OUTLINE
1. Alkenes and Dienes
a. Conjugated Diene
b. Cumulated Diene
c. Isolated Diene
2. Cis-trans Isomerism
3. E, Z Designation
4. Stability of Alkenes Figures 2, 3, and 4: Conjugated Dienes
a. Preparation of Alkenes
i. Dehydrolahogenation Cumulated Diene
ii. Dehydration ● 2 successive double bonds
b. Halogenation ● AKA “allene”
c. Hydrohalgenation ● 2 carbon atoms (sp2) share a common sp hybridized
d. Hydrohalogenation in the Presence of carbon atom
Water
e. Hydration
i. Oxymercuration
ii. Hydroboration
f. Reduction of Alkenes
g. Oxidation of Alkenes
i. Epoxidation
ii. Hydroxylation
h. Oxidative Cleavage of Alkenes
ALKENES
● Unsaturated hydrocarbon because of carbon-carbon
double bond
● AKA “olefin” → oil forming Figures 5, 6, and 7: Cumulated Dienes
● sp2 hybridized carbon atoms
● Examples: Ethylene, ⍺-Pinene, 𝛽-Carotene Isolated Diene
● 2 carbon-carbon double bonds are separated by 2 or
more single bonds (or sp3 hybridized carbon atoms)
● the delocalization breaks p orbitals
● less stable because there is no unhybridized p orbital
Figure 1: Examples of Alkenes
Figures 8 and 9: Isolated Dienes
Double Bonds
● shorter and stronger due to electron pulling property
● there is a sigma bond (stronger, head on)
CIS-TRANS ISOMERISM
● there is also a pi bond (weaker, sideways)
● mostly for di-substituted alkenes
● no rotation around the double bond
DIENES
○ creates different compounds that can be
● Unsaturated
● Contains at least 2 double bonds between carbon isolated
atoms ○ restricted rotation on the alkene
● different from E, Z Designation
Conjugated Diene ● ”same molecular formula, same attachment, but
● Has 2 double bonds separated by a single bond different position”
(“alternating”) ● normally observed in a ring (cyclic) or double bonds
● More stable compared to cumulated and isolated
diene Di-substituted alkenes
● This is because of the delocalization of electron ● because of restrictions, alkenes have 2 different
clouds in carbon atoms groups bonded to it
○ delocaization of pi electrons (in pi orbitals) ● AKA 2 substituents
● those 2 groups could either be on the same side or
opposite
CIS
● on the same side
● Example: cis-2-butene
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Figure 10: cis-2-butene Figure 13: Example of Z geometry. (Z)-2-Chloro-2-butene. On
● has 2 methyl groups on the same side the left side, the methyl group (CH3) has a higher priority
● the 2 hydrogen atoms are also on the same side compared to the hydrogen atom (H) because the carbon (C) in
● less stable because of steric strain (crowding) around (CH3) has a higher atomic number compared to (H). On the
the methyl groups right side, chlorine (Cl) is the higher priority because it has a
○ distorts bond angles higher atomic number than (C) from (CH3). Since this is a Z
○ could destabilize geometry, the higher ranks are on the same side.
TRANS Rule 1: Atomic Number
● on opposite sides ● the relative priorities of the groups depend on the
● Example: trans-2-butene ATOMIC NUMBER of the atoms that are boded
DIRECTLY to the sp2 carbon
● the greater the atomic number the higher the priority
Figure 11: trans-2-butene
● has 2 methyl groups on the opposite sides Figure 14: Examples of Z and E isomers. Bromine (Br) has a
● the hydrogen atoms are also on opposite sides higher atomic number than hydrogen (H) so it has a higher
● more stable because of little or no steric strain that priority. Also, chlorine (Cl) has a higher atomic number
can affect bond angles and bond overlaps compared to carbon (C) in (CH3) making (Cl) a higher priority.
Rule 2
E, Z DESIGNATION ● If same atom, choose another atom with higher
● for tri and tetra-substituted alkenes atomic number
● a system to specify the configuration of the groups ● in case there is a “tie”
about the carbon-carbon double bond
● most of the time, based on atomic number
E geometry
● German: ”entgegen” → means opposite
● opposite sides of the double bond
● higher-ranked (or higher priority groups) are on
opposite sides
Figure 15: Examples of Z and E isomers. On the left side,
chlorine (Cl) has a higher atomic number than carbon (C) in
(ClCH2). Although, there is (Cl) in (ClCH2), notice that the
bond is connected to the carbon (C) and not the (Cl) in
(ClCH2). In this case, since the “single” (Cl) has a higher
atomic number it will have a higher priority. On the left side,
notice that the bonds are connected to carbons. As the rule
states, if the same atom, choose another atom with a higher
atomic number. (CHCH3) and (CH2OH) both have “(CH)” in
Figure 12: Example of E geometry. (E)-2-Chloro-2-butene. On
the beginning. This means we have to pick another atom. In
the left side, the methyl group (CH3) has a higher priority
this case, oxygen (O) was chosen. Oxygen (O) has a higher
compared to the hydrogen atom (H) because the carbon (C) in
atomic number compared to carbon (C) in (CHCH3).
