OrganicChemistry-Applica4ons

KNG-CHM-102-Lecture5

Norethindrone(anoralcontracep0ve-a3oalcoholgroup+ketonegroupandcarbon–carbondoubleandtriplebonds)

Alcohols

Ethers-Anaesthe4cs

1842,inflammable

NO(1799)

Fluorocarbons(compoundscontainingonlycarbonandfluorine)haveextraordinarilylowboilingpointswhencomparedtohydrocarbonsofthesamemolecularweight-verylowpolarizabilityoffluorineatoms.

Self-lubrica4ngproper4esthatareexploitedinmaking“nons4ck”fryingpansandlightweightbearings.

FluorocarbonsandTeflon

Pheromones:Communica4onbyMeansofChemicals

Usepheromonesincourtshipassexa[ractants.warningsubstances,and“aggrega4oncompounds”tocausemembersoftheirspeciestocongregate.

Insectsexa[ractants-usedtolureinsectsintotrapsasmeansofinsectcontrol,amuchmoreenvironmentallysensi4vemethodthantheuseofinsec4cides

•  Olfactorysensi4vitytomusk-includessteroidssuchasandrosterone,largecyclicketones,andlactones(cyclicesters),

•  Mayinfluenceourbehavior.•  Compoundsusedinperfumes,

includingcivetone,anaturalproductisolatedfromglandsofthecivetcat,andpentalide,asynthe4cmusk

Humans

Carbon-alonecompounds

Lewisacidstabilizesthenega4vechargethatdevelopsontheoxygeninthetransi4onstate.

Theroleoftheenzyme’sproteinscaffold,istoholdthezincion,coenzyme,andsubstrateinthethree-dimensionalarrayrequiredtolowertheenergyofthetransi4onstate.

Reac4onisen4relyreversible,whentherela4veconcentra4onofethanolishigh

Alcoholdehydrogenasecarriesouttheoxida4onofethanolbyremovalofahydride-importantindetoxifica4on.

Alcoholdehydrogenase

VitaminAfromsourcesincludingdarkgreenleafyvegetables

Cholesterolfromanimals

Naturalrubberfromcertaintrees

Gu[apercha,anothernaturallatexfromthesapofsometrees

Compoundswithdoublebonds

fromtheseaincludedactylyneand(3E)-laurea4n,

TheSea:ATreasuryofBiologicallyAc4veNaturalProductsConcentra4onofhalidesintheoceanisapproximately0.5Min

chloride,1mMinbromide,and1mMiniodideions

Partofdefensemechanismsthatservetopromotethespecies’survivalbydeterringpredatorsorinhibi4ngthegrowthofcompe4ngorganisms

Halomon,-inpreclinicalevalua4onasacytotoxicagentagainstcertaintumorcelltypes,

Dactylyneisaninhibitorofpentobarbitalmetabolism

cyclocymopolenan4omersshowagonis4corantagonis4ceffectsonthehumanprogesteronereceptor

Sharplessasymmetrichydroxyla4on

Freeradicals

RadicalPolymeriza4onofEthene

PolyethylenecanbeproducedinadifferentwayusingZiegler–Na>acatalysts-organometalliccomplexesoftransi4onmetals.Inthisprocessnoradicalsareproduced,nobackbi4ngoccurs,and,consequently,thereisnochainbranching.Thepolyethylenethatisproducedisofhigherdensity,hasahighermel4ngpoint,andhasgreaterstrength

Adhesivecalled“superglue”isaresultofanionicpolymeriza4on.Superglueisasolu4oncontainingmethylcyanoacrylate

Methylcyanoacrylatecanbepolymerizedbyanionssuchashydroxideion,butitisevenpolymerizedbytracesofwaterfoundonthesurfacesofthetwoobjectsbeinggluedtogether.

MolecularOxygenandSuperoxideMolecularoxygeninthegroundstate-diradicalwithoneunpairedelectrononeachoxygen.Asaradical,oxygencanabstracthydrogenatomsjustlikeotherradicals.Thisisthewayoxygenisinvolvedincombus4onreac4onsandautoxida4on

InbiologicalsystemsoxygenisanelectronacceptorandbecomesbecomesaradicalanioncalledSuperoxide.

