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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