2616 CANADIAN JOURNAL O F CHEMISTRY. VOL. 43.

1965

From the pK, values presented here the urn and u, values for CGHjS are calculated
to be 0.31 and 0.24 respectively. These should be compared with the values, 0.18 and
0.29, derived by Meyers (3) for the corresponding phenols.

ACKNOWLEDGMENT
The author acknowledges helpful discussion with Dr. R. F. C. Brown and Dr. J. M.
Brown.

1. R. C. PASSERINI. In Organic sulfur compounds. Vol. I. Edited by N. Kharasch. Pergamon Press, Lon-
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 14.139.182.249 on 10/28/19

don. 1961.
2. C. C. PRICE. Chem. Eng. News, 42, No. 48, 58 (1964).
3. C. Y. MEYERS. Gazz. Chim. Ital. 93, 1206 (1963).
4. C. C. PRICEand S. OAE. Sulfur bonding. The Ronald Press Company, New York. 1962. pp. 16, 26.
5. A. ALsaRTand E. P. SERJEANT. Iorlization constants of acids and bases. Methuen and Co., Ltd.,
London. 1962. Chap. 4.
6. D. D. PERRIN. Australian J. Chem. 16, 572 (1963).
7. H. GILMANand H. S. BROADBENT.J. Am. Chem. Soc. 69, 2053 (1947).
8. A. MANGINI,R. PASSERINI, and S. SERRA. Gazz. Chim. Ital. 84, 47 (1954).
9. R. W. TAFT, JR. In Steric effects in organic chemistry. Edited by M. S. Newman. John Wiley and
Sons, Inc., New York. 1956. Chap. 13.
10. F. G. BORDWELL and G. D. COOPER. J. Am. Chern. Soc. 74, 1058 (1952).
11. J. CLARKand D. D. PERRIN. Quart. Rev. London, 18, 295 (1964).
12. C. C. PRICEand S. OAE. Sulfur bonding. The Ronald Press Company, New York. 1962. p. 10.
13. B. ROTHand J . F. BUNNETT. J. Am. Chem. Soc. 87, 334 (1965).
For personal use only.

SOME COMMENTS ON CRAIG'S RULES

On the basis of valence bond (v.b.) and other calculations, Craig proposed some rules
which ~vouldpermit the prediction of whether or not a certain fully conjugated hydro-
carbon xvould have a totally symmetric v.b. wave function and hence have aromatic
character (1-3). The rule was applied to molecules having a t least one twofold axis
passing through two or more a-centers, an axis that converts one KeltulC structure into
itself or into another of the same canonical set. The molecule is labelled with equal
numbers of spin syinbols a and p, giving different symbols t o the two ends of all double
bonds in one KCkul6 structure such that as few as possible like spins adjoin. Upon per-
forming the symmetry operation, if the sum of p, the number of interchanges of a-electron
centers effected by the operation, and q, the number of interchanges of spin symbols
required t o restore the original labelling scheme from the transformed one, is even, one
finds that the molecule will have a totally symmetric v.b. ground state and it should be
aromatic. If p +
p is odd, the v.b. ground state is non-totally syillmetric and the molecule
should not have aroiuatic stability: it ~vouldbe pseudoaromatic.
A case in which the application of Craig's rules gives ambiguous results has been
reported (4). Structure I a can be labelled as sholvn, leading to p +
p = 7. On the other
Canadian Journal of Chemistry. Volume 43 (1965)
 NOTES 2617

hand, Ib, in which the axis of symmetry transforills one I<6kulC structure into itself,
gives rise to p+q = 8. Ia and Ib are stated to belong to different group representations
and ma17 not contribute to the same linear combination v.b. resonance hybrid (4). The
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 14.139.182.249 on 10/28/19

rules are not clear, however, in that structure (Ic), in which the double bonds are arranged
exactly as in Ia, appears to be labelled in an acceptable manner but gives p + q = 12.
I t has been pointed out ( 5 ) , however, that this labelling is not acceptable since, upon
performing the symmetry operation, one finds that the resulting I<6kul6 structure has
similar spins a t the ends of some double bonds (see also IIa). This aspect of the rules can
be made clearer by specifying that the labelling with equal numbers of spin symbols a
and P should be carried out in such a way that they give different symbols to the ends of
all double bonds in both I<6kul6 structures. In any event, I exhibits aromatic properties (6).
-4 similar situation obtains with the hydrocarbon (11), the dimethyl derivative of which
For personal use only.

is reported to exhibit polyolefinic character (7).

