90
JOHN
e. PUTTER,\NU JOHN
was ever noted. Benesi and Hildebrarid,lo in estensive studies on solutions of iodine in acetone, reported a similar disagreement. A satisfactory explanation for the behavior ~f solutions of iodine in pyridine must account for the great increase in conductivity as well as for the disappearance of the original ionic species. In order to account for the fact that the limiting conductance is about twice as great as might be expected on the basis of a simple dissociation of the iodine molecule into a positive and negative ion, Autirieth and Birr' proposed a mechanism involving dissociation in to ;t ternary salt of the formula Py++,2I-. Since evidence has been presented that the ions responsible for the characteristic absorption peaks disappear with time, two alternative reactions may be proposed tentatively, one based on the preparation oi pyridylpyridiniutn chloride, best explained by the postulation of the C1Pq"- ion,l? the other on the formation of dipyridyl when pyridine is heated with iodine.I3 The equations ior the reactions arc 110) Benesi and Hiidebrand, T H I S J O I . R N A I . . 71, 2703 (IW!!!. (11) Koenigs and Creiner, Bci.., 64, 1043 f J 9 3 l ) . (12) Elderfield "Heterocyclic Coinpoiirirl*," Jnlin U'iley a r i ~ lSons. Inc.. New Tork, N. T . . 1050,pp. 113, 427. (13' IYiilink and \Yibai:t, R K . lrn:' c k i i v . . 64, 27: ' I'J35'.
H. SAYLUK
Voi. 72
.lttciiipts to isolate thew products froiii iodinepyridine misturcs led only to the iornlation of tarry residues. Summary 1. 'I'hc absorptioii spectra of solutiolis of iotiinc a n t i Iwsitive iodine salts in pyridine and their
change with time have been studied. 2. Evidence for the existence of the I P y - and I:{-- ions in solutions of iodine in pyridine has been presented. 3 . 'Tentative mechanisms have been proposed to explain the increasing conductivity and disappearance OF ahsorption bands in these solutions. LAn.RliXCF, KASSAS
~ ~ O V T R I H V T I UFYR O M 1 H E 1)EPARTMEVT
(>)I' C f i F M I i T R J ,
RECEIVED JUSE 28, 1950
1)UKF: L h l V E R 5 l l Y ]
The Vapor Pressures and Freezing Points of Some Organic Fluorine Compounds' ' Hu
JOHN c).
PUTTER^
AND
Joim H. SAYLOK
reference limb of the manometer was reduced to less than 0.01 nim. with a mercury diffusion pump and then checked with a McLeod gage. The temperature was measured with a platinum resistance thermometer, a standard resistor, and a Leeds and Xorthrup Type K2 potentiometer. The platinum resistance thermometer and the standard resistor were placed in series with a 2-volt battery and a 2000ohm resistor. The potential drops across the standard Experimental resistor and the platinum thermometer were measured with Materials.-The three fluorotoluenes were Eautman Ko- the potentiometer. From the ratio of these two potential dak Co. best grade. The three chlorobenzotrifluorides \%-ere drops and the resistance of the standard resistor the refurnished by t h e Hooker Electrochemical Company. The sistance of the platinum thermometer could be calculated. p-bis-(trifluoromethyl) -benzene was made in this LaboraThe boiling point apparatus, the manometer, the manostat, tory by Dr. A. R. Gilbert and Mr. J . B . Bond under the i~ rotary oil pump and a controlled air leak operated by the direction of Dr. C. K . Bradsher. The materials were dried manostat were connected to a surge tank. The rate at over Drierite and then distilled a t a high reflux ratio through which the air was removed from the system by the pump a silvered vacuum-jacketed glass columii packed with l/g" and the rate at which the controlled air leak admitted air to glass helices. A two junction copper-constantan thermel the system were controlled by meatis of needle valves. I n was used to measure the still head temperature. operation, with the liquid boiling in the boiliiig point apVapor Pressures.