Patented Nov.

18, 1947 2,430,874

UNITED STATES PATENT OFFICE

2,430,874
PRE PARATION OF ETHYLENEUREA
George C. Hale, Dover, N. J.
No Drawing. Application March 1, 1944,
Serial No. 524,575
6 Claims. (CI. 260-309)
(Granted under the act of March 3, 1883, as
amended April 30, 1928; 30 O. G. 757)
1. 2
The invention described herein may be manur are typical of the type of reaction wherein an
factured and used by or for the Government for ethylene derivative and ammonium carbonate are
governmental purposes, without the payment to reacted:
me of any royalty thereOn. (1) NHCH
This invention relates to the preparation of
ethyleneurea, a compound from which explosives '''
CHO -- ((NHoco
4)2 3 -Hard OsC / -- 4H. O
of special value can be derived. The compound NICE
ethyleneurea has received very little attention in Ethyleneglycol -- ammonium carbonate - ethyleneurea
the past. Its synthesis was first reported by
Fisher and Koch in 1885, who prepared it by di O (2) NHCH
gesting ethylenediamine and ethyl carbonate at (ENH,
CENE -- (NH4)2CO
(NH4)2COs - Oa-C / 2
-- 2NEI3 2HO
- 2H
a temperature of about 180° C. It is also report ECH
ed in the chemical literature to have been formed Ethylenediamine
by electrolysis of parabanic acid, by desulphuring (3) Ca NHH,
ethylene thiourea with mercuric oxide, and by s
O -- (NH4)2CO3 - O=C -- 3H2O
heating water solutions of ethyleneguanidine or
ethylenediisocyanate. C YH
I have studied the original process of Fisher Ethyleneoxide
and Koch in great detail with a view to estab The Conditions under which these reactions
lishing the most favorable conditions for the pro 20
are carried out may be those which will affect the
duction of ethyleneurea by this process. While Combination since it has been found that the
this effort was successful in producing a con product ethyleneurea, is obtained. When the ann
pound of satisfactory purity, it was objectionable monium carbonate and a selected ethylene de
because of the relatively high cost of the reac rivative are reacted in a closed vessel at elevated
tants. Obviously, it is impossible to produce a temperatures with superatmospheric pressure
compound cheaply if all of the materials used in being thereby produced. With other selected
its preparation are expensive.
Owing to special interest in certain compounds ethylene derivatives, the reactions are best car
derived from ethyleneurea, I have given much ried out at atmospheric or even reduced pressure
thought and effort to methods for the preparation 30 in order to eliminate the ammonia, produced in
of the atter which would involve the use of cheap the Course of the reaction. It Will be noted that
er or more readily available raw materials than in two of the above reactions cited, water is pro
those previously used in preparing the compound. duced While in the other ammonia and Water re
The idea, Was conceived that if ammonium car sults in addition to the ethyleneurea.
bonate, which is commercially available at low It has been found in carrying out the reactions
cost, could be used as a starting material, a Sub in which ammonia is produced, it is desirable to
stantial reduction would be gained in the cost of remove the ammonia, as completely as possible as
it is formed.
preparing ethyleneurea, and, hence, in the cost The following example is typical of the reaction
of its derivatives. There is no record SO far aS between ammonium carbonate and an ethylene
I am aware, that ethyleneurea has ever been 40 derivative.
synthesized from ammonium carbonate and, in Two hundred and ninety-one grams of ethylene
fact, no record that such a Synthesis was ever diamine and 480 grams of ammonium carbonate
attempted.
I have devised a procedure whereby ammoniuin were slowly mixed and when frothing ceased, the
carbonate can be used as a starting material for 45 mixture Was heated in a flask placed in an oil
the production of ethyleneurea, this new process bath and connected to a reflux condenser. The tem
offering great possibilities for the preparation of perature of the mixture was gradually raised to
the compound from these cheap, commercially about 145 C. and held at this point for several
hours. Upon removing the source of heat and
available chemicals. Thus, I have found that by cooling the flask to room temperature, a viscous
reacting ammonium carbonate With ethylene de 50 liquid mass was obtained. This mass was then
rivatives, such as for example ethyleneglycol, extracted with alcohol, and from the residue ob
ethylenediamine or ethyleneoxide, the desired tained by distilling off the alcohol, a white crys
compound ethyleneurea can be produced. The talline compound was obtained having a melting
reactions involving ammonium carbonate and point of 131° C., which agrees closely with the
certain desired ethylene derivatives follow, which 55 melting point of 131.8 C. for pure ethyleneurea.
 2,430,874
3 4.
It was further identified as such by the method 4. In a process for the preparation of ethyl
of mixed melting points and also by the method of eneurea, the steps comprising, forming a mixture
mixed fusion of the crystals from the experiment comprising ammonium carbonate and ethylene
with a known pure Sample of ethyleneurea. diamine, heating the mixture to a temperature
Since the process for producing ethyleneurea, of about 145° C., cooling the mixture and extract
by reaction between ammonium carbonate and ing ethyleneurea by treatment with a solvent.
ethylene derivatives was first conceived by me and 5. The process for the preparation of ethylene
means for accomplishing this general type of re urea, which comprises heating annonium car
action demonstrated by me, I do not Wish to be bonate with ethyleneoxide.
limited as to the details of the means, the basic in O 6. The process for the preparation of ethylene
gredients involved in the reaction or the methods urea, which comprises heating ammonium car
for conducting the reactions since it is obvious bonate with ethyleneglycol.
from the above that the reactions Will proceed GEORGE C. HALE.
under various detailed conditions.
I claim: 5 REFERENCES CTE)
1. The process for the preparation of ethylene The following references are of record in the
urea which comprises heating ammonium car file of this patent:
bonate with a material selected from the group UNITED STATES PATENTS
consisting of ethyleneglycol, ethylenediamine,
and ethyleneoxide. 20 Number Name Date
2. The process for the preparation of ethylene 2,276,696 Olin -------------- Mar. 17, 1942
urea, which comprises heating a mixture compris
ing ammonium carbonate and ethylenediamine. OTHER REFERENCES
3. The process as defined in claim 2 in which Fisher-Koch, Annalen, vol. 232, page 227 (1886).
Said heating is carried out at a temperature in 25 Chem. Abstracts, Vol. 32, page 488, citing: An
the neighborhood of 145° C. nalen der Chennie, vol. 532, pages 300-301 (1937).