Work Book (Phase V)

Subjective: Board Type Questions 1. Assign d, l and meso character to the following COOH (i) (ii)
H H OH OH COOH COOH
HO HO COOH H H

COOH H OH H COOH COOH

HO

(iii)

(iv)
HO H

H OH COOH

2. 3.

Write structure of (2Z, 4E) 3 ethyl 2, 4 hexadiene. Biological reduction of pyruvic acid gives (+) lactic acid, represented by Fischer projection shown. Assign R/S configuration. COOH

H3C

C O

COOH

Biological reduction

HO 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

SN

H
6.

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 C H C CH3 H and H H3C C C

8. 9.

Give the aldol condensation product of CH3CH = CHCHO. Arrange the following in increasing extent of hydration.
O O Br CHO CHO Br

10. 11.

Explain the reason for the stability of choral hydrate. 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) Outline steps of the following conversion
NH2 Br Br

13.

Br

14.

Convert (a) acetylene into n-butyl alcohol. (b) propane into 1 propanol, 2 propanol and allyl alcohol. 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 CH3

15.

Cl

CH3

Deduce the structure of the organic compound.

16. 17.

Would it be possible to form di-t-butyl ether from dehydration of t-butyl alcohol? Suggest reaction conditions for the following conversion
OH O COOH H3C O

18.

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

(c)

H N O

(d)

19.

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

OH
(c)
HO O O

HO O

(d)

20. 21.

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

O
NaOBr, 2 H2N C NH2 N2 + CO3 + Br + H2O Calculate volume of N2 gas obtained at NTP from 1mL of body fluid containing 6 g of urea.

22. 23. 24.

Barbituric acid is formed when diethyl malonate reacts with urea. What is the type of isomerism shown by it? Convert CH3COOH into (CH3)2NH. Arrange the following in increasing basic nature.
N N H Piperidine (I) N Pyridine (II) Imidazole (III) N

True and False

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25. 26.

Tertiary alcohols are more reactive towards halogen acids than secondary alcohols. 2-Pentanol or 3- pentanol on treatment with HCl gives both 2-chloropentane and 3chloropentane. Terminal Gem-dihalides on hydrolysis yield aldehydes. m-Chlorobromobenzene is an isomer of m-bromochlorobenzene. Aldehydes react with alcohols in presence of dry HCl gas to form acetals. Aldehyde group is m-directing and deactivates the benzene ring towards further electrophilic substitution reactions. Bromination of propionic acid with bromine in presence of small amount of red phosphorus gives bromopropionic acid. Acid chlorides react with aromatic hydrocarbons in presence of anhydrous AlCl3 to form aromatic ketones.

27. 28. 29. 30.

31.

32.

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. Phenol on treatment with bromine water gives..but with bromine in CS2, it mainly gives. Chloropicrin is formed by the action of on chloroform. Alkyl halide with.Ag2O gives alcohol and Ag2O gives ether. The reaction of acetyl chloride with diethylcadmium followed by hydrolysis gives.. The structure of the intermediate product formed by the oxidation of toluene with CrO3 and acetic anhydride, whose hydrolysis gives benzaldehyde, is Oxidation of o-xylene with alkaline KMnO4 gives Hell-Volhard-Zelinsky reaction involves the replacement of an .atom from the alkyl group of a monocarboxylic acid by a atom.

34.

35. 36. 37. 38. 39. 40.

IIT Level Question 41. Comment on the chirality of the following molecules H H (a) (b) H

CH3 C C CH3

C Cl

C Cl Cl

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 D3O

43.

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

OH SOCl 2

CH3

(b)
H3C

CH2CH3 CH3CH2OH SN1

Br CH2CH2CH3

44.

Identify A to E in the following

O B DIBAH H2O C OCH3 LiAlH 4 H2 O A KMnO4 H C PCl5 E

45.

Identify products in the following reaction OH (a)

() SO2 Cl2 A B C C6 H5 NMe2 ( ii) HCl
i KOH

CO 2 Et

(b)

NO2

NH4HS H2 O D E F NaNO , H SO , 00 C
2 2 4

NO2

(c)
Bu

OH Bu
( i) PbO 2 , C6H6 G ( ii) Br2

Bu

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46.

