CHAPTER 5

ALKYNES

LECTURER : PHAN THỊ HOÀNG ANH 1

NOMENCLATURE

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Compounds contain both double bond and triple bond :
- The parent chain is the longest carbon chain containing both functional groups
- Cite both designations at the at the end of the name, the “en” ending is cited first
- Number the parent chain starting from the end closest to the functional group that
appears first.

- If the same low number is obtained in both directions, number the chain in the
direction that gives the double bond the lower number.

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 STRUCTURE

sp sp

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1. Acidity of terminal alkynes

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2. Hydrogenation of alkynes
 Xúc tác Pt/C → alkane

 Xúc tác Lindlar → cis-alkene

 Na or Li/NH3(lỏng) → trans-alkene

Lindlar catalyst is prepared by precipitating palladium on calcium carbonate and treating it with lead(II) 6
acetate and quinoline.
Mc. 9.21. Predict the products of the following reactions

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3. Addition of halogen

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4. Addition of hydrogen halides
1:1 ratio

if excess hydrogen halide is present → geminal dihalide

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in the presence of a peroxide → anti-Markonikov

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5. Hydration of alkynes
• Acetylene → acetaldehyde

Markovnikov product
• Other alkynes → ketone

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6. Hydration by hydroboration-oxidation
Anti-Markonikov product
Markovnikov’s rule

Anti- Markovnikov’s rule

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Disiamylborane: Di Secondary iso amyl borane
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Mc.9.28. How would you carry out the following reactions?

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7. Ozonolysis of alkynes

Terminal alkynes → CO2

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 ALKYNE PREPARATION
Acetylene from CaC2

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Elimination of dihalides: Treatment of a 1,2-dihaloalkane (a vicinal dihalide)
with an excess amount of a strong base such as KOH (fused), KOH/ethanol or
NaNH2 results in a twofold elimination of HX and formation of an alkyne.

This second dehydrohalogenation occurs only under extremely basic conditions—for example, fused (molten) KOH or alcoholic KOH in a
sealed tube, usually heated to temperatures close to 200 °C. Sodium amide is also used for the double dehydrohalogenation. Since the
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amide ion is a much stronger base than hydroxide, the amide reaction takes place at a lower temperature
Terminal alkynes

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 Synthesis alkynes using acetylide ions
 Terminal alkynes

 Internal alkynes

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Mechanism: SN2

The alkylation reaction is limited to the use of primary alkyl bromides and alkyl iodides
because acetylide ions are sufficiently strong bases to cause elimination instead of
substitution when they react with secondary and tertiary alkyl halides

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Mc.9.41. Show the terminal alkyne and alkyl halide from which the following
products can be obtained. If two routes look feasible, list both.

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 Starting with acetylene, how could the following compounds be synthesized?

B.-pr.21-p.257 23
Mc.9.29-31. Each of the following syntheses requires more than one step.
How would you carry them out?

c)

d)
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