411
References and Notes
form of furfural, was found to form in low yields under the
reaction conditions. In addition, though furan-2(5H)-one was
found to form in traces in the reaction mixture, no other
intermediates were identified by HPLC.
1
2
3
4
5
J. Jurczak, E. Kobrzycka, J. Raczko, Pol. J. Chem. 1999, 73, 29.
a) L. Volkel, A. Lange, C. Lockemann, D. Posselt, U.S. Patent, US
2009/0235576 A1, 2009. b) N. Nghiem, B. H. Davison, M. I.
Donnelly, S.-P. Tsai, J. G. Frye, Chemicals and Materials from
Renewable Resources in ACS Symposium Series, ed. by J. J. Bozell,
American Chemical Society, Washington DC, 2001, Vol. 784, pp. 160-
Yoneyama, CEH Report: Tetrahydrofuran, SRI, Menlo Park, CA, 2001.
a) M. K. Kumar, Y. P. Reddy, V. K. Kumar, C. Sowmya, A. M. Deshmukh,
Int. J. Pharm. Sci. Rev. Res. 2010, 3, 142. b) L. Lachman, J. B. Schwartz,
Pharmaceutical Dosage Forms: Tablets, Marcel Dekker, 1990, p. 288.
Besides, an increase in reaction temperature to 353 K favors
the formation of SA, whereas with further increase in temper-
ature the yield decreases (Table S3).30 In the case of higher
temperatures, an unidentified peak at a retention time of 36.2 min
appeared for the particular reaction, though which was not
detected during the reaction under 353 K. It is known that
Amberlyst-15 favors the cyclization of 1,4-dicarbonyl com-
pounds to furan derivatives at higher temperature such as 393-
396 K.32 Therefore, the cyclization of SA and MA was not
related to the reaction pathway. Furthermore, a control experi-
ment with radical scavenger supported that the reaction does not
proceed via radical pathway (Table S4).30
6
7
To unveil the reaction progress, two reaction pathways were
proposed as shown in Schemes S1 and S2.30 In Scheme S130 the
furan ring is proposed to open up to undergo oxidation by H2O2
as demonstrated by Bunton.33 Following the proposal by
Kul’nevich et al.,34 in Scheme S2,30 the reaction was proposed
to undergo Baeyer-Villiger oxidation to form SA via furan-
2(3H)-one. Although reactions from intermediates such as
2-furanol formate and furan-2(3H)-one were hardly investigated
owing to their undersupplies and difficult synthesis, the reaction
of furan-2(5H)-one to MA was progressive in the same
conditions (Table S5).30 Moreover, it was also indicated that
the formed FA and MA could not transfer to the SA under the
reaction conditions (Tables S2 and S6).30 The time course of
NMR (Figures S1 and S2)30 was helpful in establishing the fact
that neither furan-2(5H)-one nor MA or FA was the intermediate
in the synthesis of SA from furfural under the present condition.30
Subsequently, the reusability of Amberlyst-15 was inves-
tigated. Amberlyst-15 was simply reused by decantation,
thorough washing with water at room temperature followed
by drying in vacuum. Therefore, the SO3H leaching from
Amberlyst-15 scarcely occurred. It was found that the
Amberlyst-15 was reproducible with a good yield of 68-74%
for three runs (Figure S3).30 Furthermore, the productivity of
the reaction was confirmed by the large-scale reaction using
20 mmol furfural under the same reaction conditions
(Table S7).30 SA was obtained in 66.4% as an isolated yield
(TON = 2.82) with almost complete conversion of furfural.
1H NMR (400 MHz, D2O, TMS) and 13C NMR (400 MHz, D2O,
TMS) for the synthesized product clearly demonstrate the purity
of the crystalline product (Figures S1 and S2).30
8
9
Y. Tachibana, T. Masuda, M. Funabashi, M. Kunioka, Biomacro-
W. A. Carey, W. C. Ehrhardt, L. A. Perez, A. Solov, D. T. Freese, Eur.
Patent, EP 0628539 B1, 1994.
