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Calorimetric Measurement of the CH/

Interaction Involved in the Molecular

Recognition of Saccharides by Aromatic

Compounds.

Lorena Bautista-Ibáñez , Karla Ramírez-Gualito , Beatriz-Quiroz-Garcia , Aarón Rojas-

Aguilar , Gabriel Cuevas *

1. Table S1. Chemical Shifts (ppm) 1H NMR spectra of Methyl 2,3,4,6-tetra-O-methyl- -


D-mannopyranoside upon addition of benzene to a 0.88 M chloroform solution. P. S4.
2. Table S2. Chemical Shifts (ppm) 1H NMR spectra of Methyl 2,3,4,6-tetra-O-methyl- -
D-galactopyranoside upon addition of benzene to a 0.88 M chloroform solution. P. S5.
3. Table S3. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-
mannopyranoside in 1-Methoxy-4-methylbenzene (1:10, mol:mol). Determined from
Calvet Microcalorimetry at 303.15 K. P. S6.
4. Table S4. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-
mannopyranoside in o-Xylene (1:10, mol:mol). Determined from Calvet
Microcalorimetry at 303.15 K . P. S7.
5. Table S5. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-
mannopyranoside in p-Xylene (1:10, mol:mol). Determined from Calvet
Microcalorimetry at 303.15 K . P. S8.

S1
6. Table S6. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-
mannopyranoside in m-Xylene (1:10, mol:mol). Determined from Calvet
Microcalorimetry at 303.15 K . P. S9.
7. Table S7. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-
mannopyranoside in 1,2-Dimethoxybenzene (1:10, mol:mol). Determined from Calvet
Microcalorimetry at 303.15 K . P. S10.
8. Table S8. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-
mannopyranoside in benzene (1:10, mol:mol). Determined from Calvet
Microcalorimetry at 303.15 K . P. S11.
9. Table S9. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-
galactopyranoside in 1-methoxy-4-methylbenzene (1:10, mol:mol). Determined from
Calvet Microcalorimetry at 303.15 K . P. S12.
10. Table S10. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-
galactopyranoside in o-xylene (1:10, mol:mol). Determined from Calvet
Microcalorimetry at 303.15 K . P. S13.
11. Table S11. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-
galactopyranoside in p-xylene (1:10, mol:mol). Determined from Calvet
Microcalorimetry at 303.15 K . P. S14.
12. Table S12. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-
galactopyranoside in m-xylene (1:10, mol:mol). Determined from Calvet
Microcalorimetry at 303.15 K . P. S15.
13. Table S13. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-
galactopyranoside in 1,2-Dimethoxybenzene (1:10, mol:mol). Determined from Calvet
Microcalorimetry at 303.15 K . P. S16.
14. Table S14. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-
galactopyranoside in 1,3-Dimethoxybenzene (1:10, mol:mol). Determined from Calvet
Microcalorimetry at 303.15 K . P. S17.
15. Table S15. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-
galactopyranoside in benzene (1:10, mol:mol). Determined from Calvet
Microcalorimetry at 303.15 K . P. S18.

S2
16. Table S16. Enthalpy of Vaporization of Methyl 2,3,4,6-tetra-O-methyl- -D-
mannopyranoside. Determined from DSC. P. S19.
17. Table S17. Enthalpy of Vaporization of Methyl 2,3,4,6-tetra-O-methyl- -D-
galactopyranoside. Determined from DSC. P. S20.
18. Table S18. Chemical shifts (ppm) and differences of these for methyl acetate and
mixtures of benzene-d6 and chloroform-d. P. S21.
19. Table S19. Chemical shifts (ppm) and differences of these for 1H 500 MHz NMR
spectra of compound 1 and 2 of benzene-d6 and chloroform-d. P. S22.
20. Sidgwick´s Temperature Correction on the Enthalpy of Vaporization of Methyl 2,3,4,6-
tetra-O-methyl- -D-mannopyranoside. P. S23.
21. 1H 500 MHz NMR spectra of compound 1. P S24.
22. 13C 500 MHz NMR spectra of compound 1. P S24.
23. COSY 500 MHz NMR spectra of compound 1. P S25.
24. NOESY 500 MHz NMR spectra of compound 1. P S25.
25. HSQC 500 MHz NMR spectra of compound 1. P S26.
26. HMBC 500 MHz NMR spectra of compound 1. P S26.
1
27. H 500 MHz NMR spectra of compound 2. P S27.
28. 13C 500 MHz NMR spectra of compound 2. P S27.
29. COSY 500 MHz NMR spectra of compound 2. P S28.
30. NOESY 500 MHz NMR spectra of compound 2. P S28.
31. HSQC 500 MHz NMR spectra of compound 2. P S29.
32. HMBC 500 MHz NMR spectra of compound 2. P S29.

