C) C2H5 Br + AgCN → C2 H5 NC + AgBr (D) C2H5Br + KOH → C 2H5OH +KBr

57.

Which of the following are electrophilic substitution reactions? (A) (B) FeCl3 + Cl2 →

(C)

+ fumin g H2SO4 → (D)

None of these

UV light

+ Cl2  → 58.

On treatment with a clear solution of CrO3 in dilute H2SO4, an aliphatic alcohol gives a greenish opaque solution within 2-3 seconds. The alcohol can be CH3 (A) CH3CH2OH (B)

H3C

CH

CH

CH3

OH (C)

H3CHC

CH3

CH3

(D)

OH

H3C

C

OH

CH3 59.

60.

Treatment of n-propylamine with nitrous acid gives (A) CH3CH=CH2 (B) CH3CH2CH2OH CH CH3 (C) H3C (D) none of these

OH Which of the following statements are correct?

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

The two carbon-oxygen bond length in formic acid are different. The two carbon-oxygen bond lengths in sodium formate are equal The carbon-oxygen bond length in formic acid is less than that in sodium formate. The carbon-oxygen bond length in formic acid is greater than that in sodium formate

61.

Nitration of phenol with dilute nitric acid at 293 K gives (A) o-nitrophenol (B) p-nitrophenol (C) m-nitrophenol (D) 2, 4, 6-nitrophenol

62.

The product obtained in the equation:

CH3 − NO2 + Cl2 + NaOH → is (A) ClCH2NO2 (C) Cl3CNO2 63.

(B) Cl2CHNO2 (D) CH3NH2

Phenyl cyanide can be obtained by PO ,∆

Ac O, ∆

2 5 → (A) C6H5 CONH2 

2 → (B) C6H5 − CH = NOH 

1. NaNO / HCl

2 → (D) C6H5NH2  2. CuCN

Alc. KOH

(C) C6H5 Cl → 64.

Isopropylamine can be obtained by (A) (B) (C)

LiAlH  → ( CH3 ) 2 CHO + NH 2OH → ?  H / Ni ( CH3 ) 2 CO + NH 3 → ? → 4

2

H3C CHOH +NH3  →

H3C (D) none of these 65.

Which of the following will yield p-tert. Butylphenol? CH3 (A)

Phenol H3C

C

+

H CH2   →

H (B) Phenol + ( CH3 ) 3 COH   → +

3 → (C) Phenol + ( CH3 ) 3 CCl 

AlCl

(D) None of these 66.

Which of the following statements are correct? (A) Benzaldehyde reduces Fehling’s solution NaOH

(B) C6H5 CHO + C6H5 CHO → C6H5 CH = CHC6H5 + O2 is a Claisen-Schmidt reaction. (C) pKa (formic acid) is less than pKa (acetic acid) (D) o-Toluidine is more basic than aniline 67.

68.

Which of the following statements are correct? (A) When phenol vapour is passed over Zn dust, bezene is produced. (B) The phenolic −OH group is ortho and para directing (C) o-nitrophenol has a lower boiling point than p-nitrophenol (D) Phenol is more acidic than o-cresol Which of the following will give vinyl chloride?

2+

Hg (A) CH ≡ CH + HCl  →

(B)

H2C

→ H 2C CH2 Cl2  Cl

NaOH CH2  → ∆

Cl

6000 C

(C) CH2 = CH2 + Cl2  → KOH

→ CH2Cl  → (D) ClCH2  ethanol 69.

70.

Vinyl chloride undergoes (A) addition reactions (C) substitution reactions

(B) elimination reactions (D) none of these

Which of the following methods can be used for the preparation of acetylene?

→ (A) CH 3 CHCl2 + alc. KOH  → (B) ClCH2CH2Cl + alc. KOH  liq. NH

3 → (C) ClCH 2CH2Cl + NaNH2  ∆

(D) None of these 71.

Aryl halides undergo (A) the Fittig reaction (C) the Grignard reaction

(B) the Ullmann reaction (D) none of these

72.

Which of the following reagents can be used to distinguish CH2=CHCH2Cl from CH3CH2CH2Cl? (A) Na fusion; HNO3, AgNO3 (B) Ag(NH3)2OH (C) AgNO3/C2H5OH (D) Br2/CCl4

73.

Alkyl iodides can be prepared by CCl

4 → RCH2I (A) RCH2COOAg + I2  ∆

acetone

→ RCH2I + NaCl (B) RCH2Cl + NaI  ∆ → RI + H2O (C) R − OH + HI  → CH3I (D) CH4 + I2  74.

