Molecules 2020, 25, 1084
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and BINAP (28.2 mg). Eluent СН2Сl2. Yield 79 mg (29%). H-NMR (400 MHz, CDCl3) δ 1.92 (quintet,
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4H, J = 5.9 Hz, OCH2CH2CH2N), 3.23 (q, 4H, J = 5.7 Hz, CH2N), 3.59–3.62 (m, 8H, OCH2), 3.65–3.68
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(m, 4H, OCH2), 5.02 (br. s, 2Н, NH), 6.31–6.38 (m, 4Н, H4, Н6 (Ph)), 7.36 (dd, 2Н, JHH = 8.6 Hz, JHF =
6.3 Hz, H3 (Ph)). C-NMR (100.6 MHz, CDCl3) δ 28.6 (2C, OCH2CH2CH2N), 41.8 (2C, CH2N), 69.7
(2C, OCH2), 70.4 (2C, OCH2), 70.5 (2C, OCH2), 98.4 (d, 2C, JCF = 26.9 Hz, С6 (Ph)), 102.1 (d, 2C, JCF =
22.8 Hz, С4 (Ph)), 109.3 (qd, 2C, JCF = 30.0 Hz, JCF = 2.2 Hz, С2 (Ph)), 124.9 (q, 2C, JCF = 270.0 Hz, СF3),
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128.6 (dq, 2C, JCF = 11.4 Hz, JCF = 5.7 Hz, С3(Ph)), 147,9 (dq, 2C, JCF = 12.0 Hz, JCF =1.4 Hz, С1(Ph)),
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166.2 (dq, 2C, JCF = 248.1 Hz, JCF = 1.0 Hz, С5(Ph)). F-NMR (376.4 MHz, CDCl3) δ –61.98 (d, 6F, JFF =
12.3, CF3); –107.62 (br. s, 2F, 2-F). MS (MALDI-TOF+): Calculated for C24H29F8N2О3 [М + H] 545.205,
found 545.192.
N-(3-(2-(2-(3-aminopropoxy)ethoxy)ethoxy)propyl)-2-trifluoromethyl-5-fluoroaniline (26а). Obtained as
the second product in the synthesis of compound 26. Eluent СН2Сl2–MeOH 50:1. Yield 23 mg (12%).
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H-NMR (400 MHz, CDCl3) δ 1.81 (quintet, 2H, J = 5.8 Hz, OCH2CH2CH2NH2), 1.90 (quintet, 2H, J =
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5.5 Hz, OCH2CH2CH2NHPh), 3.24 (t, 2H, J = 5.5 Hz, CH2NH2), 3.45–3.59 (m, 6H, OCH2, CH2NPh),
3.60 (s, 4H, OCH2), 3.63–3.67 (m, 4H, OCH2), 5.02 (br. s, 2Н, NH), 6.24 (ddd, 1Н, JHH = 8.6 Hz, JHF =
8.6 Hz, JHН = 2.0 Hz, H4 (Ph)), 6.33 (dd, 1Н, JHF = 12.2 Hz, JHН = 2.0 Hz, H6 (Ph)), 7.28 (dd, 2Н, JHH =
8.2 Hz, JHF = 6.3 Hz, H3 (Ph)). C-NMR (100.6 MHz, CDCl3) δ 28.6 (1C, OCH2CH2CH2N), 29.7 (1C,
OCH2CH2CH2N), 36.8 (1С, CH2NН2) 41.7 (1C, CH2N), 68.5 (1C, OCH2), 70.1 (1C, OCH2), 70.5 (1C,
OCH2), 70.6 (1C, OCH2), 70.7 (1C, OCH2), 71.2 (1C, OCH2), 98.2 (d, 1C, JCF = 26.9 Hz, С6 (Ph)), 101.2
(d, 1C, JCF = 22.8 Hz, С4 (Ph)), 129.2 (d, 1C, JCF = 11.6 Hz, С3(Ph)), 150.7 (br.s, 1C, С1(Ph)), 165.6 (d,
2C, JCF = 247.9 Hz, С5(Ph)), quaternary carbon atoms C2 and CF3 were not unambiguously
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assigned. MS (MALDI-TOF+): Calculated for C17H27F4N2О3 [М + H] 383.1958, found 383.1977.
