PHARMACEUTICAL
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ORGANIC CHEMISTRY
PHA 615 LEC
UNIT 5: ALKENES & ALKYNES
GENERAL PROPERTIES OF ALKENES & ALKYNES
UNSATURATED HYDROCABONS
• Unsaturated hydrocarbon is a hydrocarbon (HC)
molecule in which one or more carbon– carbon multiple
bonds (double bonds, triple bonds, or both) are present.
o Major subgrouping:
▪ Alkenes — has one or more C—C double bonds.
▪ Alkynes — has one or more C—C triple bonds.
▪ Aromatic HC — has a special type of
“delocalized” bonding.
• Alkenes and Alkynes follows similar reaction mechanism
while the aromatic HC have a totally different reaction
mechanism.
• Index of Hydrogen Deficiency (IHD)
o Also known as the “number of sites of
unsaturation”.
o It is the number of pairs of hydrogen atoms that must
be removed from the corresponding “saturated”
formula to produce the molecular formula of the
compound of interest.
o Hydrogen deficiency can result from cyclic structures
and the presence of multiple bonds (double/triple
bonds).
o IHD can be computed from compounds with C, N, H,
O, S, and X.
ALKENES & CYCLOALKENE
• General formula: CnH2n (for alkene) and CnH2n-2 (for
cycloalkene)
o Alkenes have 2 fewer -H atoms and cycloalkenes
have 4 fewer -H atoms compared to alkanes with the
same # of C’s.
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o Alkene as substituent is called: -alkenyl
• Alkenes are commonly found in pheromones and
terpenes.
• C2-C4 alkenes are gas, C5-C17 alkenes with 1 C=C are
liquids, and alkenes with more C’s are solid at RT.
ALKYNES & CYCLOALKYNES
• General formula: CnH2n-2 (for alkyne) and CnH2n-4 (for
cycloalkyne)
o Alkynes have 4 fewer hydrogens compared to
alkanes with the same # of C’s; occurs less commonly
compared to alkenes.
o Possess similar physical properties with alkenes and
alkanes.
o The reactions of alkynes are closely similar to that of
the alkenes and focuses on the carbons participating
in the triple bond.
▪ However, alkynes can accommodate one more
addition reaction because it possesses 2 pi bonds
in the functional group.
GENERAL REACTION MECHANISM
• Alkenes/Alkynes follows a polar mechanism on its
reaction, specifically an electrophilic addition reaction.
When pi bonds are cleaved, one of the carbons in the
double/triple bond becomes an electrophile.
• Regiospecific is when only ONE of the two addition
product orientation if formed. This principle follows the
Markovnikov’s Rule.
• Markovnikov’s Rule
o It is proposed by Vladimir Markovnikov after observing
the addition of HX to an alkene.
o The rule states “that in the addition reaction of
alkenes, the more highly substituted carbocation is
formed rather than the less highly substitute one”.
• It can also be stated as the more stable carbocation is
formed over the less stable one.
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ELECTROPHILIC ADDITION REACTIONS (AE) OF

ALKENES

HYDRATION
• Hydration is the addition of water (H2O) to alkenes.
o H2O is added to the alkene in the presence of acidic
catalyst (e.g., H3PO4, HCl, H2SO4, and H+). The
nucleophile (-OH) from H2O is added to the
carbocation and forms a 2° ROH product.
• It may be destructive to molecules; thus other methods
were also invented.
o Other methods include: Oxymercuration,
Hydroboration, and Enzymatic hydration.
• Hydration reaction follows Markovnikov’s Rule, except
hydroboration.

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HYDROHALOGENATION
• Hydrohalogenation is the addition of hydrogen halide
(HX) to alkenes.
o The nucleophile (X-) from hydrogen halides (HF, HCl,
HBr, or HI) can be added to alkenes to form
monohalogenated alkane as a product.
o It follows Markovnikov’s Rule, where the nucleophilic
(X-) is added to the more stable carbocation in an
ether catalyzed solution.

• Halogenation is the addition of halogens (X2) to alkenes.
ETHER FORMATION
• Ether Formation is the addition of alcohol (ROH) to
alkene.
o When an alcohol (ROH) is added to an alkene, it forms
an ether product.
o The nucleophile (RO-) from ROH is added to the more
stable carbocation (C+). Similar to hydration, this
reaction requires an acid catalyst (H+).
o It also follows Markovnikov’s rule to determine the
more stable carbocation to be formed.
HALOGENATION
o The nucleophile (X-) from single mole of halogen (Cl2
or Br2) is added to alkenes in the presence of
DCM/CCl4 catalyst to form dihalogenated alkanes as
products.
o It follows the same mechanism as HX and H2O
addition, with the exception of Br2 addition occurring
with anti-stereochemistry (trans-).

