June 20, 1958
COMMUNICATIONS TO THE EDITOR
3167
urements of a liquid phase above its normal boiling point. A solution of neptunyl ion (7.43 X M R b N p 2 3 7 0 ~ ( N 0 in 3 ) 30.1 M DNOS-D~Oa t 25')' has been examined from 0.6 to 1.3 p for 45 hours and from 4.5 to 252'. Deuterated solutions were used to decrease both the absorbance and the effect of temperature upon the absorbance of the solvent.2 The sample was saturated with ozone, then degassed prior to introduction into the pretreated titanium cell assembly. As the temperature was raised Np(V1) was found to be reduced to Np(V) quantitatively and irreversibly. The sharp, strong 0.98 p absorption band of TABLE I Np(V) is slightly asymmetric, the integrated abALKALINEEPIMERIZATIONa O F N-AcCm TO N-AcMm sorbance of the long wave length side being 1-2% N-Achlm greater than the short wave length side, both a t Time, formed,b Compound hr. RS-A~C~ % 25 and 251'. The position of thqmaximum shifts, N-LkC;m ( p H 11.0) 0 1.0 0 %ta decreasing rate, from 9797'A. a t 25" to 9741 24 1.0, 0 . 4 19 A. a t 251". The half intensity band width shows 48 1.0, 0 . 4 24 a striking behavior with increasing temperature, 72 1.0, 0.4 24 first decreasing (12%) from 60 cm.-' a t 25" to a Descending chromatography was conducted on borate minimum of 53 cm.-' a t about 175", then slowly The product of treated paper with butanol-pyridine-water (6: 4:3) for 20 increasing to 57 cm.-I a t 251'. hr. Synthetic N-AcMm exhibits R N - A ~0.4 Q ~under these the absorbance a t the band maximum and the half conditions. * Estimated enzymatically with NANaldolase and pyruvate.' At equilibrium, 10% of the added N- intensity band width, normalized for solvent backAcMm is converted t o NANA, the latter compound deter- ground and density change, decreases linearly (34%) from 25 to 251'. mined by the direct Ehrlich reaction. No inhibition of the enzyme was noted with artificial mixtures containing KFrom a chemical point of view the above obserAcGm and N-AcMm ( 5 : l ) . vations suggest an effect of temperature upon the solvation sphere of the NpOz+ ion, and a concomiAfter 48 hr., 1.95 g. of N-AcGm (m.p. 202-203") was recovered by fractional crystallization from tant interaction of the Nos- ion present with the ethanol. The remaining mixture (0.5 g.) contained NpOz+-solvate dipole system. Several weaker absorption bands belonging to about 90% N-AcMm, 10% N-AcGm, and traces of unidentified materials similar to those obtained Np(V) and Np(V1) ions have been studied in less in the pyridine epimerization. The N-AcMm was detail. The results do indicate clearly, however, identified by: (1) paper Chromatography'; (2) a great variability in the effect of temperature conversion to the expected quantity of NANA by upon band profile. Expansion and refineinent of measurements the addition of pyruvate and NANaldolase; ( 3 ) similar to those reported should have manifold conversion to D-mannosamine, isolated as the crystalline hydrochloride, and identified by ion-ex- implications toward a better understanding of change chromatography, optical rotation, color the nature of ions in solution, and forces operative reactions and its X-ray powder diffraction pattern. in the liquid state. The equipment, which has been designed and The alkaline epimerization of N-AcGm to N-AcMm may be a suitable method for the preparation of built a t this Laboratory for use with the Cary Model 14 Spectrophotometer, has a working range N-AcMm and of D-mannosamine. The data outlined above indicate that reversible of 0 to 250" and 0 to 1000 p.s.i. The cell space is epimerizations of N-AcMm and N-AcGm readily 7.62 cm. long X 1.00 cm. diameter, and is fabrioccurs under the conditions which other investi- cated from annealed titanium with colorless syngators have used for chemical studies on the struc- thetic sapphire windows. The entire sample cell ture of NANA. In view of the present findings, and reservoir assembly is suspended in an evacuand of our previous results,' it is concluded that the ated chamber, and positioned in a special fused N-acetylhexosamine moiety of NANA is N-acetyl- quartz mount. The sample cell a t any operating temperature is measured optically against a geoD-mannosamine. metrically similar solvent cell which is thermo( 5 ) Postdoctoral fellow, American Cancer Society. stated a t 25". Stability and reproducibility of THERACKHAM ARTHRITIS RESEARCH UNIT AND measurements over the design range are comparDEPARTMENT OF BIOLOGICAL CHEMISTRY SAUL ROSEMAN OF MICHIGAN UNIVERSITY DONALD G. COMBS able to that of operation a t room temperature. ANN ARBOR,MICHIGAN A complete discussion of the above results and RECEIVED APRIL 14, 1958 equipment will be published in articles now in preparation. I wish to express my appreciation to Dr. R. W. QUANTITATIVE SPECTROMETRY O F AQUEOUS ture with authentic material) ; (2) paper chromatography,' which showed it to be N-AcGm free of NAcMm; ( 3 ) an X-ray powder diffraction pattern which was identical to that obtained with N-AcGm. NANA has been obtained by treatment of NAcGm with oxaloacetate a t pH 11.0.4 A solution of N-AcGm (2.5 g. in 10 ml. of water) was therefore adjusted to, and maintained, a t PH 11.0 a t room temperature. Analysis of aliquots (Table I) a t 24, 48 and 72 hr. indicated that a substantial amount of N-AcMm was formed during the first day.