Identify A, B and C.
H H TsCl Pyridine CH3 OH A NaBr B

PBr 3

Identify A, B and C. 47. What is wrong in these reactions? O (a) H C

3

CH3O H3C
(b)

CH3OH OCH3 H2SO 4

OH

OH
48. Identify the products (a)
KMnO 4 Conc.H O + A ,
3

(b)

CH2
Hbr Mg Ether B C CO2 H3 O
+

HBr, peroxide D Mg Ether CO2 H3O

49.

Explain the difference in the following observation

5 N NaOH CHCH OH di. NaOH CH CHCHCH3 OH CHCH3

CHCH O CR O

CHCH3

50.

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 1.

COOH H HO OH

Configuration at C1 and C2 atoms are:

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

2.
H CH3 CH3 H

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

CH3 (A)

H (B)

CH3

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

(B) chiral enantiomers (D) racemic mixture

CH3 H HO CH3 OH H and HO HO CH3 CH3 H H

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

and

HO H CH3
CH3

H OH

(C)

(D)
OH OH
HO H

CH3 OH H CH3 and HO HO

CH3 H H CH3

4.

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

5.

COOH

H 5 C2

COOH

(C)

(D)

COOH

COOH

COOH

6.

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.

HOOC

(B) 5 (D) 3

OH O 2N 2 moles NaNH2 C OH CH A

The product A will be OOC (A)

(B)

OOC

OH O 2N

OH O 2N

C O

CH

C OH

(C)

HOOC

(D)

HOOC

O O 2N

OH O 2N

C O

CH

C O

9.
H3C CH OH CH3
Mg / ether (X)

PBr3

(Y)

H 2O

The final product is (A)

(B)

OH
(C)

(D)

O None of the above

10. 11.

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

OH

(I)

CH3 (II)

NO2 (III)

(A) I > II > III (C) II > III > I 12.

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

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 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 The reaction of with RMgX leads to the formation of

13.

14.

O
(A) RCHOHR (C) R2CHCH2OH 15. In the following compounds
NO2

(B) RCHOHCH3 (D) RCH2CH2OH

OH (I)

H3C (II)

OH (III)

OH O 2N (IV)

OH

The order of acidity is (A) III > IV > I > II (C) II > I > III > IV 16.

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

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 In the reaction of phenol with CHCl3 and aqueous NaOH at 70C (343K ), the electrophile attacking the ring is (A) CHCl3 (B) CHCl2 (C) :CCl2 (D) COCl2 The compound which gives most stable carbonium ion on dehydration is (A) (B )

17.

18.

OH
(C)

OH
(D)
OH

OH

19.

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 C CH2 X Me Me CH CH2 OH

Me

Me

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

O CH2OH NaBH4 A

(B) NaBH4 (D) NaH

A is

C O

CH3

(A)

HO

CH2OH

(B)

CH2OH

CH2OH

CH2OH

(C)

HO

CH2OH

(D)

HO

CH2OH

C O O CH2

CH2OH

22.
H3C

CH3 CH3 C OH C CH3 H P

P is

(A)
H3C

OH CH3 CH3 C C CH3

(B)
H3C

CH3 CH3 C C CH3

(C)
H3C

CH3 O C CH3 C CH3

(D)
H3C

O CH3 H

CH3

CH3 OH

23.

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

24.
H3C

CH3 C O CH2

18 H2O

A is

(A)
OH HO18

(B)
18

OH

HO

(C)
OH HO

(D)

18

OH HO
18

25.

Which one is not cyclic ether? O (A)

(B)

O
(C) (D)
O

O
26.
O H

A is (A)

OH

(B)

CH2OH

CH3 OH
OH

CH3

(C)

CH2OH

(D)

CH3

CH3

CH3

OH

27.
Oxalic acid A

O O

O O

conc. H2 SO4 Hence, A B; B is

(A)

(B)

O O

(C)
OH

O O

CH2 OH

(D)

None

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28.
CH3 CH3OH H2SO4 [B]

O CH3OH CH3O [A]

A and B are (A)

H OH3C CH3 OH and H HO OCH3 CH3

(B)
H H3CO CH3 OH
CH3 H H3CO OH

and

H HO
H H3CO

OCH3 CH3

(C)

OCH3 H3C H OH

(D)
and H H3CO OH CH3

and

CH3 OH

29.

