Linked strategy for the production of fuels via formose reaction
Jin Deng , Tao Pan , Qing Xu , Meng-Yuan Chen , Ying Zhang , Qing-Xiang Guo & Yao Fu
Anhui Province Key Laboratory of Biomass Clean Energy, Department of Chemistry,
University
of Science and Technology of China, Hefei 230026, China.
1
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1
1
1
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1
Supplementary Information
Table of Contents
Part 1. Supplementary Methods………………….……………………………2
a. Integrated optimal conditions for the transformation of formaldehyde to fuels
b. Time on steam of continuous process
c. Preparation of C9-C15 branched-chain alkanes from 4-HMF
d. 13C-NMR experiments of the base-catalyzed condensation of dihydroxyacetone
Part 2. Supplementary Notes…………………………………………………12
Part 3. Supplementary Tables…………………………………………….......13
Part 4. Supplementary Figures and Legends………………………………17
Part 5. Chromatograms for each analysis step and analytical
conditions………………………………………………………………………….20
Part 6. NMR spectrograms…………………………………………………….31
Part 7. Supplemental References…………………………………………….41
Page 1 of 41
Part 1. Supplementary Methods
a. Integrated optimal conditions for the transformation of formaldehyde
to fuels
Conversion of formaldehyde to dihydroxyacetone (DHA)
Batch process: Paraformaldehyde (10 wt% of the mixtures) and dioxane (450 ml)
were heated to 373 K under nitrogen and then catalyst solution (1 mmol% of substrate,
50 ml) was added. The mixture was stirred at 373 K for 1 h. After reaction the
reaction was quenched in ice water. The reaction mixture was analyzed by HPLC.
Analysis of the reaction mixture showed that the yield of DHA is 85% and the
conversion of formaldehyde is 99%. The reaction mixture was evaporated to remove
the solvent. The residue was poured into water (100 ml) and extracted with
dichloromethane (100 ml) three times to recycle the catalyst. The DHA aqueous
solution was used directly in the following step.
Continuous process: details seeing Reference 20, 21 and fig. S10. The
production of DHA from formaldehyde has a selectivity of 96% with a single-pass
conversion of ca. 30%.
Isolation conditions: The DHA aqueous solution was evaporated to dryness and
giving a syrupy product. The syrup was isolated to white powder of DHA dimer by
recrystallization with ethanol and acetone.
Conversion of DHA to hexoses
Batch process: DHA aqueous solution and Amberlite® IRA-900 basic ion
exchange resin (1 equiv of substrate) were stirred at 273K for 12h. After filtration to
remove the resin, the filtrate was analyzed by HPLC. 100% conversion and 98.4%
ketohexose selectivity (branched-chain ketohexose : straight-chain ketohexoses =
95.4 : 4.6) were achieved. The aqueous solution was used directly in the following
step.
Continuous process: The Amberlite® IRA-900 basic ion exchange resin was
packed in a fixed bed reactor and DHA aqueous solution was fed at LHSV =1 h-1
through the reactor at 273 K. The liquid effluent was collected for quantitative
analysis by HPLC. 100% conversion and >99% ketohexose selectivity
(branched-chain ketohexose : straight-chain ketohexoses = 94 : 6) were achieved. The
aqueous solution was used directly in the following step.
Isolation conditions: The aqueous solution was isolated to white powder of
Page 2 of 41
dendroketose by recrystallization with ethanol and acetone.
Conversion of dendroketose to 4-HMF
Batch process 1: Amberlyst®-15 acidic ion exchange resin (50 wt% of substrate)
was added in the dendroketose (20 wt%) DMSO solution. This mixture was stirred at
383 K for 5 hours and then cooled to room temperature and filtered. The product
mixture was diluted analyzed with HPLC. 100% conversion and 93% 4-HMF
selectivity was achieved.
Batch process 2: TA-p (10 wt% of substrate), dendroketose aqueous solution and
MIBK (Vorg/Vaq= 1.5) were stirred at 453 K for 2 h. After filtration to remove the
catalyst, the filtrate was analyzed by HPLC. 99% conversion and 80% 4-HMF
selectivity was achieved.
