[CONTRIBUTION

FROM THE DEPARTMENT-CHEMICALS OF E. I.

POLYCHEMICALS DU PONT
DE NEMOURS
AND COMPANY,INC.]

ETHYLENEUREA. I. SYNTHESIS FROM UREA AND

ETHYLENEDIAMINE
CARL E. SCHWEITZER
Received August 16,1949

Starting in December, 1941, at the request of the National Defense Research

Committee, methods were developed for the synthesis of ethyleneurea, 2-imid-
azolidone.' Results of this investigation indicated several possibilities for com-
mercial scale production, and removal of security restrictions has made it possible
to describe these developments in a series of papers of which this is the first.
When this investigation of an ethyleneurea synthesis was begun, there were
several preparative methods in the literature (1-5), but each of these was sub-
ject to certain limitations, judged by the requirements of a commercial process.
However, other theoretically possible routes were apparent and of these, four
were developed which were based upon the reactions of:
(A) Ethylenediamine with carbon dioxide
(B) Ethylenediamine with urea
(C) Ethylene glycol with urea or with ammonia and carbon dioxide
(D) Ethanolamine with urea
Starting with ethylenediamine and carbon dioxide as indicated in (A) above,
excellent yields (ca. 98y0) of ethyleneurea were obtained a t elevated tempera-
tures and pressures. However, this reaction, studied independently at about the
same time by others ( 6 ) , has already been described. Results were comparable
with those obtained in this laboratory.
The reaction of ethylenediamine with urea, which is the subject of this paper,
likewise proved to be a highly satisfactory method for synthesizing ethyleneurea.
It may be carried out in one step a t atmospheric pressure with yields of 98% or
better. Because operation by this route is relatively simple, it is of interest both
commercially and as an especially attractive laboratory procedure. After this
work had been completed, it was found that the ethylenediamine-urea reaction
had been tried, but the yield of ethyleneurea was less than 10% (7). Here the
important role of water as a, moderator for the reaction was not recognized. This
probably accounts for the marked difference.
Using ethylene glycol and urea (or carbon dioxide and ammonia in place of
urea) or ethanolamine and urea (C or D) it was possible to obtain ethyleneurea in
good yields and the results of these phases of the studywill be presented in papers
to follow.2
OSRD contract KO.OEMsr-373.
The following patents have been granted which pertain to certain aspects of the ethyl-
eneurea problem: Dittmar and Loder, U. s. Patent 2,416,046; Larson and Loder, U. s.
Patent 2,416,057; Loder, U. S. Patent 2,245,627; Larson, Loder, and Dittmar, C . S. Patent
2,436,311; Loder, U. S. Patent 2,474,004.
471
472 CARL E. SCHWEITZER

