NARAYANA ACADEMY

INDIA
Section: Senior(SI0&1) Date: 14-11-2014
Name of the student: Stereo Isomers & Tautomerism
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SINGLE ANSWER TYPE

1. Identify which of the following objects posses at least one plane of symmetry : (a) a tree,

(b) a glove, (c) an ear, (d) a nail, (e) a cup, (f) a filled spool of thread, and (g) an empty spool.

Draw a mirror plane in all such symmetrical objects.

The objects with at least one plane of symmetry are (d), (e) and (g) as shown in Figure. For

(f), a spool of thread has the thread wound on to it in either a clockwise or

counterclockwise fashion.

2. Find the illustrate which of the following objects posses a center of symmetry (a)a tree,(b)

a six –pointed star,(c) a five-pointed star,(d) a dumbbell (e) a nail.

The objects with a center of symmetry are (b) and (d) as shown in Figure.

3. Give the restriction, if any, on the placement of (a) a plane and (b) a center of symmetry in

a molecule.
 (a) None. The plane of symmetry can cut atoms in half or cut bonds between atoms. (b)

Yes. The plane must be at the center of the molecule, either in empty space, in an atom,

or in the center of a bond between atoms.

4. How many planes of symmetry are present in the structural formula in Problem?

Three. They are (1) the plane through B-X-B and perpendicular to the plane of the paper,

(2) the plane through A-X-A and perpendicular to the plane of the paper, and (3) the

plane that cuts all five atoms. This plane is the plane of the paper.

All planar molecules must be achiral because the plane of the atoms is a plane of

symmetry.

5. Can a tertiary amine  R1R 2 R 3 N : or a carbonion  R1R 2 R 3C :  exist as a pair of enantiomers?

Theoretically it can, but not in practice. A rapid “umbrella” type inversion converts either

enantiomer to a racemic mixture. The energy required for this inversion is very low at

room temperature, thus racemization is unavoidable and, typically, the enantiomers

cannot be separated or isolated.

6. Tricovalent S and P compounds can be isolated as enantiomers. Explain why and give

examples for each.

Trivalent S and P atoms have four sp3 orbitals: three are used for bonding and the fourth

for the unshared pair. When central S or P atoms are each bonded to three different

ligands, they will be stereocenters. Unlike N and C (second period elements), the energy

required for inversion about third period elements is sufficiently high so that the

enantiomers can be separated.

7. Write the structural formulas for the simplest chiral (a) alkane, (b) alkene, (c) alkyne, (d)

alcohol, (e) aldehyde , (f) ketone, (g) carboxylic acid, (h) amine

8. (a) What factors affect the value of obs ? (b) what is the specific rotation ? (c) Can the sign

and/or value of the specific rotation of a molecule be deduced from its structure?

(a) Since the rotation of polarized light is caused by interaction of the photon of light with

an enantiomeric molecule, the extent of rotation is a function of the structure of the

molecules and their number in the path of the light beam; the latter depends on the

concentration and the length of the tube containing the enantiometer. Other factors are :

the solvent (if present), the temperature, and the wavelength of the light used. (b) The

specific rotation, D defined to make it independent of these factors, is a true physical

constant : D  obs / lc , where obs is the observed rotation, in degrees, in a sample cell

whose path length, l, is in decimeters (dm), and the concentration, c, is in g/mL. For pure

liquids the density in g/mL is used. The subscript D tells us that the wavelength of light

used is the D line of the sodium spectrum. The temperature is indicated by a superscript,

and is usually 25o C , thus []25D . (c) No!

o

9. (a) Calculate the specific rotation of coniine, the toxic component of poison hemlock, if a

solution containing 0.75g /10mL is placed in a 1-dm polarimeter tube and its observed

rotation at 25o C(D line) is + 1.2o . (b) What is the specific rotation of the enantiomer of

coniine?
 (a) []D  1.2o / (1)(0.075)  16o (b) 16o

10. (a) Find the observed rotation of a solution of coniine containing 0.35 g/mL as measured

in a 5.0-cm tube (D line). (b) What is the observed rotation if (i) the concentration is

doubled and (ii) the length of the tube is doubled? (c) What is the specific rotation if the

concentration or the length of the tube is doubled?

