Molecules 2016, 21, 1682
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1H, CHOH), 4.22–4.19 (m, 4H, COOCH2 + ArOCH2), 4.01 (dt, J = 5.4, 1.4 Hz, 2H, -CH2CH=), 3.80
(s, 3H, OCH3), 3.77–3.60 (m, 6H, Hpip + CH2Oallyl), 3.52–3.13 (m, 6H, Hpip + CH2Npip); 13C-NMR
(100.53 MHz, DMSO-d6) δ (ppm): 165.22, 162.57, 151.85, 139.00, 135.08, 131.65, 123.79, 121.70, 120.88,
118.41, 116.62, 114.44, 112.03, 71.14, 67.93, 67.51, 66.18, 63.36, 58.35, 55.44, 52.50, 51.25, 46.90, 46.74;
HR-MS: C26H35N2O6 [M − H]− calculated 471.2489 m/z, found 471.2484 m/z.
1-{3-[(4-Allyloxyethoxybenzoyl)oxy]-2-hydroxypropyl}-4-(4-methoxyphenyl)piperazinediium dichloride (7c).
Yield: 44%; Rf: 0.82 (acetone/toluene 3:1); Rf (rev.): 0.58 (0.1 M HCl/acetone 3:2); m.p.: 170–173 ◦C;
HPLC pur. 94.28 (254 nm); IR (ATR, cm−1):
(C=O) = 1710, (arom. C=C) = 1604,
DMSO-d6)
ν
(O–H) = 3335,
ν
(C–H) = 2978,
ν
(NH+) = 2377,
1
ν
ν
ν
(C–N) = 1250,
ν
(C–O–C) = 1166; H-NMR (399.78 MHz,
δ
(ppm): 10.96 (bs, 2H, NH+pip), 8.00 (d, J = 8.7 Hz, 2H, HArCOO), 7.10 (d, J = 9.1 Hz, 2H,
HAr-pip), 7.07 (d, J = 8.7 Hz, 2H, HArO), 6.91 (d, 2H, J = 9.1 Hz, HAr-pip), 5.89 (ddt, J = 17.3, 10.5, 5.3 Hz,
1H, -CH=), 5.27 (dq, J = 17.3, 1.7 Hz, 1H, =CH2), 5.15 (dq, J = 10.5, 1.7 Hz, 1H, =CH2), 4.51–4.46 (m, 1H,
CHOH), 4.23–4.19 (m, 4H, COOCH2 + ArOCH2), 4.01 (dt, J = 5.3, 1.7 Hz, 2H, -CH2CH=), 3.79–3.60 (m,
6H, Hpip + CH2Oallyl), 3.71 (s, 3H, OCH3), 3.53–3.25 (m, 6H, Hpip + CH2Npip); 13C-NMR (100.53 MHz,
DMSO-d6) δ (ppm): 165.23, 162.57, 154.69, 142.13, 135.08, 131.64, 121.69, 118.78, 116.62, 114.56, 114.44,
71.14, 67.93, 67.51, 66.20, 63.46, 58.04, 55.32, 51.82, 50.62, 47.26, 47.19; HR-MS: C26H35N2O6 [M
calculated 471.2489 m/z, found 471.2485 m/z.
−
H]−
1-{2-Hydroxy-3-[(4-isopropoxyethoxybenzoyl)oxy]propyl}-4-phenylpiperazinediium dichloride (8a). Yield: 22%;
Rf: 0.85 (acetone/toluene 3:1); Rf (rev.): 0.25 (0.1 M HCl/acetone 3:2); m.p.: 200–202 ◦C; HPLC pur.
95.12% (254 nm); IR (ATR, cm−1):
(arom. C=C) = 1603, (C–N) = 1252,
ν
(O–H) = 3287,
ν
ν
(C–H) = 2972,
ν
(NH+) = 2559,
ν
(C=O) = 1699,
(ppm):
ν
ν
(C–O–C) = 1180; 1H-NMR (399.78 MHz, DMSO-d6)
δ
10.69 (bs, 2H, NH+pip), 7.99 (d, J = 8.7 Hz, 2H, HArCOO), 7.28–7.24 (m, 2H, HAr-pip), 7.06 (d, J = 8.7 Hz,
2H, HArO), 7.02–7.00 (m, 2H, HAr-pip), 6.88–6.84 (m, 1H, HAr-pip), 4.51–4.44 (m, 1H, CHOH), 4.23–4.21
(m, 2H, COOCH2, 4.17–4.14 (m, 2H, ArOCH2), 3.84–3.57 (m, 7H, -CH2OCH(CH3)2 + Hpip), 3.43–3.15
(m, 6H, -CH2Npip + Hpip), 1.10 (d, J = 5.9 Hz, 6H, -CH(CH3)2); 13C-NMR (100.53 MHz, DMSO-d6)
δ
(ppm): 165.23, 162.64, 149.52, 131.62, 129.16, 121.62, 120.03, 115.95, 114.46, 71.13, 67.93, 66.18, 65.76,
63.33, 58.11, 52.14, 50.71, 45.31, 45.19, 22.03; HR-MS: C25H36N2O5 [M
found 443.2535 m/z.