The rules were also applied to fulvene (111), and the results would indicate that this
n~oleculeshould be aromatic (1-3). While (111) does exhibit weak aromatic properties

(a measure of \vhich is indicated by its dipole moment of l.1D (8) caused by contributiilg
structure IV) the rules do not predict the correct answer a t all when they are applied to
fulvalene (V), which is quite polyolefinic (9). Neither does it hold for heptafulvalene (VI),
which does not behave as an aromatic con~pound(9). I t may or may not be significant
that in both of these only one uncharged conjugated structure may be written, in which
the symmetry operation transforms the molecule into itself. The rules also indicate that
the interesting systems VII and VIII (V and VI, respectively, with one extra C-C bond)
 2620 CAXADIAN JOURNAL O F CHEMISTRY. VOL. 43. 1963

Magnetic Measurements
Magnetic susceptibilities were obtained with a Gouy magnetic balance. T h e Gouy tubes were calibrated
with Hg[Co(CNS)4]. T h e magnetic data are summarized in Table 111. T h e magnetic moments reported
in this table were corrected for diamagnetic contributions by the use of Pascal's constants a s indicated by
Figgis a n d Lewis (9).
TABLE I11
Magnetic d a t a of N-rnethyl-r-butyrolactam complexes

Compound xg X lo6 X y ( ~ ~ r rX. ) lo6 T OK k f f ,B.M

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 14.139.182.249 on 10/28/19

Infrared Spectra
Infrared spectra of the complexes were obtained a s chloroform solutions on a Beckman IR-10 recording
spectrophotometer.

DISCUSSION
The analytical data of Table I indicate that, except for zinc, the colnplexes fornled are
six-coordinate. These might be expected to be octahedral species, a supposition indicated
by the magnetic data.
Coordination of the lactain caused no major change in its infrared spectrum except for
For personal use only.

a shift of the carbonyl stretching vibration. In all cases the frequency of this vibration
was lowered on complexation relative to the frequency of the free ligand. Thus the very
intense C=O absorption band appearing a t 1 680 cm-I in the free lactam gave rise to a
strong absorption band shifted of the order of 40 cin-I to lower frequency in the metal
ion con~plexes.Manganese and zinc exhibited the inininluin and maximum effects, re-
spectively. In the former case a strong band appeared a t 1 645 cm-'; this band appeared
a t 1632 cm-I for the latter metal ion. These results are in accord with earlier findings
(2), and may be interpreted as evidence for bonding of the ligand to the metal ion through
the carbonyl oxygen (3, 5, 10).
From the results of the conductivity measurements appearing in Table 11, it can be
inferred that the manganese, cobalt, nickel, and zinc coinplexes are of the 1:2 electrolyte
type. These molar conductance values in nitromethane are in reasonable agreement with
reference standards determined for this solvent a t 20 OC by Gill and Nyholm (11). The
iron complex exhibits the expected behavior of a 1:3 electrolyte type.
Finally, the magnetic moments calculated for this series of compounds fall in the range
expected for spin-free octahedral complexes (9). The zinc conlpound, for which data do
not appear in Table 111, was found to be diamagnetic, as expected.
The above findings are in agreement with the work of Bright and co-worlters (6), who
found that the electronic spectra of nickel(I1) and chromium(II1) perchlorate-lactam
systems indicated the presence of octahedral species.

