CHE 121 Alkene

Sumani Jey

1
 Alkenes
• Alkenes are also called olefins.
• They contain a carbon—carbon double bond (their
functional group).
• 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.

2
• Recall that the double bond consists of a  bond and a 
bond (the two bonds have a total of 4 electrons)

• Each carbon of the double bond is sp2 hybridized and

trigonal planar, with bond angles of approximately 120°.

• Since there are fewer hydrogen atoms in alkenes as a

result of the double bond, alkenes are referred to as
unsaturated.
3
• Bond dissociation energies of the C—C bond in ethane
( bond only) and ethylene (one  and one  bond) can
be used to estimate the strength of the  component of
the double bond.

4
5
there are two 2-butenes:

H H H CH3
C C C C
H3C CH3 H3C H
cis-2-butene trans-2-butene

“geometric isomers” (diastereomers)

6
Nomenclature of Alkenes

7
Naming an alkene in which the longest carbon chain does not
contain both atoms of the double bond

8
9
• Compounds with two double bonds are named as dienes by
changing the “-ne” ending of the parent alkane to the suffix “–
diene”. Compounds with three double bonds are named as trienes,
and with 4 double bonds as tetraenes.

• 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.

10
Naming compounds with more than one double bond

A
buta-1,3-diene

(3cis, 5cis)-octa-1,3,5,7-tetraene
B

C
(3trans, 6trans)-nona-1,3,6,8-tetraene

11
Give the UIPAC names of the following compounds

12
13
• The simplest alkene, CH2=CH2, named in the IUPAC system as
ethene, is often called ethylene.
• Some alkene or alkenyl substituents have common names.

Naming alkenes with common substituent names

14
Physical Properties
• 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 which increases
van der Waals forces.

• Alkenes are soluble in organic solvents and insoluble in water.

• 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.
15
16
• 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 .

• 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.

17
Preparation of Alkenes
• Alkenes can be prepared from alkyl halides and alcohols via
elimination reactions. Elimination reactions are reactions that
removes a portion of the molecule of which one must be a
hydrogen.

dehydrohalogenation and detosylation

dehydration
18
• Elimination reactions are stereoselective and
regioselective, so the most stable alkene is usually
formed as the major product in line with Zaitsev’s rule.

19
• Regiospecific/Regioselective – a reaction that yields only
one product (or a predominance of one constitutional
isomer) when two or more constitutional isomers are
possible products.

• Stereoselectivity – single starting material can give two

or more stereoisomeric products of which one of them is
yielded in greater amounts than the other (or even to the
exclusion of the other).

• Stereoisomeric products has a carbon with four

different groups attached to it with two groups lying in
the plane and the remaining two groups lies in such a way
that one group point towards the observer while the other
group points away from the observer.

20
 CURVED (CURLY) ARROWS
• They show movement of an electron pair

• They start on a lone pair of electrons or a full-

fledged negative charge or a pie or covalent
bond
• Clearly draw out all the bonds or atoms that are
involved at each stage of the reaction
• Remember to show clearly the molecule or ion
produced after each stage of the mechanism.
Don’t forget charges on ions. It also helps when
the atoms/groups involved are clearly shown. 21
 For example
xx -
N C -
Cl
H3C C N +
H3C Cl

The examiner is very strict about curly

arrows in mechanisms.
The C bonded to N donate its two electrons to
C bonded to Cl. The C bonded to Cl has a
partial positive charge and therefore it can
accept electrons and release the Cl.
22
Dehydrohalogenation general mechanism
-
X X
-
C C C C + HB + X
H H
:B B
-
A transition state is a very short-lived configuration of atoms
at a local energy maximum in a reaction-energy diagram.
The double bond is partially formed in the transition state
and therefore the transition state resembles an alkene.
Thus the factors which stabilize alkenes will stabilize this
nascent alkene - Hammond-Leffler postulate.

23
Dehydrohalogenation one step mechanism

H H H H
H C2H5ONa
H
H Br H H

H H
H H
O H
H H H
H Br

24
 Alkenes: Acid Catalyzed Dehydration
CH3
CH2
20% H2SO4
H3C OH
+ H2O
85 oC
CH2 H3C CH3

H
• 3° alcohols exceptionally easy to dehydrate

• Can use dilute acid, low temperatures

• Relative ease of reaction:

3° > 2° > 1°
25
 CH3 CH3

H 3C OH H 3C OH2
+
H
CH2 CH2
H H

-H2O

Base
CH2 CH3
-H+
+ H 2O H
H3 C CH3 C CH3
H2

26
a) Consider the following reactions and assume that no atom can have more than a plus or a
minus charge: Note that all curved arrows below are double headed.

1) X Y Z

2) B C D

i) Draw the structure(s) of the reactant(s) (clearly showing charges and/or lone pairs of
electrons) and product(s) if given that the product(s) has one positively charged atom.
ii) Draw the structure(s) of the reactant(s) (clearly showing charges and/or lone pairs of
electrons) and product(s) if given that the product(s) has one negatively charged
atom.
iii) Draw the structure(s) of the reactant(s) (clearly showing charges and/or lone pairs of
electrons) and product(s) if given that the product(s) has no charges.
iv) Which reaction between 1 and 2 would ably qualify as a mere resonance process?
Justify your choice using no more than three 2-line sentences.

27
Introduction to Addition Reactions of
Alkenes
• The characteristic reaction of alkenes is addition—the  bond is
broken and two new  bonds are formed.

• Alkenes are electron rich, with the electron density of the  bond
concentrated above and below the plane of the molecule.