Continuous process: Dendroketose aqueous solution and MIBK (feed ratio = 1:2)
were fed to the fixed-bed reactor with LHSV= 2 h-1 at 453 K. The liquid effluent was
collected and analyzed by HPLC. 71% conversion and 96% 4-HMF selectivity was
achieved.
Isolation conditions: The liquid effluent containing the MIBK solution of
4-HMF, the aqueous solution of 4-HMF and unconverted dendroketose was
introduced into the continuous countercurrent extractor and extracted by pure MIBK.
4-HMF in the aqueous solution was extracted into MIBK phase and organic phase
was forwarded into distillator to give the product of 4-HMF.
Hydrogenolysis of 4-HMF to 2,4-DMF
4-HMF （4 wt%） dissolved 1-butanol and pre-reduced barium promoted
CuCrO4 (20 wt% of substrate) were heated at 493K with 10 bar initial hydrogen
pressure for 3 h. After 3h, 15%Cu-10%Ru/C (20 wt% of substrate) was added to the
reactor. The reactor was pressurized with 7 bar initial hydrogen pressure and CO2 to
achieve a total system pressure of 50 bar, and was heated to 493K for 0.5h. The
product solution was analyzed by HPLC and GC-MS. 100% conversion and 72%
2,4-DMF selectivity was achieved.
Preparation of C9-C15 branched-chain alkanes from 4-HMF
The details were described below (Part 1-c).
In conclusion, under optimized conditions, the production of DHA from
formaldehyde has a selectivity of 96% with a single-pass conversion of ca. 30%; the
condensation of DHA into dendroketose achieved 100% conversion and >99%
Page 3 of 41
ketohexose selectivity (branched-chain ketohexose : straight-chain ketohexoses =
94:6); the dehydration of aqueous dendroketose into 4-HMF achieved a selectivity of
96% with a single-pass conversion of 71%; the hydrogenolysis of 4-HMF to 2,4-DMF
achieved 100% conversion and 72% 2,4-DMF selectivity; the preparation of C9-C15
branched-chain alkanes from 4-HMF achieved 100% conversion and 68% selectivity.
b. Time on steam of continuous process
Conversion of DHA to hexoses
Continuous operation was operated for 36 h at 273 K. (Figure below)
100%
Conversion/Selectivity(%)
90%
80%
LHSV=1.0h -1
70%
LHSV=0.5h -1
60%
50%
40%
DHA Conversion
30%
Branched-chain ketohexoses Selectivity
20%
Straight-chain ketohexoses Selectivity
10%
0%
0
2
4
6
8
10
12
14
16
18
20
22
24
26
28
30
32
34
36
TOS(h)
Figure S1 Time on steam of conversion of DHA to hexoses
Conversion of dendroketose to 4-HMF
Continuous operation was proceeded for 120 h with LHSV= 2 h-1 at 453 K.
(Figure below)
Page 4 of 41
100%
90%
Conversion/Selectivity(%)
80%
70%
60%
50%
LHSV=2.0h -1
40%
30%
DL-Dendroketose Conversion
20%
4-HM F Selectivity
10%
0%
0
12
24
36
48
60
72
84
96
108
120
TOS(h)
Figure S2 Time on steam of conversion of dendroketose to 4-HMF
c. Preparation of C9-C15 branched-chain alkanes from 4-HMF
Synthesis of 1,5-bis(4-(hydroxymethyl)-2-furanyl)-1,4-pentadien-3-one
(F4-Ac-F4)
1,5-bis(4-(hydroxymethyl)-2-furanyl)-1,4-pentadien-3-one (F4-Ac-F4) was
synthesized by aldol condensation of 4-hydroxymethylfurfural (4-HMF) and acetone.
