9780199277896

The citric acid cycle
The reactions that living organisms use to generate the energy they need, and to prepare the compounds they require, are called metabolism. There are two types of metabolism, depending on whether energy is generated or used. In anabolism, enzyme-catalysed reactions are used to make large complex molecules. These processes require an input of energy. In catabolism, nutrients are broken down in enzyme-catalysed reactions to provide simple starting materials for synthesis and also to supply energy. The energy released is used to convert adenosine diphosphate (ADP) into adenosine triphosphate (ATP), which acts as a mobile source of energy in living systems (see Box 15.8, p.732).
An important stage in catabolism is the citric acid cycle (sometimes called the Krebs cycle or tricarboxylic acid cycle), which is the series of nine enzyme-catalysed reactions illustrated here. In the rst step of the cycle, acetyl-CoA (formed from glucose in the body) reacts with oxaloacetic acid to form citric acid. Citric acid then undergoes a series of eight reactions in a cycle that reforms oxaloacetic acid and produces two molecules of CO. In the process, 11 molecules of ADP are converted into ATP. The cycle continues by reaction of oxaloacetic acid with another molecule of acetyl-CoA. Of particular interest to this chapter are the reactions of cisaconitic acid and the trans acid, fumaric acid, with water. In each of these enzyme-catalysed reactions, water adds to the C=C bond to form a secondary alcohol as a single enantiomer. The addition of water to a C=C bond is called a hydration reaction and this is a characteristic reaction of alkenes described in Section 21.3.
The conversion of citric acid into isocitric acid, via cisaconitic acid, takes place in the active site of the enzyme aconitase and produces a structural isomer of citric acid by exchanging the positions of one H atom and the OH group. In the rst step, an elimination reaction forms the C=C bond of cis-aconitic acid and, in the second step, H2O adds regioselectively (see Section 19.3, p.906) to the C=C bond.
Oxford University Press 2009. Andrew Burrows, John Holman, Andrew Parsons, Gwen Pilling, Gareth Price: Chemistry
Sir Hans Krebs (19001981) left Germany in 1933 to carry out research in biochemistry at the University of Cambridge, subsequently moving to the University of Shefeld and then to Oxford. He was part of a team that discovered the citric acid cycle and to mark this achievement he was awarded the Nobel Prize in Medicine in 1953.
Citric acid is responsible for the tart taste of many fruits including lemons, limes, and gooseberries.
Acetyl-CoA From the breakdown of glucose
HO2C
HO2C
CO2H (S)-malic acid Fumarase Addition of H2O to the C=C bond
H2O HO2C
CO2H fumaric acid
The citric acid cycle.
The citric acid cycle occurs inside the mitochondria of cells. Mitochondria are usually rod-shaped structures and ATP is generated on the surface of the folded inner membrane.
ba
Alkenes and alkynes: electrophilic addition and pericyclic reactions

O + H2O SCoA HO2C O CO2H oxaloacetic acid Citrate synthase Nucleophilic addition to the ketone and hydrolysis of the thioester HO citric acid
This chapter builds on the following topics.

CO2H CO2H Aconitase Elimination of H2O HO2C H2O
Hydrocarbons Section 9.5, p.415 Conformational isomers Section 10.2, p.453

CO2H CO2H cis-aconitic acid H2O
Configurational isomers: E- and Z-isomers Section 10.3, p.468 Configurational isomers: isomers with chiral centres Section 10.4, p.473 Fundamental concepts of organic reaction mechanisms Section 19.1, p.861 Polar reactions Section 19.2, p.899 Redox reactions Section 19.2, p.896 Radical reactions Section 19.2, p.904 Pericyclic reactions Section 19.2, p.905 Regioselectivity Section 19.3, p.906 Stereoselectivity Section 19.3, p.907 The mechanisms of nucleophilic substitution reactions Section 20.3, p.925 The mechanisms of elimination reactions Section 20.4, p.939
Malate dehydrogenase Oxidation of the secondary alcohol to a ketone OH Names of enzymes are shown in blue The chemical changes are shown in green SCoA = coenzyme A (a leaving group) O R C S R is a thioester
Aconitase Addition of H2O
CO2H HO2C
3 2
CO2H
OH (2R,3S)-isocitric acid Isocitrate dehydrogenase Decarboxylation and oxidation of the secondary alcohol to the ketone HO2C
CO2 CO2H
Succinyl dehydrogenase Oxidation to form an alkene
HO2C
CO2H succinic acid
Succinyl-CoA synthetase Thioester hydrolysis
-Ketoglutarate dehydrogenase Decarboxylation then oxidation of the aldehyde to a carboxylic acid and formation of a thioester
O -ketoglutaric acid
CO2 HO2C COSCoA succinyl-CoA
958
R and RO radicals also add to C=C bonds and this type of reaction is commonly used to make polymers, as illustrated in Box 20.2 (p.919).
CHAPTER 21 ALKENES AND ALKYNES: ELECTROPHILIC ADDITION AND PERICYCLIC REACTIONS
Alkenes are an important class of organic compounds that contain a C=C bond. Many natural products contain C=C bonds, such as unsaturated fatty acids (see Box 9.4, p.422). Alkenes are especially useful compounds in organic synthesis, because the C=C bond reacts with numerous electrophiles in electrophilic addition reactions. These reactions, which are discussed in Section 21.3, can be used to prepare molecules containing a range of functional groups. Alkenes also react in pericyclic reactions and some examples are described in Section 21.4. Alkynes are a class of organic compounds that contain a CC bond. Like the C=C bond in alkenes, the CC bond in alkynes reacts with electrophiles in electrophilic addition reactions (Section 21.5). Alkynes are less reactive than alkenes with electrophiles so there are fewer synthetically useful electrophilic addition reactions. This chapter begins with an overview of the structure and reactivity of alkenes and alkynes (Section 21.1) and this is followed by a discussion of the most important methods of preparing these compounds (Section 21.2).
21.1 Structure and reactivity of alkenes and alkynes

Overlap of two sp2 orbitals to give a bond, and two p orbitals to give a bond, is shown in Section 4.4 (p.199).
The C=C bond of an alkene contains one strong bond and one weaker bond. The double bond is formed by overlap of the orbitals on the two sp2 hybridized carbons. A bond is formed by end-on overlap of an sp2 orbital of one carbon with an sp2 orbital of another carbon. The bond is formed by side-on overlap of the unhybridized p orbitals. Each carbon atom in the C=C bond forms two other bonds (to atoms in the R groups). The three bonds formed by each carbon atom are in the same plane and are separated by angles of 120.
H C H ethene C
H 120 H
R C R C
R bond bonds R
R C R C
R R
R C R C
R R
an alkene
C=C bond
C=C bond
Both carbon atoms and all four hydrogen atoms are in the same plane
The CC bond of an alkyne contains one strong bond and two weaker bonds. The triple bond is formed by overlap of the orbitals on the two sp hybridized carbons. A bond is formed by end-on overlap of an sp orbital of one carbon with an sp orbital of another carbon. The bonds are formed by side-on overlap of the two unhybridized p orbitals on each carbon atom. Each carbon atom in the CC bond forms one other bond (to atoms in the R groups). The two bonds formed by each carbon atom are separated by an angle of 180.
H C C H ethyne A linear molecule

A hydrogen atom attached to a CC bond is more acidic than a hydrogen atom attached to a C=C bond (Section 19.2, p.888). Deprotonation of alkynes forms alkynyl ions (RCC), which react with electrophiles such as the d+ carbon atom in a CX bond (Section 21.2, p.964) and that in a C=O bond (Section 23.2, p.1062).
180 R C C R bonds bonds R C C R R
The two bonds are perpendicular to each other C C R R C C R
an alkyne
CC bond
CC bond
CC bond
C=C, CC, and CC bonds have different bond lengths and bond enthalpies (Table 21.1). As the number of covalent bonds that hold the two carbon atoms together increases, so the bond length decreases and the bond enthalpy increases (the bond becomes shorter and stronger). You can work out from the data in Table 21.1 that a CC bond (+347 kJ mol1) is around 82 kJ mol1 stronger than a bond in C=C (+265 kJ mol1), and around 101.5 kJ mol1 stronger than a bond in CC (+245.5 kJ mol1). This explains why a bond, and not a bond, is broken in reactions of C=C and CC bonds.
21.1 STRUCTURE AND REACTIVITY OF ALKENES AND ALKYNES
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Table 21.1 Mean bond lengths and mean bond enthalpies

Bond
CC C=C CC
Mean bond lengths /pm

153 (longest bond) 134 120 (shortest bond)
Mean bond enthalpies /kJ mol1

+347 (weakest bond) +612 +838 (strongest bond)
Notice that mean values of bond lengths and bond enthalpies are shown in Table 21.1. This is because the substituents that are attached to the bonds affect the bond lengths and strengths. The effect of substituents on the stability and reactivity of C=C bonds is particularly important.
Tables of bond lengths and bond enthalpies are given in Appendix 10 (p.1364). Assigning the stereochemistry of alkenes using E/Z nomenclature is described in Section 10.3 (p.469). For tri- and tetrasubstituted alkenes, the E-isomer is not necessarily the most stable, because the priorities used to assign the E/Z configuration are not based on the size of the substituents. Selective formation of the E-isomer of an alkene, in an E2 elimination reaction, is discussed in Section 20.4 (p.941). The E- and Z-isomers of an alkene can have different biological activities (Box 9.4, p.422).
= Factors affecting the stability and reactivity of C=C bonds

Whereas a CC bond can freely rotate (that is, one carbon atom can rotate relative to the other), rotation about a C=C bond is severely restricted (and requires high temperatures) because this requires the bond to break (Section 10.2, p.453). As a result, a C=C bond in the middle of a carbon chain can have different congurational isomers, which are called E- and Z-isomers. The relative stabilities of the E- and Z-isomers of an alkene depend on the sizes of the substituents attached to the C=C bond. In general, the more stable congurational isomer has the two largest substituents on the opposite sides of the C=C bond, because this minimizes steric strain. It is often easier to make the E- (or trans-) isomer of a disubstituted alkene, rather than the Z- (or cis-) isomer, because the E- (or trans-) isomer is more stable.
Steric strain Largest groups are on the same side of the C=C bond H3C CH3
No steric strain H CH3 Largest groups are on the opposite sides of the C=C bond
The relative stability of a C=C bond is determined from the enthalpy change (H 2 ) for the reaction of the C=C bond with H2 to form a saturated alkane (see p.963). In a series of alkenes, the less negative the value of H 2 , the more stable the alkene. The procedure is explained for benzene in Section 22.1 (p.999).
H H (Z)-but-2-ene Less stable
H3C H (E)-but-2-ene More stable
Steric strain is also present in disubstituted terminal alkenes. For example, in 2methylpropene (H2C=C(CH3)2), there is steric strain due to interaction of the two methyl groups. The stability of alkenes is also inuenced by the electronic effects of the substituents attached to the C=C bonds (see Figure 21.1). It is generally found that the greater the number of alkyl groups attached to the C=C bond, the more stable the alkene is. The relative stabilities of different C=C bonds explain why some alkenes react faster than others.
R4 R
1
H R2 R
1
H R2 R
1
R2 R2 R
1
H H ~ R
1
H H R
1
H H
H E-disubstituted
H Z-disubstituted
tetrasubstituted Most stable
trisubstituted
terminal disubstituted
monosubstituted Least stable
Figure 21.1 Relative stabilities of alkyl-substituted alkenes.
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Hyperconjugation
Hyperconjugation is introduced in Section 19.1 (p.870).
The reasons why alkyl groups stabilize C=C bonds are not well understood. One explanation uses the concept of hyperconjugation. In an alkene, hyperconjugation involves the interaction of a pair of electrons in a lled CH orbital with the empty orbital of the C=C bond. This interaction leads to the two electrons in the bond being spread over the molecule, and the delocalization of these electrons stabilizes the C=C bond (see Figure 21.2). As the number of alkyl groups on a C=C bond increases, so does the number of CH bonds that can interact with, and thereby stabilize, the C=C bond.
Side-on orbital overlap H C C H H C=C * orbital C H H CH orbital
Delocalization of the electrons in the CH bond stabilizes the alkene H H
H does not leave the moleculethis resonance form only contributes to the actual structure of the molecule
Figure 21.2 Hyperconjugation.
Electrophilic addition
Generally, increasing the number of alkyl groups attached to a C=C bond increases the stability of the alkene, but it also makes the C=C bond more reactive to electrophilic addition.
The carbon atoms in C=C and CC bonds are held together by four and six electrons, respectively, so these bonds are electron-rich and act as nucleophiles in reactions. The reactions of nucleophilic C=C and CC bonds with electrophiles, E+, are called electrophilic additionsthis name shows that the rst step in these reactions involves addition of the electrophile to the multiple bond. The carbocation formed then reacts with a nucleophile, Nu (Figure 21.3). Overall, two new bonds replace the bond. Figure 21.3 shows general addition reactions for an alkene and an alkyne.
Nu R alkene R E
Step 1
Nu
Step 2
R E
E alkyl cation Nu
R alkyne
Step 1
Nu
Step 2
R E
E vinyl cation
Figure 21.3 Electrophilic addition to alkenes and alkynes.

