Richard F. Daley and Sally J.

Daley
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Organic Chemistry
Chapter 14

Electrophilic Addition to Unsaturated Carbons

14.1 Addition Reaction Mechanisms 713 14.2 Direction and Stereochemistry of Addition Reactions 715 14.3 Addition of Hydrogen Halides 718 14.4 Addition of Water and Alcohols 722 14.5 Hydroboration-Oxidation 726 Synthesis of (-)-Isopinocampheol 730 14.6 Electrophilic Addition of Halogens 732 14.7 Addition of Hydrogen 736 14.8 Dihydroxylation Reactions 742 14.9 Addition of Carbenes 745 Synthesis of 7,7-Dichlorobicyclo[4.1.0]heptane 14.10 Oxidation of Alkenes 750 Key Ideas from Chapter 14 754

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Copyright 1996-2005 by Richard F. Daley & Sally J. Daley All Rights Reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior written permission of the copyright holder.

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Chapter 14

Electrophilic Addition to Unsaturated Carbons

Chapter Outline
14.1 14.2 Addition Reaction Mechanisms
An introduction to the AdE2 and AdE3 reaction mechanisms

Direction and Stereochemistry of Addition Reactions

The regiochemistry and stereochemistry of addition reactions

14.3 14.4 14.5 14.6 14.7 14.8 14.9 14.10

Addition of Hydrogen Halides

The scope of the addition of HCl and HBr to alkenes

Addition of Water and Alcohols

The reaction of water and alcohols with alkenes

Hydroboration-Oxidation
An introduction to the hydroboration reaction

Electrophilic Addition of Halogens

The addition of bromine and chlorine to an alkene

Addition of Hydrogen
The mechanism of hydrogenation of alkenes

Dihydroxylation Reactions
Formation of vicinal diols from alkenes

Addition of Carbenes
The formation of carbenes and their reaction with alkenes to form cyclopropane derivatives

Oxidation of Alkenes
Oxidative cleavage of alkenes

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Objectives
Understand the AdE2 and AdE3 reaction mechanisms Know the regiochemistry and stereochemistry of addition reaction mechanisms Know the scope and reactivity of addition reactions of hydrogen halides, water, alcohols, and halogens Understand the hydroboration-oxidation reaction Know the catalytic hydrogenation reaction Understand the formation of vicinal diols Know how carbenes form and how they react with alkenes Recognize the utility of the oxidation of alkenes

The grand aim of all science is to cover the greatest number of empirical facts by logical deduction from the smallest number of hypotheses or axioms. - Albert Einstein

he addition, substitution, and elimination reactions you studied in earlier chapters all involved nucleophilic reagents that reacted with electrophilic substrates. In those reactions, the nucleophilic reagent formed a new bond with an atom in the substrate that was, or readily became, electron deficient. Nucleophilic reagents are all Lewis bases. This chapter considers the reaction of an electrophilic reagent with an electron-rich atom of the substrate. Such a reaction is called an electrophilic addition reaction. Electrophilic reagents are all Lewis acids. The most important electrophilic addition reactions involve carboncarbon double or triple bonds in alkenes and alkynes. These functional groups provide the required regions of high electron density. Usually, this electron density is evenly distributed over the entire functional group. The mechanism of an addition reaction of an electrophile with a bond is the reverse of the elimination reactions covered in Chapter 13. Because a bond is lower in energy than a bond, addition reactions commonly follow a much lower energy pathway than do

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elimination reactions. When chemists use an addition reaction, they use milder reaction conditions than with an elimination reaction. The final state of an addition/elimination reaction pair depends on the reaction conditions. This chapter covers only the 1,2-addition reactions. 1,2Addition reactions are the most common type of addition reactions, although 1,4-addition reactions do frequently occur with conjugated systems. Chapter 16 discusses the 1,4-addition reactions. 1,2-Addition reactions follow one of two mechanistic pathways with one accounting for the majority of the 1,2-addition reactions.

14.1 Addition Reaction Mechanisms

An electrophilic addition reaction occurs when an electron deficient reagent adds to an electron-rich substrate in the rate determining step of the reaction.

Electrophilic addition reactions to unsaturated carbon atoms follow two general mechanisms. Both mechanistic pathways involve the addition of an electrophile, E, to a bond, followed by a reaction with a nucleophile, Nu, resulting in the formation of two new bonds. Although there are a variety of possible nucleophiles, the most common electrophile is a hydrogen ion. The following is the generalized reaction for an electrophilic addition reaction.
E Nu

C E

C Nu

The Ad stands for addition, the E for electrophilic, and the number for the kinetics of the reaction.

The two electrophilic addition mechanisms are designated as the AdE2 and AdE3 mechanisms. The AdE2 is bimolecular, or the reaction has two reagents involved in the rate-determining step. The AdE3 is trimolecular, or a reaction with three reagents involved in the ratedetermining step. The AdE2 mechanism corresponds closely to the E1 mechanism, and the AdE3 mechanism corresponds closely to the E2 mechanism. The AdE2 mechanism, shown in Figure 14.1, is a two-step mechanism that proceeds through a carbocation intermediate. The energy profile of an AdE2 mechanism is the mirror of that of an E1 mechanism. In the first step of the mechanism, the electrophilic portion of the reagent adds to the substrate to form a carbocation. The first step is a 1,3-electron pair abstraction operation. In the second step, which is a fast step, the nucleophile adds to the carbocation intermediate to complete the addition reaction. The second step is a neutralization operation.

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+ H

C H

Slow

Nu C C H + Nu

C H

Fast

Figure 14.1. The AdE2 reaction mechanism. The rate of formation of the carbocation intermediate determines the rate of the reaction. To review the mechanism of an addition to a carbonyl group see Section 7.1, page 000.

The AdE2 mechanism is similar to the pathway proposed for an addition reaction across the carbonoxygen double bond of a carbonyl group. Chemists call that addition reaction a nucleophilic addition; they call the addition to a carboncarbon double bond an electrophilic addition. Why this difference in terminology when each of these two reaction types involves the addition of both a nucleophile and an electrophile to a bond? The difference in terminology is due to the difference in the mechanisms of the two processes. In an addition reaction to the carbonyl double bond, the nucleophile adding to the partial positive charge on the carbon of the carbonyl group determines the rate of the reaction. The presence of the electrophile normally only slightly accelerates the rate of reaction. Thus, the term used to describe this reaction type is nucleophilic addition. In an addition reaction to a carboncarbon double bond, the electrophile adding to a carbon of the double bond determines the rate of reaction. The presence of the nucleophile has only a small effect on the rate. Thus, the term used to describe this reaction type is electrophilic addition. The AdE3 mechanism, shown in Figure 14.2, requires a simultaneous collision of three reactive species. These species include the substrate molecule containing the double bond, the electrophile, and the nucleophile. In an AdE3 mechanism the electrophile and the nucleophile come from two separate molecules. This is a 1,5-electron pair displacement operation. Because of the low probability of three separate reactive species approaching each other with the correct orientation and energy to react, addition reactions seldom follow this mechanism. However, an addition reaction may occur with a nonionized reagent.
Nu C C Nu C H C H H Nu C C

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Figure 14.2. The AdE3 mechanism.

