Alkynes

Chapter

General formula of alkynes is CnH2n2
They are more acidic then alkene and alkane because they have sp hybridised carbon atom which is more elctronegative.

Preparation




Properties
Alkynes resemble alkanes and alkenes in their physical properties. They share with those other hydrocarbons the properties of low
density and low water-solubility. They are nonpolar and dissolve readily in typical organic solvents such as alkanes, and diethyl
ether. Alkynes generally have slightly higher boiling points than the corresponding alkanes and alkenes due to more polar
character. Normally they are colourless and odourless gas - acetylene is also colourless and odourless but it contains garlic odour
due to impurities of PH
3

& AsH
3

.
(i) Acidity of acetylene and terminal alkynes
The CH bonds of hydrocarbons show little tendency to ionize, and alkynes are very weak acids. The ionization constant (K
a

) for methane, for example, is too small to be measured directly, but is about 10
-60


(pK
a

60).











Since it is derived from a very weak acid, a carbanion such as CH
3

is an exceptionally strong base. In general, the ability of an atom to bear a negative charge is related to its electronegati vity. Both
the electronegativity of an atom X and the acidity of HX increase across a row in the periodic table.


In above HI is strongest acid so, the basicity of the conjugate base : X
-


decreases across this series.


As the electron-attracting power of the negatively charged atom increases, the anion becomes less basic. Alkynes are more acidic
than alkenes, and alkenes are more acidic than alkanes.


This order of acidity by examining how strongly each anion holds the unshared electron pair. The ionization of acetylene yields an
anion in which the unshared electron pair occupies
sp

hybridisation.










Alkynes


Ionization of ethylene gives an anion in which the unshared electron pair occupies
sp
2

hybridisation.



The equilibrium constant for ionization of acetylene is greater than that of ethylene because an electron pair in an orbital with 50
percent s character (
sp
) is more strongly bound than an electron pair in an orbital with 33% s character (
sp
2

). Terminal alkynes (R C == CH) are similar to acetylene in their acidity where all 1-alkyne contains acidic hydrogen atom.




While acetylene and terminal alkynes are far stronger acids than ot her hydrocarbons, it must be remembered that they are,
nevertheless, very weak acids much weaker than water and alcohols. For example, hydroxide ion is too weak a base to convert
acetylene to its anion in good amounts. The position of the equilibrium described by the following equation lies overwhelmingly to
the left:




Because acetylene is a far weaker acid than water and alcohols, these substances are not suitable solvents for reactions involving
acetylide ions. Acetylide is instantly converted to acetylene by proton transfer from compounds that contain hydroxyl groups.

Amide
ion is a much stronger base than acetylide ion and converts acetylene to its conjugate base quantitatively.




Solutions of sodium acetylide (HC=CNa) may be prepared by adding sodium amide (NaNH
2
) to acetylene in liquid ammonia as the solvent. Terminal alkynes react similarly to give species of the type RC=CNa.

Anions of acetylene and terminal alkynes are nucleophilic and react with methyl and primary alkyl halides to form carbon-carbon




bonds by nucleophilic substitution. Some useful applications of this reaction will be discussed in the following section.

Alkynes are acidic in nature because as the s character increases electrons are drawn closer to the nucleus.Electronegativity order
sp > sp
2
> sp
3

so that following reactions express the acidic nature of 1 - alkynes.







(d) With Ammonical I
2



(e) With Na / liquid NH
3



(f) With Cl
2
/ FeCl
3



Westron and westrosol are used as solvent in dry cleaning industries.













Hydrogenation of alkynes
(ii) Hydrogenation of alkynes
The hydrogenation of alkynes are similar to those employed for alkenes. When reaction occurs in presence of finely divided
platinum, palladium, nickel, or rhodium, two molar equivalents of hydrogen add to the triple bond of an alkyne to yield an al kane
of same number of carbon atom.



Substituents affect the heats of hydrogenation of alkynes in the same way that they affect in alkenes. Alkyl groups release electrons
to sp hybridized carbon, stabilizing the alkyne and decreasing the heat of hydrogenation. For example, 1-butyne have higher heat
of hydrogenation than 2-butyne.
The heats of hydrogenation of alkynes are somewhat greater than twice the heats of hydrogenation of analogous alkenes.Alkenes
are intermediates in the hydrogenation of alkynes lead us to consider the possibility of stopping hydrogenation at the alkene stage.
It convert alkynes to alkenes by semihydrogenation in the presence of specially developed catalysts. The most frequently used is
the Lindlar catalyst, a palladium on calcium carbonate combination with lead acetate and quinoline. Lead acetate and quinoline
partially deactivate (poison) the catalyst, making it a poor catalyst for alkene hydrogenation while retaining its ability to catalyze
the addition of hydrogen to alkynes.



There are many other catalyst used for semihydrogenation of alkynes. These include palladium supported on barium sulphate, and
a nickel boride Catalyst prepared by reaction of nickel salts with sodium borohydride (P2, Ni2B). Hydrogenation of alkynes to
alkenes by lindlars catalyst is highly stereoselective and yields the cis (for Z) alkene by syn addition to the triple bond.



