2.3. Spectrocscopic Data of New Dendrimers (16–27)
2.3.1. Dendrimer 16 (Obtained from 12)
Dendrimer 16 was obtained as creamy powder from 0.63 g (0.28 mmol) of dendrimer 12 dissolved in 10 mL MeOH after 3h hydrogenolysis: 93.8% (0.45 g).
C86H143O19N15, M = 1691.15 g/mol (monoisotopic mass 1690.1). LRMS (ESI, MeOH): 1691.2 [M + H+]+, 846.1 [M + 2H+]2+, 564.4 [M + 3H+]3+, 423.6 [M + 4H+]4+ - main signal.
1H-NMR (500 MHz, MeOD): δ = 1.30–1.52 [br m, 20H, 5×γCH2 L-Lys and core, 3×δCH2 L-Lys, 2×O-(CH2)2-CH2-(CH2)2-NH] overlapped with 1.40, 1.42 [2s, 36H, 4×C(CH3)3], 1.54–1.66 [br m, 12H, 2×δCH2 L-Lys and core, 2×βCH2 L-Lys, 2×O-(CH2)3-CH2-CH2-NH], 1.67–1.87 [br m, 10H, 3×βCH2 L-Lys and core, 2×O-CH2-CH2-(CH2)3-NH], 2.58 (2t, J = 6.9 Hz, 6H, 3×εCH2 L-Lys), 2.78 (t, J = 7.2 Hz, 2H, CH2-Ar PEA), 3.22 [br m, 6H, εCH2 L-Lys, 2×O-(CH2)4-CH2-NH], 3.36 (m, 3H, CH2-NH PEA, εCH2 core), 3.51 (m, 3H, O-CH2-CH2-NH, CH2-NH PEA), 3.62 (m, 2H, O-CH2-CH2-NH), 3.85-4.12 (br m, 12H, 4×O-CH2, 4×αCH L-Lys), 4.47 (m, 1H, αCH core), 6.62 (m, 2H, C4-H Ph), 6.94, 7.01 (2m, 4H, C2,6-H Ph), 7.12–7.25 (br m, 5H, C2,3,4,5,6-H PEA).
13C-NMR (500 MHz, MeOD): δ = 24.2, 24.3 (γC), 24.4 [2×O-(CH2)2-CH2-(CH2)2-NH], 24.5 (γC), 28.8 [C(CH3)3], 29.9, 30.1 [δC, 2×O-CH2-CH2-CH2-CH2-CH2-NH], 32.8, 33.3, 33.4 (βC), 36.5 (CH2-Ar PEA), 39.9 (2×O-CH2-CH2-NH), 40.2 [2×O-(CH2)4-CH2-NH], 40.6 (εC core), 42.0 (CH2-NH PEA), 42.2, 42.3 (4×εC L-Lys), 55.5 (αC core), 56.2 (4×αC L-Lys), 67.7 (2×O-CH2-CH2-NH), 69.1, 69.2 [2×O-CH2-(CH2)4-NH], 80.5 [C(CH3)3], 105.7, 106.0 (C4 Ph), 106.6, 107.0, 107.1, 107.4 (C2,6 Ph), 127.4, 129.5, 129.9 (C2,3,4,5,6 PEA), 137.2, 137.8 (C1 Ph), 140.4 (C1 PEA), 157.8 [C=O (Boc)], 161.2, 161.3, 161.4, 161.7 (C3,5 Ph), 169.6, 169.7 (CONH Ph), 174.4, 175.2, 175.5 (CONH).
[α]D25 = −17.6 (c 0.75, MeOH).
M.p.: 115–123 °C.
2.3.2. Dendrimer 17 (Obtained from 13)
Dendrimer 17 was obtained as yellow powder from 1.13 g (0.52 mmol) of dendrimer 13 dissolved in 20 mL of MeOH after 10h hydrogenolysis: 1.13 g (0.52 mmol), yield 85.3% (0.725 g).
C82H132O19N16, M = 1646.02 g/mol (monoisotopic mass 1645.0). LRMS (ESI, MeOH): 823.5 [M + 2H+]2+, 549.4 [M + 3H+]3+ - main signal, 516.2 [M - Boc + 3H+]3+, 412.5 [M + 4H+]4+.
1H-NMR (500 MHz, MeOD): δ = 1.30–1.47 (br m, 18H, 5×γCH2 L-Lys and core, 4×δCH2 L-Lys) overlapped with 1.40 [s, 36H, 4×C(CH3)3], 1.52–1.75 (br m, 10H, δCH2 core, 4×βCH2 L-Lys), 1.77–1.90 (br m, 2H, βCH2 core), 2.56 (m, 8H, 4×εCH2 L-Lys), 2.93 (t, J = 7.2 Hz, 2H, CH2-Ar TA), 3.3 (m, 2H, εCH2 core), 3.40-3.65 (br m, 10H, 4×O-CH2-CH2-NH, CH2-NH TA), 4.02 (br m, 12H, 4×O-CH2-CH2-NH, 4×αCH L-Lys), 4.50 (m, 1H, αCH core), 6.64 (m, 2H, C4-H Ph), 6.92-7.08 (br m, 7H, C2,6-H Ph, C2,5,6-H TA), 7.31 (m, 1H, C7-H TA), 7.54 (d, J = 7.9 Hz, 1H, C4-H TA).