-A modification of the method of Ram- paratus, the pressure in the system was reduced to the desay and Young which has been previously described' was sired value and the two needle valves adjusted. After a used for pressures below 100-150 mm. For higher presfew minutes the resistance of the platinum thermometer ant1 sures a boiling point apparatus similar to that of Rossini and the pressure were taken. As a check on the method the co-workers6 was used. The pressure was controlled with a vapor pressure of water \vas measured. The mean deviation sulfuric acid matlostat similar to t h a t used by Huntress and of the pressure values calculated from the data of Osborne Nershberg.6 The pressure was me:isured with :t mercury :ind Meyers' and the experimental values was +=0.13Inm. itianotneter arid it cathetoitieter. The prcssurc over the for eleven measurements between 180 and 760 mm. Freezing Points.--The cooling curves of the best fractiniis i I I '1Iir work rcportrrl w a s carrird oiil uiiilci Coiitr.1t I Sliriri 1117, froin the distillations were determined in a freezing point 1'.0 !I with the ORicc of Ndval Rcscarrii :ipparatu\ patterned after that of Scliwab arid Wichers.s 2 ) l h i s paper was takcn in part from thr thr5is siiI)mittrrl lis J o h n From the cooling curves the freezing points anti the freezing C Pottrr to the I:ratluate School of Diikr. T'iiiv(~sityi n p a r l i d f u l . point delres4ons were obtained graphically by the niethod ftllmrnt oi the r c q u i r c n i r n t i lor ihr drgrcr nr Lloclor 01 Philo-nphy, of S t u l l . ~
The tneasurenients reported in this paper were made in connection with tt general program of research in this Laboratory concerning the solubility and other physical properties of organic fluorine compounds.
J u n r , 1USO. (3) Department of Chcniiatr)~, North Carolina State Collcge, Raleigh, N. C. (4) Stuckey and Sayior, THISJOCRSAL, 62, 2922 (1940 ( 3 ) Willingham, Taylor, Pignocco atid Rosaini, J . Kesear S f a n d o r d s , 36, 219 (1945). Huntress and FTer\htjPrR. F i r g C h ~ i i i .i ) : d l L l , 8. 1 4 4 I1
Results Approximately twenty to twenty-five individual (7) Osbornr and Meyers, J . Rc.wwch S a i l BUY.Sfnm'aids, 13, 1 1934)
Scliwab end \Viehers, ibid , 84, 333 ( 1 V 4 t ) i9'1 Stull. I i r d Etid Chrm , A s a l E d . , 18, 234 (li4461
($1
Jan., 1951
METHOXYMERCURATION OF N-ALLYL AMIDES
91
TABLE I BOILINGPOlNTS, FREEZINGPOINTS AND
CONSTANTS OF THE VAPOR
B. p., 'C.
Substance Benzotrifluoride p-Bis-(triEuoromethy1)-benzenc o-Fluorotoluene m-Fluorotoluene 0-Fluorotoluene o-Chlorobenzotrifluoride m-ChlorobeuzotriEuoride P-Chlorobenzotrifluoride
Prev. Range Calcd. Obsd. 102.01-102.02 102.04 102.3
116.23-116.24 114.35-114.36 116.52-116.53 116.58-116.59 152.32-152.33 137.69-137.72 138.69-138.71
116.28 114.40 116.55 116.59 152.31 137.63 138.63
- t+Bc+A
where p is the pressure in mm. and t is the temperature in degrees centigrade. The mean deviation between the observed pressures and those calculated from the equation varied from AO.24 mm. for o-fluorotoluene and p-chlorobenzotdluoride to ~ 0 . 1 0 mm. for ochlorobenzotrifluoride. Table I gives the boiling point ranges corrected to one atmosphere, the boiling points calculated from the vapor pressure equation, the freezing (10) H.S. Booth, THISJOURNAL, 67, 2066 (1935). (11) Deal, Thesis, Duke University, 1944. (12) Klemm, Klemm and Schiemann, 2. fihysik. Chcn., A166, 379 (1933).
