M. P. I.
ALKENES XI & XII
ALKENES
1. Question : bring about the following conversions :
(1)
(2)
(3)
(4)
(5)
(6)
2. Write products
1 Me3 N MeCl Me4 N Cl Hoffmann Exhaustive methylation
2 Ph3 N MeCl No Re action due to resonance
3 Me3 P MeCl Me4 P Cl
O
(4) Ph3P + MeCl RLi Ph3P CH2
Ph3PMeCl
MeCHO
(5) Ph3P + Cl A B C
(6) PPh3 + O
O
(7) Ph3P + A B
O
(8) Ph3P + A B
1
M. P. I. ALKENES XI & XII
Heat
(9) Ph3P + O
O
(10) Ph3P + MeCl A RLi B C
Heat
CHO
(11) Ph3P +
Br A RLi B Heat C
(12) Ph3P + Br A RLi B Heat C
O
O
(13) Ph3P + MeCl A RLi B C
Heat
O
PPh3 Se
(14) + A B
PPh3 Heat
O
R'2C C O
R'N C O
(15) Ph3P CR2
R'N O
R'2C NR
Question : Write products of the following with : Ph3P CH2 , Ph3P CMe2 & Ph3P
HCHO, MECHO, EtCHO, EtCOMe, PhCHO, PhCOMe, CH 3 N C O
PhCOPh, CH 2 C O, CH 2 CH CHO, Cyclohexanone, CH 3 N O
Chemical properties of alkenes :
1. Hydrogenation reaction :
i. Catalytic or direct hydrogenation
ii. Indirect hydrogenation
2
M. P. I. ALKENES XI & XII
iii. Hydroboration reduction reaction
iv. Birch reduction reaction
2. Electrophilic addition reaction :
i. Addition of HX
ii. Adition of HBr
iii. Adition of HBr in the presence of peroxides
iv. Addition of of Br2 in CCl4
v. Addition of X2 in water
vi. Addition of HOX
vii. Addition of Br2 in brine solution
viii. Addition of ICl
ix. Addition of Cl-N=O
x. Addition of IN3
xi. Addition of CH2N2
xii. Addition of CH2I2 using zinc
xiii. Reaction with NBS it is free radical substitution reaction at allylic
position
xiv. Reaction with chlorine at high temperature (500 0C) it is free radical
substitution reaction at allylic position
3. Hydration of alkenes :
i. Hydration of alkenes using dilute acids.
ii. Hydration of alkenes by OMDM reaction.
iii. Hydration of alkenes by hydroboration oxidation reaction.
4. Dimerization of alkenes using conc. H2SO4 or conc. HF.
5. Alkylation of alkenes using conc. H2SO4 or conc. HF at 00C & a
hydrocarbon contains tertiary-H atom.
6. Addition of aldehyes of prins reaction using dil acid.
7. Oxidation of alkenes :
3. Questions : Answer the followings :
Co CO
1 CH 3 CH CH 2 CO H 2O 2
As O . A.
8
Co CO
2 CH 3 CH CH 2 CO ROH 2
As O . A.
8
Co CO
3 Ph CH CH 2 CO H 2 2
As O . A.
8
3
M. P. I. ALKENES XI & XII
Co CO
4 Ph CH CH 2 CO H 2O
AsO . A.
2 8
Co CO
5 Ph CH CH 2 CO MeOH
As O . A.
2 8
Co CO
6 CH CH CO H 2
AsO . A.
2 8
Co CO
7 CH CH CO H 2O
As O . A.
2 8
Co CO
8 CH CH CO MeOH
As O . A.
2 8
Co CO
9 Me C CH CO H 2
As O . A.
2 8
Co CO
10 Me C CH CO H 2O
As O . A.
2 8
Co CO
11 Me C CH CO MeOH
As O . A.
2 8
Co CO
12 Ph C CH CO H 2
AsO . A.
2 8
Co CO
13 Ph C CH CO H 2O
As O . A.
2 8
Co CO
14 Ph C CH CO MeOH
As O . A.
