Green Chemistry
Communication
Experimental section
References
5
-(Chloromethyl)furan-2-carbonyl chloride (CMFCC) 4 and
ethyl 5-(chloromethyl)furan-2-carboxylate 5
-(Chloromethyl)furfural 3 (2.226 g, 15.40 mmol) and tert-
1
(a) E. de Jong, M. A. Dam, L. Sipos and G. J. M. Gruter, Fur-
andicarboxylic Acid (FDCA), A Versatile Building Block for a
Very Interesting Class of Polyesters, in Biobased Monomers,
Polymers, and Materials, ACS Symposuim Series 1105,
American Chemical Society, Washington, DC, 2012,
pp. 1–13; (b) S. K. Burgess, J. E. Leisen, B. E. Kraftschik,
C. R. Mubarak, R. M. Kriegel and W. J. Koros, Macro-
molecules, 2014, 47, 1383. See also updates at http://
avantium.com/yxy/yxy-technology.html.
5
butyl hypochlorite (10.5 mL, 10.1 g, 92.7 mmol) were intro-
duced into a 50 mL round-bottomed flask wrapped with alumi-
num foil. The mixture was stirred rapidly at room temperature
under air. After 24 h, a measured amount of 1,4-dioxane was
added as an internal standard and the yield of CMFCC 4 was
1
determined to be 85% by H NMR peak integration. The vola-
tiles were evaporated at room temperature and the crude
CMFCC 4 (2.90 g) was dissolved in anhydrous ethanol (20 mL).
The clear yellow solution was stirred at 50 °C for 6 h. The
solvent was evaporated and the residue was chromatographed
2 (a) A. Takagaki, S. Nishimura and K. Ebitani, Catal. Surv.
Asia, 2012, 16, 164; (b) X. Tong, Y. Ma and Y. Li, Appl.
Catal., A, 2010, 385, 1.
3 R.-J. van Putten, J. C. van der Waal, E. de Jong,
C. B. Rasrendra, H. J. Heeres and J. G. de Vries, Chem. Rev.,
2013, 113, 1499.
4 P. Mikochik and A. Cahana, U.S. Pat. Appl. Publ., US
20150047251 A1, 2015. See also http://xftechnologies.com.
5 J. A. Moore and J. E. Kelly, J. Polym. Sci., Polym. Chem. Ed.,
1984, 22, 863.
6 A. C. Braisted, J. D. Oslob, W. L. Delano, J. Hyde,
R. S. McDowell, N. Waal, C. Yu, M. R. Arkin and
B. C. Raimundo, J. Am. Chem. Soc., 2003, 125, 3714.
using CH
2
Cl
2
/hexane (1 : 1 to 3 : 1 gradient) to give ethyl
as colorless oil
) δ 7.06 (d, J = 3.5 Hz,
H), 6.44 (d, J = 3.5 Hz, 1H), 4.55 (s, 2H), 4.31 (q, J = 7.1 Hz,
5
-(chloromethyl)furan-2-carboxylate
5
a
1
(2.390 g, 82%). H NMR (300 MHz, CDCl
3
1
2
1
3
H), 1.32 (t, J = 7.1 Hz, 3H); C NMR (75 MHz, CDCl3)
δ 158.35, 153.96, 145.02, 118.54, 111.37, 61.10, 36.68, 14.26.
Performing this reaction on a 5× scale (10.47 g of CMF 3)
yielded 10.96 g of 5 (80.2%).
Furan-2,5-dicarbonyl chloride (FDCC) 11 and diethyl furan-
7
L.-C. Chou, L.-J. Huang, J.-S. Yang, F. Y. Lee, C.-M. Teng
2
,5-dicarboxylate 12
and S.-C. Kuo, Bioorg. Med. Chem., 2007, 15, 1732.
2
,5-Diformylfuran 10 (1.315 g, 10.60 mmol) and tert-butyl
8 Example: Z. Zhang, B. Liu, K. Lv, J. Sun and K. Deng, Green
Chem., 2014, 16, 2762 and references therein.
9 (a) M. Mascal and E. B. Nikitin, Angew. Chem., Int. Ed.,
2008, 47, 7924; (b) M. Mascal and E. B. Nitkin, Chem-
SusChem, 2009, 2, 859.
hypochlorite (14.4 mL, 13.8 g, 127 mmol) were introduced into
a 50 mL round-bottomed flask wrapped with aluminum foil.
The suspension was stirred rapidly at room temperature under
air for 24 h, resulting in a clear yellow solution. A measured
amount of 1,4-dioxane was added as an internal standard and 10 N. S. Simpkins and J. K. Cha, in Handbook of Reagents
1
the yield of FDCC 11 was determined to be 80% by H NMR
for Organic Synthesis: Catalytic Oxidation Reagents, ed.
P. L. Fuchs, 2013, pp. 126–132.
peak integration. The volatiles were evaporated at room tem-
perature and the crude FDCC 11 (1.840 g) was dissolved in 11 M. J. Mintz and C. Walling, Org. Synth., 1969, 49, 9.
anhydrous ethanol (20 mL). The mixture was stirred at room 12 (a) Z. Yuan, Z. Zhang, J. Zheng and J. Lin, Fuel, 2015, 150,
temperature for 5 h. The solvent was evaporated and the
residue was chromatographed using CH Cl /hexane (1 : 1 to
236; (b) S. Yin, J. Sun, B. Liu and Z. Zhang, J. Mater. Chem.
A, 2015, 3, 4992; (c) I. Viil, A. Bredihhin, U. Maeeorg and
L. Vares, RSC Adv., 2014, 4, 5689.
2
2
1
: 0 gradient) to give diethyl furan-2,5-dicarboxylate 12 as a
1
3
yellow oil (1.700 g, 76%). H NMR (600 MHz, CDCl ) δ 7.19 13 http://xftechnologies.com.
(
s, 2H), 4.39 (q, J = 7.1 Hz, 4H), 1.38 (t, J = 7.1 Hz, 6H); 14 C. Laugel, B. Estrine, J. Le Bras, N. Hoffmann,
1
3
C NMR (151 MHz, CDCl
Experimental details of preparation of derivatives 6–9 and 15 M. Gomes, A. Gandini, A. J. D. Silvestre and B. Reis,
3 are given in the ESI.† J. Polym. Sci., Part A: Polym. Chem., 2011, 49, 3759.
3
) δ 158.06, 146.89, 118.22, 61.58, 14.24.
S. Marinkovic and J. Muzart, ChemCatChem, 2014, 6, 1195.
1
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