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Y. E. Sabutskii et al.
PAPER
conjugate 8a–h and the second colored fraction (Rf = 0.82–0.92)
was the 2,2′-methylenebis(3-hydroxynaphthoquinone) 9a–h by-
product.
Anal. Calcd for C16H15NO7S (365.36): C, 52.60; H, 4.14; N, 3.83.
Found: C, 52.79; H, 4.10; N, 3.70.
N-Acetyl-S-[(3,5,8-trihydroxy-1,4-dioxo-1,4-dihydronaphtha-
len-2-yl)methyl]-L-cysteine (8d)
Red solid; yield: 70 mg (74%); mp 222–224 °C; Rf = 0.61 (system
B).
N-Acetyl-S-[(3-hydroxy-1,4-dioxo-1,4-dihydronaphthalen-2-
yl)methyl]-L-cysteine (8a)
Yellow solid; yield: 75 mg (85%); mp 190–193 °C; [α]D23 –81.0 (c
0.51, MeOH); Rf = 0.65 (system B).
IR (KBr): 3372, 2931, 1684, 1631, 1609, 1565, 1536, 1447, 1412,
1381, 1317, 1257, 1220, 1187, 1161, 1081, 973, 890, 825, 789 cm–1.
IR (KBr): 3405, 2920, 1697, 1676, 1649, 1594, 1548, 1373, 1344,
1276, 1220, 1040, 1023, 944, 729 cm–1.
1H NMR (500 MHz, DMSO-d6): δ = 1.82 (s, 3 H, COCH3), 2.78 (dd,
J = 8.8, 13.5 Hz, 1 H, SCH2), 2.98 (dd, J = 4.9, 13.5 Hz, 1 H, SCH2),
3.55 (d, J = 12.9 Hz, 1 H, ArCH2), 3.63 (d, J = 12.9 Hz, 1 H,
ArCH2), 4.43 (ddd, J = 4.9, 8.2, 8.8 Hz, 1 H, CHN), 7.29 (d, J = 9.5
Hz, 1 H, ArH), 7.36 (d, J = 9.5 Hz, 1 H, ArH), 8.16 (d, J = 8.2 Hz,
1 H, NH), 11.67 (s, 1 H, α-ОH), 12.78 (br s, 2 H, α-ОH, COOH).
13C NMR (125 MHz, DMSO-d6): δ = 22.4, 23.3, 33.8, 51.9, 110.7,
111.1, 121.5, 127.6, 130.2, 155.5, 156.3, 157.1, 169.2, 172.2, 182.8,
187.9.
1H NMR (500 MHz, DMSO-d6): δ = 1.80 (s, 3 H, COCH3,), 2.79
(dd, J = 8.7, 13.5 Hz, 1 H, SCH2), 2.97 (dd, J = 5.1, 13.5 Hz, 1 H,
SCH2), 3.55 (d, J = 12.7 Hz, 1 H, ArCH2), 3.64 (d, J = 12.7 Hz, 1 H,
ArCH2), 4.42 (ddd, J = 5.1, 8.2, 8.7 Hz, 1 H, CHN), 7.82 (m, 2 H,
ArH), 7.99 (m, 2 H, ArH), 8.15 (d, J = 8.2 Hz, 1 H, NH), 11.46 (s,
1 H, β-OH), 12.62 (br s, 1 H, COOH).
13C NMR (125 MHz, DMSO-d6): δ = 22.4, 23.9, 33.8, 52.0, 121.1,
125.9 (2 C), 130.2, 131.9, 133.4, 134.7, 155.7, 169.3, 172.2, 180.9,
183.6.
HRMS (ESI): m/z [M – H]– calcd for C16H14NO8S: 380.0446;
found: 380.0444.
HRMS (ESI): m/z [M – H]– calcd for C16H14NO6S: 348.0547;
found: 348.0566.
Anal. Calcd for C16H15NO8S (381.36): C, 50.39; H, 3.96; N, 3.67.
