Optical inactivity

Two molecules of vitamin A are formed from one molecule of -carotene. Vitamin A crystallizes in pale yellow needles m.p. 64 C. It is optically inactive. It is unstable in solution when heated in air, but comparatively stable without aeration. Vitamin A is manufactured by extraction from fish-liver oils and by synthesis from / -ionone. The role of vitamin A in vision seems to be different from its systemic function. See also relincne and rhodopsin. 

Figure A2.5.30. Left-hand side Eight hypothetical phase diagrams (A through H) for ternary mixtures of d-and /-enantiomers with an optically inactive third component. Note the syimnetry about a line corresponding to a racemic mixture. Right-hand side Four T, x diagrams ((a) tlirough (d)) for pseudobinary mixtures of a racemic mixture of enantiomers with an optically inactive third component. Reproduced from [37] 1984 Phase Transitions and Critical Phenomena ed C Domb and J Lebowitz, vol 9, eh 2, Knobler C M and Scott R L Multicritical points in fluid mixtures. Experimental studies pp 213-14, (Copyright 1984) by pennission of the publisher Academic Press.

The m.p. of the quinone obtained from the optically inactive camphor is almost identical with the above values, obtained from dextro-camphor. 

To be optically active the sample must contain a chiral substance and one enantiomer must be present in excess of the other A subslance lhal does nol rolale fhe plane of polar ized lighl IS said lo be ophcally maclive All achiral substances are optically inactive... 

Mixtures containing equal quantities of enantiomers are called racemic mixtures Racemic mixtures are optically inactive Conversely when one enantiomer is present m excess a net rotation of the plane of polarization is observed At the limit where all the molecules are of the same handedness we say the substance is optically pure Optical purity or percent enantiomeric excess is defined as... 

In this as m other reactions m which achiral reactants yield chiral products the product IS formed as a racemic mixture and is optically inactive Remember for a substance to be optically active not only must it be chiral but one enantiomer must be present m excess of the other... 

It IS a general principle that optically active products cannot be formed when opti cally inactive substrates react with optically inactive reagents This principle holds irre spective of whether the addition is syn or anti concerted or stepwise No matter how many steps are involved m a reaction if the reactants are achiral formation of one enan tiomer is just as likely as the other and a racemic mixture results... 

When a reactant is chiral but optically inactive because it is racemic any products derived from its reactions with optically inactive reagents will be optically inactive For example 2 butanol is chiral and may be converted with hydrogen bromide to 2 bromo butane which is also chiral If racemic 2 butanol is used each enantiomer will react at the same rate with the achiral reagent Whatever happens to (/ ) (—) 2 butanol is mir rored m a corresponding reaction of (5) (+) 2 butanol and a racemic optically inactive product results... 

Optically inactive starting materials can give optically active products only if they are treated with an optically active reagent or if the reaction is catalyzed by an optically active substance The best examples are found m biochemical processes Most bio chemical reactions are catalyzed by enzymes Enzymes are chiral and enantiomerically homogeneous they provide an asymmetric environment m which chemical reaction can take place Ordinarily enzyme catalyzed reactions occur with such a high level of stereo selectivity that one enantiomer of a substance is formed exclusively even when the sub strate is achiral The enzyme fumarase for example catalyzes hydration of the double bond of fumaric acid to malic acid m apples and other fruits Only the S enantiomer of malic acid is formed m this reaction... 

Only three not four stereoisomeric 2 3 butanediols are possible These three are shown m Eigure 7 10 The (2R 3R) and (2S 3S) forms are enantiomers of each other and have equal and opposite optical rotations A third combination of chirality centers (2R 3S) however gives an achiral structure that is superimposable on its (2S 3R) minor image Because it is achiral this third stereoisomer is optically inactive We call achiral mole cules that have chnahty centers meso forms The meso form m Eigure 7 10 is known as meso 2 3 butanediol... 

Structures A and A are nonsuperimposable mirror images of each other Thus although as 1 2 dichloro cyclohexane is chiral it is optically inactive when chair-chair interconversion occurs Such interconver Sion IS rapid at room temperature and converts opti cally active A to a racemic mixture of A and A Because A and A are enantiomers interconvertible by a conformational change they are sometimes re ferred to as conformational enantiomers... 

The same kind of spontaneous racemization oc curs for any as 1 2 disubstituted cyclohexane in which both substituents are the same Because such compounds are chiral it is incorrect to speak of them as meso compounds which are achiral by definition Rapid chair-chair interconversion however converts them to a 1 1 mixture of enantiomers and this mix ture IS optically inactive... 