ETHYLENEDIAMINE-UREA REACTION

Urea undergoes reaction with a variety of amines to produce alkyl-substituted

ureas (8), and with diamines to yield polyalkylureas (9). It has now been found
that urea and ethylenediamine will react to give ethyleneurea in high yields pro-
vided water is present as' a moderator.
+
N H ~ C H Z C H ~ N HNHzCONHz
~ + NHCHzCHzNHCO + 2NH3
Thus, an equimolar mixture of urea and aqueous ethylenediamine (68% dia-
mine, 32% water by weight) was permitted to reflux while water was removed
slowly and ammonia, liberated by the reaction, was allowed to escape. The mix-
ture changed from a liquid to a thick pasty mass and finally again to a clear melt
of substantially pure ethyleneurea in nearly quantitative yield. With no sacrifice
in yield it was possible to maintain a reasonably fluid charge if a 5-20% molar
excess of the diamine-water azeotrope was used. This excess diamine was
separated by vacuum-distillation from the final product.
If water is not removed as the reaction proceeds, the relatively low reflux tem-
perature retards the desired reaction but permits a partial hydrolysis of urea.
This reduces the yield of ethyleneurea. Under these conditions the chief product
appears to be crude 2-aminoethylurea which upon further heating is converted
partly to ethylenediamine and partly to a white unidentified high-melting solid.
If water is omitted from an equimolar charge of ethylenediamine and urea, the
anhydrous materials react slowly to liberate ammonia until a temperature of
about 140" is attained. At this point an extremely vigorous reaction occurs which
produces a white solid melting near 270". In one case the reaction was violent
enough to eject the thermometer and part of the solid from the flask.
Attempts to accelerate the reaction by replacing water with higher-boiling
liquids such as n-butyl alcohol, dimethylformamide or methoxymethoxyethanol
resulted in high-melting, unidentified products rather than ethyleneurea. If,
however, the desired higher temperature is attained by operating under pressure,
the reaction is accelerated and satisfactory yields of ethyleneurea may be
obtained in an aqueous system. At 245-275" the reaction is complete within an
hour.
At ordinary temperatures ethyleneurea is a white, neutral solid which is odor-
less when pure. It melts at 133.7" (corr.); [lit., 131" (1, s)]and may be distilled
a t 163"/3 mm.; 187"/10 mm.; 192"/16 mm. The last value is in good agreement
with the one published boiling point (6). Crystallized from a water solution, it is
obtained as the hemihydrate which at room temperature effloresces slowly to the
anhydrous form.
There are two crystalline modifications with a transition temperature of about
80". Optical constants, obtained under the petrographic microscope by the
method of Bryant (lo), are as follows:
ETHYLENEUREA (anhydrous)
Biaxial (+). Refractive indices (25 =!= 3"; 5461 8):a = 10.537, P = 1.563, y =
1.694; all k0.003. Optic Axial Angles: 2H, = 57" (4358 A); 59" (5461 8);60"
 ETHYLENEUREA. I 473

(6908 A); all &lo.Second anhydrous modification (unstable at room tempera-

tare) is uniaxial (+),
ETHYLENEUREA HEMIHYDRATE

Uniaxial (+). Refractiveindices (25 f 3"; 5461 A): m e g a = 1.521 ~k0.003,

epsilon > 1.56.
Solubilities in several solvents at different temperatures are given in Table I.
EXPERIMENTAL
Synthesis of ethyleneurea at one atmosphere. A mixture composed of 732 g. of the ethylene-
diamine-water azeotrope [498 g. (8.3 moles) of ethylenediamine and 234 g. (13 moles) of
mater] plus 498 g. (8.3 moles) of urea, was charged into a two-liter, three-necked, round-
bottom flask. The flask was fitted with a sturdy stirrer, a thermometer, and a 20 mm. X 60
cm. Vigreux column carrying a condenser which could be set for various reflux ratios.
TABLE I
OF ETHYLENEUREA
SOLUBILITIES
SOLVEhT
II TEm., D C .
II SOLUBILITP

Water 8 41
35 60
56 75
Methanol 64 79
Ethanol 25 ca. 23
n-Butanol 25 < 10
Chloroform 61 20
Acetone 0 c0.2
25 2
56 3-4
a Expressed as grams of anhydrous ethyleneurea per 100 grams of solution.
Contents of the flask were stirred and heated to vigorous reflux. During a four-hour period,
liberated ammonia was allowed t o escape and water was slowly removed from the top of
the column so that the temperature of the reaction mixture rose from 110' t o 24.0-250'.
At the end of approximately three hours, when the temperature had reached 160-180',
the mixture became quite pasty and rather difficult to stir, but during the final hour i t
changed to a clear, pale amber liquid. This, upon cooling, solidified to give 710 g. of ethyl-
eneurea, m.p. 127-131' (yield, 99+%). One recrystallization from chloroform brought the
melting point to 130-131' and by repeated recrystallizations from chloroform and from diox-
ane the melting point was raised to 133.7' (corr.).
Synthesis of ethyleneurea under pressure. A charge comprising 87.9 g. of the water-ethyl-
enediamine azeotrope [containing 60 g. (1.0 mole) of diamine] plus 60 g. (1.0 mole) of urea,
mas heated a t 250' in an agitated, silver-lined, steel bomb of 325-cc. capacity at a pressure
of 160 atmospheres for one hour. The resulting product was distilled at reduced pressure to
remove volatiles, including water and 10% of the charged ethylenediamine. Ethyleneurea,
66.6 g., remaining as the residue melted a t 119-125' and represented a yield of 85% based
upon the diamine and 77% based upon urea. When recrystallized from chloroform it had
m.p. 129-131'.
SUMMARY
A practical laboratory procedure is reported for the synthesis of ethyleneurea
in nearly theoretical yield from urea and ethylenediamine in the presence of water
474 CARL E. SCHWEITZER

