Advanced Materials Research Vols.

554-556 (2012) pp 764-767

Online available since 2012/Jul/26 at www.scientific.net
© (2012) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.554-556.764

An efficient synthesis of furil

Luyao Wanga, Dong Mengb, Lu Lic, Xin Caid

Department of Chemistry, Capital Normal University, Beijing, China
a
xdwly@163.com, b mingtianmengchen@163.com, c sysmul@163.com, d1206797035@qq.com

Keywords: furoin, furil, acyloin condensation, oxidation

Abstract: By employing thiamine (vitamin B1) as the catalyst, the synthesis of furoin from
furfuraldeyde has been developed. Furoin is oxidized to furil by Cu(OAc)2-NH4NO3 as an oxidant.
The reaction condition is optimized and the reaction mechanism is discussed in this paper. The
synthesized furoin and furil are characterized by means of Mass, IR and UV spectrum.

Introduction
Furil, also commonly known as 1,2-di(furan-2-yl)ethane-1,2-dione, is an important industrial
chemicals always used as building blocks for synthesis the many pharmaceuticals and luminescent
materials[1~4]. The general synthesis of furil involves the conversion of furfuraldeyde to furoin by
the acyloin condensation catalyzed with potassium cyanide, and oxidation of the latter to furil by
CuSO4 in pyridine. This method always leads to low yield, and requires handling of hazardous
cyanide residues[5]. Due to environmental concerns, there is increasing need and interest in
developing processes that minimize production of toxic waste. Thiamine (Vitamin B1) is attractive
candidates for use in these reactions because of no toxic[6]. In the present paper, we reported the
synthesis of furil by furfuraldeyde catalyzed with thiamine (VB1), then followed by oxidation with
Cu (OAc) 2 (catalyst amount) in the presence of NH4NO3. This method is friendly to environment
and provides furfuraldeyde to the corresponding furil in good to excellent yields.

The synthesis route is shown in Table 1.

Table 1. The Synthesis Route of Furil

Experimental

2.1. Instrumentation
Thin layer chromatography is carried out on silica gel (GF‐254) TLC plates. All melting points
are determined on a XT-4 melting point apparatus without correction. IR spectra are collected with
a Thermo Scientific Nicolet IS10 FT-IR spectrometer. UV spectra are collected with SHIMADZU
UV-2550 spectrometer. GC‐MS are recorded using a SHIMADZU QCMS-QP 2010 SE with
Rtx-5MS (30m * 0.25µm * 0.25mm) and electron impact ionization (EI).

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 Advanced Materials Research Vols. 554-556 765

2.2. Materials
All reagents are obtained from standard commercial vendors and used without further
purification. Furfuraldeyde is distilled under vacuum distillation before used.

2.3. Synthesis

2.3.1. Synthesis of furoin

Thiamine (VB1) (0.02 mol, 0.7 g), water (20 mL) and 95% alcohol (7.5 mL) are mixed under
ice-water bath cooling. Adjusted pH = 9 ~10 with 10% NaOH, distilled furfuraldeyde (0.050 mol,
4.8 g) is added into the above solution. The mixed solution is heated to 65~70˚C and stirred for
another 2h at pH = 9~10. The solid product generated is separated by filtration and purified by
recrystallization from 95% ethanol. The obtained product was a white needle crystal (3.6 g, 75%
yield). M.p.134 ~ 135℃ (Lit [6]:134~135˚C). IR (KBr): ν(cm−1): 3418 (νOH)，1680(νC=O)，
1498(νC=C), 1149~1037 (νC-O-C). UV (in methanol): λmax= 275nm, MS (m/z): M+ 192.

2.3.2. Synthesis of furil

CuSO4 (1.3mL 2%), NH4NO3 (0.02 mol, 1g) and 6.5mL glacial acetic acid are mixed. The
mixture was heated to 70 ~75 ˚C in oil bath with stirring. When the mixture become a
homogeneously blue solution, furoin (0.01 mol, 1.92 g) is added and refluxed for 1.5 h at 95~100˚C.
The product is separated by filtration. The filter cake is washed with 150 mL (5 x 30 mL) of cold
water, and then recrystallized from 95% ethanol. The product obtained is a brilliant yellow needle
crystal (3.05 g, 84% yield). M.p.165 ~ 166˚C (Lit [6]: 165 ~ 166˚C). IR (KBr): ν(cm-1)：3144(ν=C-H)，
1640(νC=O), 1488(νC=C), 1149~1026 (νC-O-C), UV(in methanol): λmax=301nm，MS(m/z): M+ 190.

