CFB 2013 – ORGANIC CHEMISTRY

ALKENE AND ADDITION

REACTION
LECTURE 6

TS DR. MOHD DZUL HAKIM WIRZAL

1
COURSE OUTCOME
At the end of this course, students should be able to:

1 Draw mechanism for some fundamental reactions of organic chemistry

Identify chemical reactivity from knowledge of acid/base and

2 nucleophile/electrophile properties.

Interpret the important relationship between structure and

5 reactivity of organic molecules.

2
LEARNING OUTCOME
At the end of this lecture, students should be able to:

To name alkene from the given structure and to draw its chemical
1 structures from the given name.

2 To draw a detailed addition reaction mechanism

3 To differentiate between Markovnikov’s and Anti-Markovnikov’s Rule

3
 PART 1
INTRODUCTION TO ALKENE

4
ALKENE

5
PREPARATION OF ALKENE
▪ Recall from lecture note 5 that alkenes can be prepared from alkyl halides and
alcohols via elimination reactions.

6
PREPARATION OF ALKENE (CONT.)
▪ Before dehydrogenation of ethane became the dominant method, ethylene was
prepared by heating ethyl alcohol with sulfuric acid.

▪ Other alcohols behave similarly. Secondary alcohols undergo elimination at

lower temperatures than primary alcohols.

7
PREPARATION OF ALKENE (CONT.)
▪ Tertiary alcohols dehydrate at lower temperatures than secondary alcohols.

8
ALKENE
▪ Alkenes are compounds that contain a carbon–carbon double bond.
▪ Terminal alkenes have the double bond at the end of the carbon chain,
whereas internal alkenes have at least one carbon atom bonded to each end of
the double bond.
▪ Cycloalkenes contain a double bond in a ring.

9
ALKENE (CONT.)
▪ The double bond of an alkene consists of one σ bond and one π bond.
▪ Each carbon is sp2 hybridized and trigonal planar, and all bond angles are
approximately 120°.

10
ALKENE (CONT.)
▪ Bond dissociation energies of the C – C bonds in ethane (a σ bond only) and
ethylene (one σ and one π bond) can be used to estimate the strength of the π
component of the double bond.
▪ If we assume that the σ bond in ethylene is similar in strength to the σ bond in
ethane (368 kJ/mol), then the π bond is worth 267 kJ/mol.

▪ The π bond is much weaker than the σ bond of a C – C double bond, making it
much more easily broken. As a result, alkenes undergo many reactions that
alkanes do not.

11
ALKENE (CONT.)

12
NOMENCLATURE
▪ In the IUPAC system, an alkene is identified by the suffix -ene.

13
NOMENCLATURE (CONT.)

14
NOMENCLATURE (CONT.)
▪ More examples.

15
NOMENCLATURE (CONT.)
▪ More examples.

Check if the name is

correct or not!

16
NOMENCLATURE (CONT.)
▪ Naming Stereoisomers - A prefix is needed to distinguish two alkenes when
diastereomers are possible.
▪ Using Cis and Trans as prefix.

▪ For example, cis-2-butene has two ethyl groups on the same side of the double
bond, whereas trans-2-butene has two ethyl groups on opposite sides of the
double bond.

17
NOMENCLATURE (CONT.)
▪ Using prefix E and Z.
▪ Although the prefi xes cis and trans can be used to distinguish diastereomers
when two alkyl groups are bonded to the C=C, they cannot be used when there
are three or four alkyl groups bonded to the C=C.

18
NOMENCLATURE (CONT.)

19
NOMENCLATURE – POLY FUNCTIONAL GROUP
▪ Carbon–carbon double bonds take precedence over alkyl groups and halogens
in determining the main carbon chain and the direction in which it is numbered.

▪ Hydroxyl groups, however, outrank the double bond, and a chain that contains
both an ―OH group and a double bond is numbered in the direction that gives
the carbon attached to the ―OH group the lower number.

20
COMMON NAME
▪ The simplest alkene, CH2=CH2, named in the IUPAC system as ethene, is often
called ethylene, its common name.
▪ The common names for three alkyl groups derived from alkenes are also used.

21
COMMON NAME (CONT.)
▪ The common names of certain frequently encountered alkyl groups, such as
isopropyl and tert -butyl, are acceptable in the IUPAC system.
▪ Three alkenyl groups ―vinyl, allyl , and isopropenyl —are treated the same way.

