Addition reactions of Alkenes: Following are addition reactions shown by alkenes.

(a)

Addiion of H2 or hydrogenation :

(i)

The mechanism reveals the free radical addition. The process is used to obtained vegetable ghee from hydrogenation of oil.

CH2=CH2 + H2

CH3CH3

(ii) In presence of Ni as catalyst, reaction occurs at 200300oC whereas in presence of Pt or Pd, the hydrogenation of alkenes takes place even at room temperature.

(iii) Hydrogenation of alkene is exothermic in nature. The heat of hydrogenation for alkenes are nearly 30 kcal/mol and their value is most commonly used as a scale for the stability of alkene. The lower the heat of hydrogenation of an alkene, the more is stability e.g. trans-2-butene (Hh = 27.6 k cal/mol) is more stable then cis-2-butene (Hh = 28.6 k cal/mol) and 1-butene (Hh = 30.3 kcal/mol)

(b)

Addition of halogens :

(i)

Addition of CI2 on alkene is free radical addition, whereas addition of Br2 sows electrophilic addition.

CH2=CH2 + CI2 CH2CICHCI

CH2=CH2 + Br2 (in solvent) CH2BrCH2Br

The mechanism

Br |

CH2=CH2 CH2=CH2 CH2+ CH2 Br | Br Br+ | Br Br+ | Br

CH2+ CH2 | Br |

CH2 CH2

Br

(ii)

The reactivity order of halogens : CI2 > Br2 > I2

(iii) The addition of Br2 on alkenes provide a useful test for unsaturation in molecule. The brown colour of the bromine being rapidly discharged. Thus decolorization of 5% Br2 in CCI4 by a compound suggests unsaturation in it.

(iv)

Additionof bromine on ethylene in aqueous sodium chloride solution gives ethylene dibromide and 1-bromo, 2-chloroethane.

CH2=CH2 + Br2

BrCH2CH2Br + BrCH2CH2CI

Similarly

BrCH2CH2Br + BrCH2CH2I

CH2=CH2 + Br2

BrCH2CH2Br + BrCH2CH2ONO2

(c)

Addition of halogen acids :

(i)

Electrophilic addition

(ii)

e.g.

CH2=CH2 + HX CH3CH2X

(iii)

The reactivity order for halogen acids is:

HI > HBr > HCI > HF

(iv)

Follow mechanism of reaction & Markownikoff rule in chapter 1.

(d)

Addition of hypohalous acids :

(i)

Electrophilic addition

(ii)

The reactivity order for oxyacids is:

HOCI > HOBr > HOI

CH2=CH2 + HOX CH2OH CH2X (ethylene halo hydrin)

(iii)

In place of HOX, (halogen + water) may be used to get above reaction.

(iv)

For addition of HOX on unsymmetrical alkene Markownikoff rule is followed.

CH3CH=CH2 + HO X+ CH3CHOHCH2X

(e)

Addition of H2O :

(i)

Alkenes show addition of H2SO4 which on hydrolysis yield alcohols.

CH2=CH2 + H2SO4 CH3CH2HSO4

CH3CHOHCH3

(ii) This too is electrophilic & addition on unsymmetrical alkenes obeys Markownikoff rule.

(iii)

The reaction is used to separate alkenes from a mixture of alkane and alkenes.

CH3CH=CH2

CH3CHCH3 | HSO4

CH3CHOHCH3

Note : (i) Alkene1 on addition of H2O gives alkanol2. To obtain alkanol1, its reaction with H2O2 is made.

hydroboration of alkene1 followed with

6RCH=CH2+B2H62(RCH2CH2)3B

6RCH2CH2OH+2H3BO3

(ii)

Alkene1 may also be converted to alkanol1 as:

RCH=CH2+HBr
Kharasch effect

RCH2CH2Br

RCH2CH2OH

(f)

Addition of NOCI :

CH2 = CH2 + NO+ CI CH2CICH2NO ethylene nitrosochloride

Note :

The addition of NOCI on alkene gives

. This product is stable only when the carbon atom bearing.

