Unsaturated compounds:
alkenes
Chapter 2
1
:Unsaturated compounds
Have fewer hydrogen atoms attached to the carbon chain
.than alkanes
Containing double bond are alkenes or triple bonds are •
.alkynes
2
:Unsaturated compounds
alkenes
• The alkene functional group is the carbon-carbon
double bond
-C = C-
• Sometimes called olefins, “oil-forming gas”
• General formula CnH2n , n≥2 (like cycloalkanes)
Cyclic alkene: CnH2n–2
3
:Unsaturated compounds
alkenes
• Terminal alkenes have the double bond at the end of the
carbon chain.
• Internal alkenes have at least one carbon atom bonded to
each end of the double bond.
• Cycloalkenes contain a double bond in a ring.
4
:Unsaturated compounds
alkenes
• Recall that the double bond consists of a bond and a
bond.
• Each carbon atom in a C=C double bond is sp2 hybridized
and trigonal planar, with bond angles of approximately
120°.
bond
E
bonds
5
:Unsaturated compounds
alkenes
6
alkenes
Alkene Homologous Series
(C1-C2 double bond)
• Ethene C=C
• Propene C-C=C
• 1-Butene C-C-C=C
• 1-Pentene C-C-C-C=C
• 1-Hexene C-C-C-C-C=C
• 1-Heptene C-C-C-C-C-C=C
• 1-Octene C-C-C-C-C-C-C=C
• 1-Nonene C-C-C-C-C-C-C-C=C
7
Nomenclature of Alkenes
8
Nomenclature of Alkenes
• Compounds with two double bonds are named as dienes by changing the “-ane”
ending of the parent alkane to the suffix “–diene”. Compounds with three
double bonds are named as trienes, and so forth.
• Always choose the longest chain that contains both atoms of the double bond.
• In naming cycloalkenes, the double bond is located between C1 and C2, and the
“1” is usually omitted in the name. The ring is numbered clockwise or
counterclockwise to give the first substituent the lower number.
• Compounds that contain both a double bond and a hydroxy group are named as
alkenols and the chain (or ring) is numbered to give the OH group the lower
number.
9
Nomenclature of Alkenes
Naming an alkene in which
the longest carbon chain does
not contain both atoms of the
double bond
Examples of cycloalkene nomenclature
10
Nomenclature of Alkenes
• Some alkene or alkenyl substituents have common names.
• The simplest alkene, CH2=CH2, named in the IUPAC system as
ethene, is often called ethylene.
Naming alkenes with common
substituent names
11
Nomenclature of Alkenes
Many Alkenes Are Known by Common Names
12
Nomenclature of Alkenes
hyl
et
H2 H2 5
C 3
C CH 3
4
H3C 2 C C
H2
1 CH 2
Longest chain containing C=C is 5 carbons
2-ethyl-1-pentene
13
Nomenclature of Alkenes
CH2= CH ─ CH2─ CH3 1-butene
CH3─ CH=CH─ CH3 2-butene
CH3
|
CH3─ CH=C─CH3 2-methyl-2-butene
14
Nomenclature of Alkenes
CH3
CH3─ CH2─ C=CH ─ CH3 3-methyl-2-pentene
CH2 – CH3
15
Nomenclature of Alkenes
ethyl-3,5-dimethyl-2-heptene-4 hexadiene-2,4
isopropyl-3,5-dimethyl--4
dimethyl-1,3-pentadiene-3,4
16 1,3,5-heptatriene
Nomenclature of Alkenes
17
Nomenclature of Alkenes
18
Nomenclature of Alkenes
19
Geometric Isomers of alkenes
because of restricted rotation about a carbon-carbon double
bond, an alkene with two different groups on each carbon of the
double bond shows cis-trans isomerism
• If one end of the C=C has two groups the same, cis-trans
isomers are not possible
• Both carbons of the C=C must have two different groups
attached
• Find a group common to both ends of the C=C
cis- isomers have two similar or identical groups on the
same side of the double bond.
trans- isomers have two similar or identical groups on
20 opposite sides of the double bond.
Geometric Isomers of alkenes
H H H CH3
C=C C=C
H3C CH3 H3C H
C 4H 8 C 4H 8
cis-2-Butene trans-2-Butene
The same molecular formula and the same connectivity of their atoms
.but a different arrangement of their atoms in space
21
Geometric Isomers of alkenes
E-Z Nomenclature
• Use the Cahn-Ingold-Prelog rules to assign priorities to
groups attached to each carbon in the double bond.
