A STUDY OF SOME POSSIBLE NEW METHODS FOR THE SYNTHESIS OF ETHYLENE UREA A THESIS Submitted in partial fulfillment of the requirements for the degree of Master of Science in Chemistry by Henry H. Herring, Jr. Georgia. School of Technology, Atlanta, Georgia 1940 APPROVED i ACKNOWLEDGUTNT The authcr wishes to express his sincere appre- ciation and thanks to Dr. B. B. Wroth of the Depart- ment of Chemistry and Chemical Engineering, Georgia School of Technology, for his willing guidance, help- ful advice, and tactful criticism during the study of this problem. Acknowledgment is also made to the Research Division of Picatinny Arsenal, Dover, N. J., both for the suggestion of this problem and for their proposed reactions. The author also wishes to thank Dr. H. M. Waddle for the construction of certain pieces of glass apparatus. TABLE OF CONTENTS Page Review and History of Ethylene Urea 1 Present Known Methods For The Synthesis of Ethylene Urea 9 Some Possible New Reactions For The Synthesis of Ethylene Urea 11 1. Ethylene Dibromide and Urea 12 2. Ethylene Chlorohydrin and Urea 15 3. Ethylene Glycol and Urea 18 4. Ethylene Oxide and Urea 21 5. Ethylene Glycol Diacetate and Urea . 24 6. Ethylene Glycol Mono-Ethyl Ether and Urea 26 7. Diethyl Carbonate, Ethylene Dibromide and Ammonium Hydroxide . • . • . 28 Summary 30 INTRODUCTION AND PURPOSE. The earliest recorded synthesis of ethylene urea is that of Emil Fischer and H. Koch in 1886 (1). The work of these investigators upon this compound was very limited, and a search of the literature up to the present time reveals little knowledge of any additional investigations having been attempted for its synthesis. The method of Fischer and Koch has been found to give good yields of ethylene urea, but the high cost of starting materials makes the production of this compound impractical on a large scale basis. Since ethylene urea is of interest today, primarily for its use as an intermedi- ate compound in the production of the high explosive ethylene dinitroamine, this initial high cost is prohibitive. Therefore, the chief purpose of this work is to study some pos- sible new methods for the synthesis of ethylene urea which would entail only the use of inexpensive reagents. It is also the purpose of this work to summarize the existing literature for the methods of synthesis already known. (1) Fischer and Koch, Liebig's Anrialen, 232, 227 (1386). 1 ETHYLENE UREA. Historical: NH-CH2 Ethylene urea, 02C / a heterocyclic compound, was first \NH-CH2 synthesized by Emil Fischer and H. Koch in 1887 (1), and their method is the one now generally used. The literature reveals no other method which compares in simplicity with theirs, though other reactions have been car- ried out which produce ethylene urea in various yields, a summary of which will be included in this work. The reaction as described by Fischer and Koch, consists of re- fluxing an equimolecular mixture of ethylene diamine and diethyl carbonate at 180 0 for at least six hours, at the end of which time, the product on cooling crystallizes in white needles. The conditions for obtaining yields up to 9% from this reaction have been determined by the Research Division of Picatinny Arsenal (2), and were it not for the high cost of starting materials this method would be quite acceptable for its large scale produc- tion. The nomenclature of ethylene urea is quite varied and it can be found in the literature under the following namess 2-keto-tetrahydroimida- zol (3); 2-keto-tetrahydroglyoxaline, tetrahydroiminazolone-2 (4); N'N'Ethylene Urea, 2-oxo-imidazolidine, Imidazolidone-2 (5); ethylene car- bamide (6); dihydro-2(3)-imidazolone (7). (2) Picatinny Arsenal, Dover, N. J., Communication to the Ordnance Depart- ment, Ga. Schoal of Technology, Feb. 1938. (3) Dictionary of Organic Compounds, Heilbron, Bunburg and Jones, Vol. II, 32. (4) Richter's Lexicon, Vol. I, p. 105. (5) Beilstein, 24, 2, system number 3557. (6) Fischer and Koch, Annalen, 232, 222-228 (1886). (7) Handbook of Physics and Chemistry, 22nd Edition, p. 768. 