4-HMF (4.75 g; 37.7 mmol) was dissolved in 0.5 equivalents (1.09g, 18.85mmol) of
acetone and 50ml of 0.1 M KOH. The mixture was stirred at room temperature
overnight. The solid precipitate was removed by filtration and washed to neutral with
water. The wet solid product could be used directly in the following step or dried in a
vacuum sulfuric acid desiccator under reduce pressure overnight to provide 3.68g
(71%) of F4-Ac-F4 as a yellow powder.
1
H-NMR: (400MHz, DMSO-d6, 293K, TMS): δ 4.38 (d, J=5.2, 4H), 5.12(t,
J=5.2, 2H), 6.92-6.96 (d, J=15.6, 2H), 6.98 (s, 2H), 7.50-7.53 (d, J=15.6, 2H), 7.75(s,
2H).
C-NMR: (100MHz, DMSO-d6, 293K, TMS): δ 54.49, 116.85, 122.54, 129.24,
13
129.63, 142.48, 151.12, 187.14.
Page 5 of 41
Hydrogenation of F4-Ac-F4
The hydrogenation reaction was carried out in a stainless autoclave containing
1.2g F4-Ac-F4, 60ml water, and 0.24 g 5%Pd/C (Aldrich) at the reaction conditions of
P(H2) = 5.3 MPa (ambient temperature) and T = 393 K under stirring (800 rpm). The
reaction progress was measured by 13C-NMR spectroscopy and when no aromatic
signals were detected anymore, the reaction was stopped. Then, the reactor was
cooled down to room temperature, the catalyst was separated by filtration, and the
filtrate was used directly in the following step.
Hydrodeoxygenation
The hydrogenation reaction was carried out in a stainless autoclave containing 9
ml hydrogenation crude reaction mixture, 90 mg 5%Pt/C(Aldrich) or 90 mg 5%Pd/C
(Aldrich), and 30 mg Zeolite HZSM-5 (supplied by the Catalytic Factory of Nankai
University, Si/Al=50). After flushing the reactor with H2 for three times, reactions
were conducted at 523-553 K in presence of 5.5 MPa H2 (ambient temperature) for 4
h with a stirring speed of 800 rpm. After cooled to ambient temperature, the organic
products were extracted by hexane. The organic phase was analyzed by GC-MS and
GC. Internal standard (hexadecane, TCI, purity≥99.5%) was used to determine the
amount of alkanes.
d. 13C-NMR experiments of the base-catalyzed condensation of
dihydroxyacetone (DHA)
Due to a variety of configurations of carbohydrate compounds, we first
dissolved the purified DL-dendroketose and the standard D-fructose and L-Sorbose in
heavy water respectively (containing sodium formate as a carbon chemical shift
internal standard) to confirm their respective carbon chemical shifts (Figure S3, S4
and S5).
Then, 10.5 mg of DL-dendroketose, 11.1 mg of D-fructose and 10.0 mg of
L-Sorbose were mixed and dissolved in heavy water (containing sodium formate as a
carbon chemical shift internal standard) (Figure S6).
Selecting hemiacetal carbon (less interference) as calculation object and
L-Sorbose as basis (the least configurations of the isomers) (Figure S7).
Calculation of calibration factors:
DL-Dendroketose: 10.5mg; δ: 103.197; Integral area: 0.900; Correction factor:
Page 6 of 41
0.857
D-Fructose: 11.1mg; δ: 98.086; Integral area: 0.929; Correction factor: 0.837
L-Sorbose: 10.0mg; δ: 97.749; Integral area: 1.000; Correction factor: 1.000
Then, 10wt% of DHA aqueous solution was catalyzed by IRA-900 (OH-) resin
at 273K for 12h. After filtering to remove the resin and concentrating under vacuum,
the mixture was dissolved in heavy water (containing sodium formate as a carbon
chemical shift internal standard) for 13C-NMR (Figure S8).
Calculation of the ratio of DL-dendroketose to D-fructose & L-Sorbose：
DL-Dendroketose: Integral area: 1.000; Correction factor: 0.857; Correction
integral area: 1.167;
Fructose: Integral area: 0.038; Correction factor: 0.837; Correction integral area:
0.045;
Sorbose: Integral area: 0.020; Correction factor: 1.000; Correction integral area:
0.020;
Dendroketose : (Fructose + Sorbose) = 1.167 : (0.045 + 0.020) = 94.7 : 5.3.
