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Mechanism
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SN1 & SN2

Mechanism
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SN1 mechanism:
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SN2 mechanism:
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Property SN1 SN2
Name Uni molecular nucleophilic substitution Bimolecular nucleophilic substitution
reaction reaction
Steps Two Steps: 1st formation of carbocation One Step: formation of transition
& state & Removal of nucleophile in the
2nd Substitution of same step
nucleophile
Kinetics R = K [RX] R = K [RX] [Nu]
Only one reactant in the slow step i.e. 1st Two reactant in the slow step i.e. RX
step & Nu
Intermediate carbocation transition state
Re arrangement Possible (Shift or Ring Expansion) Not Possible
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Products Two products are formed (one + ive One product is formed [If reactant is
form & one – ive) both in 50 – 50% (+) then product is (–) & vice versa]
ratio i.e. Recimic mixture is formed.
Optical Activity Product (racemic Mixture) is optically Product is optically active
inactive but both forms can be
separated chemically or physically.
Geometry Retention in 50% cases & Inversion in Inversion in 100% cases
50% cases
Yield Less More
Factor Affecting Rate ∝ Stability of carbocation Rate ∝
1
Sterric Hindrance
rate
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Favoring Factor Polar Solvent (like Water) Non Polar Solvent (like non aq.
Weak Nucleophile Medium, all organic Solvents)
Strong Nucleophile
Leaving Group Good leaving group increases the rate of Good leaving group increases the rate
the reaction of the reaction
R–I > R–Br > R–Cl > R–F R–I > R–Br > R–Cl > R–F
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Reactivity of Aromatic Compounds:-
Aromatic compounds have less tendency to show nucleophilic substitution reaction this is due to
the following reasons:-
1. The Aryl carbocation does not exist.
2. Due to partial double bond character the bond between ring & atom directly attached to the ring
gains extra stability due to resonance. The resonance in chlorobenzene is shown below in Fig.
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The presence of groups, such as – NO2, – CN, – COOH etc. on the ring makes the nucleophilic
substitution easier.
This is because meta directing groups removes electron from Ortho & Para positions thus
decreases electron density from Ortho & Para position & makes C – atom of ring electron deficit
(i.e. it gains partial positive charge) thus nucleophile will get attracted towards Carbon atom of the
ring, & nucleophile donates its L.P. of electrons to the Carbon atom which in turn transfer it
electron to the halogen & halogen will be removed in the form of X– ion (i.e. the reaction will
takes place in SN2 mechanism).
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NCERT Solved
10.6 In the following pairs of halogen compounds, which would undergo SN2 reaction faster?
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10.7 Predict the order of reactivity of the following compounds in SN1 and SN2 reactions:
(i) The four isomeric bromobutanes
(ii) C6H5CH2Br, C6H5CH(C6H5)Br, C6H5CH(CH3)Br, C6H5C(CH3)(C6H5)Br
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Intext Questions
10.7 Which alkyl halide from the following pairs would you expect to react more rapidly by an
SN2 mechanism? Explain your answer.
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10.8 In the following pairs of halogen compounds, which compound undergoes faster SN1
reaction?
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Exercise
10.9 Which compound in each of the following pairs will react faster in SN2 reaction with –OH?
(i) CH3Br or CH3I
(ii) (CH3)3CCl or CH3Cl
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10.16 Arrange the compounds of each set in order of reactivity towards SN2 displacement:
(i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
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(ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 3-Bromo-2-methylbutane
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(iii) 1-Bromobutane, 1-Bromo-2,2-dimethylpropane, 1-Bromo-2-methylbutane, 1-Bromo-3-
methylbutane.
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NCERT Exemplar
17. Which of the following alkyl halides will undergo SN1 reaction most readily?
(i) (CH3)3C—F
(ii) (CH3)3C—Cl
(iii) (CH3)3C—Br
(iv) (CH3)3C—I

Ans = (iv)
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23. Reaction of C6H5CH2Br with aqueous sodium hydroxide follows ____________.
(i) SN1 mechanism
(ii) SN2 mechanism
(iii) Any of the above two depending upon the temperature of reaction
(iv) Saytzeff rule

Ans = (i)
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25. Which of the following compounds will give racemic mixture on nucleophilic substitution by
OH– ion?

(i) (a)
(ii) (a), (b), (c)
(iii) (b), (c)
(iv) (a), (c)

Ans = (i)
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Note : In the questions 26 to 29 arrange the compounds in increasing order of rate of reaction
towards nucleophilic substitution.
26.