14.2 Direction and Stereochemistry of Addition Reactions

The addition of an unsymmetrical reagent to an unsymmetrical alkene or alkyne can, in principle, take place in either of two directions. The electrophilic portion of the reagent could add to either of the carbons involved in the double bond. Then the remaining nucleophilic portion could add to the other carbon.
E R C H C R' Nu H C R C R' H E H E H C R C R' H Nu

Nu

It turns out, however, that the AdE2 reaction is normally regiospecific. Thus, the electrophilic reagent adds to a specific area of the substrate. For example, the following reactions produce the products shown as the major product.
CH3CH CH2 HI CH3CHCH3 I 2-Iodopropane (87%) I CH3C CH3 CH2 HI CH3CCH3 CH3 2-Iodo-2-methylpropane (89%)

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Markovnikovs rule states that the electrophile adds to the less substituted carbon atom of an alkene.

In 1870, Russian chemist Vladimir V. Markovnikov formalized this regioselectivity with a rule that bears his name, Markovnikov's rule. Markovnikov's rule states that the addition of HX to a carbon carbon double bond proceeds in such a way that the hydrogen adds to the carbon atom already bearing the greater number of hydrogen atoms. Markovnikov's rule readily translates to the modern understanding of chemical mechanisms. An AdE2 reaction mechanism shows that the incoming electrophile controls the regioselectivity of the reaction. The electrophile adds to the double bond in such a way that the most stable carbocation intermediate forms. Recall from Chapters 12 and 13 that the most stable carbocation is the carbon with the greatest number of alkyl group substituents. Thus, in modern terms, according to Markovnikov's rule the electrophile adds to the double bond in such a way to form the most stable carbocation. Because the electron density in a double bond is above and below the plane of the molecule, the most favorable approach of an electrophile is to those electron-rich regions. This approach is perpendicular to the plane of the bond.
E

E
Figure 14.3. The approach of an electrophile to the orbitals of the double bond is perpendicular to the plane of the molecule.

Anti addition means the electrophile and nucleophile add 180o apart. With a syn addition they add 0o apart.

In an electrophilic addition reaction, two groups (the electrophile and the nucleophile) actually add to the double bond. The electrophilic portion of the reagent first adds to the double bond, followed by the addition of the nucleophilic portion of the reagent. The electrophilic and nucleophilic parts of a reagent add either to the opposite sides of the substrate, an anti addition, or to the same side of the substrate, a syn addition.

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E C C Nu Anti addition

E C C Nu

E C C

Nu

E C C

Nu

Syn addition

Many addition reactions are stereoselective with a number of these being stereospecific. Most electrophilic addition reactions favor anti stereochemistry indicating that the reaction mechanism is more complex than that shown in Figure 14.1. The mechanism in Figure 14.1 shows little or no preference between the syn and anti additions. To show the preference, the mechanism must show more reagent substrate interaction. For example, rather than producing a free carbocation, the first step in the bromination of a double bond is probably the formation of an intermediate bromonium ion.

Br C

A bromonium ion

This bromonium ion blocks the incoming nucleophile from reacting with one side of the ion, forcing it to react with the other side. This reaction is an anti addition. Other examples of reagentsubstrate interactions that force the reagent to add either anti or syn are presented later in this chapter.
Solved Exercise 14.1 Chemists use the following reagents in electrophilic addition reactions. Identify the electrophilic species available from each reagent. a) HBr Solution

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HBr readily ionizes forming H and Br - ions. Thus, the electrophile is the H ion. b) HOCl Solution HOCl has two possible bonds that could break: the HO and the OCl bonds. Of these two, the OCl bond is the least stable. Thus, although Cl does not really form, HOCl reacts as if it ionizes to form Cl and - OH ions with the Cl ion being the electrophile. c) Cl2 Solution Polarization of Cl2 allows the substrate to react with the ClCl bond displacing the - Cl ion. The reaction occurs as if the Cl ion is the electrophile.

14.3 Addition of Hydrogen Halides

Hydrogen halides add to the bonds of alkenes to form alkyl halides and to alkynes to form vinyl halides or gem-dihalides depending on the ratio of the reactants. These reactions are called hydrohalogenation reactions. Chemists perform hydrohalogenation reactions by bubbling the gaseous hydrogen halide through the reaction mixture in a non-nucleophilic solvent. With the addition of aqueous solutions of the hydrogen halide, water also adds to the double bond. This reaction works best with HBr or HI. The reaction of HCl is generally not acidic enough to react, unless a particularly stable carbocation intermediate can form.
CH2 CH CH HBr CH2 CH2 HI CH3CH2I HBr CH3CHBr2

A hydrohalogenation reaction is the addition of HX to a double bond. X is a halogen. Section 14.4, page 000, discusses the addition of water to alkenes and alkynes.

CHBr

A protonium ion is a complex involving a proton and an alkene.

The hydrohalogenation reaction follows Markovnikov's rule and predominantly gives the anti addition product. Chemists do not clearly understand the reasons for the stereoselectivity of the hydrohalogenation reaction. What chemists have proposed is that with a polar-protic solvent, which ionizes the hydrogen halide, the reaction proceeds through a complex between the proton and the alkene. They call this complex a protonium ion.

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H C C or A protonium ion C

H C

The protonium ion forms rapidly in the presence of a proton source. The protonium ion then reacts with the nucleophile. Because the proton blocks the nucleophile from attacking the ion on the side to which the proton is attached, the nucleophile forms a bond anti to the proton.
H C C Br

H C C

Br

Not all reactions that ionize the hydrogen halide form a protonium ion. In some cases, the protonium ion is unstable and the substrate rearranges. This rearrangement suggests that the protonium ion has significant carbocation character, thus, permitting hydride or alkyl shifts. These shifts form more stable intermediates. The following reaction shows a hydride shift.
Cl CH3CHCH CH3 CH2 HCl CH3CCH2CH3 CH3 + Cl CH3CHCHCH3 CH3

2-Chloro-2-methylbutane 2-Chloro-3-methylbutane (40%) (60%)

A polar-aprotic solvent allows the hydrogen halide to remain nonionized. Thus, when a polar-aprotic solvent is used, the ratecontrolling step involves two molecules of hydrogen halide and one molecule of alkene. The anti stereochemistry for the following example of an AdE3 mechanism arises because each molecule of hydrogen bromide approaches the alkene from opposite sides of the double bond. In this case, the rate of reaction is much slower than in a polar-protic solvent because the reaction requires three molecules to collide with the proper energy and orientation.

