Alkyne

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1 1 .

6 0 | Alkenes and Alkynes

ALKYNES
1. INTRODUCTION

1.1 Nomenclature
Alkynes are unsaturated hydrocarbons that contain (C≡C) bond. Their general formula is CnH2n–2.

Condensed Stick Bond line IUPAC name Common or trivial name


C2H2 H—C≡C—H 2 1 Ethyne Acetylene

C3H4 H3C—C≡C—H 3 2 1 Propyne Methylacetylene

C4H6 CH3—CH2—C≡CH 4 But-1-yne Ethylacetylene


3 2 1
CH3—C≡C—CH3 But-2-yne Dimethy lacetylene
4 3 2 1

C5H8 CH3—CH2—CH2—C≡C—H 4 3-Methyl-but-1-yne Propylacety lene


3 2 1
5

or 4 3-Methyl-but-1-yne Isopropyl-acetylene
3 2 1
CH3

CH3—CH—C≡C—H

or 5 Pent-2-yne Ethyl methylacetylene


4 3 2 1
CH3—CH2—C≡C—CH3

1.2 Structure
Each carbon atom of ethyne is sp-hybridized. One sp-hybridized orbital of each carbon undergoes head on overlap
with sp-hybrisized orbital of another carbon to form a sp-sp, C-C, σ-bond. The second sp-hybridized orbital of each
carbon overlaps along the internuclear axis with 1 s-orbital of each of the two hydrogen atoms forming two sp-s,
C—H, σ-bonds. Each carbon is now left with two unhybridized p-orbitals (2px and 2py) which are perpendicular to
each other as well as to the plane of the C—C sigma bond.
The two 2px– orbitals, one on each carbon, are parallel to each other and hence overlap sideways to form a π-bond.
Similar overlap between 2py– orbitals, one on each carbon, results in the formation of a second π-bond as shown
in figure.

Sp-s Sp-s
C-H, -bond C-H, -bond
1s sp sp
sp
1s
sp
(a) H C C H

sp-sp, C-C
-bond
Chem i str y | 11.61

In the plane
Below the plane
of the paper
of the paper
2px
(b) 

 2px

C C


Above the plane In the plane of


of the paper the paper

120 pm 107.9 pm
H C C H

o
180
Carbon-carbon triple bond consists of one strong σ-bond and two weak π-bonds. The total strength of C ≡ C bond
in ethyne is 823 kJ mol–1. It is stronger than the C = C bond of ethane (599 kJ mol–1) and C – H bond of ethane
(348 kJ mole–1). Further, due to the smaller size of sp-orbitals (as compared to sp2 and sp3–) and sideways overlap
of p-orbitals, the carbon-carbon bond length in ethyne is shorter (120 pm) than those of C = C (134 pm) and C–C
(154 pm).

1.3 Isomerism in Alkynes


(i) Position isomerism. The first two members, i.e., ethyne and propyne exist in one form only. However, butyne
and higher alkynes exhibit position isomerism due to the different position of the triple bond on the carbon
chain. For example,
CH3—CH2—C≡CH CH3—C≡C—CH3
But-1-yne But-2-yne
(ii) Chain isomerism. Alkynes having five or more carbon atoms show chain isomerism.
CH3
4 | 2 1
3
CH3—CH2—CH2—C≡CH CH3—CH—C≡CH

(iii) Functional isomerism: Alkynes are functional isomers of dienes


4 3 3 1 1 2 3 4
CH3 — CH2 — C ≡ CH =
CH2 CH
= — CH CH2

But-1-yne Buta-1,3-diene
(iv) Ring chain isomerism: Alkynes show ring chain isomerism with cycloalkenes. For example,

CH3—C≡CH and are ring chain isomers.


Cyclopropene
Propyne Cyclopropene
1 1 . 6 2 | Alkenes and Alkynes

2. PREPARATION OF ALKYNES

2.1 From Calcium Carbide


Alkynes are prepared by the following general methods.
1. By the action of water on calcium carbide: Ethyne (acetylene) is prepared in the laboratory as well as on a
commercial scale by the action of water on calcium carbide.
CaC2 + 2H2O → HC≡CH + Ca(OH)2


Calcium carbide Ethyne (Acetylene)
Calcium carbide needed for the purpose is manufactured by heating limestone (calcium carbonate) with
coke in an electric furnace at 2275 K.
2275K
→ CaO + CO2
CaCO3 
CaO + 3C 
2275K
→ CaC2 + CO

2. Procedure: Lumps of calcium carbide are placed on a layer of sand in a conical flask fitted with a dropping
funnel and a delivery tube. The air present in the flask is replaced by oil gas since acetylene forms an explosive
mixture with air. Water is now dropped from the dropping funnel and the acetylene gas thus formed is
collected over water.
3. Purification: Acetylene gas prepared by the above method contains impurities of hydrogen sulphide and
phosphine due to the contamination of CaS and calcium phosphide in calcium carbide. Phosphine is removed
by passing the gas through a suspension of bleaching powder. Pure acetylene is finally collected over water.

2.2 Double Dehydrohalogenation of Dihalides

Double dehydrohalogenation of a geminal dihalide


H X
| |
R—C—C—R’ + 2NaNH2 R—C≡C—R’ + 2NH3 + 2NaX
| |
H X

Geminal dihalide Sodium amide Alkyne Ammonia Sodium halide

Double dehydrohalogenation of a vicinal dihalide


H H
| |
R—C—C—R + 2NaNH2 R—C≡C—R’ + 2NH3 + 2NaX
| |
X X

Vicinal dihalide Sodium amide Alkyne Ammonia Sodium halide

The most frequent application of these procedures are in the preparation of terminal alkynes. Since the terminal
alkyne product is acidic enough to transfer a proton to the amide anion. One equivalent of base in addition to the
two equivalents required for double dehydrohalogenation is needed. Adding water or acid after the reaction is
complete converts the sodium salt to the corresponding alkyne.
Chem i str y | 11.63

2 3NaNH H2O
1. (CH3)3CCH2CHCl2 → (CH3)3CC≡CNa  → (CH3)3 CC≡CH
NH3

1,1-Dichloro-3,3- Sodium salt of alkyne 3,3-Dimethyl-


Dimethylbutane product (not isolated) 1-butyne (56-60%)

2. 3NaNH
CH3(CH2)2CHCH2Br  → CH3(CH2)7C≡CNa 
2 H2O
→ CH3(CH2)7C≡CH
NH
| 3

Br

1,2-Dibromodecane Sodium salt of alkyne 1-Decyne (54%)


Product (not isolated)

Double dehydrohalogenation to form terminal alkynes may also be carried out by heating geminal and vicinal
dihalides with potassium ter-butoxide in dimethyl sulfoxide. By heating with alcoholic solutio`n of KOH

CH2—Br
CH
| +2 KOH (alc.) 