13C-NMR (500 MHz, MeOD): δ = 24.2, 24.4 (γC), 26.3 (CH2-Ar TA), 28.8, 29.0 [C(CH3)3], 30.1 (δC), 32.90 (βC), 33.3, 33.4 (β, δC), 39.9 (4×O-CH2-CH2-NH), 40.7 (εC core), 41.4 (CH2-NH TA), 42.2 (4×εC L-Lys), 55.5 (αC core), 56.1 (4×αC L-Lys), 67.8 (4×O-CH2-CH2-NH), 80.6 [C(CH3)3], 105.8, 106.0 (C4 Ph), 107.2, 107.5, 107.6 (C2,6 Ph), 112.3 (C7 TA), 113.1 (C3 TA), 119.3 (C4 TA), 119.6 (C5 TA), 122.3 (C6 TA), 123.6 (C2 TA), 128.7 (C3a TA), 137.3, 137.9 (C1 Ph), 138.1 (C7a TA), 157.8 [C=O (Boc)], 161.3 (C3,5 Ph), 169.4, 169.6 (CONH Ph), 174.3, 175.5 (CONH).
[α]D25 = −22.7 (c 0.65, MeOH).
M.p.: 128–131 °C.
2.3.3. Dendrimer 18 (Obtained from 14)
Dendrimer 18 was obtained as white powder from 2.83 g (1.25 mmol) of dendrimer 14 dissolved in 50 mL MeOH after 7h hydrogenolysis, yield 97% (2.1 g).
C88H144O19N16, M = 1730.18 g/mol (monoisotopic mass 1729.1). LRMS (ESI, MeOH): 1752.4 [M + Na+]+, 1730.4 [M + H+]+, 865.8 [M + 2H+]2+ - main signal.
1H-NMR (500 MHz, MeOD): δ = 1.30–1.50 (br m, 12H, 5×γ, δCH2 L-Lys and core, δCH2 core) overlapped with 1.40, 1.42 [2s, 36H, 4×C(CH3)3], 1.58 [br m, 20H, 4×δCH2 L-Lys, 2×βCH2, 2×O-(CH2)2-CH2-CH2-CH2-NH], 1.75 [br m, 10H, 3×βCH2, 2×O-CH2-CH2-(CH2)3-NH], 2.75 (2m, 8H, 4×εCH2 L-Lys), 2.94 (t, J = 7.2 Hz, 2H, CH2-Ar TA), 3.21 [m, 4H, 2×O-(CH2)4-CH2-NH], 3.3 (m, 2H, εCH2 core), 3.41-3.67 (br m, 6H, 2×O-CH2-CH2-NH, CH2-NH TA), 3.89-4.09 (br m, 12H, 4×O-CH2, 4×αCH L-Lys), 4.48 (m, 1H, αCH core), 6.61 (m, 2H, C4-H Ph), 6.92-7.08 (br m, 7H, C2,6-H Ph, C2,5,6-H TA), 7.31 (m, 1H, C7-H TA), 7.54 (d, J = 7.85 Hz, 1H, C4-H TA).
13C-NMR (500 MHz, MeOD): δ = 24.1, 24.4 [γC, 2×O-(CH2)2-CH2-(CH2)2-NH], 26.3 (CH2-Ar TA), 28.8 [C(CH3)3], 29.9 [2×O-CH2-CH2-(CH2)3-NH], 30.1, 30.4 [δC, 2×O-(CH2)3-CH2-CH2-NH], 32.9, 33.1 (βC), 39.9 (2×O-CH2-CH2-NH), 40.2 [2×O-(CH2)4-CH2-NH], 40.6 (εC core), 41.3 (4×εC L-Lys), 41.4 (CH2-NH TA), 55.6 (αC core), 56.0, 56.1 (4×αC L-Lys), 67.8 (2×O-CH2-CH2-NH), 69.2 [2×O-CH2-(CH2)4-NH], 80.7 [C(CH3)3], 105.7, 106.1 (C4 Ph), 106.8, 107.2, 107.4 (C2,6 Ph), 112.3 (C7 TA), 113.1 (C3 TA), 119.3 (C4 TA), 119.6 (C5 TA), 122.3 (C6 TA), 123.6 (C2 TA), 128.7 (C3a TA), 137.2, 137.8 (C1 Ph), 138.1 (C7a TA), 157.8 [C=O (Boc)], 161.3, 161.7 (C3,5 Ph), 169.7, 169.8 (CONH Ph), 170.4, 174.3, 175.0, 175.3 (CONH).