NO group does not contain hydrogen e.g.

. If H atom is present on the carbon atom, the product.

Undergoes rearrangement to form more stable oxime.

(g)

Addition of O2 :

Alkane epoxides are cyclic ethers which on hydrolysis give diols or glycols.

(h)

Addition of HNO3 :

CH2=CH2 + HO NO2 HOCH2 CH2NO2

(fuming) 2nitroethanol

(i)

Addition of Acetyl Chloride :

CH2=CH2 + CH3COCI

CH2CI CH2COCH3

4chlorobutan-2-one or methyl-chloroethyl ketones

(j)

Addition of isoalkanes or alkylation :

(k)

Polymerization :

(i) self addition.

Alkenes on heating in presence of catalyst (O2, HF or peroxides) at high P

undergo addition polymerization i.e.

(ii)

Polymerization is reversible reaction and the strength of polymer depends upon experimental conditions.

Note :

The derivatives of alkenes of the type CH2=CHX (where X may be halogen, N, OH etc.) also undergo polymerization to

form useful polymers such as poly vinyl cyanide

, polyvinyl chloride

and polyvinyl alcohol

Fundamentals of Alkynes or Acetylenes

(i)

Alkynes have the general formula CnH2n2 & have one triple bond. i.e. acetylenic bond

e.g.

C2H2 acetylene or ethyne

C3H4 allylene or propyne

C4H6 butyne

(ii)

Acetlyenes are highly reactive and thus do not exist freely in nature.

(iii)

Carbon atoms involved in triple bond are sp hybridized having linear nature with an angle of 180o.

CHCH 2 2 sp sp

CH3CCH 4 sp3 2 2 sp sp

The linear structure of CC has been described below, e.g. C2H2

(iv)

Alkynes have the following characteristic bond lengths and bond energy.

CC spsp Bond length Bond energy 1.20 A 192 kcal mol1

CH sp1s 1.08 A 102.38 kcal mol1

(v) In acetylene the CC involves one bond formed by head on overlapping of sp-sp orbital as well as two bonds formed by lateral overlapping of pp orbitals.

(vi)

The comparative chart of bond energy and bond length of alkane, alkene and alkyne is given below :

Alkane

Bond CC CH C==C CH CC CH

Hybridized bond orbitals sp3sp3 sp31s sp2sp2 sp21s spsp sp1s

Bond length 1.54 A 1.112 A 1.34 A 1.108 A 1.20 A 1.08 A

Bond energy 82.76 kcal mol1 98.67 kcal mol1 143.1 kcal mol1 98.69 kcal mol1 192.00 kcal mol1 102.38 kcal mol1

Alkene

Alkyne

(vii)

Some important orders for alkanes, alkenes and alkynes are given below:

Bond length

CC > C=C > CC

Bond energy

CC < C=C < CC

Stability of bond

CC < C=C < CC

Reactivity of bond

CC < C=C < CC

Rigidity in bond

CC < C=C < CC

The more reactivity of CC inspite of higher bond energy is due to the presence of p bonds.

(viii) Acetylene and all terminal alkynes are acidic in nature i.e. H atom attached on triple bonded C atom behaves as acidic. The acidic character is due to the fact that in acetylene or triply bonded C atom, an increase in s character (sp hybridization) give rise to higher electronegativity to C atom and thus H atom in CH (i.e. sp1s) bond acquires more polarity to show acidic nature.

The acidic nature order however shows

H2O > C2H2 > C2H4 > C2H6

(ix) Furthermore, a decreasing trend of bond lengths (in CC & CH bonds) from alkane to alkyne can also be explained due to increasing s character from alkane to alkyne which leads to smaller size of hybrid orbitals and therefore showing more tendency for overlapping leading to smaller bond lengths.

