Sumber 2: Fessenden halaman: 134-142 & 149-150

4.2 Isomer Number And Tetrahedral Carbon

Let us begin our study of stereochemistry with methane and some of its simple substitution
producst. Any compound, however complicated that contains carbon bounden to four other atoms
can be considered to be a derivative of methane; and whatever we learn about the shapeof the
methane molecule can be appplied to the shape of vastly more complicated molecule.

The evidence of electron diffraction, x-ray diffraction, and spectroscopy shows that when carbon is
bonded to four other atoms its bonds are directed toward the corners of a tetrahedron. But as early
as 1874, years before the direct determination of molecular structure was possible, the tetrahedral
carbon atom was proposed by J. H. Van’t Hoff and independently, J. A. LeBel. Theoir proposal was
based upon the evidence of isomer number.

For any atom Y, only one substance of formula CH3 Yhas ever been found. Chlorination of methane
yields only one compouund of formula CH3 Cl; bromination yields only one compound of formula
CH3 Br. Similarly only one CH3 F is known, and ony one 𝐶𝐻3 𝐼. Indeed, the same holds true if Y
represents, not just an atom, but a group of atom ( unless the group is so complicated that in it self it
brings about isomerism); there is only one CH3 OH, only one 𝐶𝐻3 𝐶𝑂𝑂𝐻, only one 𝐶𝐻3 𝑆𝑂3 𝐻.

What does this suggest at about the arragement of atom in methhane? It suggests that every
hydrogen atom inn methane is equivalent to every other hydroogen atom, so that replacement of
any one of them gives rise to the same product. If the hydrogen atom of methane were not
equivalen, than replacement of one wouldyield a different compound that replacement of another,
and isomeric substitution products would be obtained.

In what ways can atom of methane be arranged so that the four hydrogen atoms are equivalent?
There are three such arrangements : (a) a planar arrangement (I) in which carbon is at the center of
a rectangle (or square) and a hydrogen atom is at each corner; (b) a pyramidal arrangement (II)in
which carbon is at the apex of a pyramid and a hydrogen atom is at each corner of a square base ;
(c) a tetrahedral arrangement in which carbon is at center of a tetrahedron and a hydrogen atom is
at each corner.

How do we know that each of thesearrangements could give rise to only one substance of formula
CH3 Y? As always for problem like this, the answer lies in the use of molecular models. (Gumdrops
and toothpicks can be used to make structures like I and II, for which the bond angles of ordinary
molecular models arre not suited.) For example, we make to identical models of I. In one model
wereplace, say, the upper right-hand H with a different atom Y, represented by a differently colored
ball or gumdrop ; in the other model we similary replace, say, the lower right-hand H. We next see
wether or not the two resulting models are Superimposable ; that is, we see wether or not, by any
manipulations except bending or breaaking bonds, we can make the models coincide in all their
parts. If the two models are superimposable, they simply represent two molecules of the same
compound ; if the models are not superimposable, they represent molecules of different compounds
which, since they have the same molecular formula, are by definition isomers (p. 40). Whichever
hydrogent we replace in I ( or in II or III), we gate the same structure. From any arrangement other
than these three, we would more than one structure.

As far as compounds of the formula CH3 Y are concerned, the evidence of isomer number limits the
structure of methane to one of these three possibilities.

Promblem 4.1 How many isomers of formula CH3 Y would be possible if methane were a pyramid
with a rectangular base? What are they? (hint : If you have trouble with this question now, try it
again after youb have studied sec. 4.7.)

For any atom Y and for any atom Z, only one substance of formula CH2 YZ has ever been found.
Halogenation of mmethane, for example, yields only one compound of formula CH2 ClBr.

Of the three possible structuhres of methane, only the tetrahedral one is concident whit this
evidence.

Problem 4.2 How many isomers of formula CH2 YZ would be expected from each of the following
structures for methane? (a) Structugre I with carbon at the center of a rectangle; (b) structure I with
carbon at tthe center of a square; (c) structure II; (d) structure III.

Thus, only tyhe ttetrahedral structure for methane agrees with the evidence of isomer number. It is
true that this negative evidence ; one might argue that isomers exist which have never been isolated
or detected simply because the experimental thechniques are not goood enough. But as we said
before, any compound that contains carbon bonded to four other atom can be considered to be a
derivative of methane; inn the preparation of hundresds of thousands of compounds of this sort, the
number of isomers obtained has always been consistent with the concept of the tetrahedral carbon
atom.

There is additional, positive evidence for the tetrahedral carbon atom : the finding of just the kind of
isomers – enantiomers – that are predicted for compounds of formula CWXYZ. It was the existence
of enantiomers that convinced van’t Hoff and LeBel that the carbon atom is tetrahedral. But to
understand what enantiomers are, we must first learn about the property called optical activity.

