2 Alkene Hybridization • Recall that the double bond consists of a bond and a bond. • Each carbon is sp2 hybridized and trigonal planar, with bond angles of approximately 120°.
3 Bond Dissociation Energy • Bond dissociation energies of the C-C bonds in ethane (a bond only) and ethylene (one and one bond) can be used to estimate the strength of the component of the double bond. • The bond is much weaker than the bond of a C-C double bond, making it much more easily broken. • Therefore, alkenes undergo many reactions that alkanes do not.
4 Cyclic Alkenes • Cycloalkenes having fewer than eight carbon atoms have a cis geometry. • A trans-cycloalkene must have a carbon chain long enough to connect the ends of the double bond without introducing too much strain. • trans-Cyclooctene is the smallest, isolable trans cycloalkene, but it is considerably less stable than cis-cyclooctene, making it one of the few alkenes having a higher energy trans isomer.
5 6 Calculating Degrees of Unsaturation • An acyclic alkene has the general structural formula CnH2n. • Alkenes are unsaturated hydrocarbons because they have fewer than the maximum number of hydrogen atoms per carbon. • Cycloalkanes also have the general formula CnH2n. • Each bond or ring removes two hydrogen atoms from a molecule, and this introduces one degree of unsaturation. • The number of degrees of unsaturation for a given molecular formula can be calculated by comparing the actual number of H atoms in a compound to the maximum number of H atoms possible for the number of carbons present if the molecule were an acyclic alkane. • This procedure gives the total number of rings and/or bonds in a molecule.
7 Degrees of Unsaturation for Molecules Containing Heteroatoms • Ignore O atoms in the molecule (this divalent atom is a linker and has no effect on degree of unsaturation).
• Add number of halogens to number of H's (they are equivalent
to H).
• Subtract 1 H for each N present (N’s two connections allows
extra H).
• E.g., C6H10OCl3N is equivalent to C6H12.
8 9 Naming Alkenes and Alkenols Figure 10.1
• Compounds that contain both a double bond and a hydroxy group
are named as alkenols and the chain (or ring) is numbered to give the OH group the lower number.
10 Naming Polyenes and Cyclic Alkenes • Compounds with two double bonds are named as dienes by changing the “-ane” ending of the parent alkane to the suffix “-adiene”. • Compounds with three double bonds are named as trienes, and so forth. • In naming cycloalkenes, the double bond is located between C1 and C2, and the “1” is usually omitted in the name. • The ring is numbered clockwise or counterclockwise to give the first substituent the lower number. Figure 10.2
11 12 Common Names of Alkenes and Alkene Substituents • Some alkene or alkenyl substituents have common names. • The simplest alkene, CH2=CH2, named in the IUPAC system as ethene, is often called ethylene.
Figure 10.3
13 Physical Properties of Alkenes • Most alkenes exhibit only weak van der Waals interactions, so their physical properties are similar to alkanes of comparable molecular weight. • Alkenes have low melting points and boiling points. • Melting and boiling points increase as the number of carbons increases because of increased surface area. • Alkenes are soluble in organic solvents and insoluble in water. • The C-C single bond between an alkyl group and one of the double bond carbons of an alkene is slightly polar because the sp3 hybridized alkyl carbon donates electron density to the sp2 hybridized alkenyl carbon.
14 Cis/Trans Differ in Physical Properties • A consequence of the alkene dipole is that cis and trans isomeric alkenes often have somewhat different physical properties. • cis-2-Butene has a higher boiling point (4 °C) than trans-2-butene (1 °C). • In the cis isomer, the two Csp3Csp2 bond dipoles reinforce each other, yielding a small net molecular dipole. • In the trans isomer, the two bond dipoles cancel.
15 Useful Products Formed From Ethylene Figure 10.4
16 Naturally Occurring Alkenes Figure 10.5
17 Fatty Acids • Triacylglycerols are hydrolyzed to glycerol and three fatty acids of general structure RCOOH.
• Saturated fatty acids have no double bonds in their long
hydrocarbon chains, and unsaturated fatty acids have one or more double bonds in their hydrocarbon chains. • As the number of double bonds in the fatty acid increases, the melting point decreases. 18 • Increasing the number of double bonds in the fatty acid side chains decreases the melting point of the 19 triacylglycerol. 3-D Structure of C18 Fatty Acids • The larger the number of Z double bonds, the more kinks in the hydrocarbon chain. • This causes poorer stacking and less van der Waals interactions, leading to lower melting points. Figure 10.6
20 Triacylglycerols
• Fats and oils are both triacylglycerols, but with different
physical properties. • Fats have higher melting points—they are solids at room temperature. • Oils have lower melting points—they are liquids at room temperature. • The composition (saturated vs. unsaturated) of the three fatty acids in the triacylglycerol determines whether it is a fat or an oil.
