ib chemistry on stereoisomers, e/z, cis trans, geometric, optical isomer and polarimetry
TRANSCRIPT
http://lawrencekok.blogspot.com
Prepared by Lawrence Kok
Tutorial on Stereoisomers, Cis Trans, E/Z, Optical Isomerism and Polarimetry.
IsomerismMolecules with same molecular formula but diff arrangement of atom
Two types of Isomerism
Positional Chain Isomer
Functional Gp Isomer
C – C – C – C – OH
C4H10O1
Structural Isomerism
• Same molecular formula• Diff structural formula• Diff arrangement of atom
Diff hydrocarbon chain skeleton
• Same molecular formula• Same structural formula/ same connectivity• Diff spatial arrangement of atom
Stereoisomerism
Hydrocarbon Chain Isomer
Diff functional gp position Diff functional gp
C – C – C – OH ׀ CH3
C – C – C –C ׀ OH
C – C – C – C ׀ OH
C – C – C – C ׀ OH
C – C – C – O – C
Optical IsomerGeometric Isomer
Click here khan organic videos.
Compound Ethane Ethanoic acid
Empirical formula
CH3 CH2O
Molecular formula
C2H6 C2H4O2
Full SF
Condensed SF CH3CH3 CH3COOH
Stereochemical formula
(3D)
Isomer Physical property
Chemical property
Structural isomer- Hydrocarbon chain- Functional gp position- Functional gp
DifferentDifferentDifferent
SimilarSimilar
Different
Geometrical isomer Different Similar
Optical isomer Similar Similar
H H ׀ ׀ H - C – C – H ׀ ׀ H H
H O ‖ ׀ H - C - C - OH ׀ H
Structural formula – arrangement atoms in molecule (2/3D)
H H ׀ ׀ H - C – C – H ׀ ׀ H H
CH3CH3
ethane
Display full SF Condensed SF Ball/stick model Spacefilling
Click here chemical search.
same connectivity but diff spatial arrangement
CI
Isomerism
Two types of Isomerism
Positional Chain Isomer
Functional Gp Isomer
C4H10O1
Structural Isomerism
• Same molecular formula• Diff structural formula• Diff arrangement of atom
• Same molecular formula• Same structural formula/same connectivity
• Diff spatial arrangement of atom
Stereoisomerism
Hydrocarbon Chain Isomer Optical IsomerGeometric Isomer
Requirement for geometric isomers• Presence of C=C double bond - prevent bond rotation• Presence of ring structure - prevent bond rotation• Carbon atom in double bond bonded to diff atom
Cis IsomersAtom located on same
side
Trans IsomersAtom located on diff
side
Presence C=C Presence of ring structure
CI CI ׀ ׀ C = C ׀ ׀ H H
Cis 1, 2 dichloroethene
CI H ׀ ׀ C = C ׀ ׀ H CI
Trans 1, 2 dichloroetheneCis 1, 2 dichlorocyclopropane Trans 1, 2 dichlorocyclopropane
Carbon atom bond to diff atom
double bond
C – C – C – C – OH C – C – C –C ׀ OH
C – C – C – O – C
C – C – C – OH ׀ CH3
CI CI CI
CI
H
H H H
CI CI
H H
H
H
CI
Cis 1, 3 dichlorocyclobutane Trans 1, 3 dichlorocyclobutane
sameatom
different atomχ
✓No geometric isomers
Geometric isomers
same connectivity but diff spatial arrangement
• Same molecular formula• Same structural formula/same connectivity
• Diff spatial arrangement of atom
Stereoisomerism
Geometric Isomer
