ORGANIC CHEMISTRY, 5TH EDITION L.G.

WADE-(ch9)

Propriedades Fisico-Quimicas e Reaes de Alquenos e Alquinos

Introduction
Alkynes contain a triple bond. General formula is CnH2n-2 Two elements of unsaturation for each triple bond. Some reactions are like alkenes: addition and oxidation. Some reactions are specific to alkynes. =>
Chapter 9 2

Nomenclature: IUPAC
Find the longest chain containing the triple bond. Change -ane ending to -yne. Number the chain, starting at the end closest to the triple bond. Give branches or other substituents a number to locate their position. =>
Chapter 9 3

Name these:
CH3 C CH
propyne
CH3 C C CH2 CH2 Br

5-bromo-2-pentyne
CH3 CH3 CH CH2 CH3 C C CH CH3

2,6-dimethyl-3-heptyne
Chapter 9 4

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Additional Functional Groups

All other functional groups, except ethers and halides have a higher priority than alkynes. For a complete list of naming priorities, look inside the back cover of your text.
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Chapter 9 5

Examples
CH3 CH2 CH CH2 CH C CH

4-methyl-1-hexen-5-yne
OH CH3 C C CH2 CH CH3

4-hexyn-2-ol =>
Chapter 9 6

Common Names
Named as substituted acetylene.
CH3 C CH

methylacetylene
CH3 CH3 CH CH2 CH3 C C CH CH3

isobutylisopropylacetylene =>
Chapter 9 7

Physical Properties
Apolar,Insolveis em gua. Solvel em geral nos solventes orgnicos. P.E. similar aos alcanos de mesma MM. Menos denso que a gua. Acima de 4C, gs temperatura ambiente. =>
Chapter 9 8

Electronic Structure
The sigma bond is sp-sp overlap.

The two pi bonds are unhybridized p overlaps at 90, which blend into a cylindrical shape.

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Chapter 9 9

Bond Lengths
Maior caratr S ,mais curta a ligao. Three bonding overlaps, so shorter.

Bond angle is 180, so linear geometry.

Chapter 9

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10

Acidity of Alkynes
Terminal alkynes, R-CC-H, are more acidic than other hydrocarbons. Acetylene acetylide by NH2-, but not by OH- or RO-. Maior caratr s, ento par de eltrons em nion est mais perto do ncleo. Menos separao de carga,ento mais estvel. =>
Chapter 9 11

Acidity Table

Chapter 9

12

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Formando ons Acetileto

H+ can be removed from a terminal alkyne by sodium amide, NaNH2.
CH3 C C H + NaNH2 CH3 C C: Na
+

+ NH3

NaNH2 is produced by the reaction of ammonia with sodium metal.

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Chapter 9 13

Alkynes from Acetylides

Acetylide ions are good nucleophiles. SN2 reaction with 1 alkyl halides lengthens the alkyne chain.
CH3 C C: Na
+

CH3CH2

Br

CH3

C C CH2

CH3

+ NaBr

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Chapter 9 14

Must be 1
Acetylide ions can also remove H+ If back-side approach is hindered, elimination reaction happens via E2.
Br CH3 C C: Na
+

CH3

CH CH3

CH3

C C H

H3C CH

CH2

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Chapter 9 15

Addition to Carbonyl
Acetylide ion + carbonyl group yields an alkynol (alcohol on carbon adjacent to triple bond).
R C C + C O R C C C O

H2O +

R C C C O H

H H

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Chapter 9 16

Add to Formaldehyde
Product is a primary alcohol with one more carbon than the acetylide.
H CH3 C C + H
H H2O + CH3 C C C O H H H O

H C O CH3 C C C O H
H H

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Chapter 9 17

Add to Aldehyde
Product is a secondary alcohol, one R group from the acetylide ion, the other R group from the aldehyde.
CH3 C C CH3 C O + H CH3 CH3 C C C O H

CH3 H2O + CH3 C C C O H H

Chapter 9

H H

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18

Add to Ketone
Product is a tertiary alcohol.
CH3 C C CH3 C O + CH3
CH3 H2O + CH3 C C C O H CH3 H O

CH3 CH3 C C C O CH3

H H

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Chapter 9 19

Synthesis by Elimination
Removal of two molecules of HX from a vicinal or geminal dihalide produces an alkyne. First step (-HX) is easy, forms vinyl halide. Second step, removal of HX from the vinyl halide requires very strong base and high temperatures. =>
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Reagents for Elimination