• If high priority groups are on the same side, the name is
Z (for zusammen).
• If high priority groups are on opposite sides, the name is
E (for entgegen).
22
Geometric Isomers of alkenes
E-Z Nomenclature
RULE 1
• Must rank atoms that are connected at comparison point
• Higher atomic number gets higher priority
– Br > Cl > S > P > O > N > C > H
23
Geometric Isomers of alkenes
E-Z Nomenclature
RULE 2
• If atomic numbers are the same, compare at next connection
point at same distance
• Compare until something has higher atomic number
• Do not combine – always compare
24
Geometric Isomers of alkenes
E-Z Nomenclature
RULE 3
Multiple-bonded atoms are equivalent to the same number
of single bonded atoms
25
Geometric Isomers of alkenes
E-Z Nomenclature
26
Geometric Isomers of alkenes
E-Z Nomenclature
27
Geometric Isomers of alkenes
: Example, E-Z
1 1 2 Cl
1
H3C Cl H CH CH3
C C C C
H CH2 H
2 1 2
2
2Z 5E
dichloro-(2Z, 5E)-2,5-octadiene-3,7
28
Physical Properties of alkenes
• Most alkenes exhibit only weak van der Waals
interactions, so their physical properties are similar to
alkanes of comparable molecular weight.
• Alkenes have low melting points and boiling points.
• Melting and boiling points increase as the number of
carbons increases because of increased surface area.
• Alkenes are soluble in organic solvents and insoluble in
water.
• Nonpolar compounds
• Density less than 1 g/mL
29
Physical Properties of alkenes
•The C—C single bond between an alkyl group and one of
the double bond carbons of an alkene is slightly polar
because the sp3 hybridized alkyl carbon donates electron
density to the sp2 hybridized alkenyl carbon.
30
Physical Properties of alkenes
• A consequence of this dipole is that cis and trans isomeric
alkenes often have somewhat different physical properties.
• cis-2-Butene has a higher boiling point than trans-2-butene.
31
Physical Properties of alkenes
•In the cis isomer, the two Csp3—Csp2 bond dipoles
reinforce each other, yielding a small net molecular
dipole. In the trans isomer, the two bond dipoles cancel.
32
Preparations of Alkenes
1. Dehydrohalogenation of Alkyl halides
2. Dehydration of Alcohol
3. Dehalogenation of Vicinal Halides
4. Reduction of Alkynes
33
Preparations of Alkenes
Dehydrohalogenation of Alkyl halides .1
alcohol
C C + KOH C C + KX + H2 O
Ease of dehydrohalogenation of alkyl halides
H X
1° > 2° > 3°
Alcohol
H2C CH2 + KOH heat
H2C CH2 + KX + H2O
H
X Alkene
an alkyl halide
Br
H3C alcohol / heat H3C
CH3 + KOH
CH3 + H3C CH2
2-Butene major 1-Butene minor
H H
Br Alcohol / heat
H + KOH
CH3
+
CH3
CH3 1-methylcyclohexene 3methylcyclohexene
34 major minor
Preparations of Alkenes
2. Dehydration of alcohol
acid
C C C C + H2O
alkene
H OH
Ease of dehydration of alcohols
1° > 2° > 3°
.ex
H H H H
H2SO 4
H C C H H C C H + H2O
ethylene
H OH
ethyl alcohol
+
acid serves as H donor
35
Preparations of Alkenes
2. Dehydration of alcohol
Mechanism for dehydration of an alcohol = E1
1) C C + H C C
H OH H OH2
RDS
2) C C C C + H2O
H OH2 H
3) C C C C + H
36 H
Preparations of Alkenes
2. Dehydration of alcohol
C C C C C C C C + C C C C
H OH H (major) (minor)
Saytzeff Rule:
Hydrogen is preferably removed from the carbon with least
no. of hydrogen since the alkene formed is more highly
branched and is energetically more stable.
