KETO-ENOL TAUTOMERISM IN @-DICARBONYLSSTUDIED BY NUCLEAR

MAGNETIC RESONANCE SPECTROSCOPY

11. SOLVENT EFFECTS ON PROTON CIIE?vIICALSI-IIFTS AND ON EQUILIBRIUM CONSTANTS

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JiIxx T . ROGERSAND

JANE

L. BURDETT

Departllze?tt of Cl~evr~istry,
;\.Iichigalt State University, East Lansing, lllicl~igan
Received Xovernber 13, 1964

Dedicated to Professor R. B . Sarzdi~zon the Occasion of his Sixty-Eighth Birtlzday

ABSTRACT
The effect of various solvents on the proton chemical shifts of a number of acyclic p-diketones and p-ketoesters has been observed by nuclear magnetic resonance spectroscopy.
These shifts are discussed in terms of the dissociation of intran~olecularand inter~nolecular
hydrogen bonds on dilution. A con~plexof benzcne with the en01 tautolner of the p-dicarbonyl
molecule is proposed. T h e effect of solvents on the position of the tauto~nericequilibrium is
discussed.
INTRODUCTION

Proton chelnical shifts and equilibriu~nconstants for pure 0-dicarbonyls are given in
the first paper of this series (1). Reeves (2), Reeves and Schneider (3), Schneider and
Reeves (i),and Balta-Calleja (5) have investigated solvent effects on acetylacetone by
nuclear lnagnetic resonance (n.m.r.), and Giessner-Prettre (6) has observed the effect
of solvents on the n.1n.r. spectrum of ethyl acetoacetate. T h e present study involves a
series of 0-diketones and 0-ketoesters with various substituents and has been extended
to include additional solvents. The effects of solvcnts on proton chemical shifts and on
the position of equilibrium have been determined.
EXPERIMENTAL
I~zslrurnental
Proton magnetic resonance spectra were obtained on the Varian A-GO spectrometer. Chemical shift a n d
equilibrium constant measurements have been made a t 33 f 2 "C. Chemical shift values are reported in
c.p.s. from internal tetrarnethylsilane t o within f1 c.p.s. Dilution chemical shifts are reported in c.p.s.
relative t o the pure con~pound.A positive shift of a resonance peak is one which occurs a t a higher applied
magnetic field than the corresponding peak of the pure compound. Equilibrium constants have been obtained
by integration of the areas of certain lceto and en01 resonance peaks. i l t least six integrations have been
performed, and reported percentages of en01 tauto~nerare accurate t o within f2%.
Solvent Pzrrificalion
Benzene, chloroform, acetic acid, and dioxane were purified according to Vogel (7). Other solvents were
dried and fractionally distilled.
Sample Preparation
Solutions were weighed on a n analytical balance to f0.1 mg, and mole fractions were determined t o
within f0.001. Tetramethylsilane was added as a n internal reference t o each solution; the quantity added
was the same in each case and did not affect the calculated mole fraction t o within 0.001. Spectra made
with samples in unsealed tubes were compared with those for samples sealed in vaczlo, and usually no difference in line width or shape was found. For acetic acid solutions and those using acetylacetone, tubes were
evacuated and sealed, but for the other solutions unsealed sample tubes were used.
Co?npoz~?~d
Preparation and Purificalio?~
Synthesis and purification of the p-dicarbonyls used in this study have been described in the first paper
of this series (1).
Canadian Journal of Chemistry. Volume 43 (1905)

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ROGERS A N D BURDETT: KETO-ENOL

TAUTOMERISM. 11

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RESULTS A N D DISCUSSION

Cheinical shifts a t infinite dilution for various proton groups of both the en01 and lteto
tautomers of p-diltetones and P-ketoesters are listed in Table I for carbon tetrachloride,
benzene, chloroform, and hexane. Similar data are given in Table I1 for acetylacetone
and ethyl acetoacetate in 13 different solvents. The values represent the changes in
cheinical shifts for given proton groups between pure con~poundand an infinitely dilute
solution in the given solvent, measured in c.p.s., and are positive when the solution shift
is a t higher magnetic field. In a few cases (m = masked) the values could not be measured
because of overlapping of resonances. Where hydrogen bonding occurs only a single
proton resonance is seen, and its che~nicalshift is an average of the shifts for bonded and
non-bonded protons.