In some cases, C=C bonds that have electron-withdrawing substituents can react with anions (see Box 19.8, p.901).
The reactivity of C=C and CC bonds towards electrophiles depends on the steric and electronic effects of the substituents that are attached to the multiple bonds. Generally, the more alkyl groups attached to the C=C or CC bond, the faster the rate of the electrophilic addition reaction. This is explained by the electron-donating (+I) effect of the alkyl groups, which makes the C=C or CC bond more nucleophilic and therefore more reactive to electrophiles. Conversely, electron-withdrawing (I, M) groups make the C=C or CC bond less nucleophilic and therefore less reactive to electrophiles.
CH3 is a +I group
H3C
CH3
CH3 H3C 2,3-dimethylbut-2-ene Stronger nucleophile
F F tetrafluoroethene
F is a I group
Weaker nucleophile
21.1 STRUCTURE AND REACTIVITY OF ALKENES AND ALKYNES
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Box 21.1 Ethene production in plants
NH2 Me HO2C NH2 HO OH S-adenosylmethionine (SAM) Me S O N N N NH2 N S O N N N N

ACC synthase
HO2C H2N ACC
ACC oxidase O2, vitamin C
H2C CH2 ethene
HCN + H2O + CO2 In the plant, enzymes convert HCN, a poisonous gas, into less harmful products.
HO OH
Ethene is a plant growth substance (hormone) that promotes the ripening of fruits such as apples, bananas, and tomatoes (Box 4.5, p.200). Ethene is produced in plants from S-adenosylmethionine (SAM). In the first step, SAM is converted into the amino acid 1-aminocyclopropane-1-carboxylic acid (ACC) by the enzyme ACC synthase. ACC is then converted into ethene in a second step, using the enzyme ACC oxidase in the presence of vitamin C and oxygen. Recently, several varieties of tomatoes have been genetically engineered to ripen more slowly. One way of doing this is to alter the gene sequence of the tomato so that production of the enzyme ACC synthase is decreased, which, in turn, decreases the production of ethene. This makes the fruit last longer in shipment and, on arrival, the genetically engineered fruit is treated with ethene to induce ripening.
Question
In living cells, S-adenosylmethionine (SAM) acts as an efficient methylating agent. Methylation reactions in the body regulate the biological activities of various hormones and neurotransmitters. For example, SAM reacts with norepinephrine in the presence of an enzyme to form epinephrine, which triggers a rise in blood pressure and heart rate in the body. Suggest a mechanism for the reaction below and explain why SAM is such a reactive methylating agent. (Hint. Use your knowledge of nucleophilic substitution reactions (Section 20.3, p.925) to help you propose a mechanism.)
OH
The genetic engineering of Flavr Savr tomatoes allows them to avoid spoilage during storage and transportation for much longer periods than normal tomatoes. This tomato was the first genetically engineered whole food to be brought to market. It disappeared from supermarket shelves in 1997, just three years after its introduction, partly due to supply problems, mixed taste-reviews, and marketing controversies.
OH NH2 HO
SAM Enzyme
HO HO
NHMe
HO epinephrine (adrenaline)
norepinephrine (noradrenaline)
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Summary
One strong bond and One strong bond and one weaker bond two weaker bonds The most stable The greater the H R isomer has the largest number of R groups, R R groups on the opposite R the more stable H an alkyne sides of the C=C bond the C=C bond an alkene
l
C=C and CC bonds react with electrophiles in electrophilic addition reactions.
21.2 Preparation of alkenes and alkynes

Preparation of alkenes
From halogenoalkanes and alcohols
Thermometer Condenser Mixture of liquids Heat
Elimination reactions are commonly used to make alkenes. Halogenoalkanes react with bases in E1 and E2 reactions to form a range of alkenes (see Section 20.4, p.939). Alcohols undergo elimination reactions when using reagents that convert the OH group of the alcohol into a compound that provides a good leaving group (Section 20.2, p.921). For example, heating propan-2-ol with an acid (for example, H2SO4) forms propene in an E1 reaction as shown in Figure 21.4. This type of reaction, which leads to the loss of water from a molecule, is called a dehydration reaction. The acid acts as a catalyst and all of the steps in this E1 reaction are reversible (the reverse reaction, namely addition of H2O to an alkene, is discussed in Section 21.3 on p.975). You can force the equilibrium to favour the alkene by distilling the reaction mixturethe alkene has a lower boiling point than the alcohol so it is selectively removed from the reaction mixture, displacing the position of equilibrium.
Liquid with the lowest boiling point

Distillation apparatus. Liquids with significantly different boiling points can be separated by distillation. The mixture is heated so that the liquid with the lowest boiling point is converted into a gas. The gas separates from the liquid mixture, is cooled, and condenses back into liquid form (see Section 18.4, p.838).
HO
O O S
O OH
OSO3H OSO3H H2O
OH2
propan-2-ol H2O
Protonation activates the OH group to give a better leaving group (H2O)
O HO S
O OH
+ propene
HO3SO OSO3H
The acid is regenerated

Alcohols have much higher boiling points than alkenes (of comparable molecular mass) because alcohols form intermolecular hydrogen bonds. Hydrogen bonds hold the alcohol molecules together and so extra energy is required to convert the liquid into a gas (Section 1.8, p.57).
Deprotonation of the intermediate secondary carbocation produces the alkene
Figure 21.4 Formation of an alkene from an alcohol in an E1 reaction. By partial reduction of alkynes using a Lindlar catalyst
Alkenes are formed by partial reduction of the CC bond of alkynes using hydrogen in the presence of a Lindlar catalyst (Pd/CaCO3/PbO). In the Lindlar catalyst, CaCO3 and PbO are used to reduce the catalytic activity of Pd (it is poisoned) and further reduction of the alkene bond is slow. If a platinum (or palladium) on carbon catalyst is used, addition of hydrogen to both CC and C=C bonds is fast and the alkyne is converted into an alkane.
21.2
PREPARATION OF ALKENES AND ALKYNES
963
(a)
H2 is adsorbed onto the catalyst surface R R H H
The CC bond approaches the catalyst surface R H H R
Both hydrogen atoms add to the same face of the molecule R H R Z-alkene H
The Lindlar catalyst, introduced in 1952, is named after Dr Herbert H. M. Lindlar who worked at the chemical company Hoffman La Roche in Switzerland.
R alkyne
H2
Lindlar catalyst
Surface of the metal catalyst
(b)
R alkyne R
H2
Pd/C
R R R
H2
Pd/C
R H H H HR H alkane R H H
Addition of H2 in the presence of a metal catalyst is called catalytic hydrogenationthis is an example of a reduction reaction (Appendix 4, p.1334).
H H Z-alkene It is not possible to stop at the alkene stage with a Pd/C catalyst
Surface of the metal catalyst
Figure 21.5 Catalytic hydrogenation of alkynes: (a) using a Lindlar catalyst; (b) using a palladium catalyst adsorbed on charcoal.
Addition of hydrogen to an alkene or alkyne is called hydrogenation. The catalytic hydrogenation of alkynes is summarized in Figure 21.5. Notice that the hydrogen atoms add to the same face of the CC or C=C bond which is described as a syn addition reaction (see Section 21.3, p.970). The hydrogen molecules and the CC or C=C bond come together on the surface of the metal catalyst and this leads to the transfer of hydrogen atoms to the same face of the CC or C=C bond. In the absence of the metal catalyst nothing happens (at room temperature and pressure) because of the high activation energy of the hydrogenationthe catalyst provides an alternative pathway with a lower activation energy by breaking the strong HH bond (+436 kJ mol1).
Catalytic hydrogenation of unsaturated fatty acids in vegetable oils produces solid fats (Box 9.4, p.422).
By partial reduction of alkynes using sodium in liquid ammonia

Whereas alkynes react with hydrogen and Lindlar catalyst to form Z-disubstituted alkenes, alkynes react with Na/NH3 to form E-disubstituted alkenes. When sodium metal dissolves in liquid ammonia at low temperature, the sodium atoms lose electrons to form Na+ ions (Section 26.5, p.1173). The electrons add to the CC bonds to form radical anions. As the name suggests, a radical anion has both a negative charge and an unpaired electron. The mechanism of the reduction is shown in Figure 21.6. Addition of an electron to a disubstituted alkyne forms a radical anion, which is then protonated by ammonia to form
Some catalytic hydrogenations only take place at a reasonable rate using a high pressure of hydrogen gas. These reactions are usually carried out in a sealed reaction bottle in a Parr hydrogenator. Sodium in liquid ammonia is a powerful reducing agent, which gives electrons to organic compounds in reactions called dissolving metal reductions.
R C
C R
Low temperature
R C C R radical anion
NH2 R C C R vinyl radical e H + NH2
alkyne
an electron
H2N
H H2N
R C C H
H R
C C H R E-alkene
vinyl anion
The R groups point in opposite directions to minimize steric strain
Figure 21.6 Reduction of an alkyne using sodium in liquid ammonia.
Adding one electron to a neutral organic molecule (RH) forms a radical anion (RH). Removing one electron from a neutral organic molecule forms a radical cation (RH+). Radical cations are formed in a mass spectrometer (Chapter 13.1, p.607).
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a vinyl radical. The vinyl radical accepts an electron from a sodium atom to form a vinyl anion, which is protonated by ammonia to form an E-alkene. The E-alkene is formed because the large alkyl groups in the vinyl anion (and the radical anion and vinyl radical) point in opposite directions to minimize steric strain (as shown in Figure 21.6).
By a Wittig reaction
Ammonia acts as an acid in this reaction because the radical anion and the vinyl anion are exceptionally strong bases (pKa (NH3) ~38 and pKa (H2C=CH2) ~44; Chapter 19.2, p.888).
Alkenes are also prepared from the reaction of a phosphorane (ylide, Ph3P=CHR) with an aldehyde or ketone in a Wittig reaction as shown in Figure 21.7. The Wittig reaction is perhaps the most general and versatile method for making C=C bonds. Wittig reactions are discussed in Section 23.2 (p.1063).
+ O
Ph3P=CH2 a phosphorane
Ph3P=O
triphenylphosphine oxide
Figure 21.7 A Wittig reaction.
Preparation of alkynes
Two equivalents is a short way of saying two stoichiometric equivalents, that is, twice as many moles of base as there are of the 1,2-dibromoalkane.
Alkynes are usually prepared by treating 1,2-dibromoalkanes (vicinal halides) with two equivalents of a strong base, such as sodium amide (sodamide, NaNH2). The mechanisms of these reactions can involve two consecutive E2 reactions that lead to the elimination of two molecules of HBr from the 1,2-dibromoalkane.
CH and CBr are anti-periplanar R H H Br
CH and CBr are anti-periplanar NH2

E2
R H2N H
Br R
E2
Br R 1,2-dibromoalkane (vicinal bromide)
R alkyne
NH3 + Br
bromoalkene (vinyl bromide)
NH3 + Br
1,2-Dibromoalkanes are formed by addition of Br2 to the C=C bond of an alkene (Section 21.3, p.970) so bromination followed by consecutive elimination of two molecules of HBr is a simple way to convert alkenes into alkynes.
H H3C CH3
Br2
Br H3C H Br
H CH3
2 NaNH2
H3C
CH3 + 2 NaBr + 2 NH3
H (E)-but-2-ene
but-2-yne
2,3-dibromobutane
Deprotonation of alkynes to form alkynyl anions is introduced in Section 19.2 (p.888).
Substituted alkynes are also formed from the reaction of alkynyl anions with halogenoalkanes in nucleophilic substitution reactions.
SN2
Br pent-2-yne
Br
propynyl anion
bromoethane
21.3
ELECTROPHILIC ADDITION REACTIONS OF ALKENES
965
Summary
l
Alkenes are prepared from halogenoalkanes, alcohols, alkynes, and aldehydes/ketones. X R X = I, Br, Cl
Wittig reaction
E1 or E2 Base
R alkene
H+
Ph3P=CH2
E1 or E2
H2, Lindlar catalyst, or Na/NH3
OH R R
l l
Alkynes are prepared from 1,2-dibromoalkanes. Substituted alkynes are prepared by alkylation of alkynyl anions with halogenoalkanes.
21.3 Electrophilic addition reactions of alkenes