→ ||| + 2KBr + 2H2O
CH2—Br
CH
1,2-Dibromodecane Acetylene
(Ethylene dibromide)

PLANCESS CONCEPTS

Misconception: The reaction, in fact, occurs in two steps and each step involves the loss of a
molecule of HBr as shown below:

BrCH2—CH2Br + KOH (alc.)  → CH2=CHBr + KBr + H2O
Ethylene dibromide Vinyl bromide

CH2=CH—Br + KOH (alc.) → CH≡CH+KBr+H2O
Vinyl bromide Acetylene
Aman Gour (JEE 2012, AIR 230)

Explanation: In ethylene dibromide, Br is present on a saturated carbon atom. Therefore. Like alkyl halides, it is
a reactive molecule. Consequently, on heating with alcoholic KOH, it readily eliminates a molecule of HBr to form
vinyl bromide in good yield. In contrast, due to the presence of Br on a doubly bonded carbon atom, vinyl bromide
is a highly unreactive molecule and hence on heating with alcoholic KOH, it does not easily lose a molecule of HBr
to form acetylene. Thus, with alcoholic KOH, the yield of acetylene is low. Therefore, to obtain acetylene in fairly
good yield from vinyl bromide, a much stronger base than alcoholic KOH such as NaNH2 in liquid NH2 is usually
used. Thus, dehydrohalogeneation of ethylene dibromide to acetylene is preferably carried out in the following
two stages.
H H H
KOH(alc.), NaNH2/liq.NH3
R C C H H C C H H C C H
-HBr -HBr

Br Br Br Acetylene
Vicinal dihalide Vinyl bromide

Θ
With a strong base ( NH2 ), isomerisation also taken place to give terminal alkyne.
1 1 . 6 4 | Alkenes and Alkynes

:
(i)NaNH2, 400K
Me C  C Me Me C  C Na
H2O

Me C  CH
Prop-1-yne
Dehalogenation of tri/tetra halides
Br

Me1 Br 3 (i) 2(Zn+EtOH) 4 3 2 1


Me C  C Me + 2ZnBr2
2 or
(But-2-yne) or
Br Me (ii) 2(Mg+EtOH)
2MgBr2
or
Br or
(iii) 4(NaI in acetone)
4NaBr +2I2
2,2,3,3,-Tetra bromobutane

3. By dehalogenation of tetrahalides.: Tetrahaloalkanes when heated with zinc dust in methanol undergo
dehalogenation to yield alkynes. For example
Br Br
CH3OH
H C C H + 2 Zn H C  C H + 2 ZnBr2

Acetylene
Br Br
1,1,2,2-Tetrabromoethane

2.4 Dehalogenation of Haloforms


By dehalogenation of haloforms: Chloroform and iodoform on heating with silver powder undergo dehalogenation
to form ethyne.

CH Cl3 + 6 Ag + Cl3 CH HC CH + 6 AgCl
Chloroform Ethyne
Chloroform


CH l3 + 6 Ag + l3 CH HC CH + 6 AgI
Iodoform Iodoform Ethyne

2.5 Kolbe’s Electrolytic Reaction


Kolbe’s electrolytic reaction: Acetylene can be prepared by electrolysis of a concentrated solution of sodium or
potassium salt of maleic acid or fumaric acid. Thus,

H COOK H COOK

C C Electrolysis CH
+ 2H2O + 2CO2 + H2 + 2KOH


or
C C CH
Acetylene
H COOK KOOC H
Pot. maleate Pot. fumerate
(cis isomer) (trans-isomer)

This reaction is called Kolbe’s electrolytic reaction and is believed to occur by the following steps:

CHCOOK ionaization CHCOO +


2OH- + 2 H
+
+2K ; 2 H2O
CHCOOK CHCOO
CH
CHCOO CHCOO + 2CO2
- 2e-
CH
CHCOO CHCOO
unstable
CHCOOK ionaization CHCOO + Chem i str y | 11.65
2OH- + 2 H
+
+2K ; 2 H2O
CHCOOK CHCOO
CH
At anode: CHCOO CHCOO + 2CO2
- 2e-
CH
CHCOO CHCOO
unstable

At cathode: 2H+ + 2e− →[2H] → H2

2.6 From α-diketo


α- Diketone reacts with hydrazine (NH2 – NH2) to give bis-hydrazone which on oxidation with HgO gives unstable
bis(diazo) compound which decomposes to give alkyne.

O N NH2

4
2 3 Me 2NH2 NH2 Me
1
Me Me

O N NH2
Butan-2,4-dione Bis-hydrazone of (I)
(1)
HgO

N
-N2
Me Me Me
But-2-yne Me

N
Bis-(diazo) of (I)

2.7 Industrial Method


2CH4 ( g) 
→ CH ≡ CH ( g) + 3H2 ( g)
1773 K

The reaction is highly endothermic, yet the optimum time for this reaction is 0.01 second.
∆n = nP – nR = 4 – 2 = 2 mol, and this causes a significant increase in ∆S. At this high temperature, the T∆S term in
the equation ∆G = ∆H – T∆S predominates, making ∆G = –ve , although ∆H = +ve.
But ∆H°f for C2H2 = +227 k mol–1 shows that acetylene is thermodynamically unstable, explodes readily, and gets
converted into its elements.
C2H2(g) → 2C(s) + H2 (g) , ∆H° = – 227 kJ mole–1

2.8 Berthelot Synthesis


Mearcellin Berthelot synthesized acetylene from its elements (carbon and hydrogen) by striking an electric arc
between two electrodes in an atmosphere of H2 gas.
2C + H2 CH  CH(g)
Acetylene

2.9 Higher Alkynes from Acetylene


Synthesis of higher alkynes from acetylene: Acetylene is first treated with sodium metal at 475K or with sodamide
in liquid ammonia at 196 K to form sodium acetylide. This upon treatment with alkyl halides gives alkyne.
1 1 . 6 6 | Alkenes and Alkynes

For example:
Liq.NH ,196K
3 → HC ≡ C−Na+ + NH3
HC ≡ CH + NaNH2 
Ethyne(Acetylene) Sodiumacetylide

HC  C-Na+ + CH3 Br HC  C CH3 + NaBr


Sod. acetylide Bromomethane Propyne

HC  C-Na+ + CH3 CH2 I HC  C CH2CH3 + NaI


Sod. acetylide Idoethane But-1-yne

HC  C-Na+ + CH3 CH2 CH2 Br HC  C CH2CH2CH3 + NaBr


Sod. acetylide 1-Bromopropane Pent-1-yne
(n-propyl bromide)
An analogous sequence usually terminal alkynes as starting material yields alkynes of the type RC = CR’.

