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PAPER
measurements. Thermogravimetric analyses were carried out on a
TGA2950 from TGA Instruments.
HRMS (ES, +ve): m/z [M + H]+ calcd for C34H43N4O7S2: 683.2573;
found: 683.2537.
Sulfonyl Chloride (1)
Allyl Sulfonamide (9)
To a stirred solution of Acid red 52 sodium salt (2; 49.5 g, 85.3
mmol) in CH2Cl2 (600 mL) at 0 °C, was added, sequentially, oxalyl
chloride (3; 54.1 g, 36.6 mL, 0.426 mol) slowly and DMF (1.02
mL). The resulting mixture was stirred at r.t. for 16 h then the reac-
tion was concentrated in vacuo. To the slurry, benzene (500 mL)
was added and the solvent was removed in vacuo. Et2O (400 mL)
was added to the resultant solid, which was filtered and washed with
EtOAc (100 mL) and dried under vacuum to yield 1.
To a stirred solution of sulfonyl chloride 1 (0.363 g, 0.628 mmol) in
CH2Cl2 (5 mL) at 0 °C was added, sequentially, allylamine (39.6
mg, 52 mL, 0.693 mmol) and Et3N (0.176 mL). The reaction was al-
lowed to warm to r.t. and, after 16 h, the reaction was concentrated
in vacuo and purified by chromatography over silica gel column
(MeOH–CH2Cl2, 1→5%) to give major isomer 9.
Yield: 0.158 g (42%); mp 256 °C (dec.).
IR (KBr): 3070, 2981, 2929, 1647, 1591, 1531, 1419, 1342, 1282,
1178, 1071, 1024, 920, 860, 684 cm–1.
1H NMR (400 MHz, DMSO-d6): d = 8.45 (s, 1 H), 8.12 (t, J = 6.0
Hz, 1 H), 7.95 (dd, J = 8.0, 2.0 Hz, 1 H), 7.48 (d, J = 8.0 Hz, 1 H),
7.09–6.95 (m, 7 H), 5.80–5.72 (m, 1 H), 5.23–5.10 (m, 2 H), 3.71–
3.58 (m, 10 H), 1.25–1.22 (m, 12 H).
13C NMR (100 MHz, DMSO-d6): d = 158.1, 157.6, 155.6, 148.6,
142.2, 134.5, 133.5, 133.2, 131.0, 127.0, 126.3, 117.1, 114.2, 114.0,
95.9, 45.7, 13.0.
Yield: 43.4 g (88%); pink solid.
1H NMR (300 MHz, DMSO-d6): d = 8.27 (s, 1 H), 7.73 (d, J = 7.5
Hz, 1 H), 7.15 (d, J = 7.8 Hz, 1 H), 7.05–6.91 (m, 5 H), 3.75–3.55
(m, 8 H), 1.34–1.10 (m, 12 H).
13C NMR (75 MHz, DMSO-d6): d = 160.0, 157.6, 155.4, 149.5,
147.0, 133.3, 129.5, 129.4, 126.0, 125.6, 114.2, 113.9, 95.7, 45.7,
12.9.
Methacrylate (5)
HRMS (ES, +ve): m/z [M + H]+ calcd for C30H36N3O6S2: 598.2046;
found: 598.2020.
To a stirred solution of sulfonyl chloride 1 (85.0 g, 147 mmol) in
CH2Cl2 (735 mL) at 0 °C was added, sequentially, 2-aminoethyl
methacrylate hydrochloride (29.2 g, 177 mmol) and DMAP (0.899
g, 7.37 mmol). Et3N (38.3 g, 53 mL, 295 mmol) was added drop-
wise and the reaction was allowed to warm to r.t. After 13 h, the re-
action was concentrated in vacuo and the resulting solid was
washed with EtOAc to give 5.
Amine (11)
To a stirred solution of ethylenediamine (2.50 g, 2.80 mL, 41.6
mmol) in CH2Cl2 (250 mL) at 0 °C was added, sequentially, Et3N
(1.40 g, 1.93 mL, 13.9 mmol) and DMAP (0.250 g, 2.05 mmol).
Then, sulfonyl chloride 1 (8.00 g, 13.9 mmol) was added over 2 h.
The reaction was allowed to warm to r.t. then, after 13 h, the reac-
tion was concentrated in vacuo and the resulting solid was washed
with CH2Cl2–EtOAc (1:2) to give amine 11.
Yield: 65.9 g (67%); pink solid; mp 258 °C (dec.).
IR (KBr): 2968, 1647, 1596, 1527, 1471, 1419, 1342, 1277, 1247,
1183, 1075, 916 cm–1.
1H NMR (300 MHz, CD3OD): d = 8.67 (s, 1 H), 8.13 (dd, J = 7.8,
1.8 Hz, 1 H), 7.52 (d, J = 7.8 Hz, 1 H), 7.17–6.95 (m, 6 H), 6.18 (s,
1 H), 5.66 (s, 1 H), 4.19 (t, J = 5.7 Hz, 1 H), 3.75–3.65 (m, 8 H),
3.40–3.36 (m, 2 H), 1.96 (s, 3 H), 1.34–1.30 (m, 12 H).
