chapter 08 Structure and Synthesis of Alkenes.pptVIP

E2: Diastereomers Stereospecific reaction: (S, R) produces only trans product, (R, R) produces only cis. ? H Ph CH3 Br Ph H H Ph CH3 Ph H Br CH3 Ph Ph H E2: Cyclohexanes Leaving groups must be trans diaxial. E2: Vicinal Dibromides Remove Br2 from adjacent carbons. Bromines must be anti-coplanar (E2). Use NaI in acetone, or Zn in acetic acid. Br CH3 H Br CH3 H Removing HX via E1 Secondary or tertiary halides Formation of carbocation intermediate Weak nucleophile Usually have substitution products too  Dehydration of Alcohols Reversible reaction Use concentrated sulfuric or phosphoric acid, remove low-boiling alkene as it forms. Protonation of OH converts it to a good leaving group, HOH Carbocation intermediate, like E1 Protic solvent removes adjacent H+  Dehydration Mechanism Industrial Methods Catalytic cracking of petroleum Long-chain alkane is heated with a catalyst to produce an alkene and shorter alkane. Complex mixtures are produced. Dehydrogenation of alkanes Hydrogen (H2) is removed with heat, catalyst. Reaction is endothermic, but entropy-favored. Neither method is suitable for lab synthesis End of Chapter 7 * * Chapter 7 Chapter 8Structure and Synthesis of Alkenes Organic Chemistry, 6th EditionL. G. Wade, Jr. Yunfeng Chen School of Chemical Engineering Pharmacy chyfch@ Functional Group Pi bond is the functional group. More reactive than sigma bond. Bond dissociation energies: C=C BDE 146 kcal/mol C-C BDE -83 kcal/mol Pi bond 63 kcal/mol  Orbital Description Sigma bonds around C are sp2 hybridized. Angles are approximately 120 degrees. No nonbonding electrons. Molecule is planar around the double bond. Pi bond is formed by the sideways overlap of parallel p orbitals perpendicular to the plane of the molecule.  Bond Lengths and Angles Hybrid orbitals have more s character. Pi overlap brings carbon atoms closer. Bond angle with pi orbitals increases. Angle C=C-H is 121.7? Angle H-C-H is 116. 6? Pi Bond Sideways overlap of parallel p orbi