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[1945VdW] - Acidity of organic compounds and resonance

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Acidity of Organic Compounds and Resonance
University of Kansas, Lawrence, Kansas
0 .
NCE he has weighed all the many arguments
favonng each of the various acid-base concepts
and has made a timid decision in favor of one or another, the teacher who is seriously attempting a correlation and integration of organic chemistry by application of the electronic theory is left squarely on
the hprns of a second dilemma. How can he best relate acidity to structure; i. e., bow can he teach his
students to predict by inspection of the formula
whether a given compound will manifest acid properties
and, if so, to what extent and a t what point in the molecule? If the Bronsted definition of acids is the one
adopted, this problem resolves itself into an analysis
of those structural characteristics which confer acid
properties upon a hydrogen atom in a molecule.
At the present time, this question is approached by
sponsors of the electronic theory from two complementary viewpoints. According to the first argument,
an acid hydrogen is one which is bound to another
atom or a group which has a high tendency to attract
the electrons of the covalence binding the hydrogen
(la, 2, 3). I n other words, an acid hydrogen is a
positive or electrophilic hydrogen, a center of low
electron density in which the effective nuclear charge
is relatively high.
In the general case of the type molecule Y-0-H, for
example, unless Y is an atom or group of exceedingly
low electronegativity, the hydrogen atom, because of
its attachment to highly electronegative oxygen, will
exhibit definite acid properties which become more
marked as the electron withdrawal tendency of Y is
increased. Thus, on the basis of relative electronegativities, it may be concluded not only that the
hydrogen of the hydroxyl group in primary alcohols
will show acid character, but also that it will be more
acidic than the hydrogen of secondary or tertiary
alcohols, but less acidic than the hydrogen of water.
In the case of phenol, the resonance forms in which
one of the unshared electron pairs of the oxygen is
shifted to increase the covalence between the oxygen
and the ring carbon atom (+T effect), contribute considerably to the structure of the molecule and enhance
the acidity of the hydroxyl hydrogen by placing a positive charge on the oxygen atom. Introduction on the
ring of an electron acceptor such as the nitro group, particularly a t the ortho or para position, serves to decrease
still further the electron density about the oxygen,
thereby producing an additional increase in acidity.
The carboxylic acids, according to the argument, are
even stronger because the electron withdrawal from the
hydroxyl ,group
. - due to the resonance about the doubly
bbnded oxygen (-T effect) is greater.
I n the acetone molecule, resonance (-T effect)
about the oxygen atom produces a low electron density a t the carbonyl carbon atom and a slight positive
charge is transmitted to each of the methyl carbons.
As a result, the hydrogen atoms of acetone are weakly
acidic. When the effect is doubled, as in the case of
acetylacetone, the acidity becomes much more marked.
Examples of the application of this point of view to a
host of additional organic compounds commonly considered as weak acids are too familiar to warrant further discussion. Careful study of the principle leads
to the valid assignment of acidic properties to many
organic compounds ordinarily not classified as Bronsted
acids. In chloroform, to mention only one, the
electron affinity induced in the hydrogen atom by
the electronegative chlorine atoms should render the
former somewhat acidic. Such, indeed, is probably
the case, for in the addition of chloroform to acetone
in the presence of solid sodium hydroxide, the most
feasible mechanism would involve the removal of the
proton from the chloroform molecule by the hydroxyl
ion. Attack by the resulting trichloromethyl carbanion on the electrophilic carbonyl carbon followed by
the transfer of the proton to the oxygen atom would
com~1;ltethe reaction.
Ac ,,ardingto the second viewpoint, the tendency for,
a q . m l e to release a proton is heightened when thr,
ior.! .suiting from the discharge of a proton is stabilized'
dr~eto resonance. This is especially true if the reso-,.r-.- '-e energy of the ion is greater than that of the ionogm, due either to the fact that the ion resonates among,
moie structures than does the ionogen or to the fact,
that the resonance forms of the ion are more nearly,
.,;lauy examples of the application of this principle
bC: h to inorganic and to organic compounds have been
d t ~ dpreviously. As Pauling (4) has pointed out,
resi'nance is complete in the carbonate, nitrate, and
bot, 'F ions and somewhat inhibited in the acids. The
in? sed strength of nitric acid over nitrous acid would
be I.--ticted on the basis of the fact that the nitrate
ion epresented by three equivalent resonance forms,
the trite ion by only two. In the teaching of beginnir students, this concept may be simplified cousic .bly by the explanation that the distribution of
the ,gegative charge of the ion over two or more atoms
red&ces the electron density on each atom; hence, the
attl,ction for the proton is diminished, an effect which
is I: 1 ;eased with increasing distribution of the negative
chq;e. This broad idea may be extended to correlate
the relative acidity of many com>, 8. c,?nceming
p o ~ . ,.,:~ such
as the oxygen acids of the halogens, for
exak,-2, in which the acid strength increases with a?
