ASTER PUBLIC SCHOOL,(GNW)

CH: 5 Haloalkane and Haloarene

LEVEL: 1
1. Write the structure of 2,4-dinitrobenzene.
2. Write the structure of 3-bromo-4-chlorobut-2-ene.
3. A hydrocarbon C5H12 gives only one monochlorination product. Identify the hydrocarbon.
4. What happens when bromine attacks CH2=CH-CH2-CCH?
5. Write the IUPAC name of the following compound:
a. (CH3)3CCH2Br
b. CH2=CHCH2Br.
c. Ph-CH=CH-CH3
6. Write a chemical reaction in which the iodide ion replaces the diazonium group in a diazonium salt.
7. Write the mechanism for the conversion of ethanol to bromoethane.
8. Draw the structure of following compound:
a. 1,4-Dibromobut-2-ene.
b. 2-(2-Chlorophenyl) -1-iodooctane.
c. 1-Bromo-4-sec-butyl-2-methylbenzene.
d. 3-(4-Chlorophenyl)-2-methylpropane.
e. 4-tert-butyl-3-iodoheptane.
9. Complete the following reactions:
a. Butene react with HBr in presence of peroxide.
b. Cyclohexanol react with SOCl2
c. 3-Phenylbutene react with HBr
d. C6H5N2Cl + KI
e. CH2=CH2 + Br2 in presence of CCl4.
10. Write the structure of an isomer of compound C4H9Br which is most reactive towards SN1 reaction.
11. Out of (CH3)2-CH-CH2-Cl and CH3-CH2-CH(CH3)-Cl, which is more reactive toward SN1 reaction
and why?
12. Which would undergo SN2 reaction faster in the following pair and why?
CH3-CH2-Br and CH3-CH2-I.
13. What happens when CH3-Br is treated with KCN?
14. What happens when ethyl chloride is treated with aq. KOH?
15. How methyl bromide be preferentially converted to methyl isocyanide?
16. Predict the order of reactivity of four isomeric bromobutane is S N1 reaction.
17. Which will react faster towards SN2 reaction, 1-Bromopentane or 2-Bromopentane and why?
18. Out of SN1 and SN2, which reaction occur with
a. Inversion of configuration
b. Racemisation.
19. Write chemical equation:
a. When chlorobenzene is treated with Chloromethane in presence of anhydrous AlCl3
b. Bromobenzene is treated with CH3Cl in presence of anhydrous AlCl3.
c. Chlorobenzene is treated with Cl2/FeCl3
d. Ethyl chloride is treated with AgNO2?
e. 2-Bromopentane is treated with alcoholic KOH?
20. Why chloroform is stored in dark brown bottles.
21. Why C-Cl bond length in chlorobenzene is shorter than that in CH3-Cl?
22. Chlorobenzene is extremely less reactive towards a nucleophilic substitution reaction. Give two
reason for the same.
23. Suggest a possible reason why neo-pentyl chloride, (CH3)3C-CH2Cl does not follow SN2 mechanism.
24. From the following compounds are given to you:
2-Bromopentane, 2-bromo-2-methylbutane, 1-bromopentane
a. Write the compound which is most reactive towards SN2 reaction.
b. Write the compound which is optically active.
c. Write the compound which is most reactive towards elimination reaction.
25. The dipole moment of chlorobenzene is lower than that of cyclohexyl chloride.
26. Convert
a. Aniline to bromobenzene
b. Chlorobenzene to 2-chloroacetophenone
c. Chloroethane to butane
27. Give reasons:
a. The presence of nitro group (-NO2) at o/p- positions increase the reactivity of haloarenes towards
nucleophilic substitution reactions.
b. Although chlorine is an electron withdrawing group, yet it is ortho, para-directing in electrophilic
aromatic substitution reactions. Why?
c. 2-Butanol is optically inactive compound.
d. Alkyl halides, though polar, are immiscible with water.
e. Haloalkaneeasily dissolve in organic solvents. Why?
f. P-dichlorobenzene has higher melting point than those of O and m- isomers.
g. Haloarenes are less reactive than haloalkanes towards nucleophilic substitution reaction.
h. The treatment of alkyl halide with aq. KOH leads to the formation of alcohol but in the presence
of alcoholic KOH, alkene is the major product.