Inert Solvents
There is very little effect on no st of the chemical shifts on dilution in carbon tetrachloride, hexane, carbon disulfide, dioxane, or ether, and we call these solvents inert for
that reason. The a-protons of the lteto isomer usually illove to high field by 10-15 c.p.s.
This was explained by Giessner-Prettre (6) as resulting from the brealting up of intermolecularly hydrogen-bonded polyiners on dilution. Variable temperature studies confirin
the dissociation of iilterinolecular hydrogen bonds, since the a-proton resonances occur
a t higher applied fields a t increased temperatures (8).
The a-protons of the en01 tautoiners also inove to higher field by 2-12 c.p.s. on dilution,
but the most nlarlted effect is on the hydroxyl protons, xvl~ichare shifted to higher magnetic
field by about 6-21 c.p.s. These chemical shifts are illustrated in Fig. 1where the chemical

Chemlcal
Shift
(c.p.s)

Mole F r a c t i o n Solute

FIG. 1. Chemical shift relative to pure solute of the O H proton in p-dicarbonyls in carbon tetrachloride vs. mole fraction of solute (code nu~nbersrefer to compounds of Table I).

shift of the OH proton is plotted as a function of concentration in carbon tetrachloride

solution for all the p-dicarbonyls studied. These shifts can be attributed to the brealting
LIPon dilution of the intrainolecularly hydrogen-bonded species of the en01 tautomer.

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TABLE I
Chemical shifts of the proton groups of p-diketones and p-1:etoester.s in various solvents a t infinite dilution*
Ethyl
Codc

Compound

Benzene
1
3
G
7
9

solutions
r2cetylacetone
ol-Chloroacetylacetone
Hexafluoroacetylacetone
Trifluoroacetylacetone
ol-Methylacetylacetone

CII 3
-

r2cetyl
CH 2

CHj0

CI-13"

ol-I-lk

ol-11

39
40
.46

25
25

33
29

57
24

54
29

50
39
47

OH0
-45
-29

+37
+27
-34

14
15

Butpl acetoacetate
t-Butyl acetoacetate

23
22

29
29

28
26

5
2

-36
-37

18

Ethyl acetoacetate

31

35

-35

Ethyl ol-allylacetoacetate
Ethyl ol-isoa~nylacetoacetate
Ethyl henzoylacetate

15

20
15

-34
-38
- 22

24
25
26

Ethyl ol-isohutylacetoacetate
Ethyl ol-n-hutylacetoacetate
Ethyl ol-chloroacetoacetate

-35

28
29
30

Ethyl a-ethylacetoacetate
Ethyl a-fluoroacetoacetate
Ethyl trif uoroacetoacetate

31
32

Ethyl ol-methylacetoacetate
Ethyl ol-isopropylacetoacetate

I Gk
140
17
14
12"
140
16
IG
30k
2Gc
15
20
3 1"
33"
IS
15

26

19
20
21

ISk
21"
22
1S
14k
14"
20
20
30k
270
21
28
30k
320
23
18

Methyl acetoacetate

34
Carbon
1
3
6

7
9

tetrachloride solutions
Acetylacetone
ol-Chloroacetylacetone
I-Iexafluoroacetylacetone
Trifluoroacetylacetone
a-Methylacetylacetone

19
13
24

111

9
13
43

nl
21

1G
17
32

nl
-

19
28

20
44
47

19

24
28

2s
11

38

34

10
IS

12
0
9
-

111

-2

2
0

18

24

-31
- 25
-3G
- 10

rlll<yl
ol-group

Other

20k
320
-

8(bu CH?)
se((CH3)3)
Sk((CH3)3)
-

-1, 4, 5

-2, 7, 8
n~

5, 5, -2

6, 0
-

>

+Z
tl

5
Z
Z
%
r
0

z
4
P

Co.r
W
IP

-39
.-33
--

21
3
1
-2
16

8
(7, 3, -1)"
(16, 6)"
-

23(OCH3)

O"CH3)
oe (CHs)

-.

