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Alkenes and Alkynes (2/94)(3-5/96)(6-8/01)(1,2/02)(10/03) Neuman Chapter 8 Chapter 8 Alkenes and Alkynes from Organic Chemistry by Robert C. Neuman, Jr. Professor of Chemistry, emeritus University of California, Riverside [email protected] <http://web.chem.ucsb.edu/~neuman/orgchembyneuman/> Chapter Outline of the Book ************************************************************************************** I. Foundations 1. Organic Molecules and Chemical Bonding 2. Alkanes and Cycloalkanes 3. Haloalkanes, Alcohols, Ethers, and Amines 4. Stereochemistry 5. Organic Spectrometry II. Reactions, Mechanisms, Multiple Bonds 6. Organic Reactions *(Not yet Posted) 7. Reactions of Haloalkanes, Alcohols, and Amines. Nucleophilic Substitution 8. Alkenes and Alkynes 9. Formation of Alkenes and Alkynes. Elimination Reactions 10. Alkenes and Alkynes. Addition Reactions 11. Free Radical Addition and Substitution Reactions III. Conjugation, Electronic Effects, Carbonyl Groups 12. Conjugated and Aromatic Molecules 13. Carbonyl Compounds. Ketones, Aldehydes, and Carboxylic Acids 14. Substituent Effects 15. Carbonyl Compounds. Esters, Amides, and Related Molecules IV. Carbonyl and Pericyclic Reactions and Mechanisms 16. Carbonyl Compounds. Addition and Substitution Reactions 17. Oxidation and Reduction Reactions 18. Reactions of Enolate Ions and Enols 19. Cyclization and Pericyclic Reactions *(Not yet Posted) V. Bioorganic Compounds 20. Carbohydrates 21. Lipids 22. Peptides, Proteins, and α−Amino Acids 23. Nucleic Acids ************************************************************************************** *Note: Chapters marked with an (*) are not yet posted. 0 (2/94)(3-5/96)(6-8/01)(1,2/02)(10/03) Neuman Chapter 8 8: Alkenes and Alkynes Preview 8-3 8.1 Alkenes 8-3 Unbranched Alkenes (8.1A) 8-3 Ethene. Propene. 1-Butene and 2-Butene. Other Alkenes and Cycloalkenes. Alkene Stereoisomers (8.1B) 8-7 (E)-2-Butene and (Z)-2-Butene. Other E and Z Alkenes. E,Z Assignment Rules. E and Z Stereoisomers are Diastereomers. cis and trans Isomers. More than One C=C in a Molecule (8.1C) 8-12 Polyenes. Allenes. Nomenclature of Substituted Alkenes (8.1D) 8-14 Alkyl and Halogen Substituted Alkenes. Alkyl and Halogen Substituted Cycloalkenes. Alkyl and Halogen Substituted Polyenes. Alkenes With OH or NH2 Groups. Common Names of Substituted and Unsubstituted Alkenes. Alkene Stability (8.1E) 8-17 Relative Stability of Isomeric E and Z Alkenes. C=C Substitution and Alkene Stability. Stability of Cycloalkenes. 8.2 Alkynes 8-21 Unbranched Alkynes (8.2A) 8-21 Nomenclature. Alkyne Structure. Alkyne Stability (8.2B) 8-23 C-H and C-C Bond Lengths (8.2C) 8-23 Alkanes, Alkenes, and Alkynes. Acidity of C≡C-H Hydrogens (8.2D) 8-24 Allenes (8.2E) 8-25 Nomenclature. Structure and Bonding. Bond Lengths. 1 (2/94)(3-5/96)(6-8/01)(1,2/02)(10/03) Neuman Chapter 8 8.3 Spectrometric Features of C=C and C≡C Bonds 8-27 13C NMR Spectrometry (8.3A) 8-27 C=C Bonds. C≡C Bonds. Allenes. 1H NMR Spectrometry (8.3B) 8-29 C=C-H 1H δ Values. 1H Spin-Splitting in Alkenes. Alkynes. Infrared Spectrometry (8.3C) 8-32 UV-Vis Spectrometry (8.3D) 8-33 Chapter Review 8-34 2 (2/94)(3-5/96)(6-8/01)(1,2/02)(10/03) Neuman Chapter 8 8: Alkenes and Alkynes •Alkenes •Alkynes •Spectrometric Features of C=C and C≡C Bonds Preview Alkenes are hydrocarbons with C=C bonds and alkynes are hydrocarbons with C≡C bonds. Since C=C bonds have sp2 hybridized C, atoms or groups directly attached to a C=C bond lie in a plane and are separated by approximately 120° bond angles. A molecule cannot freely rotate about its C=C bond. As a result, some alkenes have stereoisomers, in addition to structural isomers, with different relative stabilities. Alkenes can also have other functional groups. Atoms or groups directly bonded to a C≡C bond lie in a straight line since C≡C bonds have sp hybridized C. This makes it difficult to place a C≡C bond in rings of cyclic molecules. The nomenclature of alkynes is analogous to that of alkenes. C=C and C≡C bonds impart characteristic features to NMR and IR spectra of their compounds that aid in their structural identification. 