as a moderator. Variables affecting yields are discussed and certain physical

properties of ethyleneurea are recorded.
WILMINGTON98, DELAWARE
REFERENCES
(1) FISHERAND KOCH,Ann., 232,277 (1886).
(2) KLUT, Arch. Pharm., 240, 677 (1902).
(3) TAFEL AND REINDL,Ber., 34, 3286 (1901).
(4) PIERRON, Ann. chim., 191 11, 361 (1919).
(5) PUSCHINAND MITIC,Ann., 632, 300 (1937).
(6) MULVANEY AND EVANS, Ind. Eng. Chem., 40, 393 (1948).
(7) HANSEN,Masters Thesis, Massachusetts Institute of Technology, 1939.
(8) DAVIS,U.5. Patent 1,785,730;OLIN,U. 5. Patents 2,257,717 and 2,253,528.
(9) ARNOLD, U.S. Patent 2,145,242.
(10) BRYANT,J. Am. Chem. SOC.,60, 1394 (1938);J . Am. Chem. Soc., 63, 511 (1941).
[CONTRIBUTION
FROM THE POLYCHEMICALS OF E. I.
DEPARTMENT-CHEMICALS DU POST
DE NEMOURS
AND COMPANY,
h-c.]

ETHYLENEUREA. 11. SYKTHESES FROM ETHYLENE GLYCOL OR

ETHANOLAMINE AXD UREA (OR CARBON DIOXIDE
AND AMMONIA)
CARL E. SCHWEITZER
Received August 15, 1949

Of the several routes to ethyleneurea, explored in 1941 a t the request of the

National Defense Research Committee' and summarized briefly in the initial
report of this work,2 those based on ethylene glycol and urea (or carbon dioxide
and ammonia) or ethanolamine and urea are the subject of this paper.
Urea can react with glycols to produce carbamate esters without formation
of a C-N bond, Thus a t 100-200", urea and 1,3-butylene glycol yield the cor-
responding mono- and di-carbamates (1). Similarly, urea and ethanolamine pro-
duce 2-hydroxyethylurea without amination of the carbon skeleton (2).
During this investigation, however, conditions were found under which urea,
or carbon dioxide and ammonia, could be made to aminate either ethylene glycol
or ethanolamine to produce satisfactory yields of ethyleneurea. This work repre-
sents an extension of urea chemistry and is reported here in detail. Patents have
been granted which pertain to certain aspects of the pr~blern.~ Of the reactants
cited above, urea and ethylene glycol were selected for most thorough study be-
cause these raw materials were readily available a t low cost and could be made to
react a t atmospheric pressure.
ETHYLENE GLYCOL AND UREA AT ONE ATMOSPHERE

The synthesis of ethyleneurea from urea and ethylene glycol was achieved
most satisfactorily in two steps. In the first step, ethylene glycol and a several
molar excess of urea were heated gradually from 150 to 240" during a period of
several hours. Ammonia and carbon dioxide were evolved and the product was
a liquid which set to a brittle resinous solid when cool. Pyrolysis of this resin a t
240-270" under reduced pressure resulted in the formation of some ethyleneurea
(yield, based upon ethylene glycol, 25%), but a substantial portion decomposed
to a carbonaceous product. If, as the second step, the resinous intermediate was
hydrolyzed a t about 250", the yield of ethyleneurea was more than
doubled (55%).
Course of the reaction. In Table I, data are presented from two typical experi-
ments which show the relative rates of formation of ammonia and carbon dioxide.
These data serve t o indicate a possible course of the urea-ethylene glycol reac-
tion. Clearly, the synthesis of ethyleneurea did not proceed through simple elim-
ination of two moles of water from an equimolar mixture of reactants for there
1 OSRD Contract KO.OEmsr-373.

* Ethyleneurea I. (Preceding paper).