+a

w
a
c.!

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TABLE I (Cofzcludcd)
Ethyl
Codc
14
15

Compound

CH3

10
20
21

Butyl acetoacctate
t-Butyl acetoacetate
Ethyl acetoacetate
Ethyl a-allylacetoncetate
Ethyl a-isoamylacetoacetate
Ethyl benzoylacetate

24
25
26

Ethyl a-isobutylacetoacetate
Ethyl a-n-butylacetoacetate
Ethyl a-chloroacetoacetate

-3
-3
-2
-5k
-50
-3
-3
0"

28
29
30

Ethyl a-ethylacetoacetate
Ethyl a-Ruoroacetoacetate
Ethyl trifluoroacetoacetate

-1
-2
- 1'

1s

Acetyl
CII?

1
0
0
21i
20
0
1
2

CHae

CIIak

-1
0
1
1
~n

-I
0
1
1
1

m
m
1

1
1
2

111
-

3
1
-

4
0

2
2
0

-lo

31
Ethyl a-methylacetoacetate
32
Ethyl a-isopropylacetoacetate
34
Methyl acetoacetate
Chloroforni solutions
1
Acetylacetone
7
Trifluoroacety lacetone
15
t-Butylacetoacetate
1s
Ethyl acetoacetate
21
Ethyl belizoylacetate
26

Ethyl a-chloroacetoacetate

31
Ethyl a-methylacetoacetate
Hexaile solutiorls
1
Acetylacetone
IS
Ethyl acetoacetate
26
Ethyl a-chloroacetoncetate
31
Ethyl a-metliylacetoacetatc
34
Methyl acetoacetate

lo
-1
0
-

1
5
Ok
3c
0
1

-4
- lok
-50
- 2k
-2 c
-6
0
n~
m
-

-5

- 9k
- 6e
-3
-6

I
5
1

-5

-4
-2
3
0

-2

5
-3

-2

-3

111

S
8
3
2

7
7
5
7
5

*Che~nicalshifts are in c.p.s, relative to the pure compound. k = keto, e = enol, and

111

= ~nasked.

a-Ilk

a-I IC

OIIc

l"llcy1
a-(II'OLID

Other

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Trifluoroacetylacetone and hexafluoroacetylacetone are exceptions. In this case the

electronegative substituents inay lead to the formation of stronger hydrogen bonds not
appreciably broken up a t the lowest dilutions used here (-0.03 mole fraction solute).
However, the intramolecular hydrogen bond of these compounds is particularly sensitive
to heat, and increased temperatures result in marked shifts of the hydroxyl proton to
high fields (8). The small downfield shift of the hydroxyl proton of the en01 tautomer of
ethyl acetoacetate on dilution in ether and hexane is also an exception to the above
generalizations.

Hydrogen-Bonding Solvents
When the solvent molecules are able to form hydrogen bonds with the a-protons of
the keto tautomer, or with the hydroxyl proton of the en01 tautomer, the chemical shifts
of these protons do not tend to change much on going from pure liquid to solution. This
behavior is noted, in general, for the solvents chloroform, acetonitrile, acetic acid, and
ethanol, and may be the result of the simultaneous breaking up of solute-solute intermolecular hydrogen bonds and the re-forming of solute-solvent intermolecular hydroge~l
bonds. We might expect a shift of the a-proton to lower magnetic field on dilution if the
hydrogen bond to solvent molecules were stronger than that to the carbonyl group of
the p-dicarbonyl itself. Such downfield shifts are observed (Table 11) particularly for
acetylacetone and ethyl acetoacetate in dimethylsulfoxide and in methanol.
TABLE I1
Chemical shifts for the proton groups in acetylacetone and ethyl acetoacetate in various solvents a t infinite
dilution*
Ethyl
Code

Solvent

Acetylacetone
9
Acetic acid
13
Acetonitrile
5
Benzene
Carbon disulfide
3
Carbon tetrachloride
2
6
Chloroform
Din~ethylsulfoxide
12
8
Dioxane
7
Absolute ethanol
10
ethanol
Ether
4
1
Hexane
11
Methanol
Ethyl acetoacetate
9
Acetic acid
13
Acetonitrile
5
Benzene

3
2
6
12
8
7
10
4
1
11

Carbon disulfide
Carbon tetrachloride
Chloroform
Dimethylsulfoxide
Dioxane
Absolute ethanol
95% ethanol
Ether
Hexane
Methanol

Acetyl

C 1-13

CH?

