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Dec.

5 , 1952 NOTES 6121

from ethanol. If the substance remained liquid (generally


a heavy oil), it was extracted with ether, the extract dried
over magnesium sulfate, and warmed to remove the solvent.
The resulting residue was distilled under diminished pres-
sure. \ 0-CF,
Picrates.-The picrates of the azomethines were prepared
by adding a saturated solution of picric acid in either ethanol
or benzene to a solution of about 0.2 g. of the base in the 35.0 -
same solvent. The crude picrates were recrystallized from m-COOH
glacial acetic acid (except as noted in the table). m-CF,

DEPARTMENT OF CHEMISTRY p-OCH,


BOSTONCOLLEGE
CHESTNUT HILL,MASSACHUSETTS

Correlation of C136 Nuclear Quadrupole Coupling


Frequencies with Hamrnett's Sigma'
BY HARLANC. MEAL
RECEIVEDSEPTEMBER4, 1952
The nuclear quadrupole resonance frequency for
C136 has been measured for some chlorobenzene
derivatives with a frequency modulated super-
regenerative spectrometer2 (Table I). Signals

C136 NUCLEARQUADRUPOLE
INTERACTION
I
TABLE
FREQUENCIES
Benzyl Chloride/*\ \ p-CH2CI

OBSERVEDIX VARIOUS SUBSTITUTEDCHLOROBESZENE , I I


50 100 I50 200 250 300
COMPOUNDS
Tarnparafurs OK
ClJ5 frequency at
Substitilent 19GOK. c Fig. 1.
o-NOI 36.997 mc." 37,260 mc. 37.47 mc. f2.030
o-CFib 35.683
0x1 35.496" 35.824 35.97 4-1.260
375.
35.424' 35.755 35,92
35.278" 35.755 35.97
35. 215" 35.580 35.75
m-NOa 35.225" 35.457 35.60 +0.710
m-COOH 35.053 35.227 35.26 + .355 370-

m-CFs 34.632 35.073 35.23 + .42"


m-CI 34.732" 35.030 35.20 + .373
36.5-
34,724" 35.030 35.20
34.523" 34,875 35.09
34.503" 34.809 34.96
$-OH 34.672" 34.945" 35.19 - ,317 36.0-
34.4340 34,700" 34.82
m-N=C=Ob 34.653 u
#-OCHI
o-N=C=Ob
34.433 34.753 34.94 - .268
.5 35 5 -
34.415
None 34. 026" 34.622" 34.90 0.00 u
.a
p-c1 34.562" 34.7794 34.88 + .227 I
9-COOH 34.471 34.673 34.78 C .728
F35
LL 0-
p-COCHi 34.327 34.618 34.73 4- ,874 + p-COCH
p-CHO 34.381 34.607 34.67 4-1.126 n
E QP.
34.403 34.623 34.68
P-CHzCI 34.303 34.567 34.69 +0.025 34 5-
32.840 33.754 34.24 Vp-CH-CHCOON
P-OCzHs 34.180 34.381 34.44 - .25
P-NKa
p-CH=CHCOOH
Benzyl chloride
33.974"
34.227
32.417
34.146"

33.630
34.20
34.40
34.14
Data from Dean and Pound (private communication).
-

b Observations not yet complete, also, no U-values available.


0 J. D. Roberts, R. L. Webb and E. A. McElhill, THIS
.660
4- .619
34t -1.0 -0.5
I
0.0
0-
0.5
I
1.0 1.5
I
2.0

JOURNAL, 72, 408 (1950). Fig. 2.


