Efficient and Green Preparation of 2-Imidazolidinone using Sulfamic Acid as Acidic Catalyst

Full text of DOI:10.1080/00304948.2014.944406

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Organic Preparations and Procedures
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Efficient and Green Preparation of 2-
Imidazolidinone using Sulfamic Acid as
Acidic Catalyst
Jianshe Liua, Yaqiang Xiea, Liyi Yea, Huidong Yana & Song Tua
a Department of Chemical and Biochemical Engineering, College of
Chemistry and Chemical Engineering, Xiamen University, Xiamen
361005, P. R. China
Published online: 15 Sep 2014.
To cite this article: Jianshe Liu, Yaqiang Xie, Liyi Ye, Huidong Yan & Song Tu (2014) Efficient
and Green Preparation of 2-Imidazolidinone using Sulfamic Acid as Acidic Catalyst, Organic
Preparations and Procedures International: The New Journal for Organic Synthesis, 46:5, 453-456,
DOI: 10.1080/00304948.2014.944406
To link to this article: http://dx.doi.org/10.1080/00304948.2014.944406
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Organic Preparations and Procedures International, 46:453–456, 2014
Copyright © Taylor & Francis Group, LLC
ISSN: 0030-4948 print / 1945-5453 online
DOI: 10.1080/00304948.2014.944406
OPPI BRIEF
Efficient and Green Preparation
of 2-Imidazolidinone using Sulfamic Acid
as Acidic Catalyst
Jianshe Liu, Yaqiang Xie, Liyi Ye, Huidong Yan, and Song Tu
Department of Chemical and Biochemical Engineering, College of Chemistry
and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China
Increasing global concern has led the governing bodies of many countries to establish and
enforce laws to safeguard the environment and encourage the development of environ-
mentally conscious processes (Principles 7–9 of the UN Global Compact).1 Urea deriva-
tives have extensive applications such as corrosion inhibitors, antioxidants in gasoline,
and intermediates for pharmaceuticals and agrochemicals.2,3 Among urea derivatives, 2-
imidazolidinone is widely used as an intermediate for the synthesis of medicines, toiletries,
cosmetic products,4 and as delignification solvent and chemotherapeutic agents.5,6 It is also
the key intermediate in the synthesis of 1,3-dimethyl-2-imidazolidinone, which is one of the
most widely used aprotic solvents in electrochemistry.7 It has been traditionally synthesized
by the reaction of 1,2-ethylenediamine (EDA) with phosgene, triphosgene, or carbon diox-
ide. This reaction requires high pressure and leads to major toxicological and environmental
problems when phosgene is used.8–10 In addition to the need to use expensive raw materials,
many of the catalysts are expensive and harmful to human health. Accordingly, alternative
routes involving EDA reaction with urea11 and organic carbonates (such as dimethyl car-
bonate, diethyl carbonate, ethylene carbonate, and bis(p-carbomethoxylphenyl)carbonate)
have been developed.3,6,12–14
Dimethyl carbonate (DMC) is a safe, low-cost, green and eco-friendly alternative
reagent1,15 to phosgene and other carbonylating agents. Recently, sulfamic acid (NH2SO3H)
has been reported as a substitute for conventional acidic materials in catalytic and organic re-
actions because of its unique characteristics (non-toxicity, efficiency, and recyclability).16–18
We now report the use of NH2SO3H as a catalyst in the efficient synthesis of 2-
imidazolidinone from EDA and DMC in 70% yield under optimal reaction conditions
determined in this investigation.
Submitted by January 14, 2014.
Address correspondence to Song Tu, Department of Chemical and Biochemical Engineering,
College of Chemistry and Chemical Engineering, Xiamen University Xiamen 361005, P. R. China.
E-mail: tusong@xmu.edu.cn
453

