Cycloalkanes

(naphthenes)
have1+ringsofcarbonatoms
consistofonlyCandHatoms
cycloalkanew/oneringtreatedasisomersoftheiralkenecounterpart(Ex:
cyclopropane/propene)
Formula:
C
H
where
n
=numberofCatomsand
g
=numberofringsinthemolecule
n
2(n+1g)
IUPACnaming:
1. basenamelistedfirst(total#ofCinbothrings)
2. numericalprefixbeforebasename(#ofCineachring,ex.sharedC)(Ex:#C1string.#
C2ndring.SharedC)
Properties:
higherboiling/meltingpointsthanalkanes
higherdensities
strongerLDF(morecontactarea)
RingStrain:
sp3

hybridized
PE/destabilizingeffect
strainenergy
:theoreticalincreaseinenergycausedbythecompoundsgeometry
calculatedbycomparingtheexperimentalstandardenthalpychangeof
combustionhighestforcyclopropane
Reactions:
simple&biggercycloalkanesareverystable
smallcycloalkanesarelessstableBaeyerstrain/ringstrain

Alkenes
(olefin,olefine)
unsaturatedhydrocarbonsthatcontain1+C=C
simplestalkeneethylene(C
H
)producedonthelargestscaleindustrially
2
4
Formula:acyclicalkenes(monoenes)formahomologousseriesofhydrocarbons

C
H
n
2n
IUPACnaming:antoene
1. #thelongestCchainthatcontains=inthedirectionthatgivestheCatomsofthe=the
lowestpossible#s
2. Indicatethelocationofthe=bythelocationofits1stC
3. Namebranched/substitutedalkenes
4. #theCatoms,locate/namesubstituents,locate=,namemainchain
Cistransnotation
Cisusedifbothsubstituentsareonthesamesideofthebond
Transusedifsubstituentsareoneithersideofthebond
Properties:
colorless,nonpolar,combustible,almostodorless
simplestalkenesaregaseswherethecomplicatedonesarewaxysolids

Bonding:
eachCofthe=usesitsthreesp
hybridorbitals
toformsigmabondstothreeatoms
=about120,butvariesbcofstericstrainintroducedbynonbondedinteractionscreated
byfunctionalgroupsattachedtotheCofthe=
Reactions:
relativelystable,butmorereactivethanalkanesbcofreactivityofpibond
reactionsinvolve:additionstopibond,
hydrogenation,hydration,halogenation,
hydrohalogenation,halohydrinformation,oxidation,photooxygenation,polymerization,
metalcomplexation
Synthesis:
Industrialmethods:producedbyhydrocarboncracking(alkanesbreakingapartathigh
temps)
Eliminationreactions:morereliableeliminationmethodthanE1formostalkene
syntheses.MostE2eliminationsstartwithanalkylhalide(
dehydrohalogenation
)oralkyl
sulfonateester

Alkynes
unsaturatedhydrocarbonw/1+carboncarbontriplebond
Formula:
C
H
n
2n2
IUPACnaming:ethyne
Chemicalproperties:
moreunsaturated&lessreactivethanalkenes
greatertendencytopolymerize
Structure&Bonding:
180
rodlike
BenzyneUNSTABLE
strongbonds
Synthesis:
usedasafuel&precursortoothercompounds
Propynethermalcrackingofhydrocarbons
Reactions:
additionofhydrogen,halogens,andrelatedreagents
cycloadditions&oxidation
reactionsspecificforterminalalkynes

AlkylHalides(Haloalkanes)
derivedfromalkanescontaining1+halogens
usedasflameretardants,fireextinguishants,refrigerants,propellants,solvents,
pharmaceuticals

 seriouspollutant(ozonedepletion,fumigant)
IUPACnaming:halogenasaprefixtoalkane
Properties:
colorless,odorless,hydrophobic
higherboilingpointsthanalkanes(highIMF)
bettersolvents
haloalkanescont.halogensotherthanFaremorereactive
Occurence:
pharmaceuticalscontainF
perfluorinatedalkanesarebloodsub.
Production:
freeradicalhalogenation
reactswithdryHhalide
tertiaryalcoholreactsw/HCLtomaketertiarychloroalkane
Hunsdiecherreaction/Kochireaction

