[CONTRIBUTION FROM THE CHEMICAL LABORATORY OF HOWARD UNIVERSITY ]

THE PRINCIPLE OF VINYLOGY AND THE EFFECT OF ORTHO

SUBSTITUENTS ON THE REACTIVITY OF
BENZENE DERIVATIVES
A. H. BLATT
Received January 23, 1996
I n a recent article, Oskar Zwecker has discussed in considerable detail
the occurrence of steric hindrance in ortho-substituted benzene derivatives.
His point of view may be illustrated by reference to benzoic acid. The
effect on the reactivity of the carboxyl group in benzoic acid of the intro-
duction of any substituent in the ortho position will be comparable with
the effect on the reactivity of the carboxyl group in formic acid caused by
the replacement of the hydrogen atom in that acid by the same substituent.
Taking a methyl group as the substituent the following pairs are to be
compared :
I n other terms, any monosubstituted benzene derivative is comparable
with the hydrogen compound of the substituent and the effect of introduc-
ing a substituent in the position ortho to the first substituent is similar
to the effect of introducing this same substituent into the hydrogen com-
pound of the first substituent. It is not the purpose of this paper to
challenge the validity of Zweckers point of view but rather to show that
this point of view is simply a special case of a much wider generalization
-the principle of vinylogy as formulated by Fuson.2
More specifically Zweckers comparisons are valid because they form a
special case of an extension of the principle of vinylogy. As stated by
Fuson, the principle of vinylogy deals with the effect of an unsaturated
group on substituents attached to that group and shows that this effect
1 OSKAR ZWECKER, Ber., 68, 1289 (1935).
* FUSON, Chem. Rev., 16, 1 (1935). Zweckers analogies may also be considered
as following from Angelis rule. See ANQELI, Ahrens Sammlung, 28, 1 (1926).
154
REACTI VI TY OF BENZENE DERI VATI VES 155
HC02H. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
CH,CO*H.
CzHsCOzH.
....................................................
....................................................
ma y be transmitted through intervening vinylene groups. Thus the
hydrogen atoms of the methyl group in ethyl acetate are activated suffi-
ciently to condense with esters. If a vinylene group is interposed, as in
eth,yl crotonate, the hydrogen atoms in the terminal methyl group are still
sufficiently active to undergo ester condensations.
CH, C=O CH, CH=CHC=O
I I
OCzHs OCzHs
We are dealing with the effects of saturated substituents on the reactivity
of a functional groupj usually unsaturated, and we shall show that when
a given effect on the reactivity of a functional group i s produced by a saturated
1224
104
91
TABLE I*
ESTERIFICATION WITH METHANOL (T =15C.)
SUBSTANCE k
I
TABLE I1
ESTERIFICATION WITH METHANOL (2' =15OC.)
SUBSTANCE
CHZ=CH COiH.. .............................................
CH:<CH=CH C02H.. ..........................................
CzHaCH=CH COzH.. .........................................
CeH:sCH=CH CO2H.. .........................................
k
3.093
1.263
1 .54
0. 9374
substituent attached directly to that functional group, a similar effect ma y be
produced by the same substituent when i t i s separated f r om the functional
group by a n intervening vinylene group. Thus, if one compares formic,
acetic, and propionic acids, it is seen (Table I) that the replacement of
the hydrogen atom of formic acid by a methyl or an ethyl group results in
a decrease in the rate of esterification. The vinylogs of these three acids
are acrylic, crotonic, and 0-ethylacrylic acids, and a comparison of their
esterification velocities (Table 11) shows the similar effect resulting from
* Reference 1, p. 1293. To facilitate comparisons reference is made whenever
a SUDBOROUQH AND DAVIS, J . Chem. Soc., 96, 976 (1909).
possible to Zwecker's article rather than to the original sources.
SUDBOROUGH AND GITTINS, ibid., 96, 315 (1909).
156 A. H. BLATT
EUBBTANCE
the introduction of a methyl or ethyl group separated from the carboxyl
group by an intervening vinylene residue.