N NH
2 3 → (CH ) CHCH C ≡ CNa 
3 →(CH ) CHCH C ≡ CCH CH Br
(CH3 )2 CHCH2C ≡ CH  3 2 2 3 2 2 3
2 −Methy −1 −Pentyne NH3 5 −Methyl−2 −Hexyne −181%

Dialkylation of acetylene can be achieved by carrying out the sequence twice.

3 1.NaOH,NH 3 1.NaOH,NH
HC ≡ CH → HC ≡ CCH2CH3 → CH3C ≡ CCH2CH3
Acety lene 2.CH3CH2Br 2.CH3Br 2 −Pentyne(81%)

3. PROPERTIES OF ALKYNES
(i) No cis-trans isomerism: The sp hybrid orbitals are linear, ruling out cis-trans stereoisomers in which
substituents must be on different sides of the multiple bond.
(ii) Bonds: Bond length decreases in the following order: Alkane > Alkene > Alkyne

Bond length order: −C − H > = C − H > ≡ C − H


sp3 sp2 sp

Bond Strength order: ≡ C − H > = C − H > –C − H


sp sp2 sp3

As a general rule ‘more the s – character of hybrid orbitals used by an atom, closer are the bonding electrons to the
atom and shorter and stronger is any of its σ-bonds’.
(iii) Solubility and Dipole moment
Decreasing solubility in H2O: Alkynes > Alkenes > Alkanes
Alkynes are slightly more soluble in H2O because they are somewhat more polar.
The dipole moment of alkyne is greater than those in alkene because (C — C) sp bond is more polarized
than (C — C) sp2 bond: this is because C with more s character is more electronegative.
Dipole moment of but-1-yne is 0.8 D and that of but-1-ene is 0.3 D.
Due to a slightly high polarity and dipole moment of alkynes than those of alkenes (and of alkenes
higher than alkane) boiling point of alkynes > alkenes > alkanes, with the same number of C atoms.
They go from gases to liquids to solids with increasing molecular weights. There is a little difference in
boiling points of these hydrocarbons with similar C skeletons.
Chem i str y | 11.67

(iv) Smell: All alkynes are odourless except acetylene which has a garlic smell due to the presence of impurity,
phosphine.
(v) Physical state: The first three members are gases, the next eight are liquids, and the rest are solids.
(vi) Melting and Boiling points: The m.p. and b.p. of alkynes are slightly higher than those of the corresponding
alkenes and alkanes. This is probably due to the presence of a triple bond, alkynes have linear structures and
hence their molecules can be more closed packed in the crystal lattice as compared to those of corresponding
alkenes and alkanes.
(vii) Densities: Densities of alkynes like those of alkenes and alkanes increase as the molecular size increases.
However, they are all lighter than water, since densities lie in the range 0.69 – 0.77 g/cm2.
(viii) Stability: Alkynes are less stable than isomeric dienes as is evident from their heat of formation ( ∆H°f ) values.
2 4
1 5 (1,4-Pentadiene) +106.0 kJ mol-1
3
Me 5

1 +129.0 kJ mol-1
Me (Pent-2-yne)
4 3 2
4
2 1
5 H (Pent-2-yne) +144.5 kJ mol-1
Me 3

(ix) Reactivity: However, alkynes are less reactive than the corresponding alkenes towards electrophilic addition
(EA) reaction (except catalytic hydrogenation), even though they contain two π-bonds. This is due to:
(a) Greater EN of sp-hybridised C atom of alkynes than sp2 –hybridised C atom of alkenes which hold the
π - electrons of alkynes more tightly.
(b) Greater delocalisation of π -electrons in alkynes (because of cylindrical nature of their π -electrons
cloud) than in alkenes. As a result, π -electrons of alkynes are less easily available for addition reaction
than those of alkenes. So alkynes are less reactive than alkenes towards electrophilic addition reaction.
Catalytic hydrogenation, however, is an exception: Alkenes are adsorbed on the surface of
catalyst only when the plane of π-bond approaches perpendicularly. In alkynes because of the
cylindrical nature of π-bonds, approach by hydrogen along the axis of the cylinder is more effective
and thus transition state in alkynes is less strained. So alkynes react faster than alkenes with H2.
(x) Acidity of alkynes:
Terminal alkynes are more acidic than alkenes because alkyne C-atoms are sp hybridized and electrons
in an s-orbital are more tightly held than in a p-orbital also s-electrons are closer to the nucleus.
Furthermore, since the sp orbital has more s character (50% s) than sp2 (33% s) or sp2 orbital (25% s), the
electrons in sp orbital are more tightly held by the nucleus than electrons in sp2 or sp3 orbital.
In another words, sp-hybridised C is more EN than sp2, or sp3-hybridised C atom. Due to this greater
EN, the electrons of (C — H) bonds are displaced more towards the C atom than towards the H atom.
Therefore, the H-atom is less tightly held by the C atom and hence can be removed as a proton (H+ ion)
by a strong base and consequently terminal alkynes behave as acids.

R—C C — H + strong base R—C C — Base — H


As a rule, as the s character decreases from sp to sp2 to sp3 hybridised C atom, the acidic character of hydrocarbons
decreases in the following order.

