Alkynes: ethyne- sp hybridization ethyne (acetylene) Two p orbitals overlap side to side to form bonds.

. circular symmetry along the length of the triple bond

2s22p2

promotion

1 1 1 2s12px2py2pz

hybridization

1 1 (sp2)22px2py

before hybridization C-atom

sp-hybridized C-atom

overlapping of sp

Alkynes: nomenclature Alkynes are named in much the same way as alkenes. Unbranched alkynes, for example, are named by replacing the -ane of the name of the corresponding alkane with the ending -yne. The chain is numbered to give the carbon atoms of the triple bond the lower possi-ble numbers. The lower number of the two carbon atoms of the triple bond is used to designate the location of the triple bond.

The locations of substituent groups of branched alkynes and substituted alkynes are also indicated with numbers. An -OH group has priority over the triple bond when numbering the chain of an alkynol:

Monosubstituted acetylenes or 1-alkynes are called terminal alkynes, and the hydrogen attached to the carbon of the triple bond is called the acetylenic hydrogen:

The anion obtained when the acetylenic hydrogen is removed is known as an alkynide ion or an acetylide ion.

Synthesis 1. Alkynes can be synthesized from alkenes via compounds called vicinal dihalides.

Mechanism: Step 1

Step 2

Sodium amide, a strong base, is capable of effecting both dehydrohalogenations in a single reaction mixture. At least two molar equivalents of sodium amide per mole of the dihalide must be used. If the product is to be a terminal alkyne, then three molar equivalents must be used because the terminal alkyne is deprotonated by sodium amide.

2. Geminal dihalides can also be converted to alkynes by dehydrohalogenation. A geminal dihalide (abbreviated gem-dihalide) has two halogen atoms bonded to the same carbon (from the Latin geminus, twins). Ketones can be converted to gem-dichlorides through their reactions with phosphorus pentachloride, and these products can be used to synthesize alkynes.

Reactions of alkynes The hydrogen bonded to the carbon of a terminal alkyne is considerably more acidic than those bonded to carbons of an alkene or alkane The pKa values for ethyne, ethene, and ethane illustrate this point:

If we include in our comparison hydrogen compounds of other first-row elements of the periodic table, we can write the following orders of relative acidities and basicities:

Sodium ethynide and other sodium alkynides can be prepared by treating terminal alkynes with sodium amide in liquid ammonia:

sodium alkynides are useful intermediates for the synthe-sis of other alkynes. These syntheses can be accomplished by treating the sodium alkynide with a primary alkyl halide:

Hydrogenation of alkynes Depending on the conditions and the catalyst employed, one or two molar equivalents of hydrogen will add to a carboncarbon triple bond. When a platinum catalyst is used, the alkyne generally reacts with two molar equivalents of hydrogen to give an alkane:

A heterogeneous catalyst that permits hydrogenation of an alkyne to an alkene is the nickel boride compound called P-2 catalyst. The P-2 catalyst can be prepared by the re-duction of nickel acetate with sodium borohydride:

Hydrogenation of alkynes in the presence of P-2 catalyst causes syn addition of hydrogen to take place, and the alkene that is formed from an alkyne with an internal triple bond has the (Z) or cis configuration.

Other specially conditioned catalysts can be used to prepare cis-alkenes from disubstituted alkynes: Lindlar's catalyst .

An anti addition of hydrogen atoms to the triple bond occurs when alkynes are reduced with lithium or sodium metal in ammonia or ethylamine at low temperatures. This reaction, called a dissolving metal reduction, takes place in solution and produces an (E)- or trans-alkene.

Mechanism

Addition of bromine and chlorine to alkyne

It is usually possible to prepare a dihaloalkene by simply adding one molar equivalent of the halogen:

Most additions of chlorine and bromine to alkynes are anti additions and yield trans-dihaloalkenes. Addition of bromine to acetylenedicarboxylic acid, for example, gives the trans isomer in 70% yield:

Addition of hydrogen halides Alkynes react with hydrogen chloride and hydrogen bromide to form haloalkenes or geminal dihalides depending on whether one or two molar equivalents of the hydrogen halide are used. Both additions are regioselective and follow Markovnikov's rule:

Anti-Markovnikov addition of hydrogen bromide to alkynes occurs when peroxides are present in the reaction mixture. These reactions take place through a free-radical mechanism.

Oxidative cleavage Treating alkynes with ozone or with basic potassium permanganate leads to cleavage at the carbon-carbon triple bond. The products are carboxylic acids:

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