75.

The reaction of glycerol with HIO4 gives (A) formaldehyde (C) iodic acid

(B) formic acid (D) oxalic acid

On being treated with HCl, acetone gives (A) mesityl oxide (C) mesitylene

(B) phorone (D) aldol

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Match the Following 76.

Match the following: X 1. Decarboxylation 2. Hell-Volhard Zelinsky reaction 3. Grignard reagents 4. Electrolysis 5.

77.

79.

3. 4. 5.

Y LiAlH4 Aq. sodium ethanoate Sodalime Br2 in presence of red P Dry ice (solid CO2)

1. 2.

Z α-bromoacids Carboxylic acids

3. 4.

Ethane Alcohols

5.

Removal of CO2

Match the statements given in Column A with Column B. Column A Column B 1. Methanal disproportionates in the presence (a) Benzoin condensation of conc. Alkali KCN 2. C6H5CHO  (b) Acetaldehyde → C 6H5CH(OH)COC 6H5 3. 4.

78.

Reduction of aldehydes and ketones with

1. 2.

Aldehyde which gives iodoform test N2H4 /(CH3 )3 CO− K +

(CH3 )2 CO →(CH3 ) 2 CH2

Match the following Column A and Column B Column A 1. Williamson’s synthesis 2. Zeisel method 3.

Oxonium salts

4.

Phenetole

Match the following Column A and Column B Column A 1. Tollen’s reagent 2. CH3COCH3 3. HCHO 4. HCHO + NH3

(c) Wolf-Kishner reduction (d) Cannizzaro’s reaction

Column B (a) Estimation of alkoxy groups (b) Reaction of phenol with diethyl sulphate in presence of NaOH (c) Involves heating of an alkyl halide with sodium alkoxide (d) Combination of ethers with inorganic acid

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

Column B 50% NaOH solution Hexamethylenetetramine Oxidising agent Ba(OH)2

Comprehension −1 In a polyhydric alcohol, the total numbers of hydroxyl groups are estimated by the following methods: (i) A known mass of the acetyl derivative of polyhydric alcohol is taken. It is mixed with an excess volume of a standard alkali solution. Both are refluxed. Alkali is used in the hydrolysis of acetyl derivative. The unused alkali is measured by doing titration with a standard acid solution and total number of hydroxyl groups (n) can thus be calculated stoichiometrically. CH COCl

nKOH 3 A(OH)n   → A(OCOCH3 ) → A(OH)n + nCH3COOK polyhydric acetyl derivative alcohol

(ii)

Total number of –OH groups in vicinal position can be calculated by periodic acid or lead tetra acetate oxidation.

C

OH

C

O

C

O

HIO4  → or Pb(OCOCH3 )4

C

OH

Read the above paragraph carefully and give the answer of following questions: 80.

0.436 g of acetyl derivative of a polyhydric alcohol (molecular mass = 92) require 0.336 g KOH for hydrolysis. The total numbers of hydroxyl group(s) in the alcohol are: (A) 1 (B) 2 (C) 3 (D) 4

81.

The product formed by reaction of ethylene glycol and periodic acid (HIO4) is: (A) Acetic acid (B) Formic acid (C) Formaldehyde (D) Glyoxal

82.

A compound with molecular formula C4H10O3 is converted by the action of acetyl chloride to a compound with molecular weight 190. The original compound has: (A) One –OH group (B) Two –OH groups (C) Three –OH groups (D) No –OH group

83.

The ratio of the number of moles of lead tetra acetate required for the oxidation of 1 mole of glucose to that of 1 mole of fructose is: (A) 1 : 1 (B) 2 :1 (C) 5 : 4 (D) 4 : 5 Comprehension − 2

Aldehyde & Ketone are polar molecule. Nucleophiles attacks >C = O at carbon (positively charged) and electrophiles are attacked by oxygen. The characteristic reaction of Aldehyde & Ketone is nucleophilic addition to the carbon of carbonyl group. δ+

δ−

O

δ+

δ−

ˆˆˆ + H− Y ˆˆ ˆ ˆ Y

O H

In condensation of Aldehyde & Ketone takes place only when it consist α carbon atom consisting α − hydrogen , the reaction will takes place in presence of dilute alkali in this one Aldehyde is partially converted to its enolate anion by base. The enolate undergoes nucleophilic addition to the carbonyl group. The alkoxide formed in nucleophilic addition step then abstracts a proton from the solven to yield aldol consisting aldehydes & hydroxyl group. O H

Enolate

Base

R

O

ˆˆˆ + HO− ˆˆ ˆ ˆ R

O

O H R

+ H2 O O

O

OH H

R R

R

O

H2 O

H R

R Aldol

The reactivity of carbonyl compound for nucleophilic addition depends on inversely of +I effect.

