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S1

Calorimetric Measurement of the CH/

Interaction Involved in the Molecular

Recognition of Saccharides by Aromatic

Compounds.

Lorena Bautista-Ibez, Karla Ramrez-Gualito, Beatriz-Quiroz-Garcia, Aarn 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)

1

H 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.

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S2

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 CalvetMicrocalorimetry 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.

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S3

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-d6and 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-d6and chloroform-d. P. S22.

20.Sidgwicks 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.

27.1H 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 compound2

. 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.

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

solution.

[mol:mol](a)

H1 (d) H2 (dd) H3 (dd) H4 (t) H5 (ddd) H6a (dd) H6b (dd) Me(1) (s) Me(2)

CDCl34.14 3.30 3.15 3.65 3.49 3.62 3.55 3.51 3.58

1:0.5 4.12 3.32 3.11 3.65 3.45 3.59 3.51 3.48 3.57

1:1.04.11 3.33 3.08 3.57 3.42 3.59 3.49 3.45 3.56

1:1.54.10 3.34 3.06 3.54 3.40 3.58 3.48 3.42 3.56

1:2.04.09 3.35 3.04 3.53 3.38 3.57 3.47 3.40 3.55

1:2.54.09 3.41 3.03 3.51 3.37 3.57 3.46 3.39 3.55

1:3.04.08 3.46 3.02 3.50 3.35 3.56 3.46 3.37 3.55

1:3.54.08 3.45 3.01 3.49 3.34 3.56 3.45 3.36 3.55

1:4.0 4.08 3.45 3.00 3.48 3.33 3.56 3.44 3.35 3.55

1:4.54.08 3.45 3.00 3.33 3.56 3.45 3.34 3.55

1:5.04.08 2.99 3.46 3.32 3.56 3.45 3.34 3.55

1:5.54.08 3.45 2.99 3.46 3.32 3.57 3.45 3.33 3.55

1:6.04.08 3.46 2.99 3.46 3.32 3.57 3.33 3.55

(a) molar ratio between Methyl 2,3,4,6-tetra-O-methyl--D-mannopyranoside:benzene, the carbohydrate was dissolveadded in the indicated ratio.

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Table S2. Chemical Shifts (ppm) 1H NMR spectra of Methyl 2,3,4,6-tetra-O-methyl--D-galactopyranoside upon addition of ben

[mol:mol](a)

H1 (d) H2 (dd) H3 (dd) H4 (dd) H5 (ddd) H6a (dd) H6b (dd) Me(1) (s) Me(2)

CDCl34.82 3.19 3.48 3.18 3.58 3.58 3.58 3.42 3.51

1:0.54.80 3.19 3.49 3.17 3.58 3.57 3.57 3.38 3.47

1:1.04.78 3.18 3.51 3.18 3.58 3.56 3.56 3.35 3.44

1:1.54.77 3.18 3.52 3.18 3.57 3.33 3.42

1:2.04.75 3.18 3.52 3.57 3.31 3.40

1:2.54.74 3.16 3.19 3.59 3.56 3.56 3.29 3.38

1:3.04.74 3.16 3.53 3.19 3.60 3.56 3.56 3.28 3.36

1:3.54.73 3.16 3.19 3.60 3.56 3.56 3.27 3.35

1:4.04.73 3.16 3.20 3.60 3.55 3.55 3.26 3.34

1:4.54.72 3.15 3.54 3.20 3.60 3.55 3.55 3.25 3.33

1:5.04.72 3.15 3.59 3.21 3.61 3.25 3.32

1:5.54.71 3.15 3.60 3.21 3.61 3.24 3.32

1:6.04.71 3.15 3.60 3.21 3.61 3.24 3.31

(a) molar ratio between Methyl 2,3,4,6-tetra-O-methyl--D-galactopyranoside:benzene, the carbohydrate was dissolve

added in the indicated ratio.

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S6

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.

Entry

mass (a)

mg

area (b)

J

Q (c)

J*g-1 1*

,

molkJ

mHdis

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

Average: (0.938 0.105)(d)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl--D-mannopyranoside in each experiment; (b) curvearea in the thermogram.(c) heat released in the dissolution process. (d) the uncertaintyrepresents the standard deviation.

