VELAMMAL VIDYALAYA ALAPAKKAM
CLASS 12
UT1 STUDY MATERIAL
DEPARTEMENT OF CHEMISTRY
HALO ALKANES AND ARENES
1. Haloalkanes (Alkyl halides) are halogen derivatives of alkanes with general
formula [CnH2n + 1X]. (X = F, Cl, Br or I)
2. Haloarenes (Aryl halides) are halogen derivatives of arenes with general formula
Ar – X.
3. Since halogen is more electronegative than C, hence C – X bond is polar.
4. Nameing Reactions :
(a) Sandmeyer Reaction :
(b) Finkelstein Reaction : R X NaI
R
I NaX
(c) Swartz Reaction :
CH3 – Br + AgF CH3 – F + AgBr X Cl, Br
Instead of Ag – F, other metallic fluoride like Hg2F2, CoF2 or SbF3 can also be used.
(d) Wurtz Reaction :
d ry e ther
2R X 2Na R R 2NaX
(e) Wurtz-Fittig Reaction :
(f) Fittig Reaction :
5. Nucleophilic Substitution Reactions :
– |+ – –
Nu + – C – X C – Nu + X
|
haloalkane
(a) Substitution nucleophilic bimolecular (S 2) :
N
1. 1º haloalkane
2. Bimolecular, 2nd order
3. One step
Order of reactivity : 1º > 2º > 3º
Deciding factor : Steric hindrance
(a) Substitution nucleophilic unimolecular (SN1) :
slow CH3 –
(CH3)3 – C – Br + OH
step C (CH3)3 – C – OH
(Nucleophile)
1
(r.d.s) CH3 CH3 Recemization
(Fast) configuration 50%
Planar
carbo relation (Racemic mixture
cation is formed) & 50% inversion
1. 3º haloalkane
2. Unimolecular, 1st order
3. Two steps
Order of reactivity : 3º > 2º > 1º
Decidingfactor : Stability of carbo cation
CH CH
* Allylic 2 C H2 and benzylic C6 H5 CH 2 halides undergo
reaction via SN1 mechanism as the corresponding
carbo cations are resonance stabilized.
6. Aryl halides are much less reactive towards nucleophilic substitution reactions
than haloalkanes.
7. Halogen is deactivating but o, p-directing in electrophilic substitution reaction of
haloarenes.
8. CHCl3 is stored in dark bottles upto brim so that formation of poisonous gas
phosgene in presence of air and light can be avoided.
l ight
2CHCl3 + O2 2COCl
2 + 2HCl
Chloroform Carbonyl chloride (phosgene)
9. Reaction of Haloalkanes :
NaOH
R–OH
or KOH
NaI
R–I
KCN
RCN
AgCN
RNC R–O–
KNO2
N=O
AgNO2
R–NO2
R–X LAH
RH
NH3
R–NH2 R–
Mg
MgX R–R
Na, D.E.
R–O–R'
NaOR
R'COOR
R'COOAg
10. Electrophilic Substitution Reaction of Haloarenes :
Sulphonation
11. Elimination reaction: Two groups or atoms attached to two adjacent carbon
atom and simultaneous formation of multiple bonds between these carbon atom.
[Reverse of addition]
Two types (i) -Elimination E1 Two step
(ii) -elimination E2 eliminate One step
eliminate
Saytzaff's Rule
H H
| |
–
OH +H—C—C—H CH2 = CH2 + KBr + H2
| |
H Br
CH – CH – CH – CH
[Link] CH = CH + KBr + H
3 2 3 2 2 2
|
Br
81% More highly substituted Alkenes,
More stable
12. Distinguishing test for alkyl chlorides, bromides and iodide : Alkyl chlorides
react with AgNO3 to give white precipitate which is soluble in alcoholic
ammonium hydroxide. Alkyl bromides react with AgNO3 to give a yellow
precipitate which is sparingly soluble in alcoholic ammonium hydroxide. Alkyl
iodides react with AgNO3 to give dirty yellow precipitate, which is insoluble in
alcoholic ammonium hydroxide.
