Kloramfenikol

2,2-dichloro-N-((1R,2R)-1,3-dihydroxy-1-(4-
nitrophenyl)propan-2-yl)acetamide
 Cis/Trans 1,2 dikloro etena
Cis/trans 1,2 dikarboksilat etena
 How Sweet it is!

OH Cl
CH2OH CH2OH
O O
CH2OH HO CH2Cl
HO O
O OH
OH
O HO O HO
CH2OH CH2Cl
HO HO
Sucrose Sucralose or Splenda

Sucralose is 600 times sweeter

and does not get metabolized.
 Stereochemistry
Stereochemistry refers to the
3-dimensional properties and
reactions of molecules. It has its
own language and terms that need
to be learned in order to fully
communicate and understand the
concepts.
 Structural/Constitusional Isomers
1. a) CH3
CH3 CH2 CH2 CH3 CH3 CH CH3
Butane (C4H10) 2-methylpropane (C4H10)
2.
CH2 CH CH2 CH3 CH3 CH CH CH3
1-butene 2-butene
CH2
CH3 CH2 CH2
CH2 CH
CH2 C CH3 CH2 CH2
CH3
2-methylpropene cyclobutane methylcyclopropane
 Definitions
Stereoisomers compounds with the same
connectivity, different arrangement in space
Enantiomers stereoisomers that are non-
superimposible mirror images; only properties
that differ are direction (+ or -) of optical
rotation
Diastereomers stereoisomers that are not
mirror images; different compounds with
different physical properties
 More Definitions
Asymmetric center sp3 carbon with 4
different groups attached
Optical activity the ability to rotate the plane of
plane polarized light
Chiral compound a compound that is
optically active (achiral compound will not
rotate light)
Polarimeter device that measures the optical
rotation of the chiral compound
 Lingkup Stereoisomer
Isomer Konformasi : single bond rotated
Isomer Konfigurasi
Isomer Geometri : cis/trans ; E/Z
Isomer Optik :
Enantiomer : +/- ; d/l ; R/S,
Disstereomer
 Isomer Konformasi (konformer)
Konformasi : perubahan bentuk molekul
dalam ruang oleh karena adanya putaran
(rotasi) pada ikatan tunggal (single bond)
Konformasi senyawa terjadi pada :
a. Senyawa rantai terbuka (alifatis)
b. Senyawa rantai tertutup (siklis)
Konformasi Senyawa Alifatis

Etana : CH3-----CH3

Konformer Eklips/Gerhana Konformer Goyang/Gauche

Eklips/Gerhana Goyang/Gauche
-Atom Hidrogen (atau
-Atom Hidrogen (atau
gugus) tidak saling
gugus) saling menutup
menutup
- Energi tinggi karena
- Energi rendah karena
banyak terjadi
sedikit terjadi tolakan
tolakan antar atom
antar atom

Interchangeable
Konformer Eklips Konformer Goyang
 Konformer senyawa Butana
Konformer Goyang/Gauche
Konformer Eklips/Gerhana
Konformer Anti
Konformer metil tereklipskan
(lihat : model molekul hyperchem)
Konformer pada senyawa siklik :
Sikloheksana
Konformer Kursi
Konformer Setengah Kursi
Konformer Biduk Belit
Konformer Perahu / Biduk
(lihat : model molekul hyperchem)

Konformer Kursi Konformer Biduk Konformer Biduk Belit

 Isomer geometri
Terjadi pada :
Senyawa dg ikatan rangkap : alkena
Senyawa siklik
Terbentuk karena ikatan rangkap rigid/kaku
Tidak dapat ber-rotasi
Tidak dapat diubah satu sama lain
Ada 2 posisi relatif :
Bersisian = cis ; Berseberangan = trans
 Contoh

Cis 1,2 dikloroetena Trans 1,2 dikloroetena

 senyawa 2-butena, bagaimana struktur
isomer cis dan trans-nya??
 isomer cis dan trans tidak hanya terbatas
pada alkena yang tersubstitusi dua
atom/gugus.
Tetapi juga pada alkena dimana kedua atom
C rangkap mengikata dua gugus yang
berbeda.
Which of following compounds can exist as
pairs of cis-trans isomers? Draw each cis-
trans pair and indicate the geometry of each
isomer
(a). CH3CH=CH2
(b). CH3CH2CH=CHCH3
(c). (CH3)2C=CHCH3
(d). (CH3)2C=C(CH3)CH2CH3
(e). ClCH=CHCl
(f). BrCH=CHCl
 How about this ?