Requirement for geometric isomers• Presence of C=C double bond - prevent bond rotation• Presence of ring structure - prevent bond rotation• Carbon atom in double bond bond to diff atom
Cis IsomersAtom located on same
side
Trans IsomersAtom located on diff
side
Presence C=C Presence of ring structure
CI CI ׀ ׀ C = C ׀ ׀ H H
Cis 1, 2 dichloroethene
CI H ׀ ׀ C = C ׀ ׀ H CI
Trans 1, 2 dichloroethene Cis 1, 2 dichlorocyclopropane Trans 1, 2 dichlorocyclopropane
Carbon atom bond to diff atom
double bond
CI CI CI
CI
H
H H H
sameatom
different atom
Cis / Trans naming sys
click here E/Z naming system
2 diff substituent on each carbon
[Z] 1, 2 dichloroethene [E] 1, 2 dichloroethene
CI CI ׀ ׀ C = C ׀ ׀ H H
CI H ׀ ׀ C = C ׀ ׀ H CI
Atom same side Atom opposite side
[Z] 1, 2 dichlorocyclopropane [E] 1, 2 dichlorocyclopropane
E / Z naming sys
E/Z (CIP priority) 4 diff substituents
1
1 – high priority2 – low priority
1
2
1
2 2
2
1
Priority same side – ZPriority opp side - E
H H
CI CI 1 1
2 2H CI
CI H
1
1 2
2
1 – high priority2 – low priority
Priority same side – ZPriority opp side - E
E/Z naming system↓
Cahn-Ingold-Prelog (CIP)
CH3 H ׀ ׀ C = C ׀ ׀ Br OH
1 – high priority2 – low priority
Priority same side – ZPriority opp side - E
1
2
1
2C atomic mass ↓
Br atomic mass ↑
O atomic mass ↑
H atomic mass ↓
Priority same side - Z
sameatom
different atom
Cis / Trans naming sys
click here E/Z naming system
2 diff substituent on each carbon
[Z] 1, 2 dichloroethene [E] 1, 2 dichloroethene
CI CI ׀ ׀ C = C ׀ ׀ H H
CI H ׀ ׀ C = C ׀ ׀ H CI
[Z] 1, 2 dichlorocyclopropane [E] 1, 2 dichlorocyclopropane
E / Z naming sys
E/Z (CIP priority) 4 diff substituents
1
1 – high priority2 – low priority
1
2
1
2 2
2
1
Priority same side – ZPriority opp side - E
H H
CI CI 1 1
2 2H CI
CI H
1
1 2
2
1 – high priority2 – low priority
Priority same side – ZPriority opp side - E
E/Z naming system Cahn-Ingold-Prelog (CIP)
CH3 H ׀ ׀ C = C ׀ ׀ Br OH
1 – high priority2 – low priority
Priority same side – ZPriority opp side - E
1
2
1
2C atomic mass ↓
Br atomic mass ↑
O atomic mass ↑
H atomic mass ↓
Priority same side - Z
CI I ׀ ׀ C = C ׀ ׀ H Br
CH3 CH3 ׀ ׀ C = C ׀ ׀ H CI
[E] 2-chlorobut-2-eneCis 2 chlorobut-2-ene
[Z] 2-bromo-1-chloro-2-iodoethene
CI Br ׀ ׀ C = C ׀ ׀ H I
[E] 2-bromo-1-chloro-2-iodoethene
Br atomic mass ↓
H atomic mass ↓
I atomic mass ↑
2 2
1 1CI atomic mass ↑
CI atomic mass ↑
I atomic mass ↑
Br atomic mass ↓
1
1
2
2H atomic mass ↓
CH3 CI ׀ ׀ C = C ׀ ׀ H CH3
[Z] 2-chlorobut-2-eneTrans 2 chlorobut-2-ene
based on atomic mass
1 1
2 2 1
1 2
2
CH3 CH3 ׀ ׀ C = C ׀ ׀ H C2H5
Br CH3 ׀ ׀ C = C ׀ ׀ H C2H5
H CH3 ׀ ׀ C = C ׀ ׀ Br C2H5
CH3 H ׀ ׀ C = C ׀ ׀ Br OH
1
1 2
2 1 1
22
E/Z naming system Cahn-Ingold-Prelog (CIP)
H COOH ׀ ׀ C = C ׀ ׀ HOOC H
1 – high priority2 – low priority
Priority same side – ZPriority opp side - E
1
1
2
2H atomic mass ↓
C atomic mass ↑
C atomic mass ↑
H atomic mass ↓
Br H ׀ ׀ C = C ׀ ׀ CH3 OH
H atomic mass ↓
C atomic mass ↓
O atomic mass ↑1 1
2 2
Br atomic mass ↑
Br atomic mass ↑
O atomic mass ↑
