IntroductoryOrganicChemistry

Chem 212&Chem 211

ORGANICBITES3:CHIRALITY&OPTICALROTATION
Dr.LauraPavelka
DepartmentofChemistry
Pulp&Paper104
[email protected]

MORE3DVISUALIZATIONS...
Section3 Stereochemistry
Chapter5 ChiralMolecules
StructuralIsomersvs.Stereoisomers
EnantiomersandChirality
OpticalRotationandRacemicMixtures

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MAKESUREYOUKEEPALLYOURISOMERS
STRAIGHT!

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StructuralIsomers
ISOMERS differentcompoundswiththesamemolecularformula
STRUCTURAL differentconnectivity(differentnames)
STEREOISOMERS sameconnectivity,differentorientationinspace

CH3(CH2)3CH3
PENTANE
C5H12
CH3CH2CH(CH3)2 ISOPENTANE
CH3C(CH3)3
NEOPENTANE

bp =36C
bp =28C
bp =10C

STRUCTURALISOMERS
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Stereoisomers
ISOMERS differentcompoundswiththesamemolecularformula
STRUCTURAL differentconnectivity
STEREOISOMERS sameconnectivity,differentorientationinspace

trans2,3dichloro2hexene

cis2,3dichloro2hexene

STEREOISOMERS
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Stereoisomers
ISOMERS differentcompoundswiththesamemolecularformula
STRUCTURAL differentconnectivity
STEREOISOMERS sameconnectivity,differentorientationinspace

trans1,3dichlorocyclohexane

cis1,3dichlorocyclohexane

STEREOISOMERS
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Conformers
ISOMERS differentcompoundswiththesamemolecularformula
STRUCTURAL differentconnectivity
STEREOISOMERS sameconnectivity,differentorientationinspace
*CONFORMERSARENOTTRUEISOMERS ONLYDIFFERENT
REPRESENTATIONSOFTHESAMECOMPOUND*

CONFORMERS rotationalisomers
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ResonanceStructures
ISOMERS differentcompoundswiththesamemolecularformula
STRUCTURAL differentconnectivity
STEREOISOMERS sameconnectivity,differentorientationinspace
*RESONANCESTRUCTURESARENOTISOMERS ONLY
DIFFERENTREPRESENTATIONSOFTHESAMECOMPOUND*

RESONANCESTRUCTURES 2+Lewisstructurestorepresentthesamemolecule
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STEREOISOMERSCANBEFURTHER
SUBDIVIDED...

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Stereoisomers:Enantiomers
ISOMERS differentcompoundswiththesamemolecularformula
STRUCTURAL differentconnectivity
STEREOISOMERS sameconnectivity,differentorientationinspace
ENANTIOMERS nonsuperimposablemirrorimagestereoisomers
DIASTEREOMERS nonmirrorimagestereoisomers

caraway

mint

ENANTIOMERS
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Stereoisomers:Diastereomers
ISOMERS differentcompoundswiththesamemolecularformula
STRUCTURAL differentconnectivity
STEREOISOMERS sameconnectivity,differentorientationinspace
ENANTIOMERS nonsuperimposablemirrorimagestereoisomers
DIASTEREOMERS nonmirrorimagestereoisomers

trans2,3dichloro2hexene

cis2,3dichloro2hexene

DIASTEREOMERS
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HOWDOESCHIRALITYFITINTOTHIS
PICTURE?

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MORE3DVISUALIZATIONS...
Section3 Stereochemistry
Chapter5 ChiralMolecules
StructuralIsomersvs.Stereoisomers
EnantiomersandChirality
OpticalRotationandRacemicMixtures

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Chirality
CHIRALOBJECT onewithanonsuperimposablemirrorimage
1.ENANTIOMERSARE(BYDEFINITION)APAIROFCHIRALOBJECTS
2.CHIRALOBJECTSARESAIDTOHAVECHIRALITY

caraway

mint

ENANTIOMERS
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Chirality
CHIRALOBJECT onewithanonsuperimposablemirrorimage
1.ENANTIOMERSARE(BYDEFINITION)APAIROFCHIRALOBJECTS
2.CHIRALOBJECTSARESAIDTOHAVECHIRALITY

ENANTIOMERS
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Chirality
CHIRALOBJECT onewithanonsuperimposablemirrorimage
1.ENANTIOMERSARE(BYDEFINITION)APAIROFCHIRALOBJECTS
2.CHIRALOBJECTSARESAIDTOHAVECHIRALITY

ENANTIOMERS
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Chirality
CHIRALOBJECT onewithanonsuperimposablemirrorimage
1.ENANTIOMERSARE(BYDEFINITION)APAIROFCHIRALOBJECTS
2.CHIRALOBJECTSARESAIDTOHAVECHIRALITY

ENANTIOMERS
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WEARECHIRALOBJECTS!
ANDSOAREMOSTMOLECULESOFLIFE...
WHICHAREALSOMOSTLYONLY
ONEENANTIOMER!