4,4′-((((Oxybis(ethane-2,1-diyl))bis(oxy))bis(propane-3,1-diyl))bis(azanediyl))dibenzonitrile (27). Obtained
according to method A from trioxadiamine 1 (0.5 mmol, 110 mg), 4-iodobenzonitrile (1.25 mmol, 286
mg) in the presence of CuI (19 mg) and 2-isobutyrylcyclohexanone (33 mg). Eluent СН2Сl2/MeOH
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200:1 Yield 192 mg (91%). H-NMR (400 MHz, CDCl3) δ 1.86 (quintet, 4H, J = 6.2 Hz,
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OCHCH2CH2N), 3.23 (t, 4H, J = 6.3 Hz, CH2N), 3.56–3.59 (m, 8H, OCH2), 3.64–3.66 (m, 4H, ОCH2),
5.02 (br. s, 2H, NH), 6.53 (d, 4H, Jobs = 8.8 Hz, H2, H2′(Ph)), 7.36 (d, 4H, Jobs = 8.8 Hz, H3, H3′(Ph)).
C-NMR (100.6 MHz, CDCl3) δ 28.1 (2С, OCH2CH2CH2N), 41.1 (2С, CH2N), 69.3 (2С, OCH2), 69.7
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(2С, OCH2), 70.1 (2С, OCH2), 97.7 (2C, C1(Ph)), 111.8 (4С, C2, C2‘(Ph)), 120.3 (2С, CN (Ph)), 133.2 (4С,
C3, C3′ (Ph)), 152.0 (2С, C4 (Ph)). MS (MALDI-TOF+): Calculated for C24H31N4О3 [М + H] 423.2396,
found 423.2425.
3,3′-((((Oxybis(ethane-2,1-diyl))bis(oxy))bis(propane-3,1-diyl))bis(azanediyl))dibenzonitrile (28). Obtained
according to method A from trioxadiamine 1 (0.5 mmol, 110 mg), 3-iodobenzonitrile (1.25 mmol, 286
mg) in the presence of CuI (19 mg) and 2-isobutyrylcyclohexanone (33 mg). Eluent СН2Сl2/MeOH
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50:1 Yield 165 mg (78%). H-NMR (400 MHz, CDCl3) δ 1.83 (quintet, 4H, J = 5.9 Hz, CH2CH2CH2N),
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3.15 (t, 4H, J = 6.3 Hz, CH2N), 3.55–3.58 (m, 8H, OCH2), 3.64–3.67 (m, 4H, ОCH2), 6.71–6.73 (m, 4H,
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H2, H6(Ph)), 6.84 (d, 2H, J = 7.8 Hz, H4(Ph)), 7.13 (t, 2H, J = 7.8 Hz, H5 (Ph)). NH protons were not
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unambiguously assigned. C-NMR (100.6 MHz, CDCl3) δ 28.1 (2С, CH2CH2CH2N), 41.2 (2С, CH2N),
69.4 (2С, OCH2), 69.7 (2С, OCH2), 70.1 (2С, OCH2), 112.4 (2С, C3(Ph)), 114.3 (2С, CH(Ph)), 116.5 (2С,
CH(Ph)), 119.3 (2C, CN), 119.5 (2C, CH(Ph)), 129.4 (2С, C5(Ph)), 148.3 (2С, C1(Ph)). MS
(MALDI-TOF+): Calculated for C24H31N4О3 [М + H] 423.2396, found 423.2362.
2,2′-((((Oxybis(ethane-2,1-diyl))bis(oxy))bis(propane-3,1-diyl))bis(azanediyl))dibenzonitrile (29). Obtained
according to method B from trioxadiamine 1 (0.5 mmol, 110 mg), 2-bromobenzonitrile (1 mmol, 182
mg) in the presence of Pd(dba)2 (11.6 mg) and BINAP (15.7 mg). Eluent СН2Сl2/MeOH 100:1 Yield
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198 mg (04%). H-NMR (400 MHz, CDCl3) δ 1.89 (quintet, 4H, J = 6.0 Hz, CH2CH2CH2N), 3.28 (q, 4H,
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J = 6.0 Hz, CH2N), 3.57–3.61 (m, 8H, OCH2), 3.64–3.67 (m, 4H, ОCH2), 5.03 (br. s, 2H, NH), 6.59 (t, 2H,
Jobs = 7.2 Hz, H4 (Ph)), 6.63 (d, 2H, J = 8.7 Hz, H6(Ph)), 7.31–7.35 (m, 4H, Н3, H5(Ph)). C-NMR
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(100.6 MHz, CDCl3) δ 27.5 (2С, CH2CH2CH2N), 41.0 (2С, CH2N), 69.1 (2С, OCH2), 70.0 (4С, OCH2),
95.0 (2С, C2(Ph)), 110.0 (2С, CH(Ph)), 115.7 (2С, CH(Ph)), 117.7 (2C, CN), 132.4 (2C, CH(Ph)), 133.8