H atomic mass ↓
1 2
2C atomic mass ↓
based on atomic mass
2
11
2
1
1 2
2
1
E - Priority opposite side Z - Priority same side E - Priority opposite sideTrans but-2-ene-1,4-dioic acid
[Z] 1-bromo-2-methylbut-1-ene
Br atomic mass ↑
H atomic mass ↓
H H׀׀ C – C – H׀׀ H H
H׀ C – H׀ H
[E] 1-bromo-2-methylbut-1-ene
Br atomic mass ↑
H atomic mass ↓
H H׀׀ C – C – H׀׀ H H
C – bond H, H, C (Higher priority)
H׀ C – H׀ H
C – bond H, H, H(Lower priority)
[E] 3-methylpent-2-ene
C atomic mass ↑
H atomic mass ↓
H H׀׀ C – C – H׀׀ H H
C – bond H, H, C (Higher priority)
C – bond H, H, C (Higher priority)
C – bond H, H, H(Lower priority)
C – bond H, H, H(Lower priority)
H׀ C – H׀ H
[Z] 3-methylpent-2-ene
H CH3 ׀ ׀ C = C ׀ ׀ CH3 C2H5
H atomic mass ↓
C atomic mass ↑
H H׀׀ C – C – H׀׀ H H
H׀ C – H׀ H
C – bond H, H, C (Higher priority)
C – bond H, H, H(Lower priority)
CH3 H ׀ ׀ C = C ׀ ׀ H C2H5
CH3 CH2OH ׀ ׀ C = C ׀ ׀ CH3CH2 CHO
Br CH2OH ׀ ׀ C = C ׀ ׀ CI CHO
CI CH2OH ׀ ׀ C = C ׀ ׀ Br CHO
CH3 H ׀ ׀ C = C ׀ ׀ Br OH
1
22
1
E/Z naming system Cahn-Ingold-Prelog (CIP)
H COOH ׀ ׀ C = C ׀ ׀ HOOC H
1 – high priority2 – low priority
Priority same side – ZPriority opp side - E
1
1
2
2H atomic mass ↓
C atomic mass ↑
C atomic mass ↑
H atomic mass ↓
Br H ׀ ׀ C = C ׀ ׀ CH3 OH
H atomic mass ↓
C atomic mass ↓
O atomic mass ↑1 1
2 2
Br atomic mass ↑
Br atomic mass ↑
O atomic mass ↑
H atomic mass ↓
1 2
2C atomic mass ↓
based on atomic mass
2
11
2
1
1 2
2
1
E - Priority opposite side Z - Priority same side E - Priority opposite sideTrans but-2-ene-1,4-dioic acid
Br atomic mass ↑
CI atomic mass ↓
H ׀ C = O
H׀ C – H׀ OH
Br atomic mass ↑
CI atomic mass ↓
C – bond H, O, O (Higher priority)
H ׀ C – OH ׀ H
C – bond H, O, O (Higher priority)
C – bond H, O, O (Higher priority)
C – bond H, O, H(Lower priority)
C – bond H, O, H(Lower priority)
H׀ C = O
H H׀ ׀H – C – C ׀ ׀ H H
H׀ H – C ׀ H
C – bond H, H, H(Lower priority)
Z - Priority same side
H ׀ C = O
H׀ C – H׀ OH
C – bond H, O, H(Lower priority)
E - Priority opposite side
C – bond H, H, C (Higher priority)
Z - Priority same side
Pent – 2-ene 2,3-dichlorobut-2-ene
H H ׀ ׀ C = C ׀ ׀ CH3 C2H5
[E]-2,3 dichlorobut-2-ene
CI CI
׀ ׀ C = C ׀ ׀ CH3 CH3
CH3 CI ׀ ׀ C = C ׀ ׀ CI CH3
2 2 2
2
2
22 21 1
1
1
1
1
1 1
[Z] pent-2-ene [E] pent-2-ene [Z]-2,3 dichlorobut-2-ene
Draw and name isomers using E/Z convention
Draw structural formula isomer with MF below, state type of isomerism
Stereoisomerism
C2 H2 CI2CI CI ׀ ׀ C = C ׀ ׀ H H
CI H ׀ ׀ C = C ׀ ׀ CI H
Both Structural formula
Geometric IsomerCI CI ׀ ׀ C = C ׀ ׀ H H
CI H ׀ ׀ C = C ׀ ׀ H CI
Cis 1, 2 dichloroethene Trans 1, 2 dichloroethene
[Z] 1, 2 dichloroethene [E] 1, 2 dichloroethene
22
11
2
2
1
1
C3H4CI2
CI
CI
CI CI
H H H
H Both Structural formula
CI CI CI
Geometric Isomer
H H H CI
H
Cis 1, 2 dichlorocyclo propane
Trans 1, 2 dichlorocyclo propane
[Z] 1, 2 dichlorocyclo propane
[E] 1, 2 dichlorocyclo propane
Which exhibit cis/trans isomerism ?