Addition of hydrogen halides
Alkenes react with HX (where X = Cl, Br, or I) in a two-step reaction to produce halogenoalkanes. The mechanism is shown in Figure 21.8. In the rst and slower step of the reaction, the two electrons in the C=C bond (the nucleophile) are attracted towards the partially positive hydrogen atom in HX (the electrophile) and the HX bond breaks. In the transition state for this step (see margin), a partial positive charge develops on one of the carbon atoms of the C=C bond so the transition state resembles a carbocation. A new CH bond forms and the two electrons in the HX bond move on to the halogen atom. This produces an intermediate carbocation and a halide ion. In the second step, the halide ion rapidly reacts with the carbocation to form a halogenoalkane. The addition leads to a decrease in entropy (two reactants give one product) but it is thermodynamically favoured because of the enthalpy change, which has a large and negative value. Additions are exothermic because the CH and CX bonds that are formed are much stronger than the HX bond and C=C bond that are broken. Figure 21.9 shows the mechanism of the reaction in terms of orbital overlap. When HX adds to unsymmetrical alkenes (that have different groups on each carbon atom in the C=C bond), the reactions may be regioselective. The H and X atoms can add to the carbon atoms so as to selectively form the more substituted halogenoalkane, which is
X
Partial bonds
+ H
R
+
Partial positive charge on carbon The transition state for addition of HX to an alkene resembles a carbocation
For a spontaneous reaction, the Gibbs energy change for the reaction, G, is < 0, where G = H TS; see Section 15.5 (p.722).
Slow addition of H+ to the alkene R +

+
The halide ion can equally attack either side of the carbocation (like in an SN1 reaction, p.929) H
Step 1 Slow
H R
Step 2
Fast
R
The order of reactivity of addition of hydrogen halides to C=C bonds is usually: HI > HBr > HCl > HF.
X = Cl, Br, I intermediate planar carbocation
X a racemic halogenoalkane
Figure 21.8 The mechanism of the addition of HX to an alkene.
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Filled orbital of the C=C bond
Filled orbital of the new CH bond H
Empty p orbital
H H C R C R H X
X H R
C C H
Empty * orbital of the HX bond
Overlap end-on by approach of X towards X the top or bottom face of the carbocation
Filled orbital of the new CX bond
Figure 21.9 Addition of HX to an alkene showing orbital overlap.
A regioselective reaction is a reaction that leads to the selective formation of one structural isomer (that is, the reaction may give two or more structural isomers as products, but one is the major product); see Section 19.3 (p.906).
known as the Markovnikov (Markovnikoff) product (after the Russian chemist Vladimir Markovnikov). The regioselectivity is described by the Markovnikov rule, which states the following. On addition of HX to an alkene, H attaches to the carbon with fewest alkyl groups and X attaches to the carbon with most alkyl groups. The selective formation of the most substituted halogenoalkane is explained by the stabilities of the two intermediate carbocations (Figure 21.10). In the example shown in Figure 21.10, addition of H+ to a terminal alkene can form either a secondary carbocation or a primary carbocation. The secondary carbocation is selectively formed because this is more stable than the primary carbocationtwo electron-donating (+I) alkyl groups stabilize a secondary carbocation, whereas only one alkyl group stabilizes a primary carbocation. Primary carbocations are so unstable that they are rarely formed so addition of HX to a terminal alkene only produces the secondary halogenoalkane. Reaction proles for the addition of HX to the terminal alkene are shown in Figure 21.11. The transition states resemble carbocations, so the reaction to form the more stable carbocation has the lower Gibbs energy of activation.
The greater the number of (electron-donating) alkyl groups bonded to a positively charged carbon, the more stable the carbocation is (Section 19.1, p.870).
X
Alternatively, for the first step of the mechanism, you could show the C=C bond reacting with H+ (rather than HX).
+
HX
R secondary carbocation (two +I groups) H X R H
X R
The secondary H halogenoalkane is formed
R primary carbocation (one +I group)
The primary halogenoalkane is not formed
Figure 21.10 Regioselective addition of HX to a terminal alkene. Rearrangement of intermediate carbocations

Sometimes, the intermediate carbocations formed in the addition reactions undergo rearrangements to form more stable carbocations. The rearrangements involve the movement of a hydrogen atom or an alkyl group. When a hydrogen atom moves from a carbon atom next to the carbocation to the positively charged carbon, this is called a 1,2-hydride shift (see Figure 21.12). The term hydride is used because hydrogen moves with a pair of electrons (it is H that moves) and 1,2- is used to show that H moves to an adjacent carbon atom.
A rearrangement changes the way that the atoms are connected.
21.3
967
H TS Gibbs energy, G TS R X
The transition state TS that leads to the secondary carbocation is of lower energy than the transition state TS that leads to the primary carbocation H
Reactants R + HX R HX R
X X
R Progress of reaction
Figure 21.11 Reaction profiles for the addition of HX to a terminal alkene to form a primary halogenoalkane and a secondary halogenoalkane.
Me Me H 3-methylbut-1-ene Me Me H H
1,2-hydride shift
Me
H Secondary carbocation
X
The arrow shows the movement of H
Me Tertiary carbocation
X
A tertiary carbocation is more stable than a secondary carbocation
The use of 1,2- indicates that the hydride ion moves to an adjacent carbon. It is not related to the numbering of the carbon chain.
Me Me
X H
Me Me
H H
H Secondary halogenoalkane is the minor product
X Tertiary halogenoalkane is the major product
Figure 21.12 Rearrangement of a carbocation by a 1,2-hydride shift.

When an alkyl group moves from a carbon atom next to the carbocation to the positively charged carbon, this is called a 1,2-alkyl shift (WagnerMeerwein rearrangement) (see Figure 21.13). The alkyl group moves with a pair of electrons (it is R that moves) to form a more stable carbocation.
If a reaction involves an intermediate carbocation, always check to see if the carbocation can rearrange to form a more stable carbocation.
Me Me Me 3,3-dimethylbut-1-ene
Me Me
Me H
1,2-methyl shift The arrow shows the movement of Me
Me
Me Secondary carbocation
X
A tertiary H carbocation is more Me stable than a secondary Tertiary carbocation carbocation

X
Me Me Me
X H
Me Me X
Me H
Secondary halogenoalkane is the minor product
Tertiary halogenoalkane is the major product
Figure 21.13 Rearrangement of a carbocation by a 1,2-alkyl shift.
968
Worked example 21.1 Forming structural isomers by addition reactions

Reaction of vinylcyclohexane with HBr produces the two structural isomers shown here. Suggest reaction mechanisms to explain the formation of both products.
Br HBr + Minor product
Br
vinylcyclohexane (1-ethenylcyclohexane) Strategy
Major product
Identify the nucleophilic site, the electrophilic site, and the leaving group. Consider the stability of the two possible carbocations formed by addition of H+ to the C=C bond. Check if the carbocations can rearrange to form more stable carbocations.
Solution nucleophilic site + leaving group H Br electrophilic site

+
Br H Br H
A secondary carbocation is formed rather than a primary carbocation
Minor product
The minor product is formed by Markovnikov addition.
Movement of H forms a more stable carbocation H H

1,2-hydride shift
H H Br
H H
Br Secondary carbocation
Br Tertiary carbocation Major product
The major product is formed by carbocation rearrangement.
Question
Addition of HCl to the C=C bond of ethylidenecyclohexane forms products A and B in unequal amounts. Neither product arises from a rearrangement of a carbocation intermediate. Suggest structures for A and B and explain why A is formed in higher yield than B.
HCl
ethylidenecyclohexane (Ethylidene is the name for the CH3CH= group)
major product
minor product
21.3
969
Box 21.2 Adding HBr to alkenes in the presence of peroxides

When HBr adds to C=C bonds by a polar mechanism, the Markovnikov product is selectively formed. However, when a mixture of HBr, an alkene, and a peroxide (ROOR) is heated or irradiated with UV radiation (conditions that favour the formation of radicals), the regioselectivity of the addition reaction changes and the less substituted bromoalkane is selectively formedthis is called the anti-Markovnikov product. The change in regioselectivity, in the presence of a peroxide, is called the peroxide effect. The following reaction scheme shows the addition of HBr to but-1-ene by a polar mechanism and by a radical mechanism.
Arrows show formation of a secondary carbon radical R Br Br R Primary carbon radical (one +I group) H Br Br R Secondary carbon radical (two +I groups) H Br Br
Addition
Br Polar mechanism
HBr
H 2-bromobutane
Markovnikov product Br H + R Secondary bromoalkane is not formed
Abstraction
Abstraction
H Br R Br + Br
but-1-ene
HBr ROOR (peroxide)
Anti-Markovnikov product Br
Primary Regenerated bromoalkane (re-enters the is formed chain reaction)
Radical mechanism
1-bromobutane
In the presence of a peroxide, the regioselectivity of the addition changes because the reaction mechanism involves radical intermediates, not charged intermediates, and a rapid chain reaction (Section 20.2, p.917). On heating or irradiating the reaction mixture with UV radiation the weak OO bond of the peroxide (ROOR) selectively breaks to form two alkoxyl radicals (RO) in an initiation step. An alkoxyl radical then abstracts a hydrogen atom from HBr to form an alcohol and a bromine radical (atom)this is an exothermic reaction because the HO bond formed in the alcohol (~464 kJ mol1) is stronger than the HBr bond broken (~366 kJ mol1).
RO OR peroxide RO H Br
Heat or UV radiation
is explained by steric effects and also by the stability of the radical that is formedBr adds to the less hindered end of the C=C bond to form the more stable carbon-centred radical. (Br is larger than H+ so, when Br adds to the C=C bond, the steric interactions are greater than when H+ adds). Carbon-centred radicals are stabilized by +I groups (Section 19.1, p.870) so, for example, secondary carboncentred radicals are more stable than primary carbon-centred radicals. Finally, the intermediate carbon-centred radical abstracts a hydrogen atom from HBr to form the bromoalkane and Br, which can react with another molecule of the alkene. This is an exothermic reaction as the CH bond in the bromoalkane (~410 kJ mol1 for a secondary CH bond) is stronger than the HBr bond (~366 kJ mol1).
+ RO OR alkoxyl radicals RO H + Br Stronger bromine than the radical HBr bond
Question
For hydrogen halides to add to a C=C bond in a radical reaction, both addition and abstraction steps must be exothermic. If either step is endothermic, then the propagation step is too slow for the chain reaction to proceed. Reaction of HCl or HI with a terminal alkene, in the presence of a peroxide, does not produce the anti-Markovnikov addition products. Using the approximate bond enthalpies given below, explain why HCl or HI does not add to a C=C bond in a radical chain reaction. HCl CCl HI CI
Abstraction
The bromine radical then adds to a C=C bondthe addition is exothermic because a slightly stronger CBr bond (~290 kJ mol1) is formed at the expense of a weaker C=C bond (~265 kJ mol1). When Br reacts with a C=C bond, the Br selectively adds to the least hindered end of the C=C bond so the addition is regioselective. This
431 kJ mol1 346 kJ mol1 298 kJ mol1 228 kJ mol1
970
Addition of Br2 to an alkene is stereospecic: different stereoisomers of the alkene produce different stereoisomers of the product.
Br2 becomes polarized leaving group Br

Ring formation Step 1
bromonium ion H
+
electrophilic site Br +
Br R
+
Ring opening Step 2
Br H R Br R H
R R E-alkene Br2 reacts equally with the top or bottom face of the C=C bond
R Br H
The bromide ion can attack The bromine atoms add either carbon atom in the to the opposite faces of ringit approaches from the the C=C bond in an opposite side to the leaving group anti addition
Figure 21.14 Addition of Br2 to an alkene.
Addition of bromine
Interhalogen compounds with polar covalent bonds, such as + BrCl and +ICl, also add to C=C bonds.
1,2-Dibromoalkanes are also called vicinal dibromoalkanes.
Bromine adds to the C=C bond of alkenes to form 1,2-dibromoalkanes in electrophilic addition reactions. At rst sight, it may seem surprising that Br2 can act as an electrophile the Br2 molecule is not positively charged and the BrBr bond is not polarized. However, the Br2 molecule becomes polarized when it approaches a C=C bond. The electrons in the BrBr bond are repelled by the electron-rich C=C bond and move away from the Br atom that is nearer the C=C bond. This makes the Br atom nearer the C=C bond electrophilic. The mechanism of addition of Br2 to a C=C bond involves two steps as shown in Figure 21.14. Step 1 The C=C bond acts as a nucleophile and donates a pair of electrons to the polarized +BrBr molecule to form a CBr bond and Br. At the same time, the partially positive bromine atom donates a lone pair of electrons to one of the carbon atoms to form a second CBr bond. The bromine atom simultaneously bonds to both carbons to make an intermediate 3-membered ring called a bromonium ion. Note that, in the bromonium ion, the positively charged bromine is a strong I group so the electrons in the two CBr bonds are attracted away from both carbon atoms. This makes the carbon atoms in the ring electrophilic. The formation of the bromonium ion is a reversible process.
An SN2 reaction is a concerted bimolecular nucleophilic substitution reaction, which is discussed in Section 20.3 (p.926). In an anti addition, two atoms or groups of atoms add to the opposite faces of the reactant. In a syn addition, two atoms or groups of atoms add to the same face of the reactant.
Although bromonium ions are extremely reactive, some have been detected at low temperature and the bromonium ion shown here has been isolated. The two extremely bulky adamantyl groups, attached
to the 3-membered ring, hinder the approach of Br and this reduces the rate of ring opening.
Br
R A B
Syn addition Both groups add to the same face
H H A B
Step 2 Br acts as a nucleophile and rapidly reacts with the bromonium ion in an SN2 reaction. The Br approaches the bromonium ion from the opposite side to the positively charged bromine. It attacks either carbon atom in the ring to form a new CBr bond at the same time as one CBr+ bond is broken. Overall, two Br atoms add to the opposite faces of the C=C bond and this is described as an anti addition (see margin). In the reaction scheme in Figure 21.14, the Br2 molecule attacks only the top face of the C=C bond and the Br attacks only one carbon atom in the bromonium ion. However, the Br2 molecule can react equally well with the bottom face of the C=C bond and Br can react with either carbon atom in the bromonium ion. Because of this, the bromonium ion is formed as a racemate (a 1 : 1 mixture of enantiomers), which means that the dibromide
21.3
971
Step 1 Attack on either face of the C= C bond produces a racemate = Et