8.1 Alkenes Alkenes and cycloalkenes are hydrocarbons with one C=C bond. They are also commonly referred to as olefins. Unbranched Alkenes (8.1A) Unbranched alkenes are analogous to unbranched alkanes. Since the C=C can be located in different positions in unbranched alkenes with four or more C's, they have structural isomers. Ethene. The simplest alkene ethene (H2C=CH2) is planar with H-C-H and H-C-C bond angles that are close to 120°. Figure 8.2 3 (2/94)(3-5/96)(6-8/01)(1,2/02)(10/03) Neuman Chapter 8 These 120° bond angles and the planar geometry are consistent with sp2 hybridization for each of ethene's C atoms (Chapter 1). Each C uses its three sp2 atomic orbitals to form the two C-H bonds and one of the C-C bonds as we illustrate here. Figure 8.49 4 (2/94)(3-5/96)(6-8/01)(1,2/02)(10/03) Neuman Chapter 8 Figure 8.50 In addition to the σ(sp2-sp2) C-C bond just shown, the other C-C bond in C=C is π(2p-2p) that results from sideways overlap of the 2p orbitals on each sp2 C. 5 (2/94)(3-5/96)(6-8/01)(1,2/02)(10/03) Neuman Chapter 8 Propene. We show propene (CH3CH=CH2), the next higher mass alkene, in two different views. Figure 8.5 The CH3 group causes bond angles to deviate slightly from the bond angles in ethene because of its larger steric size compared to H. While the C=C bond and its directly attached atoms lie in a plane, CH3 has a normal tetrahedral geometry. Figure 8.6 Rotation about C-C single bonds is usually a low energy process (Chapter 2), so propene has different conformations due to rotation about the H3C-CH bond. The most stable one is (A) where the Ca-H bond is staggered between two C-H bonds of CH3. Conformation (B), where the C=C bond is staggered between C-H bonds of CH3, has a higher energy than (A) so it is less stable than (A). 6 (2/94)(3-5/96)(6-8/01)(1,2/02)(10/03) Neuman Chapter 8 1-Butene and 2-Butene. The next higher molecular mass alkenes after ethene and propene are the two different C4 structural isomers 1-butene and 2-butene. Figure 8.7 The number prefix in each of these names (1- or 2-) corresponds to the lower C number of the two C's of each C=C bond. Alkenes are numbered so that the C=C bond is in the longest continuous carbon chain and has the lowest possible C number. Other Alkenes and Cycloalkenes. We name other unbranched alkenes in the same way we just named 1-butene and 2-butene. We always indicate the position of the double bond in acyclic alkenes using a number that precedes the name of the parent alkene, but unbranched cycloalkenes (Figure 8.7a) do not require these number designations since one C of the C=C is always C1. Figure 8.7a We give nomenclature of branched and substituted alkenes and cycloalkenes later in this chapter. Alkene Stereoisomers (8.1B) Some unbranched alkenes can exist as two different stereoisomers. An example is 2-butene (CH3CH=CHCH3). (E)-2-Butene and (Z)-2-Butene. Atoms directly attached to a C=C bond must lie in a plane, so the terminal CH3 groups (C1 and C4) of 2-butene can be on the same or opposite sides of the C=C bond (Figure 8.8). Figure 8.8 7 (2/94)(3-5/96)(6-8/01)(1,2/02)(10/03) Neuman Chapter 8 These two stereoisomers of 2-butene do not interconvert at normal temperatures so they are different molecules with different properties and names. Interconversion requires C=C rotation that breaks the π(2p-2p) bond and this process requires a large energy input (about 270 kJ/mol). Figure 8.8a The two CH3 groups of (Z)-2-butene are on the same side of the C=C, while its stereoisomer with two CH3 groups on opposite sides of the C=C is (E)-2-butene (Figure 8.8). E is the first letter of the German word "entgegen" that means "opposite", while Z is the first letter of the German word "zusammen" that means "together". Other E and Z Alkenes. Alkenes have E and Z stereoisomers whenever the two atoms and/or groups on each C of the C=C are different from each other. This is the case for (E) and (Z)-2-butene (Figure 8.9). Figure 8.9 8 (2/94)(3-5/96)(6-8/01)(1,2/02)(10/03) Neuman Chapter 8 The two groups on Ca (CH3 and H) are different from each other, and so are the two groups (CH3 and H) on Cb. It does not matter that both Ca and Cb have identical pairs of groups (CH3 and H) because we separately consider Ca and Cb. We show other examples of alkenes with E and Z stereoisomers in Figure 8.10. Figure 8.10 We will name these alkenes after we learn the E/Z assignment rules in the next section. E,Z Assignment Rules. The rules for assigning the E and Z designations are based on those that we used in Chapter 4 to assign the R and S designations to carbon stereocenters.
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