-3
0
lgk
17O
1
-2
-4
1
-1
-2
-1
0
0
-1

-3
0
15k
13O
4k.0
0
-5
2
1
-1
-2
0
1
-2

a-Proton

CFIJ"

CHjk

CHZk

CIlc

-1

-1
25
3
2
-4
-2
1
-1
-3
3
S
-2

-1

0
33
4
1
-5
3
2
-1
-4
4
7
-3

-2
0
50
14
10
0
-5
m
m
rn
n1
17
-4

0
-4
39
13
12
2
-8
2
-1
-4
7
16
-3

1
nl
26

-2
1
32

-4
-1
36

2
0
9

4
2
0
0
2
1
-1
4
S
1

5
2
-3

13
14
3
-6
3
-1
-3
11
17
-3

9
9
3

3
-1
-3
4
7
-1

-5

2
2
0
6
10
-1

*Chemical shifts are in c.p.s. relative to the pure compound. k = keto, e = enol, m = masked. and b = hroad.

OHc

1521

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ROGERS A S D BURDETT: KETO-ENOL TAUTOMERISM. I1

On the other hand, the en01 hydroxyl proton chemical shifts for acetylacetone are quite
variable. In going from pure acetylacetone to acetic acid or chloroform solution this
proton resonance shifts upfield by 32 c.p.s. or 20 c.p.s., respectively, suggesting that the
chemical shift of the hydroxyl proton is a t higher field when involved in an intermolecular
hydrogen bond than in an intramolecular hydrogen bond (chelated structure). Exceptions
are benzene (discussed below) and acetonitrile, where there may be a particularly important long-range diamagnetic anisotropy correction. No specific conclusions can be drawn
from the data for alcohol solutions of acetylacetone, since the OH peaks of solvent and
solute are coalesced (whereas they are distinct in acetic acid solutions).
The en01 hydroxyl proton resonance for ethyl acetoacetate is very nearly unchanged
(f
6 c.p.s.) in going from pure solute to solution in a hydrogen-bonding solvent. The same
is true for the p-ltetoesters in going to chloroform solution (with the exception of ethyl
benzoyl acetate). The hydroxyl peak for the alcohol solvents is now distinct from the
en01 peak.
In the case of chlorofornl the effect of the /3-dicarbonyls, considered as solvents, on the
chemical shift of the chloroform proton resollance may be observed (Fig. 2). I t is seen

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1;0

Mole F r a c t i o n P-Dicarbonyl

FIG. 2. Chemical shift of the chloroforn~proton in 8-dicarbonyls a s solvents (code numbers refer t o
cornpounds of Table I).

that this resonance is shifted to higher field by 10-30 c.p.s. Icorinek and Schneider (9)
related this shift to the "donor strength" of the solvent molecule, and on this basis ethyl
acetoacetate would be the best donor and trifluoroacetylacetone the poorest. I t should
be noted that the largest upfield shift of the hydroxyl proton resonance on dilution in
chloroform is 31 c.p.s. for trifluoroacetylacetone and the smallest shift (nearly zero) is for

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the P-ketoesters, so that trifluoroacetylacetone .ivould also be the poorest donor on this
basis.
Benzene
Chemical shifts of the various proton groups of 0-dicarbonyls in benzene are given in
Table I for infinitely dilute solutions (relative to pure liquid). Most of the proton resonances (alkoxy and acetyl groups and a-protons) are a t higher magnetic field in benzene.
However, the hydroxyl protons of the en01 tautomer are shifted to lower magnetic field,
while the protons of alkyl a-substituents tend to be almost unchanged ( f 8 c.p.s.). I t
seems probable that these unusual chemical shifts arise from ring current effects in a
solute-solvent complex, as has been observed for a number of solutes in benzene (10, 11,
12), although no single structure for the collisional complex seems to account for all the
data in this case. If the molecules are placed roughly parallel as in Fig. 3, with the benzene