21 Properties of Fatty Acids
• Fats are derived from fatty acids having few or no double
bonds. • Oils are derived from fatty acids having a larger number of double bonds. • Saturated fats are typically obtained from animal sources, whereas unsaturated oils are common in vegetable sources. • An exception to this generalization is coconut oil, which is largely composed of saturated alkyl side chains.
22 Preparation of Alkenes • Alkenes can be prepared from alkyl halides, tosylates, and alcohols via elimination reactions.
23 Regioselectivity and Stereoselectivity of Alkene Formation • The most stable alkene (Zaitsev product) is usually formed as the major product.
24 Addition Reactions • The characteristic reaction of alkenes is addition—the bond is broken and two new bonds are formed.
• Alkenes are electron rich, with the electron density of the
bond concentrated above and below the plane of the molecule. • Therefore, alkenes act as nucleophiles and react with electrophiles. • Simple alkenes do not react with nucleophiles or bases, reagents that are themselves electron rich. 25 Syn and Anti Addition to Alkenes • Because the carbon atoms of a double bond are both trigonal planar, the elements of X and Y can be added to them from the same side or from opposite sides. • Syn addition takes place when both X and Y are added from the same side. • Anti addition takes place when X and Y are added from opposite sides.
26 Addition Reactions of Cyclohexene Figure 10.8
27 Hydrohalogenation—Electrophilic Addition of HX
• Two bonds are broken in this reaction—the weak bond of the
alkene and the HX bond—and two new bonds are formed— one to H and one to X. • Recall that the H-X bond is polarized, with a partial positive charge on H. • Because the electrophilic H end of HX is attracted to the electron-rich double bond, these reactions are called electrophilic additions. 28 How to Draw the Products of an Addition Reaction • Locate the C-C double bond. • Identify the bond of the reagent that breaks. • Break the bond of the alkene and the bond of the reagent, and form two new bonds to the C atoms of the double bond.
29 Heat of Formation for Electrophilic Addition • Addition reactions are exothermic because the two bonds formed in the product are stronger than the and bonds broken in the reactants. • For example, H° for the addition of HBr to ethylene is –14 kcal/mol.
Figure 10.9
30 Mechanism of Electrophilic Addition • The mechanism of electrophilic addition consists of two successive Lewis acid-base reactions. • Step [1] – the alkene is the Lewis base that donates an electron pair to H-Br, the Lewis acid. • Step [2] – Br¯ is the Lewis base that donates an electron pair to the carbocation, the Lewis acid.
31 Energy Diagram for Electrophilic Addition • Each step has its own energy barrier with a transition state energy maximum. • Since step [1] has a higher energy transition state, it is rate- determining. H° for step [1] is positive because more bonds are broken than formed, whereas H° for step [2] is negative because only bond making occurs. Figure 10.10
32 Markovnikov’s Rule • With an unsymmetrical alkene, HX can add to the double bond to give two constitutional isomers, but only one is actually formed:
• Markovnikov’s rule states that in the addition of HX to an
unsymmetrical alkene, the H atom adds to the less substituted carbon atom—that is, the carbon that has the greater number of H atoms to begin with.
33 Carbocation Stability and Markovnikov’s Rule • The basis of Markovnikov’s rule is the formation of a carbocation in the rate-determining step of the mechanism. • In the addition of HX to an unsymmetrical alkene, the H atom is added to the less substituted carbon to form the more stable, more substituted carbocation.
34 Hammond Postulate and Electrophilic Addition • According to the Hammond postulate, Path [2] is faster because formation of the carbocation is an endothermic process. • Thus, the transition state to form the more stable 2° carbocation is lower in energy. • The Ea for formation of the more stable 2° carbocation is lower than the Ea for formation of the 1° carbocation; the 2° carbocation is formed faster. Figure 10.11
35 Stereochemistry of Electrophilic Addition • Recall that trigonal planar atoms react with reagents from two directions with equal probability. • Achiral starting materials yield achiral products. • Sometimes new stereogenic centers are formed from hydrohalogenation.
36 Stereochemistry of Carbocation Formation • The mechanism of hydrohalogenation illustrates why two enantiomers are formed. • Initial addition of H+ occurs from either side of the planar double bond. • Both modes of addition generate the same achiral carbocation. • Either representation of this carbocation can be used to draw the second step of the mechanism.
37 Stereochemistry of Nucleophilic Attack • Nucleophilic attack of Cl¯ on the trigonal planar carbocation also occurs from two different directions, forming two products, A and B, having a new stereogenic center. • A and B are enantiomers. • Since attack from either direction occurs with equal probability, a racemic mixture of A and B is formed.
38 Reaction of 1,2-dimethylcyclohexene with HCl • Addition of HX to 1,2-dimethylcyclohexene forms two new stereogenic centers. • Four stereoisomers are formed: • Compounds A and D are enantiomers. • Compounds B and C are enantiomers. Figure 10.12