2 There are at least three isomeric compounds which appear in the literature, all of which have been well characterized. The first of these NH / \ is ethylidene urea, 0=C CH-CH3, melting point 154 ° (8). The second is \NH / CH2-0 CH2-0 \ ethylene pseudo urea, ,,CaINH or C..E112 (9), melting point CH2-NH CH2-N" (A) (B) 190-8 ° . This compound is also known as ethylene isourea or the imid of the Mu oxazolidons in the case of A and the Mu amino oxazolin in the case CHI}-- C-0 of B (10). The third is 3(or 5)-oxo-pyrazolidine, ( , a liquid CH2-NH-NH with boiling point of 133-35 ° (11). Ethylene urea has been well characterized and a survey of the existing literature shows it to possess the following properties: Molecular weight 86.05, m.p. 131 ° , crystallizes in white needles from water or chlo- reform, is soluble in water, hot alcohol and chloroform, and is insoluble in ether, carbon tetrachloride, carbon disulfide, and petroleum ether. It forms a dinitro derivative with fuming nitric acid, without the evolution of a gas, according to the equations CH2-NH % CH2-N(NO2) \ C=0 f HON% --e• 1 C=0 H2O CH2-NH' 0H2-N(NO2)" The produot crystallizes in prisms from alcohol and melts with decomposition at 210 4 (12). On boiling with water it decomposes into CO2 and dinitro- ethylene diamine. It can be found described in the literature as ethylene dinitrourea, N-10-di-nitro ethylene urea or 1-3-dinitro-imidazolidone-(2),(12). (8) Annalen der Chemie, 151, 204. (9) Gabriel, Berichte,2, 2 1150 (1889). (10) Lehbruch der Organisehen Chemie, Tweiter Band, Dreiter Teil, p. 523. (11)v Rothenburg, Journal fur Praktische Chemie 1 2 51, 72. (12) Franchimont and Klobbie, Recueil des travaux chimiques des Pay-Bas, 7, 6 and 243. 3 Recently a method for preparing this derivative has been patented by H. A. Aaronson (13), in which he avoids the use of the fuming nitric acid by using a mixed acid of 68% H2804, 22.5% HNO3 and 9.5% H20. This investigator claims a 92% to 95% yield for his method, if the time for nitration is continued at least two hours, and the temperature is kept be- low 10 0 . At higher temperatures (up to 30 ° ) the time required for the formation of the product is less, but the yields are not as favorable as those produced at the lower temperatures. The melting point as found by Aaronson and Rinkenbach (14) is 206 ° , which is in fair agreement with that of Franchimont and Ylobbie (210 ° ). Aaronson and Rinkenbach have also found the compound to possess valuable explosive properties and have patented its use as an explosive mixture. When heated it undergoes explosion in five seconds at 235 ° to 240° . When heated at 120 ° it was found to be very stable, as it liberated but little gas in the course of heating for forty hours. It is soluble in acetone, but almost insoluble in ether, alcohol, benzene, carbon tetra- chloride, and ethylene dichloride, and very slightly soluble in water (13). In addition to this dinitro derivative, ethylene urea forms a picrats (15), a micro-crystalline powder, soluble in hot water and hot alcohol, with a melting point of 207-209 ° . P. A. TrUbsbach (16) has published a paper on the conductivity of some five membered ring compounds and he has found that aqueous solutions of ethylene urea will conduct an electric current. (13) Henry A. Aaronson, U. S. Patent #2,149,260, March 7, 1939. (14) H. Rinkenbach and H. A. Aaronson, U. S. Patent #2,167,679. (15) Beilstein, 24, 2, System Number 3557. (16)P. A. Trubsbach, Zeitschrift fur Physikalische Chimie, 111 710. 4 An interesting and somewhat peculiar phenomenon is the formation of ethylene diurethane, CH-CHe - - NH NH I I H5C200C COOC2H5 when the reaction mixture of ethylene diamine and diethyl carbonate, after refluxing for six hours, is distilled at 30 mm. pressure. This reaction or change was first observed by Fischer and Koch (17) and has since been confirmed by Franchimont and Klobbie (18). The conditions for this re- action are essentially the same as given by all these authors, but during the present study it has been found that the diurethane may even be formed without distillation at reduced pressure. For example, the diurethane and not ethylene urea was the mein product formed in every case, when ethylene diamine aria: diethyl carbonate were refluxed under variable conditions. These conditions were such that the time of reflux varied from eight to forty hours and the temperature varied from 140 ° to 165°, though held con- stant during any one refluxing period. This fact was disclosed through experiments designed to check the method of Fischer and Koch (1) for the synthesis of ethylene urea. Equi- molecular portions of ethylene diamine and diethyl carbonate were refluxed for various periods as shown above and in each case the product was always ethylene diurethane and not ethylene urea. This fact constitutes a modi- fication to the existing methods of preparation (18) for this compound, and particularly to that of Fischer and Koch (17) in which they specify distil- lation at 30 mm. pressure. Moreover, it has been found that the reaction of Fischer and Koch (1) for the synthesis of ethylene urea is limited to (17) Fischer and Koch, Annalen der Chemie, 232, 228. (18) Franchimont and Klobbie, Recueil des travaux des Pays-Bas, 7, 260. 5 six hours of reflux, when an equimolecular mixture of ethylene diamine and diethyl carbonate is used.