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Br H

Br

C Br H

C H

The following are examples of hydrohalogenation reactions:

CH3 CH3 H HBr pentane, 0oC Br
1-Bromo-trans-1,2-dimethylcyclohexane (100%)

CH3 CH3

CH3CH

CHBr

HBr CH3NO2

CH3CH2CHBr2 1,1-Dibromopropane (93%)

In the second example above, the bromine adds to the carbon already bearing a bromine. The nonbonding electrons on the bromine are donated to the carbocation intermediate to stabilize it. Thus the more stable carbocation is the one bearing the bromine atom.
H
CH3
Br

H
CH3

Br C
H CH3

H C H

Br C
H

C H

C
H

C H

Reactions of hydrogen halides with alkynes follow the same rules of regiochemistry and stereochemistry that alkenes follow. In a reaction of one equivalent of hydrogen halide with an alkyne, the resulting vinyl halide has the hydrogen and the halogen trans to one another. For example, the addition of one equivalent of hydrogen bromide to 2-butyne produces Z-2-bromo-2-butene, a vinyl halide:

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CH3C

CCH3

HBr

H3C C H C

Br CH3

Z-2-Bromo-2-butene (98%)

If the vinyl halide then reacts with another molecule of hydrogen halide, the result is a gem dihalide. For example, reacting Z-2-bromo2-butene with another mole of HBr produces 2,2-dibromobutane.
CH3 C H C CH3 Br Br HBr CH3CH2CCH3 Br 2,2-Dibromobutane (100%)

The second bromine adds to the carbon bearing the bromine in a Markovnikov addition reaction. The reaction is a Markovnikov addition because the positively charged intermediate is resonancestabilized:
H CH3 C H C CH3

Br CH3

H C H

Br C CH3

H CH3 C H

Br C CH3

Br

H CH3 C H

Br C CH3

Br

Exercise 14.1 Predict the major product(s) for each of the following reactions. a)

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CH3

HBr

b)
(CH3)3CCH CH2 HI

c)
HCl

d)
CH3 C H C NO2 H HCl

Sample Solution b)
CH3

(CH3)3CCH

CH2

HI

(CH3)3CCHCH3 I Minor

(CH3)2CCHCH3 I Major

14.4 Addition of Water and Alcohols

An acid-catalyzed hydration reaction results in a net addition of water to a double bond.

Under acidic conditions, water adds to alkenes to form alcohols in an acid-catalyzed hydration reaction. The product of an acidcatalyzed hydration reaction is regiospecific, following Markovnikov's rule, but it is not stereoselective. The process, as expected with a carbocation intermediate, usually gives relatively equal amounts of both the anti and syn addition products. Because a carbocation is planar, the adding group can come in from either side. Acid-catalyzed hydration reactions are widely used in industry for producing large quantities of commercially important alcohols, but chemists seldom use them in the laboratory.

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CH3C CH3

CH2

H3O

OH CH3CCH3 CH3 2-Methyl-2-propanol (tert-Butyl alcohol) (71%)

H3O

OH

Cyclohexanol (77%)

An oxymercuration reaction is the net addition of water to a double bond via an organomercury intermediate. Other methods are replacing oxymercuration because mercury presents a hazardous waste disposal problem.

A more important laboratory method for the Markovnikov addition of water to an alkene is the oxymercuration reaction. The oxymercuration reaction is a two-step process. In the first step, an aqueous solution of mercury (II) acetate is added to a solution of the alkene in THF. During a period of reaction time, the mercury (II) acetate adds to the double bond. In the second step, a solution of NaBH4 in aqueous base is added to the reaction mixture.
Hg(OAc)2 H2O, THF OH HgOAc Not normally isolated NaBH4 H2O, OH (99%) OH

The above reaction, which produces cyclohexanol, gives a reaction yield of 99%. For most reactions of simple alkenes with water, the alcohol yields are in excess of 90%. Compounds that tend to rearrange when using the strongly acid-catalyzed hydration reaction do not rearrange in an oxymercuration reaction. Oxymercuration is both regiospecific and stereospecific. The stereospecificity results from the formation of an intermediate mercurinium ion.
HgOAc C C

A mercurinium ion

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Attack on this mercurinium ion by water produces an organomercurial alcohol. The water reacts with the more substituted carbon atom because is has a larger partial positive charge.

HgOAc C
H2O

HgOAc C HO

HgOAc C HO

The reaction then gets rid of the mercury in a demercuration reaction. In the demercuration reaction, sodium borohydride reduces the mercury to metallic mercury and replaces the mercury with hydrogen.
HgOAc C HO C NaBH4 H2O, OH HO H C C

Chemists prefer the oxymercuration reaction for the Markovnikov synthesis of an alcohol because it gives better yields than an acid-catalyzed hydration and does not involve rearrangements of the substrate.
H3C C H C H CH3 H3C H H OH C C H CH3 + HO C H H3C C CH3 H H

1) Hg(OAc)2, H2O 2) NaBH4, OH

Racemic 2-Butanol (72%)

CH3 1) Hg(OAc)2, H2O OH 2) NaBH4, OH 1-Methylcyclohexanol (86%)

CH3

Both acid-catalyzed hydration reactions and oxymercuration reactions take place with alkyne substrates. The addition follows Markovnikov's rule. The acid-catalyzed hydration reaction is slow, but speeds up when mercury (II) salts are used as a catalyst. The initial

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product of a hydration reaction is a vinyl alcohol, but the vinyl alcohol rapidly tautomerizes to form a carbonyl compound.
Tautomerism is introduced in Section 8.7, page 000, and 19.1, page 000.

OH CH3CH2CH2C CH H3O HgSO4 CH3CH2CH2C CH2

O CH3CH2CH2CCH3 2-Pentanone (86%)

O CH2 CH3CHCCH3 CH3 3-Methyl-2-butanone (83%)

Unstable vinyl alcohol

CH3CHC CH3

CH

1) Hg(OAc)2, H2O 2) NaBH4, OH

OH CH3CHC CH3

Exercise 14.2 Predict the major products for each of the following reactions. a)
CH2 H3O

b)
C CH 1) Hg(OAc)2, H2O 2) NaBH4, OH

c)
CH3 CH3 1) Hg(OAc)2, H2O 2) NaBH4, OH

d)
CH3 CH3 H3O

e)

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CH

CH2

H3O

Sample Solution a)
CH2 H3O CH3 OH

Alcoholysis is much like hydrolysis except that the reaction is with an alcohol instead of water.

Using an alcohol nucleophile in both the acid-catalyzed and the oxymercuration reaction yields an ether. Chemists seldom use an acidcatalyzed alcoholysis because of the number of side products that it forms. However, the alkoxymercuration reaction is a good synthetic method that chemists use with simple alcohols.
CH3 CH3 1) Hg(OAc)2, CH3OH 2) NaBH4, OH OCH3

1-Methoxy-1-methylcyclohexane (88%)

14.5 Hydroboration-Oxidation
Section 14.4 covered two methods for adding water to a double bond to form an alcohol following Markovnikov's rule: acid-catalyzed hydration reactions and oxymercuration reactions. In both methods the proton added to the carbon that would leave the most stable carbocation. In most reactions, this is the carbon that contained the greater number of hydrogens. Sometimes, however, chemists want to form an alcohol with the OH group bonded to that carbon. Neither of these methods forms such an alcohol. In the early 1950s, H. C. Brown of Purdue University discovered that diborane (B2H6) adds to the double bond of an alkene to form a product called an organoborane. The boron of the BH bond is the electrophilic portion of the reagent. Thus, the boron adds to the carbon that would be the less stable carbocation and the hydrogen adds to the other carbon of the alkene. If the organoborane is oxidized, it forms an alcohol that is the anti-Markovnikov addition product. In this reaction the hydrogen adds to the carbon containing the fewer hydrogens and the OH group ends up on the carbon with the greater number of hydrogens. This reaction is a hydroboration-oxidation reaction. For the

In an antiMarkovnikov reaction, the product appears to have the opposite regiochemistry to the normal mode of addition. The hydroborationoxidation reaction is a method for synthesizing alcohols via an organoboron intermediate. The net reaction is an antiMarkovnikov addition of water to the double bond.