O
HgSO 4 / H2SO 4

CH

(A)

(B)
C O CH3

CH2CHO

(C)

(D)
COOH

OH

CH2CHO

30.

What are A, B and C in the following?

O B Raney Ni, H 2 Pt, 1 mol H 2 A

NaBH4, CH 3OH

(A) (b)

C O
in all cases

OH in all cases

(C)

OH in all cases

(D)
A:

O B:

OH C:

OH

31.

COCH3 CH3

1. KBrO, 2. H + 3.

A is (A)

(B)
COOH CH3

CH3

(C)

COOH

(D)

COOH

OH

CH3 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 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 (B) formaldehyde oxime (D) acetoxime

33.

34.

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 Which of the following reagents convert C6H5COCHO to C6H5CHOHCOOH? (A) aq. NaOH (B) Acidic Na2SO3 (C) Na2CrO4/H2SO4 (D) NaNO2/HCl The enol form of acetone, after treatment with D2O, gives C CH2 O (A) H3C (B)

36.

37.

(C)

H2C

OD C OH

D3 C CH2D
(D)

C OD C

CD3

D2 C

CD3

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38.

Reduction of
C O to CH2

can be carried out with

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

3 +

(B) Na/C2H5OH (D) LiAlH4

Identify the compounds A and B in the following reaction sequence

H O NaCN ( CH3 ) 2 C = O A B HCl Heat (A) A = CH3 COOH B = ( CH3CO ) 2 O (B) A = ( CH3 ) 2 C ( OH) CN B = ( CH3 ) 2 C ( OH) COOH

(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 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
CHO OHC

41.

42.

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

CHO OHC

Major product is (A)

HOOC COOH

(B)

OH HOOC

COOH HOOC

COOH

(C)

O O

(D)

HO OH HO

O O

OH HO

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)

H3 C

NCONHNH2

(D)

CH3 H2CH3CHC

HCONHNH2

44.

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
(C)

OH OH
(D)

O OH

46.

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

OH (I) (II)

H (III)

OH

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

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

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

H3 C CH3 is

(A)

O HN H3 C CH3

(B)
H3 C

O HN CH3

Br

Br
(C)
H3 C O HN CH3

(D)

O HN 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.

CH3COOOH P. P is

(A)

(B)

O O

(C)

(D)

HO

OH

50.

X and Y in the following reaction sequence are:O

P2 O5 X R

Br2 NH2 Y OH

(A) R CN, RCH2NH2 (C) RCN, RNH2 51.

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

Multiple choice questions with more than one option correct 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 Tollens solution 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
O CH 2CH CH2

52.

53.

Product is (A)

OH

(B)

OR

(C)

CH2CH OH

CH2

CH2 CH

* CH2

(D)

OH

CH2

CH

CH2

* H2 C

CH

CH2

54.

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

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

CH3

(B) 1.5 mol (D) 480 g

Which of the product expected in the following reaction?

Cl
NaNH2 NH
3

(A)

CH3 NH2

(B)

CH3

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 H + NaBr 5

(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

+ fumin g H2SO4
(D) None of these

(C)

+ 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)

UV light

H3C
(C)

CH

CH OH

CH3

H3CHC OH

CH3

(D)

CH3 H3C C CH3 OH

59.

Treatment of n-propylamine with nitrous acid gives (A) CH3CH=CH2 (B) CH3 2CH2OH CH CH CH3 (C) H3C (D) none of these

60.

OH Which of the following statements are correct?

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(A) (B) (C) (D) 61.

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

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 The product obtained in the equation:

62.