E.g., CH3
– Cl HNO
AgNO
3 AgCl
3
White ppt.
Vinyl and aryl halides do not yield silver halide under these conditions.
MULTIPLE CHOICE QUESTIONS
1. Arrange the following compounds in increasing order of rate of reaction
towards nucleophilic substitution:
Cl Cl Cl
NO2
(a) (b) (c)
NO2
(a) a < b < c (b) a < b < a
(c) a < c < b (d) c < a < b
2. Arrange the following compound in increasing order of rate of reaction
towards nucleophilic substitution.
Cl Cl Cl
(i) CH3 NO2 NO2
(ii) (iii)
(a) i < ii < iii (b) i < iii < (c) ii < i < iii
ii
NO2
3. Which of the carbon atom present in the molecule given below are asymmetric.
OH H
HO 1
2 3 4 O
C C C C
H
O H OH
(a) 1, 2 , 3, 4 (b) 2, 3
(c) 1, 4 (d) 1, 2, 3
4. Which of the following compound will undergo recevisation when solution
of KOH hydrolyses?
CH2—Cl
(i) (ii) CH3CH2—CH2—Cl
CH3 CH3
(iii) C6H5—CH—CH2—Cl (iv) C Cl
H C2H5
(a) i and iv (b) ii and iv
(c) iii and iv (d) iv
5. In a SNl reaction on chiral centres, there is
(a) 100 % retention (b) 100 % inversion
(c) 100 % recenisation
(d) inversion is more than retention leading to recenisation
6. The reaction of C6H5—CH==CH—CH3 with HBr produces
CH CH—CH3
(a) C6H5—CH2 CH2—CH2—Br (b)
Br
Br Br
(c) C6H5—CH—CH2—CH3 (d) C6H5—CH2—CH2—CH3
7. In SN2 reactions, the correct order of reactivity fo the following compounds:
(i) CH3Cl (ii) (CH3)3CCl
(iii) (CH3)2CHCl (iv) CH3CH2—Cl
(a) i > ii > iii > iv (b) iv > iii > ii > i
(c) i > iv > iii > ii (d) iv > i > ii > iii
8. The increasing order of reactivity of the following halides for the SN l reaction
is
(i) CH3—CH—CH2—CH3 (ii) CH3—CH2—CH2—Cl
Cl
(iii) P—H3CO—C6H4—CH2—Cl
(a) iii < ii < i (b) ii < i < iii
(c) i < iii < ii (d) ii < iii < i
9. Arrange the following compounds in increasing order of their boiling point
(i) (CH3)2CH2CH2—Br (ii) CH3—(CH 2 ) Br (iii) (CH3)3C—Br
—3
(a) ii < i < iii (b) i < ii < iii
(c) iii < i < ii (d) iii < ii < i
10. Toluene reacts with halogen in thepresence of FeCl3 giving ortho and
parabola compound. The reactions is
(a) electrophilic elimination reaction (b) electrophilic substitution
(c) free radical addition reaction (d) nucleophilic substitution
11. The order of reactivity of following alcohols with halogen acid (HX) is
(i) CH3—CH2—CH2—OH
CH3
(ii) CH3—CH2—CH—OH
CH3
(iii) C6H5—CH2—CH2—OH
CH3
(a) i > ii > iii (b) iii > ii > i
(c) ii > i > iii (d) i > iii > ii
12. In the reaction
NH2
NaNO/HCl D CaCN/KCN
E + N2
0–5° C
CH3
the product is:
CN
(a) (b)
CH3
CH3
COOH
(c) (d) CH3 CH3
CH3
13. Chlorobenzene is formed by reactionj of chlorine with benzene in presence
of AlCl3. Which of the following species attacks the beneze ring in this
reaction.