37
Preparations of Alkenes
2. Dehydration of alcohol
H2SO 4
CH 3CH 2CH 2CH 2OH CH 3CH 2 HC CH2 CH 3 HC CHCH 3
n-butyl alcohol 1-butene 2-butene
H2SO 4
CH 3CH 2 HC CH3
Al 2O 2 in
CH 3 HC CHCH 3 + CH 3CH 2 HC CH2
OH heated tube
sec-butyl alcohol 2-butene 1-butene
38
Preparations of Alkenes
3. Dehalogenation of vicinal dihalides (same side)
C C + Zn C C + ZnX 2
X X
dihalides
:Example
Zn
CH 3 HC CH CH3 CH 3 HC CHCH 3 + ZnX 2
Br Br
2,3-Dibromobutane 2-butene
39
Preparations of Alkenes
4. Reduction of alkynes
R R
Pd, NiBr
C C syn (cis)
Lindlar
Catalyst H H
R C C R
R H
Na or Li NH 3
C C anti (trans)
H R
40
Preparations of Alkenes
4. Reduction of alkynes
H2 H3C CH3
Ni2B
H H
H3C C C CH3 syn addition
H3C H
Li or Na
NH3, RNH2 H CH3
anti addition
41
Reactions of alkenes
Additions to alkenes
sp2
sp3
Addition
C C + X-Y X C C Y
2 - Bonds formed
Bonds broken
42
Reactions of alkenes
1- Addition of hydrogen: Hydrogenation (reduction)
2-butene butane
43
Reactions of alkenes
2- Halogenation: Addition of Halogen
• Halogenation is the addition of X2 (X = Cl or Br) to an
alkene to form a vicinal dihalide.
44
Reactions of alkenes
3) Addition of Hydrogen halides (HX) to alkenes
C C + HX C C HX = HCL, HBr, HI
H X
Br
C C + H Br C C C C
H H Br
alkyl halide
haloalkane
45
? Orientation of addition
Markovnikov’s Rule
The addition of HX (proton acid) to the double bond of an alkenes
results in a product with the acid proton bonds to the carbon atom
that already has the greater number of hydrogen atoms.
H2C CHCH3 + H+X- CH2CHCH3 + CH2CHCH3
H X X H
major minor
Markovnikov anti Markovnikov
46
product product
? Orientation of addition
H
H
H Br
Less Stable More Stable
Carbocation Carbocation
minor major
anti Markovnikov Markovnikov
product product
47
Reactions of alkenes
4- Hydration: Electrophilic Addition of Water
• Hydration is the addition of water to an alkene to form an alcohol.
48
Reactions of alkenes
5. Addition of sulfuric acid.
| | | |
— C = C — + H2SO4 —C—C—
| |
H OSO3H
alkyl hydrogen sulfate
Markovnikov orientation.
CH3CH=CH2 + H2SO4 CH3CHCH3
|
49
OSO3H
Reactions of alkenes
6. Addition of halogens + water (halohydrin formation):
| | | |
— C = C — + X2, H2O — C — C — + HX
| |
OH X
a) X2 = Br2, Cl2
b) Br2 = electrophile
CH3CH=CH2 + Br2(aq.) CH3CHCH2 + HBr
| |
OH X
50
Reactions of alkenes
6. Addition of halogens + water (halohydrin formation):
mechanism for addition of X2 + H2O
1) C C + X--X C C + X
X
2) H2O + C C C C
X H2O X
-H
3) C C C C
51
H2O X HO X
Reactions of alkenes
7. Dimerization:
52
Reactions of alkenes
8. Alkylation:
Used to increase gasoline yield from petroleum and to
improve fuel performance.
53
Reactions of alkenes
9. Oxymercuration-demercuration.
| | | |
— C = C — + H2O, Hg(OAc)2 — C — C — + acetic
| | acid
OH HgOAc
Oxymercuration
| | | |
— C — C — + NaBH4 —C—C—
| | | |
OH HgOAc OH H
.Demercuration alcohol
54
Reactions of alkenes
10. Hydroboration-oxidation.
| | | |
— C = C — + (BH3)2 — C — C —
| |
diborane H B—
|
| | | |
— C — C — + H2O2, NaOH — C — C —
| | | |
H B— H OH
|
Alcohol
55
Reactions of alkenes
11. Polymerization.
56
Reactions of alkenes
12. Hydroxylation. (mild oxidation)
| | | |
— C = C — + KMnO4 — C — C — syn
| |
OH OH
OH
| | | |
— C = C — + HCO3H — C — C — anti
peroxyformic acid | |
OH
glycol
57
Reactions of alkenes
13. Allylic halogenation.
| | | | | |
— C = C — C — + X2, heat — C = C — C — + HX
| |
H allylic hydrogen X
CH2=CHCH3 + Br2, 350oC CH2=CHCH2Br + HBr
a) X2 = Cl2 or Br2
b) or N-bromosuccinimide (NBS)
58
Reactions of alkenes
13. Allylic halogenation.
59