3 Dittmar and Loder, U. S. Patent 2,416,046; Larson and Loder, U. S. Patent 2,416,057;
Loder, U. S. Patent 2,425,627; Larson, Loder, and Dittmsr, U. S. Patent 2,436,311; Loder,
U. S. Patent 2,474,004.
475
476 CARL E. SCHWEITZER

was no evidence that water per se was obtained from the reaction. Indeed, it did
not appear to be even a primary product since, if it had been and if it had reacted
with urea, then the quantity of carbon dioxide relative to ammonia would have
been much higher in the early stages of the reaction. From the very large quan-
tity of ammonia evolved it appeared that the primary product was a carbamate.
This carbamic acid ester of ethylene glycol subsequently lost carbon dioxide with
formation of the desired C-N bond as indicated by the following equations:
HOCH2CH20H +
2 NHzCONHz -+ NH2COOCHZCH20CONH2 2 KHa +
NHzCOOCHzCHzOCONH2 + N H z C H ~ C H ~ X H 2~ COz +
TABLE I
OF AMMONIAAND CARBON
RATESOF FORMATION DIOXIDE
VARIATION WITH TIhCE OF COMPO-
MOLE RATIO: TOTAL TIWE, SITION I N HOLES cot/
Y0LF.S &OLE3 " I / KOLES "I/
TEm.,'C. GLYCOL OLYCOL UREA
WEAiGLYCOL HOURS
CHARGED CHARGED CHABOED
Urea Glycol Biuret
--
3.5 0 156 21 .o 6.0 0.0 0.0 0.0 0.0
1.o 162 14.5 2.75 1.71 .14 0.96 .2s
2 .o 169 10.2 1.51 2.04 .36 1.74 .50
3 .O 171 8.45 0.79 2.06 .67 2.38 .65
4.0 176 6.1 .43 2.10 * 94 2.86 .82
5.0 181 4.65 -20 1.94 1.13 3.36 .96
6.0 222 0.96 .03 1.S5 1.53 4.20 1.20
7.0 275 .13 .02 0.91 1.87 4.84 1.38
8.0 260 .13 .01 .o 1.84 4.86 1.39

4.15 0 160 0.0 0.0 0 .o

1.o 170 .16 1.41 .34
2.0 172 -53 2.34 .56
3.0 175 .88 3.41 .82
4.0 181 1.13 3.72 .89
5.0 200 1.53 4.35 1.04
6.0 240 1.81 5.28 1.27
7.0 240 1.98 5.40 1.30

Once ethylenediamine had been formed, it could react with urea to produce the
resinous ethyleneurea intermediate.
The data of Table I were obtained in typical experiments in which the evolved
gases were analyzed continuously. This was accomplished by passing them
through standard sulfuric acid to remove ammonia and then through soda-lime
or through standard sodium hydroxide to absorb carbon dioxide. Aliquots of the
liquid charge were removed periodically and subjected to analyses for urea by a
method using urease (3), biuret by a colorimetric method based upon the purple
copper complex formed in alkaline solution (4),and free ethylene glycol by either
the periodate method ( 5 ) or by titration with Karl Fischer reagent of the water
released on esterification (6).
During early stages of the reaction biuret accumulated. This, of course, arose
 ETWLENEUREA. I1 477

from rapid reaction of urea with itself, but it accounted for a relatively small por-
tion of the ammonia liberated early in the reaction. As the reaction progressed
this biuret was consumed.
Ratio of urea to glycol. Variations in the mole ratio of urea to glycol, as might
be expected, have a pronounced effect upon the yield of ethyleneurea and upon
the character of the resinous intermediate. As shown in Table 11,the intermediate
changes from a clear, viscous liquid to a porous, opaque solid as the quantity of
'urea is increased. Yields of ethyleneurea, based upon ethylene glycol, increase

TABLE I1
EFFECTS
PRODUCED I N THE RATIO OF UREATO GLYCOL
BY CHANGES

RATIO YIELD OP E f B Y L E N E W E A , %
MOLES W E A : MOLE APPEARANCE OF INTEBMEDIATE:

I
GLYCOL
Based on glycol
Based On urea
1.0 2 2 Clear viscous syrup
2.0 23 11.5 Tacky, clear resin
3.0 38 12.7 Clear, brittle glass
3.5 39 11.1 Clear, somewhat porous glass
4.0 55 12.5 Opaque, porous, white solid
5.0 57 11.4 Opaque, porous, white solid

TABLE I11
EFFECTOF TIMEAND TEMPERATURE
ON YIELD

YXEW OF ETHYLENEUBEA
UPEA/GLYCOL YOLE RATIO OVER-ALL Tll53 AND TEhiPEBATURE RANGE
BASED UPON GLYCOL, %

3.0 "Standard"* 38
3.0 4.5 hrs.; 150-240" 26
3.0 9.5 hrs.; 175215" 15
3.5 "Standard" 39
3.5 4.5 hrs.; 150-240 10
5.0 "Standard" 57
5.0 3.5 hrs.; 16C-24Oo 56

with increase in urea, the sharpest rise occurring as the mole ratio changes from
3.5 to 4. The yield, based upon urea, remains about the same if the mole ratio is
two or greater.
Time and temperature. Changes in these variables have a pronounced effect
upon the yield of ethyleneurea which may be derived from ethylene glycol and
urea (after hydrolysis of resinous intermediates) and typical data are presented
in Table 111. Most satisfactory results-chemically, judged by yields, and
physically, judged by freedom from mechanical difficulties such as excessive
foaming-were obtained with charges which were heated at 160"to 240" for about
ten hours. The temperature was raised from 160" to 180" during six hours, 180"
to 240" during three hours and then maintained at 240" for one hour; this was the
478 CARL E. SCHWEITZER

"standard" schedule. If the same temperature range was observed but if the
over-all time was reduced to three or four hours, yields were lower than those
obtained with "standard" schedules and often there was troublesome foaming.
A final temperature near 240" was essential to effect complete evolution of car-
bon dioxide and to obtain maximum yields.
Attempted catalysis. A number of experiments were carried out to test the pos-
sible catalytic activity of substances such as potassium carbonate, cupric car-
bonate, ammonium chloride, ammonium sulfate, potassium silicate, boron phos-
phate, and silica gel, but in no case was there any indication that the reaction
could be catalyzed.
Water treatment of the intermediate. In order to recover the maximum quantity
of ethyleneurea, it was necessary to treat the resinous polymeric intermediate
with water. If the resin was reasonably fluid a t 234-270" it was possible to recover
ethyleneurea in high yield simply by passing superheated steam through it a t
these temperatures.
Resins obtained as products from mixtures in which the ratio of urea to glycol
was greater than 3.5 to 1 could not be steam-distilled readily because their vis-
cosities were too high. However, it was found that any of the intermediate resins
could be cleaved if they were heated with approximately an equal weight of water
to about 270" under autogenous pressures for twenty minutes to one hour. If
water treatment was carried out a t 300" or higher, ethyleneurea itself was hy-
drolyzed quite extensively and ethylenediamine was obtained.
ETHYLENE GLYCOL AND UREA UNDER PRESSURE

Investigation of the synthesis of ethyleneurea from glycol and urea under pres-
sure demonstrated that higher temperatures and therefore shorter reaction times
could be employed than at one atmosphere. Also, less urea was required
for a given yield of product, based upon glycol. Thus in three hours a t 275" and
about 400 atmospheres pressure, the yield of ethyleneurea was 47%; reducing the
reaction time resulted in lower yields. An increase in temperature permitted a re-
duction in reaction time, but a t 360", for example, substantial amounts
of ethanolamine and ethylenediamine formed a t the expense of ethyleneurea. In-
creasing the ratio of urea to glycol above four did not improve the ethyleneurea
yield.
ETHYLENE GLYCOL, AMMONIA, AKD CARBON DIOXIDE*