22
CLASSIFICATION
▪ Alkenes are classified according to the number of carbon atoms bonded to the
carbons of the double bond.
▪ A monosubstituted alkene has one carbon atom bonded to the carbons of the
double bond.
▪ A disubstituted alkene has two carbon atoms bonded to the carbons of the
double bond, and so forth.

23
CLASSIFICATION (CONT.)
▪ You must be able to classify alkenes in this way to determine the major and
minor products of elimination reactions, when a mixture of alkenes is formed.

Carbon atoms bonded

to the double bond are
screened in red.

24
STABILITY
▪ Some alkenes are more stable than others.
▪ For example, trans alkenes are generally more stable than cis alkenes because
the groups bonded to the double bond carbons are farther apart, reducing
steric interactions.

25
STABILITY (CONT.)
▪ The stability of an alkene increases as the number of R groups bonded to the
double bond carbons increases.

▪ The R groups increase the stability of an alkene because R groups are sp3
hybridized, whereas the carbon atoms of the double bond are sp2 hybridized.
▪ The higher the percent s-character, the more readily an atom accepts electron
density.
▪ Thus, sp2 hybridized carbon atoms are more able to accept electron density
and sp3 hybridized carbon atoms are more able to donate electron density.

26
STABILITY (CONT.)

▪ As a result, increasing the number of electron-donating R groups on a carbon

atom able to accept electron density makes the alkene more stable.

27
STABILITY (CONT.)
▪ For example, trans-2-butene (a disubstituted alkene) is more stable than cis-2-
butene (another disubstituted alkene), but both are more stable than 1-butene
(a monosubstituted alkene).

In summary:
▪ Trans alkenes are more stable than cis alkenes because they have fewer steric
interactions.
▪ Increasing alkyl substitution stabilizes an alkene by an electron-donating
inductive effect.

28
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 points 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.
▪ A cis alkene is more polar than a trans alkene, giving it a slightly higher boiling
point and making it more soluble in polar solvents.

29
CLASS ACTIVITY 6.1
1. Identify the alkene obtained on dehydration of each of the following alcohols:
a. 3-Ethyl-3-pentanol
b. 2-Propanol
c. 1-Propanol
d. 2,3,3-Trimethyl-2-butanol

2. Name each of the following using IUPAC nomenclature.

30
CLASS ACTIVITY 6.1
3. Female houseflies attract males by sending a chemical signal known as a
pheromone . The substance emitted by the female housefly that attracts the
male has been identified as cis-9-tricosene, C23H46. Write a structural formula,
including stereochemistry, for this compound.

31
 PART 2
REACTION OF ALKENE

32
ALKENE
▪ Ethylene is the most widely produced organic chemical, serving as the starting
material not only for the polymer polyethylene, a widely used plastic, but also
for many other useful organic compounds.

33
INTRODUCTION TO ADDITION REACTION
▪ Because the C – C π bond of an alkene is much weaker than a C – C σ bond, the
characteristic reaction of alkenes is addition: the π bond is broken and two
new σ bonds are formed.

▪ Because alkenes are electron rich, simple alkenes do not react with
nucleophiles or bases, reagents that are themselves electron rich. Alkenes react
with electrophiles.

34
INTRODUCTION TO ADDITION REACTION
▪ The stereochemistry of addition is often important in delineating a reaction’s
mechanism.
▪ 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.

35
HYDROHALOGENATION
▪ Hydrohalogenation is the addition of hydrogen halides HX (X = Cl, Br, and I) to
alkenes to form alkyl halides.

▪ Two bonds are broken in this reaction—the weak π bond of the alkene and
the HX bond— and two new σ bonds are formed—one to H and one to X.
▪ Because X is more electronegative than H, 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.

36
HYDROHALOGENATION - MECHANISM
1. The π bond attacks the H atom of HBr, thus forming a new C– H bond while
breaking the H – Br bond. Because the remaining carbon atom of the original
double bond is left with only six electrons, a carbocation intermediate is
formed. This step is rate-determining because two bonds are broken but only
one bond is formed.

2. Nucleophilic attack of Br– on the carbocation forms the new C – Br bond

37
MARKOVNIKOV’S RULE
With an unsymmetrical alkene, HX can add to the double bond to give two
constitutional isomers.

In the addition of HX to an
unsymmetrical alkene, the H atom
bonds to the less substituted
carbon atom—that is, the carbon
that has more H atoms to begin
with.

