S4 Elemental analysis of azeotrope- dried glucaric acid. 0. 2. 4. 6. 8. 10. 12. 14 ... X-ray crystal structure data for as prepared D-glucaric acid. Identification code.
Eur. J. Org. Chem. 2017 · ISSN 1099–0690 https://doi.org/10.1002/ejoc.201701343 SUPPORTING INFORMATION Title: How to Synthesise High Purity, Crystalline D-Glucaric Acid Selectively Author(s): Robert D. Armstrong,* Benson Kariuki, David W. Knight, Graham J. Hutchings*
(a) 100
120
140
F1 Chemical Shift (ppm)
80
160
5.0
4.5 F2 Chemical Shift (ppm)
4.0
(b)
C / ppm
4.00
4.25
4.50
4.75
5.00
5.25
5.50
180
180
175
175
170
170
80
80
75
75
70
70
65
Glucaric Acid 1 bond Glucaric Acid 2 bond 1,4 Lactone 1 bond 1,4 Lactone 2 bond 3,6 Lactone 1 bond 3,6 Lactone 2 bond Dilactone 1 bond Dilactone 2 bond DriedD2O
65 4.00
4.25
4.50
4.75
5.00
5.25
5.50
1H / ppm
Fig. S1 HMBC spectrum (a) and spectral assignment (b) of K- glucarate exchange product recovered from H2O through rotavap drying (50 mbar, 50 oC) followed by freeze drying. Glucaric Acid Glucaro 1,4- lactone, Glucaro 3,6- lactone, Glucaro 1,4 : 6,3 – dilactone. Filled and empty symbols represent expected 1 and 2 bond 13C – 1H interactions respectively. Isolated product.
Before Amberlyst
After Amberlyst
800
800
Thereoretical [K]
[K] / ppm
780
780
760
760
740
740
720
720
700
700
15
15
10
10
5
5
0
0 H2O
MeCN
MeOH
EtOH
Acetone
Solvent
Fig. S2 Determination of the solubility of K-glucarate in polar solvents. Conditions; K-glucarate (0.05 g), Solvent (10 ml), room temperature, vigorous stirring. Where applicable Amberlyst-15 (0.5 g).
[MeCN] / v/v% 100
80
60
40
20
1000
50
900
45
Azeotrope
800
40
700
35
600
30
500
25
400
20
300
15
200
10
100
5
0 0
20
40
60
80
[K] after Amberlyst / ppm
[K] before Amberlyst / ppm
0
0 100
[H2O] / v/v%
Fig. S3 Determination of the solubility of K-glucarate and efficacy of K+ exchange in binary H2O/ MeCN solvents of differing composition. Conditions; K-glucarate (0.05 g), Vtotal solvent (10 ml), Stirred 1 h. Sampled (filtered sample) followed by AES. Then add Amberlyst (0.5 g) and stir for 5 min. Filter and AES.
1.0 0.018
Potassium Content / mg
0.8 0.014 0.012
0.6
0.010 0.008
0.4
0.006 0.004
0.2
0.002 0.000 0
2
4
6
8
10
12
14
16
18
20
0.0 22
Glucaric Acid / mg
Fig. S4 Elemental analysis of azeotrope- dried glucaric acid.
Starting potassium remaining / %
0.016
0.010 0.0020 0.0018
0.0062 wt % K
0.0014 0.0012
0.005
0.0010 0.0008 0.0006
K content / wt%
K in solution / mg
0.0016
0.0004 0.0002 0.0000
0.000 0
10
20
30
Glucaric Acid in solution / mg
Fig. S5 Elemental analysis of azeotrope- dried glucaric acid following 2 consecutive H+ exchanges.
1.1
Intensity / a.u
1.0
0.9
0.8
0.7
3500
3000
2500
2000
Wavenumber / cm-1 Fig. S6 IR spectrum of crystallised glucaric acid
Fig. S7 NMR spectrum of synthesised glucaric acid collected at 600 mHz in D2O
2.5x108
CH3COO1H C1H3COOH
2.0x108
2.0x107 1.5x107 1.0x107 5.0x106 0.0 12
6
4
2
Chemical Shift / ppm Fig. S8 1H NMR spectrum of azeotrope- dried Glucaric Acid dissolved in D4 acetic acid, showing no H2O resonances.
Fig. S9 HMBC spectrum of Ca- glucarate exchange product recovered from H2O/ MeCN azeotrope through rotavap drying (50 mbar, 22 oC). D-Glucaric Acid
Fig. S10 HMBC spectrum of Ca- glucarate exchange product recovered from H2O through rotavap drying (50 mbar, 50 oC). D-Glucaric Acid
6x108 10
5x108
Intensity / a.u
8
58 oC
4x108
6
8
3x10
50 oC
2x108
38 oC
1x108
28 oC
0
20 oC
4
2
0
5.5
5.0
4.5
4.0
Chemical Shift / ppm
Fig. S11 1H NMR spectrum of azeotrope- dried Glucaric Acid recovered by evaporation at different temperatures Glucaric Acidref Glucaro 1,4- lactoneref, Glucaro 3,6- lactoneref, Glucaro 1,4 : 3.6 – dilactoneref
X-ray crystal structure data for as prepared D-glucaric acid Identification code
D-glucaric acid
Empirical formula
C6 H10 O8
Formula weight
210.14
Temperature
293(2) K
Wavelength
1.54184 Å
Crystal system
Monoclinic
Space group
P 21
Unit cell dimensions
a = 6.7810(3) Å
= 90°.
b = 8.6507(3) Å
= 93.587(4)°.
c = 7.2443(3) Å
= 90°.
Volume
424.12(3) Å3
Z
2
Density (calculated)
1.645 Mg/m3
Absorption coefficient
1.404 mm-1
F(000)
220
Crystal size
0.379 x 0.165 x 0.119 mm3
Theta range for data collection
6.121 to 74.155°.
Index ranges
-8