454
Tu et al.
Our efforts toward the synthesis of 2-imidazolidinone (5) focused on the use of sulfamic
acid because of its known reactivity.18 A series of experiments conducted to optimize the
reaction conditions suggested that the reaction process proceeds as shown in Scheme 1.
Scheme 1
As a result of these experiments, it was established that the reaction is best con-
ducted in two-stages of heating as illustrated in Scheme 1. It was found that an increase
in the ratio of DMC to EDA from 1.2 to 2.0 equiv. had a negligible effect on the yield.
Heating the reaction mixture for three hours at 50◦C led to the maximum production of N-
carbomethoxyethylenediamine (3) as the major product, N,Nꢀ-bis-carbomethoxyethylene
diamine (4) being formed in minor amounts; longer heating promoted increased formation
of 4 which in a separate experiment, was shown to react with 2-imidazolidinone (5) to give
N-methyl-2-imidazolidinone (6) and a small amount of 5 (thus not net increase in the yield),
However, 4 was recovered, unreacted, when heated in the presence of the catalyst sulfamic
acid only. The second stage of heating carried out at 160◦C for 15 h (longer heating led to a
decrease in yield and formation of unknown by-products), converted 3 to the final product
5 (plus a very small amount of 6) and was accompanied by the gradual disappearance of
4 as a result of its reaction with the product to give N-methyl-2-imidazolidinone (6) as
mentioned above (Scheme 1).
In conclusion, an efficient and green method for the synthesis of 2-imidazolidinone (5)
from EDA and DMC using sulfamic acid as catalyst was developed. Mechanistic studies
showed that 2-imidazolidinone was produced through two pathways. The proposed method
appears suitable for industrial application and has the potential to be useful in the preparation
of other urea derivatives.
Experimental Section
1,2-Ethylenediamine (>99%), sulfamic acid (>99%) were obtained from Sinopharm
Chemical Reagent Co., P. R. China. Dimethyl carbonate (>98%) was purchased from
Tianjin Guangfu Fine Chemical Research Institute, P. R. China. All other reagents and
solvents are of analytical grade and were used without further purification unless indicated.
The autoclave [100 ml, fitted with a thermocouple, a magnetic stirrer and a pressure gauge
(the pressure range from 0 to 60 bar)] was manufactured by Zhenjiang Global Electrical

Preparation of 2-Imidazolidinone using Sulfamic Acid as Acidic Catalyst
455
and Mechanical Parts Factory. Melting points were determined with a Tech X-6 micro-
melting-point apparatus manufactured in Beijing, P. R. China and are uncorrected. The 1H
and 13C NMR spectra were recorded in CDCl3 solution on a Bruker 400 MHz spectrometer
with TMS as the internal standard.
Preparation of 2-Imidazolidinone
A mixture of 1,2-ethylenediamine (3.0 g, 0.05 mol), dimethyl carbonate (5.4 g, 0.06 mol),
sulfamic acid (1.0 g, 0.01 mol) and 4.5 ml of methanol in an autoclave (100 ml, fitted with
a thermocouple to measure the temperature and a magnetic stirrer, at 20–60 bar)19 was
heated to and kept at 50oC for 3 h (CAUTION!). The internal temperature was then raised
to 160oC and maintained at that temperature for 15 h. After that time, heating was stopped
and the system was allowed to cool to room temperature. The low boiling point substances
were distilled off under vacuum (7.5 mm Hg). Then, acetone (15 ml) was added to the solid
residue and the suspension was stirred for 10 minutes at room temperature. The suspension
was filtered to remove insoluble material and the filtrate was distilled off under vacuum
(7.5 mm Hg) to give 3.0 g (70%) 2-imidazolidinone as a white solid, mp. 130–132◦C, lit.20
mp. 130–131oC. 1H NMR (400 MHz, CDCl3): δ 3.53 (s, 4H, CH2), 5.37 (s, 2H, NH); 13
NMR (100MHz, CDCl3): δ 40.94, 165.35.
C
Acknowledgment
This work was supported by National Nature Science Foundation of China Grant (No.
21106119) and the Fundamental Research Funds for the Central Universities, P. R. China
(No. 2011121019).
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