Molecules 2017, 22, 626
10 of 13
0
0
00
J = 7.9 Hz, 4 -H), 7.27 (1H, t, J = 7.9 Hz, 5 -H), 7.57–7.63 (6H, m, Ph), 7.84–7.88 (4H, m, Ph), 9.04 (1H, s,
-H), 9.30 (2H, s, 2-H, 6-H); 13C-NMR (125 MHz; CD OD)
66.0, 116.4, 117.9, 120.5, 128.8, 130.8, 131.6,
4
δ
3
+
+
1
31.9, 134.7, 136.1, 141.9, 142.3, 143.3, 159.7; m/z [HRMS ES+] found [M
requires 338.1539.
−
TFA] 338.1513. C H NO
24 20
1
-(2,3-Dihydroxypropyl)-3,5-diphenylpyridinium
·TFA (3i·TFA). Compound 3i was prepared according
to procedure A, from 3-aminopropane-1,2-diol (45 mg, 0.49 mmol) and phenylacetaldehyde (300
mg, 2.50 mmol). The crude product was purified by preparative HPLC (retention time 13.0 min)
−
1
to give 3i·TFA as a pale yellow oil (147 mg, 72%). νmax (neat)/cm 3292, 3070, 1667, 1597, 1485;
1
H-NMR (500 MHz; CD OD)
δ
3.60 (1H, dd, J = 11.4 and 6.0 Hz, CHHOH), 3.76 (1H, dd, J = 11.4 and
3
+
4
.7 Hz, CHHOH), 4.15–4.18 (1H, m, CHOH), 4.74 (1H, dd, J = 13.2 and 8.5 Hz, CHHN ), 4.97 (1H, dd,
+
J = 13.2 and 3.0 Hz, CHHN ), 7.57–7.64 (6H, m, Ph), 7.87–7.91 (4H, m, Ph), 9.03 (1H, t, J = 1.7 Hz, 4-H),
9
.21 (2H, d, J = 1.7 Hz, 2-H, 6-H); 13C-NMR (125 MHz; CD OD)
δ
64.3, 65.7, 71.9, 128.8, 130.8, 131.5,
3
+
+
1
34.9, 141.8, 142.5, 142.9; m/z [HRMS EI] found [M
−
TFA] 306.1488. C H NO requires 306.1489.
20
20
2
1
-(6-Hydroxyhexyl)-3,5-diphenylpyridinium
·TFA (3j·TFA). Compound 3j was prepared according to
procedure A, from 6-hydroxyhexylamine (59 mg, 0.50 mmol) and phenylacetaldehyde (300 mg,
2
.50 mmol). The crude product was purified by preparative HPLC (retention time 15.3 min) to give
−
1
1
3
j·TFA as a pale yellow oil (153 mg, 69%). νmax (neat)/cm
3070, 2932, 1598, 1484; H-NMR
(500 MHz; CD OD)
δ
1.49–1.85 (6H, m, 3
×
CH ), 2.14–2.19 (2H, m, CH ), 3.67 (2H, t, J = 6.3 Hz,
3
2
2
+
CH OH), 4.75 (2H, t, J = 7.8 Hz, CH N ), 7.58–7.65 (6H, m, Ph), 7.88–7.92 (4H, m, Ph), 9.03 (1H, t, J =
2
2
13
1.6 Hz, 4-H), 9.29 (2H, d, J = 1.6 Hz, 2-H, 6-H); C-NMR (125 MHz; CD OD)
δ
26.2, 26.8, 28.9, 32.5,
3
+
62.6, 63.4, 128.8, 130.8, 131.6, 134.9, 141.8, 142.0, 143.2; m/z [HRMS ES+] found [M
−
TFA] 332.2018.
+
C H NO requires 332.2014.
