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Stereochemistry

Chem 33

I. Chirality
the word chiral is derived from Greek and means "handed"

II. Optical Activity


enantiomers differ physically in one, somewhat obscure, way: they rotate the plane of polarized light to an equal degree but in opposite directions this phenomenon is called optical activity and molecules that cause polarized light to rotate are optically active your left and right hand are mirror images of one another that are not superimposable a polarimeter is used to detect optical activity this device consists of a monochromatic light source (typically 589 nm), a polarizer (as you would find in a pair of sunglasses), and a detector

many examples of chirality exist in the macroscopic world: shoes, ears, a spiral staircase, shells of edible snails on the molecular level, we can have nonsuperimposable "mirror image" pairs of molecules = enantiomers note: many, many molecules are "handed" (or chiral) in some way (e.g., amino acids, DNA, sugars, pharmaceutical agents)

CH3 F H3C

CH3 F CH3 H 2-fluorobutane 589 nm recall: light consists of electromagnetic waves propogating in all directions. by passing light through a piece of polarizing film, we eliminate all wave vectors except those vibrating in a single plane the physical basis for optical activity the electrons in a molecule generate their own local electric fields, which interact with the field of the light. it is this interaction that causes a net change in the plane of polarization

a tetrahedral carbon center that is substituted with 4 different groups is referred to as an asymmetric or stereogenic center. the molecule itself is said to be chiral

chiral molecules by definition do not have a plane of symmetry

more terminology
if one faces the beam of light passing through the sample: a stereoisomer that rotates light in a clockwise direction is called dextrorotatory = (+) a stereoisomer that rotates light in a counterclockwise direction is called levorotatory = () if we have a solution that contains a 50:50 mixture of dextro- and levorotatory stereoisomers = racemic mixture = () note: no rotation of light will be observed in a racemic mixture the optical rotation () that we observe for any sample will depend on concentration and the path of the light (the sample temperature and the wavelength of light are also important)

CH4

CH3Cl

CH2Cl2

CH2BrCl

CHBrClF

in order to standardize the value of , we define: specific rotation = []T = a physical constant characteristic of the molecule l c T = = = = = observed rotation length of sample container (decimeters) sample concentration (grams/mL) temperature (C) wavelength of light (typically 589 nm)

in this example, only CHBrClF is chiral. CH4, CH3Cl, CH2Cl2, and CH2BrCl are so-called achiral molecules CH3 CH3 the physical properties of enantiomers are indistiguishable molecular formula = C10H16 mp = 74 C bp = 175 C density = 0.83 g/mL

[]T =

l x c

H2C

H CH3

H2C

H CH3

S-()-limonene (turpentine)

R-(+)-limonene (orange)

so how can we differentiate between these two compounds?

important: the direction of rotation of light does not give us information about the absolute configuration (i.e., whether it is right or left handed) of the stereocenter we need some type of language (nomenclature) to indicate the "handedness" in a molecule

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