Other alternative method of catalytic partial hydrogenation for converting alkynes to alkenes is reduction by a group first metal
(lithium, sodium, or potassium) in liquid ammonia as the reaction medium. The metal- ammonia reduction is that it converts
alkynes to trans (or E) alkenes. Thus, from the same alkyne one can prepare either a cis or a trans alkene by choosing the
appropriate reagent.



(iii) Hydration of alkynes (Kocharovs reaction)
Addition of water in the presence of dil H2SO4 and HgSO4 is known as hydration of alkyne where a special kind of alcohol is
formed in which the hydroxyl group is attached with doubly bonded carbon atom. This type of alcohol is called an enol (the double
bond suffix -ene plus the alcohol suffix -ol). An important property of enols is their rapid tautomerization to aldehydes or ketones
under the conditions of their formation due to stability.



This reaction do not give good yield with ethyne because intermediate vinylic carbocation is unstable. The process by which enols
are converted to aldehydes or ketones is called ketoenol isomerism or tautomerism which we already studied in isomerism, this is
followed by the sequence of proton transfers shown in mechanism. Proton transfer to the double bond of an enol occurs readily
because the carbocation that is produced is a very stable one. The positive charge on carbon is stabilized by electron release from
oxygen back bonding and may be represented in terms of resonance resonating structure in following way.




Backbonding of an oxygen lone pair stabilizes the cation. All the atoms in B have complete octets of electrons, making it a more
stable structure than A. Only six electrons are associated with the positively charged carbon in A (less stable).In general, ketones















are more stable than their enol precursors and are the products actually isolated when alkynes undergo acid-catalyzed hydration.
The standard method by which alkyne hydration is carried out employs aqueous sulphuric acid as the reaction medium and
mercury (II) sulphate or mercury (II) oxide as a catalyst. Hg
+2
actually abstract cloud from alkyne which increases
reactivity for addition (same as cyclic mercurium species).

Overall reaction mechanism:
Step A: Formation of enol takes place in aqueous acidic solution. The first phase of its transformation to a ketone is proton transfer
to the carbon-carbon double bond.



Step B: The carbocation stabilize by backbonding of electron to form ketones.







Because alkynes possess only limited solubility in aqueous sulphuric acid so methanol or
acetic acid are added as a cosolvent.



Hydration of alkynes follows Markovnikovs rule; terminal alkynes yield methyl substituted
ketones.



Because of the regioselectivity of alkyne hydration, acetylene is the only alkyne structurally
capable of yielding an aldehyde under these conditions but not give good yield.



(iv) Reaction with CH
3
COOH

This method is just opposite to hydroboration oxidation process where product are formed
just opposite to these one. At one time acetaldehyde was prepared on an industrial scale by
this method. More modern methods involve direct oxidation of ethylene and are more
economical like Wacker process (oxidation by PdCl
2
and air)
(iv) Reaction with CH
3
COOH





Poly vinyl acetate is used as adhesive. When poly vinyl acetate undergoes hydrolysis it
forms poly vinyl alcohol which works as industrial solvent and remember poly vinyl alcohol
cannot be obtained by polymerisation of vinyl alcohol.
(v) Reaction with HCl



(vi) Reaction with HCN





(vii) Alkynylation of carbonyl compounds



When 1-alkynes in the presence of metal reacts with carbonyl compound is known as
Alkynylation of carbonyl compound, forms unsaturated alcohols.



(viii) Hydroboration followed by oxidation
Over all reaction is addition of water anti to the Markovnikovss rule and produces
aldehydes or ketones depends on alkyne structure (mechanism is similar that we follow in
alkenes)



(ix) Ozonolysis (1) O
3
(2) H
2
O






















If reductive ozonolysis takes place in the presence of Zn, it gives dicarbonyl Compound
while oxidative ozonolysis produces two moles of acids.



(x) Reaction with AsCl
3




It is an antidote for Lewisite and forms a non toxic compound after reaction with Lewisite.



(xi) Carbonylation
When acetylene reacts with CO + H
2
O or CO + ROH in the presence of nickel catalyst to
form or Esters. In both route carbonyl group is formed so known as
carbonylation if any reagent undergo further addition, addition takes place according to
marknowniffs rule.





(xii) Alcoholation of alkynes
When alkynes react with alcohol in the presence of BF
3
and HgO, they form ethers. Lewis
acids BF
3
and HgO cause to absorb electronic cloud and increase reaction rate.





(xiii) Polymerisation of alkynes
Trimerisation of ethyne forms benzene while propyne forms 1,3,5- Trimetyl benzene.



Poly Isoprene exists in two forms



















If 1 alkynes reacts with Cu
2
Cl
2
, NH
4
Cl and air, oxidative coupling takes place and dimerised
product alkadynes are formed. Remember dimerisation is the only process where double
bonds are intact, while in tetramerisation ethyne form boat shape molecule cyclooctatetraene
which is nonaromatic in nature.





(xiv) Convert alkane into alkene and alkene into alkyne
(1) Cl
2
/
hv
(2) alc KOH






(xv) How we convert Lower alkynes into higher alkyne ?





(xvi) Reaction with Hot aq. KMnO
4
or K
2
Cr
2
O
7






(xvii) Oxidation :





(b) Oxidation by alkaline KMnO
4
:





(c) Oxidation by H
2
CrO
4
or acidified K
2
Cr
2
O
7
:





(d) Oxidation by acidified KMnO
4
:





(e) Oxidation by selenium dioxide :