[CONTRIBUTION FROM
THE
Ref. obsd. 10 -29.14
114.48-114.53 116.27-116.30 116.62-116.65 152.8 138.4 139.3
measurements were made on each compound from 10 to 760 mm. The experimental data were fitted by the method of least squares to the equation log* =
-F.
11 11 11 10 10 10
2.78 -62.0 -87.7 -56.8 - 6.37 -56.7 -33.2
PRESSURE EQUATION
p., ' C . Dep. Prev. "C. obsd. 0.02 -29.05
.02 .4 .3 .05 .04 .76 .14
A B C 10 7.0202 1335.5 220.58
Ref.
- 60 - 87
12 12 - 53 12 - 7.4 to 7.6 10 10 -55.4 -34.0 10
7.0375 6.9732 7.0095 7.0574 7.0144 7.0555 7.1640
1351.6 1356,s 1382.7 1410.8 1490.4 1458.9 1536.3
208.89 217.!5 218.34 221.19 208.24 211.82 220.08
points, the freezing point depressions, and the values of the three constants in the above equation. The agreement of the data for the three fluorotoluenes with that of Stull13 is not very good. The present data for benzotrifluoride agree fairly well with that of Stull13 and Field14 but do not agree very well with that of Booth, Elsey and Burchfield. l5
Summary The vapor pressures and the freezing points of benzotrilluoride, p-bis- (trifluoromethyl) -benzene, om- and p-fluorotoluene and 0-,m- and p-chlorobenzotrifluoride have been measured. The vapor pressure data have been fitted to a suitable equation. (13) Stull, I n d . Eng. Chcm., 89, 517 (1947). 68, 2649 (1946). (14) Field, THISJOURNAL, (15) Booth, Elsey and Burchfield, i b i d . , S7, 2066 (1935).
DURHAM,NORTHCAROLINA
RECEIVED JUNE26, 1950
CHEMICAL RESEARCH DIVISIONOF LAKESIDE LABORATORIES, INC.]
Mercurial Diuretics. 11. Methoxymercuration of N-Allyl Amides B Y R.
L.ROWLAND, WENDELL L.PERRY AND SAMUEL GERSTEIN
The organic mercurials which have been investigated as diuretics have generally been those obtained by methoxymercuration of the monoallylamide of a dibasic acid. Thus Salyrgan, I, and Mercuhydrin, 11, contain a free carboxyl radical. / ,OCH2COOH
0'
\ CONHCH2CH(OCH3)CH~HgX I
COCHzCHzCOOH
I
NHCONH CH2CH (OCHa) CHZHgX I1
The increased diuretic potency of NHCONHCH&H(OCHs)CHsHgX, (111), X = C1, Br, SCHZCOOH, etc.,' which is a simplification of I1 by removal of the P-carboxypropionyl radical, has been noted. The possibility that a similar simplification of I might result in a compound with improved diuretic properties prompted the investigation of GHbCONHCH*CH(OR)CH2HgC1(IV) where R = CHJ. The methoxymercura(1) Rowland, Perry, Forrman and Friedman, THIS JOURNAL, 71, 3595 (1950).
tion products of other simple aliphatic and aryl allyl amides were also of interest in the course of an exploratory study of variation of diuretic potency and toxicity with chemical structure. Although the preparation of mercurated allylacetamide has been claimed, its physical and pharmacological properties have not been reported. No other reports are available on the preparation or properties of the mercurials obtained by the addition of mercuric acetate and alcohols to the allyl amides of unsubstituted aliphatic or aryl monocarboxylic acids. Perhaps the most nearly related compound is the isostere of IV, R = H, formed by the addition in water of mercuric acetate to the allyl amide of pyridine-3-carboxylic acid. A representative group of allyl amides was prepared. With the exception of allylacetamide and allylbenzamide, these compounds are new. Addition of mercuric acetate to the allyl amides was accomplished in methyl alcohol and, for convenience, the product was isolated as the chloromercuri derivative. The locations of the acetoxy(2) Tabern, U.S. Patent 2,163,296(1939). (3) Hartmann and Panizzon, U. S. Patent 2,136,501(1938).
