3.

Alkenes&Alkynes

Preparedby
JoyceTiong
ForUEMK1013
October2012
 Alkenes
StructureswithaC=Cbond.
Unsaturatedcompound,asitstillhasthe
capabilitytoaddtwomoreHatoms.
HasgeneralformulaofCnH2n.
Endswithasuffixene.
eg.C3H6 =propene;C9H18 =nonene.
Morereactivethanalkanes asC=Cbondhasa
bondthatismorereactivethana bond.
Occursinmanynaturallyoccurringmaterials,for
flavouring,fragrancesandvitamins.
 ExampleofAlkenes(I)

carotene

Usedasanorangepigment(occursincarrot)
andasvitaminAprecursor.
 ExampleofAlkenes(II)

Ethylene

Flammablegas
Usedasplanthormone forfruitripening
Mostwidelysynthesisedorganiccompound,
usedforalkylation,polymerisation,etc.
 NamingAlkenes

Countthenumberofcarbonsanddetermine
theparentcompound.
Numberthecarbons,withC=Cbondhaving
thelowestpossiblecarbonnumber.
Addprefixcyclo forringedalkenes.
 Example

Hex2ene 2methylhex3ene

2ethylpent1ene 2methylbuta1,3diene
 ReactionsofAlkenes(I)
Alkenesmostcommonlymadebytwo
methods:
eliminationofHXfromalkylhalide(dehydrohalogenation)
UsesheatandKOH
eliminationofHOHfromanalcohol(dehydration)
requirestrongacids(sulfuricacid,50C)
 ReactionsofAlkenes(II)
Additionofhalogens(Cl,Br)togivedihalide
alkanes
 ReactionsofAlkenes(III)
AdditionofHypohalous AcidstoAlkenes:Halohydrin
Formation.
ThisisformallytheadditionofHOXtoanalkenetogivea1,2
haloalcohol,calledahalohydrin
Theactualreagentisthedihalogen(Br2 orCl2 inwaterinan
organicsolvent)
 ReactionsofAlkenes(IV)
Hydrationofanalkene istheadditionofH
OHtoto giveanalcohol
Acidcatalystsareusedinhightemperature
industrialprocesses:ethyleneisconvertedto
ethanol
 ReactionsofAlkenes(V)
ReductionwithHHintoalkanes
OnlyreactswithC=C,noreactionwith C=Oor
C=N
 Alkene Polymerization
Formedbyattackofradicals(producedeither
bythermaldecomposition,photolysis,redox,
etc)
Alkynes

Preparedby
JoyceTiong
ForUEMK1013
October2012
 Alkynes
ContainsCC
GeneralformulaofCnH2n2
Undergoessomesimilarreactionstoalkenes
Examplesofalkynes:

Forbirthcontrolpills Antibacterialcompound
 Namingalkynes
Whenadditionalfunctionalgroupsarepresent,
suffixesarecombinedtoproducethecompound
names:
alkenynes (adoublebondandatriplebond)
alkynols (atriplebondandanalcohol)
TheIUPACrulesgivealkenesandalcoholshigher
prioritythanalkynes.So,thenumberingbeginsat
theendclosertothesehigherprioritygroups.
Allotherfunctionalgroups,exceptethersandhalides
haveahigherprioritythanalkynes.
Exampleofalkynes
 Physicalpropertiesofalkynes
Physicalpropertiesofalkynesaresimilartoalkanes
andalkenes.
Nonpolar,nearlyinsolubleinwater.
Solubleinmostorganicsolvents,e.g.acetone,ether,
alcohol,chloroformandmethylene chloride.
Boilingpointssimilartoalkane ofsamesize.
Lessdensethanwater.
Upto4carbons,gasatroomtemperature.
Manyalkyneshavecharacteristic,mildlyoffensive
odors.
 Reactionsofalkynes
I)Addition:
Hydrogen:
withmetalcatalyst(Pd,Pt,Ni),toformalkane
withLindlars catalyst,toformcisalkene
withsodiuminliquidammonia,toform transalkene
Halogen:
additionofCl2 /Br2 toformvinyldihalides
Usuallycontinuestoform tetrahalides
Hydrogenhalides:
additionHCl,HBr orHItoform
 ExamplesofAlkynesAddition
Reactions(I)
I) Addition ofHydrogen:
withmetalcatalyst(Pd,Pt,Ni)
H H

Pt, Pd or Ni
R C C R' + 2 H2 R C C R'

H H
Example:
Pt
CH C C CH3 + 2 H2 CH3 CH2 CH2 CH3

2Butyne Butane
(100%conversion)
 ExamplesofAlkynesAddition
Reactions(II)
withLindlars catalyst

cisalkene

Example:
H3C (CH2)2CH3
Lindlar's catalyst
CH3 C C (CH2)2CH3 + H2 C C
or Ni2B
H H
2hexyne cis2hexene
 ExamplesofAlkynesAddition
Reactions(III)
withsodium(Na)inliquidammonia(NH3)
R H
R C C R' + Na/NH3 C C
H R'

transalkene
Example:
H3C H
CH3 C C (CH2)4CH3 + Na/NH3 C C
H (CH2)4CH3
 ExamplesofAlkynesAddition
Reactions(IV)
II)AdditionofHalogens
Example:
transbutene cisbutene

2Butyne

Reactioncontinuestoform
tetrahalide alkane
 ExamplesofAlkynesAddition
Reactions(V)
III)Additionofhydrogenhalides
Example:

Markoniknovs rule:Theadditionofaprotonacid
tothedoublebondofanalkene resultsina
productwiththeacidprotonbondedtothecarbon
atomthatalreadyholdsthegreaterno.of
hydrogens.
 OtherReactionsofAlkynes
II)Hydrationofalkynes:
Alkyne +H2O vinylalcohol+ketone
Mercuricsulfate (HgSO4)in
Sulfuric acid(H2SO4)

III)Oxidationofalkynes:
Alkyne +neutral potassiumpermanganate
(KMnO4) ketone
Alkyne +basic KMnO4 two carboxylic
acid
 SynthesisofAlkynes
Eliminationofhydrogenhalides(HX)
RemovaloftwomoleculesofHXfromavicinalor
geminal dihalide producesanalkyne.
Step1:(HX)iseasy,formsvinylhalide.
Step2:removalofHXfromthevinylhalide
requiresverystrongbaseandhightemperatures.