Synthesis of Fuel Intermediates from HMF/Fructose
3
2
9
1.0, 19.3; GC-MS: m/z 200.1, 185, 171.1, 128.1, 115.1,
1.0; HRMS (ESI) m/z calcd for [C H NaO ] 223.0730
surface area (Quantachrome ASiQwin). The acid densi-
ties were measured by acid base titration. FT-IR spec-
trum (Fig. 1a) showed characteristic peaks at 1012 and
1
3
12
2
found 223.0735.
−
1
1
040 cm which are attributed to O=S=O stretching vibra-
−
1
2
.2.2 5-(-o, and -p-methoxy) Benzylfuran-2-carbaldehyde
tions in –SO H groups and peak at 1127 cm
for SO H
3
3
stretching. This indicates that the sulfonic acid groups have
been successively incorporated on the catalyst surface.
1
H NMR (400 MHz, CDCl ): δ 9.45 (s, 2H), 7.15–6.23 (m,
3
−
1
2
2
H), 7.06–7.12 (m, 4H), 6.77–6.88 (m, 4H), 6.05–6.09 (m,
Peaks at 1645 cm attributed for C=C stretching vibrations
1
3
−1
H), 3.99 (s, 4H), 3.24 (s, 6H); C NMR (100 MHz, CDCl)
in aromatic carbons and peak at 1670 cm
C=O stretching. Peak at 1714 cm
attributed for
3
−
1
δ 177.2, 162.4, 157.3, 151.9, 130.5, 130. 0, 128.5, 124.6,
1
2
attributed to presence
23.3, 120.7, 114.2, 110.6, 109.6, 55.4, 55.3, 34.1, 29.7,
7.2; HRMS (ESI) m/z calcd for [C H NaO ] 239.0679
of C=O stretching vibration of –COOH group. Bands at
1
−
2925 cm attributed for C–H stretching band. Bands due
1
3
12
3
−
1
found 239.0684.
to O–H stretching were observed at 3410 cm .The PXRD
Fig. 1b) showed a weak but broad peak of 2θ at 15°–30°,
(
2
.2.3 5-(mesityl) Furan-2-carbaldehyde
indicating formation of amorphous carbon having aromatic
carbon sheets oriented in a random fashion. The sharp
peaks seen indicates the formation of Fe O crystallite in
1H NMR (400 MHz, CDCl 3) δ 9.53 (s, 1H), 7.11 (d,
J=3.4 Hz, 1H), 6.90 (s, 2H), 5.92 (d, J =3.4 Hz, 1H), 4.05
3
4
the pyrolysis process. The energy dispersive X-ray analysis
(Fig. 1c) confirms that the catalyst surfaces are composed
mainly of C, O, Fe and S. Composition of S and Fe is found
to be 7.4 and 7.7% respectively from EDAX. The elemental
analysis showed composition of C to be 50 %, H to be 4 %
and S to be 9 %. SEM (Fig. 1d) image shows formation of
porous nature of the catalyst. The surface composition of
Glu–Fe O –SO H was analysed by XPS (Fig. 1e). The C 1s
1
3
(s, 2H), 2.29 (s, 3H), 2.28 (s, 6H);
C NMR (100 MHz,
CDCl ) δ 177.0, 161.9, 152.1, 136.8, 136.6, 129.6, 129.1
3
(
1
s), 109.1, 28.0, 20.8, 19.9 (s); GC-MS: m/z 228, 213,
82.1, 167.1, 156.1, 143.1, 105.1, 91.1, 77.1; HRMS (ESI)
m/z calcd for [C H NaO ] 251.1043 found 251.1048.
1
5
16
2
3
4
3
3
Results and Discussions
spectrum includes six peaks with different binding energy
values. The peaks could be assigned to the carbon atoms in
the forms of C–S (283.5 eV), C–C (284 and 284.5 eV), C–O
3
.1 Characterization of the Catalyst
(285 eV), C=O (285.5 eV), O=C–O (286 eV). The S 2p
Due to our continuous interest in this field, we have syn-
thesized a magnetic carbonaceous solid acid catalyst Glu–
Fe O –SO H. For preparation of this catalyst, we choose
spectrum showed three different peaks that can be assigned
to S–C (186.5), S–O (169 eV) and S=O (169.5 eV). O 1s
spectrum shows peaks in the range 530–535 eV indicating
the presence of Fe–O and C–O–Fe groups suggesting the
linkage of Fe O with porous carbon. BET surface area,
3
4
3
readily available D-glucose as a carbon precursor, Fe was
preloaded on glucose using FeCl and p-TSA was used as a
3
3
4
sulphonating agent to create active acidic sites. Initially Fe
pore size and pore volume was calculated using the standard
Brunauer–Emmett–Teller (BET) equation and was found to
was preloaded on glucose using FeCl . The free -OH groups
3
2
3
in glucose easily coordinated with adsorbed Fe (III) ions and be 3.38 m /g, 9.53 Å and 6.07 m /g respectively. The total
then evaporation of solvent and drying gave black Fe (III)
based complex. This complex was then pyrolysed and sul-
fonated simultaneously using p-TSA at 140 °C under nitro-
gen. The Fe preloaded on glucose was partly hydrolysed to
FeO(OH) during drying. FeO(OH) was further reduced to
Fe O by reducing components like H , CO and CO which
acid density and the sulphonic acid density of Glu–Fe O –
3 4
SO H based on acid base titration was found to be 2.87 and
3
1.46 mmol/g respectively.
3.2 Alkylation of Toluene with HMF/Fructose in
Various Solvents
3
4
2
2
are formed during carbonation process. Pyrolysis and sul-
fonation in-situ leads to formation of a polycylic aromatic
structure embedded with active Fe O , –SO H, –COOH and
To start with, HMF and fructose were screened for vari-
ous solvents for the alkylation reaction with arenes in
presence of Glu–Fe O –SO H catalyst (Table 1). Toluene
was used as a model aromatic compound for studying the
alkylation reaction with HMF. In case of alkylation of
arenes with HMF and fructose, solvents like isopropanol,
acetonitrile, DMSO, DMF, nitromethane gave formation
of corresponding mono alkylated product, a mixture of
3
4
3
–
OH sites.
The catalyst thus obtained was characterized with FT-IR
Spectrum 400), PXRD (Panalytical X’Pert Pro), Elemen -
tal analysis from EDAX (Nova Nano SEM 450), SEM
Quanta™ Scanning Electron Microscope), XPS (Prevac
Ambient Pressure Photo Electron Spectroscopy) and BET
3
4
3
(
(
1
3