= O ←→ Me − C⊕H − OΘ
Me − HC
1 1 . 6 8 | Alkenes and Alkynes

4. REACTIONS OF ALKYNES

4.1 Acidic Character


(i) Formation of alkali metal acetylides: Ethyne and other terminal alkynes (Alkynes in which the triple bond
is at the end of the carbon chain) or 1-alkynes react with strong bases such as sodium metal at 475 K or
sodamide in liquid ammonia at 196 K to form sodium acetylides with evolution of H2 gas.
475K
2HC ≡ CH+ 2Na  → 2HC ≡ C−Na+ + H2
Ethyne Monosodiume ethynide
(Acetylene) (monosodiumacetylide)

Liq.NH
3 → R − C ≡ C −Na+ + NH
R − C ≡ CH + NaNH2  3
(A ter minalalkyne) 196K (A sod. alkynide)

During these reactions, the acetylenic hydrogen is removed as a proton to form stable carbanions
(acetylide ions) Sodium acetylide is decomposed by water regenerating acetylene. This shows that water
is a stronger acid than acetylene and thus displaces acetylene from sodium acetylide.

HC ≡ C−Na+ + H2O → HC ≡ CH+ NaOH


(Monosodiumacetylide) (Acetylene)

(ii) Formation of heavy metal acetylides: Acetylenic hydrogens of alkynes can also be replaced by heavy metal
ions such as Ag+ and Cu+ ions. For example. When treated with ammoniacal silver nitrate solution (Tollen’s
reagent), alkynes form a white precipitate of silver acetylides.

CH ≡ CH + 2[Ag(NH3 )2 ]+ OH− → AgC


= CAg + 2H2O + 4NH3
Ethyne Tollensreagent Disilver ethynide

R − C ≡ CH + [Ag(NH3 )2 ]+ OH− → R − C ≡ C − Ag+ H2O + 2NH3


(Ter minalkyne) Tollensreagent Silver alkynide
(Whiteppt.)

Similarly, with ammoniacal cuprous chloride solution, terminal alkynes form red ppt. of copper acetylides.

HC ≡ CH + 2[Cu(NH3 )2 ]+ OH− → CuC ≡ CCu + 2H2O + 4NH3


(Ethyne) Dicopper ethynide

R − C ≡ CH + [Cu(NH3 )2 ]+ OH− → R − C ≡ C − Cu + H2O + 2NH3


(Terminal alkyne ) Tollensreagent Monocopper alkynide
(Re dppt.)

Unlike alkali metal acetylides are not decomposed by water. They can however, be decomposed with dilute mineral
acids to regenerate the original alkynes.

AgC ≡ CAg + 2HNO3 → HC ≡ CH + 2AgNO3


(Disilver acetylide) Acetylene

CuC ≡ CCu + 2HCl → HC ≡ CH + 2CuCl


(Dicopper acetylide) Acetylene

(iii) Formation of alkynyl Grignard reagents: Acetylne and other terminal alkynes react with Grignard reagents
to form the corresponding alkynyl Grignard reagents. For example.
Dry
HC ≡ CH + RMgX → HC ≡ CMgX + RH

(Acetylene) Grignardreagent Ether Acetylenic Alkane
Grignard reagent

Dry
R '− C ≡ CH + RMgX → R '− C ≡ CMgX
 + RH
Ter minalalkyne Grignardreagent Ether AlkynylGrignard reagent Alkane
Chem i str y | 11.69

Alkynyl Grignard reagents like usual Grignard reagents can be used to prepare a variety of organic compounds.
Importance: The formation of metal acetylides can be used:
(a) For the separation and purification of terminal alkynes from non-terminal alkynes, alkanes and alkenes.
(b) To distinguish terminal alkynes from non-terminal alkynes or alkenes.

4.2 Hydrogenation / Reduction


cat
RC ≡ CR '+ 2H2  → RCH2CH2R ' Catalyst = Pt, Pd, Ni or Rh

Alkene is an intermediate

H2 Pt
CH3CH2 CH2CH3

H2/Pd/BaSO4 H3C CH3


H3C C  C CH3 Quinoline C=C
(Lindlar’s catalyst) H H

H3C H
Na, NH3(liq.)
C=C
H CH3

The general case


H H
H2 H2
H3C C  C CH3 C=C CH3CH2 CH2CH3
PVC PVC
H3C CH3

The reaction takes place on the surface of Pt or Pd. Since the addition is twice, it is hard to see the syn addition.
But the reaction can be stopped at the alkene stage by using the following reagents.
(a) H2 + Pd + BasO4 + S or quinoline in boiling xylene (called Lindlar’s catalyst). In this case, reaction proceeds
via syn addition of H2.
(b) H2 + P-2 or Brown catalyst (H2 + Ni + B) or (H2 + Ni2B). It also proceeds via syn addition of H2.
(c) Alkali metals (Na, K, Cs) + liq. NH3 and C2H5 OH (It is called Birch reduction). It proceeds via anti-addition of H2.
(d) LiAlH4(LAH). It reduces (C ≡ C) to (C = C) via anti addition of H2; does not reduce (C = C) to (C — C) bond;
reduces (C=C) to (C —C) only when the phenyl group is attached to the -C atom of the double bond.
β α
(E.g. Ph − CH =CH − CH3 to Ph − CH2 − CH2 − CH3 )

Reduction of alkynes to (Z) – alkenes


Lindlar’s catalyst: Pd, quinoline, Pb and CaCO3 poisons the metal catalyst. So that the H2 adds only to the alkyne.
Not reactive enough for alkenes.
H H
H2
CH3(CH2)2 C  (CH2)2CH3 C=C
Pd/CaCO3/Pb
CH3(CH2)2 (CH2)2CH3
Lindlar catalyst
96% cis
H (CH2)2CH3
Na/NH3
CH3CH2 C  C (CH2)3CH3 C=C
H
CH3CH2
98% trans
H H
H2
CH3(CH2)2 C  (CH2)2CH3 C=C
Pd/CaCO3/Pb
1 1 . 7 0 | Alkenes and Alkynes
CH3(CH2)2 (CH2)2CH3
Lindlar catalyst
96% cis
H (CH2)2CH3
Na/NH3
CH3CH2 C  C (CH2)3CH3 C=C
H
CH3CH2
98% trans
Reduction of alkynes to (E) – alkenes. Reaction via Na radical dissolved in liquid NH3.
Na● + NH3 → Na+ + e– [NH3]n
Solvated electron
−33°C
Mechanism of Na/NH3 reductions: Na+  → Na+ + NH3 (e− )

R R H R H R H
Na H NH2 Na NH2 H
R C C R C C C C C C C C
+ -NaNH2 +
Na R R R H R
NaNH2

4.3 Addition of X2
Like alkenes, 1 mol of alkynes adds 2 moles of halogens and proceeds via anti-addition of halogens, and orange or
brown colour of Br2 is discharged (test for unsaturation)

