1
Supplementary Information
Simple and efficient one-pot synthesis of 5-hydroxymethylfurfural and
2,5-diformylfuran from carbohydrates.
Quentin Girka,[a,b]
Boris Estrine,*[b]
Norbert Hoffmann,*[a]
Jean Le Bras,[a]
Siniša
Marinković[b]
and Jacques Muzart[a]
a CNRS-Université de Reims Champagne-Ardenne
Institut de Chimie Moléculaire de Reims, UMR 7312
UFR des Sciences Exactes et Naturelles, 51687 Reims, France
E-mail: [email protected]
b Agro-Industrie Recherches et Développement
Green Chemistry Departement
Route de Bazancourt, 51110 Pomacle, France
E-mail: [email protected]
Electronic Supplementary Material (ESI) for Reaction Chemistry & Engineering.This journal is © The Royal Society of Chemistry 2015
2
General methods ..................................................................................................................................... 3
Determination of Biomass composition .................................................................................................. 3
Typical sugar to HMF or furfural conversion experiment ....................................................................... 4
Typical one-pot sugar to DFF conversion experiment ............................................................................ 4
HMF, furfural and DFF analysis ............................................................................................................... 4
Multigram DFF synthesis ......................................................................................................................... 4
5-(Bromomethyl)furfural synthesis ......................................................................................................... 5
Bromodimethylsulfonium bromide synthesis ......................................................................................... 5
5-(Formyloxymethyl)furfural synthesis ................................................................................................... 6
Bromomethylfurfural hydrolysis ............................................................................................................. 6
1H NMR spectrum of 2,5-diformylfuran (CDCl3, 250 MHz) ..................................................................... 7
13C NMR spectrum of 2,5-diformylfuran (CDCl3, 63 MHz) ....................................................................... 8
1H NMR spectrum of 5-(formyloxymethyl)furfural (CDCl3, 250 MHz) ..................................................... 9
13C NMR spectrum of 5-(formyloxymethyl)furfural (CDCl3, 63 MHz) ................................................... 10
1H NMR spectrum of 5-(bromomethyl)furfural (DMSOd6, 250 MHz) .................................................... 11
13C NMR spectrum of 5-(bromomethyl)furfural (DMSOd6, 63 MHz) ..................................................... 12
3
General methods
All sugar reagents and DMSO were provided by Sigma-Aldrich and used as received.
Palatinose hydrate was purchased from TCI-chemicals and dried under vacuum at
40°C for 4 days before use. NaBr and HMF were purchased from TCI Chemicals and
use as received.
HPLC experiments were performed on Shimadzu Agilent 1200 series equipped with
nucleodur C18 column and a PDA detector. HPLC grade solvents were filtrated and
degased before use.
Sartorius 20µm filters were purchased from VWR.
For anhydrous experiments, DMSOd6 was dried 48 h with 20% v/v freshly activated
3Å molecular sieve. All reagents were dried under high vacuum (0.05 mbar) for 48 h
prior to use.
Determination of biomass composition
A round bottom flask was charged with biomass (0.7 g) and sulfuric acid (12 mol/L, 12
mL). The mixture is stirred at 30 °C for 1 h, diluted with water (70 mL) and stirred at
reflux for 3 h. After cooling, the mixture is centrifugated and supernatant is used for
HPLC analysis.
Carbohydrates were analyzed by Dionex HPLC composed of a refractive index
detector, a P580 pump, an AS100 automatic injector and a STH 585 column oven with
a Bio-Rad Aminex HPX-87H column (300 × 7.8 mm; eluent: 5 mM of H2SO4 in water,
flow: 0.6 mL/min, oven temperature: 45 °C). Carbohydrates amounts were determined
using standard calibration curves.
4
Typical sugar to HMF or furfural conversion experiment
A round bottom flask equipped with condenser was charged with carbohydrate (1 g),
an appropriate amount of boric acid and DMSO (9 g). The mixture is stirred at 150°C
for an appropriate time.
Typical one-pot sugar to DFF conversion experiment
A round bottom flask equipped with condenser was charged with carbohydrate (1 g),
an appropriate amount of boric acid, NaBr (0.3 eq/glucose unit), formic acid (0.3
eq/glucose unit) and DMSO (9 g).The mixture is stirred at 150°C for an appropriate
time.
HMF, furfural and DFF analysis
After the specified time, 0.4 g of reaction mixture were taken and diluted with of
deionized water (30 mL). This solution was filtrated and used for HPLC analysis (10
µL).