(a) Cl– (b) Cl+
(c) AlCl3 (d) AlCl4–
14. H3C—CH—CH CH2 + HBr A
CH3
Br Br
(a) H3C—CH—CH2—CH3 (b) H3C—CH—CH—CH3
CH3 Br CH3
Br Br
(c) H3C—CH—CH—CH3 (d) CH3—CH—CH2—CH2—Br
CH3 Br
CH3
15. The reaction of toluene with Cl2 in the presence of FeCl3 gives ‘X’ and the
reaction with Cl2 in presence of light gives ‘Y’. Thus ‘X’ and ‘Y’ are:
(a) ‘X’ = benzyl chloride and ‘Y’ = m-chlorotoluene
(b) ‘X’ = benzyl chloride and ‘Y’ = o-chlorotoluene
(c) ‘X’ = m-chlorotoluene and ‘Y’ = p-cholorotoluene
(d) ‘X’ = p-chlorotoluene and ‘Y’ = benzyl chloride.
16. Anyl halides are less reactive toward nucleophilic substitution reaction than
alkyl halides due to
(a) the formation of stable carbonimion
(b) resonance stabilization
(c) longer carbon-halogen bond
(d) sp2 hybridised carbon attached to halogen
17. A new carbon carbon bond is possible in the following reaction reactions:
anhy. AlCl
(a) C6H6 + CH3Cl 3
(b) CH3CH2Br + CH3CH2NH2
(c) CH3—Br + CH3CH2—ONa
(d) CH3CH2—Br + kCN(alc)
18. Which of the following state are correct
(a) Benzyl halides are more reactive than vinyl and anyl halides
(b) Vinyl/halides are more reactive than alkyl halides
(c) Aryl halides are less reactive than alkylhalide
(d) Aryl halides are more reactive than benzyl halides
19. Which of the following contain sp2 hybridised carbon bonded to X?
CH2X
(a) X
(b)
X
(c) (d) H3C Cl
20. The IUPAC name of the following compound are H3C Cl
(a) 1-chloro-4-methyl benzene (b) 4-chlorotoluene
(c) 1-methyl-4-chlorobenzene (d) 4-methylchlorobenzene
Note : In the following questions a statement of assertion followed by a statement of
reason is given. Choose the correct answer out of the following choice.
(a) Both assertion and reason are Correct, and reason is the correct explanation
of the assertion.
(b) Both assertion and reason are True, but reason is not the correct explanation
of the assertion.
(c) Assertion is Incorrect, but reason is Correct.
(d) Both assertion and reason are Incorrect.
Assertion and Reasoning
21. Assertion : SN2 reaction proceeds with inversion of configuration.
Reason : SN2 reactionoccurs in one step
22. Assertion : Treatment of chloroethane with saturated solution of AgCN give
ethyl isocyanide as major product.
Reason : Cyanide ion (CN–) is an ambident nucleophile.
Matching Column Type
23. Match the items of column 1 and column 2
Column1 Column 2
(A) CH2Cl2 P. Antiseptic
(B) CCl4 Q. Insecticide
(C) (p-Cl C6H4)CHCCl3 R. Pyrene
(D) CHI3 S. Refrigerend
(a) A–R, B–Q, C–S, D–P (b) A–S, B–R, C–Q, D–P
(c) A–Q, B–P, C–S, D–R (d) A–P, B–S, C–R, D–Q
24. Match the items of column 1 and column 2
(A) CH3—CH—CH3 P. Anyl halide
X
(B) CH2=CH—CH2—X Q. Alkyl halide
(C) X R. Vinyl halide
(D) CH2=CH—X S. Allyl halide
(a) A–P, B–Q, C–S, D–P (b) A–S, B–R, C–Q, D–P
(c) A–Q, B–P, C–S, D–R (d) A–P, B–S, C–R, D–Q
Integer Type Question
25. In how many pairs, the second compound reacts faster than the first in SN1
reaction with OH–?