Br2 reacts with the top face
Step 2 Attack on either carbon atom in the ring is possible (for an unsymmetrical bromonium ion, the regioselectivity is unlikely to be 1 : 1) H
R
Me
Br2 reacts with the bottom face
Br Me
R
H
R
Br Me
R
Et Br Me
S
Et Br
H
R
Br Me
R
H +
S
Br
H
Br attacks the carbon atom on the left
Et Br H
Et Br H
Br attacks the carbon atom on the right
1 : 1 mixture of enantiomers
Br H Et
S R
Br Me H + H Et
R S
Reaction of Br with the bromonium ion of R,R configuration gives the same enantiomers, in the same ratio, as reaction of Br with the bromonium ion of S,S configuration. (Use models to check this for yourself.)
Me H
Both enantiomers of the bromonium ion react to form a dibromidering opening of only one of the enantiomers is shown in step 2
Br
Br
A 1 : 1 mixture of enantiomers is formed because the intermediate bromonium ion is a 1 : 1 mixture of enantiomers (no matter what the regioselectivity of the ring opening is (it could be 9 : 1 or 8 : 2) you still get a racemic dibromide)
Figure 21.15 Addition of Br2 to an unsymmetrical alkene to form a racemic mixture.

product is also a racemate. So, it is the relative conguration, not the absolute conguration, that is shown for both the bromonium ion and the dibromide in Figure 21.14. This is illustrated in Figure 21.15 for the addition of bromine to the unsymmetrical alkene, (E)-pent-2-ene, to form a racemic mixture of the enantiomers of the dibromide product.
The relative configuration shows the configuration of a racemate, but the absolute configuration shows the configuration of a single enantiomer (Section 10.4, p.489). Envelope and chair conformations of cycloalkanes are discussed in Section 10.2 (p.462). Whereas cyclohexane adopts a chair conformation, cyclohexene adopts a half-chair conformation. In the half-chair conformation, four of the six carbons are in the same plane and this arrangement of atoms accommodates the planar C=C bond. From your previous studies, you may have seen a mechanism for bromination of a C=C bond that involves an intermediate carbocation and not a bromonium ion. This mechanism does not tell the complete story because Br could attack either face of the carbocation and this would form a mixture of anti and syn addition products.
Evidence for the mechanism for addition of bromine to a C=C bond

Strong evidence for the formation of a bromonium ion and the overall anti addition of Br2 to a C=C bond is provided by the reaction of cyclic alkenes with bromine to produce cyclic 1,2-dibromides as shown in Figure 21.16. Rotation about the BrCCBr bond is not possible in these compounds, so the relative positions of the two bromine atoms in the products are xed. For example, addition of Br2 to cyclopentene or cyclohexene produces a trans-1, 2-dibromide (as a racemate), which has the Br atoms on opposite sides of the rings.
Br2
Br
Br
Br H H Br
Enantiomers H + Br
cyclopentene (envelope conformation)
Br H ()-trans-1,2-dibromocyclopentane Enantiomers
Br2
Br
Br
Br H +
Br H Br H Me Me H
cyclohexene (half-chair conformation)
H H Br Br ()-trans-1,2-dibromocyclohexane
The bromide ion can approach the top or bottom face of the carbocation Br
Figure 21.16 Addition of Br2 to cyclic alkenes provides evidence for the intermediate bromonium ions.
972
meso-2,3-dibromobutane Me Br2 Me H H Br Me Br Br
R
Br Me H Me H
R S
Me
H Me
H Me
(E)-but-2-ene
Br
Br
Attack at either carbon in the bromonium ion forms the same product
E/Z isomers
diastereomers
diastereomers
Me Me (Z)-but-2-ene Br2 H
Me
Br Me H
Br
Br Me H
S S
Br Me H + H Me
R R
H Me
Br (2S,3S)-2,3-dibromobutane
Br
Attack at either carbon in the bromonium ion forms a racemate
(2R,3R)-2,3-dibromobutane
Figure 21.17 Stereospecific addition of Br2 to an alkene.

Bromination of an alkene is stereospecific because the bromine atoms add to the opposite faces of the C=C bond in an anti addition.
Internal plane of symmetry Br Br Rotation R Me by 180 R Br H H H S S Me Me Br Me H meso-2,3-dibromobutane
The formation of an intermediate bromonium ion explains why addition of Br2 to a substituted alkene is stereospecic. In a stereospecic reaction, different stereoisomers of the reactant produce different stereoisomers of the product. This is shown by the reaction of Br2 with the E- and Z-isomers of but-2-ene in Figure 21.17. Addition of Br2 to the E-isomer forms a meso compoundthis compound has a plane of symmetry (see margin) and so is achiral (see Section 10.4, p.486). In contrast, addition of Br2 to the Z-isomer forms a racemate. Compare the structures of the products from both reactionsmodels will help you do this. The meso compound and the racemate are diastereomers (diastereomers have a different conguration at one of the two chiral centres). The E- and Z-isomers of but-2-ene react to form different diastereomers of 2,3-dibromobutane, so the addition of Br2 is stereospecic.
Addition of bromine in the presence of water

When water is present in the reaction of Br2 with a C=C bond, a 1,2-bromoalcohol (sometimes called a bromohydrin), rather than a 1,2-dibromoalkane, is formed as shown in Figure 21.18. The reaction is an electrophilic addition reaction, and the mechanism is similar to that for the addition of bromine shown in Figure 21.14, p.970, and in Figure 21.17 above). The rst step in the reaction involves the formation of a bromonium ion (as described in the previous section). In the second step, water acts as a nucleophile (rather than Br) and rapidly reacts with the bromonium ion in an SN2 reaction. The H2O approaches the bromonium ion from the opposite side to the positively charged bromine and attacks either carbon atom in the ring to form a new CO bond at the same time as one CBr+ bond is broken. Following deprotonation (in the third step), a 1,2-bromoalcohol is formed as a racemate. Note that the Br and OH groups add to the opposite sides of the C=C bond in an anti addition.
Use models to help you understand this.
Br Br + R R Water acts as a nucleophile

Ring formation Step 1
bromonium ion H
+
Anti addition
Ring opening Step 2
Br R
+
Br H R O H R H H
Deprotonation Step 3
Br H R R H + H3O
R H2O H
Br
H2O
Water acts as a base
OH 1,2-bromoalcohol (a racemate)
Figure 21.18 Addition of Br2/H2O to an alkene.
21.3
973
Decolorization of an orange-brown solution of bromine water is often used as a test for the presence of a C=C bond. When Br2 adds to a C=C bond, the orange-brown colour disappears.
Both H2O and Br are nucleophiles and if both reacted with the bromonium ion this would produce a mixture of a 1,2-bromoalcohol and a 1,2-dibromide. Br is a stronger nucleophile than H2O (as Br is negatively charged), so you might expect the 1,2dibromide to be the major product in these reactions. However, the rate of ring opening of the bromonium ion depends on the concentration of the nucleophilethe higher the concentration of the nucleophile, the faster the rate of ring opening. To form the 1,2bromoalcohol selectively, you need to ensure that the H2O molecules far outnumber the Br ions so water is used in excess. As there are many more H2O molecules than Br ions in the reaction mixture, H2O, rather than Br, is shown as the base in step 3 in Figure 21.18. When Br2/H2O reacts with unsymmetrical alkenes, the reactions are regioselective. The Br and OH groups add to selectively form the 1,2-bromoalcohol with the Br atom on the less substituted carbon as illustrated by the reaction in Figure 21.19.
Br is a very weak base the conjugate acid, HBr, has a very low pKa value of 9 (Appendix 9, p.1362).
Br Br
+
Larger + on the more substituted carbon H

+
Selective formation of one structural isomer Br H Me O H2O H H 1-bromopropan-2-ol (a racemate) H H H Me OH Br H + H3O H
Br H
+
Regioselective ring opening
Me Me propene (an unsymmetrical alkene) H2O
Br
Water attacks the more substituted carbon
Figure 21.19 Addition of Br2/H2O to an unsymmetrical alkene is regioselective.

The regioselectivity is explained by the structure of the bromonium ion. In the bromonium ion in Figure 21.19, the two CBr bonds are not the same length. The more substituted carbon atom forms a longer and weaker bond to bromine because this carbon atom is better at stabilizing a partial positive charge (each carbon atom has a partial positive charge because the electrons in the CBr+ bond are attracted towards the positively charged bromine atom). The methyl group is an electron-donating +I group so it helps to stabilize the partial positive charge on this carbon atom. Because the more substituted carbon has the greater partial positive charge, water selectively attacks this carbon, even though it is more sterically hindered.
In the transition state for ring opening of the bromonium ion, breaking of the CBr bond occurs to a greater extent than formation of the new CO bondthis is described as a loose SN2 transition state.
Partial bonds H2O

+
H
+
Br H
Me
H Transition state
The CBr bond breaks while the OC bond is forming
974
Worked example 21.2 Opening bromonium ions

Suggest a mechanism for the reaction of 1-methylcyclohex-1-ene with bromine in water. Give the structure of the major product and explain its stereochemistry.
Strategy
Draw the structures of the reactants. The conformation of 1-methylcyclohex-1-ene does not have to be shown (although you are always encouraged to draw a structure that shows the three-dimensional shape of the molecule). Identify the nucleophilic site, the electrophilic site, and the leaving group. Consider the structure of the bromonium ion formed by addition of Br+ to the C=C bond and decide whether the reaction with water is regioselective. Draw the structure of the product, paying particular attention to stereochemistry.
Solution Using drawings that do not show the conformation of molecules Anti addition of Br and OH HO Me + H3O Br H H trans-2-bromo-1methylcyclohexanol (The trans isomer has the groups of highest priority, in this case HO and Br, on the opposite sides of the ring (cf. cis and trans isomers of alkenes in Section 10.3, p.468) Br
Electrophilic site Me Br
+
Br
H2O Me Br H Unsymmetrical bromonium ion Water attacks the most substituted carbon
+
H2O
H O Me
Br
Leaving group
Nucleophilic site 1-methylcyclohex1-ene
Using drawings that show the conformation of molecules Br Br + Br Me Half-chair conformation of 1-methylcyclohex-1-ene Me Br H2O H2O H
+
Br Me
Br Me H O H
Br + H3O H HO Chair conformation of trans-2-bromo-1methylcyclohexanol
The product is formed as a racemate because Br2 can react equally well with either face of the C=C bond. The two possible chair conformations of cyclohexanes interconvert by a ring-flip (Section 10.2, p.464). For a substituted cyclohexane, the most stable chair conformation usually has more of the substituents in equatorial positions.
21.3
975
Axial substituents Br Me H HO Less stable
Equatorial substituents Me Ring-flip HOBr H More stable
Question
Cl2 reacts with C=C bonds to form intermediate chloronium ions that are converted into 1,2-dichlorides. Assuming that, in the presence of water, both Cl2 and Br2 react with C=C bonds by the same type of mechanism, suggest a mechanism for the reaction of ( Z)-but-2-ene with Cl2 and water, and give the structure of the major product.
Addition of water in the presence of acid