CH3 NO2 + Cl2 + NaOH

is (A) ClCH2NO2 (C) Cl3CNO2 63. Phenyl cyanide can be obtained by
2 5 (A) C6H5 CONH2

(B) Cl2CHNO2 (D) CH3NH2

PO ,
2 (B) C6H5 CH = NOH 2 (D) C6H5NH2 2. CuCN

Ac O,

(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

Alc. KOH

1. NaNO / HCl

H3C CHOH +NH3

H3C (D) none of these

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

Phenol H3C

H CH2
+

H (B) Phenol + ( CH3 ) 3 COH AlCl

3 (C) Phenol + ( CH3 ) 3 CCl

(D) None of these 66. Which of the following statements are correct? (A) Benzaldehyde reduces Fehlings solution (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. 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?
NaOH

68.

Hg (A) CH CH + HCl

2+

(B)

H2C

CH2 Cl2 H2C

Cl
6000 C

NaOH CH2

Cl

(C) CH2 = CH2 + Cl2

(D) ClCH2 CH2Cl ethanol

69. Vinyl chloride undergoes (A) addition reactions (C) substitution reactions (B) elimination reactions (D) none of these

KOH

70.

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

(A) CH 3 CHCl2 + alc. KOH (B) ClCH2CH2Cl + alc. KOH

3 (C) ClCH 2CH2Cl + NaNH2

liq. NH

(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 Alkyl iodides can be prepared by
4 (A) RCH2COOAg + I2 RCH2I

73.

CCl

(B) RCH2Cl + NaI RCH2I + NaCl (C) R OH + HI RI + H2O (D) CH4 + I2 CH3I
74. The reaction of glycerol with HIO4 gives (A) formaldehyde (C) iodic acid On being treated with HCl, acetone gives (A) mesityl oxide (C) mesitylene (B) formic acid (D) oxalic acid (B) phorone (D) aldol

acetone

75.

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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. Reduction of aldehydes and ketones with Y LiAlH4 Aq. sodium ethanoate Sodalime Br2 in presence of red P Dry ice (solid CO2) Z -bromoacids Carboxylic acids Ethane Alcohols Removal of CO2

1. 2. 3. 4. 5.

1. 2. 3. 4. 5.

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 C 6H5CH(OH)COC 6H5 (b) Acetaldehyde 3. 4. Aldehyde which gives iodoform test (CH3 )2 CO (CH3 ) 2 CH2
N2H4 /(CH3 )3 CO K +

(c) Wolf-Kishner reduction (d) Cannizzaros reaction

78.

Match the following Column A and Column B Column A 1. Williamsons synthesis 2. Zeisel method 3. 4. Oxonium salts Phenetole

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

79.

Match the following Column A and Column B Column A 1. Tollens reagent 2. CH3COCH3 3. HCHO 4. HCHO + NH3 Comprehension 1

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

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

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.
nKOH 3 A(OH)n A(OCOCH3 ) A(OH)n + nCH3COOK polyhydric acetyl derivative alcohol CH COCl

(ii)

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

OH
HIO4 or Pb(OCOCH3 )4

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

81.

82.

83.

+ H Y Y

O H

In condensation of Aldehyde & Ketone takes place only when it consist carbon atom consisting 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 R
O H R O R R R

+ HO R
Base Enolate

O
O

+ H2 O
O H H2 O R R Aldol OH O H

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

Cl Cl

H3C CH3
(C)

O H O
(D)

Cl Cl

CHO

85.

CH3

+ A
CH3 H3C H3C
(A) (CH3)2 NH (C) (CH3)3C NH2 86.

N CH3
(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 h CH3CH2CH2Br CH3CH2CH2CH3 CH3 CH2CH2CH2Br Wurtz Br Step I Step II
2

Chemist B:

CH3CH2CH2Br

Mg / Ether CH3CH2CH2MgBr Step I

CH3CH2CH2CH2OH Step II

( i) HCHO ( ii) H3O+

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

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 -bromo carboxylic acids and thus it can be used as intermediate in the synthesis of so many other compounds.
O
A?

RCH2 COH RCH COH

Br

Based on the above intermediate, answer the following questions: 92. A used to carry out this conversion is (A) PBr3 (C) P; Br2/H2O (B) PBr5 (D) Br2,

93.

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

RC Br COH
RCH COBr Br

(C)

O RCH2 COBr

(D)

No sub intermediate is formed

94.

