Page 9 of 11
Organic & Biomolecular Chemistry
DOI: 10.1039/C3OB41635F
J = 6.6 Hz, 1H, Hꢀarom.), 8.37 (d, J = 8.0 Hz, 1H, Hꢀarom.), 7.90
arom.), 128.5 (2d, Cꢀarom.), 127.8 (d, Cꢀarom.), 119.5 (q, J =
(dd, J1 = 7.8 Hz, J2 = 6.3 Hz, 1H, Hꢀarom.), 4.51 (t, J = 7.6 Hz, 60 321.3 Hz, CF3), 66.3 (d, CꢀOH), 62.1 (t, CꢀNH), 61.6 (t, CH2ꢀ
2H, CH2ꢀNꢀarom.), 3.96/3.81 (2d, J = 15.3 Hz, 2H, CH2ꢀN), 3.49
(m, 2H, CH2ꢀOH), 2.76 (m, 2H, CHꢀNMe and OH), 2.21 (s, 3H,
NꢀCH3), 1.90 (q, J = 7.5 Hz, 2H, CH2ꢀCH2ꢀCH2), 1.68ꢀ0.99 (m, 5
H, CH2ꢀCH2, CH2ꢀCH2ꢀCH2, CH3ꢀCHꢀCH3), 0.89 (t, J = 7.14 Hz,
CH2ꢀCH2), 55.3 (t, CH2), 35.9 (q, NHꢀCH3), 33.4 (t, CH2ꢀCH2ꢀ
CH2), 33.3 (t, NHꢀCH3), 19.2 (t, CH2ꢀCH2ꢀCH2), 13.2 (q, CH3ꢀ
CH2ꢀCH2);
5
Anal. Calcd. for C22H29F6N3O5S: C, 44.51; H, 4.92; Found: C,
3H, CH3ꢀCH2ꢀCH2), 0.90 (m, 2H, CH3ꢀCH2ꢀCH3), 0.91/0.83 (2d, 65 44.85; H, 4.96; νmax/cmꢀ1: 2855 (OꢀH), 1577 (CꢀC), 1453 (C=C),
6H, J = 6.45 Hz, 2 CH3);
1328 (CꢀH), 1284 (CꢀF3), 1027 (NHꢀCH3); [α]D20: ꢀ14.3 (c 0.96 in
EtOH); T5%onset: 265 °C.
13CꢀNMR (50 MHz, CDCl3): δC = 145.1 (d, Cꢀarom.), 143.9 (d,
10 Cꢀarom.), 142.8 (d, Cꢀarom.), 142.5 (s, Cꢀarom.), 128.1 (d, Cꢀ
arom.), 119.7 (q, J = 321.3 Hz, CF3), 62.7 (d, CHꢀNMe,), 62.3 (t,
1-Butyl-3-[[(2S)-2-(hydroxymethyl)pyrrolidin-1-
C, CꢀOH), 61.9 (t, CH2ꢀNꢀarom.), 54.5 (t, NMeꢀCH2), 36.1 (q, Nꢀ 70 yl]methyl]pyridinium bromide 33
CH3), 34.8 (t, CHꢀCH2ꢀCH), 33.3 (t, CH2ꢀCH2ꢀCH2), 25.3 (d, 1C.
CH3ꢀCHꢀCH3), 23.1/22.2 (2q, 2 CH3), 19.2 (t, CH2ꢀCH2ꢀCH2),
15 13.1 (t, CH3ꢀCH2ꢀCH2);
Preparation from 32 (0.58 g, 3 mmol) according to procedure for
compound 4 gave 33 as viscous brown oil in >99% yield.
1HꢀNMR (200 MHz, CDCl3): δH = 9.64 (s, 1H, Hꢀarom.), 9.24 (d,
J = 5.9 Hz, 1H, Hꢀarom.), 8.41 (d, J = 7.8 Hz, 1H, Hꢀarom.), 8.00
Anal. Calcd. for C19H31F6N3O5S2: C, 40.78; H, 5.58; Found: C,
40.59; H, 5.29; νmax/cmꢀ1: 3562 (OH), 2969 (NH), 1635 (CꢀN), 75 (dd, J1 = 7.8 Hz, J2 = 6.3 Hz, 1H, Hꢀarom.), 4.85 (m, 2H, CHꢀN
1348 (CꢀCH3), 1179 (CꢀF3), 1132 (S=O), 1052 (NHꢀCH3);
[α]36520: +7.2 (c 0.97 in EtOH); T5%onset: 244 °C.
