Addition reactions
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ADDITION REACTIONS. REACTIONS OF ALKENES. A reaction in which the double bond of an alkene is converted to a single bond and two new bonds are formed to the species it reacts with is known as an addition reaction and they are typical of alkenes and alkynes.

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ADDITION REACTIONS

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Addition reactions

ADDITION REACTIONS


Reactions of alkenes

REACTIONS OF ALKENES

  • A reaction in which the double bond of an alkene is converted to a single bond and two new bonds are formed to the species it reacts with is known as an addition reaction and they are typical of alkenes and alkynes.

  • A number of important addition reactions are illustrated in the next slides named as:

  • Halogenation

  • Catalytic Hydrogenation

  • Halogen acid addition

  • Addition of water


Addition reactions

ADDITION OF BROMINE TEST FOR UNSATURATION

The addition of bromine dissolved in tetrachloromethane (CCl4) or water (known as bromine water) is used as a test for unsaturation. If the reddish-brown colour is removed from the bromine solution, the substance possesses a C=C bond or unsaturation.

A

B

C

PLACE A SOLUTION OF BROMINE IN A TEST TUBE

ADD THE HYDROCARBON TO BE TESTED AND SHAKE

IF THE BROWN COLOUR DISAPPEARS THEN THE HYDROCARBON IS AN ALKENE

A BC

Because the bromine adds to the alkene, it no longer exists as molecular bromine and the typical red-brown colour disappears


Bromine water test movie

BROMINE WATER TEST MOVIE


Addition reactions

B) WITH HYDROGEN – HYDROGENATION

This addition of hydrogen across a double bond happens only in the presence of acatalyst – usually platinum is used in the lab reaction. This process converts an alkene into an alkane.

C) WITH HYDROGEN HALIDES

Note the possibility of isomeric products in this case.

In this reaction we end up with a substituted alkane – a haloalkane.


Addition reactions

D) WITH WATER – HYDRATION

In all of the above addition reactions, an unsaturated compound becomes fully saturated.


Addition reactions

  • ADDITION REACTIONS OF ALKYNES

  • As the alkynes are unsaturated we might expect that they will undergo addition reactions like the alkenes. This is indeed the case but the reaction can happen in two stages and, with care, can be stopped after the first stage.

  • WITH HALOGENS – TO MAKE DIHALOALKENES, THEN TETRAHALOALKANES


Addition reactions

B) WITH HYDROGEN – TO MAKE ALKENES AND THEN

ALKANES

C) WITH HYDROGEN HALIDES – TO MAKE HALOALKENES AND THEN DIHALOALKANES


Addition reactions

ELECTROPHILIC ADDITION MECHANISM

The electrophile, having some positive character, is attracted to the alkene.

The electrons in the pi bond come out to form a bond to the positive end.

Because hydrogen can only have two electrons in its orbital, its other bond breaks heterolytically. The H attaches to one of the carbon atoms.


Addition reactions

ELECTROPHILIC ADDITION MECHANISM

A carbocation is formed. The species that left now has a lone pair.

It acts as nucleophile and attacks the carbocation using its lone pair to form a covalent bond. Overall, there is ADDITION


Addition reactions

ELECTROPHILIC ADDITION OF HYDROGEN BROMIDE

ReagentHydrogen bromide... it is electrophilic as the H is slightly positive

ConditionRoom temperature.

EquationC2H4(g) + HBr(g) ———> C2H5Br(l) bromoethane

Mechanism

Step 1As the HBr nears the alkene, one of the carbon-carbon bonds breaks

The pair of electrons attaches to the slightly positive H end of H-Br.

The HBr bond breaks to form a bromide ion.

A carbocation (positively charged carbon species) is formed.

Step 2The bromide ion behaves as a nucleophile and attacks the carbocation.

Overall there has been addition of HBr across the double bond.


Addition reactions

ADDITION TO UNSYMMETRICAL ALKENES

ELECTROPHILIC ADDITION TO PROPENE

Problem•addition of HBr to propene gives two isomeric brominated compounds

• HBr is unsymmetrical and can add in two ways

• products are not formed to the same extent

• the problem doesn't arise in ethene because it is symmetrical.

