This document discusses organic chemistry concepts related to isomers and chirality. It defines constitutional isomers as compounds with the same molecular formula but different bonding patterns. Stereoisomers have the same bonding connectivity but different spatial arrangements. Optical activity is described as the ability of certain substances to rotate polarized light due to their chiral molecular structure being nonsuperimposable on its mirror image. Specific rotation is defined as the optical rotation per unit concentration and path length. Enantiomers are stereoisomers that are nonsuperimposable mirror images and have identical properties except opposite rotation. Chirality is important in biology and pharmaceuticals as often only one enantiomer is active.
This document discusses organic chemistry concepts related to isomers and chirality. It defines constitutional isomers as compounds with the same molecular formula but different bonding patterns. Stereoisomers have the same bonding connectivity but different spatial arrangements. Optical activity is described as the ability of certain substances to rotate polarized light due to their chiral molecular structure being nonsuperimposable on its mirror image. Specific rotation is defined as the optical rotation per unit concentration and path length. Enantiomers are stereoisomers that are nonsuperimposable mirror images and have identical properties except opposite rotation. Chirality is important in biology and pharmaceuticals as often only one enantiomer is active.
This document discusses organic chemistry concepts related to isomers and chirality. It defines constitutional isomers as compounds with the same molecular formula but different bonding patterns. Stereoisomers have the same bonding connectivity but different spatial arrangements. Optical activity is described as the ability of certain substances to rotate polarized light due to their chiral molecular structure being nonsuperimposable on its mirror image. Specific rotation is defined as the optical rotation per unit concentration and path length. Enantiomers are stereoisomers that are nonsuperimposable mirror images and have identical properties except opposite rotation. Chirality is important in biology and pharmaceuticals as often only one enantiomer is active.
This document discusses organic chemistry concepts related to isomers and chirality. It defines constitutional isomers as compounds with the same molecular formula but different bonding patterns. Stereoisomers have the same bonding connectivity but different spatial arrangements. Optical activity is described as the ability of certain substances to rotate polarized light due to their chiral molecular structure being nonsuperimposable on its mirror image. Specific rotation is defined as the optical rotation per unit concentration and path length. Enantiomers are stereoisomers that are nonsuperimposable mirror images and have identical properties except opposite rotation. Chirality is important in biology and pharmaceuticals as often only one enantiomer is active.
Book References: T.W.G. Solomon and C.B. Fryhle. Organic Chemistry. New York: Wiley, 2013.R.T Morrison and R.N.Boyd. Organic Chemistry. New Jersey : Prentice Hall, 1992. Eliel, Wilen and Mander, Stereochemistry of Organic Compounds, 2004 Subrata Sengupta, Basic Streochemistry of Organic Molecules, 2014 Dr. Raju Dey Assistant Professor Department of Chemistry, NITC Room No: 210E Phone no: +91-7558035591 Email: [email protected] Isomers are the compounds that have the same molecular formula but different chemical structures are called isomers.
OH O O
ethylpropylether C5H12O 1-pentanol C5H12O C5H10O
Constitutional isomers differ in the order in which the atoms are connected together, so they contain different bonding patterns (functional groups).
Stereoisomers o Same bonding connectivity – same molecular formula o Different spatial arrangements of atoms and groups – different molecular configurations
Stereochemistry: The part of chemistry, which studies the structure in three dimensions H2 C H3C CH3 H CH3 H3C CH CH CH3
C H H H H2 H3C 1,3-dimethylcyclobutane cis-1,3-dimethylcyclobutane trans-1,3-dimethylcyclobutane Do the compounds have the same molecular formula ? Hexane 3-methylpentane
No Constitutional isomers Yes Not isomers
Isomers H3C CH3 H CH3 Do the compounds have the same connectivity? H H H But different molecular configurations H3C
cis-1,3-dimethylcyclobutane trans-1,3-dimethylcyclobutane No Yes
Stereoisomers Constitutional isomers Stereoisomers Optical Activity: There are certain substances which can rotate the plane of a polarized light — such substances are called Optical Active. The substance which cannot rotate the plane of a polarized light is called Optical Inactive.
What is Plane-polarized Light?