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A monomer is a building-block molecule which make up a dimer or larger molecule.

discovery and exploration of the synthetic utility of organoboranes, Brown received the Nobel Prize in chemistry in 1979. Diborane is a dimera molecule made up of two identical simpler molecules, or monomers. Diborane consists of two monomer units of borane (BH3). These two monomers bond together in an unusual type of bond. Instead of a single bond between the two boron atoms, both boron atoms are involved in two three-centered bonds. Each bond includes three atoms: the two boron atoms and the hydrogen atom between them.
H H H B H B H H

Three-centered bonding occurs with diborane because each boron atom in BH3 has only six electrons and an empty orbital in its valence shell. Boron has an orbital that readily accepts an electron pair, so borane is a strong Lewis acid. Sharing the electrons in a BH bond with the empty orbital on a second boron atom fills the octet of the second boron atom. The second boron shares the electrons in a BH bond with the first boron atom to satisfy its octet as well. As a reagent, diborane is a difficult to handle flammable gas, that is not very reactive with alkenes. However, Brown found that dissolving diborane in THF (tetrahydrofuran) or diglyme (CH3OCH2CH2OCH2CH2OCH2CH2OCH3) produces a convenient, easy to handle solution that is very reactive with alkenes. In this solution, the THF and the diborane form a complex in which the oxygen of the ether shares a pair of electrons with a boron atom.
H O B H H Borane-THF complex

Chemists think that the hydroboration reaction is a concerted reaction with both the boron and the hydrogen adding simultaneously in a syn addition.

C H

C B

C H

C B

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The BH bond is a polar bond but, because the boron has a lower electronegativity than hydrogen, the hydrogen is the negative end of the dipole. When adding to the double bond, the boron adds to the least substituted carbon atom because it is the electrophile. Thus, although the reaction seems to add contrary to Markovnikov's rule, it really does not. In a hydroboration reaction, all three of the BH bonds are reactive.
CH3CH2CH CH2 BH3 THF (CH3CH2CH2CH2)3B Tributylborane

Hydroboration is very sensitive to steric factors. The hydroboration of butene places about 95% of the boron at C1 of the butyl group and about 5% at C2. For 2-methyl-1-propene, the amount of boron at C1 is in excess of 99%. Alkylboranes are generally pyrophoric. That is, they ignite spontaneously in air. Therefore, chemists seldom isolate them but use them directly as reactive intermediates. Although chemists use organoboranes as the intermediates for many functional groups, the one they use it for the most is the oxidation reaction that forms an alcohol. The oxidation reaction proceeds by adding an alkaline solution of hydrogen peroxide to the organoborane solution. Note that the stereochemistry of the borane reaction is retained in the oxidation step.
CH3 CH3 1) BH3/THF OH trans-2-Methylcyclopentanol (95%)
CH3 C CH2 1) BH3/THF CH3 CHCH2OH

2) H2O2, H2O, NaOH

2) H2O2, H2O, NaOH 2-Phenyl-1-propanol (97%)

The net reaction obtained with a hydroboration-oxidation reaction is an anti-Markovnikov addition of water to a double bond. The stereochemical configuration of the carbon originally bearing the

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For more on the equilibrium between geminal diol and carbonyl group see Section 7.5, page 000.

boron is retained during the reaction. The result is a stereospecific syn addition of water to a double bond with anti-Markovnikov regioselectivity. Alkynes also undergo hydroboration reactions. The resulting product from a terminal alkyne is a geminal diol that rapidly loses water to form an aldehyde.
H R H BH3 THF R H B H B H2O2 NaOH, H2O R H OH H H OH

H R

H O H

For more on tautomers, see Section 19.1, page 000.

An internal alkyne forms a vinyl alcohol that rapidly tautomerizes to a ketone.

H R R' BH3 THF B R R' H2O2 NaOH, H2O R R' H OH

H R

H O R'

Following are some examples of hydroboration of alkynes:

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O 1) BH3/THF 2) H2O2, NaOH, H2O Pentanal (74%) O 1) BH3/THF 2) H2O2, NaOH, H2O 3-Hexanone (67%) H

Synthesis of ()-Isopinocampheol
H3C CH3 CH3 1) BH3, THF 2) H2O2, NaOH (+)-a-Pinene (-)-Isopinocampheol (91%) H3C CH3 CH3 OH

Preparation of the BH3/THF Solution Fit a dry 100 mL round bottom flask with a Claisen adapter. Fit a rubber septum on the arm directly over the opening of the flask. Connect a drying tube filled with calcium chloride to the other arm of the Claisen adapter. Gently heat the glass drying tube with a flame to dry the calcium chloride. Place 520 mg (0.014 mol) of sodium borohydride in the flask and add 30 mL of freshly distilled dry THF. Cool the flask in an ice-water bath. Slowly add a solution of 1.7 g (0.014 mol) of iodine in 20 mL of dry THF. The addition should require at least 45 minutes. Maintain the solution at 0oC during the addition. ()-Isopinocampheol To the solution of BH3 in THF prepared above, add 2.8 g (0.02 mol) of (+)--pinene over the course of 10 minutes. Allow the mixture to warm to room temperature and stir. At the end of 1.5 hr., slowly add 2 mL of water to destroy any excess BH3. Mix 20 mL of 30% hydrogen peroxide with 20 mL of 3M sodium hydroxide. Add this solution cautiously to the reaction mixture. Stir for an additional 5-10 minutes. Transfer the reaction mixture to a separatory funnel and separate the layers. Wash the aqueous layer with three 15 mL portions of ethyl ether. Combine the ether and the organic layers. Wash these combined layers with 10 mL portions of water and saturated sodium chloride solutions. Dry with anhydrous sodium sulfate. Remove the drying agent and evaporate the solvent. Recrystallize the solid product by dissolving it in a minimum of boiling ethanol and adding water until the solution just becomes cloudy. Cool this mixture and collect the crystals. Yield of product is 2.9 g (93%), m.p. 5053oC.

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Discussion Questions 1. Why must the solvent and glassware be completely dry before beginning the synthesis of BH3? 2. This hydroboration reaction is stereoselective with borane reacting with only one side of the system in (+)--pinene. Explain this stereoselectivity.

Solved Exercise 14.2 Show how you would prepare 1- and 2-methylcyclohexanol from 1methylcyclohexene. Solution 1-Methylcyclohexanol can be prepared two different ways: acid-catalyzed hydrolysis or the oxymercuration-demercuration reaction. In this case, acidcatalyzed hydrolysis is simpler because the desired product comes from the most stable carbocation.

H2O H2SO4

OH

2-Methylcyclohexanol is synthesized using the hydroboration-oxidation reaction.

