1559T_ch05_70-9810/22/0520:19Pa9e71 ⊕ EQA Keys to the Chapter·71 ty)but that do not cules that are chiral.Chiral molecules can exist as either of two stereoisomeric shapes.which are related t er as an ooject is t mage Before going any further.le al is that y to it rorimage Methane sidentical imae:it is not chiral.The wo possible shapes of a ne two ule are called enantiomers What mal of models and start manufacturing chiral molecules.Prove to yourself that the model of the mirror image o cdon the onginal.This is the frst step towd developing the ability to visai Optical Activity enantiomers is so subtle that they end up for the something else that t is,itself,alre cady"handed."By analogy.a right and a left glove will have the same weight and text ce,a ng igals from our binocular visual system is"handed in its ability to perceive depth as well as left-right re For chiral m ecules.the co rpart to thi inter ith plane-po zed light:Ih of a chiral molecule.This ptical motation is the most common way of dete ecting chira onsiderable detail in this sec Molecul s possessing the ility to rotate th the two enantiomers of a chiral molecule:racemic mirure.The two enantiomers of a chiral molecule each ate light by equal amou displays no optical activity be Again,of the large number of ne terms and ideas associated with this material,it merits careful study,with a good set of models close at hand 5-3.The R-S Sequence Rules Like all the rules of nomenclature,the R-S system for molecules containing stereocenters has one purpose o cases tne s of the e ter so that you an con m their R or S th difference”is well un tood.If this gives you trouble.take it stepwise: 2.Starting at the lef.look at the first atom in each substituent chain and identify the atoms attached to it are the out from the first to the cond atom in the chain and repeat the process.If ther is direction of this move sh be chosn to examine the highest priority atom for that have the same atoms linked in the same order (i.e., identical connectivity), but that do not have identical three-dimensional shapes. The first example in Section 5-1, 2-bromobutane, is one of a vast number of mole￾cules that are chiral. Chiral molecules can exist as either of two stereoisomeric shapes, which are related to each other as an object is to its mirror image. Before going any further, let’s make one point clear: Every mol￾ecule has a mirror image, obviously. What makes a chiral molecule special is that it is not identical to its mir￾ror image. Methane is identical to its mirror image; it is not chiral. The two possible shapes of a chiral mol￾ecule differ in the same way that a right-handed object differs from a left-handed object, as gloves, shoes, and hands do. Chirality, therefore, is “handedness” on a molecular level. The two mirror-image shapes of a chiral molecule are called enantiomers. What makes a molecule chiral? The most common of several types of structural features that can make a molecule chiral is the presence of a carbon atom attached to four different atoms or groups (an asymmetric carbon atom, an example of what is called a stereocenter). At this point it is worthwhile to dust off your set of models and start manufacturing chiral molecules. Prove to yourself that the model of the mirror image of one cannot be superimposed on the original. This is the first step toward developing the ability to visualize this relationship clearly. 5-2. Optical Activity The physical difference between enantiomers is so subtle that they end up for the most part displaying iden￾tical physical and chemical properties. They can be distinguished from each other only after interacting with something else that is, itself, already “handed.” By analogy, a right and a left glove will have the same weight, color, and texture. However, interaction with, for instance, a right hand will immediately distinguish them. The fact that we can tell them apart just by looking at them reflects the fact that our brain’s interpretation of the signals from our binocular visual system is “handed” in its ability to perceive depth as well as left–right re￾lationships. For chiral molecules, the counterpart to this is their interaction with plane-polarized light: The plane of polarization of plane-polarized light is rotated when it passes through a solution of one enantiomer of a chiral molecule. This phenomenon, labeled optical rotation, is the most common way of detecting chiral molecules and is described in considerable detail in this section. Molecules possessing the ability to rotate the plane of polarized light are said to be optically active, or to display optical activity; and another term for enan￾tiomers is optical isomers. One further term of importance is the one given to a mixture of equal amounts of the two enantiomers of a chiral molecule: racemic mixture. The two enantiomers of a chiral molecule each ro￾tate light by equal amounts, but in opposite directions, so the racemic mixture displays no optical activity be￾cause the two components exactly cancel out each other’s rotations. Again, because of the large number of new terms and ideas associated with this material, it merits careful study, with a good set of models close at hand. 5-3. The R–S Sequence Rules Like all the rules of nomenclature, the R–S system for molecules containing stereocenters has one purpose: the concise, unambiguous description of a single chemical structure. In most cases the system is not particu￾larly difficult to apply, because the assignment of priorities to the groups on an asymmetric carbon is usually straightforward and use of models to view the stereocenter properly takes care of the rest. Models should be made of the examples in the chapter so that you can confirm their R or S designations. Priority rule 2 is an occasional source of trouble until the concept of “first point of difference” is well un￾derstood. If this gives you trouble, take it stepwise: 1. Write the substituent groups to be compared side-by-side, with the bond of attachment to the asymmetric atom on the left. 2. Starting at the left, look at the first atom in each substituent chain and identify the atoms attached to it in descending order of priority. If the highest priority atoms in each are the same, work your way down in priority, looking for the first nonidentical atoms (first point of difference). If no differences are found at this stage, move out from the first to the second atom in the chain and repeat the process. If there is branching here, the direction of this move should be chosen to examine the highest priority atom for Keys to the Chapter • 71 1559T_ch05_70-98 10/22/05 20:19 Page 71