H
Br
H Br- 2 1
+
HBr
(I) HC CH HC=CH H2C CH
Markovnikov’s
(EA) Br
Br 1,1-Dibromo ethane
or Ethylidene bromide

(II)
Me 4
Mechanism: Me 4 Br
2 1 HBr 2 1 HBr 3 2 1
Like alkenes it proceed
3 via the
H: formation of
Markovnikov’sintermediate
3 cyclic
CH2bromonium ion. First, electrophile
Markovnikov’s
Me (Br ⊕ ) add
Θ
and then the addition of nucleophile (EA)
But-1-yne (Br ) from anti-position
Br take place.(EA)That is whyMethis reaction is called EA
4
(electrophilic addition) reaction. The reaction is stereospecific
2-Bromo(attack by electrophile in a specific
Br manner).
2,2-Dibromo
Anti-Markovnikov’s But-1-ene
HBr+ROOR butane
free radical
H
(Peroxide)
addition H H
Br
Br Br Br
HC CH C=C C = C
R.D.S Br H
Me
Slow4 Br Me 4 1
Br Br
3 2 1 HBr+ROOR 3 2
Br H
Br
Br H Br H Br C—C
H C — C H 1,1-Dibromobutane
Br
1-Bromobut-1-ene Br H
Br (Butylidene bromide)
Br

Cl Cl
CCl4 Cl2/CCl4 - HCl
CHCH + Cl3 CH = CH H-C-C-H Cl2C = CHCl
Ba(OH)2
Cl Cl Cl Cl Trichloroethylene
or
Westron or 1,1,2,2,-tetrachloro or westrosol
BaCl2
ethane or acetylene tetrachloride
Chem i str y | 11.71

4.4 Addition of Water

Hydration of alkynes
O
||
H2O/H2SO 4
H3C − C ≡ C − H →
HgSO
H3 C − C − CH3
4

H H
H +
H2O
H3C– C ≡ C–H H3C– C = C – H H3C– C = C – H
+ –H+
s-viniylcation
OH
H an enal

H3C– C = C – H H3C– C = CH3

O O
H Ketone
enol

(Oxymercuration-demercuriation of triple bond)

Hg2+ OH2
Me – C C–H Me — C = C — H
2+

Hg

H2O Attack of H2O on


more substituted C atom
HO H H3O⊕ HO
C = C C = C H
Me H –Hg2+ Me
Hg
Tautomerise

Me – C – Me

4.5 Addition of HX

H Br Br Br
Br H
CH3 CC H C C C C

CH3 CH2 H3C CH3 CH3 CH3 H3C Br CH3


H
H
Br
H Br- 2 1
+
HBr
(I) HC CH HC=CH H2C CH
Markovnikov’s
(EA) Br
Br 1,1-Dibromo ethane
or Ethylidene bromide

(II)
Me 4 Me 4 Br
2 1 HBr 2 1 HBr 3 2 1
H: CH2 Me
3 Markovnikov’s 3 Markovnikov’s
But-1-yne Br 4
(EA) (EA) Me
2-Bromo Br
2,2-Dibromo
Anti-Markovnikov’s But-1-ene
HBr+ROOR butane
Br
H Br- 2 1
+
HBr
(I) HC CH HC=CH H2C CH
Markovnikov’s
(EA) Br
1 1 . 7 2 | Alkenes and Alkynes
Br 1,1-Dibromo ethane
or Ethylidene bromide

(II)
Me 4 Me 4 Br
2 1 HBr 2 1 HBr 3 2 1
H: CH2 Me
3 Markovnikov’s 3 Markovnikov’s
But-1-yne Br 4
(EA) (EA) Me
2-Bromo Br
2,2-Dibromo
Anti-Markovnikov’s But-1-ene
HBr+ROOR butane
free radical
(Peroxide) Br
addition

4Me Me 4 1
3 Br
2 1 HBr+ROOR 2
3 Br
H
H H
1,1-Dibromobutane
1-Bromobut-1-ene
(Butylidene bromide)

PLANCESS CONCEPTS

The order of reactivity of HX is HI > HBr > HCl > HF


Aishwarya Karnawat (JEE 2012 AIR 839)

4.6 Addition of Acids


Addition of carboxylic acids: When acetylene is passed into warm acetic acid in presence of mercury salts, first
vinyl acetate and then ethylidene diacetate is formed.

Hg2 +
3 CH COOH
HC ≡ CH + CH3COO − H → H2=
C CH − OCOCH3 
→ CH3 − CH(OCOCH3 )2
Acetylene Acetic acid 353K vinyl acetate Hg2 + Ethylidene discetate

Vinyl acetate is used for the manufacture of vinyl resin. Ethylidene diacetate, when heated rapidly to 573-673K,
gives acetic anhydride and acetaldehyde.

OCOCH3 CH3 CO
573-673K O + CH3CHO
CH3 CH
OCOCH3 CH3 CO Acetaldehyde
Ethylidene diacetate Acetic anhydride

4.7 Addition of HCN


The reaction is nucleophilic addition (NA) initiated by CN– from NaCN.
.. HCN
HC CH + CN CH = CH CH2 = CH CN
+H Vinyl cyanide
CN or
Acrylonitrile

4.8 Addition to Other Compounds


CH2 O CH3
H2SO4
HC CH + Conc. H2SO4 CH2 O S OH CH(OSO3H)2
O
Vinyl hydrogen sulphate Ethylidene hydrogen sulphate
Chem i str y | 11.73

CHCl
HOCl CHCl2 -H2O CHCl2
HC CH + HOCl
Hypochlorous CHOH 
CH(OH)2 CH=O
acid 2-chloro Dichloro acetaldehyde
eth-1-en-1-ol or 2,2-Dichloro ehtanal

CH3OH
CH3OK CH2 CH3OK CH3
HC CH + CH3OH
430-470K CH(OCH3)2
CH OCH3
under pressure
Methyl vinyl Ethylidene
ether methoxide

+
Hg
HC CH + Conc. HNO3 CH(NO3)3
oxidative
Nitroform
cleavage

4.9 Ethyne + Methanal


The addition of ethyne to unsaturated link like (>C = O) is called ethinylation. Acetylene or terminal alkyne containing
≡ CH (a methine H-atom) reacts with a carbonyl group (>C = O) in the presence of sodium or potassium alkoxide
(RONa or ROK) or NaNH2 to give alkyndiol with a small amount of alkyneol.
..
CH3O H C CH CH3OH + C CH