incr&e in the number of oxygen atoms over whici
the negative charge on the ion may be distributed,
even though trne resonance is not involved. As a
matter of fact, this general concept provides a simple
explanation of the well-known rule that an oxide or
hydroxide of a given element in a higher valence state is
more acidic than an oxide or hydroxide of that element
in a lower valence state.
As applied to organic compounds, the fact that the
stabilization by resonance of the anion resulting from
the loss of a proton contributes to the strength of the
ionogen as an acid is well illustrated by the carboxylic
acids. Although the acids themselves, as well as the
carboxylate ions, resonate between two structures,
only in the case of the ion are the two structurrs equivalent; hence, the ion is stabilized more than the ionogen, and, as a result, a carboxylic acid is more acidic
than an alcohol.
The phenols are likewise stronger acids than the
alcohols; here, again, the explanation lies in the fact
that the resonance forms of the phenolate ion are more
nearly equivalent than those of the unionized molecule. The comparatively strong acid character of the
phenylammonium ion (weak basic strength of aniline)
may be attributed to the fact that, whereas the ion is
restricted to two structures, the molecule of the conjugate hase, aniline, resonates among five structures.
By similar application of the principle, acid properties
of such compounds as 1,3-diketones,@-ketonicesters,
amides, nitroalkanes, pyrazole and, the
barbiturates, and many others find a logicL1 explanation. Conversely, the basic strength of guanidinc n a y
\e attributed to the fact that the guanidiqiur ion
esonates among three equivalent structures, wi
guanidine itself resonates among three structures a c k h
are not equivalent.
Even a hasty comparison of the two points of v'-n
~egardingacidity reveals that the "ion resonan&"
heory cannot be applied to molecules in which ihe
electronic displacements are of the inductive type oi'v.
The question of the acidic nature of a large bodq":if
,rganic compounds, therefore, is approached oi.,y
From the "positive hydrogen" viewpoint. It is pr&ably for this reason, for purposes of simplicity, tht
teachers of organic chemistry who are attemptin? an
application of the electronic theory, appear t r be
showing an increasing tendency to neglect the ion
resonance" idea. In the author's opinion, thi~''~'lnd
is to be deplored for two reasons, the first of [email protected] is
the fact that many interesting cases are encoun.' 5d
in which the "positive hydrogen" viewpoint sheds 'le
light on the problem of the comparative acid s t d 'dh
of two different compounds hut where the "ion rl.bnance" approach suggests a clear-cut decision. It wr :ld
be difficult, for example, to predict the relative .:id
strength of toluene and benzene reasoning only 1 ,m
the "positive hydrogen" principle. The "ion resonat.seM
point of view dictates that a lateral hydrogen in t +me
should be more acidic than a nuclear hydro,
pzene; that is actually the case, as shown hy me tlaI.
?n reactions (5). Further indication of the potential
acidity of the methyl hydrogen in toluene is offered by
thereported (6) condensations of fi-nitrotoluene in the
presence of sodium ethylate and by the well-known
reactivity to aldehydic reagents of the methyl group
in ortho- and para- di- and tri-nitrotoluenes. In all
such reactions of the Claisen and Knoevenagel type,
the first step is postdated (16) as the removal by the
basic catalyst of the acid hydrogen atom to form a
carbanion which in the second step adds to the electrophilic system involved in the particular synthesis.
Of the many other cases where the "ion resonance"
approach permits a much more clear-cut decision concerning acidic nature than the "positive hydrogen"
explanation, one of the most interesting is that of cyclopentadiene and many of its derivatives. The "surprising" acidity of the simple diene, as revealed by its
positive Zerewitinoff test, its reaction with metallic
potassium, and its condensations with aldehydes and
ketones in the presence of sodium ethoxide, may be
attributed to the fact that the ion resultingfrorn the loss
of a proton in cyclopentadiene resonates among five
structures all equivalent; in other words, the excess
electron density in the ion is distributed equally over
five carbon atoms.
