1.

Concept of alkenes
Alkenes are unsaturated hydrocarbons which contain one
carbon–carbon double bond. Early chemists noted that
an oily substance was formed when ethene (H2C=CH2)
the smallest alkene, reacted with chlorine. On the basis
of this observation, alkenes were originally called olefins
(oil forming). The general formula of acyclic alkenes is
CnH2n. The general formula of cyclic alkenes is CnH2n-2.

Alkenes are characterized by sp2-hybridization and

their double bond contains σ- and π-bonds.
 Alkenes play many
important roles in
biology. Ethene, for
example, is a plant
hormone — a
compound that controls
the plant’s growth and
other changes in its
tissues. Ethene affects
seed germination,
flower maturation, and
fruit ripening.
2. The nomenclature of alkenes
The systematic (IUPAC) name of an alkene
is obtained by replacing the “ane” ending of
the corresponding alkane with “ene.” For
example, a two-carbon alkene is called
ethene and a three-carbon alkene is called
propene. Ethene also is frequently called
by its common name: ethylene.
 Most alkene names need a number to indicate
the position of the double bond. The IUPAC
rules:
1. The longest continuous chain containing the functional
group (in this case, the carbon–carbon double bond) is
numbered in a direction that gives the functional group suffix
the lowest possible number. For example, 1-butene signifies
that the double bond is between the first and second
carbons of butene; 2-hexene signifies that the double bond
is between the second and third carbons of hexene.
2. The name of a substituent is cited before the
name of the longest continuous chain containing
the functional group, together with a number to
designate the carbon to which the substituent is
attached. Notice that the chain is still numbered in
the direction that gives the functional group suffix
the lowest possible number.
3. If a chain has more than one substituent,
the substituents are cited in alphabetical
order. The prefixes di, tri, sec, and tert are
ignored in alphabetizing, but iso, neo, and
cyclo are not ignored.
4. If the same number for the alkene
functional group suffix is obtained in both
directions, the correct name is the name
that contains the lowest substituent number.
5. In cyclic alkenes, a number is not needed to denote the
position of the functional group, because the ring is always
numbered so that the double bond is between carbons 1 and 2.

In cyclohexenes numbering is in the direction that puts the lowest

substituent number, not in the direction that gives the lowest sum
of the substituent numbers.
6. If both directions lead to the same number
for the alkene functional group suffix and
the same low number(s) for one or more of
the substituents, then those substituents
are ignored and the direction is chosen
that gives the lowest number to one of the
remaining substituents.
Two groups containing
a carbon–carbon
double bond are used
in common names —
the vinyl group and
the allyl group.
The vinyl group is the smallest possible group that
contains a vinylic carbon; the allyl group is the smallest
possible group that contains an allylic carbon. When
“allyl” is used in nomenclature, the substituent must be
attached to the allylic carbon.
 3. The isomery of alkenes
Although ethylene is the only two-carbon alkene, and
propene the only three-carbon alkene, there are
four isomeric alkenes of molecular formula C 4H8:

1-butene, 2-methylpropene and 2-butene (cis- and

trans-)are structural isomers of butene. cis-2-butene and
trans-2-butene are geometrical isomers of butene.
When there are 3 or 4 different substituents near
2 carbon atoms connected by double bond, the
E,Z-system is used to name the compound.

H 3C CH2 CH3
C C
H3C H2C CH2 CH2 CH3
Z-4-ethyl-3-methylheptene-3
H3C CH2 CH2 CH3
C C
H3C H2C CH2 CH3
E-4-ethyl-3-methylheptene-3
 4. The methods of extraction of
alkenes
Alkenes are in oil and gas in small amount. There are
methods of their extraction from oil and gas.

Artificial methods:
1. Dehydration of saturated alcohols

H2C CH2
H2SO4,t
CH2 CH2 + H2O
H OH ethylene
ethanol
 When the molecule contain a long brunched
carbon chain, not all carbon-hydrogen bonds
can be destroyed. If the atom of carbon is
connected with only 1 hydrogen atom, it
gives the hydrogen atom more easily than
the carbon atom which is connected with 2 or
3 atoms of hydrogen. This rule is named
Zajtsev rule.
CH3
CH3
H3C HC C CH3 H2SO4,t
H3C HC C CH3 + H2O
OH H 2-methylbutene-2
3-methylbutanol-2
 2. Dehydrohalogenation of
monohalogenalkanes
H3C HC CH2
NaOH
H3C HC CH2 + H2O + NaBr
H Br propene
1-brompropane

3. Dehalogenation of dihalogenalkanes
H3C HC CH CH3
KOH
+ Zn H3C HC CH CH3 + ZnBr2
Br Br
butene-2
2,3-dibrombutane
 4. Dehydrogenation of alkanes