28
•Because alkenes are electron rich, simple alkenes do not
react with nucleophiles or bases, reagents that are
themselves electron rich. Alkenes react with electrophiles.
• Because the carbon atoms of a double bond are both
trigonal planar, the elements of X and Y can be added to
them from the same side or from opposite sides.

29
Five addition reactions of cyclohexene

30
Hydrohalogenation—Electrophilic Addition of HX

• Two bonds are broken in this reaction—the weak  bond of the

alkene and the HX bond—and two new  bonds are formed—one
to H and one to X.

• The H—X bond is polarized, with a partial positive charge on H.

Because the electrophilic H end of HX is attracted to the
electron-rich double bond, these reactions are called
electrophilic additions.

31
To draw the products of an addition reaction:

32
• Addition reactions are exothermic because the two  bonds
formed in the product are stronger than the  and  bonds
broken in the reactants. For example, H° for the addition of HBr
to ethylene is –14 kcal/mol, as illustrated below.

33
• The mechanism of electrophilic addition consists of two
successive Lewis acid-base reactions. In step 1, the alkene is the
Lewis base that donates an electron pair to H—Br, the Lewis
acid, while in step 2, Br¯ is the Lewis base that donates an
electron pair to the carbocation, the Lewis acid.

34
Eletrophiles - species that are electron deficient
(they may have a partial positive charge or a full
blown positive charge – electron loving

Nucleophile - species that are electron rich (have

lone pairs of electrons or are negatively charged) –
nucleus loving

Carbocation is a positive intermediate form of a

carbon. It has an empty P orbital which can
accept electrons from a nucleophile

35
 Carbocation Structure and Stability
• Carbocations are planar and the tri-coordinate
carbon is surrounded by only 6 electrons in sp2
orbitals

• The fourth orbital on carbon is a vacant p-orbital

• The stability of the carbocation (measured by energy

needed to form it from R-X or double bond) is
increased by the presence of alkyl substituents

36
 Carbocation is an electrophile and
has a trigonal planar geometry
Carbocations are classified as 1°,
2°, or 3° depending on the number
of carbon atoms bonded to the
carbon bearing the positive charge

37
Alkyl groups are weak electron donors.

They stabilise the carbocation by 2 ways

1. By donating electron density by induction

(through sigma bonds). Inductive effects: Alkyl
groups donate (shift) electron density through sigma
bonds to electron deficient atoms. This stabilizes the
carbocation
2. By hyperconjugation
filled sigma bonds of the C-H
interacting with the positively
charged carbon.

38
Mechanism of Electrophilic Addition:
Rearrangements of Carbocations
• Carbocations can undergo structural rearrangements
following set patterns
• It can be a 1,2-hydride shift or 1,2-alkyl shift
• The driving force is the formation of a more stable
carbocation

39
40
Methyl shift can also occur as shown below

41
Hydrohalogenation—Markovnikov’s Rule
• With an unsymmetrical alkene, HX can add to the double
bond to give two constitutional isomers, but only one is
actually formed or predominantly formed:

• This is a specific example of a general trend called

Markovnikov’s rule.
• Markovnikov’s rule states that in the addition of HX to an
unsymmetrical alkene, the H atom adds to the less
substituted carbon atom—that is, the carbon that has the
greater number of H atoms to begin with. 42
• The basis of Markovnikov’s rule is the formation of a carbocation
in the rate-determining step of the mechanism.
• In the addition of HX to an unsymmetrical alkene, the H atom is
added to the less substituted carbon to form the more stable, more
substituted carbocation.

• Trigonal planar carbon reacts with reagents from two directions

with equal probability. 43
• This is the case because the nucleophilic attack of Cl¯ on the
trigonal planar carbocation occurs from two different directions

44
• Hydrohalogenation occurs with syn and anti addition of HX.
• The terms cis and trans refer to the arrangement of groups in a
particular compound, usually an alkene or disubstituted
cycloalkene.
• The terms syn and anti describe stereochemistry of a process—
for example, how two groups are added to a double bond.
• Addition of HX to 1,2-dimethylcyclohexene forms syn and anti
products

45
Reaction of 1,2-dimethylcyclohexene with HCI

46
Rate determining step is the slowest step in a
reaction which determine how fast the reaction
can go to form the product.
47
Hydration—Electrophilic Addition of Water
• Hydration is the addition of water to an alkene to form an
alcohol.

48
49
• Alcohols add to alkenes, forming ethers by the same
mechanism. For example, addition of CH3OH to 2-
methylpropene, forms tert-butyl methyl ether (MTBE), a
high octane fuel additive.

• Note that there are three consequences to the

formation of carbocation intermediates:
1. Markovnikov’s rule holds.
2. Addition of H and OH occurs in both syn and anti
fashion.
3. Carbocation rearrangements can occur. 50
Halogenation—Addition of Halogen
• Halogenation is the addition of X2 (X = Cl or Br) to an
alkene to form a vicinal dihalide.

51
• Halogens add to  bonds because halogens are polarizable.

• The electron rich double bond induces a dipole in an

approaching halogen molecule, making one halogen atom
electron deficient and the other electron rich (X+—X–).

• The electrophilic halogen atom is then attracted to the

nucleophilic double bond, making addition possible.

• Two facts demonstrate that halogenation follows a different

mechanism from that of hydrohalogenation or hydration.
No rearrangements occur
Only anti addition of X2 is observed
These facts suggest that carbocations are not
intermediates.

52
Carbocations are unstable because
they have only six electrons around
carbon. Halonium ions are unstable
because of ring strain. 53
Halogenation—Reaction Stereochemistry
• Consider the chlorination of cyclopentene to afford trans-1,2-
dichlorocyclopentane, with no cis products.

• Initial addition of the electrophile Cl+ from (Cl2) occurs from either
side of the planar double bond to form a bridged chloronium ion.