CI H ׀ ׀ C = C ׀ ׀ Br H
F CH3 ׀ ׀ C = C ׀ ׀ H CI
F CH3 ׀ ׀ C = C ׀ ׀ CI CH3
CH3CH=CHCH3CH3CH=CH2
CH(F)=C(CH3)2 CH(CI)=C(CI)CH3
Draw geometric isomers
CH3CH=CHCH2CH3
FCH = CHFWhich is structural isomer
CH3COCH2CH3 H H
׀ ׀ C = C ׀ ׀ CH3 C2H5
CH3 H ׀ ׀ C = C ׀ ׀ H C2H5
F F ׀ ׀ C = C ׀ ׀ H H
F H ׀ ׀ C = C ׀ ׀ H F
Which exhibit cis/trans isomerism ?
CH3CH=CHCH2CH3
FCH = CHF
Cis/ [Z] Cis/ [Z]Trans / [E] Trans / [E]
CH3CH2-O-CH2CH3 CH3CH2CH2-CH ‖ O
CH2=CH-CH-CH3׀ OH
Geometric Isomers Optical Isomers
Same chemical property– Same functional gp
• Diff physical property – Diff spatial arrangement
(Diff density, solubility, melting pt/boiling pt)
• Same chemical property – Same functional gp• Same physical property
(Same density, solubility, melting pt/boiling pt)
Vs
EnantiomerMirror image of each
other
EnantiomerMirror image of each
other
Stereoisomerism
Molecules with same molecular formula but diff spatial arrangement
• Same molecular formula• Same structural formula / same connectivity
• Diff spatial arrangement of atom
Cis IsomerAtom on same
side
Trans IsomerAtom on diff side
click here for optical rotation sugar click here for polarimeter
click here opical rotation corn syrupclick here polarimeter Pasco Demo
Mirror image
Right handed Left handed
Non superimposable
Chiral/asymmetrical/stereocentre carbon (4 diff groups)
same connectivity but diff spatial arrangement
Isomers with same Molecular Formula and Structural Formula but diff spatial arrangement • At least 1 asymmetric / chiral carbon / stereocentre , bonded to 4 diff gp
• NH2CH(R)COOH show optical isomerism• Optical isomers/mirror images call enantiomers (cannot superimpose on each other)
• Similar physical and chemical property except for the effect on rotation of plane of polarised light• Optically active – enantiomer rotate plane polarised light to one direction (clockwise / anticlockwise)
• Optically inactive – enantiomer present in equal amt (equimolar) – racemic mix and rotation cancel out each other
Optical Isomers
chiral carbon – 4 diff gp
Optically inactive – Rotation cancel out each other
Enantiomer (R) - rotate clockwiseEnantiomer (S) – rotate anticlock wise
50% 50% 70% 30%
Optically active – Net Rotation clockwise
Non superimposable
Non superimposable
1. Light pass through 1st polariser – plane polarised light produced
2. Sample introduce to tube. Sample is optically active Rotate plane of polarised light to one direction3. Turn analyzer either clockwise/anticlock wise to give light of max intensity again4. If sample rotate light 120 clockwise – Analyzer need to rotate anticlock wise 120
5. If one enantiomer rotate light 120 clockwise Another enantiomer rotate light anticlock wise 120
How polarimeter detect optical isomer ?