The authors gratefully acknowledge the aid of General Aniline and Film Corporation,
who supplied the initial sample of lactain, Dr. D. W. Meek and associates of The Ohio
State University, who made available a Gouy balance for our use, and the National
Research Council of Canada, for financial support. Coinrnunication with Drs. D. RII. Hart
and S. K. Madan is also appreciated.
 NOTES 2621
1. R. S. DRAGO,D. A. WENZ,and R. L. CARLSON. J . Am. Chem. Soc. 84, 1106 (1962).
2 . C. A. ROLLINSON
and R. C. WHITE. Inorg. Chem. 1, 281 (1962).
3. R. S. DRAGO,D. W. MEEK,M. D. JOESTEN,and L. LAROCHE. Inorg. Chem. 2, 124 (1963).
4. W. E. BULL,S. K. MADAN, and J . E. \.\'ILLIS. Inorg. Chem. 2, 303 (1963).
5. C. D. SCHMULBACH and D. M. HART. T. Ore. Chem. 29. 3122 (1964).
6. J . H. BRIGHT,R. S. DRAGO,D. M. HA<T, &d S. I<. MADAN.' I I I O ; ~ . Chem. 4, 18 (1965). D. M.
HART. Personal communication. S. I<. MADAN. Personal communication.
7. E. FISHER. J. Cheln. SOC.1382 (1955).
8. I<. STARKE. J . Inorg. Nucl. Chem. 11, 77 (1959).
9. B. N. FIGGIS and J . LEWIS. I n Modern coordination chemistry. Edited by J . Lewis and R. G. IViIkins.
Interscience Publishers, Inc., New York. 1960. p. 403.
10. C. D. SCHMULBACH and R. S. DRAGO. J . Am. Chem. Soc. 82, 4484 (1960).
11. N. S. GILL and R. S. NYHOLM. J . Chem. Soc. 3997 (1959).
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 14.139.182.249 on 10/28/19

CONCERNING THE PREPARATlON OF p-ALLYLPHENOL FROM SAFROLE BY

SODIUM - LIQUID AMMONIA REDUCTlON

During recent studies (1) of halogen elimination and of halogen and allyl group
For personal use only.

migration during the rearrangement of allyl 2,G-dichlorophenyl ether (2, 3), seine 4-allyl-
2-chlorophenol was required as reference material. One possible route for the synthesis
of 4-allyl-2-chlorophenol required the precursor p-allylphenol. Of the methods available
for the preparation of 9-allylphenol (4-8), that developed by Birch (4), involving the
sodium and liquid ainmonia reduction of safrole, appeared to be the most convenient
and productive.
A repetition of the published procedure with careful attention to Birch's directions,
and using anhydrous ethanol with the liquid ammonia, gave a substance whose boiling
point agreed with that reported (4, 5) and whose infrared spectrum (neat) supported
the structure of p-allylphenol.
Gas-liquid chromatography of this substance on a colun~npacking of 20% Apiezon L
on Gas-Chrom P (60-80 mesh) with a helium flow rate of 100 inl/min gave only one
peak with a shoulder, indicating the presence of two compounds of similar retention
times. The ultraviolet spectrum in methanol showed adsorption a t 202 p and 224 p
along with slight absorption a t 282 p . No absorption was found a t 244 p , the region of
strong absorption caused by the styrene chronlophore (9), thus indicating the absence
of p-propenylphenol, a product found by Birch (4) when safrole was reduced by sodium
in liquid ammonia in the absence of alcohol.
The nuclear magnetic resonance (n.1n.r.) spectrum of this substance (Fig. l a ) ; in
carbon tetrachloride with tetramethylsilane as internal reference, clearly showed i t to be
a mixture of p-allylphenol and 9-n-propylphenol in the molar ratio of 3:l. The boiling
points of these two substances are quite similar and are reported to be respectively
236-238' a t 760 mm pressure and 232.2-232.5 a t 763 mm pressure (5, 10). The allyl
group joined to carbon of the benzene ring shows a doublet a t 6.75 T, J = 7.0 c.p.sd for
the methylene group attached directly to aromatic ring carbon, while the vinyl methylene
protons show two characteristic, poorly resolved multiplets centered a t 4.90 T and 5.12 T.
Canadian Journal of Chemistry. Volume 43 (1965)