54
• In the second step, nucleophilic attack of Cl¯ must occur from
the backside. The side where there is no halogen.

• Since the nucleophile attacks from below and the leaving group
departs from above, the two Cl atoms in the product are oriented
trans to each other.

• Backside attack occurs with equal probability at either carbon of

the three-membered ring to yield the 2 products in 1:1 ratio

55
cis-2-Butene yields two products, whereas trans-2-butene
yields a single product.

56
Halohydrin Formation
Treatment of an alkene with a halogen X2 and H2O forms a
halohydrin by addition of the elements of X and OH to the
double bond.

57
Even though X¯ is formed in step [1] of the mechanism, its
concentration is small compared to H2O (often the
solvent), so H2O and not X¯ is the nucleophile.
58
 Because the bridged halonium ion is opened by backside
attack of H2O, addition of X and OH occurs in an anti
fashion and trans products are formed.

With unsymmetrical alkenes, the preferred product has the

electrophile X+ bonded to the less substituted carbon, and
the nucleophile (H2O) bonded to the more substituted carbon.

59
The nucleophilic attack occurs at the more substituted
carbon end of the bridged halonium ion because that carbon
is better able to accommodate the partial positive charge in
the transition state.

Explain why there is no need to show the bonds as

pointing towards you or away from you in the product? In
other words, why it is not necessary to draw the product in
3-D. 60
61
Consider the following reaction:

a. State the Markovnikov’s rule.

b. Which product has a stereoisomer? Explain and draw the
isomers.
c. Explain how 2-chloro-2-methylbutane is formed.
d. Would you expect Br2/H2O pair of reagents to form a similar
product(s) if reacted with 3-methyl-1-butene? Draw the
product(s) in 3-D.
62
(c) Draw the 3-D structure(s) of the Anti-Markovnikov’s product(s) for the following reaction.

HBr

(d) Provide the structure(s) of the major organic product(s) in the following reactions:

-
OH
Cl

63
1. Consider the following reaction:

Cl
Cl2

Cl

a) Draw the product(s) of the given reaction showing the stereochemistry of the two chlorine
substituents i.e. showing whether the substituents are pointing towards you or away
from you.

b) What would be the product(s) if the following combination of reagents is reacted with the
same alkene substrate? Show the stereochemistry (substituents pointing towards you or
away from you) of the product(s) in all cases.

(i) (a) OsO4, pyridine (b) NaHSO3, H2O

(ii) H2SO4/CH3OH
64
Hydroboration—Oxidation
Hydroboration—oxidation is a two-step reaction sequence
that converts an alkene into an alcohol.

65
Hydroboration—oxidation results in the addition of H-OH
to an alkene. This reaction follows anti-Markovnikov rule.

66
BH3 is a reactive gas that exists mostly as a dimer, diborane (B2H6).
Borane is a strong Lewis acid that reacts readily with Lewis bases.
For ease of handling in the laboratory, it is commonly used as a
complex with tetrahydrofuran (THF).

The first step in hydroboration—oxidation is the addition of the

elements of H and BH2 to the  bond of the alkene, forming an
intermediate alkylborane.

67
• The proposed mechanism involves concerted addition of H
and BH2 from the same side of the planar double bond: the
 bond and H—BH2 bond are broken as two new  bonds
are formed.
• Because four atoms are involved, the transition state is
said to be four-centered.

•The H and BH2 are added on the same face of the double
bond which means that after oxidation of the C-B bond the
H and OH are on the same face of the plane of the hence
this reaction is syn addition. molecule 68
Because the alkylborane formed by the reaction with one
equivalent of alkene still has two B—H bonds, it can react
with two more equivalents of alkene to form a
trialkylborane.

69
Since only one B—H bond is needed for hydroboration,
commercially available dialkylboranes having the general
structure R2BH are sometimes used instead of BH3. A
common example is 9-borabicyclo[3.3.1]nonane (9-BBN).

70
With unsymmetrical alkenes, the boron atom bonds to the
less substituted carbon atom.

The addition of a hydrogen atom is on a more substituted

carbon thereby violating Markovnikov rule. This reaction is
therefore said to follow anti-Markovnikov rule.

71
• This regioselectivity can be explained by considering
steric factors. The larger boron atom bonds to the less
sterically hindered, more accessible carbon atom.

• Electronic factors are also used to explain this

regioselectivity. If bond making and bond breaking are
not completely symmetrical, boron bears a - charge in
the transition state and carbon bears a + charge. Since
alkyl groups stabilize a positive charge, a more stable
transition state has a partial positive charge on the more
substituted carbon.

72
Hydroboration of an unsymmetrical alkene

73
• Since alkylboranes react rapidly with water and
spontaneously burn when exposed to air, they are
oxidized, without isolation, with basic hydrogen
peroxide (H2O2, ¯OH).

• Oxidation replaces the C—B bond with a C—O bond,

forming a new OH group with retention of configuration.

• The overall result of this two-step sequence is syn

addition of the elements of H and OH to a double bond
in an “anti-Markovnikov” fashion.

74
 Predict the Product
Predict the product when the given alkene reacts
with borane in THF, followed by oxidation with
basic hydrogen peroxide.

CH3 (1) BH3, THF H

CH3
-
(2) H2O2, OH OH
D D
syn addition
=>
75
Heating the borane intermediate result in shifting of the
borane to the terminal carbon (1o carbon). Some books
use trialkyl borane as an intermediate for this reaction.