CH3 CH2 CH3 Ni

CH2 CH CH3 + H2
propane propene

5. Hydrogenation of alkynes
Pt, Pd
CH C CH3 + H2 CH2 CH CH3
 4. Dehydrogenation of alkanes

CH3 CH2 CH3 Ni

CH2 CH CH3 + H2
propane propene

5. Hydrogenation of alkynes
Pt, Pd
CH C CH3 + H2 CH2 CH CH3
 5. Physical properties of
alkenes
Alkenes resemble alkanes in most of their physical
properties. The lower molecular weight alkenes
through C4H8 are gases at room temperature and
atmospheric pressure. Alkenes which contain carbon
atoms (C5 – C17) are liquids and alkenes with carbon
chain (≥C18) are solids.
All alkenes are not dissolvable in water but are
dissolvable in some organic solvents.
n-alkenes have higher boiling temperatures than
their isomers with brunched carbon chain.
 6. Chemical properties of
alkenes

Alkenes are very active, they can react with

many compounds, because of the presence of
double bond in their molecule.
 Vladimir Markovnikov, ahli kimia Rusia (University of Kazan),
mengamati bahwa dimana ada dua isomer dapat terbentuk, maka
salah satu isomer biasanya lebih dominan (produk utama). Dia
mengemukakan (1869) bahwa orientasi dari adisi mengikuti suatu
pola yang disimpulkan sebagai berikut:
Adisi suatu asam (HX) pada ikatan rangkap karbon-karbon dari
suatu alkena (asimetris), hidrogen (H +) dari asam akan terikat
(menuju) pada karbon yang sudah mengikat (memiliki) hidrogen
dengan jumlah yang lebih banyak. Pernyataan ini dikenal sebagai
aturan Markovnikov.
 Karash dan Mayo dari University of Chicago (1933 ),
mengemukakan bahwa bila menambahkan peroksida pada sistem
reaksi, maka asam (HBr) akan mengadisi alkena dengan arah
sebaliknya (orientasinya berlawanan aturan Markovnikov/ anti-
Markovnikov). Hal ini dikenal dengan efek peroksida (senyawa
yang mengandung ikatan O-O-).
 Karash dan Mayo juga mengemukakan bahwa adisi ini dapat terjadi
dalam mekanisme yang berbeda: Adisi Markovnikov dengan
mekanisme elektrofilik, dan adisi anti-Markovnikov berlangsung
dengan mekanisme radikal bebas.
1,2-
propanadio
 III. Reactions of
polymerization
CH2═CH2 + CH2═CH2 + CH2═CH2 + … →

−CH2−CH2− + −CH2−CH2− + −CH2−CH2− + … →

−CH2−CH2−CH2−CH2−CH2−CH2− …
 7. The nomenclature of dienes
Dienes are unsaturated hydrocarbons that contain two double
bonds. The general formula of dienes is C2H2n-2. There are 3 types of
location of double bonds in molecule.
The systematic (IUPAC) name of an dienes is obtained
by replacing the “ane” ending of the corresponding
alkane with “diene.”
8. Configurational isomers
of dienes
A diene such as 1-chloro-2,4-heptadiene has four
configurational isomers because each of the double
bonds can have either the E or the Z configuration.
Thus, there are E-E, Z-Z, E-Z, and Z-E isomers.
 9. The methods of
extraction of dienes
1. Dehydrogenation of alkanes and alkenes
Cr2O3, Al2O3, t=650
H3C CH2 CH2 CH3 -2H2 H2C CH CH CH2

2. Dehydration of diols (alcohols with 2 –OH groups)

H 2C CH2 CH CH3 Al O , t=280
2 3
H 2C CH CH CH2
-2H2O
OH OH

3. Dehydration of unsaturated alkohols

cat.
H3C CH CH CH2 OH H2C CH CH CH2
-H2O
 10. Chemical properties of dienes
1. Hydrogenation
Ni,Pt
H2C CH CH CH2 +H2 H3C CH CH CH3

2. Halogenation
Br Br
H2C CH CH CH2
Ni,Pt
H2C CH CH CH2 +Br2
Br Br
H2C CH CH H3C
 3. Hydrohalogenation

4. The Diels–Alder reaction

If a Diels–Alder reaction creates an acymmetric carbon in the
product, identical amounts of the R and S enantiomers will be
formed. In other words, the product will be a racemic mixture.