HMF and DFF analysis were performed using an AcONa water solution (50 mmol/L)
at pH=2.8 (adjusted by addition of AcOH) and acetonitrile (90/10 ratio) at a flow rate
of 1 mL.min-1
with a column temperature of 55°C. HMF and furfural analysis were
performed with 90/10 water/acetonitrile mixture at a flow rate of 0.6 mL.min-1
at 25°C.
HMF, DFF amounts were determined using standard calibration curves at 310 nm and
furfural at 280 nm.
Multigram DFF synthesis
Glucose (30 g, 0.16 mol) and DMSO (300 mL) were charged in a round bottom flask
equipped with a condenser and a magnetic stirrer. The mixture was stirred at room
temperature for 10 minutes until glucose was dissolved. NaBr (5.15 g, 0.05 mol) and
boric acid (5.15 g, 0.08 mol) were added and the mixture was stirred at 150°C for 18 h.
5
The reaction mixture was allowed to cool to room temperature and water (300 mL)
was added. DFF was then extracted with ethyl acetate (3*300 mL). The combined
organic layers were dried with MgSO4, filtered and concentrated under vacuum.
DFF was purified by column chromatography over silica gel (petroleum ether/EtOAc
8:2 or CH2Cl2 100%) as a pale yellow solid (3.8 g, 0.03 mol, 19%).
Other purification such as recrystallization or soxhlet extraction followed by silica gel
filtration where possible only when DMSO was successfully removed from organic
phase with repeated aqueous wash. Otherwise, crude product is obtain as an orange
liquid containing DMSO.
5-(Bromomethyl)furfural synthesis
5-(bromomethyl)furfural was synthesised according to already reported procedure1. To a
stirred solution of fructose (4 g, 22 mmol) and lithium bromide (3.86 g, 44 mmol) in toluene
(160 mL), an aqueous solution of HBr (7 mL, 62 mmol) was slowly added. The mixture was
heated at 65°C for 15 h and diluted with saturated aqueous sodium hydrogenocarbonate (100
mL). The aqueous layer was extracted three times with ethyl acetate (3x100 mL). Organic
layers were combined, dried with MgSO4, filtered and concentrated under vacuum at 40°C.
Crude product was purified by column chromatography over silica gel (petroleum ether/
EtOAc : 8/2) yielding 5-(bromomethyl)furfural as a light yellow oil (2,2 g, 12 mmol, 55%).
Bromodimethylsulfonium bromide synthesis2
To an ice-cooled stirred solution of dimethylsulfid (3 mL, 41 mmol) in dichloromethane (10
mL), a bromine (2.1 mL, 41 mmol) solution in dichloromethane (10 mL) was added dropwise.
1 Jadhav H., Pedersen C.M., Sølling T. and Bols M., ChemsusChem, 2011, 4, 1049-1051.
2 Liu, A.-H.; Ma, R.; Song, C.; Yang, Z.-Z.; Yu, A.; Cai, Y.; He, L.-N.; Zhao, Y.-N.; Yu, B.;
Song, Q.-W., Angew. Chem. Int. Ed. 2012, 51, 11306–11310
6
After addition was completed, the yellow solid was filtered off, washed with diethylether and
dried under vaccum.
m.p. : 80-82°C (lit.1 80-83°C)
5-(Formyloxymethyl)furfural synthesis3
In a round bottom flask, HMF (100 mg, 0.79 mmol) was dissolved in formic acid (2.5 mL).
The solution was stirred at room temperature for 3 h. After removal of volatiles under
vacuum, FMF was isolated by column chromatography over silica gel (petroleum
ether/EtOAc 8 :2) as a slighly yellow oil (120 mg, 0.78 mmol, 99%)
Bromomethylfurfural hydrolysis
A DMSOd6 (2 mL) solution containing 5-(bromomethyl)furfural (85 mg, 0.5 mmol) and water
(27 µL, 1.5 mmol) was introduced in an NMR tube and heated at 60°C.
Mixture composition was followed by 1H NMR by comparaison with pure HMF and BMF
spectrum. Proportion of each compound was determined by standard integration method.
3 Xiaoyuan Zhou and Thomas B. Rauchfuss, ChemSusChem, 2013, 6, 383-388.
7
1H NMR spectrum of
2,5-diformylfuran (CDCl3, 250 MHz)
8
13C NMR spectrum of
2,5-diformylfuran (CDCl3, 63 MHz)
9
1H NMR spectrum
of 5-(formyloxymethyl)furfural (CDCl3, 250 MHz)
10
13C NMR spectrum of 5-(formyloxymethyl)furfural (CDCl3, 63 MHz)
11
1H NMR spectrum
of 5-(bromomethyl)furfural (DMSOd6, 250 MHz)
12
13C NMR spectrum of 5-(bromomethyl)furfural (DMSOd6, 63 MHz)