1) BH3/THF 2) H2O2, NaOH

OH (Both enantiomers formed)

Exercise 14.3 Predict the major products for each of the following reactions. a)
CH3CH2CH2C CH3 CH2 1) BH3, THF 2) H2O2, H2O, NaOH

b)

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1) BH3, THF 2) H2O2, H2O, NaOH

c)
1) BH3, THF 2) H2O2, H2O, NaOH

d)
1) BH3, THF 2) H2O2, H2O, NaOH

e)
1) BH3, THF 2) H2O2, H2O, NaOH

Sample Solution d)
1) BH3, THF 2) H2O2, H2O, NaOH OH

14.6 Electrophilic Addition of Halogens

Halogens readily add to alkenes to form vicinal dihalides. Of the various halogens, chemists commonly use bromine and chlorine. They do not use fluorine because it reacts explosively and produces many side reactions. They do not use iodine because vicinal diiodides decompose readily. Formation of vicinal dihalides is a stereospecific anti-addition reaction. The first step in the mechanism of an electrophilic addition of a halogen to an alkene is the formation of a halonium ion. To form a halonium ion, the electrons of the double bond react with one halogen atom from the halogen molecule. The following carbocation is not the minimum energy intermediatethe halonium ion is lower in

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energy. Although shown here as a carbocation, many chemists consider this reaction to be a concerted reaction.

Chlorine and bromine are both electrically neutral and nonpolar. However, both are polarizible. The interaction of a chlorine or bromine molecule with an alkene leads to polarization of the molecule and loss of a chloride or bromide ion, a good leaving group. The formation of the chloronium or bromonium ion depends on the polarizibility of the halogens and the fact that chloride or bromide ions are good leaving groups. The net result is the equivalent to a reaction with Cl or Br. Because chlorine is smaller and more electronegative than bromine, the chloronium ion is not as stable as the bromonium ion. The halonium ion is a three-membered ring with considerable ring strain. This ring strain, combined with the positive charge on the electronegative halogen atom, makes the halonium ion intermediate very electrophilic. In the second step of the mechanism, reaction with a nucleophile, such as the halide ion released when the halonium ion was formed, opens the ring to give a stable vicinal dihalide.

X C

C
X

The incoming nucleophile reacts only from the side opposite the positive halogen of the halonium ion to form the anti vicinal dihalide.
Br2 Br Br trans-1,2-Dibromocyclopentane (83%)

Because the double bond region of most molecules is symmetrical and planar, the addition of the halogen produces a pair of enantiomers or a meso product.

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CH3 C H C

CH3 H

Br2

Br H C CH3

H H CH3 C C CH3 + Br Br

Br C H CH3

Racemic 2,3-Dibromobutane (88%) Br H C CH3 CH3 C H Br

H3C C H C

H CH3

Br2

meso-2,3-Dibromobutane (87%)

The Cl ion is more reactive than the Br ion, so the addition of chlorine is less stereoselective than the addition of bromine. In most cases, there is still some preference for the anti addition. However, significant amounts of syn addition also occur. Exercise 14.4 The addition reaction involving cis-2-butene forms two products, but trans-2-butene forms only one. Why? Chlorine and bromine react with alkynes in much the same way as they do with alkenes. One mole of halogen added to an alkyne forms a vicinal dihaloalkene product. The stereochemistry of this reaction is either syn or anti, and the products of the reaction are often a mixture of Z and E isomers.
Br2 CH3CH2CH2 C Br C CH3 Br +

CH3CH2CH2C CCH3

E-2,3-Dibromo-2-hexene 77%

Br C C

Br CH3

CH3CH2CH2

Z-2,3-Dibromo-2-hexene 23%

Because the bromonium ion intermediate formed from an alkyne is a three-membered ring that contains a double bond, it is less stable

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than the ion formed from an alkene. The reaction is also less stereospecific. Thus, the reaction proceeds partially via the halonium ion and partially via a vinyl carbocation.

Br

Br

Br C +

Br C R C R

Reactions of compounds containing triple bonds with two moles of the halogen per mole of substrate produce a tetrahaloalkane. Yields for electrophilic addition reactions with triple bonds are often nearly 100%.
Br Br CH3CH2CH2C CCH3 Br2 CH3CH2CH2 C C CH3 Br Br 2,2,3,3-Tetrabromohexane (94%)

Exercise 14.5 When treating 2-hexyne with one equivalent of bromine to produce a dibromoalkene, should you add the bromine to the 2-hexyne or the 2hexyne to the bromine? Explain. When other nucleophiles are present in the reaction mixture, they compete with the halide ion in reacting with the halonium ion. For example, when chemists dissolve the halogen in water and react this solution with the alkene, the water acts as a nucleophile and reacts with the halonium ion to form a molecule with a halogen on one carbon atom and a hydroxyl group on the adjacent atom. These products are called halohydrin compounds. The reaction is a stereospecific anti-addition to the alkene.
Cl2 H2O Cl

In a halohydrin reaction, a halogen and water add to a double bond forming an halo alcohol.

OH trans-2-Chlorocyclohexanol (a chlorohydrin) (89%)

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In reactions involving an unsymmetrical alkene, the reaction is also regiospecific. With an unsymmetrical alkene, a Markovnikov addition reaction occurs with the electrophile adding to the carbon with the most hydrogens. The water reacts with the most electrophilic, usually the most substituted, carbon of the halonium ion.
CH3 OH Br
trans-2-Bromo-1-methylcyclohexanol (a bromohydrin) (89%)

Br2 H2O

Exercise 14.6 Predict the major products for each of the following reactions. a)
Br2 H2O

b)
Cl2

c)
Br2

d)
Br2

Sample Solution b)

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Cl2

Cl Cl

14.7 Addition of Hydrogen

Adding hydrogen to a double or triple bond is called a reduction reaction. As the hydrogen adds to the bond, the reaction follows a stereospecific syn addition to the bond. A direct addition of hydrogen requires the presence of a metal catalyst such as platinum, palladium, rhodium, or nickel. Without the catalyst, the energy of activation is too high to make the reaction of practical value as a synthetic method. Adding hydrogen with the use of a catalyst is called a catalytic hydrogenation.
H2 catalyst H C C H

In a catalytic hydrogenation reaction, hydrogen adds to a double bond using a catalyst.

To adsorb is to accumulate hydrogen atoms on the surface of the catalyst.

With heterogeneous catalysis, the catalyst is in a different phase from the reactants.

When running a catalytic hydrogenation, chemists usually use a finely powdered catalyst suspended in an alkane, alcohol, or acetic acid solvent. They place the reaction mixture in a closed system, as this allows them to measure the amount of hydrogen reacted. They then stir or shake the whole reaction mixture, usually at room temperature. As the reaction begins, the surface of the catalyst adsorbs a number of hydrogen molecules from the hydrogen gas. This adsorption is a reversible process. Experimental evidence for reversible adsorption was obtained by mixing two isotopes of hydrogen in the presence of a catalyst. When a mixture of hydrogen (H2) and deuterium (D2) was placed in contact with a platinum catalyst, the gas quickly reached an equilibrium with H2, D2, and HD present. This scrambling did not take place in the absence of the catalyst. Catalytic hydrogenation is an example of heterogeneous catalysis. With heterogeneous catalysis, the catalyst is in a different phase than the reactants. The catalyst is a solid, but the reactants are liquids or gasses. After adsorbing the hydrogen onto its surface, the catalyst binds to one face of the bond of the double bond in the substrate. The catalyst then transfers one hydrogen to the double bond, followed by a rapid transfer of a second hydrogen that frees the product from the catalyst. When this transfer is complete, the catalyst adsorbs more hydrogen and repeats the process. The result is that the hydrogens

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add stereospecifically in a syn fashion to the bond. Figure 14.4 shows this reaction.

