COMMUNICATIONS TO THE EDITOR
1364
Vol. 79
A. R. Anderson2; maximum energy deposition extended to 7 X loz2e.v. per g. of solution. The main products were nitrite, oxygen and hydrogen : a low yield of nitrogen was observed from concentrated solution. The 100 e.v. yield of nitrogen (GN~)from a 9.4 AI solution was (3.2 0.6) X
tween values of k for various ions is noteworthy. Parameter A measures the hypothetical molecular yield a t zero concentration. It is different for HZ and HzOz, and for various types of ionizing radiation.’ A was measured in the present case using a 1.9 X M KBr solution, in which the radical 10-3. back reaction is adequately suppressedP The Particular attention was paid to variation of value of 0.82 f 0.02 is in good agreement with the hydrogen yield with [Nos-]. Calculation of GH, intercept a t zero [Nos-] in the figure. in the more concentrated solutions is complicated The present results may be interpreted in terms by absorption of energy by nitrate ion, but the of “capture” of H atoms by NOScomplication is not serious for our purposes. For NOa- 4- H --+SO2 4- OH(2) example, in the worst case (15.9 M solution), assuming that all fast neutron- y energy deposited in From the data it may be deduced that when tbe solution is available for water decomposition, “average distance” between nitrate ions is 20 A., G H ~= 0.011 f 0.001. Assuming that only the about half of the H atoms available for Hz producenergy deposited directly in the water is available, tion are consumed by reaction (1). Above a conGH, = 0.025 0.003. A value of 0.019 f 0.009 centration of 1 M (when the “average distance” embraces both these extremes. At concentrations between ions is about 11 A.), G H ~decreases less below 1 M , difference between the two G values is rapidly as [NOS-] is increased. I n 15.9 M soluless than experimental error. The figure shows a tion (melted crystals of Ca(NO3)2-4H20)more than 97% of available H atoms are intercepted. A complete account of the work, with due 0.8 acknowledgments, will be published later.
*
\
(7) A. 0. Allen, Radiation Research, 1, 85 (1954). (8) A. 0. Allen, C. J. Hochanadel, J A. Ghormley and T. W. Davis, J . Phys. Chcm., 66, 575 (1952). ,
0.5
3 0.4
ATOMIC ENERGY RESEARCH ESTABLISHMENT HARWELL, DIDCOT R. G. SOWDEU BERKS,ENGLAND RECEIVED JANUARY 15, 1957
‘i
\
0.2
A NEW POLYMERIC SULFUR-NITROGEN COMPOUND 0
0.5 1.0 1.5 2.0 [ NOs-] ‘1: (mole’” dm. - I ) . Fig. 1.-Variation of G H with ~ [X03-]i/a,
2.5
plot of G H ~DS. [NOa-]’/:. Linearity is evident up to [NOB-] of about 1 M; the data over this region follow an equation of the type GH, = A
- k[NO,-]’/:
(1)
S w ~ r s k iobserved ~,~ this relationship to hold for variation of GH,Q with [Br-] and [Cl-1. Allen and Holroyd5 confirmed and extended the Brdata. The data of Schwarzs concerning the effect of [Cu++] and [NOZ-] on GH, can be expressed by equation (1). The table shows values of A and k for the various solute ions M; solutions are approximately neutral unless otherwise indicated. .If =
A = k =
Not-
0.84 0.65
Br-
0.68 0.65
(fiH 2)
CI(PH 2)
0.78 0.93
0.75 0.88
Br-
NO,-
Cu+’
0.44
0.44
0.30
0.60
The significance of the “one-third power” relationship has been discussed qualitatively by S ~ o r s k i . The ~ parameter k affords a measure of the probability that the ion in question will react with the appropriate radical (H or OH) as i t diffuses out of a “hot spot.’’ The similarity be(2) A. R. Anderson, unpublished data. (3) T. J. Sworski, THISJOURNAL, 76, 4687 (1954). (4) T.J Sworski, Radialion Research, 2, 26 (1955). ( 5 ) A 0 . Allen and R. A. Holroyd, THISJOURNAL, 77, 5852 (1955). (6) 13. A. Schwarz. ibid., 77, 4960 (1955).
