Introduction To Organic Chemistry Chapter 5 PDF

INTRODUCTION TO ORGANIC CHEMISTRY Sixth Edition William H. Brown Thomas Poon Chapter 5 Reactions of Alkenes and Alkynes This slide deck contains animations. Please disable animation...

INTRODUCTION TO ORGANIC CHEMISTRY Sixth Edition William H. Brown Thomas Poon Chapter 5 Reactions of Alkenes and Alkynes This slide deck contains animations. Please disable animations if they cause issues with your device. Copyright ©2021 John Wiley & Sons, Inc. Reactions of Alkenes Copyright ©2021 John Wiley & Sons, 2 Inc. Energy Diagram Energy diagram: A graph of the energy changes that occur during a chemical reaction; energy is plotted on the y-axis. Reaction progress on the x-axis. Figure 5.1 An energy diagram for a one-step exothermic reaction of C and A-B to give C-A and B. Copyright ©2021 John Wiley & Sons, 3 Inc. Energy Diagram (Cont’d 1) Transition state: An unstable species of maximum energy formed during the course of a reaction; a maximum on an energy diagram. Activation energy Ea: The difference in energy between the reactants and the transition state. o Ea determines the rate of reaction. o If the Ea is large, very few molecular collisions occur with sufficient energy to reach the transition state, and the reaction is slow. o If the Ea is small, many collisions generate sufficient energy to reach Copyright ©2021 John Wiley the & Sons, transition state, 4 Inc. Energy Diagram (Cont’d 2) Also shown on an energy diagram are: o Heat of reaction H: The difference in energy between reactants and products. o Exothermic reaction: A reaction in which the energy of the products is lower than the energy of the reactants; a reaction in which heat is liberated. o Endothermic: A reaction in which the energy of the products is higher than the energy of the reactants: a reaction in which heat is absorbed. Copyright ©2021 John Wiley & Sons, 5 Inc. Energy Diagram (Cont’d 3) Figure 5.2 Energy diagram for a two-step exothermic reaction involving formation of a reaction intermediate. Copyright ©2021 John Wiley & Sons, 6 Inc. Energy Diagram (Cont’d 4) o Reaction intermediate: An energy minimum between two transition steps. Intermediates are highly reactive and rarely, if ever, can one be isolated. o Rate-determining step: The step in a reaction sequence that crosses the highest energy barrier; the slowest step in a multistep reaction. Copyright ©2021 John Wiley & Sons, 7 Inc. Mechanism Patterns Before we discuss any particular reactions and their mechanisms, let us first analyze several of the common patterns to be seen in the mechanisms we will encounter. Pattern 1: Add a Proton. In Section 2.2, we saw how curved arrows can be used to show how a proton-transfer reaction takes place. In this example, curved arrows show the redistribution of valence electrons and the formation of a new covalent bond when a proton is transferred from acetic acid to ammonia. Copyright ©2021 John Wiley & Sons, 8 Inc. Mechanism Patterns (Cont’d 1) Pattern 1: Add a proton. In this example, a proton is added across the pi bond of a C—C double bond to form a new C—H bond. Adding a proton is typical of all reactions that are catalyzed by an acid. Copyright ©2021 John Wiley & Sons, 9 Inc. Mechanism Patterns (Cont’d 2) Pattern 1: Add a proton. While it is most accurate to show proton transfer from H3O+ in aqueous solution, we will often simplify the equation to show just the proton H+ and the formation of a new covalent bond. Copyright ©2021 John Wiley & Sons, 10 Inc. Mechanism Patterns (Cont’d 3) Pattern 2: Take a proton away. Reversing Pattern 1 corresponds to taking a proton away. The mechanism for taking a proton away is similar to that for adding a proton, except that we focus our attention on the compound that loses the proton instead of the compound that adds a proton. Copyright ©2021 John Wiley & Sons, 11 Inc. Mechanism Patterns (Cont’d 4) Pattern 3: Reaction of an electrophile and a nucleophile to form a new covalent bond. Electrophile: an electron-poor species that can accept a pair of electrons to form a new covalent bond; a Lewis acid. Nucleophile: an