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Organic Chemistry 4e Carey Online Learning Center

Chapter 9: Alkynes

Summary | Alkynes | Preparation of Alkynes | Addition Reactions of Alkynes | Self Assessment | Quiz |

Addition Reactions of Alkynes Summary


Alkynes undergo addition reactions in an analogous fashion to those of alkenes. The high electron density of the p bonds makes them nucleophilic. Two factors influence the relative reactivity of alkynes compared to alkenes:

1. increased nucleophilicity of the starting p system (CC vs C=C), and 2. stability of any intermediates (for example carbocations)

Reactions:

Hydrogenation Dissolving Metal reduction Hydrohalogenation

Hydration Halogenation Ozonolysis

Hydrogenation of Alkynes

Reaction Type: Electrophilic Addition Summary

Alkynes can be partially reduced to cis-alkenes with H2 in the presence of poisoned catalysts. (eg. Pd / CaCO3 / quinoline which is also known as Lindlar's catalyst) Alkynes can be reduced to alkanes with H2 in the presence of catalysts (Pt, Pd, Ni etc.) The new C-H s bonds are formed simultaneously from H atoms absorbed onto the metal surface. The reaction is stereospecific giving only the syn addition product. The "poisoned" catalyst prevents over-reduction, which would give the alkane by reducing the alkene

Related reactions

Dissolving metal reduction of alkynes Hydrogenation of alkenes CATALYTIC HYDROGENATION Step 1: Hydrogen gets absorbed onto the metal surface. Step 2: Alkyne approaches the H atoms absorbed on the metal surface.

Step 3: CC reacts with the H atoms on the surface forming the two new C-H s bonds generating the alkene. Dissolving Metal Reduction of Alkynes

Reaction Type: Addition Summary


Alkynes can be reduced to trans-alkenes using Na in NH3 (liq.) This reaction is stereospecific giving only the trans-alkene via an anti addition. Note that the stereochemistry of this reaction complements that of catalytic hydrogenation (syn) The reaction proceeds via single electron transfer from the Na with H coming from the NH3 These reaction conditions do not reduce alkenes, hence the product is the alkene.

Related reactions:

Catalytic hydrogenation of alkynes MECHANISM FOR THE REDUCTION OF ALKYNES WITH Na / NH3 Step 1: Sodium transfers an electron to the alkyne giving a radical anion. Step 2: The radical anion removes a proton from the ammonia in an acid / base reaction. Step 3: A second atom of sodium transfers another electron to the alkyne giving

an anion. Step 4: The anion removes a proton from the ammonia in an acid / base reaction. Reaction of Alkynes with Hydrogen Halides

Reaction type: Electrophilic Addition Summary


When treated with HX alkynes form vinyl halides. Hydrogen halide reactivity order : HI > HBr > HCl > HF (paralleling acidity order). Regioselectivity predicted by Markovnikov's rule with the H adding to the C with the most H already present.

Reaction proceeds via protonation to give the more stable carbocation intermediate. Not stereoselective since reaction proceeds via planar carbocation. In the presence of excess HX, a second addition can occur to the product alkene giving a geminal dihalide

Can you suggest a reason why this regioselectivity is observed ? What would be the product from the reaction of 2-butyne with excess HBr ?

For HBr, care must be taken to avoid the formation of radicals as the alternate radical addition occurs with opposite regiochemistry:

Why does this reaction have the opposite regiochemistry ? Related Reactions

Addition of HX to alkenes MECHANISM FOR REACTION OF ALKYNES WITH HBr

Step 1: An acid/base reaction. Protonation of the alkyne to generate the more stable carbocation. The p electrons act pairs as a Lewis base. Step 2: Attack of the nucleophilic bromide ion on the electrophilic carbocation creates the alkenyl bromide. Step 3: In the presence of excess reagent, a second protonation occurs to generate the more stable carbocation.

Step 4: Attack of the nucleophilic bromide ion on the electrophilic carbocation creates the geminal dibromide. Hydration of Alkynes

Reaction type: Electrophilic Addition Summary


Alkynes can be hydrated to form enols that immediately tautomerize to ketones Reagents: aq. acid, most commonly H2SO4, with a mercury salt Regioselectivity predicted by Markovnikov's rule (review) Reaction proceeds via protonation to give the more stable carbocation intermediate (review). Not stereoselective since reactions proceeds via planar carbocation. MECHANISM FOR REACTION OF ALKYNES WITH H3O+ Step 1: An acid / base reaction. Protonation of the alkyne to generate the more stable carbocation. The p electrons act pairs as a Lewis base. Step 2: Attack of the nucleophilic water molecule on the electrophilic carbocation creates an oxonium ion. Step 3: An acid / base reaction. Deprotonation by a base generates the alcohol and regenerates the acid catalyst forming an unstable enol. Step 4: An acid / base reaction. Reprotonation by the acid catalyst occurs on the carbon. The oxygen atom

electrons help facilitate this process generating an oxonium ion. Step 5: Another acid / base reaction. Deprotonation of the oxonium ion creates the ketone. Steps 4 and 5 show the acid catalyzed tautomerization of the enol to the ketone. Halogenation of Alkynes

Reaction type: Electrophilic Addition Summary


Overall transformation : CC to X-C=C-X (and potentially to X2C-CX2) Reagent : normally the halogen (e.g. Br2) in an inert solvent like methylene chloride, CH2Cl2. Regioselectivity : not relevant since all the new bonds are the same, C-X. Reaction proceeds via cyclic halonium ion. Stereoselectivity : anti since the two C-X bonds form in separate steps one from X2 the other X-. This CHIME image shows the structure of the bromonium ion formed during the reaction of ethyne with Br2. Note how the Br is attached to both the C atoms. What is the charge on the bromine ? When the Br- nucleophile attacks, it will attack from the least hindered face, the side opposite to the Br in this intermediate. Make sure you look at the spacefilling model to show this. MECHANISM FOR REACTION OF ALKENES WITH HALOGENS Step 1: The p electrons act as a nucleophile, attacking the bromine, displacing a bromide ion but forming a

cyclic bromonium ion as an intermediate. Step 2: Attack of the nucleophilic bromide from the side away from the bromonium center in an SN2 like fashion opens the cyclic bromonium ion to give overall anti addition. Ozonolysis of Alkynes

Reaction type: Electrophilic Addition Summary


Overall transformation : CC to 2 x CO2H Ozonolysis implies that ozone causes the alkyne to break (-lysis) Reagents : ozone followed by aqueous work-up. Note that each of the CC bonds in the CC becomes a CO bond:

What would be the products of the ozonolysis reactions of: (a) ethyne ? (b) 1-butyne ? Related Reactions

(c) 2-butyne ? (d) cyclooctyne ?

Ozonolysis of Alkenes

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