Beruflich Dokumente
Kultur Dokumente
Valence
Carbon4bonds Nitrogen3bonds Oxygen2bonds Halogens1bond
FormalCharge=(Group#)(#nonbondingelectrons)(1/2#bondingelectrons)
IndexofHydrogenDeficiency
TheNUMBEROFPAIRSofHYDROGENSrequiredtobecomeaSATURATEDALKANE
ForResonanceStructuresAtomsmustnotbemoved,onlyELECTRONSMOVE
AromaticMolecules (4n+2)electrons
HydrogenBondingoccurswhenHYDROGENisbondedtoaHIGHLYELECTRONEGATIVEATOM
ConformationalIsomers
NotTRUEisomersdifferentspatialorientationsofthesamemolecule
ChiralityAchiralcarbonisbondedtoFOURDIFFERENTSUBSTITUENTS
AbsoluteConfiguration
Rectus(totheright)&Sinister(totheleft)accordingtopriority
TheLARGESTMOLECULARWEIGHTistheHIGHESTPRIORITY(1)
Hydrogenisalwaysthelowestpriority(4)andshouldbeorientedoutthebackofthepage
RelativeConfiguration
TwomoleculeshavetheSAMErelativeconfigurationaboutacarboniftheydifferbyonlyONE
SUBSTITUENTandtheothersubstituentsareorientedidenticallyaboutthecarbon
OpticalActivity&ObservedRotation
Opticallyinactivecompoundsmayhave
Nochiralcenters & Equalamountofbothstereoisomers(aracemicmixture)
OpticallyActivecompoundscanbe
1) +/drotateslightCLOCKWISE
2) /lrotateslightCOUNTERCLOCKWISE
StructuralIsomers
1) Samemolecularformula
2) DIFFERENTBONDTOBONDCONNECTIVITY
3) Isobutane(C
4
H
10
) vs. nbutane(C
4
H
10
)
4) AreNOTTHESAMEMOLECULE
StereoisomerSUBTYPEEnantiomers
1) Samemolecularformula
2) Samebondtobondconnectivity
3) MIRRORIMAGESOFEACHOTHER
4) AreNOTTHESAMEMOLECULEoppositeabsoluteconfigurationsatchiralcenters
Samechemicalandphysicalcharacteristicsexceptfor
1) Reactionswithotherchiralcompounds
2) Reactionswithpolarizedlight
StereoisomerSUBTYPEDiastereomers
1) Samemolecularformula
2) Samebondtobondconnectivity
3) AreNOTMIRRORIMAGESOFEACHOTHER
4) AreNOTTHESAMEMOLECULE
GeometricIsomers(aspecialtypeofdiastereomer)
Cisisomers&Transisomers
MesoCompounds
1) WhenTWOchiralcentersOFFSETEACHOTHER
2) OpticallyInactive
3) PLANEofSYMMETRYdividescompoundintotwohalvesthataremirrorimages
StrongerDipoleMoment
StrongerIntermolecularForces
HigherBoilingPoints
HigherEnergyLevelHigherHeatofCombustion
FunctionalGroups
Alkane H
3
CCH
3
Alcohol ROH
Alkene H
2
C=CH
2
Ether ROR
Alkyne HCCH Amine RNH
2
R
2
NH R
3
N
Hemiketal R|R|OR|OH
Ketal R|R|OR|OR
Hemiacetal H|R|OR|OH
Acetal H|R|OR|OR
MesylGroup(Ms) TosylGroup(Ts)
H|R|OR|OH
Hybridization BondAngles Shape
sp 180 Linear
sp
2
120 TrigonalPlanar
sp
3
109.5 Tetrahedral,Pyramidal,orBent
Hydrocarbons,Alcohols,&Substitutions
Alkanes
MethylCH
3
PrimaryCRH
2
SecondaryCR
2
H TertiaryCR
3
LowestDensityofallgroupsoforganiccompounds
Methane,Ethane,Propane,andButanearegasesatroomtemperature
INCREASEDMolecularWeight|INCREASEDBoilingPoint|INCREASEDMeltingPoint
INCREASEDBranching|DECREASEDBoilingPoint|INCREASEDMeltingPoint
CycloAlkanes
CHAIRandBOATconformations
LargeSubstituentsareMORESTABLEintheEQUATORIALPOSITION