LEVEL: 2
1. Which reagent cannot be used to prepare an alkyl halide from an alcohol?
a) HCl + ZnCl2 c) PCl5
b) NaCl d) SOCl2
2. CH3Br can be prepared by:
a) CH3COOAg + Br2+ ∆ c) Both are correct
b) CH4 + NBS d) None is correct
3. Increasing order of rate of Nucleophilic substitution is :
a) RF, RCl, RBr, RI c) RCl, RF, RBr, RI
b) RI, RBr, RCl, RF d) RF, RI, RCl, RBr
4. Which of the following can be prepared by treating C2H5Br with CH3NH2?
I. C2H5NHCH3 II. C2H5-NH-C2H5 III. (C2H5)2N-CH3
The correct choice is :
a) I c) I, III
b) I, II d) I, II, III
5. The addition of propene with HOCl proceeds via the addition of
a) H+ in the first step c) OH– in the first step
+
b) Cl in the first step d) Either H+ or OH– in first step
6. Which of the following is correct for the reaction?
CH3-CH=CH2 + HBr + Peroxide→
a) Electrophilic substitution c) Nucleophilic substitution
b) Anti-Markovnikov’s addition d) Markovnikov’s addition
7. Which of the following halogen exchange reaction will occur in acetone?
a) R I + NaCl c) R Cl + NaI
b) R F + KCl d) R F + AgBr
8. C6H5-CH3 +Br2 + anhy.AlCl3→, the reaction is called
a) Nucleophilic substitution c) Electrophilic substitution
b) Free radical addition d) Free radical substitution
9. C6H5N2+Cl- + Cu2Cl2 + HCl→, this reaction is named as
a) Sandmeyer c) Wurtz-Fittig
b) Swarts d) Finkelstein
10. Which is most reactive nucleophile in polar protic solvent?
a) F– c) Br–
–
b) Cl d) I–
11. Which cannot act as an ambident nucleophile?
a) CN– c) SCN–
b) NO2- d) OH–
12. Which of the following solvent is suitable for SN1 reaction?
a) Non-polar c) Polar aprotic
b) Polar protic d) All of these
13. For SN1 mechanism, which of the following is correct?
a) Inversion (100%) c) Non-polar solvent
b) Formation of carbocation d) Elimination
14. An SN2 reaction at an asymmetric carbon of a compound always gives
a) An enantiomer of the substrate c) A mixture of diastereomers
b) A product with opposite optical rotation d) A product with 100% inversion
15. Which one is the most reactive towards SN1 reaction?
a) Ph-CH2-Br c) Ph-CH(CH3)-Br
b) (Ph)2-CH-Br d) (Ph)2C(CH3)-Br
16. 2-Bromopentane is heated with EtO-Na+ in ethanol. The major product obtained is
a) 2-Ethoxypentane c) Isobutane
b) Pent-1-ene d) Pent-2-ene
17. The order of E2 elimination for alkyl halide is
a) 1° > 2° > 3° c) 2° > 3° > 1°
b) 3° > 2° > 1° d) 3° > 1° > 2°
18. C6H5-Cl + conc. (H2SO4 + HNO3) → A + NaOH at 443K→B; B is
a) 1,2-Dihydroxybenzene c) 1,4-Dinitrobenzene
b) 2-Chloronitrobenzene d) 4-Hydroxynitrobenzene
19. Replacement of Cl of chlorobenzene to give phenol requires drastic conditions. But chlorine of 2, 4-
dinitrochlorobenzene is readily replaced
a) -NO2 donates electron at meta position
b) -NO2 withdraws electron from ortho/para positions
c) -NO2 make ring electron rich at ortho& para
d) -NO2 withdraws electron from meta position
20. The reaction of toluene with Cl2 in presence of FeCl3 gives X and reaction in presence of light gives
Y. Thus, X and Y are
a) X = Benzyl chloride, Y = m-chlorotoluene
b) X = Benzal chloride, Y = o-chlorotoluene
c) X = m-chlorotoluene, Y = p-chlorotoluene
d) Y = o- and p-chlorotoluene, Y = Trichloromethyl benzene
21. Ethylidene chloride reacts with aq. KOH to form which of the following compound?
a) Acetaldehyde c) Ethyl alcohol
b) Ethylene glycol d) Acetic acid
22. CH3-Cl + NaI+ →CH3-I + NaCl
Above equilibrium is more towards right because
a) NaI is more reactive than NaCl
b) CH3I is more reactive than CH3Cl
c) NaCl is less soluble than NaI in acetone
d) It is Finkelstein’s reaction
23. The IUPAC name of the compound
CH3CH=CH-CH2-Br is
a) 4-Bromobut-2-ene c) 3-Bromobut-2-ene
b) 1-Bromobut-2-ene d) Allyl bromide
24. Which of the following belongs to the class of vinyl halides?
a) CH2=CH-CH(Br)-CH3 c) CH2=CH-Br
b) CH3-C(Br)=CH2 d) CH3-CH=CH-CH2-Br