[α]D25 = −17.4 (c 1, MeOH).
M.p.: 123–130 °C.
2.3.4. Dendrimer 19 (Obtained from 15)
Dendrimer 19 was obtained from 1.02 g (0.46 mmol) of dendrimer 15 dissolved in 25 mL MeOH after 5h hydrogenolysis: yield 96.1% (0.74 g).
C84H147O19N15, M = 1671.16 g/mol (monoisotopic mass 1670.1). LRMS (ESI, MeOH): 1671.5 [M + H+]+, 836.0 [M + 2H+]2+ - main signal.
2.3.5. Dendrimer 20 (Obtained from 16)
Dendrimer 20 was obtained in the coupling reaction of 4-(Boc-amino)benzoic acid [Boc-4-Abz-OH] (0.247 g, 1.04 mmol), HOBt (0.159 g, 1.04 mmol), EDC∙HCl (0.2 g, 1.04 mmol) with dendrimer 16 (0.4 g, 0.237 mmol), Et3N (0.26 mL, 1.9 mmol) in DMF (10 mL); obtained creamy powder, yield 60% (0.36 g).
C134H195O31N19, M = 2568.09 g/mol (monoisotopic mass 2566.4). LRMS (ESI, MeOH): 2589.8 [M + Na+]=, 1306.3 [M + 2Na+]2+ - main signal, 1295.3 [M + H+ + Na+]2+, 1311.3 [M + MeOH + H+ + Na+]2+.
1H-NMR (500 MHz, MeOD): δ = 1.33–1.51 [br m, 16H, 5×γCH2 L-Lys i core, δCH2 core, 2×O-(CH2)2-CH2-(CH2)2-NH] overlapped with 1.38, 1.40 [2s, 36H, 4×C(CH3)3 L-Lys] i 1.50 [2s, 36H, 4×C(CH3)3 PABA], 1.61 [m, 16H, 4×δCH2 L-Lys, 2×β-CH2, 2×O-(CH2)3-CH2-CH2-NH], 1.72 [br m, 10H, 3×β-CH2, 2×O-CH2-CH2-(CH2)3-NH], 2.75 (t, J = 7.16 Hz, 2H, CH2-Ar PEA), 3.09-3.25 [2m, 6H, εCH2 core, 2×O-(CH2)4-CH2-NH], 3.34 (m, 9H, CH2-NH PEA, 4×εCH2 L-Lys), 3.48 (m, 3H, O-CH2-CH2-NH, CH2-NH PEA), 3.60 (m, 2H, O-CH2-CH2-NH), 3.91 [m, 4H, 2×O-CH2-(CH2)4-NH], 4.02 (m, 8H, 2×O-CH2-CH2-NH, 4×αCH L-Lys), 4.47 (m, 1H, αCH core), 6.60 (m, 2H, C4-H Ph), 6.92, 6.99 (2m, 4H, C2,6-H Ph), 7.10-7.23 (br m, 5H, C2,3,4,5,6-H PEA), 7.48 (m, 8H, C3,5-H PABA), 7.73 (m, 8H, C2,6-H PABA).
13C-NMR (500 MHz, MeOD): δ = 24.3 (γC), 24.4 [2×O-(CH2)2-CH2-(CH2)2-NH], 24.5 (γC), 28.7 [C(CH3)3 PABA], 28.8 [C(CH3)3 L-Lys], 29.9 [2×O-CH2-CH2-(CH2)3-NH], 30.1, 30.2 [δC, 2×O-(CH2)3-CH2-CH2-NH], 32.8, 33.2 (βC), 36.5 (CH2-Ar PEA), 40.0 (2×O-CH2-CH2-NH), 40.2 [2×O-(CH2)4-CH2-NH] 40.5, 40.6 (εC), 42.0 (CH2-NH PEA), 55.6 (αC core), 56.1, 56.2 (4×αC L-Lys), 67.7 (2×O-CH2-CH2-NH), 69.2 [2×O-CH2-(CH2)4-NH], 80.6 [C(CH3)3 L-Lys], 81.2 [C(CH3)3 PABA], 105.8, 106.1 (C4 Ph), 106.7, 107.0, 107.2, 107.5 (C2,6 Ph), 118.8 (C3,5 PABA), 127.4 (C4 PEA), 129.2 (C2,6 PABA), 129.3 (C1 PABA), 129.5, 129.9 (C2,3,5,6 PEA), 137.2, 137.8 (C1 Ph), 140.4 (C1 PEA), 144.0 (C4 PABA), 154.8 [C=O (Boc) PABA], 157.8 [C=O (Boc) L-Lys], 161.2, 161.7 (C3,5 Ph), 169.6, 169.7 (CONH Ph), 169.8 (CONH PABA), 174.4, 175.1, 175.5 (CONH).
[α]D25 = −12.7 (c 1, MeOH).