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S7

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.

Entrymass (a)

mg

Area (b)

J

Q (c)

J*g-1 1*

,

molkJ

mHdis

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

Average: (2.623 0.137)(d)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl--D-mannopyranoside in each experiment; (b) curvearea in the thermogram. (c) heat released in the dissolution process. (d) the uncertaintyrepresents the standard deviation.

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S8

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

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

Entry

mass (a)

mg

Area (b)

J

Q(c)

J*g-1 1*

,

molkJ

mHdis

1 100.490 1.059 10.540 2.638

2 102.300 1.068 10.435 2.612

Average: (2.625 0.019)(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 uncertaintyrepresents the standard deviation.

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S9

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.

Entry

mass (a)

mg

Area (b)

J

Q(c)

J*g

-1

1*

,

molkJ

mHdis

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) curvearea in the thermogram. (c) heat released in the dissolution process. (d) the uncertainty

represents the standard deviation.

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S10

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.

Entry

mass (a)

mg

Area (b)

J

Q(c)

J*g

-1 1*

,

molkJ

mHdis

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 uncertaintyrepresents the standard deviation.

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S11

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.

Entry

mass(a)

mg

Area(b)

J

Q(c)

J*g-1 1*

,

molkJ

mHdis

1111.340 -1.465 -13.156 -3.293

2221.310 -3.238 -14.632 -3.662

3106.540 -1.612 -15.132 -3.787

4104.460 -1.461 -13.989 -3.501

599.860 -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) curvearea in the thermogram. (c) heat released in the dissolution process. (d) the uncertaintyrepresents the standard deviation.

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S12

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.

Entry

mass(a)

mg

Area(b)

J

Q(c)

J*g-1 1*

,

molkJ

mHdis

1100.000 6.491 64.912 16.247

2100.770 6.702 66.508 16.646

3103.500 7.387 71.373 17.864

4104.970 7.887 75.136 18.806

Average: (17.391 1.167)(d)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl--D-galactopyranoside in each experiment; (b) curvearea in the thermogram. (c) heat released in the dissolution process. (d) the uncertaintyrepresents the standard deviation.

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S13

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.

Entry

mass(a)

mg

Area(b)

J

Q(c)

J*g-1 1*

,

molkJ

mHdis

1102.950 7.765 75.420 18.877

2104.180 7.849 75.338 18.856

3102.900 7.707 74.899 18.746

4102.650 7.865 76.620 19.177

Average: (18.914 0.184)(d)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl--D-galactopyranoside in each experiment; (b) curvearea in the thermogram. (c) heat released in the dissolution process. (d) the uncertaintyrepresents the standard deviation.

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S14

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

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

Entry

mass(a)

mg

Area(b)

J

Q(c)

J*g-1 1*

,

molkJ

mHdis

1101.880 8.183 80.317 20.102

2100.840 7.732 76.673 19.190

3102.180 7.694 75.302 18.847

4104.800 7.895 75.336 18.856

Average: (19.249 0.591)(d)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl--D-galactopyranoside in each experiment; (b) curvearea in the thermogram. (c) heat released in the dissolution process. (d) the uncertaintyrepresents the standard deviation.

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S15

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.

Entry

mass(a)

mg

Area(b)

J

Q(c)

J*g-1 1*

,

molkJ

mHdis

1101.380 7.857 77.496 19.396

2101.300 7.946 78.437 19.632

3107.470 8.080 75.184 18.818

4102.250 8.047 78.701 19.698

Average:(19.386 0.400)(d)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl--D-galactopyranoside in each experiment; (b) curvearea in the thermogram. (c) heat released in the dissolution process. (d) the uncertaintyrepresents the standard deviation.

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S16

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.

Entrymass (a)

mg

Area (b)

J

Q (c)

J*g-1 1*

,

molkJ

mHdis

1103.010 7.132 69.234 17.328

2102.030 7.148 70.058 17.535

3101.370 7.691 75.866 18.988

4101.820 7.334 72.028 18.028

Average:(17.970 0.740) (d)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl--D-galactopyranoside in each experiment; (b) curvearea in the thermogram. (c) heat released in the dissolution process. (d) the uncertaintyrepresents the standard deviation.