23
26
1
-(4-Carboxybutyl)-3,5-diphenylpyridinium
·
TFA (3k·TFA). Compound 3k was prepared according to
procedure A, from 4-aminobutyric acid (51 mg, 0.49 mmol) and phenylacetaldehyde (300 mg,
2
.50 mmol). The crude product was purified by preparative HPLC (retention time 14.2 min) to give
−
1
1
3
k·TFA as a pale yellow oil (134 mg, 63%). νmax (neat)/cm 3200, 2943, 1668, 1598, 1483; H-NMR
(500 MHz; CD OD)
δ
2.43 (2H, m, CH CH CO H), 2.56 (2H, t, J = 6.8 Hz, CH CO H), 4.82 (2H, t,
3
2
2
2
2
2
+
J = 7.3 Hz, CH N ), 7.56–7.64 (6H, m, Ph), 7.88–7.92 (4H, m, Ph), 9.00 (1H, t, J = 1.6 Hz, 4-H), 9.28 (2H, d,
J = 1.6 Hz, 2-H, 6-H); C-NMR (125 MHz; CD OD)
2
13
δ 27.6, 31.3, 62.7, 128.8, 130.8, 131.5, 134.9, 141.9,
3
+
+
1
42.2, 143.1, 175.7; m/z [HRMS ES+] found [M − TFA] 318.1485. C H NO requires 318.1494.
21
20
2
1
-Cyclohexyl-3,5-diphenylpyridinium
·TFA (3l·TFA). Compound 3l was prepared according to procedure
A from cyclohexylamine (50 mg, 0.50 mmol) and phenylacetaldehyde (300 mg, 2.50 mmol). The crude
product was purified by preparative HPLC (retention time 16.2 min) to give 3l·TFA as a pale yellow
1
00
oil (113 mg, 53%). H-NMR (500 MHz; CD OD)
δ
1.46 (1H, app. qt, J = 13.2 and 3.6 Hz, 4 -Hax),
3
0
0
00
1
.63 (2H, app. q, J = 10.2 Hz, 2
×
2 -Hax), 1.82 (1H, br d, J = 13.2 Hz, 4 -Heq), 2.05 (2H, br d,
0
0
00
J = 13.8 Hz, 2
2
4
×
2 -Heq), 2.18 (2H, qd, J = 12.3 and 3.6 Hz, 2
3 -Heq), 4.82 (1H, m, CHN ), 7.56–7.64 (6H, m, Ph), 7.89–7.92 (4H, m, Ph), 9.00 (1H, d, J = 1.6 Hz,
-H), 9.25 (2H, d, J = 1.6 Hz, 2-H, 6-H); C-NMR (125 MHz; CD OD)
30.8, 131.5, 135.0, 140.5, 142.1, 143.3; m/z (ES+) 314 (M , 100%), 232 (12); m/z [HRMS ES+] found
×
3 -Hax), 2.32 (2H, br d, J = 10.6 Hz,
0
0
+
×
13
δ 25.5, 26.6, 34.3, 74.3, 129.0,
3
+
1
[
+
+
M − TFA] 314.1906. C H N requires 314.1909.
23
24
3
,5-Bis-(4-hydroxyphenyl)-1-(4-hydroxyphenethyl)pyridinium
·TFA (3o·TFA). Compound 3o was prepared
according to procedure A, from tyramine
phenylacetaldehyde [22] (17 mg, 0.13 mmol). The crude product was purified by preparative HPLC
·
HCl (5.0 mg, 0.028 mmol) and 4-hydroxy-
1
(
retention time 13.5 min) to give 3o·TFA as a pale yellow oil (9.2 mg, 66%). H-NMR (600 MHz;
+
+
CD OD)
δ 3.28 (2H, t, J = 6.7 Hz, CH CH N ), 4.87 (2H, t, J = 6.7 Hz, CH N ), 6.73 (2H, d, J = 8.2 Hz,
2 2 2
3
0
0
00
0
0
00
00
0
0
3
8
-H, 5 -H), 6.94–6.98 (6H, m, 2
×
(3 H, 5 -H), 2 -H, 6 -H), 7.57 (d, J = 8.2 Hz, 2
×
2 H, 6 -H),
37.7,
13
.71 (2H, d, J = 1.6 Hz, 2-H, 6-H), 8.77 (1H, t, J = 1.6 Hz, 4-H); C-NMR (150 MHz; CD OD)
δ
3