Cl
, Cl
(i) (ii) CH I, CH Br
3 3
Cl Cl
(iii) (CH3)3CBr, (CH3)2HBr (iv) ,
(v) CH3Cl, (CH3)2CHCl (vi) (CH2)2CHBr, CH3CH2Br
0 1 2 3 4 5 6 7 8 9
ANSWERS
1. (c) 2. (a) 3. (b) 4. (d) 5. (d) 6. (c) 7. (c) 8. (b) 9. (c) 10. (b)
11. (b) 12. (a) 13. (b) 14. (a) 15. (d)
16. (b, d) 17. (a, d) 18. (a, c) 19. (b, d) 20. (a, b)
21. (b) 22. (b) 23. (b) 24. (b)
CONCEPTUAL QUESTIONS
Q.1. Why haloalkanes are more reactive than haloarenes?
Ans. In haloarenes, there is partial double bond character b/w carbon and halogen due
to resonance effect which makes him less reactive.
(ii) In benzene, carbon being sp2 hybridised which is smaller in size than sp3
present in haloalkanes. So C–Cl bond in aryl halides is shorter and stronger.
Q.2. Why do haloalkenes under go nucleophillic substitution whereas haloarenes
under go electophillic substitution?
Ans. Due to more electro negative nature of halide atom in haloalkanes
carbon atom becomes slightly positive and is easily attacked by nucleophillic
reagents.
While in haloarenes due to resonance, carbon atom becomes slightly negative and attacked by
electrophillic reagents
Q.3. When an alkyl halide is treated with ethanolic solution of KCN, the major
product is alkyl cyanide where as if alkyl halide is treated with AgCN,the major
product is alkyl isocyanide?
Ans. Refer NCERT
Q.4 The treatment of alkyl chlorides with aqueous KOH lead to the formation of
alcohols but in presence of alcoholic KOH alkenes are major products. Explain?
Ans. In aqueous KOH,OH– is nucleophile which replaces another nucleophile.
R-X + KOH R-OH + KX
Where as in alcoholic KOH, C H O– ion is produced which is a strong base hence
2 5
-elimination took place to form alkane
C H OH + KOH C H O- + K+
2 5 2 5
CH CH -Cl + alcoholic KOH CH = CH + C H OH
3 2 2 2 2 5
Q.5 Explain why vinyl chloride is unreactive in nucleophillic substitution reaction?
Ans. Vinyl chloride is unreactive in nucleophillic substitution reaction because of
double bond character between C–Cl bond which is difficult to break.
+
H2C = C H2C—CH = Cl
|
:Cl:
Q.6 Arrange the following compounds according to reactivity towards nucleophillic
substitution reaction with reagents mentioned :-
(i) 4-nitrochlorobenzene> 2,4 dinitrochlorobemzene > 2,4,6, trinitrochlorobenzene
with CH3ONa
Ans. 2,4,6, trinitrochlorobenzene > 2,4 dinitrochlorobemzene > 4- nitrochlorobenzene
Q.7 Why Grignard reagent should be prepared under an hydrous conditions?
Ans. Grignard reagent react with H2O to form alkanes, therefore they are prepared
under anhydrous condition.
Q.8 Why is Sulphuric acid not used during the reaction of alcohols wiht KI?
Ans. It is because HI formed will get oxidized to I2 by concentrated Sulphuric acid
which is an oxidizing agent.
Q.9 p-dichlorobenzene has highest m.p. than those of ortho and m-isomers?
Ans. p-dichlorobenzene is symmetrical, fits into crystal lattice more readily and has
higher melting point.
Q. 10. Give reasons:
(i) C–Cl bond length in chlorobenzene is shorter than C–Cl bond in CH3Cl.
(ii) The dipole moment of chlorobenzene is lower than that of cyclohexyl
chloride.
(iii) SN1 reactions are accompained by racemization in optically active alkyl
halides.
Ans. (i) In chlorobenzene, each carbon atom is sp2 hybridised/ resonating structures
/ partial donable bond character.
(ii) Due to + R effect in chlorobenzene / difference in hybridization i.e., sp2
and sp3 respectively.
(iii) Due to formation of planer carbocation.
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DEPARTEMENT OF CHEMISTRY [[Link]]
VELAMMAL VIDYALAYA ALAPAKKAM.