(CH3) has a higher atomic number compared to (H). On the
Therefore, (CH2OH) that contains oxygen (O) will have a
right side, chlorine (Cl) is the higher priority because it has a
higher priority.
higher atomic number than (C) from (CH3). Since this is an E
geometry, the higher ranks are on the opposite side.
STABILITY OF ALKENES
Z geometry
● German: “zusammen” → means together
Hyperconjugation
● “Zee Zame Zide”
● stabilizing interaction between the C=C pi bond and
● on same sides of the double bond
adjacent C-H sigma bond to the substituents
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FIgure 16: Hyperconjugation in propene
● the more substituents there are, the more stable the
alkene is
● the fewer the hydrogen bonded to the sp2 cabins of
an alkene, the more stable it is
● alkyl substituents stabilize both alkenes and
carbocations
● tetra > tri > di > mono
Figure 20: Other organic compounds that can be synthesized
from alkenes
Figure 17: The relative stabilities of alkyl-substituted alkenes
Preparation (of Alkenes) by Elimination
Bond Strength
● overlapping of orbitals Dehydrohalogenation
● s orbitals overlap more efficiently than p orbitals ● loss of HX (H-halide) from alkyl halide
● C-C bond between an sp3 carbon and an sp2 carbon ● reaction with the presence of strong base (ex. KOH)
is slightly stronger than a C-C bond between two sp3
carbons
○ sp3-sp2 bond is stronger than sp3-sp3 bond
○ A general rule, the more s-character in a
hybridized orbital, the stronger a bond it will
form
Figure 21: Example of dehydrohalogenation of
bromocyclohexane to form cyclohexene
Dehydration
● loss of H2O from alcohol
● presence of strong acid (ex. H2SO4) in a solvent →
THF (tetrahydrofuran)
○ Tetrahydrofuran or oxolane, (CH2)4O, is as a
heterocyclic compound, specifically a cyclic
Figures 18 and 19: 2-Butene is more stable because it has 2 ether. It is miscible with water and most
sp3-sp2 bonds compared to the less stable 1-Butene that has organic solvents.
only 1 sp2-sp3 and 1 sp3-sp3. Also, 2-Butene is di-substituted
while 1-Butene is monosubstituted. Therefore, 2-Butene is
more stable.
REACTIONS OF ALKENES
● Alkenes are nucleophiles
● from loosely held pi electrons Figure 22: Example of dehydration of 1-Methylcyclohexanol to
● by electrophilic addition reaction form 1-Methylcyclohexene
● important starting materials for the synthesis of other
organic compounds Halogenation
● addition reaction of halogen
● halogen is incorporated into the molecules of alkene
● rapid addition of Cl, Br solvent and starting material
for PVC (polyvinyl chloride)
○ Chlorination and Bromination are the most
common and don’t require a catalyst
○ Fluorination (not usual)
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Figure 23: Ethylene undergoes chlorination to form 1. Formation of bromonium ion (Br-) → a nucleophile
1,2-dichloroethane
● for cycloalkanes, this reaction occurs with anti
stereochemistry
○ anti stereochemistry → opposite sides
● Reaction intermediates: bromonium ion (R2Br+) and
chloronium ion (R2Cl+)
○ reaction intermediates are short-lived Figure 29.
2. Water acts as a
nucleophile
○ opens the
bromo ring
○ the oxygen
with the
positive
charge in the
second figure
is called
Oxonium ion
Figures 24 and 25: Cyclopentene undergoing bromination to
Figure 30.
form trans-1,2-Dibromocyclopentane
Hydrohalogenation
3. Deprotonation
● electrophilic addition of Hydrogen Halide (HX)
(removal of H+) of
oxonium ion and
Markovnikov’s rule
Bromohydrin
● “The halogen is added to the carbon which has more
Formation
substituents and the hydrogen is added to the other
carbon with less substituent.”
Figure 31.
Hydration
● electrophilic addition of H2O
● acid catalyzed alkene hydration (ex. H3PO4 →
Phosphoric acid)
● end product → alcohol
● Oxymercuration (with mercury acetate)
● Hydroboration (borane)
Figures 26 and 27: The hydrohalogenation of alkene and
cycloalkene. In this example, HCl is the hydrogen halide.