BH2

heat

frist degree borane

second degree borane
BH2

76
 Oxymercuration-Demercuration
• Reagent is mercury(II) acetate Hg(OAc)2 which
dissociates slightly to form +Hg(OAc).
• +Hg(OAc) is the electrophile that attacks the pi
bond.
O O O O
_ +
CH3 C O Hg O C CH3 CH3 C O Hg O C CH3

• The intermediate is a cyclic mercurinium ion, a

three-membered ring with a positive charge.
77
 OAc
+
Hg
+
C C Hg(OAc) C C

• Water approaches the mercurinium ion from the side

opposite the ring (the back side of the ring leading to the
formation of the anti-addition product).
• Water molecule adds to the more substituted carbon to
form the Markovnikov product.
OAc OAc OAc
+ Hg
Hg Hg
C C C C C C
+
H O O
H2O H H
H2O
78
 Demercuration
Sodium borohydride, a reducing agent, replaces the
mercury with hydrogen.
OAc
Hg H
_
4 C C + NaBH4 + 4 OH 4 C C + NaB(OH)4
_
O O
+ 4 Hg + 4 OAc
H H

79
Alkoxymercuration-Demercuration
Uses mercuric acetate with an alcohol to add
RO-H to a double bond and form the
Markovnikov product.
H
1) Hg(OAc)2, CH3OH
CH3CH2CH CH2 CH3CH2CH CH2
2) NaBH4
OCH3

=>

80
 Predict the Product
Predict the product when the given alkene reacts with
aqueous mercuric acetate, followed by reduction
with sodium borohydride.
OH
CH3 CH3
(1) Hg(OAc)2, H2O D
(2) NaBH4 H
D
anti addition

CH3 (1) BH3, THF H

CH3
-
(2) H2O2, OH OH
D D
81
syn addition
• Oxymercuration-Demercuration
– Markovnikov product formed
– Anti addition of H-OH
– No rearrangements

• Hydroboration-Oxidation
– Anti-Markovnikov product formed
– Syn addition of H-OH

82
 Oxidative Cleavage
• Both the pi and sigma bonds break.
• C=C becomes C=O.
• Two methods:
– Warm or concentrated or acidic KMnO4 (strong
oxidizing reagent)
– Ozonolysis (uses ozone which is a mild oxidizing
reagent)
• These reactions are used to determine the
position of a double bond in an unknown
alkene. One has to work in reverse to
determine the position of unsaturation.
83
 Cleavage with concentrated/acidic MnO4-
• Permanganate is a strong oxidizing agent.
• Glycol, which is a diol, is initially formed and is
then further oxidized according to the substitution
of the carbon atoms of the double bond.
• Disubstituted carbons become ketones.
• Monosubstituted carbons becomes an aldehyde
which is further oxidized to carboxylic acids.
• Terminal double bond (=CH2) produces CO2 as
one of the products
84
 Example
H CH3
H CH3 KMnO4
C C H3C C C CH3
CH3 CH3 (warm, conc.)
OH OH

The aldehyde H CH3

carbonyl carbon H3C C + C CH3
has a hydrogen O O
atom bonded to it
and it can OH
H3C C
therefore undergo
O
further oxidation.
85
 Ozonolysis
• Reaction with ozone forms an ozonide as an
intermediate.
• Ozonides are not isolated, but are treated with a mild
reducing agent like Zn/AcOH or dimethyl sulfide
(Me2S or (CH3)2S).
• Ozone is a milder oxidative reagent than permanganate.
• Products formed are ketones (disubstituted individual
alkene carbon atom) or aldehydes (monosubstituted
individual alkene carbon atom) i.e. according to the
substitution of carbon atoms of the double bond.
86
 Ozonolysis Example
O
H CH3 O3 H CH3
C C C C
CH3 CH3 O O
H3C CH3
Ozonide

H O
(CH3)2S CH3
C O O C + CH3 S CH3 =>
H3C CH3
DMSO

The first step is usually carried out under

anhydrous conditions (dry solvents are used) to
avoid explosion. 87
 Dihydroxylation of Alkenes
• Alkene is converted to a cis-1,2-diol- (syn oxidation)
• Two reagents:
– Osmium tetroxide (very expensive), followed by
hydrogen peroxide or followed by aqueous sodium
hydrogen sulfate
– Cold, dilute aqueous potassium permanganate, followed
by hydrolysis with base

88
• Each reagent adds two oxygen atoms in a syn
fashion (i.e. added to the same face of the
double bond).
• Hydrolysis of the cyclic intermediate cleaves the
metal oxygen bonds, forming a cis-1,2-diol.

89
Josiah Chisale was tasked to come up with a protocol for the synthesis of compound A using
organic and inorganic starting materials chosen from the list below. He came up with a protocol in
which he suggested that subjecting substrate 4 under dihydroxylation reaction would give him
the target molecule. He was not 100% convinced that the protocol he came up with would work
and he decided to consult Glory Kawina, who was regarded as a genius by the majority of her
peers. Glory suggested that Josiah should expose the same substrate under halohydrin reaction
conditions. The resultant product should be exposed to basic conditions and the resultant alkoxide
will have both nucleophilic and electrophilic sites and hence can react intramolecularly to form a
cyclic product. The cyclic product should then be exposed to acidic water to get the target
molecule.