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Read the above paragraph carefully and answer the questions given below it: 84.

Which of the following undergoes aldol condensation? H (A) (B) H

H3C

Cl

H

Cl

O

Cl O

CH3 (C)

Cl

(D)

H

CHO

O

85.

O

CH3

+ A → CH3

H3C H3C

N CH3

(A) (CH3)2 – NH (C) (CH3)3C – NH2 86.

(B) (CH3)3 – N (D) None

Which one is most reactive for addition of alcohol on carbonyl group? (A) C6H5CHO (B) HCHO CH3 (C) H3C (D) CH3.CHO

O 87.

How many aldol products can form when 2 butanone & propanal reacts in presence of dilute base: (A) 4 (B) 5 (C) 6 (D) 7 Comprehension − 3

To convert 1-bromopropane into 1-bromobutane, chemists A and B designed two paths. Chemist A: CH3Br +Na hν CH3CH2CH2Br  → CH3CH2CH2CH3  → CH3 CH2CH2CH2Br Wurtz Br 2

Step −I

Step −II

Chemist B:

CH3CH2CH2Br

Mg / Ether   → CH3CH2CH2MgBr Step −I

( i) HCHO ( ii) H3O+

 → CH3CH2CH2CH2OH Step −II

HBr  → CH3CH2CH2CH2Br Step −III

Based on these methods, answer the following questions: 88.

Better yield of CH3CH2CH2CH2Br is obtained by (A) chemist A (B) chemist B (C) equally in both (D) no prediction can be made

89.

While attempting synthesis, assistant of B read the instruction as () 3 CH3CH2CH3MgBr   → ( ii) HCHO i H O+

Then product formed would have been (A) CH3CH2CH2CH2OH (C) CH3CH2CH3 90.

(B) CH3CH2CH2OH (D) all of these

Chemist A had the problem of getting so many side products in step I beside getting nbutane. These side products are (A) CH3 CH2CH3 , CH3 CH = CH2 (B) CH3 CH2CH3 , CH3 CH = CH2 , CH3 CH3 ,CH4

(C) CH3 CH2CH3 , CH3 CH = CH2 , CH3 CH3 , CH3 ( CH2 ) 4 CH3 (D) CH3 CH3 , CH3 CH = CH2 91.

Chemist A obtained a resolvable optically inactive mixture in step II, as major product. This mixture contains: (A) 1-bromobutane and 2-bromobutane (B) d-and l -2-bromopropane (C) d-and l -3-bromopentane (D) d-and l -2-bromobutane Comprehension − 4

Alkyl halides undergo SN reactions as well as E1, E2 and ECB reactions, depending on the nature of substrate and nucleophile. Carboxylic acids can be converted into α-bromo carboxylic acids and thus it can be used as intermediate in the synthesis of so many other compounds. O

O A?

→ RCH COH RCH2 COH  Br

Based on the above intermediate, answer the following questions: 92.

93.

A used to carry out this conversion is (A) PBr3 (C) P; Br2/H2O

(B) PBr5 (D) Br2, ∆

One sub-intermediate is also formed in the above reaction: O Br O (A) (B) RC

RCH COBr

COH

Br

Br

O

(C)

(D)

No sub intermediate is formed

RCH2 COBr 94.

Conversion of a carboxylic acid into α-halo carboxylic acid is called (A) Cannizzaro reaction (B) Refromatsky reaction (C) Perkin reaction (D) Hell-Volhard-Zelinsky reaction O

95.

RCH2CHCOH Br

O RCH2 CHCOH OH

For the above conversion reagent used is (A) alcoholic NaOH (C) both of these

(B) NaOH, H+ (D) none of these

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ANSWERS TO GRAND ASSIGNMENT Subjective: Board Type Questions 1.

(i) and (iii) meso (ii) d – isomer (iv) l − isomer

2.

3.

(S)

4.

(a)

cold KMnO 4  → syn addtion H

R S

HO

H

OH

(b) Br2  → anti addtion

H

Br H R

R

H

H

Br δ −

5.

Br Br

CH3

−

    →H OH , SN slow

(cis) H

CH3

2

H

H

δ −

OH

7. 8.