Sir: It has long been known that the reaction of sulfur chloride with ammonia gives sulfur This substance, a cyclic tetramer, has the structure of an eight-membered ring composed of alternating sulfur and nitrogen atoms,* with four resonating double bonds. It may be reduced to the saturated analog, H4S4N4.4 I t has been reported that the action of sulfur dichloride on ethylamine produces the corresponding N-ethyl derivative (SNCzH6)4,5 while other authors have found that n-butylamine and sulfur tetrachloride give CdHg-N=S=NC~HC,.~ We have found that when methylamine is allowed to react with a hexane solution of sulfur dichloride, a low-molecular-weight plastic polymer having the approximate composition (CH3NS), is formed. Additional products are methylamine hydrochloride and an unidentified unstable yellow oil which is presumed to contain the cyclic tetramer. The polymer has been prepared in varying molecular weights, depending on how closely the relative amounts of the two reagents were controlled; Le., exact control leads to high molecular weights. I n its lowest molecular weight foriii (ca. 600 as measured cryoscopically), the polymer (1) H . B. Van Valkenburgh and J. C Bailar, Jr., THISJOURNAL, 47, 2134 (1925).
(2) M. H. M. Arnold, J. A. C. Hugill and J. M. Hutson, J . Chcm. SOC., 1645 (1936). (3) C . S . Lu and J. Donohue, THISJOURNAL, 66, 818 (1944). (4) A. Meuwsen, Bcr., 62, 1959 (1929). (5) F. Lengfeld and J. Stieglitz. Ber., 26, 2742 (1895); A. hleuwsen and H.Holch, ibid., 64B,2301 (1931). (6) M. Goehring and G . Weis, Annew. Chem., 68, 678 (1956).
COMMUNICATIONS TO THE EDITOR
March 5, 1957
1265
Hydrolysis of the CISacid with 5 N sodium or barium hydroxide gave about 1.5 moles of a CgHaNzOzcompound, isolated as the '/2 H a 0 4 salt, 187-202' dec. Anal. C, 37.79; H, 4.79; N, 14.54; CHEMICAL RESEARCH DEPARTMENT BOB D . STONE S, 8.24; N-CHI, 4.54; neut. eq., 99.8; Amax. 0.1 RESEARCH AND ENGINEERING DIVISION MORRISL. h'IELSEN MONSANTO CHEMICAL COMPAKY N HCI: 260 mp, E = 9,800. The N-acetyl derivaDAYTON, OHIO tive of the Ce compound (m.p. 200' dec. hmax. RECEIVED JANUARY 7, 1957 0.1 N HCl: 232 mp, e = 13,200; 280 mu, E = 7,100) gave on heating 1mole of carbon dioxide and an N-acetyl compound, C,HloNZO, m.p. 119-120'. THE STRUCTURE OF ANTIBIOTIC T-1384 Anal. C, 60.36; H, 7.30; N , 19.82; N-CHa, Sir : 7.85; N-acetyl, 31.32. An antibiotic, designated T-1384 was isolated The presence of an N-methyl group, which had from an Actinomycetes type of organism by the been indicated by our analysis of T-1384, was conFermentation Biochemistry Department of these firmed by the isolation and characterization of Laboratories.' This compound is identical with methylamine following the oxidation of the CRcointhe antibiotic Netropsin,2 C32H4aNl~04.~Our data pound with acidic peroxide. The similarity of the required the assignment of ClsH2aNlo03 for the em- ultraviolet absorption spectrum of the N-acetyl pirical formula of T-1384. Subsequently, the lat- C5 compound to N-ethylpyrrole,s the empirical ter empirical formula was reported for N e t r ~ p s i n , ~formula, a positive Ehrlich test, and a positive sinanomycin,6 and congocidine.6 Reported herein Bratton-Marshall test7 after hydrolysis suggested are the data which indicate that T-1384 has that the c5 fragment was 3-amino-l-methylpyrrole. structure I, p- [4-(4-guanidinoacetamidino-l-methyl- The ease with which the (26 compound was 2-pyrrolecarboxamido) - 1- methyl-2 - pyrrolecarbox- decarboxylated suggested an a-carboxyl group. amido ] -propionamide. Comparison of the Ca fragment with a synthetic NH&NHCH&2NH-sample of 4 amino-1-methyl-2-pyrrolecarboxylic acids showed them to be identical. ?.ItH R 1' From the filtrates of the cg preparation was isolated /%alanine as its 