Target molecule

OH

OH
compound A

Organic starting materials

Inorganic starting materials

HBr, H2O, Zn, AcOH, H2SO4, NaHSO3, HCl, Cl2, Br2, KOC(CH3)3, CH3ONa, OsO4, KMnO4, O3

a) Draw a reaction equation using the protocol Josiah came up with. All the products
encountered along the way should be given in 3-D representation.

b) Draw a reaction equation using the protocol Glory came up with. All the products
encountered along the way should be given in 3-D representation.

c) What problem will Josiah most likely going to encounter if he uses Glory’s protocol as 90
given in question (b) above?
Reduction of Alkenes—Catalytic Hydrogenation

• The addition of H2 occurs only in the presence of

a metal catalyst, and thus it is called catalytic
hydrogenation.
• The catalyst consists of a metal—usually Pd, Pt,
or Ni, adsorbed onto a finely divided inert solid,
such as charcoal.
• H2 adds in a syn-fashion.
91
Because of the fact that these reactions take place on
a surface, hydrogenation of substituted cycloalkenes
produces cis-products

92
Alkenes in Organic Synthesis
Suppose we wish to synthesize 1,2-dibromocyclohexane from
cyclohexanol.

To solve this problem we must:

93
Working backwards from the product to determine the starting
material from which it is made is called retrosynthetic analysis.

94
End of Semester examination-2016
1. (a) Farnesene is a compound found in the waxy coating of apples.

(i) Draw two possible geometrical isomers of farnesene. [4 marks]

(ii) Draw the structure(s) of the oxidative cleavage product(s) using hot/ basic KMnO4
followed by acidification with H3O+ i.e. [6 marks]

1. KMnO4, -OH, heat

2. H3O+

95
Question 4

a) Show by means of reaction equations how the target molecules (TM) below can be synthesized
from the indicated starting material (ST) and any other reagent(s) of your choice: Note that you
may have to use more than one step to get the targeted molecule and draw the structures of all
intermediates. [15 Marks]

and
OH OH
Cl
Target molecules (TM)
Starting material (ST)

96
 CHE 121 Examination-2017
1. Myrcene, a fragrant compound found in bayberry wax, has the formula C10H16 and is known
not to contain any ring. When treated with excess hydrogen and a platinum catalyst (H 2/Pt),
myrcene is converted to 2,6-dimethyloctane which has a molecular formula of C10H22.
Ozonolysis of myrcene followed by treatment with dimethyl sulfide (i.e. 1. O3; 2. Me2S)
yields 2 mol of formaldehyde (HCHO), 1 mol of acetone (CH 3COCH3), and a third
compound (A) with the formula C5H6O3.

a) Draw a structural formula of 2,6-dimethyloctane [2 marks]

b) Deduce the structure of myrcene? Show how you came up with structure of myrcene. [6
marks]

c) Draw the structure of compound A? (4 marks)

d) When myrcene is reacted with Osmium tetroxide followed by aqueous sodium hydrogen
sulphite (1. OsO4, 2. NaHSO3, H2O) six (6) possible products can be formed. Draw any
four (4) of the six possible products. [8 marks] 97
 Tutorial question – Solomons OC
1. Pheromones are substances secreted by animals that produce a specific behavioural response
in other members of the same species. Pheromones are effective at very low concentrations
and include sex attractants, warning substances, and aggregation compounds. The sex
attractant pheromone of the codling moth has the molecular formula C 13H24O. Using
information you can glean from the following reaction diagram, deduce the structure of the
codling moth sex pheromone. The double bonds are known on the basis of other evidence to
be (2cis, 6trans).

98
Question 5

A first year student found an old bottle containing a chemical (unknown compound A) in his
chemistry laboratory locker. The label on the bottle indicated that the molecular formula of
the compound was C10H16. It further revealed that the structure of the compound does not
have any ring. In an attempt to identify the structural formula of the compound, the student
treated 1 mole of the unknown compound with excess hydrogen gas and palladium on
charcoal catalyst (H2/Pd-C) which converted it to 2,6-dimethyloctane (C10H22). Oxidation of
1 mole of the unknown compound using hot, concentrated and acidic potassium
permanganate (i.e. 1. hot, conc. KMnO4; 2. H3O+) yielded water, 2 moles of carbon dioxide
gas (2 × CO2 (g)), 1 mole of acetone (CH3COCH3), and a third product (P) with the formula
C5H6O5.

i) Draw a structural formula of 2,6-dimethyloctane [2 marks]

ii) Deduce the structure of the unknown compound A the student found in the locker?
Show how you came up with the structure of the compound. [6 marks]

iii) Give the IUPAC name of the compound [3 marks]

iv) Draw the structure of product P? [3 marks]

v) Draw the structure(s) of the products which could be formed if compound A is

99
subjected to ozonolysis reaction (i.e. (i) O3, (ii) Me2S). [6 marks]
Question 5

A first year student found an old bottle containing a chemical (unknown compound A) in his
chemistry laboratory locker. The label on the bottle indicated that the molecular formula of the
compound was C14H24. It further revealed that the structure of the compound does not have any ring.
In an attempt to identify the structural formula of the compound, the student treated 1 mole of the
unknown compound with excess hydrogen gas and palladium on charcoal catalyst (H2/Pd-C) which
converted it to 2,3,6,9-tetramethyldecane (C14H30). Oxidation of 1 mole of the unknown compound
A using ozonolysis (i.e. 1.O3; 2. Zn/AcOH) yielded 2 moles of acetone (CH3COCH3) and 2 moles of
a second product (P) with the formula C4H6O2.