2 8
4. Question : Solve the following problems :
R H
C O O CHN
5 5 aq. alc. Na2SO3
(1) + Os A B
C R.T. Reflux
O O
R H
O O CHN
5 5 aq. alc. Na2SO3
(2) + Os A B
R.T. Reflux
O O
O O
C5H5N at R.T. A K3[Fe(CN)6]
(3) + Os B
aq. alc. Na2SO3
O O
OsO4 as a catalyst :
H 2O 2
(4) CH2 CH CHO
OsO4
H2O2
(5) CH2 CH CH3
OsO4
CH3
4
M. P. I. ALKENES XI & XII
H 2O 2
(6) OsO4
CH COOH H 2O 2
(7) OsO4
CH COOH
4. Write the product of the following reactions :
Peracid
(i)
1 eq.
Peracid
(ii)
1 eq.
CF3CO3H
(iii)
1 eq.
MCPBA
(iv)
1 eq.
MCPBA
(v)
2 eq.
(vi) MCPBA
1 eq.
MCPBA
(vii)
H 3O +
H 2O 2
(viii)
5
M. P. I. ALKENES XI & XII
H 2O 2
(ix) AcOH
5. Write products of the following with (A) Bayer’s reagent (B) OsO 4 in
pyridine/H2O (C) Peracid/H2O.
(i) (ii) (iii) (iv)
Me
(v) (vi) (vii) (viii) H D
O
Write product of with the following :
6.
i MeOH / H ii MeO / MeOH iii NH 3 iv R NH 2
v LAH vi AlCl3 / LAH vii EtSK viii RMgX
ix NaN3 x H / KCN xi Al OR 3 xii Pure HCN
7. Question : Write the product for the following reactions :
KMnO4/H+
(1) R CH C
Heat
Me
KMnO4/H+
(2) Et CH C
Heat
Me
H
KMnO4/H+
(3) Et CH C
Heat
H
Me
KMnO4/H+
(4) H CH C
Heat
Me
Me
KMnO4/H+
(5) Me CH C
Heat
Me
6
M. P. I. ALKENES XI & XII
KMnO4/H+
(6) Heat
KMnO4/H+
(7) Heat
KMnO4/H+
(8) Heat
KMnO4/H+
(9) Heat
KMnO4/H+
(10)
Heat
KMnO4/H+
(11) Heat
KMnO4/H+
(12) Heat
KMnO4/H+
(13) Heat
KMnO4/H+
(14) Heat
+
(15) Me C C CH2 CH2 CH CH Me KMnO4/H
6 Heat
8. Oxidation of active methyl & methylene groups :
SeO2 CHO
(1) Me CHO
CHO
O
SeO2
(2) Me C Me
7
M. P. I. ALKENES XI & XII
O
SeO2
(3) Ph C Me
COOEt COOEt
SeO2
(4) O
COOEt COOEt
O
SeO2
(5) CH3 CH2 C CH3
SeO2
(6)
N CH3
SeO2
(7) Ph CH2 Ph
O
SeO2
(8)
Some other reactions of alkenes that you have to revise from previous
content :
1. Ozonolysis of alkens :
2. Oxymercuration demercuration of alkenes :
3. Hydroboration deboration :
4. Addition of carbenes :
5. Allylic halogenations :
6. Walcker process :
9. Question : Solve the following problems :
Base
(1) CH2 CH C N + Ph2C N OH
0
(2) CH2 CH C N + NH3 25 C
Ac
(3) CH2 CH C N + CH2 Base
Ac 400C
8
M. P. I. ALKENES XI & XII
Base
(4) CH2 CH C N + CH3SH
250C
O
(5) CH2 CH C N + CH3 C R Base
250C
Base
(6) CH2 CH C N + 0
OH OH OH 50 C
10. Question: Identify A to Z in the given problems.
B alc. KOH KOH K2Cr2O7/H+
A D E NBS F G H
C
Cr2O3/H+ +
KMnO4/H+ I2/OH-
I H 3O J K
Heat L
H 3O +
S.L. H 3O +
M+N O Conc. H2SO4 P NaOH Q R
Heat Heat
HNO2 HNO3 Sn/HCl HNO2 H3PO2
S T U V
W O OH-
X Y (Pink colour)