6. Racemic Mix = enantiomers in equal amt (equimolar) , cancel each other rotation
1st polarizer
1st polarizer
sample optically active
sample optically inactive= Optical activity ability- to rotate plane of polarised lightOptically active isomers –presence of asymmetrical/chiral centre- carbon bond to 4 diff gp
Product from natural sources/catalysed by enzyme
• give 1 pure optically active enantiomer• chiral and found in single enantiomer –
optically active
Products synthesised chemically• give 2 enantiomer in equal amt
/racemic mix• optically inactive rotation cancel out
each other
Light source
1st polarizer
Tube containing samplewhich able to rotate polarized light
2nd polarizer(Analyzer)
Polarizer tube
Rotated clockwise
How Polarimeter works ?
R – inactiveRacemate mix ibuprofen
S – activeRacemate mix ibuprofenIbuprofen (painkiller)
Click here notes isomers
R limonene S limonene
CH3
CH3
CH3
Product from natural source/catalysed by enzyme
• give 1 pure optically active enantiomer• chiral and found in single enantiomer –
optically active
Product synthesised chemically• give 2 enantiomer in equal amt
/racemic mix• optically inactive rotation cancel out
each other
R – inactiveRacemate mix ibuprofen
S – activeRacemate mix ibuprofenIbuprofen
(painkiller) R limonene S limonene
CH3
CH3
CH3
Stereoisomerism
Mirror image / enantiomersSame chemical/physical propertyexcept rotation of polarized light
Source/smell orange Source/smell
lemon
Mirror image / enantiomersSame chemical/physical propertyexcept rotation of polarized light
R carvone S carvone
Mirror image / enantiomersSame chemical/physical propertyexcept rotation of polarized light
Source/smell spearmint
Source/smell caraway seed
R Thalidomide (sedative) S Thalidomide (teratogenic)
• Drug company make drug with R and S (racemic mix)
• Thalidomide exist as optical isomers • Enantiomers (R) and (S)• (R) effective against morning sickness• S teratogenic, birth and limb defect
Our body synthesise enzyme which have active site for only one enantiomer
Mirror image / enantiomers
Thalidomide(pregnancy)
• (S) cause limb defect / shortening of arm /leg• (R) is effective drug• Body convert (R) to (S) by racemisation process, produce
racemic mix (R)/(S)
• Most drug in racemic mix equal (R) and (S)• Cheaper to synthesise racemic mix than pure enantiomer• Single enantiomer appear to be more effective than racemic mix • Clinical trial is essential to ensure no harmful side effect
(S), effective as pain relief(R) has no side effect!
March 2010 - Published in Science by Takumi Ito.Click HERE for info
Defect Limb due to Thalidomide• (S) bind /inactivate protein cereblon, which involve in
limb formation.• Inactivation, lead to a teratogenic effect on LIMB
DEFORMITIESPublished in Science .....• Hiroshi Handa /Takumi Ito - Developed tiny beads with
Thalidomide attach.• Thalidomide beads mix with cells extract• Protein Cereblon was bounded on beads• Lack Protein Cereblon during embryo development, cause limb
deformities
Click HERE for info/sourcehttp://www.rsc.org/chemistryworld/news/2010/march/11031001.asphttp://news.bbc.co.uk/2/hi/science/nature/8562998.stmhttp://news.sciencemag.org/sciencenow/2010/03/-thalidomide-ranks-as-one.html
Scientist discovered how Thalidomide caused Malformed Limb
History of Thalidomide 1954 - Thalidomide for morning sickness.1961 - Withdrawn, teratogenicity, birth defects result .
1990 - FDA approved for leprosy (skin disease) 1998 - FDA approved for multiple myeloma, (cancer of plasma cells in blood) 2004 - Lenalidomide derived from Thalido able to strengthen immune cells and effective against blood cancers2011 - Thalidomide + Lenalidomide inhibit formation of new blood vessels ( anti-angiogenic) of tumor cells, Tumors unable to grow due to lack of nutrition. Researchers testing thalidomide in trials for other HIV and Crohn’s disease.
