NOTES

STERIC INHIBITION OF RESONANCE

11. BOND LENGTHS IN MESO-SUBSTITUTED ANTHRACENES*
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The crystal structures of several meso-substituted anthracenes have recently been

determined by X-ray diffraction methods (I) and reasonably accurate values of the
molecular dimensions have been obtained. These detailed investigations have shown
that the molecules of 9,lO-dibromo- and 9,lO-dichloro-anthraceneare completely planar
(2, 3). I n the 9-nitro and 0,lO-dinitro derivatives, however, the bulkier nitro groups are
markedly tilted out of the aromatic planes about the C-N bonds (4), and correlation
with the characteristic nitro group infrared frequencies suggests resultant decreases in
resonance interaction between the nitro groups and the aromatic n-electrons (5). T h e
angles of tilt alone do not give directly quantitative measures of the decreases in the
conjugation compared with planar models, but resonance involving ionic structures, of
type I for 9-nitroanthracene for example, would impart a considerable amount of double
Can. J. Chem. 1959.37:825-827.

bond character to the C-N bond, and in addition cause variations in the N-0 bond
lengths when compared with those in aliphatic nitro compounds, and in the bond lengths
in the anthracene nucleus compared with those in the unsubstituted molecule. I t has been
shown t h a t in picryl iodide the C-N distances ortho to the iodine atom correspond to
single bonds, indicating resonance inhibition, while the conjugated para C-N bond is
very much shorter, suggesting a considerable amount of resonance interaction (6).
Examination of the bond length variations in meso-substituted anthracenes therefore
may give a quantitative account of the resonance interaction, and also indicate the
amount of resonance inhibition due to steric effects in those molecules with bulky sub-
stituents, such as nitro groups, in the 9 and 10 positions.
The bond lengths, together with the standard deviations, in the molecules studied are
compared in Table I with the bond lengths in anthracene (7, 8), the labelling of the
carbon-carbon bonds being shown in the diagram. The values in the substituted anthra-
cenes are quoted to 0.001 A for comparison, although as the standard deviations indicate,
the accuracy is much lower than this. T h e C-Br, C-CI, C-N, and N-0 distances in
rion-conjugated molecules are included under anthracene.
TABLE I
Bond lengths and stantlard deviations in nleso-substituted anthracenes (A)
Bond Anthracene 9,lO-Dibromo 9,lO-Dichloro 9,lO-Dinitro %Nitro
a 1.3663Z0.004 1.4093Z0.027 1.38210.015 1.35010.011 1.39910.008
b
C
d
e
C-B r
C-CI
C-N
N-0
*Issued as N.R.C. No. 5068.
tNalional Research Cozrncil Posldodorale Fellow.
Can. J. Chem. Vol. 37 (1960)
825
 826 CANADIAN JOURNAL O F CHEMISTRY. VOL. 37, 1959

Exocyclic Bonds
Since there is no resonance inhibition in the completely planar halogen derivatives,
ionic structures (11) ought to make a contribution to the ground state of the molecule.
However, the weight of structures of this type, with a positive charge on the halogen
atom, is quite small, and only a small contraction of the carbon-halogen bond lengths
below the single bond distances would be expected. The C-C1 bond distances in 9,lO-
dichloroanthracene are slightly less than the normal single bond length, but the differ-
ence is scarcely significant. The ionic structures, however, are highly polar and, although
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their weights are small, they reduce the dipole moment in 9-bromoanthracene, for
example, in comparison with a non-conjugated molecule (methyl bromide = 1.78 D ,
bromobenzene = 1.52 D , 9-bromoanthracene = 1.50 D ) .
Can. J. Chem. 1959.37:825-827.

In 9-nitroanthracene the nitro group is tilted 85' out of the plane of the aromatic
I
I rings, and the C-N bond length (1.48 A) corresponds to a single bond, indicating that
there is little or no resonance between the anthracene nucleus and the nitro group.
The C-N bond lengths in 9,lO-dinitroanthracene, where the tilt of the nitro groups is
64', are 1.45 A, so that in this molecule there is a measurable amount of resonance
interaction in spite of the large deviations from planarity. A quantitative measure of
the resonance, however, requires a knowledge of the C-N bond length in a fully con-
jugated molecule such as nitrobenzene, and this length has not been accurately measured.
(The conjugated C-N bond lengths in picryl iodide (6) and p-nitraniline (9) have been
given as 1.35 A and 1.41 A respectively.) T h e C-N bond distances in 9,lO-dinitro-
anthracene are much closer to the single bond length than to the distances in these fully
conjugated molecules, so that while there is resonance interaction between the anthracene
nucleus and the nitro group, it is much less than in completely planar aromatic nitro
compounds. The N-0 bond lengths in these nitroanthracenes also suggest that there is
little or no resonance between the aromatic rings and the nitro group in 9-nitroanthracene,
and a small but measurable interaction in 9,lO-dinitroanthracene.
C-C Bonds
Examination of Table I shows that there are no really significant differences between
the carbon-carbon bond lengths in the meso-substituted anthracenes studied and those
in the unsubstituted molecule, indicating that contributions of ionic structures are too
small to effect any measurable changes in the dimensions of the anthracene skeleton.