Br
 Aturan Chan Inglod Prelog
Urutan deret ditentukan berdasar nomor
atom (no atom tinggi lebih berprioritas)
Isotop dengan no massa tinggi berprioritas
Jika atom sama/identik, no atom dari atom
berikutnya digunakan sebagai dasar
prioritas
Atom-atom dengan ikatan rangkap atau
ganda tiga diberi kesetaraan dengan ikatan
tunggal
 Z (zusammen) together
E (entgegen) opposite
simple way to remember
ze zame zide Z
Example:
Assign E or Z configuration to the double
bond of the following compounds.
Isomer Geometri pada senyawa
siklis
 Isomer Optik
Gliseraldehid
CHO CHO

HO H H OH

CH2OH CH2OH

(-) Gliseraldehid (+) Gliseraldehid

() = - 8,7 () = 8,7
Plane-Polarized Light
Plane-Polarized Light through
an Achiral Compound
Plane-Polarized Light through
a Chiral Compound
Polarimeter Measures
Optical Rotation
 Specific Rotation, []

[] = / cl
a = observed rotation
c = concentration in g/mL
l = length of tube in dm

Dextrorotary designated as d or (+), clockwise

rotation
Levorotary designated as l or (-), counter-
clockwise rotation
Kiralitas
 Chirality Center
Carbon has four different groups attached
 Enantiomers
nonsuperimposible mirror images
mirror
plane
OH OH

H CH3 CH3 H
HO2C CO2H

(S)(+) lactic acid (R)(-) lactic acid

from muscle tissue
o
from milko
[a] = +13.5 [a] = -13.5
 Biological Activity

(R)(+) Thalidomide (S)(-) Thalidomide

O O H O O H
H N N
H
N O N O

O O
a sedative and hypnotic a teratogen
a-(p-isobutylphenyl)propionic acid

H H CH3
CH3 CO 2H HO 2C
(S)(+) ibuprofen (R)(-) ibuprofen
anti-inflammatory 80-90% metabolized to (S)(+)
SSRI Efficacy depends on
Stereochemistry
NC
O
* N(CH3)2

(+/-) Celexa
(-) Lexapro

F
 Absolute Configuration
Use Cahn, Ingold, Prelog priorities
Place the lowest priority group back
(focus down C - 4 bond)
draw arrow from 1-2-3
1 1
clockwise counterclockwise
4 2 2 4
3 3
(R) (S)
Assign Priority to each Group
on Asymmetric Center

I I 1
rotate
Cl F 4 H Cl 2
H F3
focus down C-4 bond
 Lactic Acid
1 1
OH OH
4 4
H CH3 CH3 H
HO2C CO2H
3 3 2
2
(S) (R)
C.I.P. Priorities

Low High
CH2CH2CH3 CH(CH3)2
O
CH2CH2OH CH2CH

CH2CH2CH3 CH=CH2

CO2H CH2Cl

CH2CH2Br CH(CH3)2
 Diastereomers
Stereoisomers That Are Not Mirror Images

H OH H OH
3 3
2 2
CO2H CO2H
H Br Br H
(2S,3S) (2S,3R)
same stereochemistry at C 2 (S)
opposite stereochemistry at C 3
Fischer Projections with 2
Chiral Centers
CO2H CO2H
2 2
H OH H OH

3 3
Br H H Br

CH3 CH3
(2S,3S) (2S,3R)
2 Chiral Centers
4 Stereoisomers
 Tartaric Acids
R,R S,S
CO2H CO2H

H OH HO H

HO H H OH

CO2H CO2H
R,S S,R
CO2H CO2H

H OH HO H

H OH HO H

CO2H CO2H
 Racemic Mixture
R,R S,S
CO2H CO2H

H OH HO H

HO H H OH

CO2H CO2H
Racemic Mixture (Racemate): 50/50 mixture of enantiomers

(R,R) Tartaric acid (S,S) Tartaric Acid (+/-) Tartaric acid

o
m.p. C 168-170 168-170 210-212
[a] (degrees) - 12 + 12 0
(g/mL) 1.7598 1.7598 1.7723
 Meso Compound
Internal Plane of Symmetry
Optically Inactive
R,S S,R
CO2H CO2H

H OH HO H
mirror
plane
H OH HO H

CO2H CO2H
o
rotate 180
superimposible
 2,3,4-trichlorohexane
How many stereoisomers?
Cl

* * *
Cl Cl
3 asymmetric centers
2n, n= # asymmetric centers (3)
8 stereoisomers
 n = 3; 2 n =8
CH3 CH3 CH3 CH3
S H Cl Cl H R H Cl Cl H
S H Cl Cl H R H Cl Cl H
RH Cl Cl H S Cl H H Cl
CH2CH3 CH2CH3 CH2CH3 CH2CH3

CH3 CH3 CH3 CH3

H Cl Cl H Cl H H Cl
Cl H H Cl H Cl Cl H
H Cl Cl H H Cl Cl H
CH2CH3 CH2CH3 CH2CH3 CH2CH3
A Carbohydrate
CHO
H OH R

HO H S

H OH R
H OH R
CH2OH
(+) D-Glucose
Internal Planes of Symmetry
Both are Meso
CH3 CH3 CH3 CH3

CH3 CH3 CH3 CH3

Identical, Enantiomers or
Diastereomers?
H CH2CH3
a) Br CH3 & H CH3

CH2CH3 Br

CH3
HO H
b) CH3 H NH2
H C C &
CH3 NH2 H OH

CH3