The direct synthesis of ethyleneurea from ethylene glycol, ammonia, and car-
bon dioxide under pressure was investigated until it became evident that rather
high pressures probably would be required. Best results (58% yield) were ob-
tained from a charge consisting of 1 mole of glycol, 8 moles of ammonia, 4 moles
of carbon dioxide, and 19 moles of water, which was heated for 30 minutes at 250"
Similarly, ethyleneurea was obtained when ethanolamine was used in place of ethylene
glycol. However, only a limited number of experiments were carried out so that optimum
conditions probablywere not found. Maximum yield was about 20% from a charge composed
of one mole of carbon dioxide, one mole of ethanolamine, and five moles of ammonia which
was processed a t 250' for 70 minutes under a pressure of 330 atmospheres.
 ETHYLENEUREA. I1 479

under a pressure of 900 atmospheres. If water was eliminated from a similar

charge the yield declined to 52%. Decreasing the pressure to 400 atmospheres
resulted in a yield of only 30%.
ETHANOLARIIKE AND UREA AT ONE ATMOSPHERE

Major attention mas devoted to syntheses of ethyleneurea based upon ethylene-

diamine or ethylene glycol, but reactions of ethanolamine were explored briefly.
I n general, there seemed to be no advantage over using ethylene glycol, consider-
ing availability of raw materials and their costs. Best results were obtained when
EL mixture of three moles of urea and one mole of ethanolamine was heated for
about nine hours a t 110" to 245' and the resinous intermediate hydrolyzed under
pressure. The yield of ethyleneurea was 55%, based upon ethanolamine, and
compared favorably to that obtained from four moles of urea and one mole of
ethylene glycol.
ETHANOLAMINE AND UREA UNDER PRESSURE

The reaction under pressure of ethanolamine and urea, preferably in excess

ammonia, was investigated only briefly. It was found to proceed rapidly to pro-
duce yields of approximately 38%, based upon the alkanolamine, at 300" and
about 900 atmospheres pressure.
EXPERIMENTAL
Ethylene glycol and urea at atmospheric pressure. A typical preparation of the intermediate
resin was carried out as follows: A mixture composed of 360 g. (6.0 moles) of urea and 93 g.
(1.5 moles) of ethylene glycol was placed in a three-neck, two-liter, round-bottom Pyrex
flask fitted with a ten-bulb reflux condenser, a thermometer, and an oil-sealed stirrer. The
stirrer was started and the temperature of the mixture was raised slowly from 160 to 180'
during 3 hrs., 18&240 during 3 hrs., and finally was maintained a t 240" for 1 hr. Ammonia
and carbon dioxide liberated by the reaction were allowed to escape through the reflux
condenser which was heated by steam to prevent formation of dangerous plugs of ammo-
nium carbonate. The product, a faintly cloudy, colorless white liquid, was poured into a
large evaporating dish while still hot. Upon cooling it set to a porous, opaque white solid
which weighed 172 g.
Ethyleneurea was obtained from this resinous intermediate by (a) direct thermal de-
composition or (b) water treatment. (a) Thermal decomposition. The product prepared above
(172 9.) was placed in a 500-cc. round-bottom Pyrex flask fitted with an air-condenser of
20-mm. glass tubing bent a t a 60' angle, in the manner of a glass retort. The air condenser
was connected to a water-cooled receiver attached to a vacuum pump. After the system
had been evacuated to about 1 111111. the polymer was heated to 240-2iO'. Ethyleneurea dis-
tilled from the polymer as it decomposed. Pyrolysis was continued until a rise in pressure
ndicated the formation of permanent gases. A total of 32.1 g. of ethyleneurea melting a t
125-132' was obtained; yield, based on ethylene glycol, 25%.
(b) Water treatment. A mixture of 150 g. of the intermediate resin, prepared as described
above, and 100 g. of water was charged into a silver-lined bomb of about 300-cc. capacity
and heated a t 250' under an autogenous pressure of 585 atm. for 2 hrs. The bomb was allowed
to cool and the liquid product was discharged. This was distilled at reduced pressure through
a, 20 111111. X 60 cm. Vigreux column. Water and a small quantity of ammonia were removed
at about 100 mm. pressure. The pressure was reduced and 76.5 g. of ethyleneurea distilling
a,t 160-170'/2-3 mm. was obtained. The crude product, which melted at 118-125", n-as
recrystallized from chloroform giving 60 g. of ethyleneurea, m.p. 128-131". Yield, based
upon glycol, 55%.
480 CARL E . SCHWEITZER