(i) Draw a structural formula of 2,3,6,9-tetramethyldecane [2 Marks]

(ii) Deduce the structure of the unknown compound A the student found in the locker? Show how
you came up with the structure of the compound. [6 Marks]

(iii) Give the IUPAC name of the compound [2 Marks]

(iv) Draw the structure of product P? [2 Marks]

(v) Draw the structure(s) of any four (4) products which could be formed if compound A is subjected
to reaction with cold, dilute and basic potassium permanganate (i.e. cold, dil, KMnO4, -OH).
100
[6 Marks]
Question 5

Consider the following sequence of reactions:

(i) (ii) SOCl2

OH Cl
STEP 1 STEP 2 STEP 3
OH

O
(iii) (iv)
STEP 4 STEP 5
O

(a) Give the reagents in STEPS 1, 2, 4 and 5. (12 marks)

(b) Draw the structures of the other possible alkene product(s) in STEP 4. (9 marks)

(c) Draw the structure of the carboxylic acid which would be produced if a strong
oxidizing reagent such as concentrated potassium permanganate is used to oxidize one
of the alkene products in question 5(b) above. (4 marks)

101
 Polymer
• A polymer is a compound of very high formula
mass whose long chain molecules are made of
repeating units.
• Monomer is the fundamental repeating unit of a
polymer.
• There are two major types of polymers:
– Addition polymers
– Condensation polymers

102
Section 14.5
 Addition Polymers
• Addition polymers are formed when molecules of an
alkene monomer adds to one another.

• Recall that alkenes have a double bond between two

carbon atoms of the functional group.

• Under the proper reaction conditions the double bond

opens up and attaches itself by single bonds to two other
monomer molecules.

• Each of these monomers will then in turn attach to

another monomer, and so on and on.
103
Section 14.5
 Polymerization of Ethene

• The subscripted n on polyethylene indicates that

the unit shown in brackets is repeated thousands
of times for a ‘big polymer’.
• Polyethylene is the simplest of the synthetic
polymers.
– It is significantly chemically inert and is used to make
containers.
104
Section 14.5
 Teflon
• Teflon is made by the polymerization of
tetrafluoroethene.

• This polymer is a hard, strong, chemically

resistant compound with a high melting point and
very low surface friction.

14 | 105
Section 14.5
Drawing the Structure of an
Addition Polymer - An Example
• An addition polymer prepared from vinylidene chloride,
CH2==CCl2. Draw the structure of the polymer.
• To form the polymer the double bonds of all the
monomers (CH2==CCl2) must open up and repeatedly
bond to the growing chain of monomers.
• The structure is shown as:

Section 14.5
106
 107
Section 14.5
 Condensation Polymers
• Condensation polymers are formed from molecules of
two or more reactive groups.
– Water is the other product, hence the name condensation
polymers.
• Polyethylene terephthalate (PET) is formed from the
polymerization of terephthalic acid and ethylene glycol.

14 | 108
Section 14.5
Nylon – A Condensation Polymer
• Nylon was first introduced to the public in 1939 at the
New York World’s Fair.
• Nylon is formed from the polymerization of adipic
acid and hexamethylenediamine.

109
Section 14.5
• Three methods of making addition
polymers:
– Cationic pathway: form a carbocation
intermediate. Has a carbon atom with an
empty p-orbital.
– Free radical mechanism: form a radical
intermediate. Has a carbon atom with half-
filled p-orbital.
– Anionic pathway: form a carbanion
intermediate (rare). Has a carbon atom with
filled p-orbital. 110
Cationic Polymerization

H
O
+ -
OSO3H
O S O

OH
111
Termination Step of Cationic Polymerization

• The chain growth ends when a proton is abstracted by the

weak base of the acid used to initiate the reaction.
• The loss of a hydrogen forms an alkene and ends the
chain growth so this is a termination step.

112
Cationic Polymerization Using BF3 as
Catalyst

113
Radical Polymerization

• In the presence of an initiator such as peroxide, free-

radical polymerization occurs.

114
Anionic Polymerization
For an alkene to gain electrons, strong electron-
withdrawing groups such as nitro, cyano, or carbonyl
must be attached to the carbons in the double bond.

115
Question seven

a) Use curved arrows to show a termination step in the polymerization reaction of styrene
using aqueous BF3 catalyst. Hint: Use the intermediate A given below in your reaction
mechanism.

intermediate A

b) Consider the following substrates:

N O
CO2CH3 OCH3 OH H

NO2
(a) (b) (c) (d) (f) (e)

i) Which substrate will react fastest under anionic pathway?

ii) Use structures and two short sentences of no more than 2 lines to support your answer.
116
 Alkynes
Introduction—Structure and Bonding
• Alkynes contain a carbon—carbon triple bond.
• Terminal alkynes have the triple bond at the end of the
carbon chain such that a hydrogen atom is directly bonded
to a carbon atom of the triple bond.
• Internal alkynes have a carbon atom bonded to each
carbon atom of the triple bond.
• An alkyne has the general molecular formula CnH2n-2, giving
it four fewer hydrogen atoms than the maximum possible
for the number of carbons present. Thus, the triple bond
introduces two degrees of unsaturation.

117
• A triple bond consists of 2  bonds and 1  bond.
• Each carbon is sp hybridized with a linear geometry and bond
angles of 1800.

118
• Bond dissociation energies of the C—C bonds in
ethylene (one  and one  bond) and acetylene (one 
and two  bonds) can be used to estimate the strength of
the second  bond of the triple bond.

119
• Like trans cycloalkenes, cycloalkynes with small rings
are unstable. The carbon chain must be long enough to
connect the two ends of the triple bond without
introducing too much strain.
• Cyclooctyne is the smallest isolable cycloalkyne, though
it decomposes upon standing at room temperature after
a short time.