Br CH3 Br KOH (fused) 200C CH3 C C CH2 CH3 CH CH CH2 CH3

Molten KOH or alcoholic KOH at 200C favors an internal alkyne. Sodium amide, NaNH2, at 150C, followed by water, favors a terminal alkyne.
CH3 CH2 CH2 CHCl2 1) NaNH2 , 150C 2) H2O
Chapter 9

CH3

CH2

C CH

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21

Addition of Hydrogen
Three reactions: Add lots of H2 with metal catalyst (Pd, Pt, or Ni) to reduce alkyne to alkane, completely saturated. Use a special catalyst, Lindlars catalyst to convert an alkyne to a cis-alkene. React the alkyne with sodium in liquid ammonia to form a trans-alkene. =>
Chapter 9 22

Lindlars Catalyst
Powdered BaSO4 coated with Pd, poisoned with quinoline. H2 adds syn, so cis-alkene is formed.

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Na in Liquid Ammonia
Use dry ice to keep ammonia liquid. As sodium metal dissolves in the ammonia, it loses an electron. The electron is solvated by the ammonia, creating a deep blue solution.
NH3 + Na
Chapter 9

NH3 e

+ Na

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Addition of Halogens
Cl2 and Br2 add to alkynes to form vinyl dihalides. May add syn or anti, so product is mixture of cis and trans isomers. Difficult to stop the reaction at dihalide.
CH3 C C CH3 Br2 CH3 Br Br C C CH3 + CH3 Br Br2
CH3
Chapter 9

CH3 C C Br
Br Br C C CH3 Br Br
25

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Addition of HX
HCl, HBr, and HI add to alkynes to form vinyl halides. For terminal alkynes, Markovnikov product is formed. If two moles of HX is added, product is a geminal dihalide.
CH3 C C H HBr Br CH3 C CH2
Br HBr CH3 C CH3 Br
Chapter 9 26

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HBr with Peroxides

Anti-Markovnikov product is formed with a terminal alkyne.
H CH3 C C H HBr ROOR CH3 C C H
HBr H Br CH3 C C H H Br

Br ROOR

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Chapter 9 27

Hydration of Alkynes
Mercuric sulfate in aqueous sulfuric acid adds H-OH to one pi bond with a Markovnikov orientation, forming a vinyl alcohol (enol) that rearranges to a ketone. Hydroboration-oxidation adds H-OH with an anti-Markovnikov orientation, and rearranges to an aldehyde.
Chapter 9

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Enol to Keto (in Acid)

Add H+ to the C=C double bond. Remove H+ from OH of the enol.
H CH3 C OH C H H3O
+

H CH3 C C H

H CH3 C C H OH H
H H2O

OH H

A methyl ketone

CH3 C

C H H

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Hydroboration Reagent
Di(secondary isoamyl)borane, called disiamylborane. Bulky, branched reagent adds to the least hindered carbon. Only one mole can add.
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Chapter 9 30

H3C HC CH3 CH H3C

CH3

B CH CH H CH3 H3C

Hydroboration Oxidation
B and H add across the triple bond. Oxidation with basic H2O2 gives the enol.
CH3 C C H Sia2 BH H CH3 C H C

H2O2

H CH3 C H C OH

BSia2 NaOH

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Enol to Keto (in Base)

H+ is removed from OH of the enol. Then water gives H+ to the adjacent carbon.
H CH3 C H C OH OH CH3 C H C H O

H CH3 C H C O

HOH H C O

An aldehyde

CH3 C H
Chapter 9

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32

Oxidation of Alkynes
Similar to oxidation of alkenes. Dilute, neutral solution of KMnO4 oxidizes alkynes to a diketone. Warm, basic KMnO4 cleaves the triple bond. Ozonolysis, followed by hydrolysis, cleaves the triple bond. =>
Chapter 9 33

Reaction with KMnO4

Mild conditions, dilute, neutral
CH3 C C CH2 CH3 KMnO4 H2O, neutral O O CH3 C C CH2 CH3

Harsher conditions, warm, basic

CH3 C C CH2 CH3 KMnO4 , KOH H2O, warm O CH3 C O O + O C CH2 CH3

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Chapter 9 34

Ozonolysis
Ozonolysis of alkynes produces carboxylic acids (Alkenes gave aldehydes and ketones)
CH3 C C CH2 CH3 (1) O3 (2) H2O O CH3 C OH O + HO C CH2 CH3

Used to find location of triple bond in an unknown compound. =>

Chapter 9 35