Occasionally an optically inactive sample of tartaric acid was obtained Pasteur noticed that the sodium ammonium salt of optically inactive tartaric acid was a mixture of two mirror image crystal forms With microscope and tweezers Pasteur carefully sep arated the two He found that one kind of crystal (m aqueous solution) was dextrorota tory whereas the mirror image crystals rotated the plane of polarized light an equal amount but were levorotatory... 

Although Pasteur was unable to provide a structural explanation—that had to wait for van t Hoff and Le Bel a quarter of a century later—he correctly deduced that the enantiomeric quality of the crystals was the result of enantiomeric molecules The rare form of tartanc acid was optically inactive because it contained equal amounts of (+) tartaric acid and (—) tartaric acid It had earlier been called racemic acid (from Latin racemus meaning a bunch of grapes ) a name that subsequently gave rise to our pres ent term for an equal mixture of enantiomers... 

Could the unusual optically inactive form of tartaric acid stud... 

Section 7 4 Optical activity, or the degree to which a substance rotates the plane of polarized light is a physical property used to characterize chiral sub stances Enantiomers have equal and opposite optical rotations To be optically active a substance must be chiral and one enantiomer must be present m excess of the other A racemic mixture is optically inactive and contains equal quantities of enantiomers... 

Section 7 9 A chemical reaction can convert an achiral substance to a chiral one If the product contains a single chirality center it is formed as a racemic mixture Optically active products can be formed from optically inactive... 

Achiral molecules that contain chirality centers are called meso forms Meso forms typically contain (but are not limited to) two equivalently substituted chirality centers They are optically inactive... 

The ammo acids prepared by these methods are formed as racemic mix tures and are optically inactive... 

Optically Inactive Chiral Compounds. Although chirality is a necessary prerequisite for optical activity, chiral compounds are not necessarily optically active. With an equal mixture of two enantiomers, no net optical rotation is observed. Such a mixture of enantiomers is said to be racemic and is designated as ( ) and not as dl. Racemic mixtures usually have melting points higher than the melting point of either pure enantiomer. 

A second type of optically inactive chiral compounds, meso compounds, will be discussed in the next section. 

The optical activity of malic acid changes with dilution (8). The naturally occurring, levorotatory acid shows a most peculiar behavior in this respect a 34% solution at 20°C is optically inactive. Dilution results in increasing levo rotation, whereas more concentrated solutions show dextro rotation. The effects of dilution are explained by the postulation that an additional form, the epoxide (3), occurs in solution and that the direction of rotation of the normal (open-chain) and epoxide forms is reversed (8). Synthetic (racemic) R,.9-ma1ic acid can be resolved into the two enantiomers by crystallisation of its cinchonine salts. 

Chemical Properties. The notation used by Chemical Abstracts to reflect the configuration of tartaric acid is as follows (R-R, R )-tartaric acid [S7-69A-] (4) (S-R, R )-tartaric acid [147-71-7] (5) and y j O-tartaric acid [147-73-9] (6). Racemic acid is an equimolar mixture of the two optically active enantiomers and, hence, like the meso acid, is optically inactive. 

Microorganisms and their enzymes have been used to functionalize nonactivated carbon atoms, to introduce centers of chirahty into optically inactive substrates, and to carry out optical resolutions of racemic mixtures (1,2,37—42). Their utifity results from the abiUty of the microbes to elaborate both constitutive and inducible enzymes that possess broad substrate specificities and also remarkable regio- and stereospecificities. 

Composition. Shellac is primarily a mixture of aUphatic polyhydroxy acids in the form of lactones and esters. It has an acid number of ca 70, a saponification number of ca 230, a hydroxyl number of ca 260, and an iodine number of ca 15. Its average molecular weight is ca 1000. Shellac is a complex mixture, but some of its constituents have been identified. Aleuritic acid, an optically inactive 9,10,16-trihydroxypalmitic acid, has been isolated by saponification. Related carboxyflc acids such as 16-hydroxy- and 9,10-dihydroxypalmitic acids, also have been identified after saponification. These acids may not be primary products of hydrolysis, but may have been produced by the treatment. Studies show that shellac contains carboxyflc acids with long methylene chains, unsaturated esters, probably an aliphatic aldehyde, a saturated aliphatic ester, a primary alcohol, and isolated or unconjugated double bonds. 

MethyHsopelletierine, CgHj,ON. This base, isolated by Piccinini under the name fsomethylpelletierinc, was re-examined by K. Hess ei al. It is an oily alkaline liquid, b.p. 114-7°/26 mm., miscible with water and optically inactive. The hydrochloride has m.p. 156° hydrobromlde, m.p. 151-2° the picrate melts at 158° and the aurichloride forms orange-yellow rosettes, m.p. 115-7°. The base can be resolved into d- and... 

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