Found: C, 50.64; H, 3.94; N, 3.55.
Anal. Calcd for C16H15NO6S (349.36): C, 55.01; H, 4.33; N, 4.01.
Found: C, 55.22; H, 4.31; N, 3.92.
N-Acetyl-S-[(6,7-dichloro-3,5,8-trihydroxy-1,4-dioxo-1,4-dihy-
dronaphthalen-2-yl)methyl]-L-cysteine (8e)
Red solid; yield: 92 mg (82%); mp 124–127 °C; Rf = 0.65 (system
B).
N-Acetyl-S-[(3,8-dihydroxy-1,4-dioxo-1,4-dihydronaphthalen-
2-yl)methyl]-L-cysteine (8b)
Yellow solid; yield: 66 mg (72%); mp 207–209 °C; [α]D23 –108 (c
0.12, MeOH); Rf = 0.59 (system B).
IR (KBr): 3307, 2990, 1731, 1706, 1601, 1535, 1404, 1384, 1295,
1270, 1224, 1181, 1169, 1116, 1001, 910, 863 cm–1.
IR (KBr): 3344, 2980, 1719, 1705, 1646, 1620, 1536, 1457, 1379,
1323, 1270, 1185, 1166, 1069, 929, 918, 776, 763 cm–1.
1H NMR (300 MHz, DMSO-d6): δ = 1.82 (s, 3 H, COCH3), 2.77 (dd,
J = 8.7, 13.5 Hz, 1 H, SCH2), 2.97 (dd, J = 13.5, 4.9 Hz, 1 H, SCH2),
3.55 (d, J = 12.9 Hz, 1 H, ArCH2), 3.64 (d, J = 12.9 Hz, 1 H,
ArCH2), 4.43 (ddd, J = 4.9, 8.2, 8.7 Hz, 1 H, CHN), 8.18 (d, J = 8.2
Hz, 1 H, NH), 12.25 (br s, 2 H, α-ОH, COOH), 13.75 (s, 1 H, α-ОH).
13C NMR (75 MHz, DMSO-d6): δ = 22.7, 23.7, 34.0, 52.3, 110.4,
111.1, 121.1, 129.2, 131.9, 152.8, 152.9, 158.9, 169.6, 172.5, 182.4,
186.3.
1H NMR (500 MHz, DMSO-d6): δ = 1.80 (s, 3 H, COCH3), 2.78 (dd,
J = 8.8, 13.5 Hz, 1 H, SCH2), 2.98 (dd, J = 5.0, 13.5 Hz, 1 H, SCH2),
3.53 (d, J = 12.9 Hz, 1 H, ArCH2), 3.62 (d, J = 12.9 Hz, 1 H,
ArCH2), 4.43 (ddd, J = 5.0, 8.2, 8.8 Hz, 1 H, CHN), 7.31 (dd, J =
0.8, 8.5 Hz, 1 H, ArH), 7.54 (dd, J = 0.8, 7.5 Hz, 1 H, ArH), 7.66
(dd, J = 7.5, 8.5 Hz, 1 H, ArH), 8.16 (d, J = 8.2 Hz, 1 H, NH), 12.39
(br s, 2 H, α-ОH, COOH).
13C NMR (125 MHz, DMSO-d6): δ = 22.4, 23.2, 33.8, 51.9, 114.0,
118.8, 120.5, 124.9, 130.4, 135.5, 157.0, 160.1, 169.3, 172.2, 180.2,
189.8.
HRMS (ESI): m/z [M – H]– calcd for C16H12Cl2NO8S: 447.9666;
found: 447.9676.
Anal. Calcd for C16H13Cl2NO8S (450.25): C, 42.68; H, 2.91; N,
3.11. Found: C, 42.81; H, 2.95; N, 3.06.
HRMS (ESI): m/z [M – H]– calcd for C16H14NO7S: 364.0496;
found: 364.0495.