Alkenes react with H2O in the presence of a strong acid to form alcohols. These addition reactions are called hydration reactions, because water adds to the C=C bond. Reaction of a C=C bond with water and a strong acid (for example, aqueous H2SO4) starts by protonation of the C=C bond to form a carbocation. For unsymmetrical alkenes, the addition of H+ is regioselective (this is the same as for addition of HBr to alkenes, p.966). For example, in Figure 21.20, addition of H+ to 2-methylbut-2-ene forms a tertiary carbocation rather than a less stable secondary carbocation (Figure 21.10). In the second step, a nucleophile reacts with the carbocation. The nucleophile can be water or the conjugate base of the acid (for example, HSO4 for sulfuric acid). The nature of nucleophile depends on the concentration of the acid. In dilute sulfuric acid, water reacts with the carbocation because the concentration of water is much greater than the concentration of HSO4. However, in concentrated sulfuric acid, HSO4 reacts with the carbocation to form an alkyl hydrogen sulfate (see Box 21.3, p.976). When water reacts with the carbocation in the second step, an oxonium ion is formed. In the third step, water reacts with the oxonium ion to form an alcohol and regenerate the H3O+ ion, which acts as a catalyst for the hydration reaction. Notice that all steps in the hydration reaction are reversible, so it is possible to convert the alcohol back to the alkene in a dehydration reaction (Section 21.2, p.962). Box 21.3 describes how the reaction conditions are adjusted in industry to favour formation of the alcohol.
Strong acids are introduced in Section 6.2 (p.269). Hydration of an alkene forms an alcohol. Dehydration of an alcohol forms an alkene.
Hydration of alkenes is one of a small number of reactions that has a theoretical atom efficiency of 100% (Box 1.4, p.26). All of the atoms in water and the alkene make their way into the alcohol. In theory, there is no chemical waste from the reaction but, in practice, side-reactions (including acid-catalysed polymerization) can occur.
An oxonium ion is a compound containing a positively charged oxygen.
H3O from dilute acid Me Me 2-methylbut-2-ene (Unsymmetrical alkene) Me + H O H Water in dilute acid acts as the nucleophile H
Protonation Slow
Me Me H H2O The more stable carbocation is formed Me
Nucleophilic attack Fast
Me Me H O Me H H
Deprotonation Fast
Me Me HO Me
H2O Water deprotonates the oxonium ion
H 2-methylbutan-2-ol + H3O (Regenerated)
Figure 21.20 Addition of H2O/H to an unsymmetrical alkene.
976
Box 21.3 Making ethanol on a large scale
Reactor H2C CH2 (g) + H2O (g) Solid phosphoric acid catalyst 300C, 6070 atm
Separation Gases are cooled and ethanol turns into a liquid CH3CH2OH (l)
(1 equivalent) (0.6 equivalent)
Unreacted ethene and steam are recycled

Y Flow chart for the manufacture of ethanol.
The worldwide consumption of ethanol has steadily grown in recent years, particularly after research showed that ethanol-containing petrols produce fewer pollutants than petrol itself. Currently, the most popular method for making ethanol in industry is by hydration of ethene in the presence of an acid catalyst. H2C=CH2 (g) + H2O (g) 9 H3CCH2OH (g)
H+
H 2 = 46 kJ mol1
Addition of H2O to ethene is reversible, so reaction conditions need to be chosen so as to force the equilibrium to favour the formation of ethanol. The formation of ethanol from ethene is an exothermic process, so, by Le Chateliers principle (Section 1.9, p.60), the reaction is favoured by using a low temperature. It is also favoured by a high pressure since it takes place in the gas phase and two reactant molecules are converted into a single product molecule. The rate at which ethanol is formed depends on the concentration of the reactants, so you might expect a high concentration of steam to be used. In practice, however, these conditions do not give the optimum yield of ethanol. A temperature of 300C and a ratio of ethene:steam of 1 : 0.6 are maintained in the reactor. The pressure is 6070 atmospheres. Steam and ethene are passed over a solid acid catalyst in the reactor. The rate of the reaction also depends on the temperature. The high temperature (300C) ensures the gases reach equilibrium within the short time during which they come into contact with the acid catalyst. Only 0.6 equivalent (that is, 0.6 of the stoichiometric amount) of steam is used because increasing the amount of steam is found to reduce the efficiency of the acid catalyst. Unfortunately, using a high temperature and a relatively low concentration of steam
means that only around 5% of the ethene is converted into ethanol per pass through the catalyst. However, the process is made efficient, with an overall yield of 95%, by continually recycling the unreacted ethene and steam through the acid catalyst. Although aqueous acid catalysts such as sulfuric acid and phosphoric acid can be used to prepare ethanol, solid acid catalysts are used in industry because these are easier and safer to handle than corrosive liquids. For this reason, phosphoric acid groups are coated on to the surface of zeolites (Chapter 5, p.214) to make a solid acid catalyst. Their structures have large pores and cages, and ethene and steam can pass into the interior of the zeolite where the surface is covered with phosphoric acid groups.
H H O A solid acid catalyst O O Si O O P O O Zeolite surface
This ethanol manufacturing plant in West Burlington, Iowa (USA) produces ethanol from corn. Sugars derived from corn are fermented to give ethanol, which is purified by distillation and stored in large tanks.
Question
Concentrated sulfuric acid reacts with ethene to form ethyl hydrogen sulfate, which can be converted into ethanol by reaction with water as shown below. Suggest a mechanism for the formation of ethyl hydrogen sulfate in the first stage.
H2C
Conversion of ethene to ethanol z using an aqueous acid catalyst
CH2
H2SO4
O O S O OH ethyl hydrogen sulfate
H2O
Heat
OH
H2SO4
21.3
977
Hydration of unsymmetrical alkenes

Hydration of unsymmetrical C=C bonds using H+/H2O results in alcohols that have the OH group attached to the more substituted carbon. By analogy to the addition of HX to a C=C bond (see p.965), these products can be described as the Markovnikov products and the hydrations considered to follow the Markovnikov rule.
Me Me
H+/H2O
Me H Me HO 2-methylpropan-2-ol Selectively formed Markovnikov product + Me H
Me OH
2-methylprop-1-ene (Unsymmetrical alkene)
2-methylpropan-1-ol Not formed Anti-Markovnikov product
Hydrating unsymmetrical C=C bonds to form alcohols that have the OH group attached to the less substituted carbon (the anti-Markovnikov product) requires a different approach, that starts by addition of borane (BH3) to the C=C bond (see next section).
Addition of borane followed by oxidation

Alcohols are formed from alkenes by reaction of the C=C bond with diborane (B2H6) followed by oxidation using a solution of hydrogen peroxide and aqueous sodium hydroxide. The mechanism for this transformation involves the following four stages. Look carefully at these stages rst to get an overview of the process.
BH3 Stage 1 Syn addition of H and BH2
BH2
2R R Stage 2 Two further hydroborations

3
H2O2, HO Stage 3
O
3
H2O, HO Stage 4 Hydrolysis to give alcohols
3R
OH
Oxidation: BC bonds converted to BOC bonds
= Stage 1 Addition of BH3 to C=C

Diborane (B2H6) is in equilibrium with a small amount of borane (BH3) and it is the electron-decient boron atom (see margin) of BH3 that acts as the electrophile in the electrophilic addition to the C=C bond. BH3 adds to the C=C bond to form an alkylborane in a hydroboration reaction. The mechanism is shown in Figure 21.21. The C=C bond attacks the boron atom to form a new CB bond. As the CB bond is forming, a new CH bond starts to form so the addition of BH3 involves a four-membered transition state. Two curly arrows are used to indicate the movement of electrons but you should remember that the CB bond starts to form before the CH bondthis explains why one of the carbon atoms from the alkene has a partial
Empty p orbital (the boron atom can accept a pair of electrons) H H H B H B H H 2H B H H borane (planar)
diborane
As the pair of electrons moves to boron, a partial charge develops on the more substituted carbon Stereoselectivesyn addition of H and BH2 H Me H Me H + BH2 + BH2 Me BH2 Me H Me Me H H H Regioselectiveboron adds to the less Four-membered hindered carbon transition state an alkylborane CB starts to form before CH; both bonds form on the same side of the C=C bond
The structure and properties of diborane and other boron hydrides are described in Section 25.2 (p.1139). The bonding in B2H6 is discussed in Section 4.7 (p.210). Diborane must be handled with extreme caution because it is a highly flammable gas that ignites spontaneously in moist air at room temperature.
Figure 21.21 Mechanism of the hydroboration reaction in stage 1.
978
The hydroboration reaction was discovered by Herbert C. Brown from Purdue University, who was awarded a Nobel Prize in chemistry in 1979 for his work on organoboranes. Organoboranes contain hydrogen, carbon, and boron atoms for which the chemical symbols are, by coincidence, the initials of Herbert C. Brown.
positive charge in the transition state. Overall, the H and BH2 groups add to the same side of the C=C bond in a syn addition reaction. Addition of BH3 to the C=C bond is regioselective. The C=C bond attacks the boron atom to give a partial positive charge on the more substituted carbon atom in the four-membered transition statethe more substituted the carbon atom, the more stable the partial positive charge. This explains why the BH2 group selectively adds to the less hindered carbon atom in the C=C bond. This is also favoured for steric reasons because the BH2 group is larger than an H atom.
Stage 2 Further hydroboration to give a trialkylborane

Like BH3, alkylboranes add to C=C bonds in hydroboration reactions. The two BH bonds in the alkylborane are replaced successively by two BC bonds to give rst a dialkylborane and then a trialkylborane. These hydroboration reactions are regioselective and stereoselective, because they follow the same reaction mechanism as for the formation of the alkylborane.
Me Me
Me Me H Me Me B a trialkylborane H H Me Me
H Me Me
H B H
Me
Hydroboration
H Me Me
H B
H Me Me
Me
Hydroboration
an alkylborane
a dialkylborane
Stage 3 Oxidation of the trialkylborane to produce a trialkylborate

When a trialkylborane is converted into a trialkylborate, 3 BC (3 +395 kJ mol1) and 3 OO (3 +150 kJ mol1) bonds are broken and 3 BO (3 +515 kJ mol1) and 3 CO (3 ~+360 kJ mol1) bonds are formed. The enthalpy change (H 2 ) is equal to 1635 2625 = 990 kJ mol1.
To make an alcohol, the trialkylborane is reacted with hydrogen peroxide and aqueous sodium hydroxide. The rst part of this process is an oxidation reaction that converts the trialkylborane into a trialkylborate. The three CB bonds in the trialkylborane are replaced by three stronger BO bonds and three CO bonds in the trialkylborate. The mechanism of the oxidation, shown in Figure 21.22, starts by deprotonation of hydrogen peroxide (H2O2) by the hydroxide ion to form a hydroperoxide ion (HOO). The HOO ion donates a pair of electrons to the boron atom of the trialkylboranethe hydroperoxide ion acts as a nucleophile and the trialkylborane acts as an electrophile. Note that the planar boron atom in the trialkylborane becomes tetrahedral as the BO bond
a trialkylborane Me Me H B HO + H O O H hydrogen peroxide H2O + O O H hydroperoxide ion Me Me The boron atom accepts a pair H of electrons H Me Me H Three BO bonds and three CO bonds are formed Me Me O Me Me H B O O H Me Me a trialkylborate H O
Nucleophilic attack by HOO followed by alkyl migration is repeated twice
Me Me
H B Me H Me
H Me Me Me Me H B O + HO
Rearrangement
H H Me Me
Me Me An alkyl group moves from boron to oxygen, which breaks the weak OO bond
Figure 21.22 Oxidation of a trialkylborane to produce a trialkylborate in stage 3.
21.3
979
Me Me O H O H Me Me Me Me H OH + Me Me H
H2O
O Me Me H HO B O O H
Me Me Me Me H Me Me H
O B O HO
Me Me H OH +
B O
O H Me Me
OH HO B OH + 2
Me Me H
The process is repeated twice
O Me Me B O
OH H Me Me alcohol
OH
boric acid Three BOH bonds are formed and three BOR bonds are broken
H In total, three molecules of the alcohol are formed from one molecule of the trialkylborate
Figure 21.23 Hydrolysis of the trialkylborate to produce three equivalents of alcohol in stage 4.
forms. One of the alkyl groups then moves from boron to oxygen and the hydroxide ion acts as a leaving group. Even though HO is a poor leaving group, migration of the alkyl group occurs because a CO bond is formed in place of a much weaker OO bond. The boron atom becomes planar once more. Attack by HOO followed by alkyl group migration is repeated until all three BC bonds in the trialkylborane are converted into three BO bonds in a trialkylborate.
Stage 4 Hydrolysis of the trialkylborate to produce three equivalents of alcohol

In the nal stage, the trialkylborate reacts with hydroxide ion and water in a series of three nucleophilic substitution reactions to form three molecules of the alcohol and boric acid (see Figure 21.23).
Regiochemistry and stereochemistry of the overall process

The overall process in stages 14 is the addition of water to the C=C bond. The water adds regioselectively (Section 19.3, p.906) to give the anti-Markovnikov product.
Me
(i) BH3
Me Me H
Me
OH
(ii) H2O2, HO, H2O
Conversion of the three CB bonds in trialkylboranes to give three CO bonds in the alcohols is stereospecic (Section 19.3, p.907). The alkyl groups move from B to O with retention of conguration so the tetrahedral structures of the alkyl groups do not change. This means that hydroboration followed by oxidation results in the syn addition of H and OH groups to the C=C bond. This is illustrated by the following reaction.
A CB bond is replaced by a COH bond with retention of configuration Me