Rf = 0.38 (CHCl3/MeOH 8:1).
M.p.: 144–150 °C.
2.3.6. Dendrimer 21 (Obtained from 17)
Dendrimer 21 was obtained in the coupling reaction of Boc-4-Abz-OH (0.218 g, 0.92 mmol), HOBt (0.141 g, 0.92 mmol), EDC∙HCl (0.176 g, 0.92 mmol), with dendrimer 17 (0.35 g, 0.21 mmol), Et3N (0.23 mL, 1.68 mmol) in DMF (10 mL); obtained creamy solid, yield 39.2% (0.21 g).
C130H184O31N20, M = 2522.97 g/mol (monoisotopic mass 2521.3). LRMS (ESI, MeOH): 2545.8 [M + Na+]+, 1284.0 [M + 2Na+]2+ - main signal.
1H-NMR (500 MHz, MeOD): δ = 1.34–1.43 (m, 10H, 5×γCH2 L-Lys i core) overlapped with 1.38 [s, 36H, 4×C(CH3)3 L-Lys], 1.53-1.66 (br m, 14H, 5×δCH2 L-Lys i core, 2×βCH2 L-Lys) overlapped with 1.50 [s, 36H, 4×C(CH3)3 PABA], 1.68-1.86 (br m, 6H, 3×βCH2 L-Lys i core), 2.91 (t, J = 7.1 Hz, 2H, CH2-Ar TA), 3.24 (m, 10H, 5×εCH2 L-Lys i core), 3.38-3.63 (br m, 10H, 4×O-CH2-CH2-NH, CH2-NH TA), 4.00 (br m, 12H, 4×O-CH2-CH2-NH, 4×αCH L-Lys), 4.48 (m, 1H, αCH core), 6.61 (m, 2H, C4-H Ph), 6.91-7.06 (br m, 7H, C2,6-H Ph, C2,5,6-H TA), 7.29 (d, J = 8.1 Hz, 1H, C7-H TA), 7.46 (dd, J = 8.8, 2.4 Hz, 8H, C3,5-H PABA), 7.51 (d, J = 7.9 Hz, 1H, C4-H TA), 7.72 (dd, J = 8.8, 2.4 Hz, 8H, C2,6-H PABA).
13C-NMR (500 MHz, MeOD): δ = 24.2 (γC), 26.2 (CH2-Ar TA), 28.7 [C(CH3)3 PABA], 28.8 [C(CH3)3 L-Lys], 30.1, 30.2 (δC), 32.9, 33.2 (βC), 39.9 (4×O-CH2-CH2-NH), 40.5, 40.6 (εC), 41.4 (CH2-NH TA), 55.6 (αC core), 56.1 (4×αC L-Lys), 67.7 (4×O-CH2-CH2-NH), 80.6 [C(CH3)3 L-Lys], 81.2 [C(CH3)3 PABA], 105.8, 106.1 (C4 Ph), 107.2, 107.5 (C2,6 Ph), 112.3 (C7 TA), 113.4 (C3 TA), 118.8 (C3,5 PABA), 119.3 (C4 TA), 119.7 (C5 TA), 122.3 (C6 TA), 123.6 (C2 TA), 128.7 (C3a TA), 129.2 (C2,6 PABA), 129.3 (C1 PABA), 137.3, 137.9 (C1 Ph), 138.1 (C7a TA), 144.0 (C4 PABA), 154.8 [C=O (Boc) PABA], 157.8 [C=O (Boc) L-Lys], 161.2 (C3,5 Ph), 169.7 (CONH Ph), 174.3, 175.5 (CONH).
[α]D25 = −14.7 (c 1, MeOH).
Rf = 0.38 (CHCl3/MeOH 8:1).
M.p.: 150–160 °C.
2.3.7. Dendrimer 22 (Obtained from 18)
Dendrimer 22 was obtained in the coupling reaction of Boc-4-Abz-OH (0.24 g, 1.01 mmol), HOBt (0.155 g, 1.01 mmol), EDC∙HCl (0.194 g, 1.01 mmol), with dendrimer 18 (0.4 g, 0.23 mmol), Et3N (0.26 mL, 1.84 mmol) in DMF (10 mL), obtained yellow powder, yield 50% (0.3 g).
C136H196O31N20, M = 2607.13 g/mol (monoisotopic mass 2605.4). LRMS (ESI, MeOH): 2628.5 [M + Na+]+, 1325.8 [M + 2Na+]2+ - main signal.