LEVEL: 3

1 Consider the reaction [NEET-(Phase-2)-2016]

CH3CH2CH2Br + NaCN →CH3CH2CH2CN + NaBr
This reaction will be the fastest in
a) Ethanol c) N, N’-dimethylformamide (DMF)
b) Methanol d) Water
2. Two possible stereo-structures of CH3CHOHCOOH, which are optically active, are called
a) Enantiomers c) Diastereomers
b) Mesomers d) Atropisomers
3. In an SN1 reaction on chiral centres, there is [Re-AIPMT-2015]
a) 100% retention
b) 100% inversion
c) 100% racemisation
d) Inversion more than retention leading to partial racemization
4. In the replacement reaction
Cl + MF → CF + MI. The reaction will be most favourable if M happens to be [AIPMT (Mains)-2012]
a) Na c) Rb
b) K d) Li
5. Which one is most reactive towards SN1 reaction? [AIPMT (Prelims)-2010]
a) C6H5CH(C6H5)Br c) C6H5C(CH3)(C6H5)Br
b) C6H5CH(CH3)Br d) C6H5CH2Br
6. In the following reaction, C6H5CH2Br + Mg,Ether + H2O→X, The product X is
a) C6H5CH2OCH2C6H5 c) C6H5CH3
b) C6H5CH2OH d) C6H5CH2CH2C6H5
7. Which of the following reactions is an example of nucleophilic substitution reaction?
a) 2 RX + 2 Na → R–R + 2 NaX c) RX + Mg → RMgX
b) RX + H2→ RH + HX d) RX + KOH →ROH + KX
8. (CH3)2CH-CH=CH2 + HBr → A, The product A is
a) (CH3)2CH-CH(Br)-CH3 c) (CH3)2C(Br)-CH2-CH3
b) (CH3)2CH-CH2-CH2-Br d) CH3-CH(Br)-CH(CH3)2
9. In a SN2 substitution reaction of the type
R–Br + Cl– + DMF → R–Cl + Br–
Which one of the following has the highest relative rate? [AIPMT (Prelims)-2008]
a) CH3CH2Br c) (CH3)2CH-CH2-Br
b) CH3–CH2–CH2Br d) (CH3)3C-CH2-Br
10. If there is no rotation of plane polarized light by a compound in a specific solvent, thought to be
chiral, it may mean that [AIPMT (Prelims)-2007]
a) The compound may be a racemic mixture
b) The compound is certainly a chiral
c) The compound is certainly meso
d) There is no compound in the solvent
11. For the following
I–, Cl–, Br–, The increasing order of nucleophilicity would be [AIPMT (Prelims)-2007]
a) Br–< Cl– < I– c) Cl–< Br– < l–
b) I–< Br– < Cl– d) I–< Cl–< Br-
12. Which of the following undergoes nucleophilic substitution exclusively by SN1 mechanism?
a) Benzyl chloride c) Chlorobenzene
b) Ethyl chloride d) Isopropyl chloride
13. CD2 = CH – CH2 – Br is subjected to SN1 and SN2 reactions separately, which of the following
statement is correct?
a) Both SN1 and SN2 give two products
b) Both SN1 and SN2 give only one product
c) SN1 gives two products but SN2 gives only one product
d) SN1 gives one product but SN2 gives two products
14. In Finkelstein reaction when acetone is replaced by water then
a) Reaction occurs in forward direction via SN1 pathway
b) Reaction occurs in forward direction via SN2 pathway
c) Reaction occurs in backward because NaCl formed in right hand side is soluble in water and
cannot ppt out
d) Reaction is not possible
15. Monobromination of 2-methylbutane gives how many distinct structural isomers?
a) One c) Three
b) Two d) Four
16. Grignard reagent is prepared by the reaction between
a) Magnesium and alkane c) Zinc and alkyl halide
b) Magnesium and aromatic hydrocarbon d) Magnesium and alkyl halide
17. 2-Bromopentane is heated with potassium ethoxide in ethanol. The major product obtained is
a) Trans-pentene-2 c) 2-ethoxypentane
b) Pentene-1 d) Cis-pentene-2
18. Which of the following compounds is not chiral?
a) CH3CHDCH2Cl c) DCH2CH2CH2Cl
b) CH3CH2CHDCl d) CH3CHClCH2D
19. An organic compound A(C4H9Cl) on reaction with Na/diethyl ether gives a hydrocarbon which on
monochlorination gives only one chloro derivative then, A is
a) T-butyl chloride c) Isobutyl chloride
b) Secondary butyl chloride d) N-butyl chloride
20. Reactivity order of halides for dehydrohalogenation is
a) R – F > R – Cl > R – Br > R – I c) R – I > R – Cl > R – Br > R – F
b) R – I > R – Br > R – Cl > R – F d) R – F > R – l > R – Br > R – Cl
21. CH3-CH2-Cl + NaCN→ X +Ni / H2→Y, Y in the above reacting sequence is
a) CH3CH2CH2NHCOCH3 c) CH3CH2CH2CONHCH3
b) CH3CH2CH2NH2 d) CH3CH2CH2CONHCOCH3
22. Which of the following is least reactive in a nucleophilic substitution reaction?
a) (CH3)3C –Cl c) CH3CH2Cl
b) CH2 = CHCl d) CH2 = CHCH2Cl
23. Which of the following is not chiral?
a) 2-hydroxypropanoic acid c) 2,3-dibromopentane
b) 2-butanol d) 3-bromopentane
24. The compound A on treatment with Na gives B, and with PCl5 gives C. B and C react together to give
Diethyl ether. A, B and C are in the order
a) C2H5OH, C2H6, C2H5Cl c) C2H5Cl, C2H6, C2H5OH
b) C2H5OH, C2H5Cl, C2H5O-Na+ d) C2H5OH, C2H5O-Na+, C2H5Cl
25. Elimination reaction of 2-bromopentane to form Pent-2-ene is
A. Beta-Elimination reaction B. Follows Zaitsev rule
C. Dehydrohalogenation reaction D. Dehydration reaction
a) (A), (B), (C) c) (B), (C), (D)
b) (A), (C), (D) d) (A), (B), (D)
26. Which of the following is not chiral? (2006)
a) 2-Hydroxypropanoic acid c) 2,3-Dibromopentane
b) 2-Butanol d) 3-Bromopentane
27. Which of the following undergo nucleophilic substitution exclusively by SN1 mechanism? (2005)
a) Ethyl chloride c) Chlorobenzene
b) Isopropyl chloride d) Benzyl chloride
28. An organic compound A(C4H9Cl) on reaction with Na/diethyl ether gives a hydrocarbon which on
monochlorination gives only one chloro derivative then, A is (2001)
a) T-butyl chloride c) Iso-butyl chloride
b) S-butyl chloride d) N-butyl chloride
29. Replacement of Cl of chlorobenzene to give phenol requires drastic conditions. But chlorine of 2,4-
dinitrochlorobenzene is readily replaced because
a) NO2 donates e– at meta position c) NO2 makes ring electron rich at ortho
b) NO2 withdraws e– from ortho/para and para
positions d) NO2 withdraws e– from meta position.
30. The alkyl halide is converted into an alcohol by
a) Elimination c) Addition
b) Dehydrohalogenation d) Substitution

