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Junha Jeon !
Department of Chemistry ! University of Texas at Arlington ! Arlington, Texas 76019 ! " ! Chem 2321, Fall 13 !
Introduction to Alkyne!
Ethyne or Acetylene!
Ethyne or Acetylene!
Nomenclature (IUPAC)!
" Given the presence of two pi bonds and their associated electron density, alkynes are similar to alkenes in their ability to act as either nucleophiles or as bases.!
1 !
Nomenclature of Alkynes!
Alkynes are named using the same procedure we used in Chapter 4 to name alkanes with minor modications:! 1." Identify the parent chain, which should include the C!C triple bond.! 2." Identify and name the substituents.! 3." Assign a locant (and prex if necessary) to each substituent, giving the C!C triple bond the lowest number possible.! 4." List the numbered substituents before the parent name in alphabetical order. Ignore prexes (except iso and neo) when ordering alphabetically.! 5." The C!C triple bond locant is placed either just before the parent name or just before the -yne sufx.!
Nomenclature of Alkynes!
Alkynes are named using the same procedure we used in Chapter 4 to name alkanes with minor modications:! 1." Identify the parent chain, which should include the C!C triple bond.! 2." Identify and name the substituents.! 3." Assign a locant (and prex if necessary) to each substituent, giving the C!C triple bond the lowest number possible.! 4." List the numbered substituents before the parent name in alphabetical order. Ignore prexes (except iso and neo) when ordering alphabetically.! 5." The C!C triple bond locant is placed either just before the parent name or just before the -yne sufx.!
Nomenclature of Alkynes!
Alkynes are named using the same procedure we used in Chapter 4 to name alkanes with minor modications:! 1." Identify the parent chain, which should include the C!C triple bond.! 2." Identify and name the substituents.! 3." Assign a locant (and prex if necessary) to each substituent, giving the C!C triple bond the lowest number possible.! 4." List the numbered substituents before the parent name in alphabetical order. Ignore prexes (except iso and neo) when ordering alphabetically.! 5." The C!C triple bond locant is placed either just before the parent name or just before the -yne sufx.!
Nomenclature of Alkynes!
Alkynes are named using the same procedure we used in Chapter 4 to name alkanes with minor modications:! 1." Identify the parent chain, which should include the C!C triple bond.! 2." Identify and name the substituents.! 3." Assign a locant (and prex if necessary) to each substituent, giving the C!C triple bond the lowest number possible.! 4." List the numbered substituents before the parent name in alphabetical order. Ignore prexes (except iso and neo) when ordering alphabetically.! 5." The C!C triple bond locant is placed either just before the parent name or just before the -yne sufx.!
Nomenclature of Alkynes!
1." Identify the parent chain, which should include the C!C triple bond.! 2." Identify and name the substituents.! 3." Assign a locant (and prex if necessary) to each substituent, giving the C!C triple bond the lowest number possible.! 4." List the numbered substituents before the parent name in alphabetical order. Ignore prexes (except iso) when ordering alphabetically.! 5." The C!C triple bond locant is placed either just before the parent name or just before the -yne sufx.!
Nomenclature of Alkynes!
1." Identify the parent chain, which should include the C!C triple bond.! 2." Identify and name the substituents.! 3." Assign a locant (and prex if necessary) to each substituent, giving the C!C triple bond the lowest number possible.! 4." List the numbered substituents before the parent name in alphabetical order. Ignore prexes (except iso) when ordering alphabetically.! 5." The C!C triple bond locant is placed either just before the parent name or just before the -yne sufx.!
2 !
Nomenclature of Alkynes!
1." Identify the parent chain, which should include the C!C triple bond.! 2." Identify and name the substituents.! 3." Assign a locant (and prex if necessary) to each substituent, giving the C!C triple bond the lowest number possible.! 4." List the numbered substituents before the parent name in alphabetical order. Ignore prexes (except iso) when ordering alphabetically.! 5." The C!C triple bond locant is placed either just before the parent name or just before the -yne sufx.!
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Acetylene is 19 pKa units more acidic than ethylene, which is 1019 times stronger.!
3 !
25% s!
33% s!
50% s!
Equilibrium!
Equilibrium!
Equilibrium!
Equilibrium!
4 !
Alkynide!
pKa Table!
5 !
k1!
k2!
cis-Alkene!
6 !
Reduction of Alkynes!
What about trans Alkenes?! !
Reduction of Alkynes!
What about trans Alkenes?! !
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Dissolving metal conditions can give anti addition producing the trans alkene.! Ammonia has a boiling point of 33C, so the temperature for these reactions must remain very low.! Why cant water be used as the solvent?!
" "
Dissolving metal conditions can give anti addition producing the trans alkene.! Ammonia has a boiling point of 33C, so the temperature for these reactions must remain very low.! Why cant water be used as the solvent?!
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Reduction of Alkynes!
What about trans Alkenes?! !
" "
Dissolving metal conditions can give anti addition producing the trans alkene.! Ammonia has a boiling point of 33C, so the temperature for these reactions must remain very low.! Why cant water be used as the solvent?!
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7 !
8 !
Do the pKa values for NH3 and the alkene favor the proton transfer?!
9 !
" "
Kinetic studies on the hydrohalogenation of an alkyne suggest that the rate law is 1st order with respect to the alkyne, and 2nd order with respect to HX.! Termolecular!
10 !
vs.!
11 !
Hydration of Alkenes!
Hydration of Alkynes!
Hydration of Alkynes!
Hydration of Alkynes!
Acid-catalyzed keto-enol tautomerization.! Tautomers (enol and ketone) are constitutional isomers.!
Hydration of Alkynes!
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Undesired second addition can take place.! To block out the second unit of BH3 from reacting with the intermediate, bulky borane reagents are often used.!
12 !
Halogenation of Alkynes!
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Ozonolysis of Alkynes!
13 !
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The alkynide ion can attack a methyl or 1 alkyl halide electrophile.! Alkynide ions usually act as bases with 2 or 3 alkyl halides to cause elimination rather than substitution.!
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Synthesis Strategies!
14 !
Synthesis Strategies!
Synthesis Strategies!
Practice!
15 !