Vladimir Vasilyevich Markovnikov (Russian: Влади́ мир Васи́ льевич Марко́ вников), also spelled
as Markownikoff (December 22, 1838 – February 11, 1904), was a Russian chemist.
38
MARKOVNIKOV’S RULE (CONT.)
The basis of Markovnikov’s rule is the formation of a carbocation in the rate-
determining step of the mechanism. With propene, there are two possible paths for
this first step, depending on which carbon atom of the double bond forms the new
bond to hydrogen.

Highly unstable

39
MARKOVNIKOV’S RULE (CONT.)
Example of Test Question
▪ Draw a stepwise mechanism for the following reaction.

HINT:
Because the carbon skeletons of the
starting material and product are
different—the alkene reactant has a 4°
carbon and the product alkyl halide does
not—a carbocation rearrangement must
have occurred.

40
MARKOVNIKOV’S RULE (CONT.)
Example of Test Question
▪ Draw a stepwise mechanism for the following reaction.

41
EXTENDED MARKOVNIKOV’S RULE
▪ In the ionic addition of an unsymmetrical reagent to a double bond, the positive
portion of the adding reagent attaches itself to a carbon atom of the double
bond so as to yield the more stable carbocation as an intermediate.
▪ Addition of the electrophile determines the overall orientation of the addition,
because it occurs first (before the addition of the nucleophilic portion of the
adding reagent).

42
ANTI MARKOVNIKOV’S RULE
▪ This exception concerns the addition of HBr to alkenes when the addition is
carried out in the presence of peroxides (i.e., compounds with the general
formula ROOR).

43
ANTI MARKOVNIKOV’S RULE (CONT.)

44
STEREOCHEMISTRY OF HYDROHALOGENATION
▪ Because addition converts sp2 hybridized carbons to sp3 hybridized carbons,
however, sometimes new stereogenic centers are formed from
hydrohalogenation.
▪ For example, Markovnikov addition of HCl to 2-ethyl-1-pentene, an achiral
alkene, forms one constitutional isomer, 3-chloro-3- methylhexane.

45
STEREOCHEMISTRY OF HYDROHALOGENATION
▪ The mechanism of hydrohalogenation illustrates why two enantiomers are
formed.
▪ Initial addition of the electrophile H+ (from HCl) occurs from either side of the
planar double bond to form a carbocation.
▪ Both modes of addition (from above and below) generate the same achiral
carbocation.
▪ Either representation of this carbocation can then be used to draw the second
step of the mechanism.

46
STEREOCHEMISTRY OF HYDROHALOGENATION
▪ Because hydrohalogenation begins with a planar double bond and forms a planar
carbocation, addition of H and Cl occurs in two different ways.
▪ The elements of H and Cl can both be added from the same side of the double
bond—that is, syn addition—or they can be added from opposite sides—that is,
anti addition.
▪ Both modes of addition occur in this two-step reaction mechanism.

47
HYDROHALOGENATION - SUMMARY

48
CLASS ACTIVITY 6.2
1. Outline mechanisms for the following addition reactions.

2. Provide mechanistic explanations for the following observations

49
CLASS ACTIVITY 6.2
3. Treatment of 3-methylcyclohexene with HCl yields two products, 1-chloro-3-
methylcyclohexane and 1-chloro-1-methylcyclohexane. Draw a mechanism to
explain this result.

4. Addition of HBr to which of the following alkenes will lead to a rearrangement?

a. CH2=C(CH3)CH2CH3
b. CH3CH=CHCH2CH3
c. CH3CH=CHCH(CH3)2

50
HYDRATION
▪ Hydration is the addition of water to an alkene to form an alcohol.
▪ H2O itself is weak acid, unable to protonate an alkene, but with added H2SO4,
H3O+ is formed and addition readily occurs.

51
HYDRATION - MECHANISM

▪ The π bond attacks H3O+, thus forming a new C – H bond while breaking the H –
O bond. Because the remaining carbon atom of the original double bond is left
with only six electrons, a carbocation intermediate is formed. This step is rate-
determining because two bonds are broken but only one bond is formed.

▪ Nucleophilic attack of H2O on the carbocation forms the new C – O bond.

52
HYDRATION – MECHANISM (CONT.)

▪ Removal of a proton with a base (H2O) forms a neutral alcohol. Because the acid
used in Step [1] is regenerated in Step [3], hydration is acid-catalyzed.