Syn addition of BH3
Me H BH2
Two further hydroboration reactions
Me H BR2
H2O2, HO, H2O
Me H OH
Overall syn addition of H and OH
1-methylcyclopentene
R = 2-methylcyclopentyl trans-2-methylcyclopentanol is formed as a racemate because BH3 can add equally well to either face of the C=C bond
980
Worked example 21.3 Selectivities in hydroborationoxidation reactions

1-Methylcyclohex-1-ene is treated with diborane and then with a solution of hydrogen peroxide in aqueous sodium hydroxide.
(a) Suggest structures for the intermediates and the major product of the reaction. (b) Does the process result in the selective formation of a single enantiomer (enantioselective) or of a single diastereomer (diastereoselective)? Strategy
Draw the structures of the reactants. The conformation of 1-methylcyclohex-1-ene does not have to be shown (although you are always encouraged to draw a structure that shows the three-dimensional shape of the molecule). Remember that the reactant is BH3 not B2H6. For addition of BH3 to the C=C bond, consider the regioselectivity and stereoselectivity of the addition. For oxidation of the intermediate trialkylborane (using H2O2 and HO) consider how the stereochemistry changes when the BC bonds are converted into OC bonds. Draw the structure of the product, paying particular attention to stereochemistry. Consider whether the transformation results in the selective formation of a single enantiomer or a single diastereomer.
Solution (a) Me
syn addition of BH3
Me H BH2
Two further hydroboration reactions
Me H
1-methylcyclohex-1-ene
BR2 R = 2-methylcyclohexyl
H2O2, HO, H2O
Me H Overall syn addition of H and OH OH
trans-2-methylcyclohexanol is formed as a racemate because BH3 can add equally well to either face of the C=C bond (b) This is an example of a diastereoselective transformation as trans- rather than cis-2methylcyclohexanol is selectively formed. (The trans isomer has the groups of highest priority, in this case HO and Me, on opposite sides of the ring.) The product is formed as a racemate because BH3 can add equally well to either side of the C=C bond in 1-methylcyclohex-1-ene.
21.3
981
Me H OH cis-2-methylcyclohexanol is not formedthis requires anti addition of H and OH Question
An equal mixture of enantiomers is formed Me H OH From addition of BH3 to the bottom face of the C=C bond
H Me
OH From addition of BH3 to the top face of the C=C bond
2-Methylhex-2-ene is treated with diborane and then with a solution of hydrogen peroxide in aqueous sodium hydroxide.
(a) Suggest a structure for the major product of the reaction. (b) Explain why the process is regioselective.
Reaction with peroxycarboxylic acids

Peroxycarboxylic acids (peracids, RCO3H) have an oxygen atom between the C=O and OH groups of a carboxylic acid (RCO2H). They react with alkenes by donating an oxygen atom to a C=C bond to form an epoxide, in a reaction called an epoxidation. The other product is a carboxylic acid. This reaction is an electrophilic addition. The oxygen atom in the OH group in the peroxycarboxylic acid is partially positive (because the RCO2 group is a I group and withdraws electrons) and acts as the electrophile by accepting a pair of electrons from the C=C bond. This causes the weak OO bond (an OO bond has a bond enthalpy of about +150 kJ mol1) in the peroxycarboxylic acid to break. As this bond breaks, a pair of electrons moves on to the carbonyl group and a proton is abstracted from the OH group. At the same time, a second CO bond begins to form. The entire concerted process is represented using four double-headed curly arrows as shown in Figure 21.24. From the mechanism you can see that the two CO bonds of the epoxide are formed at the same time in a concerted addition reaction. Because epoxidation takes place in a single step, the carboncarbon bond of the alkene cannot rotate and change from trans to cis conguration during the addition. This explains why the epoxide retains the conguration of the C=C bonda cis-epoxide is formed from a cis-alkene and a trans-epoxide is formed from a trans-alkene. The reaction is therefore stereospecic. Note that the peroxycarboxylic
O R O OH
A peroxycarboxylic acid (peracid)
R R An epoxide
Compare the reaction mechanisms leading to epoxides and bromonium ions to note the similarities.
meta-Chloroperbenzoic acid (abbreviated mCPBA) is a commonly used peroxycarboxylic acid. Despite being a reactive oxidizing agent, mCPBA is easy to handle, as it is a solid and it can be stored in a refrigerator.
(a)
A peroxycarboxylic acid R O
O + O
(b)
R O O
Concerted addition
A peroxycarboxylic acid H + R O
O + O
R O O H + H R O H Cl
H R
H R
Concerted addition
O R R R cis-alkene
R trans-alkene
H trans-epoxide (racemate)
R cis-epoxide (racemate)
Figure 21.24 Epoxidation is stereospecific: (a) a trans-alkene produces a trans-epoxide; (b) a cis-alkene produces a cis-epoxide.
982
The CCO bond angle in an epoxide is 60 rather than the normal tetrahedral bond angle of 109.5. Epoxides therefore have appreciable angle strain (Section 10.2, p.460) and they react to break open the ring and form products with tetrahedral bond angles.
acid can approach either side of the C=C bond equally well and so the epoxide is formed as a racemate.
Reactions of epoxides
Epoxides are important compounds in synthesis because they undergo a variety of reactions to make useful compounds. The 3-membered epoxide ring is highly strained and can be opened by reaction with a range of nucleophiles. For example, water reacts with epoxides in the presence of an acid or base catalyst to form 1,2-diols (glycols).
Acid-catalysed ring opening

Water reacts with protonated unsymmetrical epoxides to selectively attack the more substituted carbon. As in bromonium ions (p.973), the more substituted carbon atom in the 3-membered ring has the greater partial positive charge.
Water is such a weak nucleophile that it does not react with an epoxide but it will react with a protonated epoxide as shown in Figure 21.25. Protonation of the epoxide produces a much stronger electrophile that reacts with water in a nucleophilic substitution reaction. This is an SN2 type reaction as the water molecule approaches the epoxide from the opposite side to one of the CO bonds. Substitution produces a new CO bond at the same time as one of the CO bonds in the epoxide is broken. Finally, deprotonation of the oxonium ion forms a 1,2-diol that has the two OH groups in an anti arrangement. Notice that the acid is regenerated in the last step so H3O+ acts as a catalyst for the reaction.
Reaction of a C=C bond with RCO3H followed by H2O/H+ introduces two OH groups to the opposite sides of the C=C bond in an anti addition. Reactions that lead to the introduction of two OH groups are called dihydroxylations. Remember that all acidbase reactions are equilibrium reactions. The position of the equilibrium depends on the difference in pKa values between reactants and products as discussed in Section 6.2 (p.277).
H R
O R +
H O H H
The protonated epoxide is a strong electrophile H H O Protonation SN2 reaction R R H 2O H H2O
R H H O H OH H R
H trans-epoxide
H O H H Regenerated +
R H HO OH H R 1,2-diol
Deprotonation
Overall anti addition of two OH groups to the C=C bond
Figure 21.25 Acid-catalysed ring opening of an epoxide.

Alkali-catalysed ring opening
Water also reacts with epoxides in the presence of a small amount of the hydroxide ion as shown in Figure 21.26. The hydroxide ion is a stronger nucleophile than water and reacts with the epoxide in a nucleophilic substitution reaction. This is an SN2 type reaction as the hydroxide ion approaches the epoxide from the opposite side to one of the CO bonds. Finally, protonation of the alkoxide ion forms a 1,2-diol that has the two OH groups in an anti arrangement. Notice that the hydroxide ion is regenerated in the last step so it acts as a catalyst for the reaction.
HO is a stronger nucleophile than H2O R HO

+
Protonation R H O H O H R H R H HO OH H R 1,2-diol + OH Regenerated
O R
SN2 reaction
HO
H trans-epoxide
Overall anti addition of two OH groups to the C=C bond
Figure 21.26 Base-catalysed ring opening of an epoxide.
21.3
983
Box 21.4 Why is benzene carcinogenic?

Benzene is a useful component of petrol because it has a high octane number and helps to reduce the tendency of the petrolair mixture to pre-ignite in the engine (called knocking). However, benzene is known to be carcinogenic, so it is limited to a maximum of 1% by volume in petrol. Your body is constantly exposed to foreign organic compounds, such as benzene. These organic compounds are soluble in fat and they tend to build up in the membranes of cells. To remove these unwanted compounds, your body uses enzymes in the liver to catalyse a number of chemical reactions. These reactions, called biotransCytochrome P450
formations, convert fat-soluble compounds into water-soluble compounds that can be excreted from the body An important biotransformation of aromatic organic compounds is epoxidation, which is catalysed by an enzyme called cytochrome P450. In the body, benzene reacts with cytochrome P450 and O2 to form benzene oxide, which contains an epoxide ring. Because of the strain in the epoxide ring, benzene oxide reacts with various nucleophiles including water. Reaction with water opens the epoxide ring to produce catechol, which is a more polar and water-soluble molecule than benzene.
H2O O
Then transfer of H+
OH
Oxidation (2H)
O2
OH OH catechol
H OH a trans-1,2-diol
benzene
benzene oxide
More easily removed from the body than benzene
y Biotransformation of benzene
in the body
N O benzene oxide N a heterocyclic base in DNA Y Reaction of benzene oxide with DNA
Then protonation
N H N
The high reactivity of benzene oxide explains why benzene causes cancer (carcinogenic). Other nucleophiles in the body, such as the heterocyclic bases present in DNA, can react with the epoxide ring of benzene oxide to form products that no longer fit into the DNA double helix (see p.882). This can lead to mutations and cancer.
H OH
Question
Suggest a mechanism for the reaction of 1-methylcyclohexene oxide with aqueous acid and give the structure of the product.
Summary
Seven important addition reactions involving alkenes. X
HX
X = Cl, Br, I
R H
Intermediate carbocation Regioselective addition (favours Markovnikov product) Carbocation rearrangements are possible Radical reaction Regioselective addition (favours anti-Markovnikov product) Intermediate bromonium ion Stereospecific addition (anti addition)
HBr
Peroxide, heat
R Br
Br
Br2
H R Br OH
R H
Br2, H2O
H R Br
R H
Intermediate bromonium ion Stereospecific addition (anti addition) Regioselective addition
984
H+, H2O
OH R H R OH OH H
Hydration via an intermediate carbocation Regioselective addition (favours Markovnikov product) Hydration by hydroboration then oxidation Regioselective addition (favours anti-Markovnikov product) Stereospecific addition (overall syn addition) 1,2-Dihydroxylation by epoxidation then hydrolysis Stereospecific addition (overall anti addition)
BH3
then H2O2, HO
RCO3H then H2O/H or H2O/HO

+
H R
R H OH
21.4 Pericyclic reactions of alkenes

A pericyclic reaction of an alkene with a 1,3-diene to give a 6-membered ring is called the DielsAlder reaction (Section 19.2, p.905).
Pericyclic reactions are concerted (single-step) reactions that involve a change in the position of bonding electrons via cyclic transition states. The most common pericyclic reactions involving C=C bonds are cycloaddition reactions. In these reactions the C=C bond of an alkene reacts with another molecule to form a cyclic product.
Reaction with potassium permanganate or osmium tetroxide

OH R R OH A 1,2-diol
Reaction of a C=C bond with KMnO4/HO/H2O introduces two OH groups on the same side of the C=C bond in a syn addition.
Potassium permanganate or osmium tetroxide are used to convert an alkene into a 1,2-diol. Reaction of a C=C bond to form a 1,2-diol is called a dihydroxylation reaction.
Reaction with potassium permanganate followed by hydrolysis

