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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: norbert.hoffmann@univ-reims.fr

b Agro-Industrie Recherches et Développement

Green Chemistry Departement

Route de Bazancourt, 51110 Pomacle, France

E-mail: b.estrine@a-r-d.fr

Electronic Supplementary Material (ESI) for Reaction Chemistry & Engineering.This journal is © The Royal Society of Chemistry 2015

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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

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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.

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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.

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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

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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.

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1H NMR spectrum of

2,5-diformylfuran (CDCl3, 250 MHz)

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13C NMR spectrum of

2,5-diformylfuran (CDCl3, 63 MHz)

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1H NMR spectrum

of 5-(formyloxymethyl)furfural (CDCl3, 250 MHz)

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13C NMR spectrum of 5-(formyloxymethyl)furfural (CDCl3, 63 MHz)

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1H NMR spectrum

of 5-(bromomethyl)furfural (DMSOd6, 250 MHz)

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13C NMR spectrum of 5-(bromomethyl)furfural (DMSOd6, 63 MHz)