4.3 Optical Activity. Plane-pollarized light

Light posssessed certaint properties that are best understood by considering it to be a wave
phenomenon in which the vibrations occur at right angles to the direction in which the light travels.

There are an infinite number of planes passing through the line of propagation, and ordinary light is
vibrating in all these palnes.

If we concider that we are looking directly into the beam of a flashlight, Fig. 4.1 shows schematically
the sort of vibrations that are taking place, all prependicular to a line between our eye and the paper
(flashlight). Plane-polarized light is light whhose vibrations take place in only one of these possible
planes. Ordinary light is turned into plane-polarized lighht by passing it through a lens made of the
material known as polaroid or more traditionally through pieces of calcite (a particular crystalline
form of CaCO3 ) so arranged as to constitute what is called a Nicol prism.
An optically active substance is one that rootates the plane of polarized light. When polarized light,
vijbrating in a certaint plane, is passed throught an optically active substance, it emergest vibrating
in a different plane.

4.4 The polarimeter

How can this rotation of the plane of polarized light-this-optical activity-be detected? It is both
detected and measured by an instrument called the polarimeter, which is repregseented in Fig. 4.2.
it consists of a light source, two lenses (Polaroid or Nicol), and between the lenses a tube to hold
the substance that is being examined for optical activity. These are arranged so that the light passes
through one of the lenses (polarizer), then the tube, then the second lens (analyzer), and finally
reaches our eye. When thyhe tube is empty, we find that the maximum amount of light reaches our
eye when the two lenses are so arranged that they pass light vibrating in the same plane. If we
rotate the lens that is nearer our eye, say, we find that theight dims, and reaches a minimum when
the lens is at right angles to its previous position.

Let us adjust the lenses so that a maximum amount of light is allowed to pass. (in practice, it is easier
to detect a minimum than a maximum ; the principle remains tjhe same). Now let us place the
nsample to be tested in the tube. If the substance does not affect the plane of polarization, light
transmission is still at a maximum and thhe substance is said to be optically inactive. If, on the other
hand, the substance rotates the plane of polarization, then the lens nearer our eye must be rotated
to conform with this new plane if light transmission is again to be a maximum, and the substance is
said to be optically inactiv. If the rotation of the plane, and hence our rotation of the lens, is to the
right (clockwise), the substance is dextrorotatory. (latin: dexter, right) ; if the rotation is to the left
(counterclock-wise), the substance is levorotatory (latin : laevus, left).

We can determine not only that the substance has rotated the plane, and in which direction, but
also by how much. The amount of rotation is simply the number of degrees that we must rotate the
lens to conform with the light. The symbols + and – are used to indicate rotation to the right and to
the left, respectively.

The lactic acid (p. 129) that is extracted from muscle tissue rotates light to the right, and hence is
known as dextrorotatory lactic acid, or (+) – Lactic acid. The 2-metyl-1-butanol that is obtained from
fusel oil ( a by-product of the fermentation of starch to ethyl alcohol) rotates light to the left, and is
known as levorotation 2-methyl-1-butanol, or (–)-2-methyl-1-butanol.

4.5 Specific rotation

Since optical rotation of the kind we are interested in is caused by individual mollecules of the active
cmpound, the amount of rohtation depends upon how many molecules the light encourters in
passing throughthe tube.

The light will encounter twice as many molecules in a tube 20 cm long as in a tube 10 cm long, and
the rotation will be twice as large. If the active compound is in solution, the number of molecules
encountered by the light will depend upon the concentrations. For a given tube length, light will
encounter twice as many molecules in a solution of 2 g per 100 cm3 of solfent as in a solution
containing 1 g per 100 cm3 of solvent, and the rotation will be twice as large. When allowances are
made for the length of tube and the concentration , it is found that the amount of rotation, as well
as its direction, is a caracteristic of each individual optically active compound.

Spesific rotation is the number of degrees of rotation obseved if a 1 – decimeter tube is used, and
the compound being examined is presentto the extent of 1g/cm3. This is usually calculated from
observation with tube of other lengths and at different concentrations by means of the equation.

∝
[∝] =
𝐼𝑥𝑑
𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑟𝑜𝑡𝑎𝑡𝑖𝑜𝑛 (𝑑𝑒𝑔𝑟𝑒𝑒𝑠)
𝑠𝑝𝑒𝑠𝑖𝑓𝑖𝑐 𝑟𝑜𝑡𝑎𝑡𝑖𝑜𝑛 = 𝑔
𝑙𝑒𝑛𝑔𝑡ℎ (𝑑𝑚)𝑥 ⁄ 3
cm

The spesific rotation is as much a property of a compound as its melting point, boiling point, destiny,
or refractive index. Thus the spesific rotation of the 2 – methyl – 1 – butanol obtained from fusel oil
is

[∝]20
𝐷 = −5.90°

Here 20 is the temperature and D is the vave length of the light usedd in the measurement (D line of
sodium, 5893 A).