53
HYDRATION – MECHANISM (CONT.)
Example of question
Write a mechanism that explains the following reaction.

We know that a hydronium ion, formed from sulfuric acid and water, can donate a
proton to an alkene to form a carbocation. The carbocation can then accept an
electon pair from a molecule of water to form a protonated alcohol. The
protonated alcohol can donate a proton to water to become an alcohol.

54
“HYDRATION” USING ALCOHOL
▪ Alcohols add to alkenes, forming ethers, using the same mechanism.
▪ Addition of CH3OH to 2-methylpropene, for example, forms tert-butyl methyl
ether (MTBE), a high octane fuel additive

55
HYDRATION - SUMMARY
▪ The first two steps of the mechanism are similar to those of electrophilic
addition of HX—that is, addition of H+ (from H3O+) to generate a carbocation,
followed by nucleophilic attack of H2O.
▪ In unsymmetrical alkenes, H adds to the less substituted carbon to form the
more stable carbocation; that is, Markovnikov’s rule holds.
▪ Addition of H and OH occurs in both a syn and anti fashion.
▪ Carbocation rearrangements can occur.

56
OXYMERCURATION – DEMERCURATION

▪ Concerns about mercury’s toxicity have led to decreased use of mercury-based

reagents in synthetic organic chemistry.
▪ Alternatives exist for many of the transformations formerly carried out with
mercury compounds while carrying much less risk.
▪ The chemistry of several of the reactions, however, is sufficiently interesting to
examine here.

57
OXYMERCURATION – DEMERCURATION
A useful laboratory procedure for synthesizing alcohols from alkenes that avoids
rearrangement is a two-step method called oxymercuration–demercuration.

58
OXYMERCURATION – DEMERCURATION
Mechanism
Step 1: Oxymercuration

Step 2: Demercuration

59
HYDROBORATION - OXIDATION
Hydroboration–oxidation is a two-step reaction sequence that converts an alkene
to an alcohol.
▪ Hydroboration is the addition of borane (BH3) to an alkene, forming an
alkylborane.
▪ Oxidation converts the C – B bond of the alkylborane to a C – O bond.

60
HYDROBORATION – OXIDATION (CONT.)
Hydroboration–oxidation results in addition of H2O to an alkene.

61
HYDROBORATION – OXIDATION MECHANISM
The first step in hydroboration–oxidation is addition of the elements of H and BH2
to the π bond of the alkene, forming an intermediate alkylborane.

▪ The π bond and H – BH2 bonds break as the C – H and C – B bonds form.
▪ In hydroboration, the boron atom bonds to the less substituted carbon.

62
HYDROBORATION – OXIDATION MECHANISM

▪ Steric factors explain this regioselectivity. The larger boron atom bonds to the
less sterically hindered, more accessible carbon atom.
▪ In addition, because alkyl groups stabilize a positive charge, the more stable
transition state has the partial positive charge on the more substituted carbon,

63
HYDROBORATION – OXIDATION MECHANISM
The second step in hydroboration–oxidation is oxidation of alkylborane.
▪ Because alkylboranes react rapidly with water and spontaneously burn when
exposed to the air, they are oxidized, without isolation, with basic hydrogen
peroxide (H2O2, HO–).
▪ Oxidation replaces the C – B bond with a C – O bond, forming a new OH group
with retention of configuration; that is, the OH group replaces the BH2 group in
the same position relative to the other three groups on carbon.

64
HYDROBORATION – OXIDATION
Example of Test Question
▪ Draw the product of the following reaction sequence, including stereochemistry.

Solution
▪ In Step [1], syn addition of BH3 to the unsymmetrical alkene adds the BH2 group
to the less substituted carbon from above and below the planar double bond,
two enantiomeric alkylboranes are formed.
▪ In Step [2], oxidation replaces the BH2 group with OH in each enantiomer with
retention of configuration to yield two alcohols that are also enantiomers.

65
HYDROBORATION – OXIDATION

Thus, to draw the product of a hydroboration–oxidation reaction, keep in mind

two stereochemical facts:
▪ Hydroboration occurs with syn addition.
▪ Oxidation occurs with retention of confi guration.

66
HYDROBORATION – OXIDATION: SUMMARY

67
ALKENE TO ALCOHOL
▪ Hydration (H2O, H+) and hydroboration–oxidation (BH3 followed by H2O2, HO–)
both add the elements of H2O across a double bond.
▪ Despite their similarities, these reactions often form different constitutional
isomers.