electron-rich species that can donate a pair of electrons to form a new covalent bond; a Lewis base. Copyright ©2021 John Wiley & Sons, 12 Inc. Mechanism Patterns (Cont’d 5) Pattern 4: Rearrangement of a bond. A rearrangement occurs when the electrons of a sigma bond break the bond from one atom and form a new covalent bond to an adjacent atom. Copyright ©2021 John Wiley & Sons, 13 Inc. Mechanism Patterns (Cont’d 6) Pattern 5: Break a bond to form a stable molecule or ion. A carbocation can be formed when a chemical species breaks off from a molecule, taking the electrons from the former single bond with it. The chemical species formed is called the leaving group. The bond breaks because doing so forms one or more stable ions or molecules. Copyright ©2021 John Wiley & Sons, 14 Inc. Electrophilic Additions to Alkenes Addition of hydrogen halides (HCl, HBr, HI) Addition of water (H2O/H2SO4) Hydration Addition of halogens (Cl2, Br2) Halogenation Copyright ©2021 John Wiley & Sons, 15 Inc. Addition of Hydrogen Halides Carried out with the pure reagents or in a polar solvent such as acetic acid. Addition is regioselective. o Regioselective reaction: A reaction in which one direction of bond forming or bond breaking occurs in preference to all other directions. o Markovnikov’s rule: In additions of HX to a double bond, H adds to the carbon with the greater number of hydrogens already bonded to it. Copyright ©2021 John Wiley & Sons, 16 Inc. Regioselectivity Markovnikov’s rule is but one example of regioselectivity. We will see more examples in this and later chapters. Copyright ©2021 John Wiley & Sons, 17 Inc. Markovnikov’s Rule Problem: Complete these reactions by predicting the major product formed in each reaction. Copyright ©2021 John Wiley & Sons, 18 Inc. Addition of HCl to 2-Butene A two-step mechanism o Step 1: Add a proton. Formation of a sec-butyl cation, a 2° carbocation intermediate. o Step 2: Reaction of an electrophile and a nucleophile to form a new covalent bond. Reaction of the sec-butyl cation (an electrophile) with chloride ion (a nucleophile) completes the reaction. Copyright ©2021 John Wiley & Sons, 19 Inc. Addition of HCl to 2-Butene (Cont’d) Figure 5.4 Energy diagram for the two-step exothermic addition of HCl to 2-butene. Copyright ©2021 John Wiley & Sons, 20 Inc. Carbocations Figure 5.3 The structure of the tert-butyl cation. Copyright ©2021 John Wiley & Sons, 21 Inc. Carbocations (Cont’d 1) Carbocation: A species containing a carbon atom that has three bonds to it, six electrons in its valence shell, and bears a positive charge. o Bond angles about the positively charged carbon are approximately 120°. o Carbon uses sp2 hybrid orbitals to form a sigma bond to each attached group. o The unhybridized 2p orbital lies perpendicular to the sigma bond framework and contains no electrons Carbocations are: o Electrophiles: that is, they are electron-loving. o Lewis acids: that is, they are electron-pair acceptors. Copyright ©2021 John Wiley & Sons, 22 Inc. Carbocations (Cont’d 2) o A 3° carbocation is more stable than a 2° carbocation, and requires a lower activation energy for its formation. o A 2° carbocation is, in turn, more stable than a 1° carbocation, and requires a lower activation energy for its formation. o Methyl and 1° carbocations are so unstable that they are never observed in solution. Copyright ©2021 John Wiley & Sons, 23 Inc. Relative Stability of Carbocations Inductive effect: The polarization of the electron density of a covalent bond as a result of the high electronegativity of a nearby atom. o The electronegativity of a carbon atom bearing a positive charge exerts an electron- withdrawing inductive effect that polarizes electrons of adjacent sigma bonds toward it. o Thus, the positive charge of a carbocation is not localized on the trivalent carbon, but rather is delocalized over nearby atoms as well. o The larger the area over which the positive charge is delocalized, the greater the stability of the cation. Copyright ©2021 John Wiley & Sons, 24 Inc. The Inductive Effect Figure 5.5 3˚ Carbocations are more stable and require a lower activation energy for their formation than 2° carbocations. 