arom.), 4.42/3.72 (2d, J = 14.9 Hz, 2H, CH2ꢀN), 4.10 (brs, 1H,
OH), 3.50 (m, 2H, CH2ꢀOH), 2.83 (m, 2H, CH2ꢀN pyr., CHꢀN
pyr.), 2.29 (m, 1H, CH2ꢀN pyr.), 2.14ꢀ1.48 (m, 6H, CH2ꢀCH2ꢀ
CH2, 2 CH2ꢀCH2), 1.35 (sext, J = 7.75 Hz, 2H, CH2ꢀCH2ꢀCH2),
80 0.91 (t, J = 7.2 Hz, 3H, CH3ꢀCH2ꢀCH2);
20
1-Butyl-3-[[[(1S)-1-(hydroxymethyl)-2-
phenylethyl]methylamino]methyl]pyridinium bromide 29
Preparation from 28 (0.37 g, 2.67 mmol) according to procedure
for compound 4 gave 29 as brown oil in 99% yield.
13CꢀNMR (50 MHz, d6ꢀDMSO): δC = 145.2 (d, Cꢀarom.), 144.7
(d, Cꢀarom.), 143.0 (d, Cꢀarom.), 141.8 (s, Cꢀarom.), 127.7 (d, Cꢀ
arom.), 65.3 (d, CHꢀCH2ꢀOH), 63.8 (t, CH2ꢀOH), 63.8 (t, CH2ꢀN
arom.), 55.6/54.8 (2t, CH2ꢀ Nꢀ pyr., CH2ꢀN), 33.7 (t, CH2ꢀCH2ꢀ
25 1HꢀNMR (200 MHz, MeOD): δH = 8.82 (d, J = 8.8 Hz, 1H, Hꢀ
arom.), 8.60 (s, 1H, Hꢀarom.), 8.26 (d, J = 8.0 Hz, 1H, Hꢀarom.),
7.92 (t, 1H, Hꢀarom.), 7.26 (m, 5H, Hꢀarom.), 4.50 (t, J = 7.5 Hz, 85 CH2), 27.2 (t, CH2 pyr.), 23.3 (t, CH2 pyr.), 19.3 (t, CH2ꢀCH2ꢀ
2H, CHꢀN arom.), 4.03 (s, 2H,CH2ꢀOH), 3.86ꢀ3.50 (m, 2H, CH2ꢀ
NMe), 3.05 (m, 1H, CH2ꢀCH2ꢀOH), 2.92ꢀ2.64 (m, 2H, CH2ꢀPh),
30 2.41 (m, 3H, CH3ꢀN), 1.93 (quin., J = 3.6, 2H, CH2ꢀCH2ꢀCH2),
1.40 (sext. J = 4.9, 2H, CH2ꢀCH2ꢀCH2), 1.02 (t, 3H, J = 3.9, CH2ꢀ
CH2ꢀCH3);
CH2), 13.5 (q, CH3ꢀCH2ꢀCH2);
Anal. Calcd. for C15H25BrN2O ꢁ 0.5 H2O: C, 53.26; H, 7.75;
Found: C, 53.34; H, 7.35; νmax/cmꢀ1: 3535 (OH), 2879 (NꢀC),
1636(CꢀC), 1329 (C=C), 1052 (NHꢀCH3); [α]D20: +23.4 (c 0.76 in
90 EtOH); T5%onset: 279 °C.
13CꢀNMR (50 MHz, MeOD): δC = 146.3 (d, Cꢀarom.), 145.2 (d,
Cꢀarom.), 144.0 (d, Cꢀarom.), 141.6 (s, Cꢀarom.), 141.2 (s, Cꢀ
35 arom.), 130.4 (d, Cꢀarom.), 129.5 (d, 2C, Cꢀarom.), 128.7 (d, Cꢀ
arom.), 127.2 (d, Cꢀarom.), 67.9 (d, CHꢀNH), 62.8 (t, CH2ꢀCH2ꢀ
1-Butyl-3-[[(2S)-2-(hydroxymethyl)pyrrolidin-1-yl]methyl]-
pyridinium bis(trifluoromethanesulfonyl)imide 34
Preparation from 33 (2.22 g, 6.76 mmol) according to procedure
CH2), 62.2 (t, CH2ꢀCH2ꢀCH2), 36.6 (q, NꢀCH3), 34.7 (t, CH2ꢀ 95 for compound 5 gave 34 as dark brown oil in 99% yield.
OH), 34.4 (t, CH2ꢀNH), 20.4 (t, CH2ꢀ C arom.), 13.8 (q, CH2ꢀ
CH2ꢀCH3); Anal. Calcd. for C12H2ON2O ꢁ 2.3 H2O: C, 55.25; H,
40 7.79; Found: C, 55.30; H, 8.16; νmax/cmꢀ1: 3309 (OꢀH), 2872 (Nꢀ
C), 1632 (CꢀC), 1495 (C=C), 1453 (CꢀH), 1031 (NHꢀCH3);
[α]D20: ꢀ2.3 (c 0.27 in CH2Cl2); T5%onset: 225 °C.