FIG.3. Proposed cornplcx of acetylacctonc with benzene.

rings over a region of large positive charge density of the en01 molecule, the high-field
shifts of the methyl protons and the a-protons may be semiquantitatively accounted for
by the tables of Johnson and Bovey (13). However, to obtain the observed low-field shift
of the en01 proton by this mechanism the rings ~vouldhave to be tipped down by the
methyl groups, putting the en01 proton roughly in the same plane as the benzene ring
and so in a paramagnetic region.
Trifluoroacetylacetone and hexafluoroacetylacetone, where there is a large negative
charge density on the end groups of the en01 molecules, evidently do not form this type
of complex, since the hydroxyl proton and the a-proton are both now shifted to higher
field, as would be expected for a complex in which the benzene ring and the six-membered
ring of the en01 were parallel.
Basic Solvents
In triethylanline solution the @-ketoesterstend to show peaks for only the keto tautomer
and the @-diketonespeaks for only the en01 tautoiner (2, 3). For t-butyl acetoacetate and
ethyl a-allylacetoacetate both tautomers may be detected, but the peaks tend to be
broad. Cheinical shifts froin pure solute to solution are generally small, but the en01
hydroxyl proton of acetylacetone is shifted to higher field on dilution.
In diethylainine solutions of the 0-ketoesters only the lteto tautoiner is detected. The
esters, with the exception of methyl acetoacetate, tend to react with the ainine. Acetylacetone is present only as the en01 tautomer, xvhich has been shown previously to form a
complex with solvent molecules (2, 3).
Solvent Effects on Keto-En01 Equilibria
Equilibriunl constants (K,) for the equilibrium, keto 5 enol, of acetylacetone and ethyl
acetoacetate in various solvents are given in Table 111. Since both en01 and keto molecules
may form hydrogen bonds with the solvent, the relative stability of the tautomers is

ROGERS AND BURDETT: KETO-ENOL

TAUTOMERIS&I.
II

1523

TABLE 111
Equilibrium constants for tautomerization of acetylacetonc and ethyl acetoacctate in various solvents a t
0.1 mole fraction of solute
Acetylacetone
Solvent
Hexane

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arb& tetrachloride

Ether
Carbon disulfide
Benzene
Chlorofor~n
Dioxane
-.~-~
Absolute ethanol
Pure solute
95y0 ethanol
Methanol
Acetic acid
Acetonitrile
Dimethylsulfoxide
-

~-

yo en01
95
96
95
94

Kc*
19
24
19
16

82
82
81
77
74
67
62
62

*I(e = !enol]/[keto].
and mexsurements are at 33
tivfeasurementsat 0.3 mole fraction of solute.

4.6
4.6
4.3
3.4
2.8
3.0
1.6
1.6

Acetylacetonet

Ethyl acetoacetate

% en01

Ice*

yoen01

Ice*

93.6

14.7

39

0.64

79.4
81.6
78.0
74.0
78.0
67.2
76.0

3.9
4.4
3.6
2.8
3.5
2.1
3.2

11
10
7.6
7.2
5.8
1.9
4.9
3.2

0.13
0.11
0.081
0.078
0.062
0.019
0.052
0.023
~

& 2 'C.

