BIMOLECULAR NUCLEOPHILIC REACTION (SN2)

1. For each of the compounds, state which compound is better SN2 substrate? a. 2-methyl-1-iodopropane or t-butyliodide b. Cyclohexyl bromide or 1-bromo-1-methylcyclohexane c. 2-bromobutane or isopropyl bromide d. 2,2-dimethyl-1-chlorobutane or 2-chlorobutane e. 1-iodo-2,2-dimethyl propane or isopropyl iodide. 2. Arrange the following in the increasing order of nucleophilicity:-

3. From each pair, select the stronger neucleophile. a. H2O or b. or c. d. e. 4. Chloroethane when treated with aqueous solution of sodium ethoxide ( ), diethyl ether is produced as major product. On the other hand, chloroethane when treated with sodium ethoxide in acetic acid solvent, the major product is ethyl acetate. Explain. 5. Reaction of 1-chloropropane with aqueous NaCN occurs at relatively slower rate. Addition of a small amount of NaI accelerate the reaction greatly. Justify. 6. Order the following compounds in increasing reactivity towards SN2+ reaction with aqueous NaCN?
Cl H3C Cl

a.

b.

Cl
Cl

NO2
c. d.

NO2

7. In each of the following SN2+ reaction, you must make a choice between leaving groups or neuclephilic sites.
I

HO

Cl H3C

NH3

a. I

b.

Br

H3C

CH3

Cl

+
c.
N

NO2 NO2
d.
I

+ N3-

H3C O H3C
Cl Cl

(I) EtO(II) H3O

+

+
f.
I
H3C CH3 I

HS

e.

+
g.
Br O

PEt3
h.
I

+ CNBr

+ C2H5OH

i. 8. When chloroethane is treated with aqueous solution of Ba(SCN)2, CH3CH2SCN is produced as major product. However, if Hg(SCN)2 is taken as source of neucleophile, CH3CH2NCS is formed as major product, explain. 9. When an alkyl halide reacts with the thiocyanate ion, -SCN, reaction takes place at the sulphur atom. When an alkyl halide reacts with the cyanate ion, -OCN, reaction takes place at the nitrogen atom. Draw the lewis structures for both the cyanate and thiocyanate ions and explain the difference in the reactivity of these ions. 10. Explain the formation of product in the following reaction.
O Cl
14

O HO
14

11. For each of the following pairs of SN2 reactions, indicate which occurs with larger rate constant.

CH3CH2Br + H2O
a.
Br H3C
-

CH3CH2Br + OHor
H3C CH3

+
CH3

HO

+ HO

b.

or

Br

CH3CH2Cl + CH3Oc. or

CH3CH2Cl + CH3S-

CH3Cl + Id. e.
Br NH2

CH3Br + Bror or Br
OH
NH2

KOH
or Br
OH

f.

Br

KOH

12. Each of these compounds can be synthesized by an SN2 reactions. Suggest a combination of haloalkane and nuclephile that will give each product. a. CH3OCH3

b. CH3CH2CH2PH2 f. (CH3)3NH Cl
CH3
O
+ -

c. CH3CH2CN

d. CH3SH

e. CH3SCH2C(CH3)3
O H2C

g. C6H5COOCH2C6H5

h.

CH3

i. H2C

CH2

13. Arrange the following molecules/ions according to their leaving group ability in a SN2 reactions. a. HO , H2O, H3O
+

b. NH2-, NO3-, NO2- c. F-, I-, Cl-, Br-

d. F3CCOO , F3CCH2COO , F3CCH2CH2COO

-

e. CH3CH2O-, CH3CH2-, CH3COOSO 3

-

SO 3

SO 3

SO 3
F

f. F

, MeO

14. Complete the following nucleophilic substitution reactions. In each, show all electron pairs on both the nucleophile and the leaving group.
Cl
CH3

+
a.
H3C CH3

CH3COONa
Br

Ethanol

H3C

+ CH3CH2SNa Acetone
CH3

b.
H3C C Na
+ DMSO

c. 15.

+
H Br

Write product of the following SN2 reaction showing change in stereochemistry.

H

HO

Br H HO

a.

CH3

b.

H3C

CH3 H H Br CH3 CH3

CH3 H H3C Br
NaI Acetone

CH3 H CH3

NaOH

c.

d.

+ NaOCH 3

CH3OH

e. 16.

In each pair of compounds, which compound is more nucleophilic in a polar protic solvent? a. CH3O or CH3S
-

b. (CH3)3N or (CH3)3B

17.

c. CH3Cl or CH3OH d. (CH3)3N or (CH3)3P e. SH or Cl f. CH3OCH3 or CH3SCH3 Indicate which compound in each of the following pairs would react faster? a. CH3CH2Br or CH3CH2I with NaOH in acetone b. CH3CH2Br or CH3CH2I with NaOH in ethanol. c. 1-bromopropane or 2-bromopropane with NaI in acetone d. neopentyl iodide or 1-iodo pentane with CH3OH e. CH3S- or CH3O- with CH3CH2Br in DMF f. CH3S- or CH3O- with CH3CH2Br in ethanol g. (CH3)3CO- or CH3CH2O- with CH3CH2Cl in acetone. h. CH3NH2 or CH3OH with CH3CH2Br in methanol i. CH3NH2 or CH3OH with CH3CH2Br in acetone. j. CH3COO- or CH3CH2S- with CH3I in ethanol. k. CH3COO- or CH3CH2S- with CH3I in DMSO l. HOCH2CH2CH2Br or HOCH2CH2CH2 CH2Br in presence of KOH.
CH3

CH3 H3C

Cl CH3
O
-

m.

Cl

or

with CH3S- in acetone.

n.

or

with CH3CH2CH2I in acetone.