Teaching of the. "ion resonance" principle is important, in the second place, because there are a host of
organic compounds in which the correct decisions concerning relative acidities may be reached only by the
combined application of both points of view. This
statement may seem a t first to be mere academic hair
splitting. "What difference," a skeptic may ask, "is
to be found between the concept that a substance is an
acid because it possesses an electrophilic hydrogen
which should show a pronounced tendency to accept
the unshared electron pair of a base and the notion that
a substance is an acid because the ion resulting from
its discharge of a proton is stable and has little tendency to retrieve the proton?" The answer lies in the
fact that acid strength is determined not by the nature
of the ionogen, alone, or by the nature of the ion, alone,
but rather by the free energy relationship between the
two (4). Many examples can be cited to show that the
application of the "positive hydrogen" principle alone
does not lead to consistent results in predicting relative addities-comparisons of the hydrogen halides,
of the primary, secondary, and tertiary amines, and
of the alcohols and mercaptans, to mention but a few.
In all of these cases involving electron displacements
of the inductive type only, otherfactorsfrequently undetermined or not clearly understood are involved.
There are many compounds exhibiting tautomeric
displacements for which the "positive hydrogen" approach alone resdts in erroneous predictions concerning acidities; in most of these cases, however, an
extension of the "ion resonance" concept obviates the
Viewed in the light of the "positive hydrogen"
principle alone, the problem of naming the acid hydrogen in simple aldehydes is a poser. In the aldehyde molecule, a certain degree of acidity should result
est number of atoms. Application of this principle is
essentially tantamount to the explanation and prediction concerning the exact course of reactions of the type
mentioned on the basis of the relative stabilities of the
possible intermediates postulated by the mechanism.
Conversely, comparisons of d i e r e n t compounds
which form identical ions upon loss of a proton lead to
interesting interpretations of many reactions. In the
base-catalyzed allylic shift of 6,y unsaturated acids,
esters, and lactones to the corresponding a,6 isomers,
for example, the &st step appears to be the removal
of a proton from the a-carbon atom. The resulting
ion may be represented by three dzerent resonance
structures showing the unshared electron pair (negative
charge) on the a-carbon, the ?-carbon, and the oxygen
atoms, respectively. Exactly the same ion would
result from the loss of a proton by the 7-carbon atom
of the corresponding a,g unsaturated compound. That
ion, however, is more highly stabilized with respect
to the 6,y unsaturated compound than it is with the
a,@unsaturated isomer because the latter exists in
more resonance forms than the former; in other words,
the 6,y compound is a stronger acid than its a,6 isomer and its rearrangement may be looked upon simply
as the formation of a weaker from a stronger acid under
conditions favoring protolysis. Further evidence of
the more acidic nature of the @,yunsaturated compounds is not lacking; A~~Y-angelicalactone
readily with benzaldehyde in the presence of aniline,
for example, whereas the a,6 isomer does not (8).
This principle may be extended to cover a wide variety
of parallel cases.
Prediction of the course a reaction should take on
the basis of the relative stability of intermediates
postulated by the mechanism is by no means valid only
in the case of compounds which may be considered weak
Bronsted acids. The principle has wide application
in many types of reactions, a few of which are cited as
examples. It would be expected that the alkaline
hydrolysis of diethyl ethoxymethylenemalonate (7)
would be initiated by the attack of the hydroxyl ion
a t one of the electrophilic carbons of that compound.
The intermediate formed by the addition of the hydroxyl ion to the carbon bearing the ethoxyl group is an
ion of symmetrical codguration with complete resonance. It is not a t all anomalous, therefore, that the
ethoxyl group should suffer direct and facile replacement by the hydroxyl group. Likewise, a comparison
of the various ions which would be obtained by the
attachment of the carbanion of malonic ester to d i ferent carbon atoms in the 6-vinylacrylic ester molecule suggests that attachment a t the 8-carbon atom
should lead to the most stable intermediate, for only
in this ion would the various resonance structures all
- El=&, the ion resulting from the loss of a proton a t show displacement of the extra electron pair toward
the group A is more stable, due to more extensive res- the primary electron acceptor, the carbonyl oxygen.