Ethylene glycol and urea under pressure. Two charges, each composed of 60 g. (1 mole)
of urea and 62 g. (1 mole) of ethylene glycol, were processed in similar silver-lined bombs of
325-cc. capacity at 275' and a pressure estimated to have been 400 atm. for 3 hrs. The bombs
were allowed to cool t o room temperature and discharged. The combined products were
distilled under reduced pressure and 35% of the ethylene glycol was recovered. Ethylene-
urea, b.p. 16&170'/1-2 mm., wm obtained which, after crystallization from chloroform,
amounted t o 51 g. for a net yield of 47%, based on ethylene glycol.
Ethylene glycol, ammonia, and carbon dioxide. Two charges, each composed of 46.6 g.
(0.75 mole) of ethylene glycol, 102 g. (6.0 moles) of ammonia, 132 g. (3.0 moles) of carbon
dioxide, and 18 g. (1.0 mole) of water were processed in silver-lined bombs at 250' for 30
min. under a pressure of 900 atm. The products were combined and distilled at reduced
pressure to give crude ethyleneurea which was purified by crystallization from dioxane.
The final product weighed 74.8 g. Yield, based upon glycol, 58%.
Ethanolamine and urea at atmospheric pressure. Equipment described above for the reac-
tion of ethylene glycol and urea at atmospheric pressure was used in this experiment. A
mixture of 720 g. (12 moles) of urea and 244 g. (4 moles) of ethanolamine was heated with
stirring according to the following schedule: 1 hr., 110-150'; 1 hr. 150-160'; 1.5 hrs. 160-195';
1.25 hrs., 195'; 2 hrs., 195-224'; and 2 hrs., 224240'. Ammonia and carbon dioxide were
permitted t o escape through the steam-heated reflux condenser and were passed through a
scrubber containing 200-400 cc. of water. The scrubber mas made from a 1-liter, 3-neck,
round-bottom Pyrex flask fitted with a stirrer and a gas inlet tube which dipped just below
the surface of the water. Ethanolamine (35 g.) which escaped with the gases was collected
in the scrubber and recovered by distillation. The product remaining in the reaction flask
weighed 465 g. When cool i t was a very viscous clear, amber liquid.
This liquid (370 8.) was hydrolyzed by heating it with an equal weight of water to 250'
for 2 hrs. in an agitated 800-cc. silver-lined bomb under an autogenous pressure of 925 atm.
The resulting product was distilled. Ethylenediamine in 10% yield, based upon ethanol-
amine, was obtained in the first fraction. The pressure was reduced and 155 g. of ethylene-
urea, m.p. 126-129', distilling at 170-180'/4 mm. was obtained; crude yield, 551,, based upon
ethanolamine.
Ethanolamine and urea under pressure. A mixture consisting of 60 g. (1.0 mole) of urea,
61 g. (1.0 mole) of ethanolamine, and 85 g. (5.0 moles) of ammonia was processed in a silver-
lined bomb a t 300' under a pressure of 930 atm. for 10 min. The product was distilled; 12.0
g. of ethanolamine was recovered together with 59 g. of crude ethyleneurea. One recrystal-
lization from chloroform gave 35 g., m.p. ca. 123'. Assuming this product t o be 7570 pure,
the net yield, based upon ethanolamine, was 38%.

SUMMrlRY

Procedures are reported for the synthesis of ethyleneurea from ethylene glycol
or ethanolamine either with urea or with ammonia and carbon dioxide. Pressure
and other variables affecting the reactions are discussed and a mechanism is sug-
gested by which amination of the carbon skeleton takes place.
98, DELAWARE
WILMINGTON
REFEREKCES
(1) LEOPOLD AND PAQUIS, German Patent 501,852; U.S. Patent 1,817,992.
(2) SIMONS,U. S. Patent 2,249,183.
(3) Fox AND GELDARD,I n d . Eng. Chem., 16, 743 (1923).
(4) FISCHER,Ber., 96, 1105 (1902).
(5) ALLEN,CHARBOXVIER, AND COLEMAN, I n d . Eng. Chem., A n a l . Ed., 12, 384 (1940).
(6) MITCHELLAND SMITH,Aquametry, Interscience Publishers, Inc., New York, New York,
1948, p. 277.