NEPTUNIUM IONS AT ELEVATED TEMPERATURES AND PRESSURES
Sir: There are reported herein the results of what are believed to be the first quantitative spectral meas-
(1) The author is indebted to Messrs. P. M. Lantz and G. W. Parker, Chemistry Division, Oak Ridge National Laboratory, for supplying a single crystal of the N p salt, and to Dr. B. M. Benjamin, also of this Laboratory, for the necessary DNOa stock solution. (2) W. C. Waggener, J. Phys. Chcm., 69, 382 (1958); Anal. Chcm.. in press.
3168
COhlMUNICATIONS
Stoughton of this Laboratory for the help and encouragement he has given this program since its inception. CHEMISTRY DIVISION OAK RIDGENATIONAL LABORATORY \V. C . L ~ A G G E N U I I OAKRIDGE,TESNESSEE RECEIVED APRIL 24, 1968
A NEW SYNTHESIS OF SMALL KING CYCLIC SULFIDES
Sir: Lliiew iiietliod for the syiithcsis of thiiraiics aiid thietanes has becii discovered. which promises to
Cyclic carbonate
.-
-.
the formatiori of episuliicles lroiii epoxides and thiocyanate i0n.l Failure to obtxiii an appreciable amount of cyclic sulfide froiii the reaction of 44,Gtrimethyl-1,:3-dioxaii-2-one with potassium thiocy>11iatca t 1S5" may be attributed by this r~iecliailisin t ( J the a ,a, oc'-trisubstitutiori. The chief product iii the latter C ~ S C is l-iiiethyl-;3-pentcii2-01. Acknowledgment.--Lye wish t o thank the "ittiorial Science Foundation for a research grant under which this work was cxriecl out and Mr. Domld G. Huminel for supplying us with the cyclic c:irboii,ites o f 1 ,::-l)r(,I)a~icdiol~I ,%butnnediol,
Iicactlun
temp , OC
uf
Ethyleiie glycol 1.3-Propanediol 1,3-Butariediol 2,3-Ditnethyl-1,3 propAnedio1 2,2-Diethyl-1,3-propnllediol
95 140
Etliylcnc sulfide 54-5-1.5 Trimethylene sulfide 70-93 1 7()- 180 2-Methylthietaiie 101-102 175-180 3,3-Dimethylthietaii~ 115-116 1UO-195 3,3-Diethylthietanee 170.;5-17:1
55-56'' 95, i I" li15.5 li)i.5" 12U"
1 ,-l!l5~) 1 .49145",' 6 4 . 5 1.4'332 1.5102* 3.4 1.4852 1.4831" 15.8
1,4738f
1 . 1838
1.473gd,'
58.6 43 . x
M. Marcel Delepiiie, Bull. SOC. chiin. France, 742 (19201. \V. E. Haiiics, 11. L', Ilelin, C. L\', Bailey and J. S. Ball, J . I'hys. Chem., 38, 273 (1954). Griscfikewitscli-Trochirno~ski, J . Russ. Phys.-Chon. Ges., 48, 893 (Beil., XVII-XIX, 1st supp., p. 5 ) . H. J. Backer and I-tical Laboratories, West Eiiglewo(d New Jersey. J Indices of refraction taken at 18".
have corisiclerable generality. It has beeii fouiid that heating the melted cyclic carbonate of a I,?or 1,3-diol with ail equimolar amount of potassiuin thiocyanate produces the corresponding cyclic sulfide in most cases. Table I prcsciits typical data. '>
+
c ~ o ) C 4 KSCN
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+
I
HEMOGLOBIN STUDIES. 11. A SYNTHETIC MATERIAL WITH HEMOGLOBIN-LIKE PROPERTY' Sir :
'This iiletliod iiiay be coniliared with the receiitly reported pyrolysis of 1,3-oxathiolaii-2-o1le over potassium carbonate to yield ethylene sulfide, but the present process is much more convenient beC"IUSC of thc easy preparation of the cyclic carbonate froin a 1,8-or 1,3-diol and ethylene carbonate or diethyl carbonate.
It WAS suggested iroiii the experimental data 011 hemoglobin and related compounds that the UP usual stability of osyheinoglobin and oxymyoglobin could be d u e to the low dielectric coiistarit of the irniiirdidte surrouiidings of the bountl oxygen iiioleculcs 111order t o check this llypotlie sis, a synthetic iiioclel material was iiiadc by the followiiig procedure. -1 solution of the dietliyl eitcr of lieiiiiii a ~ i d.i11 excess of l-(%-I'lieiiyletli~l)-iiiiida~olc in belizelie was rcduccd by shaking with an aqueous NagS.04 KO13 solution in L' carbon monoxide atmosphere. After centrifugation, the clear, bright-red benzene solution was mixed, in CO-atmosphere. with a 10% solution of polystyrene in benzene, and then dried in a m" stream of CO a t 1 atm. pressure. The trailspawit, solid-like film, which contaitietl the coiiiple.; iiiolecules of l-(2-pheriyletliyl)-iinida~olecar~~~iiiiioii(J~yliciii~ dicthyl c5ter iriibedded in d riicLtri\ Oi dri .tiiiorphous mixture of polystyrene aid l-(2--phenylethyl)-imidazole,
+
-
11
C)CA
,e;?
, -
0
L -h
or J ~
S3
The pyrolysis is thought to proceed by 1' iiiech.inism similar to that proposed by van Tainelen for
(1) Paper I , J
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IITak\.h.rra and t B l'leischer.
THIS
J U U K N A L , 80, 1109 (19;s)
1111s worh wab suppurted in part first b y d grant from Iiesedrch Coryoratiou, a u d later by a grant (USPHS-
RG-4483) from the Division of Research Grants, Publlc Health (1) D D Reynolds. 'IHIsJUUKNAI , 7 9 , -1951 (1957)
Service.
