Paper
NJC
70.3 (PEG), 70.2 v, 70.1 (PEG), 70.0 (PEG), 70.3 (PEG), 69.9 (PEG), ArTriazole-H), 8.54 (d, J = 1.9 Hz, 1H, Ardye-2-H), 8.09 (dd, J = 1.7
69.5 (PEG), 68.7 (PEG), 66.3 (OCH2CH2NH), 66.1 (CH2CH2COO), and 7.9 Hz, 1H, Ardye-6-H), 7.62 (d, 4H, J = 8.2 Hz, Ardye-AA0-H),
57.8 (OCH3), 50.8, 39.5 (CH2NHCOAr), 33.8 (CH2COO), 32.6 7.52 (d, J = 7.8 Hz, 1H, Ardye-5-H), 7.44 (d, 4H, J = 9.4 Hz, Ardye-
( J = 133.4 Hz) (CH-P); 31P NMR (81 MHz, CD3OD) d 24.22. MS BB0-H), 6.68 (d, J = 2.2 Hz, 2H, Ar1-2,6-H), 5.34 (s, 2H, OCH2Ar-
(MALDI-TOF) m/z calculated for C99H171NaN2O49P: 2223.07 Triazole-CH2), 4.89 (t, J = 4.6 Hz, 2H, OCH2ArTriazole-CH2), 4.18
obtained: 2223.09.
(t, J = 4.4 Hz, 4H, Ar1OCH2CH2), 4.04 (t, J = 4.6 Hz, 2H, CH2-
Compound 42. Starting from 38 (0.2 g, 0.14 mmol) and CH2NHO2), 3.88–3.80 (m, 12H, OCH2CH2O and N(CH2CH3)2),
TMSBr (0.55 mL, 3 mmol, 30 equiv.), 42 was obtained 3.72–3.50 (m, 50H, OCH2CH2O), 3.32 (s, 6H, OCH2CH2OCH3),
(0.13 mmol, 94%) as an orange oil. 1H NMR (300 MHz, CD3OD) 3.18 (t, J = 5.2 Hz, 2H, CH2CH2NHO2), 3.14 (d, J = 22.0 Hz, 2H,
d 7.28 (s, 2H, Ar2-2,6-H), 6.92–6.86 (m, 3H, Ar1-2,4,6-H), 4.35– Ar1CH2P), 1.31 (t, J = 7.1 Hz, 12H, N(CH2CH3)2); 13C NMR
4.20 (m, 8H, Ar2OCH2CH2O and Ar1OCH2CH2NH), 3.92–3.82 (75 MHz, CD3OD) d 158.5 ( J = 3.3 Hz) (Ardye = N), 145.2 (Ar),
(m, 8H, Ar1OCH2CH2NH and OCH2CH2O), 3.80–3.53 (m, 54H, 142.1 (ArTriazole), 140.6 (Ar), 139.5 (Ar), 139.1 (Ar), 134.2 (Ar),
OCH2CH2O), 3.38 (s, 6H, OCH2CH2OCH3), 3.18 (d, J = 21.8 Hz, 131.8 (Ar), 129.5 ( J = 8.8 Hz) (Ar), 127.6 (ArTriazole), 127.2 (Ar),
4H, Ar1CH2P), 2.62 (t, 2H, J = 6.0 Hz, Ar2OCH2CH2COOH); 13C 127.1 (Ar), 125.8 (Ar), 116.0 (Ar), 107.8 ( J = 6.6 Hz) (Ar), 71.9
NMR (75 MHz, CD3OD) d 172.2 (COOH), 167.1 (NHCO), 158.8 (OCH2-ArTriazole), 71.0 (PEG), 70.7 (PEG), 70.6 (PEG), 70.5
(Ar), 152.3 (Ar), 141.0 (Ar), 134.8 ( J = 6.0 Hz) (Ar), 128.8 (Ar), (PEG), 70.4 (PEG), 68.8 (PEG), 68.6 (PEG), 67.5 (OCH2CH2NH),
123.8 (Ar), 114.3 (Ar), 106.4 (Ar), 72.2 (PEG), 71.7 (PEG), 70.4 62.5 (PEG), 60.2 (PEG), 57.2 (OCH3), 52.2 (ArTriazole-CH2), 48.4
(PEG), 70.25 (PEG), 70.15 (PEG), 70.1 (PEG), 70.0 (PEG), 69.95 (N(CH2CH3)2), 42.1 (CH2NHSO2), 33.9 ( J = 138.5 Hz) (CH-P),
(PEG), 69.4 (PEG), 68.8 (PEG), 66.3 (OCH2CH2NH), 66.1 10.8 (N(CH2CH3)2); 31P NMR (81 MHz, CD3OD) d 24.09. MS
(CH2CH2COO), 57.8 (OCH3), 50.8, 39.6 (CH2NHCOAr), 34.6 (MALDI-TOF) m/z calculated for C71H112N6O26PS2: 1559.67,
(CH2COO), 33.6 ( J = 134.5 Hz) (CH-P); 31P NMR (81 MHz, obtained: 1559.56; calculated for
CD3OD) 25.19. MS (MALDI-TOF) m/z calculated for 1581.67, obtained: 1581.55.