Figure S3 13C-NMR of DL-Dendroketose
Page 7 of 41
Figure S4 13C-NMR of D-Fructose
Figure S5 13C-NMR of L-Sorbose
Page 8 of 41
Figure S6 13C-NMR of DL-dendroketose, D-fructose and L-Sorbose
Figure S7
13C-NMR
of DL-dendroketose, D-fructose and L-Sorbose (L-Sorbose
as basis)
Page 9 of 41
Figure S8 13C-NMR of the base-catalyzed condensation of dihydroxyacetone
Page 10 of 41
Figure S9
13C-NMR
of the base-catalyzed condensation of dihydroxyacetone for
different time
Page 11 of 41
Part 2 Supplementary Notes
Sample PTE and liquid fuel yield calculations for comparing linked strategy and
gasfication-FT route
Lower heating values (LHV) of compounds are:
Methanol (32.04g/mol): 19.93MJ/kg
Formaldehyde (30.03g/mol): 15.98MJ/kg
Dihydroxyacetone (90.08g/mol): 14.48MJ/kg
Dendroketose (180.16g/mol): 14.13MJ/kg
4-HMF (126.11g/mol): 20.93MJ/kg
2,4-DMF (96.13g/mol): 32.17MJ/kg
Formaldehyde production:
3CH4O → 3CH2O + 3H2
(1)
3CH4O + 1.5O2 → 3CH2O + 3H2O
(2)
6 CH2O → 2 C3H6O3
(3)
2 C3H6O3 → C6H12O6
(4)
Formose reaction:
Aldol condensation:
Acid dehydration:
C6H12O6 → C6H6O3 + 3H2O
(5)
C6H6O3 +3H2 → C6H8O + 2H2O
(6)
Hydrogenolysis:
Combined Eq.1 to Eq.6, the net reaction is:
6CH4O + 1.5O2 → C6H8O + 8H2O
(7)
The theoretically PTE of methanol to 2,4-DMF is 0.81 and yield of 2,4-DMF is
0.5kg(2,4-DMF)/kg(methanol) according to Eq.7. The maximum PTE of biomass to methanol is 0.65 and
maximum yield of methanol is 554kg(MeOH)/Mg(dry biomass) according to Spath, P.L. and Dayton,
D.C.10. So, we can estimate that the PTE of biomass to 2,4-DMF is 0.53 and yield of 2,4-DMF is
277kg(2,4-DMF)/Mg(dry biomass). Whereas, the maximum PTE of biomass to FT is 0.43 and maximum
yield of FT fuel is 159kg(FT fuel)/Mg(dry biomass) according to Spath, P.L. and Dayton, D.C.10. So, we
can conclude that linked strategy has ca. 1.2 times energy recovery and ca. twice liquid fuels yield
compared with gasification-FTS route.
Combined Eq.2 to Eq.5, the net reaction of formaldehyde to 4-HMF is:
6CH2O → C6H6O3 + 3H2O
(8)
The theoretically PTE of formaldehyde to 4-HMF is 0.92 and yield of 2,4-DMF is
0.7kg(4-HMF)/kg(formaldehyde) according to Eq.8.
Page 12 of 41
Part 3 Supplementary Tables
Tables S1. Batch process for conversion of DHA to hexoses at different temperature.
DHA (0.5g), IRA-900 basic ion exchange resin (0.5g), and water (5ml). And
continuous process at different LHSV. DHA aqueous solution concentration (10
wt.%) and IRA-900 basic ion exchange resin as catalyst. Conversion is calculated
based on the amount of unconverted DHA. Ketohexoses selectivity is defined as
[Yieldbranched-chain ketohexoses × ( 1+Straight-chain ketohexoses/Branched-chain
ketohexoses)]/ConversionDHA × 100. The ratio of Branched-chain ketohexoses/
Straight-chain ketohexoses (abbreviated as B/S in this table) is calculated based on the
ratio of Yield4-HMF to Yield5-HMF after acid catalyst dehydration of ketohexoses.