(a) obs  []D (lc)  16o (0.50)(0.35)  2.8o . (b) (i) Doubling the concentration doubles the observed

rotation because the number of molecules in the path of the light beam doubles, therefore

 obs  5.6o . (ii) Doubling the length of the tube also doubles the number of molecules

encountered by the light beam; again  obs  5.6o . (c) The specific rotation is a constant and

is independent of concentration and path length.

11. How can we decide whether an observed rotation of a solution of an optically active

compound is 170o and not actually 190o ?

If the tube length or the concentration is halved, a compound that is dextrorotatory will

rotate the plane-polarized light to one half of its previous rotation, or 85o , but if it is

levorotary, the observed rotation will be 95o

12. A newly discovered compound is thought to be chiral, but shows no rotation in a specific

solvent. Does this mean that the compound is assuredly achiral?

No. It might be racemic. If not, it may be fortuitous that there is no rotation in the solvent

used. If there is no rotation in two other solvents, the compound is probably achiral. Also,

if the wavelength of the light used is changed, rotation may occur.

13. The specific rotation of a pure enantiomer is 12o . What will be its observed rotation if it is

isolated from a reaction with (a) 20% racemization and 80% retention and (b) 80%

racemization and 20% inversion?

(a) obs  0.80(12o )  9.6o ; (b) obs  0.20(12o )  2.4o

14. Optical purity (OP)  (obs / []D ) 100% . (a) What is the OP of a sample isolated from a reaction

having an  obs  6.0o if []D , = 12o ? (b) Calculate the molar % composition. (Assume all

measurements are taken in a 1.0-dm tube at the same concentrations and with the same

wavelength)

(a) OP  (6.0o / 12o ) 100%  50%

(b) The mixture has 50% (+) and 50% () , which is the same as 75%(+) and 25% (-)

15. What is the percentage composition of a mixture of the two enantiomers in questions

number 13. Whose rotation is - 9.0o ?

The OP (9o / 12o ) 100  75% so 75% of the mixture consists of (-) enantiomer and 25% is the

1
racemate. The total % of (-) is thus 75% + (25%)  87.5% and the remaining 12.5% is (+).
2

16. Assign R and S designations to the following compounds:

a) b)

c) d)

a) R, (b) S, (c) S, (d) R

17. What are the general rules for switching ligands or rotating Fischer structures?

(1) An even number of switches results in no change in the configuration. (2) An odd

number of switches changes the configuration to that of the enantiomer. (3) The structure

cannot be rotated out of the plane of the paper. (4) Any rotation of Fischer projections that
 interconverts horizontal and vertical ligands is not allowed. Hence, the structure can be

rotated in the plane through 180o , but not through 90o

18. Identify each of the following as R or S :

In E, the priority order is CH2Cl  CH(CH3 )2  CH3  H . The compound is S. In F, the priority

order is CH2OH  CN  C  CH  CH3 . The compound is S. CH2OH has priority over C  N

because one O counts before three N’s. In G, the priority order is NH2  COOH  CHO  H . The

compound is R.

19. Esterification of (-)- lactic acid with methanol gives (+) –methyl lactate :

CH3CH(OH)COOH  CH3OH 

HCl
CH 3CH(OH)COOCH 3  H 2O

Has the configuration changed ?

No. Even though the sign of rotation changes, there is no changing of bonds to the chiral

C.

20. Compare the physical and chemical properties of diastereomers

Diastereomers have different physical properties, e.g. melting and boiling points, refractive

indices, solubilities in different solvents, crystalline structures, and specific rotations.