S3
1. Table S1. Chemical Shifts (ppm) 1H NMR spectra of Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside upon addition of benzene to a 0.88 M chloroform
solution.

[mol:mol]
a H1 (d) H2 (dd) H3 (dd) H4 (t) H5 (ddd) H6a (dd) H6b (dd) Me(1) (s) Me(2) (s) Me(3) (s) Me(4) (s) Me(5) (s)
()

CDCl3
4.14 3.30 3.15 3.65 3.49 3.62 3.55 3.51 3.58 3.53 3.56 3.41
1:0.5
4.12 3.32 3.11 3.65 3.45 3.59 3.51 3.48 3.57 3.48 3.57 3.36
1:1.0
4.11 3.33 3.08 3.57 3.42 3.59 3.49 3.45 3.56 3.47 3.56 3.33
1:1.5
4.10 3.34 3.06 3.54 3.40 3.58 3.48 3.42 3.56 3.45 3.56 3.30
1:2.0
4.09 3.35 3.04 3.53 3.38 3.57 3.47 3.40 3.55 3.44 3.55 3.28
1:2.5
4.09 3.41 3.03 3.51 3.37 3.57 3.46 3.39 3.55 3.43 3.55 3.26
1:3.0
4.08 3.46 3.02 3.50 3.35 3.56 3.46 3.37 3.55 3.43 3.55 3.25
1:3.5
4.08 3.45 3.01 3.49 3.34 3.56 3.45 3.36 3.55 3.42 3.55 3.24
1:4.0
4.08 3.45 3.00 3.48 3.33 3.56 3.44 3.35 3.55 3.41 3.55 3.23
1:4.5
4.08 3.45 3.00 3.33 3.56 3.45 3.34 3.55 3.41 3.55 3.22
1:5.0
4.08 2.99 3.46 3.32 3.56 3.45 3.34 3.55 3.41 3.55 3.21
1:5.5
4.08 3.45 2.99 3.46 3.32 3.57 3.45 3.33 3.55 3.40 3.55 3.24
1:6.0
4.08 3.46 2.99 3.46 3.32 3.57 3.33 3.55 3.40 3.55 3.20
(a) molar ratio between Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside:benzene, the carbohydrate was dissolved in CDCl3 and further benzene was
added in the indicated ratio.

S4
Table S2. Chemical Shifts (ppm) 1H NMR spectra of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside upon addition of benzene to a 0.88 M chloroform solution.

[mol:mol]
a H1 (d) H2 (dd) H3 (dd) H4 (dd) H5 (ddd) H6a (dd) H6b (dd) Me(1) (s) Me(2) (s) Me(3) (s) Me(4) (s) Me(5) (s)
()