5. Polymerization
nCH2=CH−CH=CH2 → −(−CH2−CH=CH−CH2−)−n
 11.The nomenclature and
isomery of alkynes
Alkynes are unsaturated hydrocarbons which
contain only one triple (−C≡C−) bond. They
conform to the general formula C2H2n-2, for one
triple bond. The IUPAC system for naming alkynes
employs the ending -yne instead of the -ane used
for naming of the corresponding saturated
hydrocarbons:
The numbering system for locating the triple bond and
substituent groups is analogous to that used for the
corresponding alkenes:

Hydrocarbons with more than one triple bond are called

alkadiynes, alkatriynes, and so on, according to the
number of triple bonds. Hydrocarbons with both double and
triple bonds are called alkenynes (not alkynenes). The
chain always should be numbered to give the multiple
bonds the lowest possible numbers, and when there is a
choice, double bonds are given lower numbers than triple
bonds. For example,
 12. The nomenclature and
isomery of alkynes
Alkynes (or acetylenes) are hydrocarbons that
contain one carbon-carbon triple bond. This bond
consists of one σ-bond and two π-bonds. The carbon
atoms which are connected by triple bond are
characterized by sp-hybridization. The general
formula of acyclic alkynes is CnH2n-2. The simplest
alkyne is acetylene (CH≡CH).
The IUPAC system for naming alkynes employs the
ending -yne instead of the -ane used for naming of
the corresponding saturated hydrocarbon:
 The numbering system for locating the triple bond
and substituent groups is analogous to that used for
the corresponding alkenes:

Both acetylene and ethyne are acceptable IUPAC

names for HC≡CH. The position of the triple bond
along the chain is specified by number in a manner
analogous to alkene nomenclature.
Hydrocarbons with more than one triple bond are
called alkadiynes, alkatriynes, and so on,
according to the number of triple bonds.
Hydrocarbons with both double and triple bonds
are called alkenynes (not alkynenes). The chain
always should be numbered to give the multiple
bonds the lowest possible numbers, and when
there is a choice, double bonds are given lower
numbers than triple bonds. For example,
The hydrocarbon substituents derived from
alkynes are called alkynyl groups:

Alkynes are characterized by structural isomery:

isomery of carbon chain and different location of
triple bond (isomery of location).
 13. The methods of extraction
of alkynes
1. Acetylene was first characterized by the French chemist P. E. M.
Berthelot in 1862 and did not command much attention until its large-
scale preparation from calcium carbide in the last decade of the
nineteenth century stimulated interest in industrial applications. In the first
stage of that synthesis, limestone and coke, a material rich in elemental
carbon obtained from coal, are heated in an electric furnace to form
calcium carbide. Calcium carbide is the calcium salt of the doubly
negative carbide ion .
Carbide dianion is strongly basic and reacts with water to form
acetylene:
 2. Beginning in the middle of the twentieth
century, alternative methods of acetylene
production became practical. One of these is
based on the dehydrogenation of ethylene. At
very high temperatures most hydrocarbons, even
methane, are converted to acetylene. Acetylene
has value not only by itself but is also the starting
material from which higher alkynes are prepared.
 3. Alkylation of acetylene
NaNH2 C2H5Br
HC CH HC CNa HC C CH3
-NH3 -NaBr

4. Dehydrohalogenation of dihalogenalkanes and

halogenalkenes

H Br
2NaOH, t
HC CH HC CH + 2NaBr + 2H2O
(C2H5OH)

Br H
 Natural products that contain carbon–
carbon triple bonds are numerous. Two
examples are tariric acid, from the seed fat of
a Guatemalan plant, and cicutoxin, a
poisonous substance isolated from water
hemlock.
 14. Physical properties
The most distinctive aspect of the chemistry of acetylenes
is their acidity. As a class, compounds of the type RC≡CH are
the most acidic of all simple hydrocarbons.
In the homological row the first 3 alkynes (C2-C4) are
gases, alkynes with carbon chain C5-C15 are liquids and next
alkynes are solids.

15. Chemical properties

I. The reactions of joining
1. Halogenation
2. Hydrohalogenation

3. Hydration
 II. The reactions of substitution
1. The formation of acetylenides. Because of
their acidity alkynes can react like acids. In these
reactions the atoms of hydrogen are changed to
the atoms of metal.

HC≡CH + 2Ag(NH3)2OH → Ag−C≡C−Ag + 4NH3 + 2H2O

Silver acetylenide

2. The substitution of the atom of hydrogen in ≡C−H

–radical to atom of halogen:

CH3−CH≡C−H + Br2 → CH3−CH≡C−Br + HBr

 III. The reactions of the oxidation and
reduction
1. The oxidation of alkynes. In this reaction the
catalyst is KMnO4.

HC≡CH + 4[O] → COOH−COOH

2. The reduction of alkynes.

IV. The reactions of dimerisation,
trimerisation and tetramerisation
2HC≡CH → HC≡C−CH=CH2
vinilacetylene

3HC≡CH →