too weak to be detected with frequency modulation have been plotted against Hammett's substituent
and oscilloscope display were observed using mag- parameter sigma3 (Fig. 2 ) . Limits of error as-
netic field modulation, phase-sensitive detection signed are the mean deviations given by Hammett
and pen recording. Temperature dependences of or arbitrarily taken to be 0.1 unit for sigma; for
the frequencies were determined (Fig. 1) and extra- the frequencies the expected maximum error in the
polated to absolute zero. These, together with the extrapolation is used. Where crystallographically
data of Dean and Pound similarly extrapolated, non-equivalent chlorines give rise to multiple
(1) The research reported in this paper was made possible by sup-
port extended Harvard University by the ONR under Contract N5ori
lines the frequencies of the several lines are plotted.
76, Task Order V. (3) L. P. Hammett. "Physical Organic Chemistry," McGraw-Hill
(2) C . Dean and R. V. Pound, J . Chrm. Phys., 20, 195 (1952). Book Co., Inc.. New York, N. Y..1040, Chap. VII.
6121, NOTES Vol. 74

In the case of p-chlorobenzyl chloride it is thought suggestions, to Dr. Christopher Dean for consider-
that the two lines arise from the two chemically able help with the instrumentation, to Miss Janet
different chlorines in the molecule. The higher Hawkins who supplied the p-deuterochlorobenzene,
frequency was assigned to the chlorine on the ring and to Dr. Harry C. Allen, Jr., for constant advice
on the basis of the result obtained with benzyl and encouragement.
chloride. u-Values for the ortho substituents were MALLINCKRODTCHEMICAL
LABORATORY
calculated from the ionization constants of the HARVARDUNIVERSITY
corresponding benzoic acids, for p-CH2Cl from MASS.
CAMBRIDGE.
nuclear nitration data,315 for p-OH from the
ionization constant of p-hydroxybenzoic acid.6 Preparation of Radiohypophosphate Ion
The work of Taft indicates that obtaining ortho
U-values in this fashion is a dubious procedure7 B Y THERALD LIOELLER AVD GLADYS H. QUIST'i
although the fit is satisfactory. Further work with RECEIVED
JUXE 20, 1952
ortho substituted chlorobenzene compounds may
help elucidate the polar effects of such substituents. In conjunction with investigations on the hypo-
One might expect a relation to exist between the phosphates of thorium and the rare earth elements,'
resonance frequency and sigma since the latter is a hypophosphate ion (Pz06-4) containing phosphorus-
nieasure of the electron density a t a given carbon 32 was required. This was best prepared as the
atom in the ring3 and the quadrupole frequency is disodium dihydrogen salt by the direct oxidation
closely related to the location of bonding elec- of elemental radiophosphorus with sodium chlorite
trons.8 Solid state influences might upset this by an adaptation of the procedure of Leininger and
relation but these are apparently relatively con- ChulskL2 Attempted preparations involving ex-
stant in the present compounds. In iodine8 and change of inactive hypophosphate with radio-
chloral hydrates they cause larger deviations. orthophosphate and with radiopyrophosphate gave
The U-values assigned to the substituents 9- negative results, in keeping with other observa-
CHO, P-COCHB, p-COOH and p-CH=CHCOOH t i o n ~ ~ - 'upon the general absence of exchange
are probably too large as a result of resonance among the oxidation states of phosphorus.
stabilization of the phenoxide ion in the experi- Experimental
nients used to determine those values.'O Ham- Chlorite Oxidation of Radiophosphorus.-One-gram
niett states that these values are probably only samples of red phosphorus were sealed in evacuated quartz
valid for phenol and aniline derivatives. There tubes and irradiated in the pile at the Oak Ridge Sational
Laboratories. As received after irradiation, these samples
is a wider difference between the meta and para had activities approaching 50 millicuries per gram of phos-
values for these compounds than for compounds phorus. The tubes were opened in a dry-box in a carbon