1H-NMR (500 MHz, MeOD): δ = 1.33–1.51 [br m, 16H, 5×γCH2 L-Lys i core, δCH2 core, 2×O-(CH2)2-CH2-(CH2)2-NH] overlapped with 1.38, 1.39 [2s, 36H, 4×C(CH3)3 L-Lys] i 1.50 [2s, 36H, 4×C(CH3)3 PABA], 1.54-1.87 [br m, 26H, 4×δCH2 L-Lys, 5×βCH2 L-Lys i core, 2×O-CH2-CH2-CH2-CH2-CH2-NH], 2.91 (t, J = 7.1 Hz, 2H, CH2-Ar TA), 3.09-3.24 [2m, 4H, 2×O-(CH2)4-CH2-NH], 3.31 (m, 10H, 5×εCH2 L-Lys i core), 3.39-3.64 (2br m, 6H, 2×O-CH2-CH2-NH, CH2-NH TA), 3.88 [m, 4H, 2×O-CH2-(CH2)4-NH], 4.00 (br m, 8H, 2×O-CH2-CH2-NH, 4×αCH L-Lys), 4.49 (m, 1H, αCH core), 6.57 (m, 2H, C4 Ph), 6.88-7.07 (br m, 7H, C2,6 Ph, C2,5,6-H TA), 7.29 (d, J = 8.1 Hz, 1H, C7-H TA), 7.48 (m, 8H, C3,5-H PABA), 7.51 (d, J = 8.0 Hz, 1H, C4-H TA), 7.72 (m, 8H, C2,6-H PABA).
13C-NMR (500 MHz, MeOD): δ = 24.2, 24.3 (γC), 24.4 [2×O-(CH2)2-CH2-(CH2)2-NH], 26.2 (CH2-Ar TA), 28.7 [C(CH3)3 PABA], 28.8, 29,0 [C(CH3)3 L-Lys], 29.9 [2×O-CH2-CH2-(CH2)3-NH], 30.1, 30.2 [2×O-(CH2)3-CH2-CH2-NH, δC], 32.9, 33.2 (βC), 40.0 (2×O-CH2-CH2-NH), 40.2 [2×O-(CH2)4-CH2-NH], 40.5, 40.7 (εC), 41.4 (CH2-NH TA), 55.6 (αC core), 56.1, 56.2 (4×αC L-Lys), 67.7 (2×O-CH2-CH2-NH), 69.2 [2×O-CH2-(CH2)4-NH], 80.6 [C(CH3)3 L-Lys], 81.2 [C(CH3)3 PABA], 105.8, 106.1 (C4 Ph), 106.7, 107.0, 107.2, 107.4 (C2,6 Ph), 112.3 (C7 TA), 113.1 (C3 TA), 118.8 (C3,5 PABA), 119.3 (C4 TA), 119.7 (C5 TA), 122.3 (C6 TA), 123.6 (C2 TA), 128.7 (C3a TA), 129.2 (C2,6 PABA), 129.3 (C1 PABA), 137.8 (C1 Ph), 138.1 (C7a TA), 144.0 (C4 PABA), 154.8 [C=O (Boc) PABA], 157.8 [C=O (Boc) L-Lys], 161.2, 161.7 (C3,5 Ph), 169.7 (CONH Ph), 169.8 (CONH PABA), 174.3, 175.1, 175.5 (CONH).
[α]D25 = −9.9 (c 1, MeOH).
Rf = 0.44 (CHCl3/MeOH 8:1).
M.p.: 149–155 °C.
2.3.8. Dendrimer 23 (Obtained from 19)
Dendrimer 23 was obtained in the coupling reaction of Boc-4-Abz-OH (0.427 g, 1.8 mmol), HOBt (0.276 g, 1.8 mmol), EDC∙HCl (0.345 g, 1.8 mmol), and dendrimer 19 (0.69 g, 0.41 mmol), Et3N (0.45 mL, 3.28 mmol) in DMF (15 mL); obtained white powder, yield 39.1% (0.41 g). LRMS (ESI, MeOH): 2569.6 [M + Na+]+, 1296.3 [M + 2Na+]2+ - main signal.
1H-NMR (500 MHz, DMSO): δ = 0.83 (br t, 3H, CH3 DDA), 1.18–1.50 (br m, 44H, 5×γ, δCH2 L-Lys i core, 2×βCH2, CH2-2-11 DDA) overlapped with 1.35 [s, 36H, 4×C(CH3)3 L-Lys] i 1.48 [s, 36H, 4×C(CH3)3 PABA], 1.55-1.78 (br m, 6H, 3×βCH2), 2.56-3.09 (m, 2H, εCH2), 3.19 (m, 10H, 4×εCH2, CH2-1 DDA), 3.30-3.48 (br m, 8H, 4×O-CH2-CH2-NH), 3.89 (m, 4H, 4×αCH L-Lys), 4.00 (m, 8H, 4×O-CH2-CH2-NH), 4.37 (m, 1H, αCH core), 6.62 (m, 2H, C4-H Ph), 6.77 (m, 4H, 4×αCH-NH L-Lys), 7.00, 7.07 (2m, 4H, C2,6-H Ph), 7.50 (d, J = 8.7 Hz, 8H, C3,5-H PABA), 7.74 (d, J = 8.7 Hz, 8H, C2,6-H PABA), 7.86 (m, 1H, εCH2-NH core), 7.98 (m, 4H, 4×O-CH2-CH2-NH), 8.24 (m, 4H, 4×εCH2-NH L-Lys), 8.36 (2m, 2H, NHCH2-1 DDA, αCH-NH core), 9.55 (br s, 4H, 4×C4-NH PABA).