1HꢀNMR (200 MHz, DMSO): δH = 9.04 (s, 1H, Hꢀarom.), 8.97
(d, J = 5.9 Hz, 1H, Hꢀarom.), 8.53 (d, J = 7.8 Hz, 1H, Hꢀarom.),
8.08 (dd, J1 = 7.8 Hz, J2 = 6.3 Hz, 1H, Hꢀarom.), 4.60 (m, 3H,
CHꢀN arom., OH), 4.27/3.66 (2d, J = 14.5 Hz/ J = 14.7, 2H, CH2ꢀ
100 N), 3.42 (brs, 2H, CH2ꢀOH), 2.84/2.71 (m, 2H, CH2ꢀN pyr., CHꢀ
N pyr.), 2.27 (m, 1H, CH2ꢀN pyr.), 1.91 (m, 3H, CH2ꢀCH2ꢀCH2,
CH2ꢀCH2), 1.75ꢀ1.42 (m, 3H, 2 CH2ꢀCH2), 1.30 (sext, J = 7.8 Hz,
2H, CH2ꢀCH2ꢀCH2), 0.92 (t, J = 7.3 Hz, 3H, CH3ꢀCH2ꢀCH2); 13Cꢀ
NMR (50 MHz, d6ꢀDMSO): δC = 145.0 (d, Cꢀarom.), 143.9 (d, Cꢀ
1-Butyl-3-[[[(1S)-1-(hydroxymethyl)-2-
45 phenylethyl]methylamino]methyl]pyridinium
bis
(trifluoromethane sulfonyl)imide 30
Preparation from 29 (1.28 g, 5 mmol) according to procedure for 105 arom.), 143.0 (s, Cꢀarom.), 141.0 (d, Cꢀarom.), 127.4 (d, 1C, Cꢀ
compound 5 gave 30 as dark brown oil in 99% yield.
arom.), 119.7 (q, J = 321.9 Hz, CF3), 65.1 (d, CHꢀN pyr.), 63.7 (t,
CH2ꢀOH), 60.5 (t, CH2ꢀN arom.), 54.7/54.0 (2t, CH2ꢀ N pyr.,
CH2ꢀN), 32.6 (t, CH2ꢀCH2ꢀCH2), 27.3 (t, CH2 pyr.), 22.5 (t, CH2ꢀ
CH2ꢀCH2), 18.7 (t, CH2ꢀCH2ꢀCH2), 13.1 (q, CH3ꢀCH2ꢀCH2);
1HꢀNMR (200 MHz, CDCl3): δH = 8.48 (d, J = 6.1 Hz, 1H, Hꢀ
50 arom.), 8.26 (s, 1H, Hꢀarom.), 8.03 (d, J= 8.0 Hz, 1H), 7.73 (m,
1H, Hꢀarom.), 7.31ꢀ7.05 (m, 5H, Hꢀarom.), 4.34 (t, J = 7.6 Hz,
2H, CHꢀN arom), 3.92 (dd, J1 = 15.6 Hz, J2 = 14.5 Hz, 2H, CH2ꢀ 110 Anal. Calcd. for C17H25F6N3O5S2 ꢁ 0.9 H2O: C, 37.42; H, 4.95;
N), 3.60 (m, 2H, CH2ꢀOH), 2.99 (m, 1H, CHꢀCH2ꢀOH), 2.61 (m,
2H, CH2ꢀPh), 2.32 (s, 3H, NꢀCH3), 1.80 (q, J = 7.6 Hz, 2H, CH2ꢀ
55 CH2ꢀCH3), 1.25 (sext, J = 7.5 Hz, 2H, CH3ꢀCH2ꢀCH2), 0.89 (t, J =
7.3 Hz, 3H, CH3ꢀCH);
Found: C, 37.32; H, 4.48; νmax/cmꢀ1: 3551 (OꢀH), 2880 (NꢀC),
1636(CꢀC), 1346 (C=C), 1132 (S=O), 1178 (CꢀF3), 1052 (NHꢀ
CH3); [α]D20: +16.9 (c 1.20 in EtOH); T5%onset: 280 °C.
13CꢀNMR (50 MHz, CDCl3): δC = 144.9/143.6 (2d, Cꢀarom.), 115 1-Methyl-3-[[[dimethyl[(1R,2S)-2-hydroxy-1-methyl-2-
142.6/142.4 (2s, Cꢀarom.), 139.5 (d, Cꢀarom.), 129.2 (d, Cꢀ
phenyl]ethyl]ammonio]methyl]pyridinium diiodide 35
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