Combustion(radical&exothermicreaction)
CH
4
+ 2O
2
+ energy CO
2
+ 2H
2
O+ heat
COMBUSTIONisaRADICALREACTION
HEATOFCOMBUSTIONchangeinenthalpyofacombustionreaction
Halogenation(radical&exothermicreaction)
AlkaneswillreactwithHALOGENSinthepresenceofheatorlighttoformaFREERADICAL
HOMOLYTICCLEAVAGEbondisbrokenwithoneelectrongoingwitheachatom
1) INITIATION
a. Halogenisdiatomicmolecule,andHOMOLYTICCLEAVAGEresultsin2freeradicals
2) PROPAGATION
a. HALOGENRADICALremoveshydrogenfromalkane,creatinganALKYLRADICAL
b. ALKYLRADICALreactswithdiatomicmoleculecreatingALKYLHALIDEandaNEWHALOGEN
RADICAL
3) TERMINATION
a. TWORADICALSBONDorRADICALbondstothewallofthecontainertoendthechainreaction
StabilityofALKYLRADICALS: 3>2>1>methyl
FluorineVERYREACTIVE,majorproductisPRIMARY
ChlorineREACTIVE,majorproductiswhateverisLEASTSTERICALLYHINDERED
BromineSELECTIVE,majorproductisTERTIARY
Dehydrationofanalcohol(E1Reaction)
Alcohol+ hotconcentratedH
2
SO
4
Alkene+ H
2
O+ HSO
4
SaytzeffRuleMAJORproductofELIMINATIONistheMOSTSUBSTITUTEDALKENE
Dehydrohalogenation(E1orE2Reaction)
E1MechanismWITHOUTastrongbase2stepsunimolecular(substrateonly)
1) HalogendropsoffformingaCARBOCATION
2) Hydrogenisremovedleavingalkene
E2MechanismSTRONGBULKYBASE1stepbimolecular(substrate&nucleophile)
1) BaseREMOVESahydrogenadjacenttothehalogen
2) Halogendropsoffleavingalkene
InELIMINATION,basepullsoffahydrogen
InSUBSTITUTION,nucleophileattackscarbon
CatalyticHydrogenation(additionreaction)
Heterogeneouscatalyst(Ni/Pd/Pt)promotesSYNaddition
HydrogenationisEXOTHERMICwithhighenergyofactivation
OxidationOfAlkenes
OZONOLYSISozoneisVERYreactive,breakingrightthroughalkenesandalkynes
AlkenesINTOtwoCARBONYLGROUPS
AlkynesINTOtwoCARBOXYLICACIDS
ElectrophilicAddition
ElectrophilesattractedtoelectronsPOSITIVELYCHARGED & AlkenesareELECTRONRICH
WhenHF/HCl/HBr/HIareaddedtoanalkene:
MarkovnikovsrulethehydrogenwilladdtothecarbonwiththeMOSTHYDROGENS
HBr&Peroxides(ROOR)addtoalkenesANTIMARKOVNIKOV
HydrationofanAlkene
Alkene+ colddiluteH
2
SO
4
+ H
2
O Alcohol
Oxymercuration/Demercuration
1) Oxymercurialionattacksalkene,formingtriangularmercurycomplex
2) H2OattacksANTItoformanALCOHOL,losingthemercurygroup
3) IfROHisusedinsteadofwater,anETHERisformed
Hydroboration
Alkene+ BH3+ peroxide Alcohol(antimarkovnikov)
HalogenationOfAnAlkene
Br
2
andCl
2
addANTItoalkenestoformVICDIHALIDES
Benzene
UndergoesSUBSTITUTION,notaddition
Flatmolecule,stabilizedbyRESONANCE
Ortho/Meta/Para
ElectronDonatingGroups(ACTIVATEStheRing)
STRONGLYdonating(ortho/paradirecting)
O
OH NR
2
MODERATELYdonating(ortho/paradirecting)
OR
WEAKLYdonating(ortho/paradirecting)
R
ElectronWithdrawingGroups(DEACTIVATEStheRing)
STRONGLYwithdrawing(metadirecting)
NO
2
NR
3
+
CCl
3
MODERATELYwithdrawing(metadirecting)
Carbonyls SO
3
H CN
WEAKLYwithdrawing(ortho/paradirecting)
Halogens