C H Pt

C H

C H

C H Pt

C H

Pt

Figure 14.4. The three steps in catalytic hydrogenation.

Following are some examples of catalytic hydrogenation.

CH3CH2CH CH2 H2 (50 PSI) Pt, 25 C
o

CH3CH2CH2CH3 Butane (97%) CH3 D D CH3

CH3 CH3

D2 (50 PSI) Pt, 25 C

o

cis-1,2-Dideutero-1,2-Dimethylcyclohexane (95%)

Isolated double or triple carboncarbon bonds hydrogenate more readily than carbonoxygen double bonds. Hydrogenations involving aldehydes and ketones require extended reaction times, and hydrogenations involving carboxylic acids require high temperature as well as extended reaction times. Benzene is very difficult to hydrogenate and requires very high pressures and temperatures.
O H2 (50 PSI) Pt, 25oC Cyclohexanone (97%) O

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CH2CH

CH2

H2 (50 PSI) Pt, 30 C

o

CH2CH2CH3

Propylbenzene (98%)

Alkynes hydrogenate more rapidly than alkenes. Hydrogenation with a platinum or palladium catalyst reduces the alkyne all the way to the alkane.
CH2C CH H2 (50 PSI) o Pt, 25 C CH2CH2CH3

Propylbenzene (97%)

Lindlars catalyst is a deactivated hydrogenation catalyst suitable for hydrogenating triple, but not double, carboncarbon bonds.

Sometimes chemists want to stop the reaction of an alkyne at the alkene. To do so, they use a deactivated, or poisoned, catalyst. A deactivated, or poisoned, catalyst is a catalyst of palladium coated with particles of barium sulfate treated with quinoline. This catalyst, called Lindlar's catalyst, reduces an alkyne to a cis alkene.
H2 (55 PSI) Pd/BaSO4 Quinoline, 30 C
o

CH3CH2 C H C

CH2CH3 H

CH3CH2C

CCH2CH3

Z-3-Hexene (81%)

CCH3

H2 (50 PSI) Pd/BaSO4 Quinoline, 30 C

o

H C C

H CH3

Z-1-Phenyl-1-propene (87%)

To form a trans alkene from an alkyne, the addition of hydrogen must take place with anti stereochemistry. Chemists accomplish the anti stereochemistry by reacting the alkyne with sodium in liquid ammonia.

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Na NH3

H C R C

R H

A solution of sodium in liquid ammonia has a deep blue color due to the solvation of electrons from the sodium with the ammonia.
NH3
+

Na

(NH3)e Blue

Na

The mechanism for this reaction initially involves the addition of an electron to the triple bond to form a radical anion. The radical anion forms with the nonbonding pair and unpaired electrons trans to one another because the trans configuration places the electrons farther apart than they would be if they were in the cis configuration.
e R

R'

R'

Next in the mechanism, the radical anion intermediate removes a proton from the ammonia solvent to become a neutral radical.
R
C

H R'

NH2 R

H
C

C R'

The neutral radical then picks up another electron from the solution to form a vinyl anion.
R' C H C

e R

R' C H

Finally, the ammonia solvent protonates this vinyl anion to form the trans double bond.
R' C H H R NH2 R' C H C R H

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Here are some examples of this reaction.

Na NH3 CH3CH2CH2 C H E-2-Hexene (84%) C CH3 H

CH3CH2CH2C CCH3

Na NH3 H

H C C

E-1,2-Dicyclohexylethene (93%)

Exercise 14.7 Predict the major products for each of the following reactions. a)
C CH D2 Pt

b)
CH3CH2 C H C CH3 H H2 Pt

c)
C C CH3 Na, NH3

d)
CH3CH2 C H C CH3 H D2 Pt

Sample Solution c)

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H C C CH3 Na, NH3 C C

CH3 H

14.8 Dihydroxylation Reactions

A dihydroxylation reaction forms a diol from, in this case, a double bond.

A dihydroxylation reaction adds two OH groups to a double bond to form a diol. The reaction of an alkene with cold alkaline potassium permanganate (KMnO4) or with osmium tetroxide (OsO4) in an aqueous hydrogen peroxide solution readily yields a 1,2dihydroxyalkane. 1,2-Dihydroxyalkanes are often called glycols. With KMnO4 and OsO4, the dihydroxylation reaction yields a syn diol.
OsO4 H2O, H2O2

OH OH

OsO4 and KMnO4 react in similar ways to form an intermediate cyclic ester from an alkene. In a concerted reaction, two of the oxygens from the reagent add to the double bond of an alkene forming the cyclic ester.
C O Os O O C O O O Os O O

The hydrogen peroxide in the reaction mixture then readily oxidizes the cyclic ester to produce the diol and regenerate the osmium tetroxide.
H2O2 O Os O O O HO OH

OsO4

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Osmium tetroxide is an expensive, highly toxic reagent that gives high yields and is very selective for carboncarbon multiple bonds. Potassium permanganate is much less expensive, less toxic, gives lower yields and oxidizes a number of other functional groups. However, in most cases, chemists prefer to use potassium permanganate.
CH3 OsO4 CH3 H2O, H2O2 OH CH3 OH

CH3 cis-1,2-Dimethylcyclopentane-1,2-diol (81%)

HO KMnO4 KOH, H2O H H OH

erythro-Octane-4,5-diol (73%)

Exercise 14.8 Chemists often use permanganate ion to detect the presence of an alkene. They do so because the solution is purple and, as it reacts with an alkene, the solution becomes colorless and a brown precipitate of MnO2 forms. Reasoning by analogy to the OsO4 reaction, write a mechanism for the oxidation of an alkene by cold alkaline potassium permanganate solution. Three-membered cyclic ethers, known as epoxides, react to form trans diols. The cyclic ether is very strained and readily reacts with aqueous acid to produce a diol. The most common method of forming an epoxide is the reaction of an alkene with a peroxy acid.
O CH3COOH H H CHCl3 H H

O cis-3,4-Epoxyhexane (67%)

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An epoxidation reaction forms a threemembered cyclic ether from an alkene.

An epoxidation reaction with a peracid accomplishes a syn addition of oxygen to a double bond. This reaction is stereospecific, indicating that the addition of the oxygen to the double bond is a concerted reaction. The generally accepted mechanism for an epoxidation reaction involves the transfer of the oxygen farthest from the carbonyl carbon to the double bond.
C C

C +

C O

O H

O C

C H3C

H3C

Because the reaction is concerted, the substrate has no opportunity to rotate and change its geometry. Thus, a cis alkene becomes a cis epoxide, and a trans alkene becomes a trans epoxide.
CH3 O CH3COOH CHCl3 CH3 CH3 O CH3 1,2-Dimethyl-1,2-epoxycyclohexane (52%)
O CH3COOH CHCl3 O H

H
(62%)

Exercise 14.9 Chemists commonly use meta-chloroperoxybenzoic acid (MCPBA) to form epoxides because of its desirable solubility characteristics. What products form from the reaction of MCPBA with Z-2-methyl-3-hexene?

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O Cl COOH

m-Chloroperoxybenzoic acid

Any moderately strong aqueous acid can protonate the epoxide oxygen. Three-membered rings have so much ring strain that they react more readily than larger rings or acyclic compounds. Because of this ring strain, a protonated epoxide reacts with a nucleophile. The reaction is essentially the reaction of a bromonium ion with a nucleophile, in this case water, adding to the backside of the epoxide. The reaction product is a vicinal diol with a net anti hydroxylation.

