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Reactions of Alkenes: Organic Chemistry, 5
Reactions of Alkenes: Organic Chemistry, 5
Jo Blackburn Richland College, Dallas, TX Dallas County Community College District 2003,Prentice Hall
Reactivity of C=C
Electrons in pi bond are loosely held. Electrophiles are attracted to the pi electrons. Carbocation intermediate forms. Nucleophile adds to the carbocation. Net result is addition to the double bond. =>
Chapter 8 2
Electrophilic Addition
Step 1: Pi electrons attack the electrophile.
E C C + E
+
C +
Chapter 8
=>
Types of Additions
=>
Chapter 8 4
Addition of HX (1)
Protonation of double bond yields the most stable carbocation. Positive charge goes to the carbon that was not protonated.
CH3 CH3 CH3 C CH CH3 H Br CH3 C CH CH3 + H
X
Chapter 8
=>
5
Addition of HX (2)
CH3 CH3 C CH CH3 H Br CH3 CH3 C CH CH3 + H + Br _
=>
Regiospecificity
Markovnikovs Rule: The proton of an acid adds to the carbon in the double bond that already has the most Hs. Rich get richer. More general Markovnikovs Rule: In an electrophilic addition to an alkene, the electrophile adds in such a way as to form the most stable intermediate. HCl, HBr, and HI add to alkenes to form Markovnikov products. =>
Chapter 8 7
R O
O R
R O H
+ Br
=>
Electrophile
9
Propagation Steps
Bromine adds to the double bond.
Br
+
C C
C C Br
H Br
C C Br H
Br
Electrophile =>
10
Anti-Markovnikov ??
CH3 CH3 C CH CH3
Br
Hydration of Alkenes
H C C alkene + H2O
+
H OH C C alcohol
Reverse of dehydration of alcohol Use very dilute solutions of H2SO4 or H3PO4 to drive equilibrium toward hydration. =>
Chapter 8 12
+ C C
H + H O H + H2O C C
H + H O H C C + H2O
H H O C C + H3O +
=>
13
Chapter 8
CH3 C CH CH3 + H O+ H
CH3 CH3 C CH CH3 +O H H H H2O
Chapter 8
=>
14
Indirect Hydration
Oxymercuration-Demercuration
Markovnikov product formed Anti addition of H-OH No rearrangements
Hydroboration
Oxymercuration (1)
Reagent is mercury(II) acetate which dissociates slightly to form +Hg(OAc). +Hg(OAc) is the electrophile that attacks the pi bond.
O CH3 O CH3 O _ C O + Hg O C CH3 O
C O Hg O C CH3
=>
Chapter 8 16
Oxymercuration (2)
The intermediate is a cyclic mercurinium ion, a three-membered ring with a positive charge.
OAc C C
+
Hg(OAc)
Hg C C
=>
Chapter 8
17
Oxymercuration (3)
Water approaches the mercurinium ion from the side opposite the ring (anti addition). Water adds to the more substituted carbon to form the Markovnikov product.
OAc Hg C C H2O
+
OAc Hg C C H O H2O H
Chapter 8
OAc Hg C C O H
=>
18
Demercuration
Sodium borohydride, a reducing agent, replaces the mercury with hydrogen.
OAc Hg 4 C C O H _ + NaBH4 + 4 OH H 4 C C O H + NaB(OH) 4 _ + 4 Hg + 4 OAc
=>
Chapter 8 19
anti addition
Chapter 8
=>
20
Alkoxymercuration Demercuration
If the nucleophile is an alcohol, ROH, instead of water, HOH, the product is an ether.
C C (1) Hg(OAc) 2, CH 3OH O Hg(OAc) C C H3C H3C (2) NaBH4 O H C C
=>
Chapter 8 21
Hydroboration
Borane, BH3, adds a hydrogen to the most substituted carbon in the double bond. The alkylborane is then oxidized to the alcohol which is the anti-Mark product.
C C (1) BH3 C C H BH2
Chapter 8
(2) H2O2, OH
C C H OH
=>
22
Borane Reagent
Borane exists as a dimer, B2H6, in equilibrium with its monomer. Borane is a toxic, flammable, explosive gas. Safe when complexed with tetrahydrofuran.
H 2 O
THF
Chapter 8
B2H6
O B H H
THF . BH3
=>
23
Mechanism
The electron-deficient borane adds to the least-substituted carbon. The other carbon acquires a positive charge. H adds to adjacent C on same side (syn).
=>
Chapter 8 24
Actually, Trialkyl
H H3C C C H H3C 3 H3C C C H H + BH3 H H C H3C C H H B H C H CH3
H C CH3 CH3
CH3
Borane prefers least-substituted carbon due to steric hindrance as well as charge distribution. => 25 Chapter 8
Oxidation to Alcohol
Oxidation of the alkyl borane with basic hydrogen peroxide produces the alcohol. Orientation is anti-Markovnikov.
