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12.6: Hydration of Alkynes

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    418171
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    Objectives

    After completing this section, you should be able to

    • write the equation for the reaction of water with an alkyne in the presence of sulfuric acid and mercury(II) sulfate.
    • describe keto-enol tautomerism.
    • predict the structure of the ketone formed when a given alkyne reacts with sulfuric acid in the presence of mercury(II) sulfate.
    • identify the reagents needed to convert a given alkyne to a given ketone.
    • identify the alkyne needed to prepare a given ketone by hydration of the triple bond.
    • write an equation for the reaction of an alkyne with borane.
    • write the equation for the reaction of a vinylic borane with basic hydrogen peroxide or hot acetic acid.
    • identify the reagents, the alkyne, or both, needed to prepare a given ketone or a given cis alkene through a vinylic borane intermediate.
    • identify the ketone produced when a given alkyne is reacted with borane followed by basic hydrogen peroxide.
    • identify the cis alkene produced when a given alkyne is reacted with borane followed by hot acetic acid.
    • explain why it is necessary to use a bulky, sterically hindered borane when preparing vinylic boranes from terminal alkynes.
    • predict the product formed when the vinylic borane produced from a terminal alkyne is treated with basic hydrogen peroxide.
    • identify the alkyne needed to prepare a given aldehyde by a vinylic borane.
    Key Terms

    Make certain that you can define, and use in context, the key terms below.

    • enol
    • keto-enol tautomeric equilibrium
    • tautomerism
    • tautomers
    Study Notes

    Rapid interconversion between tautomers is called tautomerism; however, as the two tautomers are in equilibrium, the term tautomeric equilibrium may be used. This section demonstrates the equilibrium between a ketone and an enol; hence, the term keto-enol tautomeric equilibrium is appropriate. The term “enol” indicates the presence of a carbon-carbon double bond and a hydroxyl (i.e., alcohol) group. Later in the course, you will see the importance of keto-enol tautomerism in discussions of the reactions of ketones, carbohydrates and nucleic acids.

    It is important to note that tautomerism is not restricted to keto-enol systems. Other examples include imine-enamine tautomerism

    imine-enamine tautomerism.svg

    and nitroso-oxime tautomerism

    nitroso-oxime tautomerism.svg

    However, at the moment you need only concern yourself with keto-enol tautomerism.

    Notice how hydroboration complements hydration in the chemistry of both alkenes and alkynes.

    hydroboration and hydration scheme of alkenes and alkynes.svg

    Mercury(II)-Catalyzed Hydration of Alkynes

    As with alkenes, hydration (addition of water) of alkynes requires a strong acid, usually sulfuric acid, and is facilitated by the mercuric ion (Hg2+). However, the hydration of alkynes gives ketone products while the hydration of alkenes gives alcohol products. Notice that the addition of oxygen in both reactions follows Markovnikov rule.

    terminal alkene reacts with 1. Hg(OAc)2:H2O:THF then 2. NaBH4 to give secondary alcohol.svg

    During the hydration of an alkyne, the initial product is an enol intermediate (a compound having a hydroxyl substituent attached to a double-bond), which immediately rearranges to the more stable ketone through a process called enol-keto tautomerization.

    terminal alkyne reacts with H2O:H2SO4:HgSO4 to give a ketone.svg

    Tautomers are defined as rapidly inter-converted constitutional isomers, usually distinguished by a different bonding location for a labile hydrogen atom and a differently located double bond. The keto and enol tautomers are in equilibrium with each other and with few exceptions the keto tautomer is more thermodynamically stable and therefor favored by the equilibrium. This mechanism for tautomerization will be discussed in greater detail in Section 22-1.

    enol undergoes tautomerization to the favored keto form.svg

    General Reaction

    For terminal alkynes, the addition of water follows the Markovnikov rule, and the final product is a methyl ketone. For internal alkynes the addition of water is not regioselective. Hydration of symmetrical internal alkynes produces a single ketone product. However, hydration of asymmetrical alkynes, (i.e. if R & R' are not the same ) produces two isomeric ketone products.

    when reacting with H2O:H2SO4:HgSO4, terminal alkynes form methylketone, symmetrical internal alkynes form a single ketone product, and asymmetrical internal alkynes form a mixture of ketone products.svg

    Mechanism

    The mechanism starts with the electrophilic addition of the mercuric ion (Hg2+) to the alkyne producing a mercury-containing vinylic carbocation intermediate. Nucleophilic attack of water on the vinylic carbocation forms a C-O bond to produce a protonated enol. Deprotonation of the enol by water then produces a organomercury enol. The mercury is substituted with H+ to produced a neutral enol and regenerate the Hg2+ catalyst. The enol is converted to the ketone product through keto-enol tautomerization the mechanism of which is provided in Section 22-1.