DHA
Temp. Time LHSV
Ketohexoses
Entry
Conversion
B/S
(K)
(h)
(h-1)
Selectivity (%)
(%)
1
273
12
100
98.4
95.4:4.6
2
278
12
100
97.8
94.6:5.4
3
283
12
100
97.1
93.8:6.2
4
293
12
100
95.6
91.5:8.5
5
303
12
100
91.1
88.3:11.7
6
273
0.5
100
>99
93.3:6.7
7
273
1.0
100
>99
94.1:5.9
8
273
2.0
90.9
>99
94.8:5.2
9
273
3.0
66.0
>99
95.8:4.2
10
273
5.0
41.6
>99
96.1:3.9
Page 13 of 41
Tables S2. Continuous process for conversion of dendroketose to 4-HMF at different
LHSV. Dendroketose aqueous solution concentration (10 wt.%), MIBK as organic
phase and tantalum phosphate as catalyst. Conversion is calculated based on the
amount
of
unconverted
dendroketose.
Selectivity
is
defined
as
Yield4-HMF/Conversiondendroketose × 100.
LHSV
Feed ratio
Conversion
Selectivity
Entry
(/h-1)
(org : aq)
(%)
(%)
1
1.0
1.5 : 1.0
92
75
2
1.0
2.0 : 1.0
91
81
3
1.0
2.5 : 1.0
92
81
4
0.5
2.0 : 1.0
96
46
5
1.5
2.0 : 1.0
86
85
6
2.0
2.0 : 1.0
71
96
Page 14 of 41
Tables S3. Properties of DMFs
DMFs
CAS
Number
B.p
(°C)
Density
(g/ml)
625-86-5
3710-43-8
93.5
94.0
0.8995
0.8996
Page 15 of 41
Water
Solubility
(g/L)
2.3
3.2
Caloric
Value
(kJ/g)
33.7
34.0
RON
119
120
Tables S4. Toxicities of DMFs33
DMFs
Carcinogenicity Mutagenicity
Probability
Probability
Rat Oral
LD50
(mg/kg)
Chronic
LOAEL
(mg/kg)
Skin
Sensitization
Probability
n/a
Negative
653.4
46.9
Negative
n/a
Negative
625
23.3
Negative
Page 16 of 41
Part 4 Supplementary Figures and Legends
Fig. S10. Annotated schematic diagram of the process for the conversion of
aqueous solution of formaldehyde to aqueous solution of DHA.
Page 17 of 41
Fig. S11: Annotated schematic diagram of the process for the conversion of
aqueous solution of DHA to aqueous solution of dendroketose.
Page 18 of 41
Fig. S12: Annotated schematic diagram of the process for production of 4-HMF
from aqueous solution of dendroketose with simulated countercurrent extraction
and evaporation steps.
Page 19 of 41
Part 5 Chromatograms for each analysis step and analytical
conditions
Conversion of formaldehyde to dihydroxyacetone (DHA)
The reaction mixture and isolated product DHA were analyzed by HPLC. HPLC
was performed with a Hitachi L-2000 HPLC system equipped with L-2130 pumps
and a L-2455 photodiode array detector. DHA was analyzed by reversed-phase
chromatography on a 5C18-PAQ packed column (250×4.6mm, Nacalai Tesque , 10:90
v/v methanol: water (containing 0.1% H3PO4), 1.0 ml/min, 303 K, 271 nm).
Formaldehyde was determined colorimetrically with chromotropic acid on a UV-VIS
spectrophotometer (570 nm).