1° and methyl carbocations are so difficult to form that they are never observed in solution or in any of the reactions we will discuss. Copyright ©2021 John Wiley & Sons, 25 Inc. Copyright ©2021 John Wiley & Son, I 26 nc. Copyright ©2021 John Wiley & Sons, 27 Inc. Markovnikov’s Rule (Cont’d 1) The chemical basis for the regioselectivity embodied in Markovnikov’s rule lies in the relative stabilities of carbocation intermediates. The reason why the proton of H—X adds to the less substituted carbon of the double bond is that this mode of addition leads to the more stable carbocation intermediate. Copyright ©2021 John Wiley & Sons, 28 Inc. Carbocation Rearrangements As we have seen, the product of electrophilic addition to an alkene involves rupture of a pi bond and formation of two new sigma bonds in its place. In the following addition only 17% of the expected product is formed. Rearrangement: A reaction in which the connectivity of atoms in the product is different from that in the starting material. Copyright ©2021 John Wiley & Sons, 29 Inc. Carbocation Rearrangements (Cont’d 1) In the rearrangements we examine, typically either an alkyl group or a hydrogen atom migrates with its bonding electrons from an atom to an adjacent electron-deficient atom as illustrated in the following mechanism. The key step in this type of rearrangement is called a 1,2-shift. Copyright ©2021 John Wiley & Sons, 30 Inc. Carbocation Rearrangements (Cont’d 2) a proton. Proton transfer from HCl to Step 1: Add the alkene to give a 2° carbocation intermediate. Step 2: Rearrangement of a bond. Migration of a methyl group with its bonding electrons from the adjacent carbon gives a more stable 3° carbocation. Copyright ©2021 John Wiley & Sons, 31 Inc. Carbocation Rearrangements (Cont’d 3) Step 3: Reaction of a nucleophile and an electrophile to form a new covalent bond. Reaction of the 3° carbocation (an electrophile and a Lewis acid) with chloride ion (a nucleophile and a Lewis base) gives the rearranged product. Copyright ©2021 John Wiley & Sons, 32 Inc. Addition of H2O to an Alkene Addition of H2O to an alkene is called hydration. o Acid-catalyzed hydration of an alkene is regioselective: hydrogen adds preferentially to the less substituted carbon of the double bond. Thus H– OH adds to alkenes in accordance with Markovnikov's rule. Copyright ©2021 John Wiley & Sons, 33 Inc. Addition of H2O to an Alkene (Cont’d 1) Step 1: Add a proton. Proton transfer from the acid catalyst (H3O+) to propene gives a 2° carbocation intermediate. Copyright ©2021 John Wiley & Sons, 34 Inc. Addition of H2O to an Alkene (Cont’d 2) Step 2: Reaction of a nucleophile and an electrophile to form a new covalent bond. Reaction of the carbocation intermediate with water completes the valence shell of carbon and gives an oxonium ion. Copyright ©2021 John Wiley & Sons, 35 Inc. Addition of H2O to an Alkene (Cont’d 3) Step 3: Take a proton away. Proton transfer from the oxonium ion to water gives the alcohol and regenerates the acid catalyst. Copyright ©2021 John Wiley & Sons, 36 Inc. Addition of H2O to an Alkene (Cont’d 4) Problem: Account for the fact that the acid- catalyzed hydration of alkenes can be used to prepare both 2° and 3° alcohols but, with the exception of ethanol, it cannot be used to prepare 1° alcohols. Copyright ©2021 John Wiley & Sons, 37 Inc. Addition of H2O to an Alkene (Cont’d 5) Problem: Draw the structural formula of an alkene that undergoes acid-catalyzed hydration to give each alcohol as the major product. More that one alkene may give each alcohol as the major product. Copyright ©2021 John Wiley & Sons, 38 Inc. Carbocation Rearrangements (Cont’d 4) also occur during the acid- Rearrangements catalyzed hydration of alkenes, especially where the carbocation formed in the first step can rearrange to a more stable carbocation. Copyright ©2021 John Wiley & Sons, 39 Inc. Carbocation Rearrangements (Cont’d Problem: 5) Propose a mechanism for the following transformation. Copyright ©2021 John Wiley & Sons, 40 Inc. Carbocations—Summary The carbon