Mechanism

Two possibilities


Addition reactions

ADDITION TO UNSYMMETRICAL ALKENES

MARKOWNIKOFF’S RULE

A Russian scientist, Markownikoff, investigated the products of the addition of hydrogen halides to alkenes. He found that, when two products were formed, one was formed in a larger quantity. His original rule was based only on this reaction. The modern version uses carbocation stability as a criterion for predicting the products.

In the electrophilic addition to alkenes the major product isformed via the more stable carbocation (carbonium ion)


Carbocation stability

Carbocation Stability

Build up of charge in one place leads to instability. If it can be spread around or neutralised in some way, stability is increased. Alkyl groups are electron releasing and can “push” electrons towards the carbocations thus reducing the charge density.

least stable most stable

methyl < primary (1°) < secondary (2°) < tertiary (3°)


Addition reactions

ADDITION TO UNSYMMETRICAL ALKENES

MARKOWNIKOFF’S RULE

In the addition to propene, path A involves a 2° carbocation, path B a 1° carbocation.

As the2° ion is more stable, the major product (i.e. 2-bromopropane) is formed this way.

PATH A

SECONDARY

CARBOCATION

MAJOR PRODUCT

PATH B

PRIMARY

CARBOCATION

MINOR PRODUCT


Addition to unsymmetrical alkenes

ADDITION TO UNSYMMETRICAL ALKENES

MARKOWNIKOFF’S RULE

When an unsymmetrical reagent adds to the double bond:

  • the positive part (electrophile) of the reagent will join to the to the carbon atom containing more number of hydrogen atoms

  • the negative part (nucleophile) of the reagent will join to the carbon atom containing less number of hydrogen atoms


Addition reactions

OTHER ADDITION REACTIONS

DIRECT HYDRATION

Reagentsteam

Conditionshigh pressure

Catalystsulphuric acid ( H2SO4)orphosphoric acid (H3PO4)

Productalcohol

EquationC2H4(g) + H2O(g) C2H5OH(g)

Useethanol manufacture

Comments It may be surprising that water needs such vigorousconditionsto react with ethene. It is a highly polar molecule and you wouldexpect it to be a good electrophile.

However, the O-H bonds are very strong so require a greatdeal ofenergy to be broken. This necessitates the need for a catalyst.


Addition reactions

OTHER ADDITION REACTIONS

HYDROGENATION

Reagenthydrogen

Conditionsnickel catalyst - finely divided

Productalkanes

EquationC2H4(g) + H2(g) ———> C2H6(g)

ethane

Usemargarine manufacture


Addition reactions

ELECTROPHILIC ADDITION OF BROMINE

ReagentBromine. (Neat liquid or dissolved in tetrachloromethane, CCl4 )

ConditionRoom temperature. No catalyst or UV light required!

EquationC2H4(g) + Br2(l) ——> CH2BrCH2Br(l) 1,2 - dibromoethane

Mechanism

It is surprising that bromine

should act as an electrophile

as it isnon-polar.

SEE NEXT SLIDE FOR AN EXPLANATION OF THE BEHAVIOUR OF BROMINE


Addition reactions

ELECTROPHILIC ADDITION OF BROMINE

It is surprising that bromine should act as an electrophile as it is non-polar.

Explanation...as a bromine molecule approaches an alkene, electrons in

the pi bond of the alkene repel the electron pair in the

bromine-bromine bond thus inducing a dipole.

NON-POLAR

POLAR

AS A NON-POLAR BROMINE MOLECULE APPROACHES AN ALKENE, ELECTRONS IN THE PI ORBITAL OF THE ALKENE REPEL THE SHARED PAIR OF ELECTRONS IN THE Br-Br BOND

THE ELECTRON PAIR IS NOW NEARER ONE END SO THE BROMINE MOLECULE IS POLAR AND BECOMES ELECTROPHILIC.


