有机化学课件4Alkynes.ppt

* CHAPTER 4, Alkynes Carbon-carbon triple bond result from sp orbital on each C forming a sigma bond and unhybridized pX and py orbitals forming a π bond The remaining sp orbitals form bonds to other atoms at 180o to C-C triple bond. The bond is shorter and stronger than single or double Breaking a π bond in acetylene (HCCH) requires 318 kJ/mole (in ethylene it is 268 kJ/mole) 4.1 Structure of Alkynes 4.2 Naming Alkynes General hydrocarbon rules apply wuith “-yne” as a suffix indicating an alkyne Numbering of chain with triple bond is set so that the smallest number possible include the triple bond Diyines, Enynes, and Triynes A compound with two triple bonds is a diyine An enyne has a double bond and triple bond A triyne has three triple bonds Number from chain that ends nearest the first multible bond. If there is a choice, double bonds receive lower numbers. Alkynes as substituents are called “alkynyl” 4.3 Reactions of Alkynes: Addition of H2, HX and X2 Addition reactions of alkynes are similar to those of alkenes Intermediate alkene reacts further with excess reagent Regiospecificity according to Markovnikov Addition of H2 to Alkynes: Reduction Addition of H2 over a metal catalyst (such as palladium on carbon, Pd/C) converts alkynes to alkanes (complete reduction) The addition of the first equivalent of H2 produces an alkene, which is more reactive than the alkyne so the alkene is not observed Conversion of Alkynes to cis-Alkenes从炔烃制备顺/反烯烃 Addition of H2 using chemically deactivated palladium on calcium carbonate as a catalyst (the Lindlar catalyst Pd/CaCO3 ) or P-2 Ni produces a cis alkene The two hydrogens add syn (from the same side of the triple bond) Conversion of Alkynes to trans-Alkenes Anhydrous ammonia (NH3) is a liquid below -33oC. Alkali metals dissolve in liquid ammonia and function as reducing agents Alkynes are reduced to trans alkenes with Sodium or lithium in liquid ammonia Addition of HX to Alkynes Involves Viny