Alcohols
anyorganiccompoundinwhichtheOHisboundtoasaturatedCatom
Formula:
C
H
OH
n
2n+1
IUPACnaming:
nameofalkanechainloseseandaddsol(positionofOHgroupcanbeindicatedby#
b/talkanename&ol)
ifhigherprioritygroupispresent(aldehyde,ketone,carboxylicacid),thenhydroxyused
Toxicity:
ethanolstoxicitycausedbymetabolite,acetaldehyde&aceticacid
tertiaryalcoholscannotbemetabolizednotoxicity
treatment:admin.ethanol
Phys./Chem.Properties:
odor
hydroxylgroupmakeitpolar
canbeusedasproticsolvents
higherboilingpoint
canundergooxidationornucleophilicsub.reactions
App.:
alcoholicbeverages
antifreeze
antiseptics
fuels
preservatives

 solvents
Production:
Ziegler&Oxoprocesses
hydrationreactions
biologicalroutes
LabSynthesis:
substitution
reduction
hydrolysis

Thiols
(mercaptan)
organosulfurcompoundthatcontainsaCbondedsulfhydryl(CSHorRSH)
sulfurtakesplaceofOinhydroxylgroupofalcohol
IUPACnaming:
thiol
addedtonameofalkane
mercaptan
replacesalcohol
sulfanyl.mercapto
usedasprefix
Structure/Bonding
sizeofchalcogenidediffers
CSHanglesalmost90
lesspolarthanhydroxylgroup
PhysicalProp:
garlicodor
lowerboilingpt
lesssolubleinwaterthanalcohols
Characterization:
detectedbyodor
Prep:
reactionofhydrogensulfidew/methanol
synthesisofmethanethiol
Reactions:
Salkylation
Acidity
Redox
Biologicalimportance:
cysteine/cystine
cofactors(nonproteinbasedhelpermolecules)

Ethers
containethergroup
SymbolROR
IUPACnaming:
alkoxyalkane
ifetherisapartofmorecomplexmoleculemethoxy
Structure/Bonding:
COClinkageofabout104
3
sp

Trivialnames:
simpleetherscompositeof2substituentsfollowedbyether
Phys.Prop.:
nohydrogenbonds
lowboilingpoint(becomelowerasCchaingetslonger)
slightlypolar
lowerethersarehighlyvolatile
Reactions:
ethercleavage
peroxideformation
Lewisbases
Alphahalogenation

Epoxides
cyclicetherwitha3atomring
highlystrained
IUPACnaming:epoxy
Synthesis:
olefinperoxidation
intramolecularSN2substitution
nucleophilicepoxidation
asymmetricepoxidation
Reactions:
Nucleophilicaddition
Hydrolysis
Reductionofanepoxidew/lithiumaluminumhydrideandwatergen.analcohol
Reductionw/tungstenhexachlorideandnbutyllithiumgen.thealkene

Aldehyde
organiccompoundw/formylgroup(functionalgroupw/RCHOstructure)
aldehydegroup:
groupw/oR
IUPACnaming:
1. Acyclic
aliphatic
aldehydesarenamedasderivativesofthelongestcarbonchain
containingthealdehydegroup.Thus,HCHOisnamedasaderivativeofmethane,
andCH
CH
CH
CHOisnamedasaderivativeof
butane
.Thenameisformedby
3
2
2
changingthesuffix
e
oftheparent
alkane
to
al
,sothatHCHOisnamed
methanal
,andCH
CH
CH
CHOisnamed
butanal
.
3
2
2
2. whenaCHOgroupisattachedtoaring,thesuffix
carbaldehyde
maybeused.
Thus,C
H
CHOisknownas
cyclohexanecarbaldehyde
.Ifthepresenceof
6
11
anotherfunctionalgroupdemandstheuseofasuffix,thealdehydegroupis
namedwiththeprefix
formyl
.Thisprefixispreferredto
methanoyl
.
3. Ifthecompoundisanaturalproductora
carboxylicacid
,theprefix
oxo
maybe
usedtoindicatewhichcarbonatomispartofthealdehydegroupforexample,
CHOCH
COOHisnamed
3oxopropanoicacid
.
2
4. Ifreplacingthealdehydegroupwitha
carboxylgroup
(COOH)wouldyielda
carboxylicacidwithatrivialname,thealdehydemaybenamedbyreplacingthe
suffix
icacid
or
oicacid
inthistrivialnameby
aldehyde
.

