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Addition Reactions of Alkynes

A carbon-carbon triple bond may be located at any unbranched site within a carbon chain or
at the end of a chain, in which case it is called terminal. Because of its linear configuration (
the bond angle of a sp-hybridized carbon is 180º ), a ten-membered carbon ring is the
smallest that can accommodate this function without excessive strain. Since the most
common chemical transformation of a carbon-carbon double bond is an addition reaction, we
might expect the same to be true for carbon-carbon triple bonds. Indeed, most of the alkene
addition reactions discussed earlier also take place with alkynes, and with similar regio- and
stereoselectivity.

1. Catalytic Hydrogenation
The catalytic addition of hydrogen to 2-butyne not only serves as an example of such an
addition reaction, but also provides heat of reaction data that reflect the relative
thermodynamic stabilities of these hydrocarbons, as shown in the diagram to the
right. From the heats of hydrogenation, shown in blue in units of kcal/mole, it would
appear that alkynes are thermodynamically less stable than alkenes to a greater degree than
alkenes are less stable than alkanes. The standard bond energies for carbon-carbon bonds
confirm this conclusion. Thus, a double bond is stronger than a single bond, but not twice as
strong. The difference ( 63 kcal/mole ) may be regarded as the strength of the π-bond
component. Similarly, a triple bond is stronger than a double bond, but not 50% stronger.
Here the difference ( 54 kcal/mole ) may be taken as the strength of the second π-bond. The
9 kcal/mole weakening of this second π-bond is reflected in the heat of hydrogenation
numbers ( 36.7 - 28.3 = 8.4 ).
Since alkynes are thermodynamically less stable than alkenes, we might expect addition
reactions of the former to be more exothermic and relatively faster than equivalent reactions
of the latter. In the case of catalytic hydrogenation, the usual Pt and Pd hydrogenation
catalysts are so effective in promoting addition of hydrogen to both double and triple carbon-
carbon bonds that the alkene intermediate formed by hydrogen addition to an alkyne cannot
be isolated. A less efficient catalyst, Lindlar's catalyst, prepared by deactivating (or
poisoning) a conventional palladium catalyst by treating it with lead acetate and quinoline,
permits alkynes to be converted to alkenes without further reduction to an alkane. The
addition of hydrogen is stereoselectively syn (e.g. 2-butyne gives cis-2-butene). A
complementary stereoselective reduction in the anti mode may be accomplished by a
solution of sodium in liquid ammonia. This reaction will be discussed later in this section.

——> cis R-CH=CH-R


R-C≡C-R + H2 & Lindlar catalyst
R-C≡C-R + 2 Na in NH3 (liq) ——> trans R-CH=CH-R + 2 NaNH2

Alkenes and alkynes show a curious difference in behavior toward catalytic hydrogenation.
Independent studies of hydrogenation rates for each class indicate that alkenes react more
rapidly than alkynes. However, careful hydrogenation of an alkyne proceeds exclusively to
the alkene until the former is consumed, at which point the product alkene is very rapidly
hydrogenated to an alkane. This behavior is nicely explained by differences in the stages of
the hydrogenation reaction. Before hydrogen can add to a multiple bond the alkene or
alkyne must be adsorbed on the catalyst surface. In this respect, the formation of stable
platinum (and palladium) complexes with alkenes has been described earlier. Since alkynes
adsorb more strongly to such catalytic surfaces than do alkenes, they preferentially occupy
reactive sites on the catalyst. Subsequent transfer of hydrogen to the adsorbed alkyne
proceeds slowly, relative to the corresponding hydrogen transfer to an adsorbed alkene
molecule. Consequently, reduction of triple bonds occurs selectively at a moderate rate,
followed by rapid addition of hydrogen to the alkene product. The Lindlar catalyst permits
adsorption and reduction of alkynes, but does not adsorb alkenes sufficiently to allow their
reduction.

2. Addition by Electrophilic Reagents


When the addition reactions of electrophilic reagents, such as strong Brønsted acids and
halogens, to alkynes are studied we find a curious paradox. The reactions are even more
exothermic than the additions to alkenes, and yet the rate of addition to alkynes is slower by
a factor of 100 to 1000 than addition to equivalently substituted alkenes. The reaction of one
equivalent of bromine with 1-penten-4-yne, for example, gave 4,5-dibromo-1-pentyne as the
chief product.