13C-NMR (500 MHz, DMSO): δ = 13.9 (C12 DDA), 22.0, 23.0, 23.3 (γC, C11 DDA), 26.2 (C3 DDA), 28.0, 28.1 [C(CH3)3], 28.6, 28.9-29.0 (δC, C2, C4-C9 DDA), 31.2, 31.5, 31.7 (βC, C10 DDA), 38.1 (4×O-CH2-CH2-NH), 38.4, 39.2 (εC, C1 DDA), 53.5 (αC core), 54.3 (4×αC L-Lys), 66.4, 66.5 (4×O-CH2-CH2-NH), 77.9 [C(CH3)3 L-Lys], 79.2, 79.3 [C(CH3)3 PABA], 103.7, 104.0 (C4 Ph), 105.9, 106.3 (C2,6 Ph), 117.0, 117.3 (C3,5 PABA), 127.8 (C2,6 PABA), 128.0 (C1 PABA), 136.2, 136.7 (C1 Ph), 142.0 (C4 PABA), 152.5, 152.6 [C=O (Boc) PABA], 155.3 [C=O (Boc) L-Lys], 159.3 (C3,5 Ph), 165.3, 165.6 (CONH Ph), 171.4, 172.5 (CONH).
[α]D25 = −12.0 (c 1, MeOH).
Rf = 0.77 (CHCl3/MeOH 8:1).
M.p.: 142–149 °C.
2.3.9. Boc-Deprotected Dendrimers
General. A procedure for tert-butoxycarbonyl (Boc) group removal was performed using concentrated HCl and ethyl acetate using 0.15 - 0.32 g (0.059–0.126 mmol) of the respective dendrimer dissolved in 1 mL MeOH and 5–10 mL sat. HCl/AcOEt. Complete Boc group removal was detected after 1 h. Deprotected dendrimers 24–27 are in the form of octahydrochlorides.
2.3.10. Dendrimer 24 (Obtained from 20)
0.26 g (0.101 mmol) of dendrimer 20 yielded pale yellow powder, yield 91.3% (0.19 g).
C94H131O15N19×8HCl, M = 2058.85 g/mol (monoisotopic mass 1766.0). LRMS (ESI, MeOH): 884.1 [M + 2H+]2+, 589.7 [M + 3H+]3+ - main signal.
1H NMR (500 MHz, MeOD): δ = 1.47 [br m, 16H, 5×γCH2 L-Lys i core, δCH2 core, 2×O-(CH2)2-CH2-(CH2)2-NH], 1.54–1.78 [br m, 16H, 4×δCH2 L-Lys, 2×O-CH2-CH2-CH2-CH2-CH2-NH], 1.80-1.97 (br m, 10H, 5×βCH2 L-Lys i core), 2.76 (t, J = 7.2 Hz, 2H, CH2-Ar PEA), 3.21 [br m, 4H, 2×O-(CH2)4-CH2-NH], 3.34 (m, 5H, CH2-NH PEA, 2×εCH2), 3.39 (t, J = 6.9 Hz, 6H, 3×εCH2), 3.46 (m, 1H, CH2-NH PEA), 3.54, 3.69 (2m, 4H, 2×O-CH2-CH2-NH), 3.85-4.00 [br m, 8H, 4×αCH L-Lys, 2×O-CH2-(CH2)4-NH], 4.09 (m, 4H, 2×O-CH2-CH2-NH), 4.45 (m, 1H, αCH core), 6.64 (m, 2H, C4-H Ph), 6.96, 7.02 (2m, 4H, C2,6-H Ph), 7.09-7.23 (br m, 5H, C2,3,4,5,6-H PEA), 7.50 (m, 8H, C3,5-H PABA), 7.99 (m, 8H, C2,6-H PABA).
13C NMR (500 MHz, MeOD): δ = 23.2, 23.4, 24.6 [γC, 2×O-(CH2)2-CH2-(CH2)2-NH], 29.9-30.0, 30.1 [δC, 2×O-CH2-CH2-CH2-CH2-CH2-NH], 32.3, 32.4, 32.8 (βC), 36.5 (CH2-Ar PEA), 40.2 (2×O-CH2-CH2-NH), 40.5 [εC, 2×O-(CH2)4-CH2-NH], 40.7 (εC), 42.0 (CH2-NH PEA), 54.5 (4×αC L-Lys), 55.8 (αC core), 67.6, 67.7 (2×O-CH2-CH2-NH), 69.3 [2×O-CH2-(CH2)4-NH], 105.8, 106.2 (C4 Ph), 106.8, 107.0, 107.3, 107.7 (C2,6 Ph), 124.4 (C3,5 PABA), 127.4 (C4 PEA), 129.5, 129.9 (C2,3,5,6 PEA), 130.4 (C2,6 PABA), 135.0 (C1 PABA), 136.3 (C4 PABA), 137.2, 137.8 (C1 Ph), 140.4 (C1 PEA), 161.2, 161.8 (C3,5 Ph), 168.4-168.5 (CONH PABA), 169.8 (CONH Ph), 170.0, 170.5, 174.5 (CONH).