11 Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., ed. by
H.-G. Mary, John Wiley & Sons, New York, 1997, Vol. 22, p. 1074.
12 J. M. Berg, J. L. Tymoczko, L. Stryer, Biochemistry, 6th ed., Freeman,
New York, 2006.
13 M. J. Van der Werf, M. V. Guettler, M. K. Jain, J. G. Zeikus, Arch.
14 S. Yamada, H. Haramaki, S. Matsumoto, Y. Akazawa, Jpn Patent, JP
0931,011, 1997.
15 T. V. Lysyak, I. S. Kolomnikov, Yu. Ya. Kharitinov, Koord. Khim. 1983,
9, 1000.
16 X. Wang, G. Yedi, Chin. Chem. Lett. 1993, 4, 407.
17 L. P. Kyrides, J. A. Bertsch, U.S. Patent, US 1 927 289, 1933.
18 U. Pomilio, Z Electrochem. 1915, 21, 444.
19 J. F. Norris, E. O. Cummings, U.S. Patent, US 1 457 79 1, 1943.
21 a) R. Ishikawa, A. Kurusu, Jpn Patent, JP 9 95,464, 1997. b) J. H.
Murib, C. E. Frank, U.S. Patent, US 3 923 881, 1975.
22 E. P. Grunskaya, L. A. Badovskaya, V. V. Poskonin, Yu. F. Yakuba,
23 V. I. Krupenskii, Zh. Obshch. Khim. 1996, 66, 1874.
24 M. Taniyama, Toho Reiyon Kenkyu Hokoku 1954, 1, 40.
25 V. I. Krupenskii, Nauchn. Tr.-Leningr. Lesotekh. Akad. im. S. M. Kirova
1973, 158, 68.
33, 3132. b) H. F. McShane, Jr., W. W. Gilbert, U.S. Patent, US 2 772
291, 1956.
27 B. Cornils, P. Lappe, Dicarboxylic Acids, Aliphatic in Ullmann’s En-
cyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co.,
28 a) A. Takagaki, M. Ohara, S. Nishimura, K. Ebitani, Chem. Commun.
29 R. Kunin, E. F. Meitzner, J. A. Oline, S. A. Fisher, N. Frisch, Ind. Eng.
30 Supporting Information is available electronically on the CSJ-Journal
31 H2O2 labeled as 30% was used for the reaction; however the actual
concentration was estimated as 25.7% by iodometric titration. The
H2O2 efficiency was calculated with the formula described as
{(H2O2,input ¹ H2O2,remain)/H2O2,input} © 100.
In conclusion, we have found that Amberlyst-15 is a highly
effective heterogeneous catalyst for direct oxidation of inedible
biomass-based 2-furaldehyde to succinic acid in good yields
in aqueous media under mild reaction conditions, with the
advantage of reusability of catalyst without significant loss of
catalytic activity and selectivity. Although the detailed catalytic
mechanism needs to be further studied precisely, the above-
mentioned process promises to be a viable alternative to current
synthesis of SA using microorganism since it has the advantages
of easy purification and high yields of succinic acid.
32 Handbook of Reagents for Organic Synthesis: Reagents for High-
Throughput Solid-Phase and Solution-Phase Organic Synthesis, ed. by
P. Wipf, John Wiley & Sons Ltd, England, 2005, p. 242.
34 V. G. Kul’nevich, L. A. Bodovskaya, G. F. Muzychenko, Khim.
Geterotsikl. Soedin. 1970, 582.
This work was supported by a Grant-in-Aid for Scientific
Research (C) (No. 22560764) of the Ministry of Education,
Culture, Sports, Science and Technology (MEXT), Japan.
Chem. Lett. 2012, 41, 409-411
© 2012 The Chemical Society of Japan