Because of their differences in molecular shape and polarity, they often can be separated

from each other by chromatography. Diastereomers have different chemical properties

toward both chiral and achiral reagents. Neither any two diastereomers nor their

transition states are mirror images of each other and so will not necessarily have the same

energies. The H s will be somewhat different and thus the rate of reaction will differ.

However, since the disterecomers have the same functional groups, their chemical

properties are not too dissimilar.

21. Compare chemical and physical properties of (a) enantiomers and (b) an enantiomer and

its racemic form.

(a) The chemical properties of enantiomers are the same toward achiral reagents, solvents,

catalysts, and conditions. Towards chiral reagents, solvents, catalysts, and conditions,

enantiomers reacts at different rates. The transition states produced from the chiral

reactant and the individual enantiomers and not mirror images. They are diastereomeric,

and hence have different enthalpies; the H values are different, as are the rates of

reaction and the amounts of product formed. With the exception of rotation of plane-

polarized light, enantiomers have identical physical properties. e.g. boiling and melting

points, and solubility. (b) The chemical properties are the same towards achiral reagents,

but chiral reagents react at different rates. Enantiomers are optically active; the racemate

is optically inactive – it does not rotate the plane of polarized light. Other physical

properties, such as crystalline form, melting point, and solubility, of an enantiomer and

its racemate may differ.

22. (a) Why is a meso compound achiral? (b) What structural feature must a meso compound

have?

(a) At least one conformer has either plane or a point of symmetry, which makes it

superposable upon its mirror image. (G and H in problem). (b) It must have at least one

pair of similar stereocenters.

23. Why are the following stereoisomers meso?

 In (a) and (b), a plane of symmetry cuts through the center carbon and the two horizontal

ligands revealing that the top half of the molecule is the mirror image of the bottom half. It

does not matter which ligands are attached to this carbon because they are within the

symmetry plane. This is also true in (c) if n=1 or an odd number. However, if n is an even

number, the symmetry plane cuts through the central C-C bond.

24. Give methods for resolving a racemate.

Both physical and chemical properties of enantiomers toward achiral reagents are

identical. In rare cases the crystals of (+) enantiomer can be hand separated from those of

the (-) enantiomer of the racemate. This is the method used by Louis Pasteur (the chiral

agent) in 1848 with a microscope and a pair of tweezers, and its was possible only

because he noticed that the sodium ammonium salt of racemic tartaric acid crystallized

into mirror image crystals that were large and well formed. Pasteur was also the first

investigator to resolve a racemate chemically, and his method is used today. An optically

pure compound, for example, a (+) base, is reacted with a racemic acid, resulting in two

salts: a(+) (+) salt an a (-) (+) salt. Since these are diastereomers, they have different

solubilities and are separable by fractional crystallization, after which the enantiomers are

recovered. If the diasteromers are liquids, they may be separable by fractional distillation,

or organisam, usually can metabolize only one enantiomer of a racemate, while leaving

behind a pure solution of the unused one. Today the same result is obtained by using the

enzyme that catalyzes the cell reaction rather than the whole microbe. Another technique

is to pass a solution of a racemate through a chromatography column containing a chiral

adsorbent. One of the enantiomers is preferentially adsorbed, or may preferentially eluted.

A variant of this method is to elute with a chirla solvent.

25. How many stereoisomers of (a) methylcyclopropane and (b) methylclobutane are possible ?

Draw them.

One stereoisomer of each; there is a plane of symmetry (dashed line) through the CH3 and

H bisecting the ring. Monosubstituted carbocyclic compounds do not have stereoisomers.

26. Draw all the stereoisomers (a) 1,2-dimethylcyclopropane, (b) 1,2-dimethylcylobutane, and

(c) 1,3-dimethylcyclobutane.

For (a) and (b). Three each : cis-1,2 are meso, and trans-1,2 exist as a pair of enantiomers

in each case.

(c) Two : cis-1,3 has a plane of symmetry ; trans-1,3 has a plane and a center of

symmetry. In both isomers C I and C3 are stereocenters. Switching H and Me converts one

stereoisomer to another.