in which resonance is blocked. The same reso- dioxide atmosphere by cutting grooves around the tips with
nance effects in the chlorine substituted molecule a small emery wheel, continuing grinding until small holes
developed to admit carbon dioxide, and then cracking off
might be expected to diminish the quadrupole fre- the tips. Each sample of active phosphorus was then mixed
quency by increasing the double bond character of thoroughly with 25 g. of inactive red phosphorus.
the C-C1 bond. The deviation of the *-OH sub- The mixed solids were converted by chlorite oxidation to
stituent may arise from hydrogen bonding of the disodium dihydrogen hypophosphate 6-hydrate as described
by Leininger and Chulski.2 To obviate losses and reduce
chlorine through the hydroxyl of an adjacent mole- contamination hazards, the reaction vessel was of Pyrex with
cule as in chloral h ~ d r a t e . ~
Also the a-value as- the central tube sealed in. Connection t o the receiving
signed to the hydroxyl group is not well defined." flask was made with Tygon tubing. Both reaction vessel
and receiving flask were surrounded by '/*-in. lead sheeting,
The deviation of the p-OCH, compound is unex- and all operations were conducted in well-ventilated hoods
plained. with ample precautions taken to prevent radiation hazards.
The ClS6 quadruple frequency in p-deutero- The preparations proceeded as described,* yielding products
chlorobenzene has been observed to be equivalent, of high purity and activity. The high-activity waste
liquors which accumulated were stored in lead-shielded con-
within experimental error (4kc.), to that in chloro- tainers until activities had decreased to safe levels before
benzene. disposal.
Attempted Orthophosphate-Hypophosphate Exchange.-
The author would like to express his appreciation Radiophosphoric acid, obtained from the Oak Ridge Na-
to Professor E. Bright Krilson, Jr., who suggested tional Laboratories, was diluted with 0.1 M sodium dihy-
this research and lent valuable assistance in dis- drogen orthophosphate solution to an activity of some 5000
counts per minute per milliliter. Equal aliquots of this
cussions, to Professor J. D. Roberts of M. I. T., who solution and of a 0.1 M disodium hypophosphate solution
supplied the p-chlorocinnamic acid, the 0- and the were mixed, adjusted to pH 1, 5 and 10 and temperature
m-chlorobenzotrifluorides, and for several valuable equilibrated a t 2 5 , 60 and 90". At various time intervals,
2-rnl. samples were withdrawn, diluted with 2 ml. of 12 AJ
(4) J. F. J. Dippy arid R . H . Lewis, J . Chem. Soc., 343 (1935); hydrochloric acid, and treated with a few drops of concen-
J . 1,'. J. Dippy, F. R . Williams and R . H. I.ewis, i b i d . , 1426 (1937). trated thorium nitrate solution (7 g. of the salt in 50 ml.).
(5) C. K. Ingold, et ol., ibid., 675 (1949); 905, 918, 929 (1938); Under these conditions, only thorium hypophosphate is
1959 (1931). precipitated,' and precipitation of thorium is quantitative.
(6) G. E. K. Branch and D . L. Yabroff,THISJ O U R N A L , 66, 2668
(1934). (1) G. H. Quinty, Doctoral Dissertation, University of Illinois,
(7) R. W. Taft, Jr., i b i d . , 74, 2729, 3120 (1952). 1951.
(8) C. H. Townes and B. P. Dailep. J . Chem. Phyr., 20, 35 (1952). (2)E. Lrininger and T . Chulski, THISJOURNAL, 71, 2385 (1949).
(9) H. C. Allen, THISJOURNAL, 74, 6074 (1952). (3)J. N. Wilson, i b i d . , BO, 2697 (1938).
(10) G. N. Burkhardt, C. Horrex and D. 1. Jenkins, J. Chem. Soc., (4)C. Perrier and E. SegrP, Rirercu sci., 9 , I, 638 (1938).
1654 (1936); G. N. Burkhardt, W. G. K . Ford and E. Sinnleton, i b i d . , (6)D . E. Hull, TIIISJOURNAL, 63, 1269 (1941).
17 (1936). (6)R. C. Vogel and N. Podall, i b i d . , 72, 1420 (1950).
(11) E. Berliner and I.. C. Monack, THISJ O U R N A L , 74, 167-1 (7) V. D. Ionin, -4.F.Lukovnikov. hI. B. Xeiman and A n . N. Nes-
(1952). meyanov, Doklady A k u d . Xauk S.S.S.R., 67, 463 (1949).

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