Fig. S13: Chromatogram and contour map of conversion of DHA to hexoses by
HPLC
Page 20 of 41
Fig. S14: Chromatogram and contour map of isolated DHA by HPLC
Conversion of DHA to hexoses
The reaction products and isolated product dendroketose were analyzed by
HPLC. HPLC was performed with a Waters system equipped with 1525 pumps, a
2996 photodiode array detector and a 2414 differential refraction detector. Hexoses
were analyzed by reversed-phase chromatography on a Sugar-D packed column
(250×4.6 mm, Nacalai Tesque, 75:25 acetonitrile/water, 1.0 ml/min, 303 K).
Page 21 of 41
Fig. S15: Chromatogram of conversion of DHA to hexoses by HPLC
Fig. S16: Chromatogram of isolated dendroketose by HPLC
Conversion of dendroketose to 4-HMF
The reaction mixtures and isolated product 4-HMF were analyzed by HPLC.
HPLC was performed with a Hitachi L-2000 HPLC system equipped with L-2130
pumps and a L-2455 photodiode array detector. HMF was analyzed by reversed-phase
chromatography on a 5C18-PAQ packed column (250×4.6mm, Nacalai Tesque, 10:90
methanol/water, 1.0 ml/min, 303 K, 280 nm).
Page 22 of 41
Fig. S17: Chromatogram and contour map of conversion of condensation raw
materials of DHA to HMFs by HPLC
Page 23 of 41
Fig. S18: Chromatogram and contour map of conversion of dendroketose to
4-HMF by HPLC
Hydrogenolysis of 4-HMF to 2,4-DMF
All liquid products were analyzed by HPLC (Hitachi system equipped with
L-2130 pumps, a L-2450 photodiode array detector, a L-2200autosampler and with a
250×4.6mm 5C18-PAQ packed column from Nacalai Tesque) and by GC-MS
(Thermal Trace GC Ultra with a PolarisQ ion trap mass spectrometer) with a TR-5MS
capillary column (30m×0.25mm×0.25μm). Product identification occurred by a
combination of mass spectroscopy, U.V. signature, and retention times in both HPLC
and GC-MS. Products 5 and 6 were purchased from Adamas and calibrated for HPLC
Page 24 of 41
and GC analyses. Product 2 was reduced from 4-HMF in methanol with NaBH4 at
273K, identified by NMR and calibrated for HPLC and GC analyses. Product 3 was
synthesized according to 31, identified by NMR and calibrated for HPLC and GC
analyses. Product 4 was synthesized according to 32, identified by NMR and
calibrated for HPLC and GC analyses.
Method Used for GC/MS
The method for the GC/MS with TR-5MS crossbond 5% diphenyl, 95% dimethyl,
polysiloxane was as follows: An initial oven temperature of 323 K was held for 2
minutes; next, temperature was ramped at 20 K/min until 598 K was reached. Column
pressure started at 100 kPa, held for 3 minutes, ramped at 1 kPa/min until 113 kPa
was reached, and then held at 113 kPa for 0.75 minutes. Column flow was 1.7 ml/min.
Method Used for HPLC with the 5C18-PAQ Column
Column temperature was set at 313 K and flow rate at 0.7 ml/min with 50% water
pH=2 and 50% methanol.
Compound Characterization
Mass spectroscopy was performed starting at 50 m/z. The mass spectra and the
retention times matched those of commercially available compounds or synthesized.
For all the compounds described below, the retention times for the GC-MS and the
HPLC, as well as the UV signature in the HPLC matched those of the corresponding
purchased or synthesized compounds.
1
H-NMR, 13C-NMR spectra were recorded on a Bruker Avance 400 spectrometer
at ambient temperature in CDCl3 unless otherwise noted.
The chromatogram was listed as Figure 3b in the paper.
The following compound numbers correspond to Figure 3 in the paper.
Compound 1: 4-hydroxymthylfurfural (CAS # 158360-01-1):
1H-NMR:
(400 MHz, CDCl3, 293K, TMS): δ 2.56 (s, 1H), 4.62 (s, 2H), 7.28(s,
1H), 7.67(s, 1H), 9.60 (s, 1H).
13C-NMR:
(100MHz, CDCl3, 293K, TMS): δ 56.1, 120.8, 128.4, 145.4, 153.3,
178.2.