(i) (a) < (b) < (c)

(ii) (c) < (b) < (a)
(iii) (a) < (c) < (b)
(iv) (c) < (a) < (b)

Ans = (iii)
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27.

(i) (a) < (b) < (c)

(ii) (a) < (c) < (b)
(iii) (c) < (b) < (a)
(iv) (b) < (c) < (a)
Ans = (iv)
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28.

(i) (c) < (b) < (a)

(ii) (b) < (c) < (a)
(iii) (a) < (c) < (b)
(iv) (a) < (b) < (c)
Ans = (iv)
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29.

(i) (a) < (b) < (c)

(ii) (b) < (a) < (c)
(iii) (c) < (b) < (a)
(iv) (a) < (c) < (b)
Ans = (iii)
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Consider the following reaction and answer the questions no. 32–34.

32*. Which of the statements are correct about above reaction?

(i) (a) and (e) both are nucleophiles.
(ii) In (c) carbon atom is sp3 hybridised.
(iii) In (c) carbon atom is sp2 hybridised.
(iv) (a) and (e) both are electrophiles.
Ans = (i, iii)
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33*. Which of the following statements are correct about this reaction?
(i) The given reaction follows SN2 mechanism.
(ii) (b) and (d) have opposite configuration.
(iii) (b) and (d) have same configuration.
(iv) The given reaction follows SN1 mechanism.

Ans = (i, ii)

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34*. Which of the following statements are correct about the reaction intermediate?
(i) Intermediate (c) is unstable because in this carbon is attached to 5 atoms.
(ii) Intermediate (c) is unstable because carbon atom is sp2 hybridised.
(iii) Intermediate (c) is stable because carbon atom is sp2 hybridised.
(iv) Intermediate (c) is less stable than the reactant (b).
Ans = (i, iv)
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Answer Q. No. 35 and 36 on the basis of the following reaction.

35*. Which of the following statements are correct about the mechanism of this reaction?
(i) A carbocation will be formed as an intermediate in the reaction.
(ii) OH– will attach the substrate
(b) from one side and Cl– will leave it simultaneously from other side.
(iii) An unstable intermediate will be formed in which OH– & Cl– will be attached by weak bonds.
(iv) Reaction proceeds through SN1 mechanism.
Ans = (i, iv)
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36*. Which of the following statements are correct about the kinetics of this reaction?
(i) The rate of reaction depends on the concentration of only (b).
(ii) The rate of reaction depends on concentration of both (a) and (b).
(iii) Molecularity of reaction is one.
(iv) Molecularity of reaction is two.
Ans = (i, iii)
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46. Which of the compounds will react faster in SN1 reaction with the –OH ion?
CH3—CH2—Cl or C6H5—CH2—Cl
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48. Haloarenes are less reactive than haloalkanes and haloalkenes. Explain.
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64. Which of the following compounds would undergo SN1 reaction faster and why?
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67. How do polar solvents help in the first step in SN1 mechanism?
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73. Aryl halides are extremely less reactive towards nucleophilic substitution. Predict and explain
the order of reactivity of the following compounds towards nucleophilic substitution:
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74. tert-Butylbromide reacts with aq. NaOH by SN1 mechanism while n-butylbromide reacts by
SN2 mechanism. Why?
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89. Assertion: Presence of a nitro group at ortho or para position increases the reactivity of
haloarenes towards nucleophilic substitution.
Reason: Nitro group, being an electron withdrawing group decreases the electron density over the
benzene ring.
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97. Why are aryl halides less reactive towards nucleophilic substitution reactions than alkyl
halides? How can we enhance the reactivity of aryl halides?
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alcohols
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Q. 1. Write the mechanism for preparation of ethanol from ethene. [SP 13][AI 09, 11C,
12][DB 09, 10C][F 09, 10][NCERT]
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Q. 2. Write mechanism of preparation of ethene from ethanol. [SP 09,11,15] [AI 10C, 11C, 12,
13][F 09, 10][DB 09][NCERT]
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Q. 3. Write mechanism of formation of ether from ethanol. Does this reaction follow SN1 or
SN2 pathway? [SP 09, 11][F 09, 13][DB 13][AI 08C, 11C]
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Q. 4. Why is the preparation of ether by acid dehydration of secondary alcohol not a suitable
method? [AI 08C][NCERT]
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Q. 5. Predict the major product of acid-catalysed dehydration of (i) 1-Methyl cyclohexanol and
(ii) butan-1-ol. [NCERT]
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Q. 6. The following is not an appropriate reaction for preparation of t-butyl ethyl ether
[NCERT]

(i) What would be the major product of this reaction?

