5/15/2012 1 Session 26 Organic Chemistry, UNAM School of Medicine 1 Electrophilic addition reactions of Electrophilic addition reactions of Electrophilic addition reactions of Electrophilic addition reactions of alkenes alkenes alkenes alkenes Dr L.H.A. Prins (Ph.D.) Dept. of Pharmacy UNAM Learning Outcomes 2 By the end of this session, the student should understand: Electrophilic addition of hydrogen halides to alkenes Addition of water to alkenes Addition of alcohol to alkenes Addition of hydrogen to alkenes Organic Chemistry, UNAM School of Medicine
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5/15/2012
1
Session 26
Organic Chemistry, UNAM School of Medicine1
Electrophilic addition reactions of Electrophilic addition reactions of Electrophilic addition reactions of Electrophilic addition reactions of
alkenesalkenesalkenesalkenes
Dr L.H.A. Prins (Ph.D.)
Dept. of Pharmacy
UNAM
Learning Outcomes
2
� By the end of this session, the student should understand:
�Electrophilic addition of hydrogen halides to alkenes
�Addition of water to alkenes
�Addition of alcohol to alkenes
�Addition of hydrogen to alkenes
Organic Chemistry, UNAM School of Medicine
5/15/2012
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Reactivity of alkenesReactivity of alkenesReactivity of alkenesReactivity of alkenes
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� Double bond of alkenes – consist
of a σ & a π bond
� ̟ bond is weaker than the σ bond
� ∴ ̟ bond is broken when an
alkene undergoes a reaction
� Alkenes = e−-rich, because ̟ bond consists of a cloud of e− above
& below ̟ bond
� ∴ Alkenes = nucleophiles & they can react with electrophiles
Organic Chemistry, UNAM School of Medicine
Electrophilic Electrophilic Electrophilic Electrophilic addition addition addition addition of of of of hydrogen halides hydrogen halides hydrogen halides hydrogen halides
� All alkene reactions have one feature in common: Delocalised ̟
e− of the C-C double bond are attracted to an electrophile (E)
� Each reaction starts with addition of E to one of the sp2 carbons of
the alkene & concludes with addition of a nucleophile (Nu) to the
other sp2 carbon
� ∴ End result = ̟ bond breaks & sp2 carbons form new σ bonds
with the E & Nu
Organic Chemistry, UNAM School of Medicine
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Electrophilic Electrophilic Electrophilic Electrophilic addition addition addition addition of of of of hydrogen halides hydrogen halides hydrogen halides hydrogen halides
Electrophilic Electrophilic Electrophilic Electrophilic addition addition addition addition of of of of hydrogen halides hydrogen halides hydrogen halides hydrogen halides
� Electrophilic addition reaction of alkenes make them an
important class of organic compounds, because they can be used to
synthesise a wide variety of other compounds
� Product obtained depends on electrophile & nucleophile used in the
addition reaction
� If electrophilic reagent that adds to an alkene is a hydrogen halide
(HF, HCl, HBr or HI) – reaction product will be a halo-alkane
(alkyl halide)
Organic Chemistry, UNAM School of Medicine
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Electrophilic Electrophilic Electrophilic Electrophilic addition addition addition addition of of of of hydrogen halides hydrogen halides hydrogen halides hydrogen halides
� Because alkenes above have the same substituents on both sp2 carbons, it
does not make any difference which sp2 carbon the E & Nu attach to
� ∴ Same product will be obtained in either case
� But what happens if alkene does not have the same substituents on both
sp2 carbons?
Organic Chemistry, UNAM School of Medicine
Electrophilic Electrophilic Electrophilic Electrophilic addition addition addition addition of of of of hydrogen halides hydrogen halides hydrogen halides hydrogen halides
� When reaction is carried out, only product isolated is tert-butyl
chloride (product 1)
� Step 1 of reaction (addition of E (H+) to an sp2 carbon ) = rate-
determining step!
� ∴The particular carbocation that is formed faster determines final
product of reaction
Organic Chemistry, UNAM School of Medicine
HCl orHCl
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Electrophilic Electrophilic Electrophilic Electrophilic addition addition addition addition of of of of hydrogen halides hydrogen halides hydrogen halides hydrogen halides
� Why is tert-butyl carbocation formed faster than isobutyl carbocation?
