Communications
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(Eds.: G. Centi, R. A. van Santen), Wiley-VCH, Weinheim,
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Experimental Section
Preparation of the Rh-Re/SiO2 catalyst: An aqueous solution of
RhCl3 (302 mg,1.4 mmol) in water (10 mL) was added to silica (2 g,
Wacker HDK T40; BET surface area 328 m2 gÀ1, pore volume
0.742 cm3 gÀ1) and stirred for 2 h at room temperature. After drying
at 383 K for 13–14 h, this material was stirred with an aqueous
solution of NH4ReO4 (193 mg, 0.7 mmol) in water (10 mL) for 2 h,
followed by drying at 383 K for 13–14 h. Calcination in air at 773 K for
3 h gave a material with 6.5 wt% Rh and 6 wt% Re.
Hydrogenation of HMF to THFDM: HMF (500 mg, 4 mmol)
dissolved in ethanol (30 mL) and Raney nickel catalyst (50 mg) were
added to a 100 mL stainless steel autoclave (Parr). The reactor was
flushed three times with nitrogen and subsequently with hydrogen.
After flushing, the reactor was pressurized to 90 bar, and the reaction
mixture was stirred and heated to 1008C for 14 h. GC analysis showed
100% conversion and 99% selectivity to THFDM.
Hydrogenation of THFDM to 1,2,6-HT: THFDM (100 mg,
0.8 mmol), Rh-Re/SiO2 catalyst (25 mg), water (2 mL), and a Teflon
stirring bar were added to a 8 mL glass vial capped with a septum. The
vial was then pierced with a small needle and placed in a stainless-
steel autoclave. The lid of the autoclave was closed and stirring was
started at 1000 rpm. After pressurizing three times with first nitrogen
and then hydrogen, the autoclave was pressurized to 10 bar and the
temperature was raised to 808C. After 1 h, the pressure was raised to
80 bar and the reactions were continued for 20 h. The autoclave was
then allowed to cool to ambient temperature and the pressure was
released. GC analysis showed 21% conversion and 97% selectivity to
1,2,6-HT.
Cyclization of 1,2,6-HT to 2-THPM: In a 100 mL three-neck
round-bottom flask, 1,2,6-hexanetriol (3.354 g, 25 mmol) was dis-
solved in sulfolane (25 mL). Trifluoromethanesulfonic acid (13.3 mL,
0.15 mmol) was then added. The reaction mixture was heated to
1258C for 30 min. GC showed full conversion with 2-THPM as the
only product.
Hydrogenation of 2-THPM to 1,6-HD: 2-THPM (100 mg,
0.9 mmol), the Rh-Re/SiO2 catalyst (10 mg), water (2 mL), and a
Teflon stirring bar were added to a glass vial and hydrogenation was
effected as described above for the hydrogenation of THFDM, except
at a temperature of 1808C. After 4.5 h, GC analysis showed 17%
conversion and 100% selectivity to 1,6-HD.
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Ullmannꢁs Encyclopedia of Industrial Chemistry, Wiley-VCH,
Weinheim, 2002.
One-pot hydrogenation of THFDM to 1,6-HD: The same
procedure was used as described above for the hydrogenation of
THFDM to 1,2,6-HT, but with an additional 15 mg of acid catalyst
added (See Table 2).
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1,6-HD to caprolactone: In a two-necked round-bottom flask
with a condenser under an inert atmosphere, [{Ru(Cymene)Cl2}2]
(0.02 mmol) and DPPF (0.022 mmol) were suspended in MIBK
(5 mL) at room temperature. 1,6-HD (1.0 mmol), K2CO3 (0.2 mmol),
and MIBK (25 mL) were then added, and the mixture was refluxed
for 0.5 h. GC analysis showed 100% conversion of 1,6-HD with
complete selectivity to caprolactone.
In all cases, samples were isolated by distillation or column
chromatography and further analyzed by NMR and MS.
Received: March 28, 2011
Published online: June 22, 2011
Keywords: biomass · caprolactam · caprolactone ·
.
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hydroxymethylfurfural · sustainable chemistry
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Screening for Potential Candidates from Sugars and Synthesis
Gas (Eds.: T. Werpy, G. Petersen), U. S. Department of Energy
(DOE) by the National Renewable Energy Laboratory a DOE
national Laboratory, 2004.
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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