To these illustrations we shall add but one other-a case in which the
reactivity of the functional group is enhanced rather than decreased by
the introduction of a substituent. Ethyl chloride is hydrolyzed more
rapidly than methyl chloride and the same relationship holds true for
the corresponding bromides.? The vinylogs of these halides are found
in allyl bromide and crotonyl bromide and the data of Table I11show that
a methyl group introduced into allyl bromide, even though separated
from the halogen atom by an intervening vinylene group, has an effect
similar to that brought about by the introduction of a methyl group into
methyl chloride or bromide.
The application of this extension of the principle of vinylogy to the
ortho-substituted benzene derivatives requires but little explanation.
When benzoic acid is used as an illustration and a developed Kekule
formula is written, it is obvious that a vinylene group intervenes between
the ortho position and the carboxyl group (and three vinylene groups be-
k
CHFCH CHaBr.. . . .. . . . . . . . . .. . , . . . . . , , . . . . . . . . , . . . . . . . . . . . .
CHsCH=CH CH2Br ...........................................
tween the ortho position and the carboxyl group).
of benzoic acid is, therefore, not formic acid but acrylic acid.
The open-chain analog
COZH COZH
I I
I
C
/ \
HC CH
I
CH
//
CH2
Zweckers comparison between benzoic and toluic acids on the one hand
and formic and acetic acids on the other is valid because the effect of the
ortho substituent on the reactivity of the functional group is transmitted
qualitatively unchanged by the intervening vinylene group. I n other words
t Reference 1, pp. 1301-2.
6 JUVALA, Bey. , 63, 2001 (1930).
REACTIVITY OF BENZENE DERIVATIVES 157
S'JEBTANCE
COzH
I
\/
h
COzH
it is a direct consequence of the extension of the principle of vinylogy as
stated and illustrated in the preceding paragraphs.
k
0.283
COzH
I
COzH
I
0.092
0.056
0.051
TABLE V7
HYDROLYBIS (2' =30C.)
SUBSTANCE k
I
CHzCl
I
0
\/
CHzCl
I
CH3-f)
\/
1
4.95
6 SUDBOROUQH AND TURNER, J . Chem. SOC., 101, 238 (1912).
7 OLIVIER, Rsc. trnv. chinz., 41, 648 (1922). I n the case of the substituted benzyl
halid.es there is an indication that the influence of a substituent can be transmitted
through two intervening vinylene groups, for the hydrolysis velocity of p-tolyl-
methyl chloride is 9.4 in the units given in Table V. However, the inclusion of
para substituents would unduly extend the length of the present discussion.
158 A. H. BLATT
Two sets of examples may be given to show the application of the
principle. We may compare the series of ortho-substituted benmic acids
(Table IV) with the @-substituted acrylic acids (Table I I ), and the pair,
benzyl chloride and o-tolylmethyl chloride (Table V), with the pair,
allyl bromide and crotonyl bromide (Table 111). I n each case the effect
of the saturated substituent on the reactivity of the functional group is
transmitted qualitatively unchanged through the intervening vinylene
group. Since this discussion is not intended to be exhaustive, further il-
lustrations are omitted. Doubtless other cases will occur to the reader,
and it may be stated that the application of this extension of the principle
of vinylogy leads to many interesting predictions.
Zwecker has used his results and those of others as the basis for a criti-
cism of the common concept of hindrance as a spatial phenomenon. With-
out entering into a discussion of this point it seems advisable to point out
that most organic chemists will agree both that hindrance is effective only
in reactions involving addition and that hindrance is not the sole factor
that determines the occurrence and rate of chemical transformations. It
is unfortunate that in the usual illustrations of hindrance, e. g. , the non-
esterification of 2,4,6-trisubstituted benzoic acids, the steric effects are
so predominant that other influences are masked completely. This, and
the failure to recognize the qualification that hindrance affects addition
reactions only, are responsible for much of the confusion regarding those
borderline cases where at least two effects-hindrance to reaction by a
substituent and activation of the reacting group by the same substituent-
may be nearly balanced. I n such cases the effect of the substituent may
be either to retard or to accelerate the reaction. A more detailed study
of hindrance in just such borderline cases would be of value in clarifying
the issue.
SUMMARY
It has been pointed out that the effects of saturated substituents on a
functional group may be transmitted qualitatively unchanged through
an intervening vinylene group. This extension of the principle of vinylogy
has been used to correlate the effects of ortho substituents on the reactivities
of various benzene derivatives with the behavior of the analogous open-
chain compounds.