Structure/Bonding:
2
sp
hybridized,planarcarboncenterconnectedby=toOandatoH

PhysProp&Characterization:
smalleraldehydesmoresolubleinH2O
volatilealdehydeshavepungentodors
IDedbyspectroscopicmethods
formaldehyde/acetaldehyde
App.&Occurence:
foundinessentialoils&odors(cinnamaldehyde,cilantro,vanillin)
Synthesis:
oxidativeroutes(alcoholoxidation)
Specialtymethods(ozonolysis,organicreduc,rosenmundreaction,wittigreaction,
formylationreactions,nefreaction,zinckereaction,etc)
CommonReactions:
reduction/oxidation
nucleophilicadditionreactions
oxygen/nitrogen/carbonnucleophiles
bisulphitereaction
Ketones
organiccompoundwithstructureRC(=O)RwhereRandRcanbeavarietyof
Ccontainingsubstituents
simplecompoundsw/acarbonylgroup(C=O)simplebctheydonthavereactive
groupslikeOHorClattacheddirectly
IUPACnaming:

ane
to
anone
acetone/benzophenone
oxo
istheIUPACnameforaketonefunctionalgroup

Structure/Properties:
2
sp
hybridized

trigonalplanar,120
polar
nucleophilicatO/electrophilicatC
Classes:diketones,unsaturatedketones,cyclicketones
Characterization:
Hatomattachedtoitscarbonylgroup=easiertooxidize
absorbstronglyintheinfraredspectrumnear17001/cm
Synthesis:
oxidationofhydrocarbons
preparedbyoxidationofsecondaryalcohols
Reactions:
Withwater(hydration)gives
geminaldiols
Withan
acetylide
togivethe
hydroxyalkyne
With
ammonia
ora
primaryamine
givesan
imine
With
secondaryamine
givesan
enamine
With
Grignard
and
organolithiumreagents
togive,afteraqueousworkup,a
tertiary
alcohol
Withanalcoholsor
alkoxides
togivesthe
hemiketal
oritsconjugatebase.Witha
diol
to
the
ketal
.
With
sodiumamide
resultinginCCbondcleavagewithformationoftheamide
RCONH
andthealkaneR'H,areactioncalledtheHallerBauerreaction.
2
Withstrong
oxidizingagents
togive
carboxylicacids
.
Electrophilicaddition
,reactionwithan
electrophile
givesaresonancestabilizedcation
With
phosphoniumylides
inthe
Wittigreaction
togivethe
alkenes
With
thiols
togivethe
thioacetal
With
hydrazine
or1disubstituted
derivatives
ofhydrazinetogive
hydrazones
.

 Witha
metalhydride
givesametalalkoxidesalt,hydrolysisofwhichgivesthealcohol,
anexampleof
ketonereduction
With
halogens
toforman
haloketone
,areactionthatproceedsviaan
enol
(see
Haloformreaction
)
With
heavywater
togivean
deuterated
ketone
Fragmentationinphotochemical
Norrishreaction
Reactionof1,4aminodiketonesto
oxazoles
bydehydrationinthe
RobinsonGabriel
synthesis
Inthecaseofarylalkylketones,withsulfurandanaminegiveamidesinthe
Willgerodt
reaction
With
hydroxylamine
toproduce
oximes
With
reducingagents
toformsecondaryalcohols
With
peroxyacids
toform
esters
inthe
BaeyerVilligeroxidatio
n
Biochemistry:
formationoforganiccompoundsinphotosynthesisoccursviatheketone
ribulose1,5biphosphate
fructose
ketonebodies:acetone,acetoacetate,betahydroxybutyrate
Applications:
solvents,polymerprecursors,pharmaceuticals

Esters
chemicalcompoundsrevivedfromanacidinwhich1+OHgroupisreplacedbyan
Oalkylgroup
derivedfromacarboxylicacid&analcohol
Formula:R,ORsinglebondedtoC&OdoublebondedtoC
IUPACnaming:
oate