SN1(substitution/nucleophilic/unimolecular)
1) HydrogendropsoffformingaCARBOCATIONratedeterminingstep
2) Nucleophileattacksthecarbocation
SN2(substitution/nucleophilic/bimolecular)
1) Nucleophileattackssubstratefrombehindknocksleavinggroupfreewhilebindingtosubstrate
Nucleophilicity
ABASEisastrongerNUCLEOPHILEthanitsconjugateacid,butaBASEisNOTNECESSARILYaNUCLEOPHILE
IfaNUCLEOPHILEbehavesasaBASE,ELIMINATIONRESULTS
LESSBULKYNUCLEOPHILE,withNEGATIVECHARGE&POLARIZABILITYaddto
nucleophilicity
Solvents
POLARPROTICSOLVENTSstabilizethenucleophileandanycarbocationthatforms
INCREASES
N
1SPEED DECREASES
N
2SPEED
POLARAPROTICSOLVENTScannotformhydrogenbonds
INCREASES
N
2SPEED DECREASES
N
1SPEED
LeavingGroups
ThebestleavinggroupsarethosethatareSTABLEWHENTHEYLEAVE
TheWEAKERtheBASE,theBETTERtheLEAVINGGROUP
SN1vs.SN2
SN1 SN2
Nucleophile N/A StrongNucleophile
Substrate 2/3 Methyl/1/2(unhindered)
Solvent Polarsolventincreasesrate PolarsolventDECREASESrate
Speed [Substrate] [substrate][nucleophile]
Stereochemistry CreatesRACEMICmixture INVERTSaroundchiralcenter
Skeleton Maybeskeletalrearrangement NOrearrangement
Alcohols
BPgoesupwithincreasingMolecularWeight
ROHhydrogenbonds,dramaticallyraisingMPandBP
AlcoholscanbehaveasACIDS,withmethylOHbeingtheSTRONGESTACID
GrignardSynthesisofAlcohols
OxidationOfAlcohols
OxygenHydrogenratioINCREASESOxidationoccurred
OxygenHydrogenratioDECREASESreductionoccurred
ThePinacolRearrangement
InVICINALDIOLS,DEHYDRATIONproductisaKETONEorALDEHYDE
Ethers
ALMOSTALWAYSTHEANSWERtoSOLVENTQUESTIONSontheMCAT
ROR+ HBr ROH+ RBr
AciditiesOfFunctionalGroups
Carbonyls&Amines
TheCarbonyl
CarbonDOUBLEBONDEDtooxygen PLANARStereochemistry PARTIALPOSITIVEonthecarbon
Aldehydes&Ketones
ALDEHYDE R(C=O)H KETONE R(C=O)R
FORMALDEHYDE H(C=O)H ACETONE CH3(C=O)CH3
LowerBoilingPointthanALCOHOL
carbonisVERYACIDIClosesaprotontobecomeanENOLATEION(stabilizedbyresonance)
Indicarbonyls,theENOLATEIONICformismoreprevalent
KETOENOLTautomerization
FormationofAcetals
KETONE+ALCOHOL HEMIKETAL+ALCOHOL KETAL
Acetals/KetalscanactasBLOCKINGGROUPS
toPRESERVEaCARBONYLGROUP
AldolCondensation
Aldehyde+Aldehyde Ketone+Ketone Aldehyde+Ketone
hydrogenisabstracted,forminganENOLATEION
carbonofENOLATEattackscarbonylcarbonofothermolecule,formingALKOXIDEION
ALKOXIDEIONgrabsahydrogentobecomeanALDOL(aldehyde&alcohol)
Halogenation&HaloformReaction
HALOGENSaddtoKETONESatthecarboninpresenceofacidorbase
METHYLKETONEwithBASE,thecarbonisCOMPLETELYHALOGENATED
HALOFORMbreaksoff(CHCl3/CHBr3/CHF3)leavingCARBOXYLATEION
WittigReaction
Ketone/Aldehyde+ Ylide(carbanion) ALKENE
UnsaturatedCarbonyls
Alsocalled1,4additionaddingHXformsENOLTAUTOMERandthenKETO
CarboxylicAcids
CarboxylicAcid RCOOH FormicAcid HCOOH
BenzoicAcid C6H5COOH AceticAcid CH3COOH
Ifthenameendsinate RCOO
MakeSTRONGHYDROGENBONDStoformdimmers
ThiseffectivelydoublesM.W.significantlyincreasingB.P.
