有机化学英文课件hapter7.pptVIP

Organic Chemistry William H. Brown Christopher S. Foote Brent L. Iverson Nomenclature IUPAC: use the infix -yn- to show the presence of a carbon-carbon triple bond Common names: prefix the substituents on the triple bond to the word “acetylene” Cycloalkynes Cyclononyne is the smallest cycloalkyne isolated it is quite unstable and polymerizes at room temp the C-C-C bond angle about the triple bond is approximately 155°, indicating high angle strain Physical Properties Similar to alkanes and alkenes of comparable molecular weight and carbon skeleton Acidity The pKa of acetylene and terminal alkynes is approximately 25, which makes them stronger acids than ammonia but weaker acids than alcohols (Section 4.1) terminal alkynes react with sodium amide to form alkyne anions Acidity terminal alkynes can also be converted to alkyne anions by reaction with sodium hydride or lithium diisopropylamide (LDA) because water is a stronger acid than terminal alkynes, hydroxide ion is not a strong enough base to convert a terminal alkyne to an alkyne anion Alkylation of Alkyne Anions Alkyne anions are both strong bases and good nucleophiles They participate in nucleophilic substitution reactions with alkyl halides to form new C-C bonds to alkyl groups; they undergo alkylation because alkyne anions are also strong bases, alkylation is practical only with methyl and 1° halides with 2° and 3° halides, elimination is the major reaction Alkylation of Alkyne Anions alkylation of alkyne anions is the most convenient method for the synthesis of terminal alkynes alkylation can be repeated and a terminal alkyne can be converted to an internal alkyne Preparation from Alkenes Treatment of a vicinal dibromoalkane with two moles of base, most commonly sodium amide, results in two successive dehydrohalogenation reactions (removal of H and X from adjacent carbons) and formation of an alkyne Preparation from Alkenes for a terminal alkene to a terminal alkyne, 3 moles of base are required P