onance, than an ion resulting from the loss of a proton It is to be expected, then, that the condensation (7)
at any other point in the molecule. In other words, the of &vinylacrylic ester with malonic ester would occur
negative charge on the ion formed upon removal of a in the 1,6 manner (Michael condensation). Consideraproton from A is most widely distributedover thegreat- tion of the entire principle of vinylogy from the standfrom the primary electron displacement, the -T effect
at the carbonyl oxygen, which reduces the electron
density on the carbonyl carbon; the positive charge
on the latter is of course transmitted inductively to
the a-carbon atom and on down the chain with progressively diminishing intensity. The thinking student
who reasons that the effect should not be greater than
the cause must conclude that the electron density of
the hydrogen atom attached to the carbonyl carbon is
lower than that of a hydrogen atom attached to the
a carbon. The hydrogen of the carbonyl carbon is
potentially acidic, i t is true, as indicated by the basecatalyzed condensation of formaldehyde to sugars and
by the benzoin condensation of benzaldehyde. For
simple aldehydes possessing a hydrogen atom on the
a carbon, however, the first step of the mechanism
postulated to explain such reactions as the aldol condensation and halogenation in basic solution is the
removal of the proton by the basic catalyst, not from
the carbonyl carbon, but from the a-carbon atom.
This apparent ambiguity is readily explainable by the
fact that only one reasonable electronic structure may
be written for the ion resulting from the loss of the
carbonyl hydrogen atom, whereas the loss of an a
hydrogen produces a stabilized resonance hybrid of
the keto-en01 type.
This principle may be extended broadly to cover the
behavior of a host of organic compounds which are said
to react according to the principle of vinylogy (7).
I n the base-catalyzed condensation of ethyl crotonate
with ethyl oxalate, for example, the reaction must be
initiated by the removal of a proton from the 7-carbon
atom. Invariably, the inquiring student, again troubled
by an effect greater than its cause, points out that the
hydrogen on the a-carbon atom should be more "positive." He is not to be satisfied by the statement that
vinylogous systems behave as they do because they
are vinylogous; the empirical answer that, other things
being equal, the tautomeric effect will operate more
readily the more extended the conjugation offers little
consolation to the inquisitive mind. It may be very
clearly shown, however, that the ion formed by the
loss of a proton from the 7-carbon atom of ethyl crotonate is stabilized with respect to the ion which would
b e formed by a loss of the proton from the a-carbon
atom, due to the f a d that the former may be represented by one more resonance structure than the latter.
As a matter of f a d , this may be stated as a general rule
designed to explain the behavior of compounds which
illustrate the principle of vinylogy in reactions such
as the Claisen, Knoevenagel, and malonic ester type
condensations in which a carbanion is postulated as an
intermediate: in compounds of the type A-(C--C)).
point of this general concept should prove both interesting and profitable to the individual teacher.
Remick (9), in his excellent critical review of the
status of the electronic theory as applied to organic
chemistry, has indicated the inconsistencies in the
attemptsto account
theoretically for the high
p/o ratio usually found when benzene derivatives containing an ortho-para directing substituent are further substituted. A clue to the correct explanation
may, perhaps, be found in the fact that the mechanism
of para substitution in a benzene derivative possessing
a substituent which can increase its covalence with the
carbon of the ring (+T effect) requires the intermediate
formation of an ion or group possessing the p-benzoquinoid structure, whereas for ortho substitution the
intermediate is of the less stable
(1) a. WATSON,
H. B., "Modern Theories of Organic Chemistry." 2nd ed., Oxford Press, London, 1941, pp. 29-31;
b. pp. 152-7.
(2) HI,,, G.A. AND L. KELLEY,-organic chemistry," TI,^
Blakiston Company, Philadelphia. 1943, p. 615.
dissoc~ationconstants of chlorophenyl and phenetyl boric
acids." I.Am. Chem. Soc.. 56, 939 (1934).
(4) PAUL~NG,
L., "The Nature of the Chemical Bond," 2nd
ed., Cornell University Press, Ithaca, 1940, pp. 201-14.
( 5 ) G ~ ~ H.,
~ ~ , chemistry," 2nd ed., johnwiley
and Sons, Inc.. New York, 1943, Vol. I , p. 534.
(6) REIssERr, A.. "Einwirkung von Oxalester und Natriumithylat auf Nit:otaluole. Synthese nitrirter Phenylbrenztraubensiuren, Ber.. 30, 1030-53 (1897).
(7) PUSON.
1-27 R.
C., "The principle of vinylagy," Chem. Revs., 16,
(8) T ~ E L E'Yleber
ungesittigte y-Lactane,". Ann., 319,
147 (1901).
Organic Chem-
istrv." Tohn WilevandSons. Inc.. New York. 1943. D. 104.
i.F., ref. (5). P. 159.
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