CDCl3
4.82 3.19 3.48 3.18 3.58 3.58 3.58 3.42 3.51 3.62 3.54 3.42
1:0.5
4.80 3.19 3.49 3.17 3.58 3.57 3.57 3.38 3.47 3.62 3.52 3.39
1:1.0
4.78 3.18 3.51 3.18 3.58 3.56 3.56 3.35 3.44 3.61 3.50 3.35
1:1.5
4.77 3.18 3.52 3.18 3.57 3.33 3.42 3.59 3.49 3.33
1:2.0
4.75 3.18 3.52 3.57 3.31 3.40 3.58 3.48 3.31
1:2.5
4.74 3.16 3.19 3.59 3.56 3.56 3.29 3.38 3.58 3.47 3.30
1:3.0
4.74 3.16 3.53 3.19 3.60 3.56 3.56 3.28 3.36 3.58 3.47 3.29
1:3.5
4.73 3.16 3.19 3.60 3.56 3.56 3.27 3.35 3.58 3.46 3.27
1:4.0
4.73 3.16 3.20 3.60 3.55 3.55 3.26 3.34 3.58 3.46 3.26
1:4.5
4.72 3.15 3.54 3.20 3.60 3.55 3.55 3.25 3.33 3.57 3.46 3.26
1:5.0
4.72 3.15 3.59 3.21 3.61 3.25 3.32 3.57 3.46 3.25
1:5.5
4.71 3.15 3.60 3.21 3.61 3.24 3.32 3.57 3.46 3.24
1:6.0
4.71 3.15 3.60 3.21 3.61 3.24 3.31 3.57 3.46 3.24

(a) molar ratio between Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside:benzene, the carbohydrate was dissolved in CDCl3 and further benzene was
added in the indicated ratio.

S5
Table S3. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside in 1-Methoxy-4-

methylbenzene (1:10, mol:mol). Determined from Calvet Microcalorimetry at 303.15 K.

a b c
mass ( ) area ( ) Q() dis H m ,
Entry
mg J J g
* -1 1
kJ * mol

1 102.960 0.386 3.746 0.938

2 102.710 0.375 3.654 0.915

3 101.160 0.422 4.170 1.044

4 97.750 0.304 3.107 0.778

5 105.380 0.429 4.066 1.018


(d)
Average: (0.938 ± 0.105)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside in each experiment; (b) curve


area in the thermogram.(c) heat released in the dissolution process. (d) the uncertainty
represents the standard deviation.

S6
Table S4. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside in o-Xylene (1:10,

mol:mol). Determined from Calvet Microcalorimetry at 303.15 K.

a b (c)
mass ( ) Area ( ) Q dis H m ,
Entry
mg J
*
J g
-1 1
kJ * mol

1 106.010 1.194 11.261 2.189

2 102.170 1.060 10.375 2.597

3 105.840 1.056 9.981 2.498

4 101.640 1.048 10.309 2.580


(d)
Average: (2.623 ± 0.137)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside in each experiment; (b) curve


area in the thermogram. (c) heat released in the dissolution process. (d) the uncertainty
represents the standard deviation.

S7
Table S5. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside in p-Xylene (1:10,

mol:mol). Determined from Calvet Microcalorimetry at 303.15 K.

a b (c)
mass ( ) Area ( ) Q
dis H m ,
Entry
* -1 1
mg J J g kJ * mol

1 100.490 1.059 10.540 2.638

2 102.300 1.068 10.435 2.612

(d)
Average: (2.625 ± 0.019)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside in each experiment; (b) curve


area in the thermogram. (c) heat released in the dissolution process. (d) the uncertainty
represents the standard deviation.

S8
Table S6. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside in m-Xylene (1:10,

mol:mol). Determined from Calvet Microcalorimetry at 303.15 K.

a b (c)
mass ( ) Area ( ) Q
dis H m ,
Entry
* -1 1
mg J J g kJ * mol

1 109.820 1.298 11.815 2.957

2 102.170 1.239 12.125 3.035

Average: (2.996 ± 0.055)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside in each experiment; (b) curve


area in the thermogram. (c) heat released in the dissolution process. (d) the uncertainty
represents the standard deviation.

S9
Table S7. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside in 1,2-

Dimethoxybenzene (1:10, mol:mol). Determined from Calvet Microcalorimetry at 303.15 K.

a b (c)
mass ( ) Area ( ) Q dis H m ,
Entry
mg J
*
J g
-1 1
kJ * mol

1 101.360 0.428 4.219 1.056

2 102.730 0.433 4.210 1.054

Average: (1.055 ± 0.002)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside in each experiment; (b) curve


area in the thermogram. (c) heat released in the dissolution process. (d) the uncertainty
represents the standard deviation.