Br2/H2O
11. Question: Identify A to Z in the given problems.
9
M. P. I. ALKENES XI & XII
B Br2 alc. KOH CCl NaOH KMnO4
C
D hv E F H O4 G H
2 2
Zn-Hg Br2 Me2CHMgBr Br2
I Heat J K L M N
HCl hv hv
NaNH2 KMnO4/OH-
O P + R CaO A
Heat
I2 + OH-
MeCO3H HIO4 LAH
F S U+T V
HCl Mg
W Y MeCl Z
Et2O
Na/ Et2O
10
M. P. I. ALKENES XI & XII
ALKADIENES
Cummulated Isolated Conjugated
____________________________________________________
H.O.H. i.e. HH2 ------------ Decreases
Stability -------------------- Increases
Reactivity ------------------ Decreases
Methods of preparation of conjugated dienes :
1. By dehydrohalogenation of alkenyl halides :
OH-
Br Heat
Mechanism :
OH-
Br Heat Br
OH-
Br Heat
2. By dehydrogenation of alkenes :
Pd-C Pd-C
Heat Heat
3. From isolated dienes :
i. Acidic mechanism :
H+ - H+
H
ii. Alakaline medium :
OH- H 2O
Heat
11
M. P. I. ALKENES XI & XII
4. Preparation of isolated dienes :
Br2 alc. NBS Br
Br
hv KOH
Mg / Et2O
Br
MgBr
SN-2
5. Preparation of cumulated dienes :
Br2 alc. NBS Br
Br
hv KOH
Br2/CCl4
Br
Zn Br alc.
CH2 C CH2 Br Br
Heat KOH
Br
CH2 C CH2
Note : is unstable in the presence of alc. KOH or NaNH2.
CH2 C CH2 alc. KOH CH3 C CH
or NaNH2
Properties of conjugated dienes :
1. Electrophilic 1,2 and 1,4 addition reactions:
2. 1-4-addition reaction: 1,4-addition reaction is characteristic reaction for
conjugated dienes if temp. is not mentioned from TCP.
3. K.C.P.(Kinetically controlled product) :
4. (i) Normally 1,2 addition reaction will take place easier to form because less
energy is required , small energy barrier favoured at low temperature.
5. (ii) More stable intermediate will form whatever the stability of products.
(Observed irreversible reactions.)
6. T.C.P( Thermodynamically controlled product) : 1,4 addition :
7. (i) More energy is required
8. (ii) Favoured at room temperature more stable product (alkene) will form
….. be the stability of intermediate.
12
M. P. I. ALKENES XI & XII
9. Question: Find TCP and KCP
Cl Cl
HCl
1. 1eq .
TCP KCP
Cl
2.
HCl
1eq .
KCP & TCP same
Cl
Cl
3.
HCl
1eq .
KCP TCP
Br
4.
HBr
1eq .
Same KCP & TCP same
Cl Cl
5.
HCl
1eq.
Cl
TCP
KCP
(1.6 addn) TCP
Cl
6.
HCl
1eq.
Cl
KCP TCP
Cl
7.
HCl
1eq . Same KCP & TCP
10. Free radical addition reactions.
11. Addition of carbenes.
12. Diels-Alder reaction.
13
M. P. I. ALKENES XI & XII
13. Polymerizations :
(1) n CH2 CH CH CH2 CH2 CH CH CH2
n
(2) n CH2 C CH CH2 CH2 C CH CH2
n
Cl Cl
Chloroprene Neoprene
(3) n CH2 C CH CH2 CH2 C CH CH2
n
Me Me
Isoprene Natural rubber
(4) n CH2 CH CH CH2 + n CH2 CH CH2 CH CH2 CH CH CH2
Ph Ph n
Buna-S
(5) n CH2 CH CH CH2 + n CH2 CH CH2 CH CH2 CH CH CH2
CN CN n
Buna-N
(6) n CH2 CH CH CH2 + n CH2 CH + n CH2 CH
CN Ph
CH2 CH CH2 CH CH2 CH CH CH2
CN Ph
ABS plastic : If styrene is more.
ABS rubber : If Butadiene is more.
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