HC≡C-CH2-CH=CH2 + Br2 ——> HC≡C-CH2-CHBrCH2Br

Although these electrophilic additions to alkynes are sluggish, they do take place and
generally display Markovnikov Rule regioselectivity and anti-stereoselectivity. One problem,
of course, is that the products of these additions are themselves substituted alkenes and can
therefore undergo further addition. Because of their high electronegativity, halogen
substituents on a double bond act to reduce its nucleophilicity, and thereby decrease the
rate of electrophilic addition reactions. Consequently, there is a delicate balance as to
whether the product of an initial addition to an alkyne will suffer further addition to a
saturated product. Although the initial alkene products can often be isolated and identified,
they are commonly present in mixtures of products and may not be obtained in high yield.
The following reactions illustrate many of these features. In the last example, 1,2-
diodoethene does not suffer further addition inasmuch as vicinal-diiodoalkanes are relatively
unstable.

As a rule, electrophilic addition reactions to alkenes and alkynes proceed by initial formation
of a pi-complex, in which the electrophile accepts electrons from and becomes weakly
bonded to the multiple bond. Such complexes are formed reversibly and may then
reorganize to a reactive intermediate in a slower, rate-determining step. Reactions with
alkynes are more sensitive to solvent changes and catalytic influences than are equivalent
alkenes. For examples and a discussion of mechanisms click here.
Alkynes Physical Properties

Alkynes are compounds which have low polarity, and have physical properties that are
essentially the same as those of the alkanes and alkenes.

1. They are insoluble in water.


2. They are quite soluble in the usual organic solvents of low polarity (e.g. ligroin, ether,
benzene, carbon tetrachloride, etc.).
3. They are less dense than water.
4. Their boiling points show the usual increase with increasing carbon number.
5. They are very nearly the same as the boiling points of alkanes or alkenes with the
same carbon skeletons.

Alkynes

The alkynes are the third homologous series of organic compounds of hydrogen and carbon,
where there is at least one triple-bond between the atoms in the molecules.

The alkenes are said to be unsaturated because of the existence of a multiple bond in the
molecule. The general structure of the alkene series of hydrocarbons is CnH2n-2. The first
member of the ethene series is ethyne (previously called acetylene). The names of all alkynes
end in "-yne". Rules for the systematic naming of alkynes are similar to those for alkenes. In
the case of higher members of the alkene series, the triple bond may be between the terminal
carbon atoms of the chain, or may be between internal carbon atoms in the chain.

Ethyne (Acetylene) HCCH


Propyne HCCCH3
1-Butyne HCCCH2CH3
1-Pentyne HCC(CH2)2CH3
1-Hexyne HCC(CH2)3CH3
1-Heptyne HCC(CH2)4CH3
1-Octyne HCC(CH2)5CH3
1-Nonyne HCC(CH2)6CH3
1-Decyne HCC(CH2)7CH3
2-Butyne CH3CCCH3
2-Pentyne CH3CCCH2CH3

Alkynes Chemical Properties

Combustion of Alkynes

Ethyne burn in air with a luminous, smoky flame, (forming carbon dioxide and
water).

2 C2H2 + 5 02 ==> 4 CO2 + 2 H2O


The ethynes are highly dangerously explosives when mixed with air or oxygen.
Oxidation of Alkynes

Ethyne is oxidised by a dilute aqueous solution of potassium permanganate to form


oxalic acid. Thus, if ethyne is bubbled through a solution of potassium permanganate
the solution is decolourised. This is Baeyer's test for unsaturated organic compounds.

KMnO4

HCCH ==> O = COH

Ethyne O = COH

Oxalic Acid
Addition Reactions of Alkynes

Because of the unsaturated nature of ethyne addition reactions can occur across the
triple bond.

Addition of Hydrogen

When acetylene and hydrogen are passed over a nickel catalyst at 150 degC, (or over
platinum black catalyst at room temperature) ethene is first formed and then this is
further reduced to ethane.

Ni

150degC

HCCH + H2 ===>

Ethyne

Ni

150degC

H2C=CH2 + H2 ===> C2H6

Ethene Ethane
Addition of Halogens

Ethyne reacts explosively with chlorine at room temperature, forming hydrogen


chloride and carbon. To control the reaction, acetylene and chlorine (also bromine)
are added in retorts filled with kieselguhr (hydrated silica) and iron filings.

HCCH + Cl2 ==> ClHC=CHCl + Cl2 ==> Cl2HCCHCl2

Addition of Hydrogen Halides.

Ethyne reacts with the halogen acids. Hydrogen iodide adding on the most readily, at
room temperature. A similar reaction occur with hydrogen bromide at 100 degC.
Reaction with hydrogen chloride occurs very slowly.

HCCH + HCl ==> H2C=CHCl + HCl ==> CH3CHCl2

Addition of Water (Hydration)

Hydration of ethyne occurs when the gas is passed into dilute sulphuric acid at 60
degC. Mercuric sulphate is used as a catalyst for the reaction, and the product formed
is ethanal (i.e. acetaldehyde).

HgSO4

60 degC

HCCH + H2O ==> CH3CHO