.. CH3OH
3 2 1
HC C CH2 = O HC C CH2 O H C C CH2OH
Propargyl alcohol or
Formaldehyde
Prop-2-yn-1-ol

CH3O
..
C C CH3OH

CH2 = O
1 2 3 4
CH3OH
HOCH2 C C CH2OH + CH3O O H2C C C CH2OH
But-2-yn-1,4-diol

4.10 Nucleophilic Addition


Because of the greater electronegativity of the sp-hybridized carbons as compared to sp2 hybridized carbons,
alkynes are more susceptible to nucleophilic addition reactions than alkenes.
For example, when acetylene is passed into methanol at 433-473 K in presence of a small amount (1-2%) of
potassium methoxide under pressure, methyl vinyl ether is formed.

3 CH O−K +
HC ≡ CH + CH3O − H 
→ CH=
2 CH − OCH3
Acety lene Methanol 433− 473K Methyl vinyl ether

CH3O−K +
HC ≡ CH + CH3O − H 
→ CH=
2 CH − OCH3
Acety lene Methanol 433− 473K Methyl vinyl ether

Methyl vinyl ether is used for making polyvinyl ether plastics.


1 1 . 7 4 | Alkenes and Alkynes

4.11 Propargylic Halogenation


Alkenes undergo allylic substitution with NBS, whereas alkynes undergo propargylic halogenation with NBS, Cl2SO2
(sulfuryl chloride). Me3COCl(t-butyl hypchlorite), and Cl2 at 500°C.
O

4Me NBS+CCl4 4Me 2 1


2 1 3
H H + N-H
3 +h
But-1-yne Br
3-Bromo but-1-yne O

Propargylic
H-atom O-Cl 4Me
3 2 1 OH
H +
+CCl4 + h
Cl
3-Chlorobut-1-yne

Reaction proceeds via free radical mechanism to give propargylic radical, which is stabilized by resonance via
extended π-bonding.

4.12 Hydroxylation of Alkynes


Hydroxylation of alkyne with aqueous or neutral KMnO4 solution (Baeyer’s reagent) test for unsaturation)
Pink colour of KMnO4 is discharged and brown black precipitate of MnO2 is obtained. This reaction converts alkynes
first to enediols and then further gives tetraols, which being unstable lose H2O to give diketones.

OH OH
1 2 3 4 aq. KMnO4 1 2 3 4 OH (But-2-en 2,3 diol)
Me C C Me Me C C Me
OH
OH OH
But-2-yne aq. KMnO4

1 2 3 4 Me Me
Me C C Me -2H2O
HO C C OH
O O
Butan 2,3 dione
OH O H
Unstable

Me C C Me Me C C Me
OO
(Break two bonds and add O O
O atom on both sides)

OH
1 OH
OH 3
OH aq. KMnO4 H
2 H 2 1
3
OO 4
O O
But-1-en-3-yne
3,4-Dihydroxy-2-oxo
butan-1-al
Chem i str y | 11.75

4.13 Oxidation Reactions

4.13.1 Oxidative Cleavage


(a) Alkynes are oxidatively cleaved in alkaline or acidic conditions at higher temperature, as mentioned.

R C R COOH

H C [H COOH] CO2

1
Me 3
(i) 6 Me 3
2 3 4 7 [O] 1 1 4
C C
5 Me 2 COOH + HOOC 2 Me
Hept-3-yne Propanoic Butanoic
acid acid
(ii) Me Me
3
3 2 1 [O] 1
C C H 2 COOH+[HCOOH]

But-1-yne Propanoic
acid CO2
6 3
(iii) Me Me
5 4 3 2 1 [O] 2 1
C C C C Me COOH + [HOOC COOH]
Oxalic acid
Hexa-2,4-diyne Propanoic
acid
+HOOC-Me 2CO2
Ethanoic
acid

CrO3 in CH3COOH oxidizes alkenes but does not affect alkynes

4.14 Ozonolysis of Alkynes


Alkyne form ozonides with O3 and are decomposed by H2O to give diketones, which are then oxidised by H2O2 or
KMnO4/NaIO4 or peracids; given acids, and on reduction with metal / acid, LAH, or NaBH4 give diols.
O

(i) HC CH + O3 H C C H

O O

H2O

H2C CH2 Reduction


H C C H + H2O2
Zn+CH3COOH
OH OH or O O

 
or HO OH
OH LAH or NaBH4
HO Glyoxal
Glycol H2O2
[O]
2CO2 2HCOOH
Formic or
methanoic acid
1 1 . 7 6 | Alkenes and Alkynes

Terminal alkynes give HCOOH as one of the products which is further oxidized to CO2
These oxidative cleavage reactions are rarely used for synthesis because alkynes are not readily available. They are
used to locate the position of a triple bond in an alkyne.

4.15 Hydroboration of Alkynes


•• Terminal alkynes of HBO reaction give aldehyde, whereas internal alkynes give ketone.

•• Alkynes react with BH3 or B2H6 complexed with THF (tetrahydrofuran O) to give trivinyl borane, which upon

subsequent treatment with alkaline H2O2 gives alcohols corresponding to anti-Markovnikov’s addition of H2O
to alkynes, which on tautomerisation give corresponding aldehydes or Ketones.
•• If trivinyl borane is treated with acid(CH3COOH), it gives cis-alkene (proceeds via syn-addition of H2).