A cold, dilute solution of potassium permanganate (potassium manganate(VII), KMnO4) reacts with a C=C bond in a pericyclic reaction to produce, after reaction with aqueous sodium hydroxide, a 1,2-diol. The mechanism for this reaction, shown in Figure 21.27, involves a concerted cycloaddition reaction to form a manganate ester.
Tetrahedral
manganese(VII) O O Mn O R
Six electrons delocalized around the ring O H O R H cyclic transition state Mn O R O
manganese(V) O H O Mn O R R H manganate ester O Two new CO bonds form on the same face of the C=C bond
O R
Cycloaddition
trans-alkene
HO , H2O
Hydrolysis of the two MnO bonds
manganese(IV) MnO2 The manganese is reduced + R
H OH OH R H 1,2-diol Overall stereospecic syn addition of two OH groups
Figure 21.27 Reaction of an alkene with MnO4 followed by alkaline hydrolysis gives a 1,2-diol.
21.4
PERICYCLIC REACTIONS OF ALKENES
985
The C=C bond acts as a nucleophile and attacks an oxygen atom on MnO4 to form a CO bond. As this happens, a pair of electrons moves on to manganese and a pair of electrons in an adjacent Mn=O bond moves to form a second CO bond. Both CO bonds are formed on the same face of the alkene in a syn addition. The reaction of KMnO4 with a C=C bond is usually carried out in the presence of aqueous hydroxide so that the manganate ester is immediately hydrolysed to form a 1,2-diol (together with MnO2). Because the cycloaddition reaction takes place in a single step, the manganate ester, and subsequently the 1,2-diol, retain the conguration of the C=C bonda cis-1,2-diol is formed from a cis-alkene and a trans-1,2-diol is formed from a trans-alkene. The reaction is therefore stereospecic. Note that KMnO4 can react equally well with the top or bottom face of the C=C bond so the 1,2-diol is formed as a racemate.
Decolorization of a purple aqueous solution of KMnO4 is often used as a test for the presence of a C=C bond in a molecule.
Enantiomers Reaction MnO4 on the top face R R H OH R OH R + R H OH H
R OH R R Reaction on the bottom MnO4 face
H The 1,2-diol is formed as an equal mixture of enantiomers
To obtain a 1,2-diol from the reaction of an alkene with a dilute solution of KMnO4, the reaction mixture must be kept cold. KMnO4 is such a powerful oxidizing agent that, at room temperature or above, it oxidizes 1,2-diols to form ketones and carboxylic acids. This is an example of oxidative cleavage, which is discussed later in this section.
R R OH R H OH R
KMnO4 The CC bond is cleaved at room temperature or above
O H + R O R ketone
KMnO4
The aldehyde is oxidized further
R O OH carboxylic acid
KMnO4 in aqueous hydroxide is used as a stain in thin layer chromatography (TLC) to show up the positions of colourless compounds on the TLC plate (Section 12.3, p.575). Compounds containing C=C bonds react with the KMnO4 to give a yellow spot on a purple background. A pencil is used to mark the plate, to show where the compounds are applied, and to indicate the position reached by the solvent.
Reaction with osmium tetroxide followed by hydrolysis

Like KMnO4, osmium tetroxide (OsO4) reacts with a C=C bond in a pericyclic reaction to produce, after reaction with water, a 1,2-diol. The mechanism for this reaction is still under debate but the simplest possible mechanism involves a concerted cycloaddition reaction to form an osmate ester (see Figure 21.28). The C=C bond acts as a nucleophile and attacks an
O Os O
OsO4 osmium tetroxide O (osmium(VIII) oxide)
986
Reaction of a C=C bond with OsO4/H2O introduces two OH groups on the same side of the C=C bond in a syn addition.
osmium(VIII) O O Os O R O R
Six electrons delocalized around the ring O Os HO O R R H cyclic transition state

2 H2O
Cycloaddition
trans-alkene
osmium(VI) O O Two new CO Os HO bonds form on O the same face of R R the C=C bond H osmate ester
Hydrolysis of the two OsO bonds
osmium(VI) O O Os O O O HO Os O + R
H OH OH R H 1,2-diol Overall stereospecific syn addition of two OH groups
OH The osmium is reduced
Figure 21.28 Reaction of an alkene with osmium tetroxide followed by hydrolysis to give a 1,2-diol.
Osmium tetroxide (OsO4) is tetrahedral. The colourless solid is usually contaminated by a small amount of osmium dioxide (OsO2), which is yellow-brown in colour. In 2004, a plot to detonate a bomb, believed to contain osmium tetroxide, was foiled by British intelligence sources.
oxygen atom on OsO4 to form a CO bond. As this happens, a pair of electrons moves on to osmium (which is in the +8 oxidation state) and a pair of electrons in an adjacent Os=O bond moves to form a second CO bond. Both CO bonds are formed on the same face of the alkene in a syn addition. The reaction of OsO4 with a C=C bond is usually carried out in the presence of water so that the osmate ester is immediately hydrolysed to form a 1,2-diol together with Os(OH)2O2. Note that the dihydroxylation reaction is stereospecic and, as OsO4 can react equally well with the top or bottom face of the C=C bond, the osmate ester is formed as a racemate.
Reaction with osmium tetroxide in the presence of an oxidizing agent

Unfortunately, osmium tetroxide is expensive and toxic so, to reduce the amount of OsO4 needed in dihydroxylation reactions, an oxidizing agent is usually added to the reaction mixture. As soon as OsO4 is converted into Os(OH)2O2, the oxidizing agent selectively oxidizes Os(OH)2O2 back to OsO4 so only a small amount of OsO4 is required. A common oxidizing agent that is used is potassium hexacyanoferrate(III) (potassium ferricyanide, K3Fe(CN)6). Another oxidizing agent that can be used to convert Os(OH)2O2 into OsO4 is periodic acid (HIO4). However, HIO4 also oxidizes 1,2-diols to form carbonyls. So, when OsO4/HIO4 reacts with a C=C bond, the product is an aldehyde and/or ketone as shown below, not a 1,2-diol. The mechanism of oxidation of the 1,2-diol involves an intermediate periodate ester that breaks down to form two C=O bonds together with iodic acid.
HIO4 and HIO3 are called hypervalent compounds because the iodine atoms in these compounds have more than eight electrons in the valence shell. Hypervalency is discussed in Section 4.5 (p.204).
iodine(VII) R OH R OH R + O HO I O tetrahedral periodic acid O

H2O
HO O O R O I O R R H periodate ester
iodine(V)
O I O iodic acid + R O H aldehyde
HO R O R ketone
H 1,2-diol Produced from reaction of the C=C bond with OsO4/H2O
Because the oxidation reaction with HIO4 cleaves the CC bond in the 1,2-diol, chemists call this reaction oxidative cleavage. Oxidative cleavage is an important way of making carbonyl compounds. Other oxidizing agents that convert a C=C bond into two C=O bonds include KMnO4 (see p.985) and ozone (O3), which is discussed in the following section.
21.4
PERICYCLIC REACTIONS OF ALKENES
987
Worked example 21.4 Oxidation of C=C bonds

Suggest reagents for converting (E)-pent-2-ene into products A and B. More than one step may be required in each case.
HO H
H OH
HO H A Strategy
(E)-pent-2-ene
HO H B
Recognize the functional groups in the products to identify what types of reactions are involved. Look at the stereochemistry of products A and B to determine if they are formed in a syn addition or an anti addition reaction. Choose the appropriate reagents.
Solution
Compound A is a 1,2-diol that is formed by the syn addition of two OH groups on to the C=C bond of (E )-pent-2-ene. A could be formed by reacting (E )-pent-2-ene with OsO4/H2O (or with a cold dilute solution of KMnO4 followed by aqueous sodium hydroxide). Compound B is a 1,2-diol that is formed by the anti addition of two OH groups on to the C=C bond of (E)-pent-2-ene. B is formed by reacting (E )-pent-2-ene with RCO3H (to make an epoxide) followed by H+/H2O (or HO/H2O).
Question
Give the structures of the products from reaction of (E)-pent-2-ene with OsO4/H2O followed by HIO4.
Reaction with ozone

Ozone (O3) is used to convert a C=C bond into two C=O bonds.
R R R R
1. O3, Low temperature

2. Oxidizing or reducing agent
R R O +
O R
The preparation and properties of ozone are described in Section 27.5 (p.1223).
Aldehydes, ketones, and/or carboxylic acids are formed, depending on the structure of the alkene and whether, after the reaction with ozone, an oxidizing or reducing agent is used. Ozone (O3) is a symmetrical bent molecule. The two oxygen atoms at the ends of the molecule share a negative charge and the central oxygen atom is positively charged. Because O3 has both a positive charge and a negative charge it is called a dipolar reagent.
O O O O The major resonance forms of ozone O
988
Ozone is a 1,3-dipole
1
Six electrons delocalized around the ring

1,3-Dipolar cycloaddition Low temperature
Contains two weak OO bonds HO R O O
H O R H
O O R
R R trans-alkene Contains one weak OO bond R O H 1,3-Dipolar O O

cycloaddition
cyclic transition state
R H molozonide (Unstable)
Reverse 1,3-dipolar cycloaddition
H
+ O
O O H R
The aldehyde flips over
O H R +
O O R H A carbonyl oxide (a 1,3-dipole)
H R ozonide (More stable than the molozonide)
aldehyde
Figure 21.29 Reaction of an alkene with ozone to form an ozonide.

Other 1,3-dipoles that react with C=C bonds include nitrones and nitrile oxides.
R N
1
O
3
R
1
O
3
a nitrone
a nitrile oxide
Addition of nucleophiles to C=O bonds is discussed in Chapters 23 and 24.
R H O R O O H H
R O O R O H
Diastereomers of an ozonide.
O3 reacts with a C=C bond (usually at low temperature) in a concerted cycloaddition reaction to form a molozonide (primary ozonide) as shown in Figure 21.29. The C=C bond donates two electrons to the positively charged oxygen atom in O3 to form a CO bond. As this happens, one of the partially negatively charged oxygen atoms in O3 donates two electrons to one of carbon atoms of the C=C bond to form a second CO bond. In O3, the two oxygen atoms that react to form the CO bonds have a 1,3-relationship. Because of this, O3 is called a 1,3-dipole and the reaction of O3 with a C=C bond is called a 1,3-dipolar cycloaddition. The molozonide is unstable because it contains two weak OO bonds (an OO bond has a bond enthalpy of around +150 kJ mol1) and it immediately undergoes a reaction that is the reverse of a 1,3-dipolar cycloaddition. The electrons move in the molozonide to break an OO and a CC bond to produce a C=O bond and a carbonyl oxide, which is a 1,3-dipole. Finally, the carbonyl oxide reacts with the C=O bond in a second 1,3-dipolar cycloaddition to form an ozonide. This requires the aldehyde to ip over so that the negatively charged oxygen atom in the 1,3-dipole can attack the partially positive carbon atom in the C=O bond. Note that the ozonide is formed as a mixture of diastereomers because the 5-membered ring is formed with the R groups on the same or the opposite sides of the ring. Although ozonides are more stable than molozonides, ozonides are extremely reactive (they can explode) and are not usually isolated from reactions. Instead, the ozonide is converted into more stable carbonyl compounds by reaction with a reducing or oxidizing agent as shown in Figure 21.30. Reaction of an ozonide with a reducing agent produces aldehydes and/or ketones. Reaction with an oxidizing agent produces carboxylic acids and/or ketones. Transformation of a C=C bond into two carbonyl compounds by reaction with O3, followed by an oxidizing or reducing agent, is called ozonolysis.
Ozonizers are used in industry and in households to make ozone. Ozone is used to purify water or air, as it rapidly oxidizes and destroys any bacteria and viruses that are present. The picture shows an ozonizer used for purifying water supplies.
21.5
ELECTROPHILIC ADDITION REACTIONS OF ALKYNES
989
R O H R O OH
R H O O O
Reducing conditions Me2S, Zn, or PPh3
R O H R O HO
aldehydes +
H R Ozonide produced from RCH=CHR
Oxidizing conditions H2O2
carboxylic acids
R R O O O
Reducing conditions Me2S, Zn, or PPh3
R O R ketone
R O H aldehyde
H R Ozonide produced from R2C=CHR
Oxidizing conditions H2O2
R O R ketone
R O OH carboxylic acid
Figure 21.30 Reactions of ozonides.
Summary
Important pericyclic reactions involving alkenes.
KMnO4, HO/H2O low temperature or OsO4/H2O
H OH R H OH R
1,2-dihydroxylation via a manganate ester or an osmate ester Stereospecific addition (overall syn addition) R O
KMnO4, HO/H2O high temperature or O3, low temperature then H2O2 (oxidizing agent)
O R OH + HO Oxidative cleavage to form carboxylic acids
O R R
OsO4, HIO4 or O3, low temperature then Me2S (reducing agent)
H O
Oxidative cleavage to form aldehydes
21.5 Electrophilic addition reactions of alkynes

Alkynes undergo similar electrophilic addition reactions to those of alkenes. The electronrich CC bond acts as a nucleophile in these reactions. When comparing the relative reactivity of CC and C=C bonds, the relative nucleophilicity of the bonds needs to be considered as does the stability of any intermediates, such as carbocations.
HCCH and RCCH react with strong bases to form alkynyl ions (Section 19.2, p.888). Alkynylsodium salts are strong nucleophiles that react with various electrophiles (Section 23.2, p.1061).
Addition of hydrogen halides

Alkynes react with HX (where X = Cl, Br, or I) in a two-step reaction (Figure 21.31) to produce halogenoalkenes (vinyl halides). The mechanism of addition of HX to a CC bond is analogous to the addition of HX to a C=C bond (p.965).
Organosodium compounds are R normally ionic R
C Na
E + Na
990
Regioselective addition of H+ to form the most stable carbocation H R +