bearing a positive charge is sp2 hybridized with bond angles of 120° about it. The order of carbocation stability is 3°>2°>1°. Carbocations are stabilized by the electron- withdrawing inductive effect of the positively charged carbon. Methyl and 1° carbocations are so unstable that they are never formed in solution. Carbocations may undergo rearrangement by a 1,2-shift, when the rearranged carbocation is more stable than the original carbocation. The most commonly observed pattern of rearrangement is from a 2° to 3° carbocation. Copyright ©2021 John Wiley & Sons, 41 Inc. Carbocations—Summary (Cont’d) Carbocation intermediates undergo three types of reactions: 1. Rearrangement by a 1,2-shift to a more stable carbocation. 2. Addition of nucleophile to form a new covalent bond (e.g., halide ion, H 2O). 3. Loss of a proton to give an alkene (the reverse of the first step in both the addition of HX and the acid-catalyzed hydration of an alkene). Copyright ©2021 John Wiley & Sons, 42 Inc. Addition of Cl2 and Br2 Problem: Treatment of 2-methylpropene with methanol in the presence of an acid catalyst gives tert-butylmethyl ether. At one time this compound was added to gasoline to increase octane rating. Due to environmental concerns, however, it is no longer used for this purpose. Propose a mechanism for this reaction. Copyright ©2021 John Wiley & Sons, 43 Inc. Addition of Cl2 and Br2 (Cont’d 1) Carried out with either the pure reagents or in an inert solvent such as CH2Cl2. Copyright ©2021 John Wiley & Sons, 44 Inc. Addition of Cl2 and Br2 (Cont’d 2) Addition is stereoselective. Stereoselective reaction: A reaction in which one stereoisomer is formed or destroyed in preference to all others that might be formed or destroyed. Addition to a cycloalkene, for example, gives only a trans product. The reaction occurs with anti stereoselectivity. Copyright ©2021 John Wiley & Sons, 45 Inc. Addition of Cl2 and Br2 (Cont’d 3) Step 1: Reaction of a nucleophile and an electrophile to form a new covalent bond. Reaction of the pi bond (a nucleophile) with bromine (an electrophile) gives a bridged bromonium ion intermediate Copyright ©2021 John Wiley & Sons, 46 Inc. Addition of Cl2 and Br2 (Cont’d 4) Step 2: Reaction of a nucleophile, and an electrophile to form a new covalent bond. Attack of bromide ion from the side opposite the bridged bromonium ion opens the three-membered ring. Copyright ©2021 John Wiley & Sons, 47 Inc. Addition of Cl2 and Br2 (Cont’d 5) The addition of chlorine or bromine to cyclohexene and its derivatives gives a trans-diaxial product because only axial positions on adjacent carbon atoms are anti and coplanar. The initial trans- diaxial conformation is in equilibrium with the more stable trans-diequatorial conformation. Copyright ©2021 John Wiley & Sons, 48 Inc. Hydroboration-Oxidation The result of hydroboration followed by oxidation of an alkene is hydration of the carbon-carbon double bond. Because –H adds to the more substituted carbon of the double bond and –OH adds to the less substituted carbon, we refer to the regiochemistry of hydroboration/oxidation as anti-Markovnikov hydration. Copyright ©2021 John Wiley & Sons, 49 Inc. Copyright ©2021 John Wiley & Son, I 50 nc. Reduction of Alkenes Alkenes react with H2 in the presence of a transition metal catalyst to give alkanes. o The most commonly used catalysts are Pd, Pt, and Ni. o The reaction is called catalytic reduction or catalytic hydrogenation. Copyright ©2021 John Wiley & Sons, 51 Inc. Reduction of Alkenes (Cont’d 1) o The most common pattern is syn addition of hydrogens; both hydrogens add to the same face of the double bond. o Catalytic reduction is predominantly syn stereoselective. Copyright ©2021 John Wiley & Sons, 52 Inc. Catalytic Reduction of an Alkene Figure 5.6 Syn addition of H2 to an alkene involving a transition metal catalyst. a) H2 and the alkene are absorbed on the catalyst. b) One H is transferred forming a new C-H bond. c) The second H is transferred. The alkane is released. Copyright ©2021 John Wiley & Sons, 53 Inc. Copyright ©2021 John Wiley & Son, I 54 nc. Copyright ©2021 John Wiley & Sons, 55 Inc. Heats of Hydrogenation Copyright ©2021 John Wiley & Sons, 56 Inc. Heats of Hydrogenation (Cont’d 1) Reduction involves net conversion of a weaker pi bond to a stronger sigma bond. The greater the degree of substitution of a double bond, the lower its heat of hydrogenation. o The greater the degree of substitution, the more stable the double bond. The heat of hydrogenation of a trans alkene is lower than that of an isomeric cis alkene. o A trans alkene is more stable than its isomeric cis alkene. o The difference is ©2021 Copyright dueJohn toWiley nonbonded & Sons, interaction57 Inc. Heats of Hydrogenation (Cont’d 2) o Figure 5.7 Heats of hydrogenation of cis-2- butene and trans-2-butene. o trans-2-butene is more stable than cis-2-butene by 4.2 kJ/mol. Copyright ©2021 John Wiley & Sons, 58 Inc. Reactions of Alkynes (Cont’d 1) As we saw in Chapter 4, one of the major differences between the chemistry of alkanes, alkenes, and alkynes is that terminal alkynes are weak acids. Copyright ©2021 John Wiley & Sons, 59 Inc. Alkylation of Terminal Alkynes Treatment of a 1-alkyne with a very strong base such as sodium amide, NaNH2, converts the alkyne to an acetylide anion. Copyright ©2021 John Wiley & Sons, 60 Inc. Acetylide Anions in Synthesis An acetylide anion is both a strong base and a nucleophile. As a nucleophile, it can donate a pair of electrons to an electrophilic carbon atom and form a new carbon-carbon bond. In this example, the electrophile is the partially positive carbon of chloromethane. As the new carbon-carbon bond is formed, the carbon-halogen bond is broken. Because an alkyl group is added to the original alkyne, this reaction is called alkylation. Copyright ©2021 John Wiley & Sons, 61 Inc. Acetylide Anions in Synthesis (Cont’d 1) of alkylation of acetylide anions is The importance that the two-carbon molecule acetylene can be used to create larger carbon skeletons. For reasons we will discuss fully in Chapter 7, this type of alkylation is successful only for methyl and primary alkyl halides (CH3X and RCH2X). Copyright ©2021 John Wiley & Sons, 62 Inc. Reduction of Alkynes (Cont’d 2) Treatment of an alkyne with H2 in the presence of a transition metal catalyst, most commonly Pd, Pt, or Ni, results in addition of two moles of H2 and conversion of the alkyne to an alkane. Copyright ©2021 John Wiley & Sons, 63 Inc. Reduction of Alkynes (Cont’d 3) By the proper choice of catalyst it is possible to stop the reaction at the addition of one mole of H2. The most commonly used catalyst for this purpose is the Lindlar catalyst, which consists of finely powdered palladium metal deposited on solid calcium carbonate that has been specially modified with lead salts. Reduction (hydrogenation) of alkynes over Lindlar catalyst is syn stereoselective, the two hydrogens are added from the same face of the triple bond to give a cis alkene. Copyright ©2021 John Wiley & Sons, 64 Inc. Reduction of Alkynes (Cont’d 4) Problem: Starting with acetylene and any other necessary reagents, propose a synthesis for each of the following compounds. Any compound made in one part of the problem may be used as a starting material for another part of the problem. (a) 1-Butyne (b) 1-Butene (c) 1-Butanol (d) 2-Butanol (e) 3-Hexyne (f) cis-3-Hexene (g) Hexane (h) 3-Hexanol (i) 3,4-Dibromohexane Copyright ©2021 John Wiley & Sons, 65 Inc. Reactions of Alkenes (Cont’d 2) End Chapter 5 Copyright ©2021 John Wiley & Sons, 66 Inc. Copyright Copyright © 2021 John Wiley & Sons, Inc. All rights reserved. Reproduction or translation of this work beyond that permitted in Section 117 of the 1976 United States Act without the express written permission of the copyright owner is unlawful. Request for further information should be addressed to the Permissions Department, John Wiley & Sons, Inc. The purchaser may make back-up copies for his/her own use only and not for distribution or resale. The Publisher assumes no responsibility for errors, omissions, or damages, caused by the use of these programs or from the use of the information contained herein. Copyright ©2021 John Wiley & Sons, 67 Inc.