UV/vis: λmax 280.0 nm;
M.S.: m/z (% of max intensity) 50(45), 51(80), 52 (62), 53 (60), 69(100), 70(34),
80 (50), 81 (26), 97 (70), 98 (26), 109 (23), 125 (20), 126 (25). {Actual MW 126.11}
Retention time: 8.62 min in GC/MS and 4.70 min in HPLC using the methods
described above.
Page 25 of 41
Compound 2: 2,4-furandimethanol (CAS # 294857-29-7):
(400 MHz, DMSO-d6, 293K, TMS): δ 4.31 (d, J=0.8, 2H), 4.35 (d,
1H-NMR:
J=0.4, 2H), 5.00(br, 2H), 6.25 (s, 1H), 7.42(d, J=0.8, 1H).
13C-NMR:
(100MHz, DMSO-d6, 293K, TMS): δ 54.8, 55.7, 107.3, 126.9, 138.4,
155.6.
UV/vis: λmax 216.9 nm;
M.S.: m/z (% of max intensity) 53 (49), 54 (20), 69 (22), 81 (100), 82 (56), 97
(14), 110 (5), 111 (19), 127 (8), 128 (23). {Actual MW 128.13}
Retention time: 9.16 min in GC/MS and 4.57 min in HPLC using the methods
described above.
Compound 3: 2-methyl-furan-4-methanol (CAS # 20416-19-7):
1H-NMR:
(400 MHz, CDCl3, 293K, TMS): δ 1.67 (br, 1H), 2.27 (d, J=0.4, 3H),
4.48(d, J=0.4,2H), 6.03 (s, 1H), 7.26(s, 1H).
13C-NMR:
(100MHz, CDCl3, 293K, TMS): δ 13.50, 56.73, 105.8, 126.0, 138.0,
153.1.
UV/vis: λmax 215.0 nm;
M.S.: m/z (% of max intensity) 51 (51), 53 (42), 55 (52), 65 (74), 66 (30), 67 (35),
69 (52), 83 (45), 84 (38), 95 (55), 97(72), 111(52), 112(100). {Actual MW 112.13}
Retention time: 6.23 min in GC/MS and 6.69 min in HPLC using the methods
described above.
Compound 4: 2,4-dimethylfuran (CAS # 3710-43-8):
1H-NMR:
(400 MHz, CDCl3, 293K, TMS): δ 1.96 (d, J=0.8, 3H), 2.22(d, J=0.8,
3H), 5.81 (s, 1H), 7.02(s, 1H).
13C-NMR:
(100MHz, CDCl3, 293K, TMS): δ 9.77, 13.48, 108.4, 120.7, 137.4,
162.2.
UV/vis: λmax 216.1 nm;
M.S.: m/z (% of max intensity) 51 (28), 53 (55), 65 (73), 67 (100), 81 (26), 95
(75), 96(91), 97(5). {Actual MW 96.13}
Retention time: 2.53 min in GC/MS and 20.91 min in HPLC using the methods
described above.
Page 26 of 41
Compound 5: furan-3-methanol (CAS # 4412-91-3):
1H-NMR:
(400 MHz, CDCl3, 293K, TMS): δ 1.91 (s, 1H), 4.54(s, 2H), 6.43 (d,
J=0.4, 1H), 7.39 (t, J=1.6, 1H), 7.41(s, 1H).
13C-NMR:
(100MHz, CDCl3, 293K, TMS): δ 56.62, 109.8, 125.2, 139.9, 143.5.
UV/vis: λmax 216.1 nm;
M.S.: m/z (% of max intensity) 51(47), 53(41), 55(21), 69(54), 70(25), 81(100),
95(15), 97(76), 98 (95), 99(5). {Actual MW 98.10}
Retention time: 5.05 min in GC/MS and 5.49 min in HPLC using the methods
described above.