+
Step 1 Slow
H H R X
H
Step 2 Fast
X = Cl, Br, I
Intermediate vinyl cation
R A halogenoalkene
Figure 21.31 Alkynes react with HX (where X = Cl, Br, or I) to produce halogenoalkenes.
A secondary vinyl cation H H R More stable because of the +I effect of R
A primary vinyl cation H H R
A secondary alkyl cation H R H C H
A secondary vinyl cation H H C
R The sp2 carbon is more electronwithdrawing than the sp3 carbon, so the H2C= group cannot stabilize the cation so well as the H3C group
HX adds selectively to unsymmetrical alkynes to form the more substituted halogenoalkene as predicted by Markovnikovs rule. This is because addition of H+ to the CC bond selectively forms the more stable vinyl cation. In Figure 21.31, a secondary vinyl carbocation is selectively formed because this cation is more stable than a primary vinyl carbocation (see margin). Because a CC bond is more electron-rich than a C=C bond, you might expect the CC bond to react faster with HX. However, addition of HX to a CC bond is slower than addition to a C=C bond. The reason for this is the different stabilities of vinyl and alkyl cations. Addition of H+ to a CC bond forms a vinyl cation, whereas addition of H+ to a C=C bond forms an alkyl cation (for example, RCH+CH3). A vinyl cation is less stable than a similarly substituted alkyl cation, because of the electronic effects of an alkylidene group (for example, =CH2) versus an alkyl substituent (for example, CH3). The greater the s character of a hybrid orbital on carbon, the closer the electrons are held to the positively charged nucleus, and the more electron-withdrawing it is. So, the sp2 carbon (33% s character) of the alkylidene group is more electron-withdrawing than an sp3 carbon of an alkyl substituent (25% s character), and it cannot stabilize the adjacent positive charge as well as an alkyl group. Because the vinyl cation is less stable than a similarly substituted alkyl cation, the Gibbs energy of activation for its formation will be higher and it will be formed more slowly. Addition of HX to a CC bond can often be stopped after addition of one equivalent of HX. If two equivalents of HX react with a CC bond, a second molecule of HX adds to the halogenoalkene to form a geminal dihalogenoalkane (geminal indicates that both halogen atoms are on the same carbon atom).
One equivalent of HBr
Br
A second equivalent of HBr
Br
Br
pent-1-yne A terminal alkyne
2-bromopent-1-ene A halogenoalkene
2,2-dibromopentane A geminal dihalogenoalkane
Addition of borane followed by oxidation

Aldehydes or ketones are formed from alkynes by reaction of the CC bond with diborane (B2H6) followed by oxidation using a solution of hydrogen peroxide and aqueous sodium hydroxide. A terminal alkyne (RCCH) reacts to form an aldehyde, while an internal alkyne (RCCR) reacts to form a ketone. The aldehyde or ketone is formed by overall addition of H2O to the CC bond so this is an example of a hydration reaction as illustrated in Figure 21.32. The mechanism for this transformation involves four stages and is very similar to the reaction of an alkene with B2H6 (which reacts as BH3) then H2O2/HO (p.977). Notice that stage 3 produces an enol that rearranges to form an aldehydean H atom moves from oxygen to carbon and
Enols have an OH group attached to a C=C bond; see Section 9.6 (p.431). Tautomerism is discussed in Section 23.3 (p.1074).
21.5
ELECTROPHILIC ADDITION REACTIONS OF ALKYNES
991
the position of the double bond changes. The equilibrium between an aldehyde (or ketone) and an enol is called tautomerism.
H R terminal alkyne
BH3
Stage 1
H BH2
2R
Stage 2
H B 3
H2O2, HO
Stage 3
3R enol
OH
Stage 4
3R
vinylborane Syn addition of H and BH2 Two further hydroborations
trivinylborane HO replaces B
aldehyde Tautomerism
Figure 21.32 Hydroboration of a terminal alkyne followed by oxidation produces an aldehyde.
Worked example 21.5 Synthesis of a pheromone

Pheromones are volatile chemicals that are emitted by an individual and trigger a response in an individual of the same species. For example, the female pea moth (Cydia nigricana) attracts males for mating by producing a sex pheromone that contains (E )-dodec-10-enyl ethanoate. Farmers use this compound as a lure to trap pea moths and prevent destruction of valuable pea crops. An outline of a synthesis of (E)-dodec-10-enyl ethanoate is shown below. The synthesis uses a tetrahydropyranyl (THP) group, which is a protecting group for alcohols. A protecting group converts a reactive functional group into an unreactive form such that, after the desired transformation(s), the original functional group can be regenerated.
Br
1
O O THP protecting group
HC CNa
O
2
Pea moths attack peas, sweet peas, and vetch in the UK. The moths lay eggs on pea flowers and the resulting caterpillars tunnel into the pod and feed on the peas.
O
3
O O (E)-dodec-10-enyl ethanoate
4
(a) Provide a mechanism to explain how compound 1 is converted into alkyne 2. (b) Suggest reagents for converting alkyne 2 into aldehyde 3.
992
Strategy (a) Consider the type of reaction involved and identify the nucleophile and electrophile. (b) Look at the structures of the reactant and product to determine what reaction is required. Consider how a CCH bond can be regioselectively hydrated to form an aldehyde. Solution (a) This is a nucleophilic substitution reaction. The partially positive carbon adjacent to the
Br atom in compound 1 is the electrophile and NaCCH is the nucleophile.
Br
SN2 reaction
Na
CH
2
+ NaBr
(b) Addition of B2H6 (which acts as BH3) followed by H2O2/HO. Question

Suggest reagents for converting alkyne 2 into compound 4.
O
4
Summary
Two important electrophilic addition reactions of alkynes:
H
HX
R X H H
X = Cl, Br, I
Via an intermediate vinyl carbocation H Regioselective addition (favours Markovnikov product) Slower than addition of HX to a C=C bond
BH3 then H2O2, HO
R H
O Hydration via an intermediate enol Regioselective addition to give an aldehyde
HCCH and RCCH react with strong bases to form alkynylmetal reagents (for example, HCCNa), which can act as nucleophiles.
CONCEPT REVIEW
993
Concept review
By the end of this chapter you should be able to do the following.
l
Describe how alkenes are prepared from halogenoalkanes, alcohols, alkynes, and aldehydes/ketones. Describe how alkynes are prepared from 1,2-dibromoalkanes and how substituted alkynes are prepared by alkylation of alkynyl anions (RCC) with halogenoalkanes. Understand how C=C and CC bonds react in electrophilic addition reactions. Write reaction mechanisms to explain how C=C bonds undergo the addition reactions shown below.
l l
Terminal alkene OH R H
H+, H2O
Disubstituted alkene Br H R
Br2
R H Br OH
X R H
HX X = Cl, Br, I HBr
H R
Peroxide, heat
Br R
Br2, H2O
H R Br
R H
BH3, then H2O2, HO
RCO3H then H2O and H+ or HO
OH H R R H OH
H R OH
Write reaction mechanisms to explain how C=C bonds undergo the pericyclic reactions shown below.
O R H + H O
OsO4, HIO4 or O3, Me2S (reducing conditions)
O R + HO O R OH
H OH R H OH R
KMnO4, low temperature or OsO4/H2O
KMnO4, high temperature or O3, H2O2 (oxidizing conditions)
994
Write reaction mechanisms to explain how CC bonds undergo the addition reactions shown below. H R X
HX
H H H
X = Cl, Br, I
BH3 then H2O2, HO
R H
Questions
1
Suggest mechanisms for the following electrophilic addition reactions. Cl
(a)
HCl
(b)
HBr
Br
(c)
HBr ROOR, UV radiation
Br
(d)
2
Br2, MeOH
OMe Br
Suggest reagents (ah) for the following transformations. More than one step may be required for each transformation. (The relative stereochemistry of the products is shown, not the absolute stereochemistry.) Me OH HO Me H a Me OH O CHO b OH Me Br d H Me H OH Me OH H OH e O CO2H f h Me O H
EXERCISES
995
An outline of a racemic synthesis of -multistriatin, a pheromone of the elm bark beetle, is shown below.
O HO HO 1 H O O 2 O O O 3 (The relative stereochemistry is shown) O O -multistriatin (A 1:1 mixture of enantiomers)
(a) Suggest reagents for a one-step synthesis of 1 from but-2-yne-1,4-diol. (b) Give the IUPAC name of compound 1. (c) Suggest a reagent for a one-step synthesis of 3 from 2. (d) Suggest a structure of the product formed from the reaction of 3 with HO/H2O. (e) Name the functional group(s) present in compounds 2, 3, and -multistriatin. 4
Draw the product from reaction of prop-1-yne (HCCCH3) with each of the following reagents:
The European elm bark beetle (Scolytus multistriatus) carries Dutch elm disease fungus from tree to tree. The female beetle burrows into the bark creating long narrow chambers.
(a) HBr (2 equivalents); (b) NaNH2 then PhCH2Br followed by Na/NH3; (c) NaNH2 then EtI followed by H2/Pd/C. 5
Linalool (C10H18O) is found in lavender flowers and is one of the constituents of lavender oil. It has a single chiral centre and both R and S enantiomers (see p.480) are found in lavender oil. To determine the structure of linalool, the following reactions were carried out.
C10H22O
H2, Pd/C Reaction 1
linalool (C10H18O)
1. Disiamylborane then H2O2, HO 2. O3, Me2S Reaction 3
HO OH
CHO
Reaction 2
O3 then H2O2
HO2C OH
CO2H
O HCO2H B H disiamylborane
(a) Use the information in reaction 1 to determine the number of C=C bonds in
linalool.
(b) From the products in reaction 2, what are the two possible structures of linalool? (c) Use the information in reaction 3 to determine the structure of linalool.
(Hint. Disiamylborane reacts with a C=C bond in a hydroboration reaction.)
(d) Explain why the reaction of disiamylborane with linalool is chemoselective.

(Hint. Consider the size of disiamylborane.)
Lavender oil from the lavender plant is widely used in perfumery.

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The citric acid cycle

Acetyl-CoA From the breakdown of glucose

CO2H (S)-malic acid Fumarase Addition of H2O to the C=C bond

CO2H fumaric acid

The citric acid cycle.

Alkenes and alkynes: electrophilic addition and pericyclic reactions

This chapter builds on the following topics.

Hydrocarbons Section 9.5, p.415 Conformational isomers Section 10.2, p.453

Aconitase Addition of H2O

Succinyl dehydrogenase Oxidation to form an alkene

CO2H succinic acid

Succinyl-CoA synthetase Thioester hydrolysis

CO2 HO2C COSCoA succinyl-CoA

CHAPTER 21 ALKENES AND ALKYNES: ELECTROPHILIC ADDITION AND PERICYCLIC REACTIONS

21.1 Structure and reactivity of alkenes and alkynes

H C C H ethyne A linear molecule

180 R C C R bonds bonds R C C R R

The two bonds are perpendicular to each other C C R R C C R

21.1 STRUCTURE AND REACTIVITY OF ALKENES AND ALKYNES

Table 21.1 Mean bond lengths and mean bond enthalpies

Mean bond lengths /pm

Mean bond enthalpies /kJ mol1

= Factors affecting the stability and reactivity of C=C bonds

H H (Z)-but-2-ene Less stable

H3C H (E)-but-2-ene More stable

tetrasubstituted Most stable

monosubstituted Least stable

Figure 21.1 Relative stabilities of alkyl-substituted alkenes.

CHAPTER 21 ALKENES AND ALKYNES: ELECTROPHILIC ADDITION AND PERICYCLIC REACTIONS

Side-on orbital overlap H C C H H C=C * orbital C H H CH orbital

Delocalization of the electrons in the CH bond stabilizes the alkene H H

Figure 21.2 Hyperconjugation.

Figure 21.3 Electrophilic addition to alkenes and alkynes.

CH3 H3C 2,3-dimethylbut-2-ene Stronger nucleophile

21.1 STRUCTURE AND REACTIVITY OF ALKENES AND ALKYNES

Box 21.1 Ethene production in plants

NH2 Me HO2C NH2 HO OH S-adenosylmethionine (SAM) Me S O N N N NH2 N S O N N N N

HO2C H2N ACC

ACC oxidase O2, vitamin C

H2C CH2 ethene

CHAPTER 21 ALKENES AND ALKYNES: ELECTROPHILIC ADDITION AND PERICYCLIC REACTIONS

C=C and CC bonds react with electrophiles in electrophilic addition reactions.

21.2 Preparation of alkenes and alkynes

Liquid with the lowest boiling point

OSO3H OSO3H H2O

Protonation activates the OH group to give a better leaving group (H2O)

The acid is regenerated

Deprotonation of the intermediate secondary carbocation produces the alkene

PREPARATION OF ALKENES AND ALKYNES

H2 is adsorbed onto the catalyst surface R R H H

The CC bond approaches the catalyst surface R H H R

Surface of the metal catalyst

Surface of the metal catalyst

By partial reduction of alkynes using sodium in liquid ammonia

NH2 R C C R vinyl radical e H + NH2

The R groups point in opposite directions to minimize steric strain

Figure 21.6 Reduction of an alkyne using sodium in liquid ammonia.

CHAPTER 21 ALKENES AND ALKYNES: ELECTROPHILIC ADDITION AND PERICYCLIC REACTIONS

Figure 21.7 A Wittig reaction.

CH and CBr are anti-periplanar R H H Br

CH and CBr are anti-periplanar NH2

Br R 1,2-dibromoalkane (vicinal bromide)

bromoalkene (vinyl bromide)