often solvent dependent. For comparison purposes all values of Table I11 have been
derived from the spectra of solutions 0.1 or 0.3 mole fraction in solute a t 33 "C. Figure 4
sho~vsthe percentage of en01 tautomer tl~rougl~out
the concentration range for ethyl
acetoacetate in various solvents, and siinilar results have been obtained for acetylacetone.
The p-diketones are principally in the ell01 form and the "inert" solvents favor this
form, since the internally hydrogen-bonded en01 molecule is less polar than the keto
molecule. In polar solvents the fraction of lceto molecules increases. The electrostatic
repulsion between carbonyl groups of the keto form is reduced in a polar solvent. Also,
the solvation energy of lteto molecules is presuillably greater than for en01 lnolecules in
polar solvents (14) and the solubility of the lceto tautomer is greater in these solvents (15) ;
hence, one might expect the equilibrium t o shift toward the lceto tautonler on dilution in
polar solvents.
The P-ketoesters are principally in the keto forin and the fraction of lceto tautoiner
increases on dilution in polar solvents for the reasons mentioned above. In hydrogenbonding solvents this effect is particularly marlced and the en01 tautonler becomes
difficult to detect in acetic acid or climethylsulfoxide solution.
Values for the fraction of en01 tautomer reported here for acetylacetoile and ethyl
acetoacetate agree reasonably well, where they inay be compared, with those of Meyer
(16), I<abachniIc ct al. (17, 18), and ;Clurthy et al. (19), but less well with the values of
Conant and Thompson (20). Since Inany of the previous results were based on bromine
titration, where errors may be large, close agreement with the n.m.r. data ~vouldnot
be expected.
Powling and Bernstein (21) sho~vedthat the enthalpy, and also the free energy, of
tautomerization for several systems was a linear function of the solvent quantity [ ( E - 1)/
( 2 ~ l)lp/ilf. This latter quantity, when multiplied by the difference between the
squares of the dipole lnoinents of the tautoiners, gives the difference between the enthalpy
of the tautomerization in dilute solution and in the gas phase. Although our measurements (Table 111) are for illoderatcly concentrated solutions, we have plotted A l i vs.

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43. 1965

Mole F r a c t i o n Solute

FIG. 4. Percentage of en01 tautolner for ethyl acetoacetate in various solvents (code nuinbers refer to
solvents of Table 11).

[(E- 1 ) / ( 2 ~f l)lp/M for acetylacetone (Fig. 5) and ethyl acetoacetate (Fig. 6); in the
former case the values for solute mole fraction 0.3 were used, since the probable error in
AF becomes very large in the inore dilute solutions where the fraction of lteto isomer is
low.
For ethyl acetoacetate a straight line drawn according to the method of least squares
(omitting the alcohols) has an intercept a t AF = 0.16 kcal/mole, sonlewhat above the
gas phase value of 0. The poillts for solvents where important specific internlolecular
interactions might be expected (acetic acid, chloroform, and perhaps benzene) are scattered rather widely, but the points for a group of 'inert' solvents (hexane, carbon tetrachloride, ether, carbon disulfide, and acetonitrile) do fall close to a line extrapolating to
AF = 0.
For acetylacetone the plot (Fig. 5) is less informative. The least-squares line (omitting
the points for the alcohols) has an intercept AF = - 1.79 kcal/mole, considerably higher
than the gas phase value of - 1.5 ltcal/mole. Indeed, for two 'inert' solvents, hexane and
carbon disulfide, AF is Inore negative for the solutions than for the gas phase-an
unexplained anomaly previously found for several tautomeric systenls (21).

ROGERS .AND DURDETT: KETO-ENOL T:IUTOA,lERISM. I1

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ACETYLACETONE

ETHYL ACETOACETATE

FIG. 5 . Free energy of taiitomerization for acetylacetone vs. solveilt property (code numbers refer t o
solvents of Table 11).
FIG.6. Frce energy of tauto~nerizationfor ethyl acetoacetate vs. solvent property (code numbcrs refcr
to solvents of Table 11). The point G is the value reported for the gas pllasc.
I t is interesting to note that the points for methyl and ethyl alcohol appear t o fall on
lines of different slope; in the case of acetylacetone this line extrapolates almost exactly
to the gas phase value of AF as was observed b y Powling and Bernstein (21).
T h e scatter of points in these graphs is perhaps not too surprising in view of the rather
concentrated solutions used, the specific interactions expected in hydrogen-bonding
solvents, the possible substantial entropy eflects in these systems (8), and the errors a t
present associated with the n.1n.r. method for determining I<, when the amount of one
tautomer is below about 10%; further research will be required for a more complete
understanding of the factors influencing tautoineric equilibria.

CANADIAN JOURNAL O F

CHEMISTRY. VOL. 43,

1965

ACI<XO\VLEDGMENT

This research was supported through a contract with the Atoinic Energy Co~nmission
and a grant from the National Science Foundation. We also thank Varian Associates for
the use of their equipment a t the Varian Applications Laboratory in Pittsburgh.
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