Alkenes
Hydrocarbons containing double bonds
C C
double bond
the functional group
center of reactivity
Commercial Uses:
Ethylene
Commercial Uses:
Propylene
Other Polymers
Molecular Formula of Alkene
Noncyclic alkene: Cyclic alkene:
CnH2n CnH2n–2
CH3CH2=CH2
Special Nomenclatures
Structure of Alkene
Isomers of Alkene
Dipole Moments of Alkene Isomers
Conversion of alkene isomers requires breaking of
the π bond between the two sp2 carbons
Cis-Trans Interconversion in Vision
Alkene Synthesis
Overview
• E2 dehydrohalogenation (-HX)
• E1 dehydrohalogenation (-HX)
• Dehalogenation of vicinal dibromides (-X2)
• Dehydration of alcohols (-H2O)
Removing HX via E2
• Strong base abstracts H+ as X- leaves from
the adjacent carbon.
• Tertiary and hindered secondary alkyl
halides give good yields.
• Use a bulky base if the alkyl halide usually
forms substitution products.
Removing HX via E1
• Secondary or tertiary halides
• Formation of carbocation intermediate
• Weak nucleophile
• Usually have substitution products too
Dehydration of Alcohols
• Reversible reaction
• Use concentrated sulfuric or phosphoric
acid, remove low-boiling alkene as it forms.
• Protonation of OH converts it to a good
leaving group, HOH
• Carbocation intermediate, like E1
• Protic solvent removes adjacent H+
Industrial Methods
• Catalytic cracking of petroleum
– Long-chain alkane is heated with a catalyst to
produce an alkene and shorter alkane.
– Complex mixtures are produced.
• Dehydrogenation of alkanes
– Hydrogen (H2) is removed with heat, catalyst.
– Reaction is endothermic, but entropy-favored.
• Neither method is suitable for lab synthesis
Addition of Hydrogen to Alkenes
Catalytic Hydrogenation of an Alkene
Catalytic Hydrogenation of an Alkene
An alkene is an electron-rich molecule
A nucleophile
Nucleophile: an electron-rich atom or molecule
that shares electrons with electrophiles
Examples of Nucleophiles
Nucleophiles are attracted to electron-deficient
atoms or molecules (electrophiles)
Examples of Electrophiles
Electrophilic Addition of HBr to Alkene
Utilization of Curved Arrows
Rules for Use of Curved Arrows
∆H° can be calculated from bond dissociation
energies
Transition State versus Intermediate
intermediate
intermediate
Transition states have partially formed bonds
Intermediates have fully formed bonds
Electrophilic Addition of HBr to 2-Butene
The rate-limiting step controls the overall rate of the
reaction
Addition of Hydrogen Halides
What is the product?
Carbocation formation is the rate-limiting step
a more stable
carbocation
Markovnikov’s Rule
The electrophile adds to the sp2 carbon that is bonded to
the greater number of hydrogens
In a regioselective reaction, one constitutional isomer is the
major or the only product
tert-Butyl cation is formed faster and it is more stable
Addition of Water to Alkene
Hydration of Propene
Acid-Catalyzed Addition of Alcohol
Rearrangement of Carbocation
1,2-hydride shift a more stable
carbocation
Rearrangement of Carbocation
a more stable
1,2-methyl shift carbocation
Addition of Halogens to Alkene
Addition of Halogens
in the Presence of Water
Consider the transition states …
Oxymercuration and Mercuration
of Alkene
Demercuration by Reduction
Addition of Borane
Hydroboration–Oxidation
Anti-Markovnikov’s rule in product formation
Anti-Markovnikov Markovnikov
addition addition
(a pericyclic reaction)
Formation of Alkyl Boranes
OH Replacement of Boron
Anti-Markovnikov Addition
of an OH Group
Oxidation of Alkenes with Peroxyacids
Mechanism of Epoxidation of an Alkene
The addition of oxygen to an alkene is a stereospecific
reaction
Hydroxylation of Alkenes
Mechanism for cis-Glycol Formation
Higher yields of the diol are obtained with osmium
tetroxide
Oxidative Cleavage of 1,2-Diols
Oxidative Cleavage of Alkenes by
Ozonolysis
The alkene and ozone undergo a concerted cycloaddition
Mechanism of ozonide formation
The molozonide is unstable because it has two O–O
bonds
Ozonide is stable
Ozonides can be cleaved to carbonyl compounds
Examples of the Oxidative Cleavage of
Alkenes by Ozonolysis
A peroxyacid, OsO4, and (cold basic) KMnO4 break only
the π bond of the alkene
Ozone and acidic KMnO4 break both the π bond and the
σ bond
Table 20.1 Summary of the Methods Used to Oxidize an Alkene
Reaction of Carbene with Alkene
Synthesis of Bromobutane
Generation of Radicals
Addition of Radicals to Alkene
Relative Stabilities of Alkyl Radicals
Calculating the Change in H°