CH3 H CH3 C C H B H CH3 H CH3 C C H OH H
=>
Chapter 8 26
H CH3 OH D
syn addition
Chapter 8
=>
27
Hydrogenation
Alkene + H2 Alkane Catalyst required, usually Pt, Pd, or Ni. Finely divided metal, heterogeneous Syn addition
Chapter 8
28
=>
Addition of Carbenes
Insertion of -CH2 group into a double bond produces a cyclopropane ring. Three methods:
Diazomethane Simmons-Smith: methylene iodide and Zn(Cu) Alpha elimination, haloform =>
Chapter 8 29
Diazomethane
N N CH2 diazomethane N N CH2
CH2
heat or uv light
H N2 + C H carbene
C C C
H H
C C
H C H
=>
30
Simmons-Smith
Best method for preparing cyclopropanes.
CH2I2 + Zn(Cu) ICH2ZnI a carbenoid
=>
Chapter 8
31
Alpha Elimination
Haloform reacts with base. H and X taken from same carbon
CHCl3 + KOH K CCl3 + H2O
+-
Cl
C Cl Cl
Cl + Cl
Cl
Cl Cl
=>
32
Stereospecificity
Cis-trans isomerism maintained around carbons that were in the double bond.
H C C H3C H CH3 CHBr3 NaOH, H2O H C C H3C Br H
CH3 Br
=>
Chapter 8 33
Addition of Halogens
Cl2, Br2, and sometimes I2 add to a double bond to form a vicinal dibromide. Anti addition, so reaction is stereospecific.
Br C C + Br2 C C Br
=>
Chapter 8
34
=>
Chapter 8
35
Mechanism (2)
Halide ion approaches from side opposite the three-membered ring.
Br Br C C C C Br Br
=>
Chapter 8 36
Examples of Stereospecificity
=>
Chapter 8 37
Formation of Halohydrin
If a halogen is added in the presence of water, a halohydrin is formed. Water is the nucleophile, instead of halide. Product is Markovnikov and anti.
Br C C H2O Br C C H O H
Br C C H H2O
Chapter 8 39
+ H3O
=>
Regiospecificity
The most highly substituted carbon has the most positive charge, so nucleophile attacks there.
=>
Chapter 8 40
OH CH3 D Cl
=>
Chapter 8
41
Epoxidation
Alkene reacts with a peroxyacid to form an epoxide (also called oxirane). Usual reagent is peroxybenzoic acid.
O C C + R C O O H O C C O + R C O H
=>
Chapter 8 42
Mechanism
One-step concerted reaction. Several bonds break and form simultaneously.
C
O O
C O C +
O
H
C O
H O
=>
Chapter 8 43
Epoxide Stereochemistry
Since there is no opportunity for rotation around the double-bonded carbons, cis or trans stereochemistry is maintained.
O H CH3 C C H CH3 Ph C O O H H CH3 O C C H CH3
=>
Chapter 8
44
H O C C
OH C C O H H
H2O
H2O
=>
45
Chapter 8
One-Step Reaction
To synthesize the glycol without isolating the epoxide, use aqueous peroxyacetic acid or peroxyformic acid. The reaction is stereospecific.
O CH3COOH H
Chapter 8
OH H OH
=>
46
O Os C C
O Os O
C OH C OH + OsO4
=>
48
Chapter 8
Stereospecificity
If a chiral carbon is formed, only one stereoisomer will be produced (or a pair of enantiomers).
H C C H CH2CH3 cis-3-hexene
Chapter 8
CH2CH3
CH2CH3 H H C C OH OH
=>
CH2CH3 m eso-3,4-hexanediol
49
Oxidative Cleavage
Both the pi and sigma bonds break. C=C becomes C=O. Two methods:
Warm or concentrated or acidic KMnO4. Ozonolysis
Cleavage with MnO4 Permanganate is a strong oxidizing agent. Glycol initially formed is further oxidized. Disubstituted carbons become ketones. Monosubstituted carbons become carboxylic acids. Terminal =CH2 becomes CO2. =>
Chapter 8 51
Example
H CH3 C C CH3 CH3 KMnO4 (warm, conc.) H CH3 H3C C C CH3 OH OH
H H3C C O + CH3 C CH3 O
H3C C
Chapter 8
OH
=>
52
Ozonolysis
Reaction with ozone forms an ozonide. Ozonides are not isolated, but are treated with a mild reducing agent like Zn or dimethyl sulfide. Milder oxidation than permanganate. Products formed are ketones or aldehydes. =>
Chapter 8 53
Ozonolysis Example
H CH3 C C CH3 CH3 O3 H C H3C O O O C CH3 CH3
Ozonide
(CH3)2S H C O H3C O C CH3 + CH3 CH3 O S CH3
=>
DMSO
54
Chapter 8
End of Chapter 8
Chapter 8
55