[α]D25 = −1.9 (c 1, MeOH).
M.p.: 175–191 °C.
2.3.11. Dendrimer 25 (Obtained from 21)
0.15 g (0.059 mmol) of dendrimer 21 yielded grey powder, yield 91.7% (0.11 g).
C90H120O15N20×8HCl, M = 2013.73 g/mol (monoisotopic mass 1720.9). LRMS (ESI, MeOH): 1721.8 [M + H+]+, 888.4 [M + MeOH + H+ + Na+]2+, 861.4 [M + 2H+]2+ - main signal, 592.6 [M + MeOH + 2H+ + Na+]3+, 574.6 [M + 3H+]3+.
1H-NMR (500 MHz, MeOD): δ = 1.45 (m, 10H, 5×γCH2 L-Lys and core), 1.62 (m, 10H, 5×δCH2 L-Lys and core), 1.71-1.96 (br m, 10H, 5×βCH2 L-Lys and core), 2.92 (m, 2H, CH2-Ar TA), 3.34 (m, 8H, 4×εCH2 L-Lys), 3.44 (m, 3H, εCH2 core, CH2-NH TA), 3.52 (m, 5H, 2×O-CH2-CH2-NH, CH2-NH TA), 3.68 (m, 4H, 2×O-CH2-CH2-NH), 3.92 (m, 4H, 4×αCH L-Lys), 4.08 (br m, 8H, 4×O-CH2-CH2-NH), 4.45 (m, 1H, αCH core), 6.67 (2m, 2H, C4-H Ph), 6.97-7.07 (br m, 7H, C2,6-H Ph, C2,5,6-H TA), 7.31 (d, J = 8.04 Hz, 1H, C7-H TA), 7.48 (m, 9H, C4-H TA, C3,5-H PABA), 7.98 (m, 8H, C2,6-H PABA).
13C-NMR (500 MHz, MeOD): δ = 23.2, 24.6 (γC), 26.2 (CH2-Ar TA), 30.0, 30.1 (δC), 32.3, 32.8 (βC), 40.2 (4×O-CH2-CH2-NH), 40.5, 40.7 (εC), 41.4 (CH2-NH TA), 54.5 (4×αC L-Lys), 55.9 (αC core), 67.6, 67.7 (4×O-CH2-CH2-NH), 105.9, 106.3 (C4 Ph), 107.3, 107.6 (C2,6 Ph), 112.3 (C7 TA), 113.1 (C3 TA), 119.3 (C4 TA), 119.6 (C5 TA), 122.3 (C6 TA), 123.6 (C2 TA), 124.3, 124.4 (C3,5 PABA), 128.7 (C3a TA), 130.4 (C2,6 PABA), 135.0 (C1 PABA), 136.3 (C4 PABA), 137.4 (C1 Ph), 138.1 (C7a TA), 161.2, 161.3 (C3,5 Ph), 168.5 (CONH PABA), 169.6 (CONH Ph), 170.5, 174.4 (CONH).
[α]D25 = −5.5 (c 1, MeOH).
M.p.: 200–211 °C.
2.3.12. Dendrimer 26 (Obtained from 22)
0.27 g (0.104 mmol) of dendrimer 22 yielded yellow powder, yield 96.8% (0.21 g).
C96H132O15N20×8HCl, M = 2097.89 g/mol (monoisotopic mass 1805.0). LRMS (ESI, MeOH): 930.4 [M + MeOH + H+ + Na+]2+, 925.4 [M + 2Na+]2+, 903.4 [M + 2H+]2+ - main signal, 620.6 [M + MeOH + 2H+ + Na+]3+, 602.6 [M + 3H+]3+.
1H-NMR (500 MHz, MeOD): δ = 1.46 [br m, 14H, 5×γCH2 L-Lys and core, 2×O-(CH2)3-CH2-CH2-NH], 1.53–1.78 [br m, 18H, 5×δCH2 L-Lys and core, 2×O-CH2-(CH2)2-(CH2)2-NH], 1.88 (m, 10H, 5×βCH2 L-Lys and core), 2.92 (t, J = 7.1 Hz, 2H, CH2-Ar TA), 3.20 [m, 4H, 2×O-(CH2)4-CH2-NH], 3.34 (m, 4H, 2×εCH2), 3.39 (m, 7H, 3×εCH2, CH2-NH TA), 3.52 (m, 3H, O-CH2-CH2-NH, CH2-NH TA), 3.68 (m, 2H, 2×O-CH2-CH2-NH), 3.85-3.99 [br m, 8H, 4×αCH L-Lys, 2×O-CH2-(CH2)4-NH], 4.07 (m, 4H, 2×O-CH2-CH2-NH), 4.46 (m, 1H, αCH core), 6.60, 6.65 (2m, 2H, C4-H Ph), 6.91-7.07 (br m, 7H, C2,6-H Ph, C2,5,6-H TA), 7.31 (d, J = 8.1 Hz, 1H, C7-H TA), 7.50 (m, 9H, C4-H TA, C3,5-H PABA), 7.98 (m, 8H, C2,6-H PABA).