HALOHYDRIN FORMATION
• Halohydrin Formation is the addition of halogen (X2) in
H2O to alkenes.
o A nucleophile of -X and -OH is added to the alkene
molecule following Markovnikov’s rule forming a
halohydrin product.
o This reaction proceeds with an anti-stereochemistry
(trans-) orientation.

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HYDROGENATION
• Hydrogenation is the addition of hydrogen (H2) to
alkenes.
o An H2 atom is added to alkenes in the presence of
Pd/PtO2 catalysts forming saturated products.
Addition of H2 atoms occurs with a syn
stereochemistry (cis-).
o This reaction is also generally called “reduction”
since the double bond is reduced to a single bond.
OXIDATION REACTION
• Oxidation Reaction is the exposure of alkene to an
oxidizing agent (e.g., KMnO4).
o Hydroxylation (mild oxidation) is done by reacting
alkenes with KMnO4 in basic solution (H2O/NaOH)
producing a vicinal diol product with syn
stereochemistry (cis-).
o Bond cleavage (strong oxidation) is similar to mild
oxidation in terms of the presence of oxidizing agent
(KMnO4), but the reaction takes place in acidic
solution (H3O+). Carbons in the double bond are
converted into different products depending on the
degree of oxidation.
▪ 2 oxidized bonds = ketone; 3 oxidized bonds
=RCOOH; and 4 oxidized bonds = CO2.

EPOXIDATION
• Epoxidation is the addition of peracid (RCOOOH) to
alkene:
o Peracid or also known as peroxy acid (RCOOOH) is a
class of organic compound with a -OOH group.
o m-chloroperoxybenzoic acid (mCPBA) is a compound
classified as a peroxy acid and a common reagent
used for this reaction.

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OZONOLYSIS ELECTROPHILIC ADDITION REACTIONS (AE) OF

• Ozonolysis is the oxidation reaction of alkene using ozone
(O3).
o This is the oxidative cleavage of the C-C multiple
bonds (double/triple bonds) among alkenes/alkynes. It
results in the formation of carbonyl products with the
more stable carbocation.
o It makes use of reactive O3 with a metal catalysts Zn.
ALKYNES
HYDROGENATION
• Hydrogenation is the addition of hydrogen (H2) to
alkynes.
o An atom of H2 adds to alkynes in the presence of Pd/C
or a Lindlar’s catalyst.
▪ Using a Lindlar’s catalyst specifically results into
an alkene with syn stereochemistry (cis-).

POLYMERIZATION
• Polymerization is the addition of a radical to alkenes.
o It follows the same 3 phases of radical mechanism
using Benzyloxy radical (BzO•). This reaction results
in the formation of longer carbon chains with
repeating polymers.
o The radical adds up to the alkene to undergo
propagation of the polymer.
HYDROHALOGENATION
• Hydrohalogenation is the addition of hydrogen halide
(HX) to alkynes.
o Alkynes can also react with HX forming
monohalogenated alkenes.
o With excess HX, alkynes can undergo further reaction
forming geminal halides or dihalide alkanes.
o It follows Markovnikov’s Rule, where the nucleophilic
(X-) is added to the more stable carbocation formed.

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HALOGENATION
• Halogenation is the addition of halides (X2) to alkynes.
o Alkynes can react with X2 similar to alkenes forming
vicinal halide.
o With excess X2, the reaction can result into the
formation of tetrasubstituted alkyl halide.
o It follows the same mechanism with X2 and alkenes
and forms anti-stereochemistry (trans-) product.

ACETYLIDE FORMATION
• Acetylide Formation is an elongation reaction of alkyne
with sodium amide (NaNH2) and an alkyl halide (RX).
o This reaction is specific only for terminal alkynes,
which are weakly acidic and react with NaNH2 forming
the acetylide ion.
o The acetylide ion is basic and nucleophilic and reacts
with primary RX forming longer chain alkynes (alkyne
elongation).

HYDRATION
• Hydration is the addition of water (H2O) to alkynes.
o H2O is added to alkynes in the presence of
H2SO4/HgSO4 catalyst to form an enol (alkene
alcohol) intermediate product.
o The enol intermediate product rearranges to a more
stable isomer, a ketone (more common) or an
aldehyde. This is called tautomerization (keto-enol
conversion).

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