27. Use chair conformers to discuss the stereochemistry of (a) cis – and (b) trans-1,2-diG-

cyclohexanes.

(a) In one conformer of the cis-isomer one (G) is (e) and the other is (a). Through ring flip

this conformer is inrapid equilibrium with the other chair conformer, where the G’s
 change position; the (e) becomes (a) and the (a) becomes (e) Although each equal –energy

conformer is chiral, the molecule is achiral because these conformers are enantimers

comprising an optically inactive, nonresolvable conformational racemate.

(b) he lower energy conformer with the G’s (e,e) flips to give the higher energy (less

prevalent) (a,a) conformer which we can ignore. The (e,e) conformer, as well as the (a,a)

conformer, has an enantiomer and hence exists as a resolvable racemate.

Note that the analyses using chair conformers and flat rings give the same answer about

the ring stereochemistry. Chemists knew the correct stereochemistry of cyclic compounds

before they were aware of conformational theory.

28. Show that both cis-and trans-1,4-diG-cyclohexanes are achiral even though the ring is

not flat.

Both the cis and trans-1,4-isomers have a plane of symmetry bisecting the chair through
I
C and 4
C and their ligands. In addition, the trans-isomer with both G’s in the (e) or (a)

position has a center of symmetry. These diastereomers are both achiral. I C and 4 C are

stereocenters but neither is asymmetric.

29. Draw the enantiomers of 3-bromocyclohexene and give R/S designation for each.
30. How can a reaction of one enantiomer at a site other than the chiral C result in an achiral

product? Give an example.

(1) If the reaction makes two identical ligands at the formerly chiral C, the product is

achiral

(1) CH3CH(OH)CH 2Cl 

reduction
 CH3CH(OH)CH 3 achiral

(2) If the product molecule has a plane or center of symmetry, it is achiral

(2)

31. (a) Identify all of the products possible from the radical monochlorination of (S)-2-

Chlorobutane. (b) Give their stereoidentity.

(a) (S)  CH3CHClCH 2CH3 

 ClCH 2CHClCH 2CH3 (D)  CH3C(Cl) 2 CH 2CH3 (E)

CH3CHClCHCICH3 (F)  CH3CHClCH2CH2Cl(G)

(b) D is still chiral and the C2 - configuration is unchanged because no bonds have been

broken. However, because of the change in priorities (CH2Cl  CH2CH3 ) , it is R. E is achiral

since C2 with two Cl’s has a plane of symmetry. Two diastereomers corresponding to F are

formed. C2 is still S, but C3 can be R or S. These diasteromers are 2S, 3S which is optically

active, and meso 2S, 3R. Attack at C4 does not affect the configuration at C2 , nor does the

priority order change; G is S

32. Explain the reaction

(R)  CH3CHIC2 H5 137 I  

 CH 3CHIC2 H 5 containing 2% 137
I
obs 15.90 o
obs 15.26 o

Note : Replacement of I with 137

I does not change the sign or value of the rotation.
 The optical purity of the recovered iodide is (15.26/15.90)100%=96%. Hence, 4% of the

iodide is racemic. This means that 2%, the same percentage that contains isotopic I, has

been converted to the S. It is concluded that every reaction with 137 

I resulted in an

inversion at C* .

33. Predict what would happen to optically active 2-iodobutane in the presence of I 

Optically active RI should react with I  with inversion at C* and eventually be racemized.

34. Predict whether the following reactions occur with racemization, retention, or inversion of

configuration, and give your reason.

