9.

Alkenes
Alkenes are unsaturated hydrocarbons
H C H C H H
H H C H C H C H H

general formula is CnH2n

contain a carbon-carbon double bond somewhere in their structure

Ethene

Propene

The arrangement of bonds around the >C=C< is planar and has the bond angle 120o
H H C H C H C H H

Numbers need to be added to the name when positional isomers can occur

But-1-ene

C H

But-2-ene

Stereoisomerism Stereoisomers have the same structural formulae but have a different spatial arrangement of atoms E-Z isomers exist due to restricted rotation about the C=C bond Single carbon-carbon covalent bonds can easily rotate alkenes can exhibit a type of isomerism called E-Z stereoisomerism

H H C H H H C C

H H C H

two different groups attached either end of the restricted double bond- leads to EZ isomers

Z- but-2-ene
H H C H C H H H C H C H

These are two isomers as the lack of rotation around the double bonds means one cannot be switched to the other

Priority group side 1

Priority group side 2 Z-1,2-dichloroethene E-1,2-dichloroethene

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)!edis etisoppE ehT( negegtne namreg eht morf E dellebal si ti dnob elbuod eht fo edis etisoppo eht no si mota ytiroirp eht fI

If the priority atom is on the same side of the double bond it is labelled Z from the german zusammen (The Zame Zide!)

dnob elbuod detcirtser smota/spuorg tnereff d owt eht fo sdne htob dehcatta smota/spuorg tnereffiid owt era erehT )b( smota/spuorg tnereffiid owt smota/spuorg tnereff d owt no tator detc rtser .dnob elbuod C=C eht dnuora noiitator detciirtser si erehT )a( noiitator detciirtser no tator detc rtser :nehw esira sremosioerets Z-E

But-1-ene is a structural isomer of But-2ene but does not show E-Z isomerism Naming E-Z stereoisomers On both sides of the double bond determine the priority group

mota ytiroirp eht sa dessalc si A reggib eht htiw mota ehT :puorG YTIROIRP

selliihportcelle se hportce e .selliihportcelle dellac era seiceps se hportce e eseht :snortcele ekil hcihw seiceps yb kcatta ot elbarenluv erofereht era yehT

C=C double covalent bond consists of one sigma () bond and one pi () bond.

yt sned nortce e .ytiisned nortcelle ytiisned nortcelle yt sned nortce e hgiih hg h desopxe desopxe hgiih evah dna desopxe era sdnob hg h desopxe
H H C H C C H H H C H H

But-1-ene

two identical groups attached to one end of the restricted double bond no E-Z isomers

ene-2-tub- E ene-2-tub- E ene-2-tub- E

Electrophilic Addition Reactions of Alkenes Electrophiles: electron pair acceptor The double bonds in alkenes are areas with high electron density. This attracts electrophiles and the alkenes undergo addition reactions 1. Reaction of bromine with alkenes
H
H C H C H H

Addition reaction: a reaction where two molecules react together to produce one

H C Br H

As the Br2 molecule approaches the alkene, the pi bond electrons repel the electron pair in the Br-Br bond. This INDUCES a DIPOLE. Br2 becomes polar and ELECTROPHILIC (Br+).

2. Reaction of hydrogen bromide with alkenes

H H C H C H C H H C H H + HBr
H H C H H C H H C Br H C H H

This reaction can lead to two products when the alkene is unsymmetrical

If the alkene is unsymmetrical, addition of hydrogen bromide can lead to two isomeric products.

Minor product

Markownikoffs Rule In most cases, bromine will be added to the carbon with the fewest hydrogens attached to it

WHY?
This carbocation intermediate is more stable because the methyl groups on either side H of the positive carbon are electron releasing and reduce the charge on the ion which stabilises it.
H C H H C + H C H H

In electrophilic addition to alkenes, the major product is formed via the more stable carbocation intermediate.
In exam answers Draw out both carbocations and identify as primary, secondary and tertiary State which is the more stable carbocation e.g. secondary more stable than primary State that the more stable carbocation is stabilised because the methyl groups on either (or one) side of the positive carbon are electron releasing and reduce the charge on the ion. (If both carbocations are secondary then both will be equally stable and a 50/50 split will be achieved)