Conversion of a carboxylic acid into -halo carboxylic acid is called (A) Cannizzaro reaction (B) Refromatsky reaction (C) Perkin reaction (D) Hell-Volhard-Zelinsky reaction
O RCH2CHCOH Br O RCH2 CHCOH OH

95.

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. 2. (i) and (iii) meso (ii) d isomer (iv) l isomer

3. 4.

(S) (a)
cold KMnO 4 syn addtion
H H
Br2 anti addtion

R S OH

HO

(b)
Br H R R Br
Br Br CH3 (cis) H H H

5.
OH , SN slow
2

CH3 H H CH3 H (trans)

HO

OH

(T.S)

7. 8.

Chiral enantiomers

H3CHC

CHCHO

CH2

CH

CHCHO

( H2O )

CH3(CH=CH)3CHO In this case condensation of allylic hydrogen and not that of vinylic hydrogen takes place.
11. C CH3 CH3 (C6H5)3P = O

13.

NH2 Br Br2

NH2 Br i NaNO + HCl; 00 C Br Br

() 2 ( ii) H3 PO 2 + H2 O
Br Br

15.
H3C

OH CH3

21. 22. 24.

22.4 10 7 LN 2 at NTP

Tautomerism III < I < II

True and False 25. 27. 29. 31. T T T F 26. 28. 30. 32. T F T T

Fill In the Blanks 33. 34. 35. 36. 37. 38. 39. 40. phenolphthalein, indicator 2, 4, 6-tribromophenol, 4-bromophenol nitric acid moist, dry butanone C6H5CH(OCOCH3)2 phthalic acid 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 3 CH groups. Hence it is not a chiral molecule.

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42.

(a)
* *

Cl

(b)
* *

OD

43.

(a)

H Cl

CH3

(b)

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

H3C

OC2H5

H5 C2 O

CH3

CH2CH2CH3 CH2CH2CH3 (inversion) (retention) A mixture is formed due to SN1 reaction (racemisation)
44.

O A: CH2OH O C: C OH D: B: O C Cl C H

E : H2/Pd/BaSO4 or sulphur in quinoline. 45.

Cl A: OH Cl Cl B: OH Cl Cl C: OH Cl

CO2Et NH2

CO2H

N2 HSO4

OH But

O But

D: NO2

E: NO2

F: NO2

G:

But ( one e transfer oxidation)

t Bu

46.
A:

H B:

Br C:

CH3

OTs

CH3

CH3

Br

47.

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

O CH3O CH3OH OCH3 OH (actual product) Nu attacks here

(b) Carbocation undergoes rearrangement

H2SO4 OH -H2O -H 1, 2 methyl shift

48.
COOH A: COOH B:

CH3 Br

CH3 COOH C: D:

CH2COOH

50.

COOH HS NH2 COOH HS NH3 O At pH = 5 HS NH3 At pH = 9 C O

At pH = 1

( > pKa of

COOH )

O C S NH3 O

( < pKa value of

NH3 )

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Objective: 1. 5. 9. 13. 17. 21. 25. 29. 33. 37. 41. 45. 49. 53. 57. 61. 65. 69. 73. 76. 77. 78. 79. 80. 84. 88. 92. C B A A C C D B D B A C B A, D A, B A, B A, B, C A, B B, C 2. 6. 10. 14. 18. 22. 26. 30. 34. 38. 42. 46. 50. 54. 58. 62. 66. 70. 74. A B B D B C B D B C B B C A, D A, B, C A, B, C C, D A, B, C A, B, C 3. 7. 11. 15. 19. 23. 27. 31. 35. 39. 43. 47. 51. 55. 59. 63. 67. 71. 75. A D B D A D A B B B A A C, D A,B A, B, C A, B, D A, B, C, D A, B, C A, B 4. 8. 12. 16. 20. 24. 28. 32. 36. 40. 44. 48. 52. 56. 60. 64. 68. 72. C A B D C A B D A B B A A, B, C A, C, D A, B, C A, B, C A,B,C, D C, D

135, 241, 352, 423, 514 1d, 2a, 3b, 4c 1c, 2a, 3d, 4 b 1c, 2d, 3a, 4b C A B C 81. 85. 89. 93. C C C B 82. 86. 90. 94. B A C D 83. 87. 91. 95. A C D B