N-Acetyl-S-[(3,5,8-trihydroxy-6,7-dimethyl-1,4-dioxo-1,4-dihy-
dronaphthalen-2-yl)methyl]-L-cysteine (8f)
Red solid; yield: 85 mg (83%); mp 216–219 °C; Rf = 0.64 (system
B).
Anal. Calcd for C16H15NO7S (365.36): C, 52.60; H, 4.14; N, 3.83.
Found: C, 52.83; H, 4.16; N, 3.74.
N-Acetyl-S-[(3,5-dihydroxy-1,4-dioxo-1,4-dihydronaphthalen-
2-yl)methyl]-L-cysteine (8c)
IR (KBr): 3379, 2951, 1733, 1619, 1598, 1549, 1428, 1383, 1322,
1189, 1036, 892, 818 cm–1.
Yellow solid; yield: 73 mg (80%); mp 200–203 °C; [α]D23 –78.0 (c
0.51, MeOH); Rf = 0.64 (system B).
1H NMR (500 MHz, DMSO-d6): δ = 1.82 (s, 3 H, COCH3), 2.18 (s,
3 H, ArCH3), 2.19 (s, 3 H, ArCH3), 2.77 (dd, J = 8.9, 13.5 Hz, 1 H,
SCH2), 2.96 (dd, J = 4.9, 13.5 Hz, 1 H, SCH2), 3.54 (d, J = 12.9 Hz,
1 H, ArCH2), 3.62 (d, J = 12.9 Hz, 1 H, ArCH2), 4.43 (ddd, J = 4.9,
8.2, 8.9 Hz, 1 H, CHN), 8.16 (d, J = 8.2 Hz, 1 H, NH), 12.49 (br s,
2 H, α-ОH, COOH), 13.47 (br s, 1 H, α-ОH).
13C NMR (125 MHz, DMSO-d6): δ = 11.9, 12.4, 22.4, 23.3, 33.8,
52.0, 107.4, 108.3, 121.5, 135.9, 139.4, 156.4, 156.7, 157.4, 169.3,
172.2, 181.0, 186.2.
IR (KBr): 3384, 2850, 1692, 1645, 1638, 1597, 1536, 1478, 1383,
1293, 1217, 1161, 1062, 1038, 938, 815 cm–1.
1H NMR (500 MHz, DMSO-d6): δ = 1.81 (s, 3 H, COCH3), 2.78 (dd,
J = 8.9, 13.5 Hz, 1 H, SCH2), 2.97 (dd, J = 5.0, 13.5 Hz, 1 H, SCH2),
3.53 (d, J = 12.9 Hz, 1 H, ArCH2), 3.61 (d, J = 12.9 Hz, 1 H,
ArCH2), 4.42 (ddd, J = 5.0, 8.2, 8.9 Hz, 1 H, CHN), 7.27 (dd, J =
0.8, 8.5 Hz, 1 H, ArH), 7.51 (dd, J = 0.8, 7.5 Hz, 1 H, ArH), 7.72
(dd, J = 7.5, 8.5 Hz, 1 H, ArH), 8.16 (d, J = 8.2 Hz, 1 H, NH), 11.34
(s, 1 H, α-ОH), 11.50 (br s, 1 H, COOH), 12.66 (s, 1 H, β-ОH).
13C NMR (125 MHz, DMSO-d6): δ = 22.4, 23.8, 33.8, 51.9, 113.9,
118.4, 121.5, 123.0, 132.3, 137.0, 155.6, 160.1, 169.2, 172.2, 182.9,
184.5.
HRMS (ESI): m/z [M – H]– calcd for C18H18NO8S: 408.0759;
found: 408.0759.
Anal. Calcd for C18H19NO8S (409.41): C, 52.81; H, 4.68; N, 3.42.
Found: C, 52.98; H, 4.70; N, 3.31.
HRMS (ESI): m/z [M – H]– calcd for C16H14NO7S: 364.0496;
found: 364.0491.
Synthesis 2014, 46, 2763–2770
© Georg Thieme Verlag Stuttgart · New York