OH2

O
H2O

OH OH2

-H

OH OH

Solved Exercise 14.3 Any strong acid can open the ring of an epoxide when forming the vicinal diol. Why is hydrochloric acid never used to form the diol? What product forms in the reaction of epoxycyclohexane with hydrochloric acid? Solution Although hydrochloric acid is a strong acid, it also produces the Cl - iona good nucleophile. The Cl - ion competes with water to form significant amounts of 2-chlorocyclohexanol. OH O HCl H2O Cl + OH OH

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Exercise 14.10 What reagents would you use to form meso-3,4-hexanediol and dl-3,4hexanediol from Z-3-hexene?

14.9 Addition of Carbenes

This chapter repeatedly discusses occasions when a threemembered ring is either an intermediate or, in the case of an epoxide, the final product of an addition reaction. The addition of a carbene to a double bond is another of these occasions. When a carbene adds to a double bond, the product is a cyclopropane ring. Carbenes are unlike almost all other reagents presented in this book in that the carbon of a carbene possesses only six electrons in its valence shell and is electrically neutral. There are two forms of carbenes. Both are sp2 hybridized and are relatively close in energy to each other. The first, called a singlet carbene, has a pair of electrons in an sp2 hybrid orbital, although the p orbital is empty. The second, called a triplet carbene, has the one of electron each in the sp2 and p orbitals. With some exceptions (halogens bonded to the deficient carbon) the triplet state is somewhat more stable than the singlet state because the two nonbonding electrons are further apart.

A carbene is a neutral disubstituted carbon atom with two nonbonding electrons. It needs two more electrons to complete its octet.

H C H Singlet

H C H Triplet

The two forms of carbene

Although carbenes are electrically neutral, they are very reactive electrophiles because the carbon is electron deficient. In an addition reaction, the carbene adds to the electron-rich bond of an alkene to form a cyclopropane ring.
C C

CH2

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A photolysis reaction is run by shining light of the proper wavelength onto the reaction.

Methylene (:CH2) is the simplest example of a carbene. The methods used to produce methylene involve heating diazomethane or exposing it to ultraviolet light in a process called photolysis. The products of both methods are methylene and nitrogen.

CH2

CH2
Diazomethane

or UV light

CH2 +

N2

Diazomethane, however, is difficult to work with because it is a very toxic, unstable compound. It is so unstable that it sometimes detonates without warning. Methylene generated from diazomethane is also extremely reactive and not only forms the cyclopropane ring by adding to the double bond but inserts itself into any CH bonds in the molecule.
CH2N2 CH3 C H Methylcyclopropane 39% CH3 C H C H 1-Butene 15% C CH3 H +

CH3CH

CH2

CH3

E-2-Butene 26% CH3 + CH3CH2CH CH2

Z-2-Butene 20%

The Simmons-Smith reagent is the product of a reaction between zinc and methylene iodide. A carbenoid reagent forms products as though it were a carbene.

Diazomethane's instability and lack of selectivity kept it from being very useful as a routine laboratory reagent. Then two chemists at DuPont discovered a synthetically useful alternate to diazomethane. This reagent, the Simmons-Smith reagent, involves the addition of methylene iodide (CH2I2) to copper or silver activated zinc. In an addition reaction, the Simmons-Smith reagent forms an organometallic reagent that reacts with alkenes similarly to a carbene. Thus, chemists call a Simmons-Smith reagent a carbenoid because it reacts similarly to a carbene.
CH2I2 Zn(Cu) ICH2ZnI Simmons-Smith reagent

The Simmons-Smith reagent is both regiospecific and stereospecific. Thus, the product of a Simmons-Smith reaction

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contains only cyclopropane rings that retain the stereochemistry of the double bond in the substrate.
CH2I2 Zn(Cu) H CH3CH2 H CH3

1-Ethyl-2-methylcyclopropane (74%)

In an addition reaction, a Simmons-Smith reagent gives moderate to good yields of the cyclopropane from an alkene. It also gives few, if any, side products.
CH2I2 Zn(Cu)

Bicyclo[4.1.0]heptane
(63%)

A halogenated carbene forms by a reaction of a base with a halogenated alkane. The reaction requires one hydrogen and at least two halogens. The most commonly used halogens are CHCl3, CHBr3, and RCHBr2. The presence of the halogens makes the hydrogen slightly acidic and reactive with a 50% aqueous solution of sodium or potassium hydroxide.

Br3C H
An elimination reaction eliminates atoms or groups from the same atom.

OH

Br3C

Br

CBr2

In this dehydrohalogenation reaction, called an elimination reaction, the hydrogen and the halogen are eliminated from the same carbon atom. All the eliminations covered in Chapter 13 are eliminations because the groups leaving are on adjacent carbon atoms. The halocarbene that results from the elimination adds to a double bond to form a halogenated cyclopropane.
CHBr3 KOH Br Br

7,7-Dibromobicyclo[4.1.0]heptane (87%)

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Phase Transfer Catalysis

The formation of a halogenated carbene usually involves a two-phase reaction. Because the base is insoluble in the organic solvent, a phase transfer catalyst is used to move the hydroxide ion from the aqueous layer into the organic layer. A common type of phase transfer catalyst is a quaternary ammonium salt. An example is benzyltriethylammonium chloride. As the chloride, benzyltriethylammonium chloride is insoluble in chloroform but quite soluble in water. However, as the quaternary ammonium hydroxide, it is somewhat soluble in the organic solvent. Thus, it can transport the hydroxide ion from the aqueous layer to the organic where the hydroxide ion reacts. After reacting, the halide ion is transported back to the organic layer.

CH2CH3 Cl CH2N CH2CH3

CH2CH3 OH Cl CH2N CH2CH3

OH

CH2CH3

CH2CH3

More soluble in water than in chloroform.

More soluble in chloroform than the quaternary ammonium chloride.

Synthesis of 7,7-Dichlorobicyclo[4.1.0]heptane
CHCl3 NaOH Cl Cl (83%)
Place 0.5 mL (0.005 mol) of cyclohexene in a flask. Add 1.25 mL of 50% aqueous sodium hydroxide and 1.25 mL (0.012 mol) of chloroform. Place a magnetic stir bar into the flask and add 50 mg of benzyltriethylammonium chloride. Cap the flask to prevent loss of vapors and stir vigorously for 12 hours at room temperature. An emulsion should form during the reaction time. Add 4 mL of water and 1.5 mL of methylene chloride to the reaction mixture. Stir gently to break the emulsion. Separate the layers. Add another 1.5 mL of methylene chloride to the reaction mixture. Stir for 5 minutes and separate the layers. Repeat with a third portion of methylene chloride. Combine the organic layers and wash with 2 mL of saturated sodium chloride solution. Separate the layers and dry the organic layer over anhydrous sodium sulfate. Remove the drying agent and evaporate the solvent using a rotary evaporator. Yield of product is 0.68 g (83%), b.p. 195-200oC. Discussion Questions 1. Why is it necessary to stir the reaction vigorously? What would happen to the product yield if the reaction mixture was not stirred vigorously? 2. Near the end of the isolation of the product, the reaction mixture is washed with saturated sodium chloride solution. Why?

