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.
y y y y y

alkynes are hydrocarbons: made up of only carbon and hydrogen atoms there is a triple bond between 2 carbon atoms general formula: CnH2n-2 name ends in "yne" prefix determined by the number of carbon atoms in the chain: eth prop but pent hex hept oct non dec C2 C3 C4 C5 C6 C7 C8 C9 C10

Basic Reactions
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 Ethyne ==> O = COH 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 Ethyne Ni 150degC H2C=CH2 Ethene + H2 ===> C2H6 Ethane + H2 ===>

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

Nitrile Formation When a slight excess of ethyne and ammonia are passed over an alumina catalyst at 573 degK, ethanonitrile (i.e. acetonitrile) is produced.
573 degK HCCH Ethyne + NH3 ==> CH3CN + H2 Ethanonitrile

Polymerisation of Alkynes due to Triple Bond The products obtained by polymerising ethyne depend on the conditions used. When ethyne is passed through a glass tube at 4000C a little benzene is formed. This is not a suitable way to make benzene in quantity but it is an example of direct conversion from an open chain to an aromatic compound, (i.e. one with a closed-ring benzenoid structure)
400 degC 3 C2H2 Ethyne ==> C6H6 Benzene

Two molecules of ethyne can be combined to produce vinyl ethyne, HC(CCH=CH2, by passing the ethyne into a saturated solution of cuprous chloride in ammonium chloride continuously in such a way that low conversions of starting material occur.
Cu2Cl2 NH4Cl 2 HC CH Ethyne ==> HCCCH = CH2 Vinyl Ethyne

This linear polymerisation can be extended by altering the conditions of reaction. For example,

HCCCH=CH2 Vinyl Ethyne

HCCH Ethyne

==>

CH2=CHC(CCH=CH2 DiVinyl Ethyne

Substitution Reaction of Alkynes The reactions of ethynes indicate acidic properties for the hydrogens which are attached to the carbon atoms involved in the triple bond. Ethynes readily form compounds with metal.

When ethyne is passed through a solution of sodium in liquid ammonia then sodiumacetylide is formed and hydrogen is liberated.
liq.NH3 HCCH + 2Na ==> 2HCCNa + H2 Sodium Acetylide

The other hydrogen atom in ethyne can be similarly replaced. When ethyne is passed into a solution of cuprous chloride in ammonia, cuprous acetylide is produced.
HCCH + Cu2Cl2 + NH4OH ==> CuCCCu Copper Acetylide

Silver acetylide is formed when ethyne is passed into an ammoniacal solution of silver nitrate.
AgNO3 NH4OH HCCH ==> AgCCAg Silver Acetylide + 2 H NO3

These substitution reactions which ethynes undergo to form compounds with metals are not occur with the alkenes. These reactions can be used as tests to distinguish between acetylene and ethylene. When acetylene is passed through an ammonical solution of silver nitrate or cuprous chloride, at room temperature, precipitates of silver acetylide (white) or cuprous acetylide (red) are formed. In addition to distinguishing ethyne from ethene by chemical means, these reactions provide a useful method for the preparation of higher alkynes:
HCC-Na+ + CH3I ==> HCCCH3 Propyne + NaI

Addi i
Al

h drogen, halogens, and rela ed reagents

ti l li l: CR t i t l ll i t t t
[]

t i ti ll i t t l it i X t X li t i l t i l i l l

t t i t D i

t t t " i l t t l t ti t t l

l l iti i

t l ll

t l t

"

RC CR + l i Li l i t l t

cis-RC li ti i

l / il i

i t t t l t ti

i t l t l

t l i l

t i

t i t t l ti i l i l t l

l i l ti l l t l i t

i il l

ti

l i li

l lt t

li

RC CR +

RCB CRB

iti l -H bonds across C C is general for silanes, boranes, and related hydrides. The hydroboration of al ynes gi es vinylic boranes which oxidi e to the corresponding aldehyde or ketone. In the thiol-yne reaction the substrate is a thiol. Hydrohalogenation gives the corresponding vinyl halides or alkyl dihalides, again depending on the number of equivalents of HX added. The addition of water to alkynes is a related reaction except the initial enol intermediate converts to the ketone or aldehyde. Illustrative is the hydration of phenylacetylene gives acetophenone,[ ] and the (Ph3P)AuCH3-catalyzed hydration of 1,8-nonadiyne to 2,8-nonanedione:[] PhC CH + H2O PhCOCH3 HC CC H12C CH + 2H2O CH3COC H12COCH3

Cycloadditions and oxidation

Alkynes undergo diverse cycloaddition reactions. Most notable is the Diels-Alder reaction with 1,3-dienes to give 1,4-cyclohexadienes. This general reaction has been extensively developed and electrophilic alkynes are especially effective dienophiles. The "cycloadduct" derived from the addition of alkynes to 2-pyrone eliminates carbon dioxide to give the aromatic compound. Other specialized cycloadditions include mu lticomponent reactions such as alkyne trimerisation to give aromatic compounds and the [2+2+1]cycloaddition of an alkyne, alkene and carbon monoxide in the PausonKhand reaction. Non-carbon reagents also undergo cyclization, e.g. Azide alkyne Huisgen cycloaddition to give triazoles.

Cycloaddition processes involving alkynes are often catalyzed by metals, e.g. enyne metathesis and alkyne metathesis, which allows the scrambling of carbyne (RC) centers: RC CR + R C CR 2 RC CR

Oxidative cleavage of alkynes proceeds via cycloaddition to metal oxides. Most famously, potassium permanganate converts alkynes to a pair of carboxylic acids.

USES OF ALKYNES y y y y y y y Acetylene is used as an illuminant. It is used for the production of oxy-acetylene flame. The temperature of the flame is above 3000oC. It is employed for cutting and welding of metals. Acetylene is used for artificial ripening of fruits. It is used as a general anesthetic under the name naracylene. Acetylene has synthetic applications. It serves as a starting material for the manufacture of a large variety of substances. On electrical decomposition acetylene produces finely divided carbon and hydrogen. Hydrogen is used in airships. C2H2 > 2C + H2 Alkynes are relatively rare in nature. Triynes, species with the linkage RC C-C CC CR', occur in certain plants (Ichthyothere, Chrysanthemum, and other members of the Asteraceae family). These compounds are highly bioactive, e.g. as nematocides.[] 1-Phenylhepta-1,3,5-triyne is illustrative of a naturally occurring triyne. Alkynes occur in some pharmaceuticals, including the contraceptivenorethynodrel. A carbon-carbon triple bond is also present in marketed drugs such as the antiretroviral Efavirenz and the antifungal Terbinafine. Molecules called ene-diynes feature a ring containing an alkene ("ene") between two alkyne groups ("diyne"). These compounds, e.g. calicheamicin, are some of the most aggressive antitumor drugs known, so much so that the ene-diyne subunit is sometimes referred to as a "warhead." Ene-diynes undergo rearrangement via the Bergman cyclization, generating highly reactive radical intermediates that attack DNA within the tumor.