S10
Table S8. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside in benzene (1:10,

mol:mol). Determined from Calvet Microcalorimetry at 303.15 K.

(a) (b) (c)


mass Area Q dis H m ,
Entry
mg J
*
J g
-1 1
kJ * mol

1 111.340 -1.465 -13.156 -3.293


2 221.310 -3.238 -14.632 -3.662
3 106.540 -1.612 -15.132 -3.787
4 104.460 -1.461 -13.989 -3.501
5 99.860 -1.596 -15.977 -3.999

Average: (-3.649 ± 0.269) (d)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside in each experiment; (b) curve


area in the thermogram. (c) heat released in the dissolution process. (d) the uncertainty
represents the standard deviation.

S11
Table S9. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside in 1-methoxy-4-

methylbenzene (1:10, mol:mol). Determined from Calvet Microcalorimetry at 303.15 K.

(a) (b) (c)


mass Area Q dis H m ,
Entry
mg J
*
J g
-1 1
kJ * mol

1 100.000 6.491 64.912 16.247


2 100.770 6.702 66.508 16.646
3 103.500 7.387 71.373 17.864
4 104.970 7.887 75.136 18.806

(d)
Average: (17.391 ± 1.167)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside in each experiment; (b) curve


area in the thermogram. (c) heat released in the dissolution process. (d) the uncertainty
represents the standard deviation.

S12
Table S10. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside in o-xylene (1:10,

mol:mol). Determined from Calvet Microcalorimetry at 303.15 K.

(a) (b) (c)


mass Area Q dis H m ,
Entry
mg J
*
J g
-1 1
kJ * mol

1 102.950 7.765 75.420 18.877


2 104.180 7.849 75.338 18.856
3 102.900 7.707 74.899 18.746
4 102.650 7.865 76.620 19.177

(d)
Average: (18.914 ± 0.184)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside in each experiment; (b) curve


area in the thermogram. (c) heat released in the dissolution process. (d) the uncertainty
represents the standard deviation.

S13
Table S11. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside in p-xylene (1:10,

mol:mol). Determined from Calvet Microcalorimetry at 303.15 K.

(a) (b) (c)


mass Area Q dis H m ,
Entry
mg J
*
J g
-1 1
kJ * mol

1 101.880 8.183 80.317 20.102


2 100.840 7.732 76.673 19.190
3 102.180 7.694 75.302 18.847
4 104.800 7.895 75.336 18.856

(d)
Average: (19.249 ±0.591)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside in each experiment; (b) curve


area in the thermogram. (c) heat released in the dissolution process. (d) the uncertainty
represents the standard deviation.

S14
Table S12. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside in m-xylene

(1:10, mol:mol). Determined from Calvet Microcalorimetry at 303.15 K.

(a) (b) (c)


mass Area Q dis H m ,
Entry
mg J
*
J g
-1 1
kJ * mol

1 101.380 7.857 77.496 19.396


2 101.300 7.946 78.437 19.632
3 107.470 8.080 75.184 18.818
4 102.250 8.047 78.701 19.698

(d)
Average:(19.386 ± 0.400)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside in each experiment; (b) curve


area in the thermogram. (c) heat released in the dissolution process. (d) the uncertainty
represents the standard deviation.

S15
Table S13. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside in 1,2-

Dimethoxybenzene (1:10, mol:mol). Determined from Calvet Microcalorimetry at 303.15 K.

(a) (b) (c)


mass Area Q dis H m ,
Entry
mg J
*
J g
-1 1
kJ * mol

1 103.010 7.132 69.234 17.328


2 102.030 7.148 70.058 17.535
3 101.370 7.691 75.866 18.988
4 101.820 7.334 72.028 18.028

(d)
Average:(17.970 ± 0.740)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside in each experiment; (b) curve


area in the thermogram. (c) heat released in the dissolution process. (d) the uncertainty
represents the standard deviation.

S16
Table S14. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside in 1,3-

Dimethoxybenzene (1:10, mol:mol). Determined from Calvet Microcalorimetry at 303.15 K.