� Answer lies in the stability of the carbocation
� Carbocation classification - according to # of alkyl substituents bonded
to + charged C
� Carbocation stability ↑ as the # of alkyl substituents bonded to +
charged C ↑
Organic Chemistry, UNAM School of Medicine
� tert-butyl cation (a 3° carbocation)� isobutyl cation (a 1° carbocation)
RegioselectivityRegioselectivityRegioselectivityRegioselectivity of electrophilic addition of electrophilic addition of electrophilic addition of electrophilic addition
reactionsreactionsreactionsreactions
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� In both cases: More stable 3° carbocation formed more rapidly than less stable 2° carbocation
� ∴ Major product of each reaction = one that results from forming the 3°carbocation
Organic Chemistry, UNAM School of Medicine
Hl
Major product Minor product
Major product Minor product
HBr
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RegioselectivityRegioselectivityRegioselectivityRegioselectivity of electrophilic addition of electrophilic addition of electrophilic addition of electrophilic addition
reactionsreactionsreactionsreactions
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� The 2 products of each of these reactions are structural isomers of
one another
� Reaction in which 2 or more structural isomers could be obtained as
products, but 1 of them predominates (obtained in larger amounts
than the other products), is called a regioselective reaction
� Regioselectivity = the preferential formation of one structural
isomer over the other
Organic Chemistry, UNAM School of Medicine
RegioselectivityRegioselectivityRegioselectivityRegioselectivity of electrophilic addition of electrophilic addition of electrophilic addition of electrophilic addition
reactionsreactionsreactionsreactions
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� Addition of HBr to 2-pentene is not regioselective:
� Addition of H+ to either sp2 carbons produces a 2° carbocation, both carbocation intermediates have the same stability, so both will be
formed equally easily� ∴∴∴∴Approximately equal amounts of the two alkyl halides will be
� By examining all addition reactions of hydrogen halides to alkenes we
have seen so far, we can devise a rule that applies to all electrophilic
addition reactions to alkenes: the electrophile (H+) adds to the sp2
carbon that is bonded to the greater number of hydrogens
� This rule is referred to as Markovnikov’s rule
Organic Chemistry, UNAM School of Medicine
HCl
H+ will preferentially add to C-1 & NOT to C-2!!
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2
Electrophilic Electrophilic Electrophilic Electrophilic addition of Haddition of Haddition of Haddition of H2222O O O O ---- HydrationHydrationHydrationHydration
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� When H2O is added to an alkene, no reaction takes place
� Reason: O–H bonds of H2O are too strong – water is too weakly acidic –
to allow the H to act as E to start the reaction by adding to the
nucleophilic alkene
� If an acid (ex. HCl or H2SO4) is added as a catalyst, a reaction will
occur
� Reason:The acid provides an electrophile (H+)
� Product of the reaction is an alcohol
� Hydration = addition of H2O to any molecule
Organic Chemistry, UNAM School of Medicine
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Electrophilic Electrophilic Electrophilic Electrophilic addition of Haddition of Haddition of Haddition of H2222O O O O ---- HydrationHydrationHydrationHydration
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� First 2 steps of mechanism for acid-catalysed addition of H2O to alkene -
essentially the same as first 2 steps of mechanism for addition of
hydrogen halide to alkene. Results in formation of a protonated alcohol
� Protonated alcohols = very strong acids (proton donors)
� ∴ In 3rd step of reaction, protonated alcohol loses a proton (H+) to form
the final product, an alcohol
Organic Chemistry, UNAM School of Medicine
Electrophilic Electrophilic Electrophilic Electrophilic addition of Haddition of Haddition of Haddition of H2222O O O O ---- HydrationHydrationHydrationHydration
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� A H+ (donated from HCl or H2SO4) adds to alkene in 1st step & a
H+ is returned to reaction mixture in final step
� ∴ H+ is not consumed in the reaction
� The acid acts as a catalyst in the reaction – this is an acid-
catalysed reaction
Organic Chemistry, UNAM School of Medicine
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Electrophilic Electrophilic Electrophilic Electrophilic addition of alcohol (Raddition of alcohol (Raddition of alcohol (Raddition of alcohol (R----OH)OH)OH)OH)
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� Alcohols react with alkenes in the same way that H2O does
� As with addition of H2O, addition of alcohol requires an acid catalyst
� Product of reaction = ether
� Mechanism for acid-catalysed addition of alcohol is essentially the
same as mechanism for acid-catalysed addition of H2O
� Only difference: Nu is ROH instead of H2O
Organic Chemistry, UNAM School of Medicine
HCl
Electrophilic Electrophilic Electrophilic Electrophilic addition of alcohol (Raddition of alcohol (Raddition of alcohol (Raddition of alcohol (R----OH)OH)OH)OH)
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� NB!!! - Do not memorise the products of alkene addition
reactions
� Know the reaction mechanism
� When presented with a reaction, ask yourself: “Which is the
electrophile?” & “Which is the nucleophile?”
Organic Chemistry, UNAM School of Medicine
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Electrophilic Electrophilic Electrophilic Electrophilic addition addition addition addition of of of of hydrogen (Hhydrogen (Hhydrogen (Hhydrogen (H2222) ) ) ) ----