▪ With H2O + H2SO4, electrophilic addition of H and OH places the H atom on the
less substituted carbon of the alkene to yield a 2° alcohol.
▪ In contrast, addition of BH3 gives an alkylborane with the BH2 group on the less
substituted terminal carbon of the alkene. Oxidation replaces BH2 by OH to yield
a 1° alcohol.
68
ALKENE TO ALCOHOL - SUMMARY
Conditions Regiochemistry Stereochemistry Rearrangement
Hydration
H2O, with acid catalyst Markovnikov Syn and Anti Frequent
such as H2SO4
Oxymercuration-demercuration
1. Hg(Oac)2, THF-H2O Markovnikov Syn and Anti Seldom
2. NaBH4, HO-
Hydroboration-oxidation
1. BH3, THF Anti-Markovnikov Syn Seldom
2. H2O2, HO-

69
CLASS ACTIVITY 6.3
1. Write the structure of the major organic product obtained by hydroboration-
oxidation of each of the following alkenes.
a. 2-Methylpropene
b. Cyclopentene
c. cis-2-Butene
d. 3-Ethyl-2-pentene
e. 3-Ethyl-1-pentene

2. Redo the reaction, but used H2O with H2SO4 as catalyst. Compare the alcohol
formed from both methods.
3. Which alkene would be expected to give the following alcohol by
oxymercuration - demercuration?

70
CLASS ACTIVITY 6.3
4. Given that 2-methyl-1-pentene undergoes oxymercuration–demercuration
approximately 35 times faster than 2-methyl-2-pentene, predict the major
product from oxymercuration–demercuration of limonene.

71
HALOGENATION
▪ Halogenation is the addition of halogen X2 (X = Cl or Br) to an alkene, forming a
vicinal dihalide.

72
HALOGENATION (CONT.)
An example is the addition of chlorine to ethene.

This addition is a useful industrial process because 1,2-dichloroethane can be used

as a solvent and can be used to make vinyl chloride, the starting material for
poly(vinyl chloride).

73
HALOGENATION (CONT.)
When bromine is used for this reaction, it can serve as a test for the presence of
carbon–carbon multiple bonds. If we add bromine to an alkene (or alkyn), the red
brown color of the bromine disappears almost instantly as long as the alkene (or
alkyne) is present in excess:

This behavior contrasts markedly with that of alkanes. Alkanes do not react
appreciably with bromine or chlorine at room temperature and in the absence of
light.

74
HALOGENATION - MECHANISM
Attention – Halogenation has different mechanism than hydrohalogenation and
hydration.

▪ Four bonds are broken or formed in this step: the electron pair in the π bond and
a lone pair on a halogen atom are used to form two new C – X bonds. The X – X
bond is also cleaved heterolytically, forming X–. This step is rate-determining.
▪ The three-membered ring containing a positively charged halogen atom is called
a bridged halonium ion. This strained three-membered ring is highly unstable,
making it amenable to opening of the ring in the second step.

75
HALOGENATION – MECHANISM (CONT.)

▪ Nucleophilic attack of X– opens the ring of the halonium ion, forming a new C – X
bond and relieving the strain in the three-membered ring.

Two facts demonstrate that halogenation follows a different mechanism from that
of hydrohalogenation or hydration.
▪ First, no rearrangements occur, and second, only anti addition of X2 is observed.

76
HALOGENATION – MECHANISM (CONT.)
To draw the products of halogenation:
▪ Add Br2 in an anti fashion across the double bond, leaving all other groups in
their original orientations. Draw the products such that a given Br atom is above
the plane in one product and below the plane in the other product.
▪ Sometimes this reaction produces two stereoisomers, as in the case of cis-2-
butene, which forms an equal amount of two enantiomers. Sometimes it
produces a single compound, as in the case of trans-2-butene, where a meso
compound is formed.

77
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.

78
HALOHYDRIN FORMATION - MECHANISM

▪ Four bonds are broken or formed in this step: the electron pair in the π bond and
a lone pair on a halogen atom are used to form two new C – X bonds in the
bridged halonium ion.
▪ The X – X bond is also cleaved heterolytically, forming X–. This step is rate
determining.

79
HALOHYDRIN FORMATION - MECHANISM

▪ Nucleophilic attack of H2O opens the halonium ion ring, forming a new C – O
bond. Subsequent loss of a proton forms the neutral halohydrin.
▪ 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.

80
HALOHYDRIN FORMATION - STEREOCHEMISTRY
▪ Because the bridged halonium ion ring is opened by backside attack of H2O,
addition of X and OH occurs in an anti fashion and trans products are formed.