(a) CH3CH2CH  OH  CH2Br  OH 

 CH3CH2CH  OH  CH2OH  Br 

(b) CH3CH2CH  CH2  D2 

catalyst
 CH3CH2CH  D CH2D

(c) CH3CH2CH  OH  CH  CH3 2  CH3COCl 

 CH3CH2CH  OCOCH3  CH  CH3 2  HCl

(d) CH3CH2  NH2  COOH  NaOH 

 CH3CH  NH2  COO Na   H2O

(e) CH3CH2CH2CH  Cl  CH3  OH 

 CH3CH2CH2CH OH  CH3  Cl 

(a),(c) and (d) Retention;no bond-brecking occurs at the chiral Cc.(B)

Racemisation;although the product has a chiral center (D being sufficiently different from

H),both enantiomers are formed in equal amounts because D 2 adds to the enantiotopic

faces of the alkene equally .(e)Inversion

35. State whether the following statements are true or false. Give your reason

(a) A compound with the S configuration is the (-) enantiomer

(b) An achiral compound can have chiral centers.

(c) An optically inactive substance must be achiral

(d) In chemical reactions the change from an S reactant to an R product always signals an

inversion of configuration

(e) When an achiral molecule reacts to give a chiral molecule the product is always

racemic

(a)False;the sign of rotation is not related to the configuration.(b)True;an example is

ameso compound.(c)False;a racemate shows no optical activity.(d)False;the priority

 sequence of ligands may change.(e)False;if an optically active chiral co-reactant,solvent, or

catalyst such as an enzyme is used,the product will likely be opctically active.

36. Optically active A has the molecular formula C6 H12 and catalytic hydrogenation converts it

to achiral C6 H14 . Give the structure of A.

A is 3-methyl-1-pentene, which is converted to achiral 3-methylpentane by addition of H 2

37. Two optically active alkenes, B and C, have the same molecular formula, C5H9Cl . After

addition of one mole of H 2 to each, B is converted to D (achiral), and C forms E (optically

active). Give the structures of B,C,D, and E.

In both B and C, one of the ligands on the chiral C must be CH  CH2 that adds H 2 to form

a C2 H5 group. B already has a C2 H5 group on its chiral C, making the product achiral.

However, since C does not have an ethyl ligand, the product remains active.

38. How many stereoisomers can be obtained by catalytic hydrogenation of both double bonds

in the following compound F ?

Three. If H 2 adds to both double bonds from the same face, the product will be meso G. If

H 2 adds to the double bonds from opposite faces, the product will be rac H, having both

enantiomers in equal amounts

39. Define the terms erythro and threo and illustrate with Fischer diagrams using 3-chlro-2-

butanol (CH3CH(OH)CHClCH3 ) .

These terms are used to describe diastereomers with two chiral C’s (usually adjacent),

when both C’s have two sets of identical ligands. In fig.(a) the identical ligands are H and

Me. When the different ligands, in this case OH and Cl, are on the same side of the

vertical bonds as in the molecule is called erythro (related to the sugar erythrose). When

they are on opposite sides as in fig.(b) the molecule is called threo (related to the sugar

threose). The relationship of the erythro to a meso structure is apparent if we change OH

to Cl.

40. 2,3-Pentadiene, CH3CH  C  CHCl has no chiral C’s, yet it is a chiral molecule (it has two

enantiomers). Explain with the aid of orbital structures.

C 2 is sp hybridized and has one p-orbital overlapping in the xy plane with the p-orbital of

C1 , and the other over lapping in the xz plane with the p orbital of C 3 to form the two

double bonds. The two ligands (H, Cl) attached to C1 are therefore in a plane at right angles

to the plane of the two ligands (H, CH3 ) attached to C3 . The mirror images are not identical,

as can be shown by rotating one of the structures, in this case B in fig. (a) 180o out of the

plane of the paper in order to superpose the H and Cl ligands in the plane of the paper.

The ligands extending in back and in front of the plane of the paper will not match. see

fig. (b) This is an example of a chiral molecule that has two steroeocenters (C1 and C3 ) , but

no chiral centers.
41. Draw the two enantiomers of 4-chloroethenylcyclohexane, C, shown in Figure

This is best done by considering the ring to be flat

42. Draw all the stereisomers of 1,2,3-trimethylcyclohexane and give their stereiodentity.

There are two meso structures and one pair of enantiomers.