The order of stability for carbocations is tertiary > secondary >primary

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enatubomorb-2

%09 tcudorp rojaM

%01

ene-2-tuB

enahteomorbiid-2,1 enahteomorb d-2,1 enahteomorbiid-2,1 enahteomorb d-2,1

enaklaolah enak ao ah enakllaollah

enaklaolahid

tnegaer fo epyT tnegaer fo epyT rB ,elihportcelE :tnegaer fo epyT tnegaer fo epyT msiinahceM ms nahceM noitiddA cilihportcelE :msiinahceM ms nahceM snoitidnoC )thgil VU ni ton( erutarepmet mooR :snoitidnoC enimorB :tnegaeR enekla :puorg lanoitcnuf ni egnahC tnegaer fo epyT tnegaer fo epyT H ,elihportcelE :tnegaer fo epyT tnegaer fo epyT noitiddA cilihportcelE :msinahceM erutarepmet mooR :snoitidnoC rBH ro lCH :tnegaeR enekla :puorg lanoitcnuf ni egnahC enek a :puorg ano tcnuf n egnahC eneklla :puorg llanoiitcnuf nii egnahC

+ Br2

C Br

The INTERMEDIATE formed, which has a positive charge on a carbon atom is called a CARBOCATION

.dnob ip hcir-nortcele eht ot detcartta si + H ehT .H naht evitagenortcele erom si rB esuaceb elucelom ralop a si rBH

3. Reaction of sulphuric acid with alkenes

CH2=CH2 + H2SO4

CH3CH2OSO2OH

Stage 1: electrophilic addition H2SO4 is best drawn as

Stage 2: hydrolysis

With unsymmetrical alkenes a minor and major product can also be formed similar to the addition of HBr. The same explanation applies Direct Industrial hydration of alkenes to form alcohols Industrially alkenes are converted to alcohols in one step rather than the two in the above sulphuric acid reaction. They are reacted with water in the presence of an acid catalyst. This reaction can be called hydration

The high pressures needed mean this cannot be done in the laboratory. It is preferred industrially as there are no waste products and so has a high atom economy. It would also mean separation of products is easier (and cheaper) to carry out. Testing for Alkenes with Bromine water Bromine water decolourises in the presence of a double bond. This can be used as a test for the presence of an double bond in a molecule. It can be used quantitatively to show the presence of multiple double bonds in compounds like polyunsaturated oils

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) g(

For ethene CH CH +H O
2 ) g( 2 = = 2

CH CH OH (l)

tnegaer fo epyT tnegaer fo epyT OS H ,elihportcelE :tnegaer fo epyT tnegaer fo epyT noitiddA cilihportcelE :msinahceM :snoiitiidnoC :sno t dnoC erutarepmet moor: :snoiitiidnoC :sno t dnoC OS H detartnecnoc :stnegaeR etahpllusnegordyh llyklla eneklla etahp usnegordyh yk a enek a etahpllusnegordyh llyklla eneklla etahp usnegordyh yk a enek a
2 4 2

puorg ano ttcnuff n egnahC puorg ano cnu n egnahC puorg llllanoiiiittcnuff niiii egnahC puorg ano cnu n egnahC 1 egattS 1 ega S 1 egattS 1 ega S

Stage 2 Change in functional group alkyl hydrogensulphate alcohol Reagents: : water Conditions: warm mixture Type of reaction: hydrolysis CH3CH2OSO2OH + H2O CH3CH2OH + H2SO4

H-OSO2OH
In exams. It real structure is
H O S H O O O

Overall role of sulphuric acid is that of a catalyst (as it is regenerated)

Essential Conditions high temperature 300 C high pressure 70 atm strong acidic catalyst of H3PO4

Addition Polymers Addition polymers are formed from alkenes This is called addition polymerisation Poly(alkenes) like alkanes are unreactive due to the strong C-C and C-H bonds be able to recognise the repeating unit in a poly(alkene) n Monomer Ethene
H H C H C CH3

H
Polymer polyethene
H C CH3 CH3 C H

H C

H C

H C

H C

H C

CH3 H

CH3 H

CH3 H

Polypropene is recycled

propene

poly(propene)

Polyethene: is used to make plastics bags, buckets, bottles. It is a flexible, easily moulded, waterproof, chemical proof, and low density plastic. Polypropene is a stiffer polymer, used in utensils and containers and fibres in rope and carpets
You should be able e.g. For but-2-ene to draw the polymer CH3 repeating unit for any H3C CH CH alkene It is best to first draw out the monomer with groups of atoms arranged around the double bond

H
C H3C C

CH3

H C

CH3 C H

H
CH3

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