Optical Rotation depends upon several factors:
Concentration of the optically active substance —
o higher the concentration higher is the magnitude of optical rotation
Length of the polarimeter tube —
o higher the length of the polarimeter tube higher is the magnitude of optical rotation Optical Rotation is caused by individual molecules of the optically active compounds
The amount of rotation depends upon how many numbers of
molecules of optically active substance encounts by the plane- polarized light while passing through the polarimeter tube. o Evidently higher the concentration of the optically active substance and higher the length of the polarimeter tube higher will be the number of molecules that will encounter the plane-polarized light. Specific Rotation[a] of an optically active substance can be defined as the optical rotation per unit concentration(gm/mL) of sample per unit length(dm) of the polarimeter tube.
where, o t C a a = optical rotation a = Cxl C = concentration in gm/mL l = length of the polarimeter tube in decimeter
Specific Rotation of 2-methyl-1-butanol : -5.90° mL·g−1·dm−1
20 a = - 5.90o D
Here '20' is the temperature and ‘D’ is the wave length of the radiation used in the measurement (D line of sodium, 5893 Å). Q. Optical rotation of an optically active substance having concentration 0.5 gm/mL is found to be + 10° when measured in a polarimeter tube of 1 meter length. Calculate the Specific Rotation of the sample.
But the Specific Rotation value in literature is found to be + 74°. Explain
the anomaly in the results. Chiral meaning handedness( from the greek word cheir, meaning hand). Chiral objects are not superimposable on its mirror image, like our hand. Mirror image of our right hand is left hand yet they are not superimposable each other.
The term superimposable meaning all parts of each object must coincide Which substances are Optically Active? Only those substances whose molecular configuration is not superimposable on its mirror image are optically active.
Case of cis-2-butene:
H3C CH3 H3C CH3 Superimposable C C C C H H cis -2-butene is optically inactive H H mirror mirror image Case of trans-1,3-dimethylcyclobutane: H H H H Me H H Me Superimposable H trans-1,3-dimethylcyclobutane Me Me H is optically inactive. H H H H mirror
Case of propionic acid:
COOH COOH
C C Superimposable H CH3 H Propionic acid is optically inactive H H3C H mirror image mirror Case of lactic acid: COOH COOH Nonsuperimposable C C H H Lactic acid with the molecular CH3 H3C HO OH configuration (A) is optically active (A) (B) mirror mirror image
Case of trans-1,2-dimethylcyclopropane: H H Me H H Me Nonsuperimposable trans-1,2-dimethylcyclopropane with the molecular H H configuration (X) is optically active H Me Me H (X) (Y) mirror mirror image Enantiomers can be defined as the two stereoisomers having o Same bonding-connectivity. COOH COOH
C C H o Different molecular configurations. HO CH3 (A) H3C (B) OH H
o The molecular configurations are mirror image of each other.
Enantiomers have identical physical and chemical properties except the
sign of rotation. Q. If the specific rotation of pure (R)2-bromobutane is 48 degrees what will be the specific rotation for pure (S)2-bromobutane ? Human body’s are structurally chiral, with the heart lying to the left of center and liver to the right. Helical sea shells are chiral and most are spiral and right-handed screw. Even DNA is chiral molecule and double helical form of DNA turns in a right-handed way. Similarly protein building bolck e.g. amino acids are chiral(except glycine) and all of these are classified as being left handed. The molecule of natural sugars are almost all classified as being right- handed. In fact most of the molecules associated with life are chiral and often found only in one mirror image form. Chirality has tremendous importance in our daily lives. Most of the pharmaceuticals are chiral and usually only one mirror image form of a drug provides the desire effect. Other mirror image form is often found inactive or less active even sometime toxic (e.g. thalidomide)
O O O O O O NH H NH H NH N O N O N O this carbon centre is asymmetric as it is O O O attached with four different groups R-enantiomer S-enantiomer Our sense of taste and smell also depend on chirality. If one mirror image form of chiral molecule have certain odor and taste, other mirror image may completely different in odor and taste. The food we eat is largely made of molecules of one mirror-image form.