43. Write the structures of the reactants and products in the following reactions. What is the

stereoidentity of B and C ?

44. How many 2,3,4,5-tetrahydroxyadipic acids, HOOC (CHOH)4 COOH are possible? Give their

R/S designations.

Ten. There are four chiral carbons but two pairs are similar and some stereoisomers ae

meso. The following are enantiomeric pairs: RRRR and SSSS; RRRS and SSSR; RRSR and
 SSRS; RSSR and SRRS. RSRS and RRSS are two different meso diastereomers because

the top and bottom halves have mirror images.

45. (R)  CH2  CHCH(CH3 )C2 H5 and D 2 in the presence of a catalyst. Draw the structure of the

reactant all the products. Give R/S designations.

46. Write the structures of the three meso diastereomers of C6 H12Cl2

Here meso structures can be identified easily by their plane of symmetry in at least one of

their conformations, which divides them into mirror image halves, each with three C's .

The isomers are :

47. The following compounds do not have C  O groups, yet have H’s with enhanced acidity

bonded to carbon. Show the carbanions (conjugate bases) and give a reason for their

stability. (a) CH 3 NO2 , (b) CHCNO, (c) HCCl3 , (d) CH3C  CH , (e) cyclopentadiene, (f) Ph2CH 2 . (g) 2,4-

dinitrotoluene, (h) RSCH 2 SR , (i) Me3 S  , (j) Ph3 PMe , (k) CH3SO2CH3 (dimethyl sulfone).
48. Select(a) the strongest and (b) the two weakest acids in Problem 47 and justify your

choices.

Sol: (a) CH 3 NO2 . The more electronegative the atom, in this case O, to which the- charge is

delocalized, the more stable is the base and the more acidic is the parent. The-charge in

(g) is also dispersed to O but the delocalization is less effective because some aromaticity

of the benzene ring is lost. (b) CH 3C  CH and Ph2CH 2 because the -charge is only on very

weakly electronegative C’s. The anion of cyclopentadiene (e) also has a -charge on C, but

its attainment of aromaticity is a good stabilizing effect.

49. (a) Account for the fact that nitroform, HC  NO2 3 (trinitromethane), and cyanoform, HC  CN 3

( tricyanomethane), are both strong acids  ka  1 but chloroform is a very weak acid. (b)

Why is CH3SO2CH3  pKa  31 much less acidic than CH3 NO2  pKa  10 ?

Sol: (a) The conjugate bases of HC  NO2 3 and HC  CN 3 are extremely weak (stable) because their

negative charges are delocalized by extended p  p   bonding to electronegative atoms in

each of three gropus. Hence the acids are strong. Typically, p  d  delocalization, as in
 Cl3C : , is far less significant than p  p  bonding. The overlap is less effective because of

the longer bond length and difference in size of the 2p and 3d orbitals. (b) p-d  bonding

in  : CH 2 SO2CH 3 is less effective for the same reason.

50. Compare the acidities of the (C), and justify your choice.

Sol: A>B>C. The- charge of each conjugate base is delocalized to the more electronegative O.

The delocalization in the anion of A is most extensive because two O’s participate and

additional stabilization arises from the strong inductive effect of N because of its

formal+charge. In the anion of C, cross-conjugation with the O of OR competes with

delocalization of the – charge to O, thereby attenuating the delocalization from C and

making the anion a stronger base than the one from B.

51. What is the essential structure unit needed for tautomerism?

Sol: X=Y-Z-H, where X is an electronegative heteroatom such as O and N. A triple bond could

replace the double bond

52. Which two enols are in equilibrium with (a) 2-butanone, (b) 1-phenyl-2-butanone, (c)

p  O2 NC6 H 4CH 2  COCH 2 ph, and (d) bicycle [4.1.0]-2-heptanone? Which is more stable?