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S17

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.

Entry

Mass(a)

mg

Area(b)

J

Q(c)

J*g-1 1*

,

molkJ

mHdis

1103.930 6.810 65.524 16.400

2101.010 6.585 65.193 16.317

3107.720 6.727 62.453 15.631

4104.470 6.825 65.326 16.350

Average: (16.175 0.364)(d)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl--D-galactopyranoside in each experiment; (b) curvearea in the thermogram. (c) heat released in the dissolution process. (d) the uncertaintyrepresents the standard deviation.

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S18

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.

Entry

mass(a)

mg

Area(b)

J

Q(c)

J*g-1 1*

,

molkJ

mHdis

1109.150 7.109 65.126 16.300

2103.990 6.914 66.491 16.642

3106.640 7.124 66.800 16.719

4104.080 6.856 65.870 16.487

Average: (16.537 0.185)(d)

(a) mass of Methyl 2,3,4,6-tetra-O-methyl--D-galactopyranoside in each experiment; (b) curvearea in the thermogram. (c) heat released in the dissolution process. (d) the uncertaintyrepresents the standard deviation.

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S19

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

from DSC at.333.15 K.

Entry

m1(a)

mg

m2(b)

mg

m3(c)

mg

Total Area(d)

mJ

Peak Area(e)

mJ

Qvap

J*g-1 1*

,

molkJ

mHvap

1 22.079 0.374 21.414 6818.470 490.803295.49

573.959

2 12.229 0.157 11.911 4253.721 543.176311.53

077.972

3 10.750 0.089 10.519 4052.467 692.274319.43

479.950

4 11.546 0.091 11.303 4243.765 680.740315.23

678.899

5 8.857 0.071 8.669 3186.662 714.540285.16

271.373

6 9.187 0.071 8.995 3217.475 750.902274.22

168.634

7 12.583 0.145 12.272 4176.816 760.071278.41

769.684

8 11.936 0.094 11.685 3997.167 713.453281.03

070.338

9 11.233 0.102 10.983 3759.066 730.605 275.745

69.016

10 9.268 0.062 9.084 3402.849 793.733287.22

971.890

11 10.244 0.088 10.021 3588.507 712.434287.00

871.835

12 9.148 0.077 8.950 3338.167 714.444293.14

273.370

>=< )15.333

exp

( KTmHgl

= (73.077 3.897) kJ mol-1

>=< )15.298( KTmHgl

= (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 vaporizationprocess; (e) area corresponding only to the pumping peak, when first derivate changes.

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S20

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

from DSC at 313.15 K.

Entry

m1(a)

mg

m2(b)

mg

m3(c)

mg

Total Area(d)

mJ

Peak Area(e)

mJ

Qvap

J*g

-1 1*

,

molkJ

mHvap

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

>=< )15.313exp

( KTmHgs = (104.345 5.533) kJ mol

-1

>=< )15.298( KTmHgs = (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 vaporizationprocess; (d) area corresponding only to the pumping peak.

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S21

Table S18. Chemical shifts (ppm) and differences of these for methyl acetate and mixtures

of benzene-d6and 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

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S22

Table S19. Chemical shifts (ppm) and differences of these for1H 500 MHz NMR spectra of

compound 1 and 2 of chloroform-dand benzene-d6.

1 2

CDCl3 C6D6 = CDCl3C6D6 CDCl3 C6D6 = CDCl3C6D6

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

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S23

Sidgwicks Temperature Correction on the Enthalpy of Vaporization of Methyl 2,3,4,6-tetra-O-

methyl--D-mannopyranoside

1molkJ177.75)

1molkJ2.1(

1molkJ73.077)15.298(

1molkJ1.2)K298.15(077.73

)K298.15exp(2

1061

molkJ/)K298.15()exp(

=

=

=

=

Hgl

Hgl

TxmHglTmH

gl

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

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S24

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

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

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S25

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

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S26

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

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

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S27

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

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S28

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

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

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S29

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.

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