Decarboxylation
CARBOXYLATEIONLOSESCO2tobecomeKETOENOLTAUTOMERS
CarboxylicAcidDerivativesACYLCHLORIDES
MOSTREACTIVEOFALLCARBOXYLICACIDDERIVATIVES
ACIDCHLORIDE+ H2O CARBOXYLICACID+ HCl
ACIDCHLORIDE+ ROH ESTER+ HCl
ACIDCHLORIDE+ RNH2 AMIDE+ HCl
ACIDCHLORIDE+ RCOOH ANHYDRIDE+ HCl
ALDEHYDES/KETONES NucleophilicADDITION
CARBOXYLICACIDS/DERIVATIVES NucleophilicSUBSTITUTION
CarboxylicAcidDerivativesESTERIFICATION
CarboxylicAcidDerivativesTRANSESTERIFICATION
CarboxylicAcidDerivativesACETOACETICESTERSYNTHESIS
ACETOACETICESTER+ RX+ H+/HEAT KETONE+ CO2
CarboxylicAcidDerivativesREACTIVITIES
Amide Ester CarboxylicAcid AcidAnhydride AcylChloride
Amines
Ammonia NH3
AmineDegreedependsonnumberofATTACHEDRGROUPS
1) ActasLEWISBASEDONATINGLONEPAIROFELECTRONS
2) ActasaNUCLEOPHILEwhereLONEPAIRofELECTRONSattacksPOSITIVECHARGE
3) NitrogencantakeonaFOURTHBOND(+)
4) NitrogencanHYDROGENBONDincreasingBOILINGPOINTandSOLUBILITY
CondensationwithKetones
AMINE+ ALDEHYDE/KETONE WATER+ IMINE/ENAMINE
WolffKishnerReduction
HYDRAZINE+ALDEHYDE/KETONE ALKANE+WATER+N2
AlkylationofAmine
HofmannElimination
Amines&NitrousAcid
NITROUSACID+1AROMATICAMINE DIAZONIUMION
TheDiazoniumGroupisEASILYREPLACED
Amides
Acetamide Nethylacetamide
Lactams(CYCLICAMIDES)
HofmannDegradation
PhosphoricAcid
Whenheated,phosphoricacidformsPHOSPHORICANHYDRIDES
Triphosphatesexistasnegativeions,suchasATP
Biochemistry&LabTechniques
FattyAcids
LONGCARBONCHAINWITHCOOHontheend
AminoAcids
ZwitterionDIPOLARION(onesideandoneside+)
BASICAMINOACIDS
Histidine
Arginine
Lysine
ISOELECTRICPOINTthepHwhere100%oftheaminoacidsareZWITTERIONS
Carbohydrates
1) GENERALFORMULAC
n
(H
2
O)
n
2) CanhaveeitherALDEHYDEorKETONEgroupstobecalledALDOSEorKETOSE
3) ANOMERICCARBONtheONLYCARBONattachedtoTWOOXYGENS
LabTechniques
SPECTROSCOPY
NuclearMagneticResonance(NMR)
InfraredSpectroscopy(IR)
UltravioletSpectroscopy(UV)
SPECTROMETRY
MassSpectrometry
SEPARATIONTECHNIQUES
Chromatography
Distillation
Crystallization
Extraction
NMR
1) EachpeakisaCHEMICALLYEQUIVALENTHYDROGEN
2) SPLITTINGPEAKSiscreatedbyNEIGHBORINGHYDROGENSasbyn+1(n=#ofneighboringcarbons)
3) TotheLEFTisDOWNFIELD(unshieldedbyelectronegativeatoms)
IRSpectroscopy
CARBONYLGROUP 1700
OHGROUP 32003600
UltravioletSpectroscopy
UVstartsaround220nm(butadiene)
1) EachadditionalCONJUGATEDBONDadds3040nmtothewavelengthABSORBEDMOST
VisibleSpectrum
Ifcompoundhas8+CONJUGATEDDOUBLEBONDS,itsabsorbanceenterstheVISIBLESPECTRUM
Carotenehas11CONJUGATEDDOUBLEBONDS,withanabsorbanceofabout500nm
CaroteneabsorbstheBLUEGREENcolorof500nm,anddisplaystheCOMPLEMENTARYCOLORofred
orange
MassSpectrometry
MassSpectrometrygivestheMOLECULARWEIGHT
Samplemoleculesarebombardedbyelectrons,causingthemtobreakapartandIONIZE
Ionsareacceleratedthroughamagneticfield,mostare+1
RADIUSOFCURVATUREdependsupontheMASStoCHARGERATIO(m/z)
BASEPEAKthelargestpeak
PARENTPEAKthepeakmadebythemolecularion(sameasORIGINALMOLECULEbutwithoutONE
ELECTRONsoithasa+1charge)
Chromatography
SeparationofamixturebypassingitoverorthroughamatrixthatADSORBSdifferentcompoundswith
DIFFERENTAFFINITIES
MOBILEPHASE/STATIONARYPHASE
TheMOREPOLARcompoundmovesmoreSLOWLYbecauseitbindstothePOLARSTATIONARYPHASE
Distillation
SeparationbaseduponVAPORPRESSURE
SeparatesasolutionoftwovolatileliquidswithaBOILINGDIFFERENCEofatleast20C
ThecompoundwiththeLOWERBOILINGPOINT(HIGHERVAPORPRESSURE)willboiloffandcanbe
captured
Crystallization
WorksontheprinciplethatPURESUBSTANCESFORMCRYSTALSmoreeasilythanimpuresubstances
CrystallizationisVERYINEFFICIENT
Extraction
BasedonSOLUBILITYDUETOSIMILARPOLARITIES
LIKEDISSOLVESLIKE