COMMUNICATIONS TO THE EDITOR
July, 1948
2613
methyl-L-glucosamine to be a-L16the configuration of streptobiosamine is represented by structure 11. The levorotations of streptosonic acid LABORATORY OF ORGANIC CHEMISTRY UNIVERSITY OF WISCONSIN WILLIAMS. JOKXSON lactone3 and dihydrostreptosonic acid lactone P. GRABER support the applicability of Hudson's rules t o MADISON, WISCONSIN ROBERT RECEIVED JUNE 14, 1948 these streptose derivatives, since it is established conclusively that the configuration about C4 of these lactones is L. That the lactone of dihydroSTREPTOMYCES ANTIBIOTICS. XM. DIHYDRO- streptosonic acid lactone involves the secondary STREPTOSONIC ACID LACTONE AND CONFIGURA- hydroxyl group a t C4 is shown by the liberation of TION OF STREPTOSE AND STREPTOBIOSAMINE formaldehyde when the lactone reacts with two Sir : equivalents of periodic acid. 2-Methyl pentaacetyldihydrostreptobiosamin(6) Lemieux, DeWalt and Wolfrom, ibid., 69, 1838 (1947). idel was allowed to react stepwise with ethyl merFREDERICK A. KUEHL,JR. captan-hydrogen chloride, acetic anhydride, and RESEARCH DEPARTMENT MARYNEALEBISHOP mercuric chloride for the preparation of amor- MERCKAND Co., INC. EDWINH. FLY" N. J. KARLFOLKERS phouspentaacetyldihydrostreptobiosamine.2Ace- RAHWAY, RECEIVED MAY27, 1948 tylation of this compound gave hexaacetyldihydrostreptobiosamine.2 Oxidation by bromine and hydrolysis by hydrochloric acid of pentaacetyldihydrostreptobiosamine gave the known N-methyl- CHARACTERISTICS OF THE DROPPING MERCU ELECTRODE IN FUSED SALTS L-glucosamine and the new dihydrostreptosonic acid lactone, m. p. 143-144", [ a ] D -32" (c, 0.40 Sir : in water). Reaction of the lactone with hydraIn a preliminary investigation of the applicabilzine gave dihydrostreptosonic acid hydrazide, ity of polarographic techniques to fused salt media m. p. 137-139", [ @ I D f23" (c, 0.9 in water). we have obtained typical polarographic reduction Application of Hudson's rules of rotation to waves for the cations of a number of salts disstreptosonic acid diamide3 and dihydrostrepto- solved in a fused salt solvent. The results indisonic acid hydrazide shows that the hydroxyl cate that the Ilkovic is applicable to group a t Cz of streptose lies on the right. Since the melt employed, a ternary eutectic consisting i t has already been shown4 that the hydroxyl of 66.65 mole yo ammonium nitrate, 25.76y0 groups a t CZand CI of streptose are cis, and that lithium nitrate, and 7.59% ammonium chloride the configuration about C4 is 2arolbthe configura- (m. p. 86.2°).3 tion of L-streptose is represented by structure I. Mercury was used for the dropping electrode On the basis of these data, and the calculations and the stationary unpolarized anode pool in a of the glycosidic linkage between streptose and N- cell maintained a t 125 * 0.5" in an oil-bath. Drops were collected in a Pyrex spoon, washed, dried, and weighed for tests of the Ilkovic equa0 I tion. Characteristic reduction waves were obtained with nickel(II), copper(II), and bismuth(III), the latter two exhibiting maxima. A trace of I potassium iodide eliminated the maximum in the CH: case of copper. Varying degrees of success have I been had with other solute salts, prime difficulties r-CHOH being limited solubility in or reaction with the solvent electrolyte.
to be of the same order of activity as the authentic material.
ii::
i r
I
0
I
H
I
L
-
OHC-COH L--CH I
I I
0
-CH
~
I I
TESTOF
HCOH H°CH I
I
CHiOH
I1 (1) Brink, Kuehl. Flynn and Folkers, THISJ O W ~ N A L , 68, 2557 (1946). (2) Stavely, Wintersteiner, Fried, White and Moore, ibid., 69, 2742 (1947). (3) Kuehl, Flynn,Brink and Folk-6, ibid., 88,2679 (1946). (4) Brink:,Knehl, Flynn and Folktrr, ibid., 88,2406 (1946). (5) Fried, Walz, and Wintateiner. iW., 68, 2746 (1946).
C,
NO.
mmol./l.
1
1.95 4.98 6.77 9.97 12.8 12.8
2 3 4 5 6
TABLEI ILKOVIC EQUATION
THE id,
m
amp.
mg./sec
3.74 10.0 12.8 17.2 21.6 16.6
1.41 1.45 1.37 1.45 1.40 0.658
p
id Lm6X.i
sec.
4.0 4.5 3.9 3.4 3.5 7.6
1.21 1.22 1.22 1.10 1.09 1.22
(1) D. Ilkovic, CoU. Csechosbt. Cham. Commur., 8, 498 (1934). (2) I. M. Kolthoff and J. J. Lingane. "Polarography," Interscience Publisherr, Inc., New York, N.Y.,1941, p. 88. (3) E. P. Perman and R. H. Wilson, J . Chcm. SOL. U6. 1 7 9 (low).