LEVEL: 4
Assertion and Reason based question:
(1) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is the correct
explanation of the Assertion (A).
(II) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not correct
explanation of the Assertion (A).
(III) Assertion (A) is correct, but Reason (R) is incorrect statement.
(IV) Assertion (A) is incorrect, but Reason (R) is correct statement.
(V) Assertion (A) and Reason (R) Both are incorrect.

1. A : Dow’s process is an example of nucleophilic substitution reaction.

R : In this process, benzyne is formed as an intermediate.
Sol. Answer (2)
2. A : When alkyl halide is reacted with AgCN then alkyl isocyanide is formed.
R : AgCN is a covalent compound and only the site of nitrogen is available for the reaction.
Sol. Answer (1)
3. A : In Hunsdiecker reaction, alkyl chloride is formed in poor yield.
R : In this reaction, carbanion is formed as an intermediate.
Sol. Answer (3)
4. A : Primary alkyl halides on oxidation with DMSO gives aldehydes.
R : DMSO is used as polar aprotic solvent.
Sol. Answer (2)
5. A : Haloalkanes react with KCN to give alkyl cyanide as the main product while with AgCN they form
isocyanide as the main product.
R : In KCN, K form ionic bond due to which one lone pair present on carbon, so carbon act as donor but
in
AgCN, Ag form covalent bond and carbon has no lone pair so N-atom act as donor.
Sol. Answer (1)
6. A : In benzyne the hybridisation of triply bonded carbon is sp2.
R : The second alpha-bond is formed by sp2 hybrid orbital.
Sol. Answer (1)
7. A : Halogen is deactivating group due to –I effect.
R : Halogen is ortho-para directing due to +M effect.
Sol. Answer (2)
8. A : The number of optically active isomers of tartaric acid is two.
R : Tartaric acid contains two asymmetric carbon.
Sol. Answer (2)
9. A : Chlorobenzene on reaction with sodium metal in the presence of dry ether gives diphenyl.
R : This reaction is called Ullmann reaction.
Sol. Answer (3)