1. TROTTER,
J. .kta Cryst. 11, 564 (1958).
2. TROTTER,
J. Acta Cryst. 11, 803 (1958).
3. TROTTER,
J. Acts Cryst. 12, 54 (1959).
4. TROTTER,
J. Acta Cryst. (In press).
5. TROTTER,
J. Can. J. Chem. 37, 351 (1959).
 NOTES 827
6. HUSE,G. and POWELL, H. M. J. Chem. Soc. 1398 (1940).
7. SINCLAIR,
V . C., ROBERTSON, J. M., and MATHIESON,A. McL. Acta Cryst. 3, 251 (1950).
8. CRUICKSHANK, D. W . J. Acta Cryst. 9, 915 (1956).
9. DONOHUE, J. and TRUEBLOOD, I<. N. Acta Cryst. 9, 960 (1956).
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A CRYSTALLINE DERIVATIVE OF 2-0-(4-0-METHYL-a-D-GLUCOPYRANOSYLURONIC

ACID)-D-XYLOPYRANOSE

2-0-(4-O-Methyl-a-~-glucop~~ra11osyluronc acid)-D-xylopyranose, the structure of

which was first established by Jones and Wise ( I ) , has so far been isolated from some
thirty natural plant products. Since no crystalline derivative of this amorphous com-
pouncl has hitherto been known, it has been characterized by identification of the products
Can. J. Chem. 1959.37:825-827.

obtained on hydrolysis of the original and of the methylated acid. A crystalline p-nitro-
benzoate of the derived 2-0-(4-0-methyl-a-D-glucopyranosyl)-glycerol has been prepared
(2) but the acetate of the ~ - 0 - ( ~ - 0 - m e t h y ~ - a - ~ - ~ c o p y r a n o s y ~ ) -is~ -reportecl
x y l i t o to
~
be amorphous (3). A crystalline tetraacetate of the methyl ester methyl glycoside of the
aldobiouronic acid has now been prepared and characterized.
Partial hydrolysis of a 4-0-methyl glucuroiloxyla~lfrom white birch wood yielded
2-0-(4-0-methy~-a-~-g~uco~yranosy~i1ronic acid)-D-xylopyranose, the structure of which
had previously (4) been uneq~~ivocally established. Treatment of the clerived methyl
ester methyl glycoside with acetic anhydride in pyridine gave a sirup, a portion of which
crystallizecl immediately from an ethyl ether solution. After recrystallization, white,
small crystals were obtained, easily soluble in acetone, chloroform, ethyl acetate, and
tetrahyclrofuran, but only sparingly so in ethyl ether ancl ethanol. The methyl 2-0-[methyl-
(2,3-c~i-0-acety~-~-0-methy~-a-~-g~~1co~3~~ra11osy1) uronate] -3,4-di-O-acety1-~-xy10pyrano-
side had m.p. 200-201' C, [a]:' +100° in chloroform, and was further characterizecl
through its infrared spectrum and its X-ray diffraction pattern. The residual sirup had
a specific rotation slightly lower than that of the crystalline portion (+85"). The data
reported by Smith and co-workers (3) for the methyl ester methyl glycoside pentaacetate
of two related, anomeric aldobiouronic acids would otherwise suggest that the xylo-
pyranoside moiety was present in the P-configuration. Preparation of inethyl ester
methyl glycoside tetraacetates of specimens of the same aldobiouronic acid obtained
from various natural products gave crystalline compounds with properties identical
with those of the present derivative. T h e corresponding benzoate and p-nitrobenzoate
esters were amorphous and could not be induced to crystallize.

EXPERIMENTAL
2-O-(4-O-Methyl-a-~-glucopyranosy~uronic acid)-D-xylopyranose
A 4-0-methyl glucuronoxylan (200 g) from white birch wood (6) was dissolved in
72% sulphuric acid (100 ml). After 24 hours a t room temperature, the solution was
diluted to 4000 1111 and boiled under reflux for 9 hours. Neutralization with barium