Me

3Me CC Me 3BH3+THF Me C=C B


But-2-yne
H
n
itio
n - add
Sy H H2O2/OH
COO
CH 3
4 1
Me
Me Me
3 2
C=C Me CH=C

H H OH
Z-But-2-ene

Tautomerise

4 1 2 1
Me CH2 C Me

O
Butan-2-one

4.16 Polymerisation

1. Linear Polymerisation

 
1
Cu2Cl2 2 3 4 1 2
HC CH + HC CH CH CH + 3 4 5 6
NH4Cl or CH2 = CH C C CH = CH2
1 2 3 4 Cu2Cl2 + NH4Cl or
Cu +O2
2+ 1 6
CH2 = CH C CH 23 4 5
Vinyl acetylene
H C C C C H
But-1-en-3-yne
But-1,3-dyne Divinyl acetylene or
1mol 1mol Hexa-1,5-dien-3-yne
HCl HCl

 
Cl
Cl
H2 + Ni2B 4 3 2 1 Peroxide/h
HC C C = CH2 CH2 = CH C = CH2
Polymerisation CH2 CH = C CH2
n

Cl
Chloroprene or Neoprene or
2-Chloro-buta-1,3-diene Polycholoropene
Chem i str y | 11.77

2. Cyclic Polymerisation
CH CH 1 2
CH
8 3
CH CH CH CH
Red hot tube Ni(CN)4
or 3 (HC CH) or 4 (HC CH) 4
or THF 7
CH CH CH CH
Hot copper 6 5
Benzene CH CH
HC Cycloocta
1,3,5,7 tetra-ene
Me
3. Propyne Me
CH
CH CH
or 3 (Me C CH) Red hot tube
Me CH C Me
Me Me
HC 1,3,5-Trimethyl benzene or Mesitylene

4.17 Isomerization
When alkynes are heated with NaNH2 in an inert solvent such as kerosene oil or paraffin oil, they undergo
isomerization. i.e. 2-alkynes isomerize to 1-alkynes and vice versa.

Uses of alkynes
(i) Acetylene and its derivatives are widely used in synthetic organic chemistry for synthesis of cis-and trans-
alkenes, methyl ketones etc.
(ii) Oxyacetylene flame is used for cutting and welding of metals.
(iii) Acetylene is used as illuminant in hawker’s lamp and in light houses.
(iv) Acetylene is used for the ripening of fruits and vegetables.
(v) Acetylene is used for manufacture of ethyl alcohol, acetaldehyde, acetic acid, vinyl plastics, synthetic rubbers
such as Buna N and synthetic fibers such as Orlon.

PLANCESS CONCEPTS

Difference between Alkenes and Alkynes

Test Alkene Alkyne


1. Flame observed on comnustion Luminous Smoky
2. Br2/CCl4 solution Orange colour is discharged Orange colour is discharged
3. Cold aq. or alkaline KMnO4 Pink colour is discharged with the Pink colour is discharged with the
solution (Baeyer's reagent) formation of diol compound formation of dicarbonyl compound
4. Ammoniacal AgNO3 solution No action Whote ppt. of silver alkynide (given
[Ag(NH3)2]+ (Tollens reagent) by only terminal alkynes)
5. Ammoniacal CuCl solution No action Red ppt. of copper acetylide (given
by only terminal alkynes)
6. Reactivity towards electrophilic Alkenes are more reactive than alkynes
addition reaction (e.g. HX, X2)
7. Reactivity towards cataytic Alkynes are more reactive than alkenes
8. Reactivity towards nuclephilic Alkynes are more reactive than alkenes
addition reaction (e.g. CN+)
1 1 . 7 8 | Alkenes and Alkynes

POINTS TO REMEMBER

H
HX
C-C
X
H
HBr
C-C
(Peroxides)
Halogenation Br
Reaction H
X2
C-C
X
H
X2/H2O(”HOX”)
C-C
(NBS, H2O/DMSO)
X

H OH Anti-Markovikov
1. BH3, THF
+ C-C regiochemistry
2. H2O2, HO Syn addition
H OH
Syn 1. OsO4
C-C Syn addition
addition 2. NaHSO2, H2O

+
HO OH
KMnO4, HO /H2O
C-C Syn addition
Hydroxylation

C=C
+
H Markovnikov
H /H2O regiochemistry
C-C
OH Carbocation
Anti intermolecular
addition H
1. Hg(OAC)2, H2O Markovnikov
C-C regiochemistry
2. NaBH4
OH

H H
H2, Pt
Reduction C-C Syn addition

Cl Cl
Dichloro methylene insertion C
CHCl3, KOH
C C
Ring forming
Reaction
H H

Methylene insertion C
CH2I2, ZN(Cu), ether
C C
Chem i str y | 11.79

X H
2 HX
R C-C H Markovnikov
regiochemistry
Halogenation X H
Reaction X H
2 HX2 X
R C-C
X X

H H
Complete reduction
R C-C H
H2, Pt
H H
Reduction
H H
H2, Lindlar catalyst
C=C Syn addition
R H
Partial
reduction
H H
Li, NH3 (liq.)
C=C Anti addition
R H

R C C H

O H
+ Markovnikov
H /H2O
C-C H regiochemistry
HgSO4
Carbonyl R H Enol intermediate
compound
forming reaction H O Anti-Markovnikov
1. BH3, THF C-C regiochemistry
+ R
2. H2O2, HO Enol intermediate
H H

Chain
NaNH2
lengthening R - C  C - CH2 - R Alkyne anion intermediate
RCH2Br
reaction

[O]
RCOOH + CO2
Alkaline or
Acidic condition
Oxidation

1. O3
+ R - CH - CH2 + CO2
2. Zn, H3O
OH OH
1 1 . 8 0 | Alkenes and Alkynes

Solved Examples

JEE Main/Boards
Example 1: Identify A to C.

2Na Na+NH3+EtOH
HC CH (A) (B)
2CO2/H3O H2/Pd/CaCO3
(C)

Sol: It is an example of ethinylation (addition of ethyne to unsaturated link like C group).


First step is the reaction with the sodium metal to form disodium acetylide with evolution of hydrogen gas.
This reaction shows the acidic character of alkynes.
During this step acetylenic hydrogens are removed as a proton to form stable carbanion.
Now the carbanion reacts with two moles of carbon dioxide and forms an adduct which on treatment with acid
yields acid.
Next step is reduction using Lindlar Catalyst (H2/Pd-CaCO3) the addition is syn.
On treatment with (NH3+EtOH) trans product is formed thus the addition is anti.

