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Alkyne Reactions and Properties Explained

Terminal alkynes are more acidic than other hydrocarbons due to the electron-donating acetylide ions they form. They undergo addition reactions like alkenes due to their electron-rich pi bonds. Catalytic hydrogenation adds hydrogen across the triple bond to form an alkane, while reaction with halogens adds one or two moles of halogen to form dihaloalkenes or haloalkanes. Oxidation of alkynes with permanganate forms an α-diketone, while ozonolysis cleaves the triple bond to form two carboxylic acids.

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132 views17 pages

Alkyne Reactions and Properties Explained

Terminal alkynes are more acidic than other hydrocarbons due to the electron-donating acetylide ions they form. They undergo addition reactions like alkenes due to their electron-rich pi bonds. Catalytic hydrogenation adds hydrogen across the triple bond to form an alkane, while reaction with halogens adds one or two moles of halogen to form dihaloalkenes or haloalkanes. Oxidation of alkynes with permanganate forms an α-diketone, while ozonolysis cleaves the triple bond to form two carboxylic acids.

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Vidhan Patni
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Physical properties

Terminal alkynes are much more acidic than other hydrocarbons.

Acetylide ions are strong nucleophiles.


Methods of Preparation
(i) By dehydrohalogenation of vicinal dihalides (1,2-dihalides).

(ii) By dehydrohalogenation of geminal dihalides (1,1-dihalides).


Methods of Preparation
By dehalogenation of vicinal tetrahalides

Kolbe’s Electrolysis
Addition Reactions of Alkynes
Many of the reactions of alkynes are similar to the corresponding reactions of
alkenes because both involve pi bonds between two carbon atoms. Like the pi bond
of an alkene, the pi bonds of an alkyne are electron-rich, and they readily undergo
addition reactions.
Catalytic Hydrogenation
In the presence of a suitable catalyst, hydrogen adds to an alkyne, reducing it to an
alkane.

Lindlar’s catalyst* is a poisoned palladium catalyst, composed of powdered barium


sulfate coated with palladium, and poisoned with quinoline.
Catalytic Hydrogenation

Sodium metal in liquid ammonia reduces alkynes with anti stereochemistry, so this
reduction is used to convert alkynes to trans alkenes.
Mechanism

Step 1: An electron adds to the alkyne, forming a radical anion.

Step 2: The radical anion is protonated to give a radical.


Mechanism

Step 3: An electron adds to the radical, forming an anion.

Step 4: Protonation of the anion gives an alkene.


Addition of Halogens

Bromine and chlorine add to alkynes just as they add to alkenes. If 1 mole of
halogen adds to 1 mole of an alkyne, the product is a di-haloalkene. The
stereochemistry of addition may be either syn or anti, and the products are often
mixtures of cis and trans isomers.
Addition of Hydrogen Halides
Hydrogen halides add across the triple bond of an alkyne in much the same way
they add across the alkene double bond.
Addition of Hydrogen Halides
When 2 moles of a hydrogen halide add to an alkyne, the second mole usually adds
with the same orientation as the first.
Addition of Hydrogen Halides
Peroxides catalyze a free-radical chain reaction that adds HBr across the double
bond of an alkene in the anti-Markovnikov sense.
Hydration of Alkynes
Alkynes undergo acid-catalyzed addition of water across the triple bond in the
presence of mercuric ion as a catalyst.
Addition of HOX to Alkynes
Oxidation of Alkynes
Oxidation of alkynes occurs with the same reagents used to oxidize alkenes:
permanganate and ozone.

If an alkyne is treated with cold aqueous potassium permanganate under nearly


neutral conditions, an 𝞪-diketone results.
Oxidation of Alkynes

If the reaction mixture becomes warm or too basic, the diketone undergoes oxidative
cleavage. The products are the carboxylate salts of carboxylic acids, which can be
converted to the free acids by adding dilute acid.
Oxidation of Alkynes

Ozonolysis of an alkyne, followed by hydrolysis, cleaves the triple bond and gives two
carboxylic acids.

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