C71H111NaN6O26PS2:
d
C
C
54H94NO29P2: 1282.53, obtained: 1282.46; calculated for
54H93NaNO29P2: 1304.53, obtained: 1304.45.
Compound 54. Starting from 53 (0.11 g, 0.06 mmol), 54 was
obtained (0.055 mmol, 94%) as a dark yellow-green foam
Compound 43. Starting from 39 (0.08 g, 0.03 mmol) and without further purification. 1H NMR (300 MHz, CD3OD)
TMSBr (0.16 mL, 1.2 mmol, 40 equiv.), 43 was obtained d 8.82 (s, 1H, ArTriazole-H), 8.61 (m, 1H, Ardye-2-H), 8.18
(0.028 mmol, 93%) as an orange oil. 1H NMR (300 MHz, CD3OD) (m, 1H, Ardye-6-H), 7.72–7.52 (m, 9H, Ardye-5-H, Ardye-AA0-H
d 7.27 (s, 4H, Ar3-2,6-H and Ar2-4-H), 7.11 (d, J = 1.7 Hz, 2H, Ar2-2,6- and Ardye-BB0-H), 7.36 (s, 2H, Ar2-2,6-H), 7.28 (d, 2H, J = 7.6 Hz,
H), 6.90–6.85 (m, 3H, Ar1-2,4,6-H), 6.82 (m, 1H, Ar2-4-H), 4.30–4.18 Ar1-2,6-H), 6.97 (d, 2H, J = 7.6 Hz, Ar1-3,5-H), 5.49 (s, 2H,
(m, 18H, Ar1OCH2CH2NH, Ar2OCH2CH2NH and Ar3OCH2CH2O), OCH2ArTriazole-CH2), 4.95 (m, 2H, OCH2ArTriazole-CH2), 4.30
3.95–3.83 (m, 18H, Ar1OCH2CH2NH, Ar2OCH2CH2NH and OCH2- (m, 4H, Ar2OCH2CH2), 4.21 (t, 2H, J = 4.7 Hz, Ar1OCH2CH2NH),
CH2O), 3.80–3.53 (m, 108H, OCH2CH2O), 3.38 (s, 12H, OCH2- 4.08 (t, J = 4.7 Hz, 2H, CH2CH2NHO2), 3.88–3.80 (m, 6H,
CH2OCH3), 3.12 (d, J = 21.6 Hz, 4H, Ar1CH2P), 2.63 (t, 4H, OCH2CH2O and Ar1OCH2CH2NH), 3.82–3.50 (m, 58H, OCH2-
J = 6.6 Hz, Ar3OCH2CH2COOH); 13C NMR (75 MHz, CD3OD) d CH2O and N(CH2CH3)2), 3.38 (s, 6H, OCH2CH2OCH3), 3.22
172.1 (COOH), 168.2 (NHCO), 159.9 (Ar), 158.8 (Ar), 152.2 (Ar), (t, J = 5.2 Hz, 2H, CH2CH2NHO2), 3.20 (d, J = 22.0 Hz, 2H,
140.8 (Ar), 136.2 (Ar), 134.3 (Ar), 129.0 (Ar), 114.3 (Ar), 106.5 (Ar), Ar1CH2P), 1.38 (t, J = 7.1 Hz, 12H, N(CH2CH3)2); 13C NMR
105.8 (Ar), 104.5 (Ar), 72.2 (PEG), 71.5 (PEG), 70.3 (PEG), 70.2 (75 MHz, CD3OD) d 167.8 (NHCO), 157.9 ( J = 3.3 Hz) (Ar),
(PEG), 70.1 (PEG), 70.0 (PEG), 69.95 (PEG), 69.9 (PEG), 69.4 (PEG), 152.1 (Ardye = N), 145.2 (Ar), 142.7 (ArTriazole), 140.6 (Ar), 139.5
68.6 (PEG), 66.2 (OCH2CH2NH), 65.8 (CH2CH2COO), 57.8 (OCH3), (Ar), 138.1 (Ar), 130.8 ( J = 8.8 Hz) (Ar), 130.3 (Ar), 128.9 (Ar),