2,4-dinitrophenyl derivative, \NCHa /I \N&HcHzcHz I Anal. C, 42.52; H , 3.69; N, m.p. 144-146'. O=C I 16.32. This derivative was identified by compariCHa I son with an authentic synthetic sample. NH2 I, R = NH, T-1384 11, R = 0 , C~e.Ko Hydrolysis data on the c15 acid had shown it to Mild alkaline hydrolysis of T-1384 gave the contain two moles of 4-amino-1-methyl-2-pyrrolecompounds C15H20Ne03, C3H6N30 and ammonia. carboxylic acid and one mole of /3-alanine. Since The CI compound was identified as glycocyamidine the c16 acid could not be decarboxylated readily by comparison with a known sample. Apparently and since it gave a positive test for an aromatic the same Cl5HzoNoOa compound was obtained by amine, the order of its fragments were postulated hydrolysis of N e t r o p ~ i n and , ~ ~ congocidine.6 ~ We to be C~+26-b-alanine. This order was also sughave now established the structure of this com- gested by the ultraviolet absorption data. The pound as p- [4-(4-amino-l-methyl-2-pyrrolecarbox- structures of the Cle acid and amide were estabamido) -1methyl - 2 - pyrrolecarboxamido l-propiona- lished to be p- [4-(4-amino-l-methyl-2-pyrrolecarmide. boxamido) -1-methyl- 2 pyrrolecarboxamido 1- proAlkaline hydrolysis (0.5 N NaOH) of the above pionic acid and the corresponding propionamide c 1 6 amide gave ammonia and the corresponding Cl6 by comparison with synthetic sample^.^ acid hemihydrate, m.p. 190-105° dec., Amax. 0.1 When T-1384 sulfate was treated with one equiN HCI: 285 mp, E = 20,300. Anal. C, 52.84; H, valent of barium hydroxide a t room temperature 5.70; N, 20.11; N-CHB, S.31; HzO, 2.43; neut. for 3 hours, there was produced ammonia and a amide both new compound C1aH26N*0*'1/2H*S04.1/~Hp0, eq., 379, 323. The c16 acid and C I ~ m.p. gave a positive Bratton-Marshall test? for an aro- 200' dec. Anal. C, 43.88; H, 5.77; N, 25.12; S, matic amine while their N-acetyl derivatives gave 3.38. h max. 0.1 N HCI: 234 mu, E = 19,600; negative tests. The ultraviolet absorption spectra 299 mp, E = 21,500. From spectral and hydroof these N-acetyl derivatives and T-1384 (Amax lytic data this ClsNg compound is postulated to be 0.1 N HCI, 234 mu, E = 19,400, 300 mfi, e = the N-guanidinoacetyl derivative of the c16 22,400) were comparable indicating the presence of amide, 0-[4(4-guanidinoacetamido-1-methyl-2-pyrthe same chromophoric system in these compounds. rolecarboxamido) - 1- methyl - 2 - pyrrolecarboxamido]-propionamide, structure 11. A comparison of (1) S. De Voe, C. Ervin and N . Bohonos, unpublished data. (2) Netropsin is the Trademark of Chas. Pfizer and Co. We wish the ClsNp compound with a synthetic sampleg of I1 to thank Dr. A. C. Finlay of Chas. Pfizer and Co. for a sample of confirmed its structure. Netropsin which was shown to be identical with T-1384 by chroAll features of the structure of T-1384 now have matography and by spectral comparisons. been established except the position and nature of (3) A. C. Finlay, F . A. Hochstein, B. A. Sobin and F. X. Murphy, THIS JOURNAL,73, 341 (1851). the group giving rise to ammonia upon very mild (4) E. E. van Tamelen, D. M. White, I. C. Kogon and A. D. G . hydrolysis. Potentiometric titration of T-1384 Powell, i b i d . , 78, 2157 (1956).
may be pulled slowly into strings, but i t shatters on being struck. Higher molecular weight material is more brittle.
I1
I-[NH_-
(5) K. Watanabe, J . of Anlibiolics, 9 (Ser. A), 102 (1856). (6) M. Julia and N. Joseph, Comfit. rend., 843, 961 (1956). (7) A. C. Bratton a n d E. K . Marshall, J. B i d . Chem., 128, 527 (1939).
(8) R. A. Friedel and M. Orchin, "Ultraviolet Spectra of Aromatic Compounds," John Wiley and Sons, Inc., New York, N. Y . , 1951. (9) M . J. Weiss, J. S. Webb and J. M. Smith, Jr., THIS JOURNAL, 79, 1266 (1957).