13C-NMR (500 MHz, MeOD): δ = 23.2, 23.3, 24.5 [γC, 2×O-(CH2)2-CH2-(CH2)2-NH], 26.2 (CH2-Ar TA), 29.9, 30.0, 30.1 [δC, 2×O-CH2-CH2-CH2-CH2-CH2-NH], 32.3, 32.4, 32.9 (βC), 40.2 (2×O-CH2-CH2-NH), 40.5 [εC, 2×O-(CH2)4-CH2-NH], 40.7 (εC), 41.4 (CH2-NH TA), 54.4, 54.5 (4×αC L-Lys), 55.8 (αC core), 67.6 (2×O-CH2-CH2-NH), 69.2, 69.3 [2×O-CH2-(CH2)4-NH], 105.8, 106.2 (C4 Ph), 106.8, 107.0, 107.3, 107.6 (C2,6 Ph), 112.3 (C7 TA), 113.1 (C3 TA), 119.3 (C4 TA), 119.6 (C5 TA), 122.3 (C6 TA), 123.6 (C2 TA), 124.3 (C3,5 PABA), 128.7 (C3a TA), 130.3 (C2,6 PABA), 135.0 (C1 PABA), 136.3 (C4 PABA), 137.2, 137.8 (C1 Ph), 138.1 (C7a TA), 161.2, 161.8 (C3,5 Ph), 168.5 (CONH PABA), 169.8 (CONH Ph), 170.0, 170.5, 174.4 (CONH).
[α]D25 = +0.06 (c 1, MeOH).
M.p.: 189–196 °C.
2.3.13. Dendrimer 27 (Obtained from 24)
0.32 g (0.126 mmol) of dendrimer 24 yielded creamy powder, yield 97.7% (0.25 g).
C92H135O15N19×8HCl, M = 2038.86 g/mol (monoisotopic mass 1746.0). LRMS (ESI, MeOH): 874.1 [M + 2H+]2+ - main signal, 583.0 [M + 3H+]3+.
1H NMR (500 MHz, DMSO): δ = 0.87 (br t, 3H, CH3 DDA), 1.22–1.33 (br m, 18H, CH2-3-11 DDA), 1.47 (m, 12H, 5×γCH2 L-Lys and core, CH2-2 DDA), 1.63 (m, 10H, 5×δCH2 L-Lys and core), 1.89 (m, 10H, 5×βCH2 L-Lys and core), 3.16 (m, 2H, CH2-1 DDA), 3.33 (m, 8H, 4×εCH2 L-Lys), 3.46 (m, 2H, εCH2 core), 3.54, 3.68 (2m, 8H, 4×O-CH2-CH2-NH), 3.93 (m, 4H, 4×αCH L-Lys), 4.10 (m, 8H, 4×O-CH2-CH2-NH), 4.47 (m, 1H, αCH core), 6.68 (m, 2H, C4-H Ph), 6.99, 7.05 (2m, 4H, C2,6-H Ph), 7.50 (dd, J = 8.5, 2.65 Hz, 8H, C3,5-H PABA), 7.99 (m, 8H, C2,6-H PABA).
13C NMR (500 MHz, DMSO): δ = 14.4 (C12 DDA), 23.2, 23.7, 24.7 (γC, C11 DDA), 28.0 (C3 DDA), 29.9, 30.1 (δC, C2 DDA), 30.4-30.8 (C4-C9 DDA), 32.3, 32.9 (βC), 33.0 (C10 DDA), 40.2 (4×O-CH2-CH2-NH), 40.5 (εC core, C1 DDA), 40.8 (4×εC L-Lys), 54.5 (4×αC L-Lys), 55.9 (αC core), 67.7 (4×O-CH2-CH2-NH), 106.0, 106.3 (C4 Ph), 107.3, 107.6 (C2,6 Ph), 124.4, 124.7 (C3,5 PABA), 129.9, 130.4 (C2,6 PABA), 134.9 (C1 PABA), 136.3 (C4 PABA), 137.3, 137.9 (C1 Ph), 161.2, 161.3 (C3,5 Ph), 168.5 (CONH PABA), 169.6 (CONH Ph), 170.5, 174.4 (CONH).
[α]D25 = −4.7 (c 1, MeOH).
M.p.: 182–199 °C.