    Step 1: Electrophilic addition of Hg2+

    mercury mechanism step 1.svg

    Step 2: Nucleophilic attack by water

    mercury mechanism step 2.svg

    Step 3: Deprotonation

    mercury mechanism step 3.svg

    Step 4: Substitution

    mercury mechanism step 4.svg

    Step 5: Tautomerization

    mercury mechanism step 5.svg

    Hydroboration–Oxidation of Alkynes

    The hydroboration-oxidation of alkynes is analagous to the reaction with alkenes. However, where alkenes for alcohol products, alkynes for aldehyde or ketone products. In both cases the addition is anti-Markovnikov and an oxygen is placed on the less alkyl substituted carbon. With the hydroboration of an alkyne the presences of a second pi bond allows the initial product to under tautomerization to become the final aldehyde product.

    terminal alkene reacts with 1. BH3, then 2. H2O2 and hydroxide to give a primary alcohol.svg

    terminal alkynes react with 1. BH3, then 2. H2O2:hydroxide to give an enol, which tautomerizes into an aldehyde.svg

    Alkynes have two pi bonds both of which are capable of reacting with borane (BH3). To limit the reactivity to only one alkyne pi bond, a dialkyl borane reagent (R2BH) is used. Replacing two of the hydrogens on the borane with alkyl groups also creates steric hindrance which enhances the anti-Markovnikov regioselective of the reaction. Disiamylborane (Sia2BH) and 9-borabicyclo[3.3.1]nonane (9-BBN) are two common reagents for this hydroboration reaction. The oxidation reagents (a basic hydrogen peroxide solution) are the same for both alkenes and alkynes.

    structures of disiamylborane (Sia2BH) and 9-borabicyclo[3.3.1]nonane (9-BBN).svg

    General Reaction

    The hydroboration of terminal alkynes produces aldehyde products while internal alkynes produce ketone products. The hydroboration of symmetrical alkynes produces one ketone product and asymmetrical alkynes produce a mixture of product ketones.

    general hydroboration reactions; a terminal alkyne gives an aldehyde while an internal alkyne gives a ketone.svg

    Mechanism

    The mechanism starts with the electrophilic addition of the B-H bond of the borane. The hydrogen atom and the borane all on the same side of the alkyne creating a syn addition configuration in the alkene product. Also, the addition is anti-Markovnikov regioselective which means the borane adds to the less substituted carbon of the alkyne and the hydrogen atom adds to the more substituted. The oxidative work-up replaces the borane with a hydroxy group (-OH) creating an enol intermediate. The enol immediately tautomerizes to the product aldehyde for terminal alkynes and the product ketone for internal alkynes.

    Hydroboration Mechanism.svg

    Comparison of Mercury(II)-Catalyzed Hydration and Hydroboration–Oxidation of Alkynes

    These two reactions are complementary for the reaction of a terminal alkyne because the produce distinctly different products. The mercury(II) catalyzed hydration of a terminal alkyne produces a methyl ketone, while the hydroboration-oxidation produces an aldehyde.

    comparison of reactions of terminal alkynes; hydroboration-oxidation with 1. Sia2BH or 9-BBN followed by 2. hydrogen peroxide:hydroxide gives aldehyde, while hydration with water, sulfuric acid, and mercury sulfate gives a methylketone.svg

    For internal alkynes, the regioslectivity of these reactions are rendered ineffective. The reactions are redundant in that they both produce the same ketone products.

    comparison of reactions of internal alkynes; hydroboration-oxidation with 1. Sia2BH or 9-BBN followed by 2. hydrogen peroxide:hydroxide gives ketone, while hydration with water, sulfuric acid, and mercury sulfate also gives a ketone.svg

    Exercise \(\PageIndex{1}\)

    Draw the structure of the product formed when each of the substances below is treated with H2O/H2SO4 in the presence of HgSO4.

    a)

    structure of but-1-yne.svg

    b)

    structure of 3,3-dimethylbut-1-yne.svg

    Answer

    a)

    structure of butan-2-one.svg

    b)

    structure of 3,3-dimethylbutan-2-one.svg

    Exercise \(\PageIndex{2}\)

    Draw the structure of the keto form of the compound shown below. Which form would you expect to be the most stable?

    structure of cyclohex-1-en-1-ol.svg

    Answer

    structure of cyclohexanone.svg

    The keto form should be the most stable.

    Exercise \(\PageIndex{3}\)

    What alkyne would you start with to gain the following products?

    structures of a) 1-phenylpropan-2-one and b) 2-methylhexan-3-one.svg

    Answer

    for a) prop-2-yn-1-ylbenzene, for b) 2-methylhex-3-yne.svg

    Exercise \(\PageIndex{4}\)

    What alkyne would you start with to gain the following product?

    structure of 1-(3,4-dimethylcyclopentyl)ethan-1-one.svg

    Answer

    4-ethynyl-1,2-dimethylcyclopentane undergoes hydration to give 1-(3,4-dimethylcyclopentyl)ethen-1-ol, which tautomerizes to 1-(3,4-dimethylcyclopentyl)ethan-1-one.svg

    Exercise \(\PageIndex{5}\)

    Draw the product(s) of the following reactions:

    predict the products of ethynylcyclohexane under mercury(II)-catalyzed hydration, ethynylcyclohexane under hydroboration-oxidation conditions, pent-2-yne under mercury(II)-catalyzed hydration, pent-2-yne under hydroboration-oxidation conditions.svg

    Answer

    ethynylcyclohexane under mercury(II)-catalyzed hydration gives 1-cyclohexylethan-1-one, ethynylcyclohexane under hydroboration-oxidation conditions gives 2-cyclohexylacetaldehyde, ethynylcyclohexane under mercury(II)-catalyzed hydration gives 1-cyclohexylethan-1-one, ethynylcyclohexane under hydroboration-oxidation conditions gives 2-cyclohexylacetaldehyde, pent-2-yne under mercury(II)-catalyzed hydration gives pentan-2-one and pentan-3-one, pent-2-yne under hydroboration-oxidation conditions gives pentan-2-one and pentan-3-one

    For internal alkynes, there is no difference in the reaction products.


    12.6: Hydration of Alkynes is shared under a CC BY-SA 4.0 license and was authored, remixed, and/or curated by Steven Farmer, Dietmar Kennepohl, William Reusch, & William Reusch.