120
Nomenclature
• Alkynes are named in the same general way that alkenes are
named.
• In the IUPAC system, change the –ane ending of the parent alkane
name to the suffix –yne.
• Choose the longest continuous chain that contains both carbon
atoms of the triple bond and number the chain to give the triple
bond the lower number.
• The simplest alkyne, H-CC-H, named in the IUPAC system as
ethyne, is more often called acetylene, its common name.
• The two-carbon alkyl group derived from acetylene is called an
ethynyl group.
• Compounds with two triple bonds are named as diyne, those with
three are named as triyne so on and so forth.
• Compounds with both a double and triple bond are named as
enyne. The chain is numbered to give the first site of unsaturation
(either C=C or CC) the lower number otherwise priotize the
alkene. 121
A substituent receives the lowest number if there is no
functional group suffix,

Cl Br
3-bromo-2-chloro-4-octyne
CH3CHCHC CCH2CH2CH3 not 6-bromo-7-chloro-4-octyne
because 2 < 6
1 2 3 4 5 6 7 8

or if the same number for the functional group suffix

is obtained in both directions

CH3 1-bromo-5-methyl-3-hexyne
CH3CHC CCH2CH2Br not 6-bromo-2-methyl-3-hexyne
because 1 < 2
6 5 4 3 2 1
In common nomenclature, alkynes are named as substituted
acetylenes
124
125
126
127
Physical Properties
• The physical properties of alkynes resemble
those of hydrocarbons of similar shape and
molecular weight.
• Alkynes have low melting points and boiling
points.
• Melting point and boiling point increase as the
number of carbon atoms increases.
• Alkynes are soluble in organic solvents and
insoluble in water.

128
Acetylene and Other Interesting Alkynes
• Acetylene (H-CC-H) is a colorless gas that burns in
oxygen to form CO2 and H2O. The combustion of
acetylene releases more energy per mole of product
formed than any other hydrocarbons. It burns with a
very hot flame and is an excellent fuel.

129
•Ethynylestradiol and norethindrone are two components of
oral contraceptives that contain a carbon-carbon triple
bond.
Both molecules are synthetic analogues of the naturally
occurring female sex hormones estradiol and progesterone, but
are more potent so they can be administered in lower doses.
Most oral contraceptives contain both of these synthetic
hormones.
They act by artificially elevating hormone levels in a woman,
thereby preventing pregnancy.
• RU-486 and levonorgestrel are two other synthetic
hormones. RU-486 blocks the effects of progesterone, thus
preventing pregnancy. It is used to induce abortions within
the first few weeks of pregnancy. Levonorgestrel interferes
with ovulation, and so it prevents pregnancy if taken within
a few days of unprotected sex.

131
Histrionicotoxin

132
Preparation of Alkynes
• Preparation by elimination reactions. A strong
base removes two equivalents of HX from a
geminal or vicinal dihalide to yield an alkyne
through two successive elimination reactions.

133
Synthesis of propyne from propane

Br2, heat
CH3CH2CH3 CH3CH2CH2-Br + CH3CHCH3
Br
KOH(alc)

CH3CHCH2 CH3CH=CH2
Br2
Br Br

KOH
NaNH2
CH3CH CH CH3C CH
Br
• Acetylene, the simplest alkyne, is produced industrially
from methane and steam at high temperature

135
Preparation of Alkynes by Alkylation of Acetylene and
Terminal Alkynes
• Because sp hybridized C—H bonds are more acidic than sp2
and sp3 hybridized C—H bonds, terminal alkynes are readily
deprotonated with strong base in a BrØnsted-Lowry acid-
base reaction. The resulting ion is called the acetylide ion.

Acetylide anions are strong nucleophiles and will undergo

nucleophilic substitution reactions with methyl and primary
alkyl halides, resulting in the formation of a C-C bond.

_ R THF R
R C C + + NaBr
C Br R C C C
H SN2 H
Na + H H
new C-C
bond formed

136
137
• Acetylide anions react with unhindered alkyl halides to yield
products of nucleophilic substitution.
• Because acetylides are strong nucleophiles, the pathway of the
reaction is by substitution, and thus the reaction is fastest with
CH3X (methyl halide) and 10 alkyl halides. Ignore the use of SN2 in
the reaction equation.

138
• Steric hindrance around the carbon holding the halide causes 2° and
3° alkyl halides to undergo elimination reaction to form as alkene
product as shown with 2-bromo-2-methylpropane below.
• Thus, nucleophilic substitution with acetylide anions forms new
carbon-carbon bonds in high yield only with unhindered CH3X and 1°
alkyl halides.

139
Alkylation of acetylide anions is a general method of
making higher alkynes from simpler alkynes.

H C C H + H2N: Na+ H C C

H C C + H3CH2CH2C-Br H3CH2CH2C C C H
pentyne

H3CH2CH2C C C H + H2N: Na+ H3CH2CH2C C C

pentyne

H3CH2CH2C C C + H3C-I H3CH2CH2C C C CH3

2-hexyne

140
• Carbon—carbon bond formation with acetylide anions is a
valuable reaction used in the synthesis of numerous natural
products.

Use of acetylide anion reactions in the synthesis of two marine natural products

141
Introduction to Alkyne Reactions—Addition reactions
• Like alkenes, alkynes undergo addition
reactions because they contain relatively weak 
bonds.
• Two sequential reactions can take place:
addition of one equivalent of reagent forms an
alkene, which can then add a second equivalent
of reagent to yield a product having four new
bonds.

142
Four addition reactions of 1-butyne

143
Hydrohalogenation—Electrophilic Addition of HX
• Alkynes undergo hydrohalogenation, i.e the, addition of
hydrogen halides, HX (X = Cl, Br, I).

• Two equivalents of HX are usually used: addition of one

mole forms a vinyl halide, which then reacts with a
second mole of HX to form a geminal dihalide.

144
145
146
• Electrophilic addition of HX to alkynes is slower than
electrophilic addition of HX to alkenes, even though alkynes are
more polarizable and have more loosely held  electrons than
alkenes.

• Markovnikov addition in step [3] places the H on the terminal

carbon to form the more substituted carbocation A, rather than
the less substituted carbocation B.

147
• Carbocation A is stabilized by resonance, but B is not.
• Two resonance structures can be drawn for carbocation
A, but only one Lewis structure can be drawn for
carbocation B.