(x) IUPAC Nomenclature : The IUPAC name is derived from the IUPAC name of alkanes by replacing ending ane by yne alongwith the position of triple bond e.g. Alkaneane + yne = Alkyne

CH3CH2CCH but-1-yne

(xi) Alkynyl groups : Residual part left after the removal of one H atom from alkyne is known as alkynyl group. According to IUPAC nomenclature, these groups are named by replacing terminal (e) of alkyne by yl e.g.

HCC

ethynyl

HCCCH2

2-propynyl

CCCH3

1-propynyl

Isomerism : Ethyne does not show isomerism. Higher alkynes show following types of isomerism chain position and functional isomerism. C3H4 : (a) CH3CCH propyne (b) CH2=C=CH2 allene

C4H6 : (a)

CH3CH2CCH but-1-yne

(b)

CH3CCCH3 but-2-yne

(c)

CH3HC=C=CH2 buta-1, 2-diene

(d)

CH2=CHCH=CH2 buta-1, 3-diene (a) & (c) are functional isomers. (c) CH3CHCCH | CH3

(a) & (b) ; (c) & (d) are position isomers C5H8 : (a) CH3CH2CH2CC (b) CH3CH2CC

(d)

CH3CH2CH=C=CH2

(e)

CH2=CHCH=CHCH3 (f) CH2=CCH=CH2 | CH3

(a) & (b) are position isomers; (a) & (c) are chain isomers, (a) & (d) are functional isomers.

General methods of preparation of alkenes

(i)

By cracking :

CH3CH2CH3

C2H4 + CH4

(ii)

By dehydration of alcohols :

(a) Removal of H2O from a substrate molecule by a suitable dehydrating agent e.g. conc. H2SO4, AI2O3, H3PO4, P2O5. Some other dehydrating agents are KHSO4, BF3, dry HCI, CaCI2 etc.

(b)

This involves elimination.

(c)

e.g.

RCH = CH2

RCH2CH2OH

RCH=CH2

RCH = CH2

CH3CH2CHCH3 | OH (d)

CH3CH=CHCH3 + CH3CH2CH=CH2 Major Minor (Cf. Saytzeff rule)

The case of dehydration shows the order : tertiary > secondary > primary alcohols.

(iii)

By dehydrohalogenation of monohalides:

(a)

Removal of HX from a substrate by alcoholic KOH or NaNH2

(b)

This too is elimination

(c)

RCH2CH2X

RCH=CH2

CH3CH2CHCH3 | X (d)

CH3CH = CHCH3 + CH3CH2CH=CH2 Major Minor (Cf. Saytzeff rule)

The case of dehydrohalogenation shows the order:

For alkyl halides: tertiary > secondary > primary alkyl halides

For halogens in halides : iodide > bromide > chloride

(iv)

By halogenations of dihalides:

(a)

Removal of X2 from a substrate Zn dust/CH3OH or ZnCu couple in alcoholic solution.

(b)

e.g.

CH3CHX2
gem dihalide

CH2=CH2

CH2XCH2X
vicinal dihalide

CH2=CH2

Note : Metallic sodium can also be used in place of zinc.

(v)

By Kolbes electrolysis :

(a)

Electrolysis of aqueous solutions of sodium or potassium salts of saturated dicarboxylic acids gives alkene.

(vi)

By partial hydrogenation of alkynes:

(a)

Hydrogenation of alkynes in presence of Lindlar catalyst gives alkenes.

CHCH

CH2=CH2

RCCH

RCH=CH2

(b)

Lindlar catalyst is Pd on CaCO3 deactivated by lead acetate which prevents further hydrogenation.

(c)

Use of Pd or Pd-charcoal poisoned by BaSO4 and quinoline give better results. (Cram et. Al)

(vii)

By heating quaternary ammonium compounds :

(viii)

By Grignard reagents :

(ix)

Action of Copper alkyl on Vinyl Chlorides : Vinyl chloride on alkylation with copper alkyl form higher alkenes.