 RCO2RwhereRandRarethehydrocarbonpartsofthecarboxylicacid/alcohol
Structure/Bonding:
containa
carbonyl
center,120CCO&OCOangles
flexiblefunctionalgroupslessrigid(lowermeltingpoint)&morevolatile(lowerboiling
point)thanthecorrespondingamides
pKaaround25
Phys.Properties:
morepolarthanethersbutlesspolarthanalcohols
participateinhydrogenbondsashydrogenbondacceptors(notdonors!)
volatile
Apps&Occurrence:
responsibleforaromaofmanyfruits
polyesters
Preparation:
Esterification
chemicalreactioninwhich2reactants(alcohol/acid)formanesterasthe
reactionproduct
alcoholysis
alkylationofcarboxylatesalts
Esterodorants:
allylhexanoate(pineapple),benzylacetate(strawberry),butylacetate(apple),etc

CarboxylicAcids
organiccompoundthatcontainsacarboxylgroup(C(O)OH)
RC(O)OHwithRreferringtotherestofthemolecule
salts/estersofcarboxylicacidscalled
carboxylates

IUPACnaming:

PhysProperties:
polar
hydrogenbonding
dimericpairs
higherboilingptthanH2O(tendencytoformstabiliseddimers)
BronstedLowryacids
strongodor
Characterization:
IDedbyinfraredspectroscopy
Occurrence/Apps:

 polymers,pharm.,solvents,foodadditives,aceticacid
Synthesis:
industrialroutes(oxidationofaldehydes&hydrocarbonsw/airusingcobalt&
manganesecatalysts)
labmethods(oxidationofprimaryalcohols)
Reactions:
HellVolhardZelinskyhalogenation

Amines
organiccompounds/functionalgroupsthatcontainabasicNatomw/alonepair
derivativesofammonia
structure:RCONRR
IUPACnaming:
amino
or
amine
Nshowssubstitutiononthenitrogenatom
PhysProperties:
Hbonding(highboilingptthanphosphines)
somesolubility(decreaseswiththeincreasein#ofCatoms)
chiral
bases
Synthesis:
alkylation
reductiveroutes(hydrogenation)
Reactions:
alkylation,acylation,sulfonation
diazotization
conversiontoimines

Biologicalactivity:
breakdownofaminoacidsreleasesamines
neurotransmitters
Applications:
dyes,drugs,gastreatment

Amides
(acidamide)
compoundw/functionalgroup
referstoCBofammonia
formula:
R
E(O)
NR'
n
x
2
IUPACnaming:
addtermamidetothestemoftheparentacidsname
Structure/Bonding:
derivativesofammonia
RC(O)NH2
secondaryamines
Properties:
veryweakbases
lesssolublethancomparableamines/carboxylicacids
Characterization:
IRspectra16501/cm
App/Occurrence:
nylonsarepolyamides
peptidebonds
proteins(hairsilk)
Reactions:
dehydration,Hofmannrearrangement,amidereduction,VilsmeierHaackreaction

Aromaticity
describesanunusuallystablenatureofsomeflatringsofatomsusuallyw/=
Theory:Theuseofadoubleheadedarrowindicatesthattwostructuresarenotdistinctentities
butmerelyhypotheticalpossibilities.AC=CbondisshorterthanaCCbond,butbenzeneis
perfectlyhexagonalallsixcarboncarbonbondshavethesame
length
,intermediatebetween

thatofa
single
andthatofa
doublebond
.Abetterrepresentationisthatofthecircular
bond
(Armstrong's
innercycle
),inwhichtheelectrondensityisevenlydistributedthroughabond
aboveandbelowthering.Thismodelmorecorrectlyrepresentsthelocationofelectrondensity
withinthearomaticring.
Characteristics:
delocalizedconjugatedpisystem,mostcommonlyanarrangementofalt./=
coplanarstructure
contributingatomsarrangedin1+rings
#ofpidelocalizede
Importance:
20basicbuildingblocksofproteins
Types:
neutralhomocyclics,heterocyclics,polycyclics,sub.aromatics,atypicalaromatic
compounds