81
HALOHYDRIN FORMATION - STEREOCHEMISTRY
▪ With unsymmetrical alkenes, two constitutional isomers are possible from
addition of X and OH, but only one is formed.
.

82
HALOHYDRIN FORMATION - STEREOCHEMISTRY
▪ The preferred product has the electrophile X+ bonded to the less substituted
carbon atom—that is, the carbon that has more H atoms to begin with in the
reacting alkene.
▪ Thus, the nucleophile (H2O) bonds to the more substituted carbon.

83
HALOHYDRIN FORMATION - SUMMARY

84
CLASS ACTIVITY 6.4
1. Give the structure of the product formed when each of the following alkenes
reacts with bromine.

a. 2-Methyl-1-butane
b. 3-Methyl-1-butane
c. 2-Methyl-2-butane
d. 1-Methylcyclopentene

2. Redo the reaction in part 1, but used bromine in water, instead of only bromine.
3. Redo the reaction in part 1, but used bromine in the presence of H2O2 and OH-,
instead of only bromine.

85
KEEPING TRACK OF REACTIONS
▪ Lecture 4-6 introduced three basic kinds of organic reactions: nucleophilic
substitution, β elimination, and addition, respectively.
▪ In the process, many specific reagents have been discussed and the
stereochemistry that results from many different mechanisms has been
examined.
▪ How can we keep track of all the reactions?

86
KEEPING TRACK OF REACTIONS (CONT.)
To make the process easier, remember that most organic molecules undergo only
one or two different kinds of reactions. For example:
▪ Alkyl halides undergo substitution and elimination because they have good
leaving groups.
▪ Alcohols also undergo substitution and elimination, but can do so only when OH
is made into a good leaving group.
▪ Alkenes undergo addition because they have easily broken π bonds.

87
KEEPING TRACK OF REACTIONS (CONT.)
▪ You must still learn many reaction details (Lecture 7-8: Reaction of Aromatic
Compounds), and in truth, there is no one method to learn them.
▪ You must practice these reactions over and over again, not by merely looking at
them, but by writing them.
▪ Learning reactions is really a two-step process.
1. First, learn the basic type of reaction for a functional group. This provides
an overall organization to the reactions.
2. Second, learn the specific reagents for each reaction. It helps to classify the
reagent according to its properties. Is it an acid or a base? Is it a
nucleophile or an electrophile? Is it an oxidizing agent or a reducing agent?

88
KEEPING TRACK OF REACTIONS (CONT.)
Example of Test Question.
▪ Draw the product of each reaction.

The reactant is a 1° alkyl halide, which can

undergo substitution and elimination. The
reagent [KOC(CH3)3] is a strong, big, and
bulky base, favoring the source of
elimination by an E2 mechanism.

89
KEEPING TRACK OF REACTIONS (CONT.)
Example of Test Question.
▪ Draw the product of each reaction.

The reactant is an alkene, which undergoes

addition reactions to its π bond. The reagent
(Br2 + H2O) serves as the source of the
electrophile Br+, resulting in addition of Br
and OH to the double bond.

90
ALKENE IN ORGANIC SYNTHESIS
▪ Alkenes are a central functional group in organic chemistry. Alkenes are easily
prepared by elimination reactions such as dehydrohalogenation and
dehydration.
▪ Because their π bond is easily broken, they undergo many addition reactions to
prepare a variety of useful compounds.

91
ALKENE IN ORGANIC SYNTHESIS
To solve this problem we must:
▪ Work backwards from the product by asking: What type of reactions introduce
the functional groups in the product?
▪ Work forwards from the starting material by asking: What type of reactions
does the starting material undergo?

92
ALKENE IN ORGANIC SYNTHESIS
▪ Working backwards from the product to determine the starting material from
which it is made is called retrosynthetic analysis.
▪ We know reactions that answer each of these questions.

93
ALKENE IN ORGANIC SYNTHESIS

▪ Cyclohexene is called a synthetic intermediate, or simply an intermediate,

because it is the product of one step and the starting material of another.
▪ We now have a two-step sequence to convert cyclohexanol to 1,2-
dibromocyclohexane, and the synthesis is complete.
▪ Take note of the central role of the alkene in this synthesis

94
CLASS ACTIVITY 6.5
1. Devise a synthesis of each product from the given starting material. More than
one step is required.

a. b.

c. d.

95