Compound 6: 3-methylfuran (CAS # 930-27-8):
1H-NMR:
(400 MHz, CDCl3, 293K, TMS): δ 2.02 (d, J=1.2, 3H), 6.22(s, 1H),
7.17 (q, J=1.2, 1H), 7.30 (t, J=1.2, 1H).
13C-NMR:
(100MHz, CDCl3, 293K, TMS): δ 9.53, 112.2, 119.8, 139.3, 142.7.
UV/vis: λmax 215.3 nm;
Retention time: overlap with the peak of solvents in GC/MS and 13.02 min in
HPLC using the methods described above.
Preparation of C9-C15 branched-chain alkanes from 4-HMF
Aldol condensation of 4-HMF with acetone
The reaction mixtures were analyzed by HPLC. HPLC was performed with a
Hitachi L-2000 HPLC system equipped with L-2130 pumps and a L-2455 photodiode
array detector. The products (including F4-Ac-F4) were analyzed by reversed-phase
chromatography on a 5C18-PAQ packed column (250×4.6mm, Nacalai Tesque, 60:40
methanol/water, 1.0 ml/min, 303 K, 254 nm).
Hydrogenation of F4-Ac-F4
The reaction progress was measured by
13
C-NMR spectroscopy and when no
aromatic signals were detected anymore, the reaction was stopped. 13C-NMR spectra
were recorded on a Bruker Avance 400 spectrometer at ambient temperature in D2O.
Hydrodeoxygenation
The organic products were extracted by hexane. The organic phase was analyzed
by GC-MS and GC. Internal standard (hexadecane, TCI, purity≥99.5%) was used to
determine the amount of alkanes.
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Fig. S19: Chromatogram and contour map of aldol condensation of 4-HMF with
acetone by HPLC
The method for the GC/MS with TR-5MS (30 m × 0.25 μm × 0.25 mm)
crossbond 5% diphenyl, 95% dimethyl, polysiloxane was as follows: An initial oven
temperature of 353 K was held for 2 minutes; next, temperature was ramped at 6
K/min until 523 K was reached. Column flow was 2.7 ml/min. The carrier gas was
Page 28 of 41
helium and the split ratio was 30. The mass range was 20-300.
The method for GC (GC2014, Shimazu, FID) with RTX-5 (30 m × 0.25 μm ×
0.25 mm) crossbond 5% diphenyl, 95% dimethyl, polysiloxane was as follows: The
vaporization temperature was 523 K. An initial oven temperature of 353 K was held
for 2 minutes; next, temperature was ramped at 6 K/min until 523 K was reached.
Column flow was 2.7 ml/min. The carrier gas was nitrogen and the split ratio was 30.
Fig. S20
GC Chromatogram of hydrodeoxygenation (5%Pt/C & HZSM-5 @
553K)
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Fig. S21
GC Chromatogram of hydrodeoxygenation (5%Pd/C & HZSM-5 @
553K)
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Part 6 NMR spectrograms
DHA:
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DL-dendroketose:
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4-hydroxymthylfurfural:
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2,4-furandimethanol:
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2-methyl-furan-4-methanol:
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2,4-dimethylfuran:
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furan-3-methanol:
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3-methylfuran:
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4-(4-hydroxymethyl-2-furyl)-3-butene-2-one:
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1,5-bis-(4-hydroxymethyl-2-furyl)-1,4-pentadien-3-one:
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Part 7
Supplemental References:
31. Ancerewicz, J. & Vogel, P. A new approach to the synthesis of long-chain polypropionates
based on the diels-alder monoadditions of 2,2’-ethylidenebis [3,5-dimethylfuran]. Helv. Chim.
Acta. 79, 1393-1414 (1996).
32. Friedrich, M., Wächtler, A. & Meijere, A.de. Extending the scope of a known furan synthesis –
a novel route to 1,2,4-trisubstituted pyrroles. Synlett, 619-621 (2002).
33. Crews, C. Factors affecting the formation of furan in heated foods (Report No. FD
07/03 2007); available at
(http://www.foodbase.org.uk//admintools/reportdocuments/397-1-699_Factors_Affect
ing_Furan_Formation.pdf).
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