7,7-Dichlorobicyclo[4.1.0]heptane

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Exercise 14.11 Predict the major products for each of the following reactions. a)
CH3 C H C CH2CH3 CH3 CH3CHBr2 NaOH

b)
CHCl3 NaOH

c)
CH2I2 Zn(Cu)

d)
CHBr2 KOH

Sample Solution b) This reaction produces two isomers in which the threemembered rings are either cis or trans to each other.
CHCl3 Cl Cl Cl

NaOH Cl

14.10 Oxidation of Alkenes

The oxidation of an alkene generally involves breaking the carboncarbon double bond to form two carbonyl-containing compounds.

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R1 C R2 C

R3 H

Oxidation

R1 C R2 O + O C

R3 H (or OH)

For more about the reaction of cold alkaline potassium permanganate, see Section 14.8, page 000.

Whether the carbonyl compounds produced are aldehydes, ketones, or carboxylic acids depends on the oxidizing reagent and on the alkene used. Cold alkaline potassium permanganate forms a vicinal diol. If the solution is too concentrated, too warm, or too acidic, oxidative cleavage occurs, and mixtures of ketones and carboxylic acids form.

KMnO4, OH H2O, warm

H3O

O + O OH

Ozonolysis is the reaction of ozone (O3) with an alkene.

A more widely used method for the oxidative cleavage of double bonds is ozonolysis. Ozone is readily prepared by passing an electric discharge through a stream of oxygen gas. This mixture of ozone and oxygen is then bubbled into a solution of the alkene forming a compound called a molozonide. The molozonide is quite unstable and spontaneously rearranges to form an ozonide.
C

C
O

C O

C
O

C
O

Molozonide

Ozonide

Ozonides are not much more stable than the molozonides, so they are rarely isolated. Low molecular weight ozonides are frequently explosive. Ozonides are treated with a reducing agent to convert them

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to carbonyl compounds. One of the most common reducing agents is zinc metal in acid.

Zn H3O

O +

Following are some examples of ozonolysis.

1) O3 2) Zn, H3O O + O H 2-Pentanone (63%) Propanal

1) O3 2) Zn, H3O

CHO CHO Hexanedial (72%)

Exercise 14.12 Predict the major products for each of the following reactions. a)
1) O3 2) Zn, H3O

b)
KMnO4, OH H3O H2O, warm

c)

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O 1) O3 OCH3 2) Zn, H O 3

Sample Solution a)
1) O3 2) Zn, H3O CHO CHO

Before the development of spectroscopy, ozonolysis was widely used to determine the position of double bonds in alkenes. After an ozonolysis reaction, the structure of the alkene can be reconstructed by the position of the two oxygen atoms from the carbonyl groups. Simply connect the carbon atoms to which the oxygen atoms are bonded to form a double bond. The only uncertainty is whether the double bond has an E or Z configuration.

or

Ozonolysis O +

O H

Exercise 14.13 Propose structures for the alkenes that would yield the following carbonyl compounds on reaction with ozone followed by zinc metal in acid. a)
O + O

b)

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O +

c)
O O

Sample solution b)

Or

Ozonolysis

O +

Key Ideas from Chapter 14

A carboncarbon double or triple bond undergoes an addition reaction bonding a new atom or group of atoms to each of the carbons of the original multiple bond. One of the groups that adds to the multiple () bond is an electrophile, the other is a nucleophile. An addition reaction to a multiple bond follows one of two possible reaction mechanisms, AdE2 and AdE3. In the AdE2 mechanism, the electrophile adds to the bond forming a cation. In the AdE3 mechanism, both the nucleophile and the electrophile add to the bond in a concerted addition. The rate of reaction for an AdE2 mechanism depends on the concentration of both the electrophile and the substrate. Thus, the mechanism follows second order kinetics.

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Many AdE2 reactions proceed through a carbocation. The ones that do lose the stereochemistry contained in the reaction site of the substrate. Other AdE2 reactions, especially those where the electrophilic reagent has nonbonding electron pairs, form a three-membered ring intermediate. The net reaction is usually an anti addition to the multiple bond. The rate of reaction for the AdE3 mechanism depends on the concentrations of the electrophile, nucleophile, and substrate. Thus, the mechanism follows third-order kinetics and is a concerted reaction. The net reaction is normally an anti addition to the multiple bond. As an addition to a carboncarbon multiple bond proceeds, the electrophile adds to the less highly substituted carbon, and the nucleophile adds to the more highly substituted carbon. This direction of adding is called Markovnikov's rule. Hydrogen halides add to the bonds of alkenes and alkynes to form organohalogen compounds. In a polar-protic solvent this reaction proceeds through a carbocation. In a polar-aprotic solvent the reaction proceeds through an AdE3 mechanism. An acid-catalyzed addition of water is an AdE2 reaction and proceeds via a carbocation. The oxymercuration reaction proceeds through an AdE2 reaction via a cyclic mercurinium ion intermediate. Nucleophilic substitution by water followed by reduction with NaBH4 produces an alcohol with net anti addition. The reaction is both stereospecific and regiospecific. Hydroboration is a stereospecific and regiospecific syn addition to an alkene forming an organoborane. The organoborane can be oxidized to form an alcohol. The alcohol is the antiMarkovnikov product. Halogens add to alkenes to form vicinal dihalides. For bromine, the reaction proceeds stereospecifically via a three-membered ring bromonium ion. With chlorine, the reaction is less stereospecific. The reaction does not work well with iodine.

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In a water solvent, the water competes with the bromine nucleophile and reacts with the bromonium ion to form a halohydrin product. Catalytic hydrogenation reduces a multiple bond by adding hydrogen to the bond. Catalysts such as platinum, palladium, or nickel are the most common ones in use. Hydrogen adds to the multiple bond to form an alkane. Lindlar's catalyst catalyzes the reduction of a triple bond to a double bond in a syn addition to form a cis alkene. The reaction stops there; the double bond is not reduced. Reaction of a triple bond with sodium in liquid ammonia reduces a triple bond to a double bond in an anti addition to form a trans alkene. Reaction of an alkene with osmium tetroxide or potassium permanganate forms a vicinal diol. The reaction is syn stereospecific. An epoxide forms from an alkene by a syn addition of oxygen using a peroxy carboxylic acid as the reagent. Hydrolysis of an epoxide forms a vicinal diol. The diol is a net anti addition of the hydroxyl groups. The addition of a carbene to a double bond forms a cyclopropane ring. Carbene generated from diazomethane also inserts a methylene group into any carbonhydrogen bond in the molecule. The Simmons-Smith reagent is called a carbenoid reagent because it adds to a double bond as a carbene and forms a cyclopropane ring. Chemists usually choose the SimmonsSmith reagent in preference to diazomethane because the Simmons-Smith reagent is regiospecific for a double bond. Halogenated carbenes can form from an elimination of a halogenated hydrocarbon. A carbon bearing at least one hydrogen and two halogens eliminates the hydrogen and one of the halogens to form a carbene. Alkenes readily oxidize with warm potassium permanganate to form ketones or carboxylic acids. Ozonolysis, followed by

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reaction with zinc and acid, forms ketones and aldehydes from alkenes.

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