2G 14
COMMUNICATIONS TO TIIE EDITOR
The results obtained by varying the concentration of nickelous nitrate in the ternary solvent are presented in Table I. Test no. 6 was made on same solution as no. 5 but with a different capillary. With a value of 13.29 g./cc. for the density of mercury at 125O, the Tlkovic equation beconies
Vol. 70
measured with a jacketed counter. Comparative approximate rate constants based on transdiiodoethylene as unity were as follows: Allyl iodide much greater than 200 1.0 Trans-diiodoethylene Iodobenzene 0.002 Ethyl iodide less than 0.001
The rate constant for allyl iodide could not be obtained with any precision, for exchange was with the synbols having the usual meaning given 6OY0 complete in twenty seconds under the normal by Kolthoff and Lingane.2 The agreement of the experimental data with the Ilkovic equation can illumination of the laboratory desk. This amount be seen from the essential constancy of the ratio of exchange corresponds to a rate approximately 200 times as fast as the rate of exchange of transid/Cm'/'tZa, in the last column of the table. diiodoethylene under the much more intense ilThe average deviation in the ratio is *4.3%. lumination employed in the other experiments. Substitution of the average ratio, 1.18, into the When the laboratory was darkened to an extent Ilkovic equation gives a diffusion coefficient equal such that the necessary operations could barely to 9.2 X lo-' cm.2/sec. for the nickel bearing ion. be carried out, exchange of allyl iodide was %yo Work is in progress to eliminate the solubility complete in twenty seconds. Therefore, at least a and solvent instability difficulties by employing large fraction of the exchange appears to involve more stable solvent electrolytes, e.. g., alkali free atoms, but the possibility of an accompanyhalides, a t higher temperatures. This will also ing dark reaction is not excluded. Studies allow investigation of a number of metals for the of the separation procedure demonstrated that dropping electrode. allyl iodide underwent no more than 1% of INSTITUTE FOR THE STUDY OF METALS exchange with iodide ion under the conditions N. H. NACHTRIEBemployed in the reduction of the iodine. UNIVERSITY OF CHICAGO CHICAGO, ILL. M. STEINBERG A solution of ethyl iodide which was illuminated RECEIVED MAY7, 1948 for one week underwent a significant amount of exchange, but the data did not permit the calculation of a reliable rate constant. EXCHANGE REACTIONS BETFCTEEN IODINE ATOMS That exchange in the last three compounds in AND ORGANIC IODIDES the table requires free atoms is indicated by the Sir : fact that duplicate solutions stored in the dark Several workers have reported exchange reac- for as much as one week underwent no more than tions between organic iodine compounds and inor- 1% of exchange. ganic iodides, but there are very few known exWe are undertaking a more thorough investigaamples of exchanges with neutral iodine atoms or tion of the kinetics of these reactions. molecules. Methyl iodide' and several diiodoCONTRIBUTION FROM THE CHEMICAL LABORATORIES phenols2 have been shown to exchange with ele- OF COLUMBIA UNIVERSITY mentary iodine in polar solvents, but the mecha- NEWYORK27, N. Y. RICHARD M. NOYES nisms of these reactions were not elucidated. RECEIVED JUNE7, 1948 Noyes, Dickinson and Schomakera demonstrated that neutral atoms were involved in the exchange AN INTERRELATIONSHIP OF THYMIDINE AND of l12-diiodoethylene with elementary iodine in VITAMIN Biz saturated hydrocarbon solvents. Sir : We have now observed atomic exchange reacIn a series of studies on factors functionally retions with some other representative organic iodides. The experiments were conducted with lated to folic acid and p-aminobenzoic acid, thymiiodine-131 supplied by the Oak Ridge National dine was isolated from liver as afactor preventLaboratory and obtained on allocation from the ing the toxicity of a competitive antagonist of United States Atomic Energy Commission. Hex- folic acid.' The recently reported isolation of ane solutions 0.002 molar (0.004 normal) in radio- vitamin BIZas a growth factor for Lactobacillus active iodine and 0.04 molar in organically com- lactis Dorner2f3necessitated a study of the funcbined iodine: were illuminated with a tungsten tion of the vitamin to determina whether or not lamp a t about 30'. The iodine in each solution it is identical with a factor found in this Laborawas then extracted by shaking it with an acidic tory to be concerned with the biosynthesis of aqueous solution of sodium sulfite, and the activi- thymidine. As vitamin BIZhas been isolated usties in one or both of the separated solutions were ing an assay with Lactobadlus Zactis Dorner, this organism was utilized in the present investigation. (1) H.A. C. M c K a y , Nalurr, 139, 283 (1937). A medium suitable for assay techniques has not (2) W. H. Miller, G . W . Anderson. R. IC. Madison and D . J. id =
F14nD'/8Cma/at~~x
Wlej, S&uc8.100, 340 (1944). (8) R. M. Noyes. R. G . Dictinson and V. Scbomaku, "xu J O U ~ ~ A L1,17,
1219 (IQ46).
(1) Shive, J J.,Tare JOUWAL, in prem (2) Ricker, J J., S c b , LOT, SO6 (1948), ( 8 ) Shorb, uid., 101, 397 (1948).
