excluded. It is probable that the ΔG solv takes into account the presence of OHs,
which favours the solubility in water.
The presence and number of O−H⋯O IHBs, and the O−H⋯π and C−H⋯O
interaction seem to influence ΔG solv and this effect is different for different solvents.
The first five lowest energy conformers (with a-b-e-f-g-h in common) have the
smallest absolute values of ΔG solv in water. Conformers in which either O41−H50
or O46−H60 is not engaged in the O−H⋯π IHB have the greatest absolute values
of ΔG solv in water. Conformers in which only O41−H50 or O46−H60 is engaged
Table 8 Solvent effect (free energy of solvation, ΔG solv ) of selected conformers of jozimine A 2 in
the three solvents considered Results from HF/6-31G(d,p) and DFT/6-31+G(d,p) single point
PCM calculations on the in-vacuo-optimized geometries
Conformer
ΔG solv (kcal/mol)
HF
DFT
chlrf
actn
aq
chlrf
actn
aq
a-b-e-f-g-h-p-v-x
7.19
17.60
−4.12
7.37
18.30
−4.12
a-b-e-f-g-h-q-v-x
6.95
17.66
−4.39
7.29
18.16
−4.64
a-b-e-f-g-h-q-t-x
7.15
17.77
−4.04
7.32
18.14
−4.57
a-b-e-f-g-h-q-v-y
6.81
17.67
−4.70
7.19
17.93
−5.09
a-b-e-f-g-h-p-t-x
7.17
17.89
−4.50
7.22
17.96
−4.87
a-b-f-h-q-v-x
5.76
16.21
−7.62
6.65
16.98
−7.54
a-d-e-f-g-h-q-v-x
6.97
17.86
−5.37
7.61
−
a
−
a
b-c-e-f-g-h-q-t-x
7.19
17.91
−5.46
7.61
18.44
−5.50
a-b-e-g-q-t-x
5.78
16.21
−7.54
6.57
16.93
−7.72
b-c-e-f-g-h-p-v-x
6.84
18.05
−5.26
7.50
18.36
−5.60
a-d-e-f-g-h-p-v-x
7.17
17.95
−5.55
7.50
18.36
−5.57
a-b-e-g-p-v-x
6.38
15.89
−7.96
6.44
16.72
−7.83
a-b-f-h-p-v-x
5.74
15.95
−7.90
6.47
−
a
−7.86
a-b-e-g-p-t-x
6.01
15.96
−8.09
6.61
16.94
−7.73
a-b-f-h-p-t-x
5.88
15.94
−8.13
6.62
16.93
−7.76
c-d-e-f-g-h-p-v-x
7.57
18.43
−6.35
7.95
18.87
−6.33
a-d-e-g-p-t-x
6.13
16.10
−9.25
6.68
16.93
−8.49
a-b-q-v-y
4.89
−
a
−12.31
−
a
−
a
−11.36
a-b-p-t-x
5.65
14.61
−11.38
5.61
15.32
−10.92
c-d-f-h-p-v-x
6.74
17.09
−8.42
7.30
17.83
−8.25
c-d-f-h-q-v-x
6.80
17.12
−8.53
7.48
18.00
−
a
b-c-q-v-y
5.36
15.08
−12.30
5.85
15.53
−11.91
a-d-q-v-y
5.76
15.07
−12.03
5.88
15.54
−11.81
c-d-q-v-y
6.10
15.53
−12.02
6.59
16.50
−11.77
c-d-p-t-x
5.91
15.47
−11.86
6.56
16.70
−11.23
a The calculation for this conformer did not converge in the given solvent
324
M. K. Bilonda and L. Mammino
which favours the solubility in water.
The presence and number of O−H⋯O IHBs, and the O−H⋯π and C−H⋯O
interaction seem to influence ΔG solv and this effect is different for different solvents.
The first five lowest energy conformers (with a-b-e-f-g-h in common) have the
smallest absolute values of ΔG solv in water. Conformers in which either O41−H50
or O46−H60 is not engaged in the O−H⋯π IHB have the greatest absolute values
of ΔG solv in water. Conformers in which only O41−H50 or O46−H60 is engaged
Table 8 Solvent effect (free energy of solvation, ΔG solv ) of selected conformers of jozimine A 2 in
the three solvents considered Results from HF/6-31G(d,p) and DFT/6-31+G(d,p) single point
PCM calculations on the in-vacuo-optimized geometries
Conformer
ΔG solv (kcal/mol)
HF
DFT
chlrf
actn
aq
chlrf
actn
aq
a-b-e-f-g-h-p-v-x
7.19
17.60
−4.12
7.37
18.30
−4.12
a-b-e-f-g-h-q-v-x
6.95
17.66
−4.39
7.29
18.16
−4.64
a-b-e-f-g-h-q-t-x
7.15
17.77
−4.04
7.32
18.14
−4.57
a-b-e-f-g-h-q-v-y
6.81
17.67
−4.70
7.19
17.93
−5.09
a-b-e-f-g-h-p-t-x
7.17
17.89
−4.50
7.22
17.96
−4.87
a-b-f-h-q-v-x
5.76
16.21
−7.62
6.65
16.98
−7.54
a-d-e-f-g-h-q-v-x
6.97
17.86
−5.37
7.61
−
a
−
a
b-c-e-f-g-h-q-t-x
7.19
17.91
−5.46
7.61
18.44
−5.50
a-b-e-g-q-t-x
5.78
16.21
−7.54
6.57
16.93
−7.72
b-c-e-f-g-h-p-v-x
6.84
18.05
−5.26
7.50
18.36
−5.60
a-d-e-f-g-h-p-v-x
7.17
17.95
−5.55
7.50
18.36
−5.57
a-b-e-g-p-v-x
6.38
15.89
−7.96
6.44
16.72
−7.83
a-b-f-h-p-v-x
5.74
15.95
−7.90
6.47
−
a
−7.86
a-b-e-g-p-t-x
6.01
15.96
−8.09
6.61
16.94
−7.73
a-b-f-h-p-t-x
5.88
15.94
−8.13
6.62
16.93
−7.76
c-d-e-f-g-h-p-v-x
7.57
18.43
−6.35
7.95
18.87
−6.33
a-d-e-g-p-t-x
6.13
16.10
−9.25
6.68
16.93
−8.49
a-b-q-v-y
4.89
−
a
−12.31
−
a
−
a
−11.36
a-b-p-t-x
5.65
14.61
−11.38
5.61
15.32
−10.92
c-d-f-h-p-v-x
6.74
17.09
−8.42
7.30
17.83
−8.25
c-d-f-h-q-v-x
6.80
17.12
−8.53
7.48
18.00
−
a
b-c-q-v-y
5.36
15.08
−12.30
5.85
15.53
−11.91
a-d-q-v-y
5.76
15.07
−12.03
5.88
15.54
−11.81
c-d-q-v-y
6.10
15.53
−12.02
6.59
16.50
−11.77
c-d-p-t-x
5.91
15.47
−11.86
6.56
16.70
−11.23
a The calculation for this conformer did not converge in the given solvent
324
M. K. Bilonda and L. Mammino