Hydrohalogenation in the presence of water Figure 32: Ethylene (an alkene) undergoes electrophilic
● through electrophilic addition addition of H2O to form ethanol (an alcohol)
● addition of X2 (halogen) in the presence of water to
yield halohydrin (X and OH) Hydration: Oxymercuration
○ If the X (halogen) is Br → “bromohydrin” ● initially involves electrophilic addition of Hg2+
○ If the X (halogen) is Cl → “chlorohydrin” ● in the end part, there’s demercuration → removal of
● In laboratories, NBS (N-bromosuccinamide) is Hg
utilized for more controlled release of Br2 ● Hg(OAc)2 → mercury acetate (aq) in THF
● NaBH4 → sodium borohydride (helps in
demercuration)
Markovnikov’s rule
● “the OH group attaches to the more highly substituted
carbon atom, and the H+ attaches to the less highly
substituted carbon.”
Figure 28: An alkene forming a halohydrin through
hydrohalogenation in the presence of water
Hydrobromination of Propene
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Epoxidation
● formation of epoxide (oxirane) as product
● oxirane → cyclic ether with an oxygen atom in a
three-membered ring
● there could be some carboxylic acid products
Figure 33: Example of oxymercuration ● an alkene can be formed to epoxide by peroxy acid
Hydration: Hydroboration
● B-H bonds
● involves trialkylborane intermediate (RBH2)
● BH3 (borane) → very reactive (acts as a Lewis Acid)
Figures 37 and 38: Examples of Epoxidation
Hydroxylation
Figure 34: Example of hydroboration
● to oxidize alkenes
● by treating an alkene with osmium tetroxide (OsO4)
Syn Stereochemistry
○ could also be potassium permanganate
● same side
(KMnO4) → must be Basic
● the opposite of anti
● formation of 1,2-diol (a vicinal glycol) → alcohol with
● Boron and hydrogen add to the alkene from the same
2 OH groups
face of the double bond with boron attaching to the
○ forms a cyclic intermediate
less highly substituted carbon
○ with Syn stereochemistry
○ Syn Non-Markovnikov Addition of Water
Figure 39: Examples of hydroxylation
Cleavage of Alkenes (Oxidative Cleavage)
Figure 35: Example of hydroboration
● alkenes could synthesize aldehydes and ketones
● 1,2-Diols are oxidized to ketones and/or aldehydes
Hydrogenation: Alkene Reduction
● Intermediate product → ozone (O3) adds rapidly to a
● Alkene to alkane
C=C bond to become molozonide that spontaneously
● addition of H atom on the surface of solid (metal)
rearranges to form an ozonide
catalyst (heterogenous reaction)
○ C=C bond could break with strong oxidizing
● catalyst examples
agents, cutting it to 2 pieces (ex. ozone, O3)
○ Platinum or Platinum dioxide (AKA Adams’
catalyst → Roger Adams)
○ Palladium
Reduction
● increases electron density on carbon
○ forming C-H
○ or breaking either (C-O, C-N, C-X)
● with Syn stereochemistry
Figure 40: Example of oxidative cleavage
SUMMARY POINTS:
● Alkenes and Dienes → double bonds
○ Conjugated Diene → alternating single
Figure 36: Example of hydrogenation and double bonds
○ Cumulated Diene → successive double
Oxidation of Alkenes bonds
○ Isolated Diene → double bonds
Oxidation separated by single bonds
● decrease electron density on carbon ● Cis-trans Isomerism → mostly for di-substituted C
○ forming (C-O, C-N, C-X) ○ Cis → same side
○ or breaking C-H
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○ Trans → opposite side
● E, Z Designation
○ E → entgegen → opposite side
○ Z → zusammen → zee zame zide
○ Rule 1 → Atomic Number
○ Rule 2 → Choose another atom with
higher atomic number
● Stability of Alkenes
○ Hyperconjugation → more substituents,
more stable → less H atoms, more stable
○ Bond Strength → sp3-sp2 bond is
stronger than sp3-sp3 bond
○ Reaction of Alkenes → addition reaction
○ Preparation of Alkenes → elimination
reaction
■ Dehydrohalogenation → loss of
HX → base: KOH
■ Dehydration → loss of H2O →
acid in THF (solvent)
○ Halogenation → addition of halogen
■ anti stereochemistry →
opposite
○ Hydrohalogenation → addition of
hydrogen halide
■ Halogen to more substituents
■ Hydrogen to less substituents
○ Hydrohalogenation in the Presence of
Water → addition of halogen in the
presence of water → yields halohydrin
○ Hydration → addition of H2O → end
product: alcohol
■ Oxymercuration → mercury
acetate in THF
● OH to more substituents
● H to less substituents
■ Hydroboration → borane
● syn stereochemistry →
same side/face of
double bond
● B to less substituents
(Syn Non-Markovnikov
addition)
○ Reduction of Alkenes → addition of H →
catalyst: platinum or palladium
○ Oxidation of Alkenes
■ Epoxidation → forms epoxide
(oxirane) by peroxy acid
■ Hydroxylation → forms 1,2-diol
(glycol)
○ Oxidative Cleavage of Alkenes →
ozone to molozonide to ozonide →
alkenes to ketones and/or aldehydes
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