Write structural formula isomers for C4H9OH, state which isomer show optical isomerism
Butan -1-ol Butan-2-ol 2-methylpropan-2-ol 2-methylpropan-1-ol
All structural isomers
Stereoisomers (Optical Isomers)
Write structural formula of cyclic isomers for C3H4CI2, state type of isomerism
Structural formula
Geometric IsomersCis/Tans isomerism
Optical IsomersEnantiomer, mirror image
Cyclic ring geometric isomers
CH3-CH2-CH2-CH3
׀ OH
CH3-CH2-CH-CH3 ׀ OH
CH3 ׀ CH3-C-OH ׀ CH3
CH3-CH-CH2-OH ׀ CH3
chiral centre
chiral centre
CI CI
CI
CI
H
H H H
H
H H H CI
CI CI CI
Trans 1, 2 dichlorocyclopropaneCis 1, 2 dichlorocyclopropaneStereoisomers (Optical Isomers)
CI CI CI CI
H H H H
chiral centre
chiral centre
* *
Optical IsomerismWhich carbon has chiral center?
Draw all stereoisomers CHBr=CHCH(OH)CH3
CHBr=CHCH(OH)CH3
Optical isomersGeometric isomers
Chiral carbon with 4 diff gp Double bond prevent bond rotationCis / Z Trans / E
CH3CH2C*H(CH3)(CI)
CH3C*H(NH2)COOH CH3C*H(OH)CH2OH C2H5C*H(OH)CH2OH
C2H5
H H׀ ׀ C = C׀ ׀ Br CH(OH)CH3
H CH(OH)CH3
׀ ׀ C = C׀ ׀ Br H
H ׀ CHBr=CH-C–CH3
׀ OH
H ׀ CH3-C-CH=CHBr ׀ OH
R (enantiomer) S (enantiomer)
chiral centre
Non chiral centre
NOT mirror imagesuperimposable
χrotate it
They are same. Superimposable
Mirror imageNon superimposable
chiral centre
Optical Isomers
Enantiomers Diastereomers
Same connectivityHave chiral carbon
Non superimposableMirror image each
other
Same connectivity Have chiral
carbonNon
superimposableNo Mirror image
diff chemical/physical property
2 chiral centre 22 = 4 stereoisomer 3 chiral centre 23 = 8 stereoisomer
click here to view diastereomers
same chemical/physical property
Mirror image Not Mirror image
diff configuration at one or more of equivalent stereocentre
chiral centre
not mirror imagesame configuration
mirror image diff configuration
2, 3 - dibromopentane
Diastereomers
A B C D
Enantiomer/mirror image Enantiomer/mirror image
Diastereomer/NOT mirror image
Enantiomer/mirror image Diastereomer/NOT mirror image
2n n = chiral centre
Isomers with same Molecular Formula and Structural Formula but diff spatial arrangement • At least 1 asymmetric / chiral carbon / stereocentre , bonded to 4 diff gp
• NH2CH(R)COOH show optical isomerism• Optical isomers/mirror images call enantiomers (cannot superimpose on each other)
Optical Isomers
chiral carbon – 4 diff gp
Non superimposable
Non superimposable
click here diastereomers
Optical Isomers
Enantiomers Diastereomers
Same connectivityHave chiral carbon
Non superimposableMirror image each
other
Same connectivity Have chiral
carbonNon
superimposableNo Mirror image
diff chemical/physical property
click here diastereomers
same chemical/physical property
Mirror image Not Mirror image
diff configuration at one or more of equivalent stereocentre
chiral centre
not mirror imagesame configuration
mirror imagediff configuration
Video on diastereomers
Acknowledgements
Thanks to source of pictures and video used in this presentation
Thanks to Creative Commons for excellent contribution on licenseshttp://creativecommons.org/licenses/
Prepared by Lawrence Kok
Check out more video tutorials from my site and hope you enjoy this tutorialhttp://lawrencekok.blogspot.com