Superoxideisinvolvedinbothposi4veandnega4vephysiologicalroles:Theimmunesystemusessuperoxideinitsdefenseagainstpathogens,yetsuperoxideisalsosuspectedofbeinginvolvedindegenera4vediseaseprocessesassociatedwithagingandoxida4vedamagetohealthycells.Theenzymesuperoxidedismutaseregulatesthelevelofsuperoxidebycatalyzingconversionofsuperoxidetohydrogenperoxideandmolecularoxygen.Hydrogenperoxide,however,isalsoharmfulbecauseitcanproducehydroxyl(HO·)radicals.Theenzymecatalasehelpstopreventreleaseofhydroxylradicalsbyconver4nghydrogenperoxidetowaterandoxygen:

NitricOxide

Nitricoxide,synthesizedinthebodyfromtheaminoacidarginine,servesasachemicalmessengerinavarietyofbiologicalprocesses,includingbloodpressureregula4onandtheimmuneresponse.Itsroleinrelaxa4onofsmoothmuscleinvascular4ssues

The1998NobelPrizeinPhysiologyorMedicinewasawardedtoR.F.Furchgo[,L.J.Ignarro,andF.MuradfortheirdiscoverythatNOisanimportantsignalingmolecule.

Lipidoxida4on

Calicheamicinγ1I:RadicalDeviceforSlicingDNABackbone

Extraordinarilydeadlyforcancercells,ini4atesapoptosis(programmedcelldeath),ledtodevelopmentofthedrugMylotarg,totreatacutemylogenousleukemia.Mylotargcarriestwocalicheamicin“warheads”onanan4bodythatdeliversitspecificallytothecancerouscells.Innature,bacteriacalledMicromonosporaechinosporasynthesizesCalicheamicinγ1Iachemicaldefenseagainstotherorganisms.

ThelaboratorysynthesisofthiscomplexmoleculebytheresearchgroupofK.C.Nicolaou(ScrippsResearchIns4tute,UniversityofCalifornia,SanDiego),

An4oxidants

•  VitaminE(a-tocopherol)iscapableofac4ngasaradicaltrap,inhibitsradicalreac4onsthatcouldcausecelldamage.

•  VitaminCisalsoanan4oxidant,butsupplementsover500mgperdaymayhaveprooxidanteffects

•  BHTaddedtofoodstopreventautoxida4on,trapsradicals.

OrganicTemplatesEngineeredtoMimicBoneGrowth

Helprepairbrokenbones,offsetosteoporosis,andtreatbonecancer

Arg-Gly-AspRGD

Intersec4onofnanotechnologySelf-assembledfiberpromotescalciumcrystalliza4onalongitsaxis,muchlikenature’scollagentemplateandbioengineering.

Bonesgrowbyadhesionofspecializedcellstoalongfibrousnaturaltemplatecalledcollagen(i)Promotethebindingofbone-growingcells(ii)facilitatecalciumcrystalliza4on.

OzoneDeple4onandChlorofluorocarbons(CFCs)

Stratosphere-al4tudesofabout25km,veryhighenergy(veryshortwavelength)UVlightconvertsdiatomicoxygen(O2)intoozone(O3).

Theozoneproducedinstep2canalsointeractwithhighenergyUVlight:Highlyenerge4cUVlightintoheat

ExistenceofthiscycleshieldsEarthfromradia4onthatisdestruc4vetolivingorganisms

MakeslifepossibleonEarth’ssurface.Evenarela4velysmallincreaseinhigh-energyUVradia4onatEarth’ssurfacewouldcausealargeincreaseintheincidenceofskincancers.

Typicalfreonsaretrichlorofluoromethane,CFCl3(calledFreon-11),anddichlorodifluoromethane,CF2Cl2(calledFreon-12).InJune1974F.S.RowlandandM.J.Molinashowedthatinthestratospherefreonisabletoini4ateradicalchainreac4onsthatcanupsetthenaturalozonebalance.The1995NobelPrizeinChemistrywasawardedtoP.J.Crutzen,M.J.Molina,andF.S.Rowland

Produc4onofchlorofluoromethanes(andofchlorofluoroethanes)calledchlorofluorocarbons(CFCs)orfreonsbeganin1930.usedasrefrigerants,solvents,andpropellantsinaerosolcans.

In1985aholewasdiscoveredintheozonelayeraboveAntarc4ca.Chlorineatomdestruc4onoftheozone-afactorintheforma4onofthehole.Thisozoneholehascon4nuedtogrowinsize,SuchaholehasbeendiscoveredintheArc4cozonelayer.Shouldtheozonelayerbedepleted,moreofthesun’sdamagingrayswouldpenetratetothesurfaceofEarth.Industrializedna4onsoftheworldceasedproduc4onofchlorofluorocarbonsasof1996,andover120na4onshavesignedtheMontrealProtocol1987