2H2C = CHCI

2H2C=CHR + CuCI2
alkene

2H2C = CHCI
propene

2H2C=CHR + CuCI2

Following are the miscellaneous reactions of alkenes:

1.Isomerization

(i)

Alkenes on heating to 500 to 700oC or on heating in presence of catalyst {AICI3 or AI2(SO4)3} undergo isomerization.

(ii)

The isomerisation involves migration of olefinic bond or alkyl group.

CH3CH2CH = CH2
butene-1 butene-2

CH3CH=CHCH3 or (CH3)2C=CH2
isobutene

2.

Allylic substitution

(i)

The alkyl group of the alkene (except C2H4) undergoes substitution at high temperature in presence of CI2 or Br2.

(ii)

It is free radical substitution

(iii)

The substitution occurs at acarbon to the double bond.

CH3CH=CH2 + CI2

CH3CICH=CH2 + HCI

CH3CH2CH=CH2 + CI2

CH3CHCICH = CH2 + HCI

Note :

At normal temperature halogens show addition reactions with alkenes.

3.

Wohl-Ziegler bromination. (Allylic bromination with NBS)

4.

Oxy-mercuration-demercuration

This method involves synthesis of alcohols from alkenes. Here addition occurs according to Markownikoffs rule

Uses :

(i)

In plastic formation i.e., polyethene, polypropene etc. and synthetic rubber formation.

(ii)

In oxy-ethylene welding.

(iii)

As food preservatives (C2H4) and ripening of fruits.

(iv)

As general anaesthetic (C2H4 with 10% O2)

(v) In preparation of mustard gas An oily liquid having high vaporizing tendency. Its vapours have high penetrating power and penetrate even thick boots and causes painful blisters on skin as well as inside the body, causing death ultimately. It was used I world war.

CH2 || CH2
sulphur monochloride

CH2 + S2CI2 + || CH2

mustard gas or

CH2CI |

CH2CI | + S

CH2SCH2

Ozonolysis of alkenes : A test for unsaturation in molecule.

(a) On passing ozone through a solution of alkenes in inert solvent i.e. CHCI3 or CCI4 or ether, addition of ozone takes place round double bond of alkene to form ozonides.

(b) The mono ozonides are highly explosive in nature and are generally decomposed during hydrolysis or by reduction with hydrogen in presence of catalyst to give two molecules of carbonyl compounds.

(c) The complete process of ozonide formation (step a) and then their decomposition to give carbonyl compounds (step b) is known as ozonolysis.

(d) The ozonolysis thus involves the replacement of an olefinic bond C=C by two carbonyl groups C =O. The total number of carbon atoms in two carbonyl compound is equal to total number of carbon atoms in alkene.

(e) The ozonolysis is used to detect the position and nature of unsaturation in a molecule. For this purpose first ozonides are formed. The solution is evaporated to get the ozonides as viscous oil which are then either hydrolysed directly with water using Zn dust as reducing agent or reduced by H2 is presence of Pd or Pt. The Zn dust used during hydrolysis checks the formation of H2O2 which can otherwise oxidize the products (carbonyl compounds) to respective acids. Identification of aldehydes & ketones formed during ozonolysis suggests the nature & position of unsaturation in molecule.

(f)

A symmetrical alkene give rise to two molecules of same carbonyl compound.

(h)

(i)

An alkene of the type RCH=CHR gives two aldehydes RCHO & RCHO

(ii)

An alkene of the type R2C = CHR gives R2C = O + RCHO

(iii)

An alkene of the type R2C=CR2 gives ketones only R2C=O&R2C=O

(i)

Reduction of ozonide can also be made by Zn/Acid, H2-Raney Ni or triphenyl phosphine to carbonyl compounds.

(j)

Reduction of ozonide by LiAIH4 or sodium borohydride gives corresponding alcohols.