50.8, 39.4 (CH2NHCOAr), 34.5 (CH2COO), 34.1 ( J = 136.2 Hz) 128.1 (ArTriazole), 126.5 (Ar), 124.7 ( J = 9.6 Hz) (Ar), 120.1 (Ar),
(CH-P); 31P NMR (81 MHz, CD3OD) d 24.03. MS (MALDI-TOF) m/z 114.4 (Ar), 106.1 (Ar), 72.1 (OCH2-ArTriazole), 71.5 (PEG), 70.7
calculated for C79H127N3O34P2: 1723.78, obtained: 1723.46; calcu- (PEG), 70.6 (PEG), 70.5 (PEG), 70.4 (PEG), 69.4 (PEG), 69.2
lated for C29H53NaO14P: 679.31, obtained: 679.24.
(PEG), 68.5 (PEG), 67.8 (PEG), 66.1 (OCH2CH2NH), 62.5 (PEG),
60.8 (PEG), 57.8 (OCH3), 53.2 (ArTriazole-CH2), 48.6 (N(CH2-
General procedure for the conversion of phosphonate ester to
phosphonic acid by TMSBr (McKenna’s method28) (52, 54, 56,
58, and 60)
CH3)2), 42.8 (CH2NHSO2), 39.4 (CH2NHCOAr), 32.9 ( J
135.1 Hz) (CH-P), 11.2 (N(CH2CH3)2); 31P NMR (81 MHz,
CD3OD) 26.69. MS (MALDI-TOF) m/z calculated for
80H121N7O28PS2: 1722.74, obtained: 1722.61; calculated for
=
d
TMSBr (10.0 equiv. per ethyl phosphonate) was added dropwise
to a solution of ethyl phosphonate (51, 53, 55, 57, 59) in CH2Cl2
at 0 1C. After stirring overnight at room temperature, the
C
C
80H120NaN7O28PS2: 1744.74, obtained: 1744.63.
Compound 56. Starting from 55 (0.1 g, 0.03 mmol), 56 was
volatiles were evaporated and MeOH was added to the crude obtained (0.028 mmol, 95%) as a dark yellow-green foam
product and then evaporated several times. The phosphonic without further purification. 1H NMR (300 MHz, CD3OD) d
acid was obtained without further purification.
8.68 (s, 2H, ArTriazole-H), 8.57 (m, 2H, Ardye-2-H), 8.08 (m, 1H,
Compound 52. Starting from 51 (0.12 g, 0.07 mmol), 52 was Ardye-6-H), 7.62–7.55 (d, 8H, J = 9.2 Hz, Ardye-AA0-H), 7.48 (d,
obtained (0.06 mmol, 90%) as a dark yellow-green foam without 2H, J = 8.0 Hz, Ardye-5-H), 7.38–7.30 (m, 8H, Ardye-BB0-H), 7.27
1
further purification. H NMR (300 MHz, CD3OD) d 8.77 (s, 1H, (s, 4H, Ar2-2,6-H), 6.53 (m, 2H, Ar1-2,6-H), 6.45 (m, 1H, Ar1-4-H),
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New J. Chem., 2014, 38, 5226--5239 | 5235