(a) (b) (c)


Mass Area Q dis H m ,
Entry
mg J
*
J g
-1 1
kJ * mol

1 103.930 6.810 65.524 16.400


2 101.010 6.585 65.193 16.317
3 107.720 6.727 62.453 15.631
4 104.470 6.825 65.326 16.350

(d)
Average: (16.175 ± 0.364)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside in each experiment; (b) curve


area in the thermogram. (c) heat released in the dissolution process. (d) the uncertainty
represents the standard deviation.

S17
Table S15. Enthalpies of Solution of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside in benzene (1:10,

mol:mol). Determined from Calvet Microcalorimetry at 303.15 K.

(a) (b) (c)


mass Area Q dis H m ,
Entry
mg J
*
J g
-1 1
kJ * mol

1 109.150 7.109 65.126 16.300


2 103.990 6.914 66.491 16.642
3 106.640 7.124 66.800 16.719
4 104.080 6.856 65.870 16.487

(d)
Average: (16.537 ± 0.185)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside in each experiment; (b) curve


area in the thermogram. (c) heat released in the dissolution process. (d) the uncertainty
represents the standard deviation.

S18
Table S16. Enthalpy of Vaporization of Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside. Determined

from DSC at.333.15 K.

(a) (b) (c) (d) (e)


m1 m2 m3 Total Area Peak Area Qvap vap H m ,
Entry
mg mg mg mJ mJ
*
J g
-1 1
kJ * mol

295.49
1 22.079 0.374 21.414 6818.470 490.803 73.959
5

311.53
2 12.229 0.157 11.911 4253.721 543.176 77.972
0

319.43
3 10.750 0.089 10.519 4052.467 692.274 79.950
4

315.23
4 11.546 0.091 11.303 4243.765 680.740 78.899
6

285.16
5 8.857 0.071 8.669 3186.662 714.540 71.373
2

274.22
6 9.187 0.071 8.995 3217.475 750.902 68.634
1

278.41
7 12.583 0.145 12.272 4176.816 760.071 69.684
7

281.03
8 11.936 0.094 11.685 3997.167 713.453 70.338
0

275.74
9 11.233 0.102 10.983 3759.066 730.605 69.016
5

287.22
10 9.268 0.062 9.084 3402.849 793.733 71.890
9

287.00
11 10.244 0.088 10.021 3588.507 712.434 71.835
8

293.14
12 9.148 0.077 8.950 3338.167 714.444 73.370
2

g
= 333.15 K ) > = (73.077± 3.897) kJ mol
-1
< l H m (T
exp

g
< l H m (T = 298.15 K ) > = (75.177 ± 3.897) kJ mol
-1

(a) initial mass of Methyl 2,3,4,6-tetra-O-methyl- -D-mannopyranoside in each experiment; (b)


residual mass after vaporization; (c) evaporated mass; (d).total curve area of the vaporization
process; (e) area corresponding only to the pumping peak, when first derivate changes.

S19
Table S17. Enthalpy of sublimation of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside. Determined

from DSC at 313.15 K.

(a) (b) (c) (d) (e)


m1 m2 m3 Total Area Peak Area Qvap vap H m ,
Entry
mg mg mg mJ mJ *
J g
-1 1
kJ * mol

1 10.900 0.146 10.734 5242.193 501.490 441.664 110.543

2 12.443 0.072 12.348 5828.598 631.089 420.924 105.352

3 11.166 0.101 11.044 4985.671 690.690 388.889 97.334

4 10.194 0.074 10.101 4733.062 794.535 389.913 97.590

5 9.042 0.088 8.937 4509.534 775.573 417.801 104.570

6 10.602 0.083 10.499 5008.272 809.251 399.934 100.099

7 10.069 0.082 9.968 5430.304 994.637 444.979 111.373

8 10.390 0.105 10.266 5369.683 944.175 431.098 107.898

g
= 313.15 K ) > = (104.345 ± 5.533) kJ mol
-1
< s H m (T
exp

g
< s H m (T = 298.15 K ) > = (105.245 ± 5.533) kJ mol
-1

(a) initial mass of Methyl 2,3,4,6-tetra-O-methyl- -D-galactopyranoside in each experiment; (b)


residual mass after vaporization; (c) evaporated mass; (d).total curve area of the vaporization
process; (d) area corresponding only to the pumping peak.

