3842
NOTES
TABLEB STRONGEST ARCLINESOF ELEMENT 61 A. REGION
IN THE
3000-3450
yield and it appears likely that an equilibrium is involved CeH&HL!OOCHa
Wave length, d.
Relative intensity
3366.06 0.03 3377.64 * .03 3391.25 .03 3418.67 * -03 3427.42 .* .03 3441.09 * .03 3449.81 =t .03
Weak Weak Medium Weak Strong
Weak Medium
Vol. 71
+
NH&HlCOONa CeH&H&!ONHCH&OONa f CHsOH ANTIBIOTICS RESEARCH DEPARTMENT THEUPJOHNCOMPANY KALAMAZOO 99, MICHIGAN RECEIVED MAY5, 1949
Alkyl Derivatives of Ethylenediamine BY ALBERTE. FROST,Ja.,STANLEY CHABEREK, Jn., AND ARTHURE. MARTELL
Unfortunately, it was impossible to compare In the course of other work a number of symthese (arc) spectra with the (spark) spectrum observed by Timma.6 His observations covered metrical dialkyl ethylenediamines have recently the 3630-4400 A.region; aside from the fact that been prepared and characterized. A number of the methods of excitation used were different, other amines, containing a smaller or larger his principal lines could not be looked for in the number of alkyl groups, and a few dialkyl piperpresent arc spectrum with any hope of success azines were obtained as by-products. The bybecause of interference by CZ and CN bands. products not previously reported for this method However, the spark lines he mentioned as due to and their properties are listed in Table I. The element 61 were observed in the spectrum of aliTABLEI quots of samples 1, 2 and 3 when excited by the BY-PRODUCTS copper spark technique. B. P . , %.C.P., Calcd. N, % (5) D. Timma, MonC-166 (U.S. Atomic Energy Commission). Amine OC. Mm. Found OAKRIDGENATIONAL LABORATORY OAK RIDGE,TENN. RECEIVED JANUARY 26, 1949
A Convenient Synthesis of Phenaceturic Acid' BY JAREDH. FORD
N,N'-Dioctylpiperazine N,N,N',N'-Tetraoctylethylenediamine N,N'- Didodecylpiperazine N-Monobenz ylethylenediamine N,N,N'-Tribenzylethylenediamine Trioctyldiethylenetriamine"
187-190
1
.....
53-55
9.02
9.09
130-133
5.51
5.29
6.63
6.34
265-275
8
54-56
155-160
5
.....
225-235
4
99-100
18.65 18.72 8.48
8.64
Phenaceturic acid was required as a starting material in numerous experiments directed toward 213-215 2 . . . .. 9.55 9.28 the synthesis of benzylpenicillin.2 The following Anal. Calcd. for CMHBIM: C, 76.5; H, 14.0. method which employs methyl phenylacetate Found: C, 76.4; H, 14.0. as the starting material was found to be more convenient than the literature method8 in which method of preparation, which involved the reaction of ethylene dichloride with an excess of phenylacetyl chloride was used. primary amine, has been described by The main products were characterized as the Experimental Glycine (75.1 g.) was added to a solution of 23 g. of dipicrates and as the phenylureas, which are sodium in 850 ml. of anhydrous methanol, and the mixture listed in Table 11. Attempts to prepare the was boiled under reflux a few minutes to obtain a clear solu- phenylurea from tribenzylethylenediamine were tion. One hundred fifty grams of methyl phenylacetate unsuccessful, and it was found that picrates could was then added and the solution was boiled under reflux for three days. The methanol WIW distilled off and the not be formed readily from dioctylpiperazine, didodecylpiperazine residue was dissolved in 400 ml. of cold water which con- tetraoctylethylenediamine, tained 20 g. of sodium bicarbonate. The resulting solu- and tribenzylethylenediamine. The picrate obtion was twice extracted with ether to remove unchanged methyl phenylacetate, and then acidified to PH 2 with con- tained with dibenzylethylenediamine was shown centrated hydrochloric acid. After standing overnight in a by analysis to be the monopicrate. Repeated refrigerator, the product was filtered, washed with cold recrystallization from various solvents did not water and dried in a vacuum oven. The resulting white change the melting point or the analysis. crystals melted at 139-141' (lit.,a 143"); yield, 122.6 g. For this method of preparation, it was found (63.5%). One recrystallization from hot water (400 ml;) gave 114.2 g. of product which melted at 143-144 . that the separation of the insoluble crystalline From the ether extracts were obtained 42.1 g. (28%) of monohydrate obtained by treating the reaction methyl phenylacetate; b. p. 9f3-98' (14 mm.). product with a dilute aqueous solution of strong A longer period of heating did not increase the base provided the most convenient method of (1) Thin work was done under contract between the Office of Scientilr Reecarch and Devdopmcnt and The Upjohn Company (Contract OSRD-CUU-899). (2) Clarke, Johnson and Robinson, "The Chemistry of Penicillin," Princeton University Preea, Princeton, N . J., 1949. (3) Hotter, J . prokt. Chsm., 121 88, 98 (1888).
(1) Sebrell and Clifford, U. S. Patent 1,948,817 Web. 20, 1934). (2) Kyrides, U. S. Patent 2,126,560 (Aup. 9, 1938); U. S. Potent 2,267,685 (Dec. 23, 1941). (3) Zienty and Thielke, THISJOURNAL, 67, 1040 (1945). (4) Zieaty, +bid., 68, 1388 (1946). (5) Clifford, U. S. Patent 2,216,620 (Aug. 9, 1988).