−
H]− calculated 443.2540 m/z,
1-{2-Hydroxy-3-[(4-isopropoxyethoxybenzoyl)oxy]propyl}-4-(2-methoxyphenyl)piperazinediium dichloride (8b).
Yield: 25%; Rf: 0.82 (acetone/toluene 3:1); Rf (rev.): 0.29 (0.1 M HCl/acetone 3:2); m.p.: 154–156 ◦C;
HPLC pur. 98.87% (254 nm); IR (ATR, cm−1):
(C=O) = 1701, (arom. C=C) = 1603,
DMSO-d6)
ν
(O–H) = 3318,
ν
(C–H) = 2969,
ν
(NH+) = 2560,
1
ν
ν
ν
(C–N) = 1251,
ν
(C–O–C) = 1166; H-NMR (399.78 MHz,
δ
(ppm): 10.67 (bs, 2H, NH+pip), 7.99 (d, J = 8.7 Hz, 2H, HArCOO), 7.07 (d, J = 8.7 Hz, 2H,
HArO), 7.03–6.89 (m, 4H, HAr-pip), 4.49–4.44 (m, 1H, CHOH), 4.23–4.21 (m, 2H, COOCH2), 4.17–4.15 (m,
2H, ArOCH2), 3.80 (s, 3H, OCH3), 3.72–3.70 (m, 2H, -CH2OiPr), 3.68–3.40 (m, 5H, Hpip + -CH(CH3)2),
3.35–3.08 (m, 6H, -CH2Npip + Hpip), 1.11 (d, J = 6.4 Hz, 6H, -CH(CH3)2); 13C-NMR (100.53 MHz,
DMSO-d6) δ (ppm): 165.19, 162.62, 151.82, 139.23, 131.60, 123.57, 121.62, 120.84, 118.29, 114.44, 111.96,
71.11, 67.91, 66.12, 65.74, 63.27, 58.27, 55.40, 52.63, 51.16, 46.82, 46.67, 22.01; HR-MS: C26H37N2O6
[M − H]− calculated 473.2646 m/z, found 473.2640 m/z.
1-{2-Hydroxy-3-[(4-isopropoxyethoxybenzoyl)oxy]propyl}-4-(4-methoxyphenyl)piperazinediium dichloride (8c).
Yield: 34%; Rf: 0.81 (acetone/toluene 3:1); Rf (rev.): 0.23 (0.1 M HCl/acetone 3:2); m.p.: 193–195 ◦C;
HPLC pur. 95.60 (254 nm); IR (ATR, cm−1):
(C=O) = 1698, (arom. C=C) = 1601,
DMSO-d6)
ν
(O–H) = 3270,
ν
(C–H) = 2970,
ν
(NH+) = 2561,
1
ν
ν
ν
(C–N) = 1247,
ν
(C–O–C) = 1179; H-NMR (399.78 MHz,
δ
(ppm): 10.74 (bs, 2H, NH+pip), 7.99 (d, J = 8.7 Hz, 2H, HArCOO), 7.07–7.03 (m, 4H,
HArO + HAr-pip), 6.89 (d, J = 9.1 Hz, 2H, HAr-pip), 4.50–4.44 (m, 1H, CHOH), 4.23–4.21 (m, 2H, COOCH2),
4.17–4.14 (m, 2H, ArOCH2), 3.76–3.57 (m, 10H, -CH2OCH(CH3)2 + OCH3 + Hpip), 3.45–3.22 (m, 6H,
-CH2Npip + Hpip), 1.10 (d, J = 5.9 Hz, 6H, -CH(CH3)2); 13C-NMR (100.53 MHz, DMSO-d6)
δ
(ppm):
165.24, 162.63, 154.24, 142.82, 131.62, 121.63, 118.41, 114.48, 114.46, 71.13, 67.93, 66.17, 65.76, 63.38, 58.05,