Alkynes — Core Principles

Core Principles

Alkynes are unsaturated hydrocarbons containing at least one carbon-carbon triple bond ($C equiv C$). The carbon atoms involved in the triple bond are $sp$ hybridized, resulting in a linear geometry with $180^circ$ bond angles.

The general formula for acyclic alkynes with one triple bond is $C_nH_{2n-2}$. They are highly reactive due to the presence of two pi bonds. Key preparation methods include dehydrohalogenation of vicinal or geminal dihalides using strong bases like $NaNH_2$.

Characteristic reactions include addition reactions such as hydrogenation (partial hydrogenation with Lindlar's catalyst yields *cis*-alkenes, while Na/liq. $NH_3$ yields *trans*-alkenes), halogenation, hydrohalogenation (following Markovnikov's rule), and hydration (Kuccherov's reaction, forming aldehydes or ketones via enol-keto tautomerism).

Terminal alkynes possess an acidic hydrogen, allowing them to react with strong bases and form metal acetylides, which is a key distinguishing feature used in tests with Tollens' reagent and ammoniacal cuprous chloride.

Alkynes also undergo oxidation and polymerization reactions.

Important Differences

vs Alkenes vs. Alkynes

Aspect	This Topic	Alkenes vs. Alkynes
Functional Group	Carbon-carbon double bond ($C=C$)	Carbon-carbon triple bond ($C equiv C$)
General Formula (acyclic, one multiple bond)	$C_nH_{2n}$	$C_nH_{2n-2}$
Hybridization of multiple bond carbons	$sp^2$	$sp$
Geometry around multiple bond	Trigonal planar ($120^circ$)	Linear ($180^circ$)
Number of $pi$ bonds	One $pi$ bond	Two $pi$ bonds
Acidity of C-H (if terminal)	Non-acidic (vinyl H)	Acidic (acetylenic H)
Reactivity towards Electrophiles (first step)	Generally more reactive	Generally less reactive
Partial Hydrogenation (stereochemistry)	N/A (already an alkene)	Can yield *cis* (Lindlar) or *trans* (Na/liq. $NH_3$) alkenes
Hydration Product (terminal)	Alcohol	Aldehyde (ethyne) or Ketone (other terminal alkynes)

Alkenes and alkynes are both unsaturated hydrocarbons, but they differ significantly in their degree of unsaturation, bonding, and reactivity. Alkynes possess a carbon-carbon triple bond ($C equiv C$) with $sp$ hybridized carbons and a linear geometry, while alkenes have a carbon-carbon double bond ($C=C$) with $sp^2$ hybridized carbons and trigonal planar geometry. Alkynes have two $pi$ bonds, making them more unsaturated than alkenes with one $pi$ bond. A key distinction is the acidity of terminal alkynes, which allows them to form metal acetylides, a property absent in alkenes. While both undergo addition reactions, the stereochemistry of partial hydrogenation is unique to alkynes, and their hydration products differ.