Results and discussion

3.1. IR and UV spectrogram of furion and furil

Infrared spectrogram of the synthesized furion and furil are in accordance with the standard
spectrogram. For furil is di-carbonyl molecules, it has stronger conjugative effect than furoin (only
one carbonyl). IR spectrum of νC=O (furil) decreases from 1680 cm-1 to 1640 cm-1 compare with
νC=O (furoin), and UV spectrum of λmax(furil) changes from 275nm to 301nm compare with
λmax(furoin). It indicates that conjugate effects make the wavelength red shift.

3.2 Reaction mechanism from furion to furil

The reaction mechanism from furfuraldeyde to Furion Catalyzed with VB1 is shown in Table 2. The
catalytic reaction involves removal of proton from 2-position of thioring by base to form the ylide 2,
2 attacks a molecule of furfuraldehye to give 3, 3 undergoes a proton transfer to form 4, 4 attacks
another molecule of aldehye to give 5, and undergoes a proton transfer to give 6, then loses
thiamine to give furion 7.
766 Advances in Chemistry Research II

Table 2. The Reaction Mechanism from furfuraldeyde to Furion Catalyzed with VB1

The oxidation reaction of furoin is complicated. The furoin can be oxidized to the diketone furil
using Cu (OAc) 2 and NH4NO3. Only catalystic amount of copper (II) acetate is necessary because
the Cu2+ is continuously recycled. The pattern is shown in Table 3.
Table 3. Recycling of Copper Ion in Furoin Oxidation

OH O O
C CH2
O OH O (1) C C
O O
(2)

2Cu2+ 2Cu+

(3)

(4)
N2 + 3H2O NH4NO3 + 2H+

In the first redox cycle, furion donates an electron to Cu2+，forming furil (1) and Cu+ (2). The Cu+
ions are reoxidized to Cu2+ by ammonium nitrate(NH4NO3) formed Cu2+ in theses redox cycles (3),
then ammonium nitrite (NH4NO3) decomposes to nitrogen and water under the reaction conditions
(4).The completely reaction is shown in Eq 1.

O H O O
C C + NH4NO3 Cu(OAc)2
C C + N2 + 2H2O
O OH O O O

Eq 1. The Completely Reaction from Furion to Furil

3.3 Optimization of the reaction conditions

Given the information at hand we decided to attempt optimization of the reaction conditions to
obtain furoin from furfuraldeyde in high yield. It is found that the initial pH has an important effect
on the outcome of the reaction. If too much base is used in complex mixture, the yield is poor. An
initial pH of approximately 9.0 gives the best results.
The yield of furion depends on the stability of thiamine. Thiamine contains an aminopyrimidine
ring and a thiazole ring. It is stable in acidic condition, but unstable in alkaline solutions. If too
much base used in the reaction mixture, the thiazole ring is broken, and the thiamine will lost
catalyst activity. It will cause the poor yield of furion.
 Advanced Materials Research Vols. 554-556 767

Conclusions
It is an excellent way to synthesis furil by acyloin condensation catalyzed with thiamine, then
oxidation with Cu (OAc)2 and NH4NO3. In preparation of furion, the optimal condition is the
reaction mixture pH ≈ 9.0. This method of synthesis furil has some advantages of being
commercially available, inexpensive and relatively non-toxic.

Acknowledgements
This work is financially supported by the Ministry of Education of Beijing’s University Key
Teacher (2010). The authors gratefully acknowledge fruitful discussions with Dr. Tingting Zheng.

References
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[2] A.K.Singh, D. K. Palit. Chemical Physics Letters, Vol.357 (2002) p.173
[3] S.A.Tymonko, B.A.Nattier and R.S. Mohan. Tetrahedron Letters, Vol. 40(1999), p. 7657
[4] C.J. Sandroff, I.Y. Chan, Chemical Physics Letters. Vol. 97 (1983) p. 60
[5] S.J. Wang, Q. Gua, X.D. Chen, T.Q. Zhao and Y.M Zhang, European Journal of Chemistry,
Vol.2 (2011), p. 173
[6] R. S. Pimpim, C. C. C. Rubeg, R. V. F. Bravo and C. Kascheres. Synthetic Communications,
Vol.27 (1997), p. 811
Advances in Chemistry Research II
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An Efficient Synthesis of Furil

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