Why?

In each case, the first written enol is more stable.

(a) The first enol has the more substituted double bond.

(b) C  C and Ph are conjugated.

(c) extends the delocalization of the conjugated

system.

(d) . The exocyclic C  C increases the strain in the cyclopropy ring.

53. (a) Write structure for the stable keto and enol tautomers of 2,4-pentanedione (A), a

typical dicarbonyl compound. (b) Why are such enols of  -dicarbonyl compounds more
 stable than those of monocarbonyl compounds? (c) Account for the fact that the enol

content of A is 15% in H 2O and 92% in hexane. (d) How can the enol be chemically

detected and separated?

Sol: a)

(b) This enol is more stable because it has a conjugated C  C  C  O   system and

intramolecular H-bonding(chelation). (c) water forms H-bonds with the C  O ' s, thereby

inhibiting the intramolecular H-bonding that helps stabilize the enol. (d) The enol

decolorizes a solution of Br2 in CCl4 . The more volatile enol tautomer is separated by

careful distillation of the mixture in a fused quartz apparatus (eliminates base from glass).

54. Account for the given variation in enol content for each of the following  -dicarbonyl

compounds:  EtOCO2 CH2  A , <1%; CH 3COCH 2COOEt (B), 7.7%; CH3COCH 2COCH3 (C), 76%; and

PhCOCH 2COCH 3 (D), 89%.

Sol: Cross-conjugation retards the ability of the C  O of the ester group to help stabilize the

enol. Diethyl malonate (DEM), A, with two ester groups, has a lower enol content than

acetoacetic ester (AAE), ethyl acetoacetate, B, with one COOR which has a lower content

than the diketone C. The Ph group stabilizes the enol by extending the conjugation for  

bond delocalization as shown:

Note that extended conjuction is achieved by preserving the group.

54. Account for the fact that 1,3-cyclohexanedione readily undergoes base or acid-catalyzed

deuterium exchange where as 2,6-bicyclo[2.2.2]octanedione does not.

Sol: 1,3-Cyclohexanedione behaves as a typical  -diketone. The  C of the bicyclic compound

is at a bridgehead where it is sterically prevented from assuming the flat geometry needed
 for extended  delocalization (Bredt’s rule). Without stabilization the carbanion cannot

form.

56. Explain why the enol content of biacetyl, MeCOCOMe, is (a) somewhat higher than that of

butanone and (b) much less than that of 1,2-cyclohexanedione.

Sol: Adjacent C  O ' s are destabilizing because of the   , s on the O’s of C  O . (a) MeCOCOMe

relieves much of this electrostatic repultion by acquiring the conformation with anti O   , s.

Some repulsion is further relieved in the enol but the enol content is still small because

this relief is associated with a loss of C  O resonance energy. (b) The cyclohexane ring is

rigid and the O   , s must be syn. The only way to avoid the repulsion is for one of the

C  O ' s to completely enolize.

57. Should cyclobutenone (F) or triketocyclobutane (G) be more easily enolized?

Hypothetical enol of Enol of G:

F doesn’t enolize because its enol is a flat ring with 4n  n  1  e, s and is antiaromatic. G

enolizes because its enol has 4n  2  n  0  e, s and is stabilized by its aromaticity.

58. (a) Account for the fact that 1,3,5-trihydroxybenzene reacts with H 2 NOH to give an oximino

derivative, whereas phenol and 1,3-dihydroxybenzene do not. (b) Expalin why 1,2,4-

trihydroxybenzenes (A) and 1,2,3-trihyoxybenzenes (B) do not react with H 2 NOH .

a) The triketo tautomer of this isomer has considerable because of the large resonance

energy of its three C  O groups. Therefore it has sufficient concentration in the phenol-

keto equilibrium to react to give a trioxime.

b) The triketo tautomers of A and B are destabilized by the adjacent C  O ' s and have an

insufficient concentration to react with H 2 NOH .