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BiologicalChirality

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BiologicalChirality

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BiologicalChirality

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BiologicalChirality

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BiologicalChirality

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ENANTIOMERSHAVETHE
SAMEPHYSICALPROPERTIES...
(IDENTICALINTERMOLECULARFORCES)
...EXCEPTFOROPTICALROTATION!

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OpticalRotation

(+)2butanol
BoilingPoint
Meltingpoint
Density

99.5C
115C
0.808

SpecificRotation[]
+13.5
(opticalrotation)
opticallyactive
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()2butanol
99.5C
115C
0.808
13.5
opticallyactive
25

WHATISOPTICALROTATION?
...ANDHOWDOWEMEASUREIT?

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MORE3DVISUALIZATIONS...
Section3 Stereochemistry
Chapter5 ChiralMolecules
StructuralIsomersvs.Stereoisomers
EnantiomersandChirality
OpticalRotationandRacemicMixtures

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MeasuringOpticalRotation
OPTICALROTATION rotationofplanepolarizedlightasit
passesthroughachiralobject
1.
2.

ALLCHIRALMOLECULESWILLROTATEPLANEPOLARIZEDLIGHT
ENANTIOMERSROTATEINEQUALAMOUNTS,OPPOSITEDIRECTIONS

POLARIZEDLIGHT

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MeasuringOpticalRotation
OPTICALROTATION rotationofplanepolarizedlightasit
passesthroughachiralmolecule
1.
2.

ALLCHIRALMOLECULESWILLROTATEPLANEPOLARIZEDLIGHT
ENANTIOMERSROTATEINEQUALAMOUNTS,OPPOSITEDIRECTIONS

POLARIMETER

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MeasuringOpticalRotation
OPTICALROTATION rotationofplanepolarizedlightasit
passesthroughachiralmolecule
1.
2.

ALLCHIRALMOLECULESWILLROTATEPLANEPOLARIZEDLIGHT
ENANTIOMERSROTATEINEQUALAMOUNTS,OPPOSITEDIRECTIONS

POLARIMETER

...BUTWECANNOTPREDICTWHICH
DIRECTIONANENANTIOMERWILL
ROTATELIGHTBASEDONSTRUCTURE!

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OpticalRotationData

(+)2butanol
SpecificRotation[]=

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()2butanol

observedrotationangle
(concentration)(celllength)

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OpticalRotationData

(+)rotation
SpecificRotation[]

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()rotation

+13.5
opticallyactive
clockwise
(+)2butanol

13.5
opticallyactive
counterclockwise
()2butanol

dextrorotatory

levorotatory

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OpticalRotationData

SpecificRotation[]

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(+)rotation

()rotation

(natural)

(unnatural)

+31.4
opticallyactive
clockwise
(+)glutamicacid

31.4
opticallyactive
counterclockwise
()glutamicacid

dextrorotatory

levorotatory

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RacemicMixtures

(+)2butanol

()2butanol

1:1mixture
SpecificRotation[]

0
notopticallyactive!
racemicmixture

RACEMICMIXTURES 50:50mixturesof(+)and()

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RacemicMixtures

1:1mixture(+)2butanol&()2butanol

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COMPOUNDSTHATROTATEPLANE
POLARIZEDLIGHT(i.e.CHIRALOBJECTS)
ARESAIDTOBEOPTICALLYACTIVE...

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TheFirstOpticallyActiveObjects

LOUISPASTEUR(1822 1895)

()tartaricacid

(+)tartaricacid

THEFIRSTENANTIOMERS!
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TheFirstOpticallyActiveObjects

LOUISPASTEUR(1822 1895)

()tartaricacid

(+)tartaricacid

TARTARICACID opticalrotationclockwise
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TheFirstOpticallyActiveObjects

LOUISPASTEUR(1822 1895)

50:50
()tartaricacid

(+)tartaricacid

RACEMICACID nomeasuredopticalrotation
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OrganicBites3:MainObjectives
1.
2.
3.
4.
5.

Identifystructuralisomersvs.stereoisomers.
Define/identifyenantiomersanddiastereomers.
Recognize/Identifychiralobjects.
Understandopticalrotationand(+)/()notation.
Explainthetermsopticallyactiveandracemic
mixture.

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