O O
2Na
H C CH Na C C Na OO C C C C O
O C
O
O C

H3O
1 4
COOH
HOOC 2 3 HOOC H
H2/Pd/CaCO3 1 2 3 4 Na + NH3 + EtOH 23
Syn-additon
HOOC COOH Anti- addition
H H (A) H COOH
(C) But-2-yn-1,4-dioic acid
Maleic acid or Fumaric acid (B) or
cis-But-2-en-1,4-dioic acid trans-But-2-en-1,4-dioic acid

Example 2: Identify B to G.
2
1 3 Br2 1. NaNH2
Me (B) (C)
2. H2O
Propene
NBS + CCl4 + h
(A)
Cl2+ 500oC (D)
1. Li (D)
(E) 2. Cul (F) (G)

Sol:
•• Addition of Br2 across double bond forms 1,2-dibromo propane.
•• This on treatment with soda lime undergoes double dehalogenation to form an alkyne
•• Now alkyne on the treatment with a brominating agent (NBS- N-Bromosuccinimide) and CCl4 as a solvent in
presence of light.
•• On the other side, the first step is Allylic chlorination using Cl2 at 500 ◦C.
Chem i str y | 11.81

•• The reaction proceeds through radical formation.


•• Now Allyl chloride undergoes chain lengthening reaction to form Hex-1-en-5-yne.
•• The reaction is known as Corey house synthesis

Br
2 3 Br2 3 2
1 Me 1 1. NaNH2
Me Me C CH
2. H2O
(A) Br
(B) (C)
1,2-Dibromopropane Prop-1-yne

o
Cl2 at 500 C Propar-
Allylic gylic NBS + CCl4 + h
radical radical
chlorination brominating

2 3 3 2 1
Cl H
1 Br

 
(E) (D)

 
Allyl chloride 3-Bromoprop-1-yne
or or
3-Chloro prop-1-ene propargylic
bromide
Coerey 1. Li
-House 2. Cul
R’

 1
2 3

2
CuLi

Br
3 2 1
H
2 4 5 6
1 3
(F) (D)
Diallyl lithium R R’
cuperate
(G)
Hex-1-en-5-yne

Example 3: Alkenes are more reactive than alkynes towards electrophilic addition reaction, yet vinyl acetylene
reacts with 1 mole of HBr at triple bond. Explain why.

Sol:
•• Alkynes are less stable than isomeric diene.
•• Compound (A) is a conjugate diene whereas compound (B) is an alkyne.
•• As heat of formation of diene is less than the heat of formation of alkyne, Vinyl acetate reacts with 1 mole of
HBr to form a conjugate diene and formation of compound (B) is not favoured.
Br
4 3 2 1 HBr
CH3 CH C CH H2 C CH C CH H2C CH C CH2
4 3 2 1
Br Vinyl acetylene
3-Bromobut-1-yne 2-Bromobut-1,3-diene
(B) (A)

The product A (Conjugated diene) is more stable than B (an alkyne)


1 1 . 8 2 | Alkenes and Alkynes

Example 4: There are two path (a) and (b) For the preparation of a compound (a)
 1 2 3

Me
=
4 5
Me

(2-methylpent-1-en-3-yne), which path is correct and why? Also name the paths (a) and (b). Path (a)

Sol: Path (b) is correct because in path (a) compound

does not occur.


 
Me

Br
vinyl halide which is not reactive, so the reaction

Path (a) is the alkylation of alkyne, whereas path (b) is propinylation (type of ethinylation), i.e., addition of propyne
to unsaturated link like (> C = O) group.
Me

Br Path (a)
H Me NaC Me Me
Me Me
Path (b) O + H2 O (A)
Me
Me
Conc. H2SO4+ 
Me
Me -H2O
OH

JEE Advanced/Boards
Example 1: Complete the following missing reagents

C CH

(A)
?
(a)

(B)
Br
?
(b)  (C)
2 CuLi
?
(c)

(D)
Br
?
?
(e) (d)
Br
(F) (E)

Sol: (i)
(a) HBr + Peroxide
First step is addition of HBr, it takes place according to Markovnikov’s rule.
(b) (1) Li (2) CuI (Corey – House): Second step is Corey House synthesis.

(c) Br Third step is the reaction with alkyl halide.

(d) Br2/CCl4
Bromination using Br2 and CCl4 as a solvent
(e) KOH(s), at 473 K
Last step is double dehalogenation using base like KOH at 473 K
Chem i str y | 11.83

(ii) Cis compound on addition with Br2 (Anti addition) forms a racemic mixture or enantiomer.
Trans compound on addition with Br2 (Anti addition) produces Meso compound (it contains plane of
symmetry)

H H
H
and
H

cis trans

  
Br2(Anti-addition) Br2(Anti-addition)
racemic or (+) (E) meso and (E)

H Br
H Br H Br
+ Enantiomer
Br H

Due to the plane of


symmetry

Example 2: Convert the following

? ? ?
(B) C Cl
(a) (b) (c)
(D)

 
? (G)

Cl (d) CuLi H
2
(E) (F)
(H)

Sol:
Cl Allylic
Cl2 alc. KOH chlorination
(a) Cl
+ h
(b) (SO2Cl2 + )
(a) (B) (c )
(A) or (D)
( O Cl + (

Cl

 
1 2 2
1. Li 3 Me
(D) 3 H
2. Cul
Cl (d) CuLi
2
(b) (E) (F) Less stable More stable
Vinyl Divinyl
isolable diene conjugated diene
chloride lithium
(G) (H)
cuperate
3-Ethenyl cyclo 3-Ethylidene cyclo
pent-1-ene pent-1-ene
1 1 . 8 4 | Alkenes and Alkynes

Example 3: Convert the following.

2 Br ?
3 (B) ? (C) ? (D) ? Hept-2-yne
Me 1
(E)
Write the structure of (E).

Sol: The structure of E is

7
Me 5
3 2 1
Me
6 4
First prepare 3C – atom alkyne (Me − C ≡ C − H) from (A) and then react 4C – atom RX with alkynide ion to get (E).

Reaction:
Br
2 Br alc.KOH Br2 2
3 3 1
Me 1 (B) Me
Propyne (C) Br
(A)
1,2-Dibromopropane

2NaNH2
Double dehalogenation
Me H
Propene
2NaNH2
3 1
4
Me 2 Br 7
1 2 3 5 Me
Butyl bromide 4
Me C C Me C C
6
Propynide ion Hept-2-yne
(D) (E)

Example 4: Complete the following:

1 mol C2H5Br NaNH2 CH3I


HC CH B C D (E)
NaNH2
Ethyne
(A)
Sol:

1 mol C2H5Br 1 2 4
HC CH HC CNa HC C C C2H5
NaNH2
(A) Sodium ethynide But-1-yne
(B) (C)

NaNH2
CH3I
CH3 C C C2H5 NaC C C2H5
(E) (D)
Pent-2-yne Sodium butynide

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