(ii) Write a suitable reaction for the preparation of t- butyl ethyl ether?
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Q. 7. Write Williamson synthesis of 2-ethoy-3-methylpentane starting from ethanol & 3-
methylpentan-2-ol. [NCERT]
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Q. 8. Which of the following is an appropriate set of reactants for the preparation of l-
methoxy-4-nitrobenzene and why? [NCERT]
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Q. 9. Write the names of reagents and equations for the preparation of following ethers by the
Williamson synthesis:
(i) l-Propoxypropane (ii) Ethoxybenzene (iii) 2-Methyl-2-methoxnrropane (iii) 1-
Methoxyethane [NCERT]
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Q. 10. Illustrate with examples the limitations of Williamson synthesis for the preparation of
certain type of ethers. [NCERT]
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Q. 11. Write the mechanism of the reaction of HI with methoxymethane [SP 15][NCERT]
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Q. 12. Give the major products that are formed by heating each of the following with HI
[NCERT]
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Q. 13. Predict the products of the following reactions: [NCERT]
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Q. 14. When 3 - methylbutan-2-ol is treated with HBr, the following reaction takes place:
[NCERT]

Give a mehanim for this reaction

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Q. 15. Explain the fact that in aryl alkyl ethers (i) the alkoxy group activates the benzene ring
towards electrophilic substitution and (ii) it directs the incoming substituents to ortho – and
para – positions in benzene ring. [NCERT]
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Aldehyde Ketone
& Acid
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Cause of Nucleophilic addition reactions in carbonyl compounds

Mechanism
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Relative reactivity of carbonyl compounds.

Aldehydes are more reactive than ketones due to following two factors.

(i) Inductive effect:

𝟏 𝟏
EDG ∝ ∝
𝐌𝐚𝐠𝐧𝐢𝐭𝐮𝐝𝐞 𝐨𝐟 +𝐢𝐯𝐞 𝐜𝐡𝐚𝐫𝐠𝐞 𝐫𝐞𝐚𝐜𝐭𝐢𝐯𝐢𝐭𝐲 𝐨𝐟 𝐜𝐚𝐫𝐛𝐨𝐧𝐲𝐥 𝐜𝐨𝐦𝐩𝐨𝐮𝐧𝐝
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EWG ∝ Magnitude of +ive charge ∝ reactivity of carbonyl compound

1. NO2 CH2CHO > ClCH2CHO > CH3CHO > CH3CH2CHO

Nitroacetaldehyde Chloroacetaldehyde Acetaldehyde Propionaldehyde

2. CH3.CO.CH3 > CH3.COCH(CH3)2 > CH3.CO.C(CH3)3

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(ii) Sterric hindrance:

𝟏
Sterric Hindrance on carbonyl C atom ∝
𝐑𝐞𝐚𝐜𝐭𝐢𝐯𝐢𝐭𝐲 𝐨𝐟 𝐜𝐨𝐦𝐩𝐨𝐮𝐧𝐝
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Effect of aryl group on the reactivity of the carbonyl group

Resonance effect is more powerful then inductive effect.

Thus the aromatic aldehydes and ketones are less reactive than the aliphatic compounds
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Q. 1. Explain the mechanism of a nucleophilic attack on the carbonyl group of an

aldehyde or a ketone. [SP 11]
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Q. 2. How would you account for the following:

(i) Aldehydes are more reactive than ketones towards nucelophiles. [DB 08]
(ii) Would you expect benzaldehyde to be more reactive or less reactive in nucleophilic
addition reactions than propanal? Explain your answer. [NCERT]
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Q. 3. Arrange the following in order of their reactivity in nucleophilic addition reactions:

(i) ethanal, propanal, propanone, butanone. [DB 12][NCERT]

(ii) Benzaldehyde, p-Tolualdehyde, p- Nitrobenzaldehyde, Acetophenone. [NCERT]

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(iii) Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyltert-butyl ketone. [NCERT] [AI 12]
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Q. 4. Arrange following compounds in order of reactivity towards Nucleophilic addition

reaction
(i) CH3CHO, C6H5CHO, HCHO [AI 15]
(ii) CH3–CHO, C6H5COCH3, HCHO [AI 16]
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Amines
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Acylation of amine
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Q. . Show the mechanism of acylation of ethanamine [SP 11]
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NCERT &
NCERT Exemplar
Questions