Q. What will happen if we eat food which made from the other mirror image form of the naturally available sugar? Origin of chirality in space In 1969 a meteorite has discover that fell to earth near Murchison, Victoria, in Australia. It is one of the most studied meteorites due to its mass (>100 kg), and richness in organic compounds. Upon careful analysis of revealed that it contains 7-9% excess of four L-amino acid. Origin of distribution is uncertain but some scientist speculate that electromagnetic radiation emitted in a corkscrew fashion form the poles of spinning neutron star could lead to a bias of one mirror image over another one, when molecule form in interstellar space. Solomonons and Fryhle: P-181 The Stereogenic Center Carbon atom with four different groups w o Chiral center x C y o Asymmetric center o Stereo center z
# Recognition of symmetry elements and chiral centers # Projection formulae and their interconversions # Prochiral relationship, homotopic, enantiotopic and diasteriotopic groups and faces # Racemic modifications, R and S nomenclature # Geometrical isomerism, E and Z nomenclature # Conformational analysis : cyclohexane derivatives, stability and reactivity # Conformational analysis of disubstituted cyclohexanes Symmetry elements in organic molecule
Simple axis of symmetry
Plane of symmetry Center of symmetry Alternate axis of symmetry Simple axis of symmetry(Cn) A molecule is said to possess an n-fold simple axis of symmetry when the molecule is rotated through angle 360°/n about that axis then obtained form is indistinguishable from the original one. The axis is designated Cn and the operation is called a Cn operation. C2 water molecule O O O H H H H H H contains a C2 axis
C3 H H H bromoform molecule contains a C3 axis C C C Br Br Br Br Br Br Br Br Br C2 H H H Cl Cl H Cl H H Cl H H H H C2 H H cis-1,3-dichlorocyclobutane cis-1,3-dichlorocyclobutane trans- 1,3-dichlorocyclobutane trans- 1,3-dichlorocyclobutane contains a C2 axis contains a C2 axis
C2 H C3 H H Br H H Br H C2 H H trans-1,2-dibromoethane Cyclopropane contains a C2 axis contains a C3 axis perpendicular to three C2 axes: D3h C6 Cl Cl Cl Cl C2 Cl Cl C2
Hexachlorobenzene one C6 axis perpendicular to six C2 axes Twistane
Twistane possesses three mutually perpendicular C2 axes as shown
above. Therefore, it is a molecule in the point group D2 and is dissymmetric. It is a chiral molecule and thus can exist in two enantiomeric forms. Q.
Find the symmetry elements
Et Et Me H H Me Optical Activity: C C
H H Plane of symmetry (s): A plane of symmetry is an imaginary plane that bisects a molecule into halves that are mirror images of each other Me Me Me
Me Me Me
The plane of symmetry is connected with optical activity i.e. if a compound
possesses a plane of symmetry, then its molecular configuration is superimposable on its mirror image and consequently the compound is optically inactive. Optical activity:
Plane of symmetry Plane of symmetry F Cl
Cl F Me Me
Me Et
x Find ? Plane of symmetry Symmetry elements in organic molecule
o Simple axis of symmetry
o Plane of symmetry
o Center of symmetry
o Alternate axis of symmetry
Simple axis of symmetry(Cn) A molecule is said to possess an n-fold simple axis of symmetry when the molecule is rotated through angle 360°/n about that axis then obtained form is indistinguishable from the original one. The axis is designated Cn and the operation is called a Cn operation. C2 water molecule O O O H H H H H H contains a C2 axis
C3 H H H bromoform molecule contains a C3 axis C C C Br Br Br Br Br Br Br Br Br Plane of symmetry (s): A plane of symmetry is an imaginary plane that bisects a molecule into halves that are mirror images of each other Me Me Me
Me Me Me
The plane of symmetry is connected with optical activity i.e. if a compound
possesses a plane of symmetry, then its molecular configuration is superimposable on its mirror image and consequently the compound is optically inactive. Center of symmetry (i): An imaginary point within the molecule such that if an atom (or point) is connected to it by using a straight line and that line is extrapolated to an equal distance beyond, it meets an identical atom (or point).
Ph COOH
H H H H
COOH Ph Center of symmetry (i)
COOH
. H H . H H
COOH
a-Truxillic acids: obtained by the [2 + 2]
photocycloadditions of cinnamic acid Center of symmetry point passes through the C=C
Plane of symmetry F Cl
Cl F Alternate axis of symmetry (Sn): A molecule is said to posses n-fold alternating axis of symmetry if, when the molecule is rotated through angle 360°/n about that axis and then a reflection is followed in a plane perpendicular to that axis then obtained form is indistinguishable with the original one. A CH3 H H CH3 900 rotation H H CH3CH3 CH3CH3 H H about the axis AB CH3 H H CH3 ind is t ing
B reflection on the plane
u is
of the ring which is obviously
ha
CH3 H perpendicular to the axis AB
bl e
H H CH3CH3
CH3 H Alternate axis of symmetry (S1):
Me Me Me Me Me Me reflection plane passing Me through cyclobutane Me (360/1)o rotation C1-C2 & C3-C4 Alternate axis of symmetry (S2):
COOH H COOH
H reflection plane pass (360/2)o rotation through cyclobutane ring H H H COOH H H COOH H H H H
COOH H COOH Relation between Sn / s / i
S1 = Plane of symmetry (s)
S2 = Center of symmetry (i) H Me
Alternate axis of symmetry/S4 Me
H
H Me
Me H H H Me H Me Me
H Me reflection plane Me Me perpendicular to the H H rotation axis and (360/4)o rotation passing through the N N N N