13C NMR (75 MHz, CD3OD): d = 167.2, 158.0, 156.4, 155.8, 145.8,
142.9, 136.0, 134.1, 132.3, 131.2, 127.8, 126.2, 125.4, 113.9, 113.6,
95.6, 63.1, 45.4, 41.6, 17.0, 11.4.
Yield: 6.74 g (81%); pink solid; mp 248 °C (dec.).
IR (KBr): 2968, 2912, 1647, 1587, 1470, 1415, 1338, 1252, 1174,
1080, 684 cm–1.
1H NMR (300 MHz, CD3OD): d = 8.67 (s, 1 H), 8.17 (d, J = 8.1 Hz,
1 H), 7.58 (d, J = 7.8 Hz, 1 H), 7.14–6.96 (m, 6 H), 6.18 (s, 1 H),
5.66 (s, 1 H), 4.19 (t, J = 5.7 Hz, 1 H), 3.73–3.66 (m, 8 H), 3.51–
2.97 (m, 4 H), 1.40–1.15 (m, 12 H).
HRMS (ES, +ve): m/z [M + H]+ calcd for C33H40N3O8S2: 670.2257;
found: 670.2236.
13C NMR (75 MHz, CD3OD): d = 158.0, 155.8, 145.9, 141.6, 132.2,
131.4, 128.0, 126.4, 113.9, 113.6, 95.6, 45.4, 44.0, 39.6, 11.4.
UV/Vis: lmax (e) = 567 nm (44500) (shoulder around 530 nm).
HRMS (ES, +ve): m/z [M + H]+ calcd for C29H37N4O6S2: 601.2155;
found: 601.2124.
Methacrylamide (7)
UV/Vis: lmax (e) = 566 (39400), 534 nm (32500; minor peak).
To a stirred solution of sulfonyl chloride 1 (209.4 mg, 0.363 mmol)
in CH2Cl2 (5 mL) at 0 °C was added, sequentially, N-(3-aminopro-
pyl)methacrylamide hydrochloride (65 mg, 0.363 mmol) and Et3N
(0.109 g, 0.15 mL, 1.07 mmol). The reaction was allowed to warm
to r.t. and, after 13 h, the reaction was concentrated in vacuo and pu-
rified by chromatography over silica gel column (MeOH–CH2Cl2,
1→5%) to give 7.
Monomeric Polymer (12)
To a stirred solution of methacrylate 5 (2.12 g, 3.16 mmol) in DMF
(32 mL) was added AIBN (38 mg, 0.232 mmol). The reaction was
heated at 70 °C for 24 h then cooled to r.t. and poured into EtOAc
(120 mL) at 0 °C. The solid was filtered and washed with EtOAc
(200 mL), CH2Cl2 (200 mL) and dried in vacuo to yield the polymer
12.
Yield: 0.162 g (65%); pink solid; mp 260 °C (dec.).
IR (KBr): 2976, 2942, 2619, 1651, 1596, 1475, 1338, 1174, 1075,
920, 680 cm–1.
1H NMR (400 MHz, DMSO-d6): d = 8.45 (s, 1 H), 7.96–7.90 (m,
3 H), 7.49 (d, J = 8.0 Hz, 1 H), 7.06–6.96 (m, 4 H), 5.65 (s, 1 H),
5.32 (s, 1 H), 3.67–3.65 (m, 8 H), 3.18–3.13 (m, 2 H), 2.94–2.89
(m, 2 H), 1.86 (s, 3 H), 1.68–1.64 (m, 2 H), 1.25–1.22 (m, 12 H).
13C NMR (100 MHz, DMSO-d6): d = 168.0, 158.1, 157.6, 155.5,
148.6, 142.0, 140.5, 133.5, 133.2, 131.1, 126.9, 126.2, 119.3, 114.1,
95.9, 45.7, 37.0, 29.8, 19.1, 13.0.
Yield: 1.71 g (81%); pink solid.
IR (KBr): 2981, 2938, 2675, 1647, 1591, 1475, 1337, 1183, 1071,
1032, 920, 804, 675 cm–1.
1H NMR (300 MHz, CD3OD): d = 8.67 (s, 1 H), 8.12–7.99 (m, 1 H),
7.51–7.49 (m, 1 H), 7.12–6.95 (m, 5 H), 4.13–4.11 (m, 2 H), 3.70–
3.68 (m, 8 H), 1.45–1.30 (m, 12 H).
13C NMR (75 MHz, DMSO-d6): d = 161.9, 157.6, 155.5, 148.5,
147.1, 142.2, 133.6, 133.4, 133.2, 131.2, 127.0, 126.7, 126.1, 125.7,
114.1, 114.0, 95.9, 63.0, 45.8, 17.2, 13.0.
UV/ Vis: lmax = 567 nm (shoulder around 530 nm).
Synthesis 2008, No. 6, 957–961 © Thieme Stuttgart · New York