S20
Table S18. Chemical shifts (ppm) and differences of these for methyl acetate and mixtures
of benzene-d6 and chloroform-d.

Composition CH3COb rel


c
CH3Ob rel
c

CDCl3 2.052 0.000 3.663 0.000


1:0.5 2.005 0.047 3.620 0.043
1:1.0 1.964 0.088 3.584 0.079
1:2.0 1.900 0.152 3.526 0.137
1:3.0 1.851 0.201 3.482 0.181
1:4.0 1.817 0.235 3.451 0.212
1:5.0 1.790 0.262 3.428 0.235
1:6.0 1.769 0.283 3.410 0.253
1:7.0 1.753 0.299 3.396 0.267
1:8.0 1.743 0.309 3.388 0.275
1:9.0 1.733 0.319 3.379 0.284
1:10 1.722 0.330 3.369 0.294
Bencene-d6 1.695 0.357 3.347 0.316

S21
Table S19. Chemical shifts (ppm) and differences of these for 1H 500 MHz NMR spectra of
compound 1 and 2 of chloroform-d and benzene-d6.

1 2
CDCl3 C6D6 = CDCl3 C6D6 CDCl3 C6D6 = CDCl3 C6D6
H1 4.79 4.68 0.11 4.15 4.14 0.01
H2 3.56 3.47 0.09 3.31 3.68 -0.37
H3 3.49 3.68 -0.19 3.15 2.97 0.18
H4 3.42 3.75 -0.33 3.65 3.45 0.20
H5 3.55 3.82 -0.27 3.57 3.33 0.24
H6a 3.59 3.67 -0.08 3.62 3.64 -0.02
H6b 3.59 3.61 -0.02 3.54 3.50 0.04
Me1 3.37 3.14 0.23 3.50 3.37 0.13
Me2 3.47 3.24 0.23 3.58 3.56 0.02
Me3 3.48 3.24 0.24 3.52 3.27 0.25
Me4 3.51 3.48 0.03 3.56 3.46 0.10
Me5 3.40 3.24 0.16 3.40 3.10 0.30

S22
Sidgwick´s Temperature Correction on the Enthalpy of Vaporization of Methyl 2,3,4,6-tetra-O-

methyl- -D-mannopyranoside

g g 1 2
l H m (Texp ) l H m ( 298.15 K ) / kJ mol = 6 x10 (T 298.15 K )
exp
g 1
73.077 l H ( 298.15 K ) = 2.1 kJ mol
g 1 1 1
l H ( 298.15) = 73.077 kJ mol ( 2.1 kJ mol ) = 75.177 kJ mol

The same correction procedure applies for the Methyl 2,3,4,6-tetra-O-methyl- -D-
galactopyranoside.

S23
1
H 500 MHz NMR spectra of compound 1 in benzene-d6.

13
C 125 MHz NMR spectra of compound 1 in benzene-d6.

S24
COSY 500 MHz NMR spectra of compound 1 in benzene-d6.

S25
NOESY 500 MHz NMR spectra of compound 1 in benzene-d6.

HSQC 500 MHz NMR spectra of compound 1 in benzene-d6.

S26
HMBC 500 MHz NMR spectra of compound 1 in benzene-d6.

S27
1
H NMR 500 MHz spectrum of compound 2 in benzene-d6.

13
C NMR 125 MHz spectrum of compound 2 in benzene-d6.

S28
COSY NMR 500 MHz spectrum of compound 2 in benzene-d6.

NOESY NMR 500 MHz spectrum of compound 2 in benzene-d6.

HSQC NMR 500 MHz spectrum of compound 2 in benzene-d6.

S29
HMBC NMR 500 MHz spectrum of compound 2 in benzene-d6.

S30