6alkynesanddienes.pptVIP

Chapter 6 Alkynes and Dienes Text 1: Chapter 9 , Chapter 15 Text 2: Chapter 4 Contents Alkynes (chapter 9) The structure Nomenclature Reactions Synthesis Dienes (chapter 15) The structure of conjugated dienes Conjugative effect Reactions of dienes 1,2- and 1,4-addition Diels-Alder cycloaddition (simple introduction) II. Dienes C-C bond lengths of 1,3-butadiene Conformations of 1,3-butadiene (1,3-丁二烯构象） rate (kinetic ) control reaction (速率控制或动力学控制） equilibrium (thermodynamic) control reaction (平衡控制或热力学控制） 2) The Diels-Alder reaction (狄尔斯-阿尔德尔反应) In 1928 two German chemists, Otto Diels and Kurt Alder, developed a 1,4-cycloaddition reaction of dienes. They were awarded the Nobel Prize for chemistry in 1950) B. The reaction is a syn addition and the configuration of the dienophile is retained in the product. C. The diene, of necessity, must react in the s-cis conformation rather than the s-trans. D. The Diels-Alder reaction occurs primarily in an endo rather than an exo fashion when the reaction is kinetically controlled Summary for conjugated dienes Assignments Text 1: 9-29, 34, 35, 38 Text 2: p 98-100: 2, 8, 9, 11, 12, 16, 19 3) Oxidation of Alkynes Identification of C-C triple bonds diketone 二酮 Reaction of acetylide anionswith electrophiles SUMMARY OF ALKYNE CHEMISTRY catalyst if terminal Tautomerization Tautomerization SYN addition of H2 -H2/Pd/C, quinoline poison to afford Z alkene ANTI addition of H2 -Na/NH3 to afford E alkene Reaction of internal alkynes: Hydrogenation KMnO4 or O3 5. Preparations of Alkynes 1) Synthesis of alkynes from acetylides R1 = R2 = H, 1°alcohol R1 or R2 = H, 2°alcohol R1 and R2 ≠ H, 3°alcohol 2) Double dehydrohalogenation of alkyl dihalides (二卤代烷脱两分子卤化氢) (9-8, p 382-385) NaNH2 give terminal alkynes; KOH give internal alkynes. For example: Rearrangements of C≡C (p 383 Fig. 2) ? Problem: Synthesis of alkynes from alkenes 2. Problem: Show how you would accomplish the