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General Procedure for Peripherally Modified Propyleneimine Dendrimers (D-nX)
A solution of DAB-Am-8 dendrimer, Acr-nX, in THF (2.0 mol×L–1 for Acr-nX) was stirred
at 50◦C for 72 h under an N2 atmosphere. The solution was concentrated under reduced
pressure. The residue was dissolved to a minimal volume of CHCl3 and the resulting
solution was poured into an excess of CH3OH. The precipitated sticky solid or viscous oil
were separated from the solvents by decantation. This operation was repeated further two
times and dried in vacuo to give D-nX.
D-6PPO1 was prepared from 0.33 g of DAB-Am-8 dendrimer (0.43 mmol) and 7.0 g
of Acr-6PPO1 (19 mmol). Yield: 1.3 g (47%). 1H NMR (CDCl3): δ (ppm) = 7.43 (q, J =
6.4 Hz, 64H, ArH), 6.89 (t, J = 11 Hz, 64H, ArCH), 4.03 (t, J = 6.4 Hz, 32H, OCH2), 3.91
(t, J = 6.9 Hz, 32H, PhOCH2), 3.79 (s, 48H, OCH3), 2.75 (t, J = 7.3 Hz, 32H, N−CH2),
2.41 (t, J = 7.3 Hz, 84H, N−CH2 and CH2C=O), 1.85–1.29 (m, 284H, CH2).
D-6BPO1 was prepared from 0.28 g of DAB-Am-8 dendrimer (0.31 mmol) and 6.0 g
of Acr-6BPO1 (15 mmol). Yield: 1.7 g (76%). 1H NMR (CDCl3): δ (ppm) = 8.07 (d, J =
9.2 Hz, 32H, ArH), 7.08 (d, J = 9.2 Hz, 32H, ArH), 6.92 (t, J = 8.7 Hz, 64H, ArCH), 4.12
(t, J = 6.4 Hz, 32H, OCH2), 3.98 (t, J = 6.4 Hz, 32H, PhOCH2), 3.78 (s, 48H, OCH3),
2.74 (t, J = 7.3 Hz, 32H, N−CH2), 2.42 (t, J = 6.9 Hz, 84H, N−CH2 and CH2C=O),
1.91–1.31 (m, 284H, CH2).
D-6PPF was prepared from 0.33 g of DAB-Am-8 dendrimer (0.43 mmol) and 7.0 g
of Acr-6PPF (20 mmol). Yield: 1.9 g (72%). 1H NMR (CDCl3): δ (ppm) = 7.43 (m, 64H,
ArH), 7.05 (t, J = 8.7 Hz, 32H, ArH), 6.88 (d, J = 8.2 Hz, 32H, ArCH), 4.04 (t, J = 6.4 Hz,
32H, OCH2), 3.91 (t, J = 6.4 Hz, 32H, PhOCH2), 2.74 (t, J = 6.4 Hz, 32H, N−CH2), 2.39
(t, J = 6.9 Hz, 84H, N−CH2 and CH2C=O), 1.84–1.31 (m, 284H, CH2).
D-6PPF3 was prepared from 0.25 g of DAB-Am-8 dendrimer (0.32 mmol) and 6.0 g
of Acr-6PPF3 (15 mmol). Yield: 1.3 g (59%). 1H NMR (CDCl3): δ (ppm) = 7.37 (d, J =
7.8 Hz, 32H, ArH), 7.08 (t, J = 6.4 Hz, 32H, ArH), 6.89 (d, J = 7.7 Hz, 32H, ArCH), 4.06
(t, J = 6.4 Hz, 32H, OCH2), 3.94 (t, J = 5.5 Hz, 32H, PhOCH2), 2.74 (t, J = 6.4 Hz, 32H,
N−CH2), 2.41 (t, J = 6.8 Hz, 84H, N−CH2 and CH2C=O), 1.86–1.30 (m, 284H, CH2).
D-3PC5 was prepared from 0.44 g of DAB-Am-8 dendrimer (0.57 mmol) and 6.5 g of
Acr-3PC5 (18 mmol). Yield: 2.1 g (57%). 1H NMR (CDCl3): δ (ppm) = 7.08 (d, J = 8.6 Hz,
32H, Ar–H), 6.78 (d, J = 8.6 Hz, 32H, Ar–H), 4.21 (t, J = 6.3 Hz, 32H, CH2–OCO), 3.97
(t, J = 5.9 Hz, 32H, CH2–O–Ar), 2.74 (t, J = 6.8 Hz, 32H, CH2–COO), 2.30–2.50 (m,
100H, CH2–N and Ar–CH), 1.95–2.15 (m, 32H, O–CH2CH2CH2–O), 1.83 (d, J = 10.9 Hz,
64H, cyclohexyl CH2eq), 1.60–1.73 (br, 4H, N–CH2CH2CH2CH2–N), 1.47–1.60 (br, 16H,
cyclohexyl CH–CH2), 1.10–1.47 (m, 184H, alkyl CH2 and cyclohexyl CH2ax), 0.95–1.10
(m, 32H, CH2CH3), 0.89 (t, J = 7.3 Hz, 48H, CH3).
D-6PC5 was prepared from 0.48 g of DAB-Am-8 dendrimer (0.62 mmol) and 12 g of
Acr-6PC5 (30 mmol). Yield: 2.5 g (56%). 1H NMR (CDCl3): δ (ppm) = 7.08 (d, J = 8.6 Hz,
32H, Ar–H), 6.79 (d, J = 8.6 Hz, 32H, Ar–H), 4.04 (t, J = 6.8 Hz, 32H, CH2–OCO), 3.89
(t, J = 6.3 Hz, 32H, CH2–O–Ar), 2.76 (t, J = 7.3 Hz, 32H, CH2–COO), 2.30–2.50 (m,
100H, CH2–N and Ar–CH), 1.12–1.90 (m, 396H, alkyl CH and CH2), 0.94–1.10 (m, 32H,
CH2CH3), 0.89 (t, J = 7.3 Hz, 48H, CH3).
D-12PC5 was prepared from 0.26 g of DAB-Am-8 dendrimer (0.34 mmol) and 8.0 g
of Acr-12PC5 (17 mmol). Yield: 1.1 g (38%). 1H NMR (CDCl3): δ (ppm) = 7.09 (d, J =
8.6 Hz, 32H, Ar–H), 6.80 (d, J = 8.6 Hz, 32H, Ar–H), 4.03 (t, J = 6.8 Hz, 32H, CH2–OCO),
3.90 (t, J = 6.3 Hz, 32H, CH2–O–Ar), 2.76 (t, J = 7.2 Hz, 32H, CH2–COO), 2.30–2.50
(m, 100H, CH2–N and Ar–CH), 1.17–1.98 (m, 588H, alkyl CH and CH2), 0.94–1.10 (m,
32H, CH2CH3), 0.89 (t, J = 7.2 Hz, 48H, CH3).