Reduction to alcohols with sodium borohydride and lithium aluminum hydride

Reduction to Alcohols with Sodium Borohydrideand Lithium Aluminum Hydride


Addition reactions

CARBONYL COMPOUNDS - REDUCTION WITH NaBH4

  • Reagent sodium tetrahydridoborate(III) (sodium borohydride), NaBH4

  • Conditionsaqueous or alcoholic solution

  • MechanismNucleophilic addition (also reduction as it is addition of H¯)

  • NucleophileH¯ (hydride ion)

  • Product(s)Alcohols Aldehydes are REDUCED to primary (1°) alcohols.

  • Ketones are REDUCED to secondary (2°) alcohols.

  • Equation(s)CH3CHO + 2[H] ——> CH3CH2OH

    • CH3COCH3 + 2[H] ——> CH3CHOHCH3

  • NotesThe water provides a proton


  • Addition reactions

    CARBONYL COMPOUNDS - REDUCTION WITH NaBH4

    Reagentsodium tetrahydridoborate(III) (sodium borohydride), NaBH4

    Conditionsaqueous or alcoholic solution

    MechanismNucleophilic addition (also reduction as it is addition of H¯)

    NucleophileH¯ (hydride ion)

    Aldehyde

    Primary alcohol

    Water is added


    Addition reactions

    CARBONYL COMPOUNDS - REDUCTION WITH NaBH4

    Reagentsodium tetrahydridoborate(III) (sodium borohydride), NaBH4

    Conditionsaqueous or alcoholic solution

    MechanismNucleophilic addition (also reduction as it is addition of H¯)

    NucleophileH¯ (hydride ion)

    ANIMATED MECHANISM


    Grignard addition preparation of alcohols

    Grignard Addition - Preparation of Alcohols

    • Grignard reagents are prepared from the reaction of alkyl halides with magnesium in ether solvent.

    • The alkyl group assumes a negative character and is a nucleophile.

    • When presented with an aldehyde or ketone, the Grignard attacks the carbonyl carbon in a base-initiated nucleophilic addition.

    • Neutralization of the negative intermediate results in the preparation of an alcohol.

    • Grignard reagents react with formaldehyde to form primary alcohols, with other aldehydes to form secondary alcohols, and with ketones to produce tertiary alcohols.


    Grignard preparation of alcohols

    Grignard Preparation of Alcohols


    Grignard reaction mechanism

    Grignard Reaction Mechanism


    Polymers

    Polymers

    • Polymers are long chain molecules that are formed by the joining together of a large number of repeating units, called monomers, by a process of polymerisation.

    • Polymers,can be made artificially and these are usually referred to as plastics, but there are also a great number of naturally occurring polymers.

    • One type of polymerisation reaction is known as additionpolymerisation. In this the monomers contain double bonds and in the addition reaction new bonds (shown coloured below) form between these monomer units.

    • The simplest polymerisation reaction of this type is that of ethene when heated under pressure with a catalyst to form polyethene, commonly known as ‘polythylene’.


    Polythylene

    Polythylene

    • polyethylene formation may also be represented by the equation below in which the repeating unit is shown in square brackets.


    Polyvinyl chloride pvc

    Polyvinyl Chloride (PVC)

    Another common addition polymer is poly(chloroethene), better known as PVC (short for its old name of PolyVinyl Chloride), formed by the polymerisation of chloroethene


    Monomer polymer

    Monomer Polymer

    Chloroethene

    Polyvinyl chloride (PVC)


    Monomer polymer1

    Monomer Polymer

    Tetrafluoroethene

    Polytetrafluoroethene (Teflon)


    Polypropene

    Polypropene

    Polypropene is another common adition polymers.


    References

    REFERENCES

    • http://chemweb.calpoly.edu/cbailey/BaileyText/SGpdf/Chapter11.pdf

    • http://www.knockhardy.org.uk/ppoints.htm

    • http://www.chem.ucalgary.ca/courses/350/Carey5th/Ch09/ch9-8.html


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