columbia大学有机化学课件 （三十六）.pptVIP

9.5Acidity of Acetyleneand Terminal Alkynes Acidity of Hydrocarbons Compound pKa HF 3.2 H2O 16 NH3 36 45 CH4 60 Acetylene Compound pKa HF 3.2 H2O 16 NH3 36 45 CH4 60 Carbon: Hybridization and Electronegativity Sodium Acetylide Sodium Acetylide Sodium Acetylide 9.6Preparation of AlkynesbyAlkylation of Acetylene and Terminal Alkynes Preparation of Alkynes Carbon-carbon bond formation alkylation of acetylene and terminal alkynes Functional-group transformations elimination Alkylation of Acetylene and Terminal Alkynes Alkylation of Acetylene and Terminal Alkynes The alkylating agent is an alkyl halide, andthe reaction is nucleophilic substitution. The nucleophile is sodium acetylide or the sodium salt of a terminal (monosubstituted) alkyne. Example: Alkylation of Acetylene Example: Alkylation of a Terminal Alkyne Example: Dialkylation of Acetylene Limitation Effective only with primary alkyl halides Secondary and tertiary alkyl halides undergo elimination Acetylide Ion as a Base 9.7Preparation of Alkynesby Elimination Reactions Preparation of Alkynesby Double Dehydrohalogenation Geminal dihalide ? Alkyne Geminal dihalide ? Alkyne Vicinal dihalide ? Alkyne 28 29 30 31 32 H C C In general, hydrocarbons are exceedingly weak acids H2C CH2 Acetylene is a weak acid, but not nearlyas weak as alkanes or alkenes. H2C CH2 HC CH 26 C H H+ + H+ + H+ + 10-60 10-45 10-26 sp3 C : sp2 sp H C C C C H C C C C : : Electrons in an orbital with more s character are closer to thenucleus and more strongly held. Objective: Prepare a solution containing sodium acetylideWill treatment of acetylene with NaOH be effective? NaC CH H2O NaOH + HC CH NaC CH + No. Hydroxide is not a strong enough base to deprotonate acetylene. H2O NaOH + HC CH NaC CH + – HO .. .. : H C CH HO H .. .. + + C CH : – weaker acidpKa = 26 stronger acidpKa = 16 In acid-base reactions, the equilibrium lies tothe side of the weaker acid. Solution: Use a stronger base.