(T.S)

H

HO

CH3 H (trans)

Chiral – enantiomers

H3CHC

CHCHO

H

CH2

CH

CHCHO

∆ ( −H2O )

CH3(CH=CH)3CHO In this case condensation of allylic hydrogen and not that of vinylic hydrogen takes place. CH3

11. C

(C6H5)3P = O CH3

NH2

13.

NH2 Br

Br Br2

Br

Br

() 2  ( ii) H3 PO 2 + H2 O → i NaNO + HCl; 00 C

Br

Br

OH

15. H3C

CH3

21.

22.4 ×10 −7 LN 2 at NTP

22.

Tautomerism

24.

III < I < II

True and False 25.

T

26.

T

27.

T

28.

F

29.

T

30.

T

31.

F

32.

T

Fill In the Blanks 33.

phenolphthalein, indicator

34.

2, 4, 6-tribromophenol, 4-bromophenol

35.

nitric acid

36.

moist, dry

37.

butanone

38.

C6H5CH(OCOCH3)2

39.

phthalic acid

40.

alpha hydrogen, halogen

IIT level Questions 41.

(a) There is no chiral carbon, but the molecule is chiral (an allene) (b) There is no chiral carbon and there is a plane of symmetry between two CH3 groups. Hence it is not a chiral molecule.

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42.

Cl

(a)

OD

(b)

*

*

*

* D

43.

D

H

(a)

Cl

H

CH3

There is no change in configuration (stereospecific retention) C2 H5 C2 H5

(b)

H3C

H5 C2 O

OC2H5

CH3

CH2CH2CH3 CH2CH2CH3 (inversion) (retention) A mixture is formed due to SN1 reaction (racemisation) O

44.

A:

CH2OH

B:

C

O C:

H

O

C

OH

D:

C

Cl

E : H2/Pd/BaSO4 or sulphur in quinoline. OH

45. Cl

OH Cl

A:

OH

Cl

Cl

B:

CO2Et NH2

Cl

Cl

C:

CO2H

N2 HSO4

OH

O But

E:

D: NO2

F: NO2

But

G: NO2 But

But ( one e transfer oxidation) −

46.

H

H

H

A:

B: OTs

CH3

47.

Br

H

H

CH3

Br

C: CH3

H

−

(a) In basic medium Nu attacks oxiranes at the less substituted carbon. O CH3OH

CH3O

OCH3 OH (actual product) Nu attacks here

(b) Carbocation undergoes rearrangement H2SO4

1, 2 methyl shift

-H2O

OH

-H

CH3

48. COOH A:

Br B:

COOH

CH3

CH2COOH

COOH C:

50.

D:

COOH HS NH2

At pH = 1

COOH HS NH3 O

At pH = 5

C

O

( > pKa of

HS

− COOH)

NH3 At pH = 9

( < pKa value of

− NH3 )

O C

O

S NH3

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26513942

Objective: 1.

C

2.

A

3.

A

4.

C

5.

B

6.

B

7.

D

8.

A

9.

A

10.

B

11.

B

12.

B

13.

A

14.

D

15.

D

16.

D

17.

C

18.

B

19.

A

20.

C

21.

C

22.

C

23.

D

24.

A

25.

D

26.

B

27.

A

28.

B

29.

B

30.

D

31.

B

32.

D

33.

D

34.

B

35.

B

36.

A

37.

B

38.

C

39.

B

40.

B

41.

A

42.

B

43.

A

44.

B

45.

C

46.

B

47.

A

48.

A

49.

B

50.

C

51.

C, D

52.

A, B, C

53.

A, D

54.

A, D

55.

A,B

56.

A, C, D

57.

A, B

58.

A, B, C

59.

A, B, C

60.

A, B, C

61.

A, B

62.

A, B, C

63.

A, B, D

64.

A, B, C

65.

A, B, C

66.

C, D

67.

A, B, C, D

68.

A,B,C, D

69.

A, B

70.

A, B, C

71.

A, B, C

72.

C, D

73.

B, C

74.

A, B, C

75.

A, B

76.

1–3–5, 2–4–1, 3–5–2, 4–2–3, 5–1–4

77.

1–d, 2–a, 3–b, 4–c

78.

1–c, 2–a, 3–d, 4 –b

79.

1–c, 2–d, 3–a, 4–b

80.

C

81.

C

82.

B

83.

A

84.

A

85.

C

86.

A

87.

C

88.

B

89.

C

90.

C

91.

D

92.

C

93.

B

94.

D

95.

B