• Markovnikov’s rule applies to the addition of HX to vinyl

halides because addition of H+ forms a resonance-
stabilized carbocation.
148
a) Consider the following reaction:

i) Use structures and short sentences of no more than 2-lines to explain why this
reaction follows Markovnikov’s rule.
ii) Would it be prudent to draw the product given above in 3-D representation? Explain.

149
Halogenation—Addition of Halogen
• Halogens X2 (X = Cl or Br) add to alkynes just as they do
to alkenes. Addition of one mole of X2 forms a trans
dihalide, which can then react with a second mole of X2
to yield a tetrahalide.

150
151
Hydration—Electrophilic Addition of Water
• In the presence of strong acid and Hg2+ catalyst, the
elements of H2O adds to the triple bond, but the initial
addition product, an enol, is unstable and rearranges to
a product containing a carbonyl group—that is, a C=O.
This rearrangement is usually catalyzed by either an acid
or a base and it is known as tautomerization.

• Tautomerization, is defined as a process of converting one tautomer

into another.

152
• Consider the conversion of a general enol A to the carbonyl compound
B. A and B are tautomers in which A is the enol form and B is the keto
form of the tautomer.

Equilibrium favors the keto form largely because the C=O is

much stronger than a C=C. Analyze cases where there is a
possibility of intramolecular hydrogen bonds.
O OH O O

153
enol-form keto-form
Practice question:
154
Draw a general base catalyzed tautomerization rearrangement.
• Internal alkynes undergo hydration with concentrated
acid, whereas terminal alkynes require the presence of
an additional Hg2+ catalyst—usually HgSO4—to yield
methyl ketones by Markovnikov addition of water.

155
156
Hg2+ is added to increase the rate of water addition
mostly to terminal alkynes
Hydroboration—Oxidation
Hydroboration—oxidation is a two step reaction sequence
that converts an alkyne to a carbonyl compound.

158
• Hydroboration—oxidation of an internal alkyne forms a
ketone.
• Hydroboration of a terminal alkyne adds BH2 to the less
substituted, terminal carbon. After oxidation to the enol,
tautomerization yields an aldehyde. Remember that this
reaction follows Anti-Markovnikov’s rule.

159
160
 Oxidation and Reduction
Reduction of Alkynes
• There are three different ways in which H2 can add to the triple
bond:
Reduction of an Alkyne to an Alkane

• Addition of H2 over a metal catalyst (such as palladium on

carbon, Pd/C) converts alkynes to alkanes (complete reduction)
• The addition of the first equivalent of H2 produces an alkene,
which is more reactive than the alkyne so the alkene is not
observed i.e. it further reacts to form an alkane.
Reduction of an Alkyne to a Cis Alkene
• Palladium metal is too reactive to allow hydrogenation of
an alkyne to stop after one equivalent of H2 adds.
• To stop at a cis alkene, a less active Pd catalyst is used—
Pd adsorbed onto CaCO3 with added lead(II) acetate and
quinoline. This is called Lindlar’s catalyst.
• Compared to Pd metal, the Lindlar catalyst is deactivated
or “poisoned”.
• With the Lindlar catalyst, one equivalent of H2 adds to an
alkyne to form the cis product.
• Reduction of an alkyne to a cis alkene is a stereoselective
reaction, because only one stereoisomer is formed.
7-cis-Retinol synthesis (Hoffmann-
LaRoche):

165
Reduction of an Alkyne to a Trans Alkene
• In a dissolving metal reduction (such as Na in NH3), the
elements of H2 are added in an anti fashion to form a trans
alkene.
• Dissolving metal reduction of a triple bond with Na in NH3 is a
stereoselective reaction because it forms a trans product
exclusively.
• Dissolving metal reductions always form the more stable trans
product preferentially.
• The trans alkene is formed because the vinyl carbanion
intermediate formed is more stable when the larger R groups are
further away from each other to avoid steric interactions.
Protonation of this anion leads to the more stable trans adduct.
 Oxidative Cleavage of Alkynes
• Oxidizing reagents (O3 or KMnO4) cleave internal alkynes,
producing two carboxylic acids
• Terminal alkynes are oxidized to a carboxylic acid and carbon
dioxide
• Neither process is useful in modern synthesis – were used to
elucidate structures because the products indicate the structure of the
alkyne precursor

170
7. Oxidation

KMnO4

R-CC-R´ hot KMnO4 RCOOH + HOOCR´

carboxylic acids

O3; then Zn, H2O

CH3CH2CCCH3 + KMnO4 →CH3CH2COOH +

HOOCCH3

CH3CCH + hot KMnO4 → CH3COOH + CO2

CH3CCCH3 + O3; then Zn, H2O → 2 CH3COOH

6. Ag+ terminal alkynes only!

CH3CH2CCH + AgNO3 → CH3CH2CC-Ag+



CH3CCCH3 + AgNO3 → NR (not terminal)

formation of a precipitate is a test for terminal alkynes.

Synthesis: Example 1

O
?
CH3CH2C CH CH3CH2CCH2CH2CH3
Example 2
Example 3
Question three
a) Consider the following sequence of reactions:

STEP 1 STEP 2 STEP 3

Cl2
One alkene geometrical isomer Meso chlorinated product(s)

(i) Give the reagents in STEPS 1, 2 and 3.

(ii) Draw the structure of the one alkene geometrical isomer formed in STEP 3.

(iii) Draw the structure(s) of the Meso chlorinated product(s).

(iv) How would you manipulate this protocol to form products that are not Meso isomers?

(v) Draw the structure(s) of the product(s) that could result from manipulation done in
question three (iv).
180