The Journal of Organic Chemistry
ARTICLE
(50 mL), stirred for 24 h in contact with air. The yellow solid formed was
collected and crystallized from acetonitrile-DMF 4:1 yielding 2.20 g
(77%) of a solid still containing DMF, which was removed by drying
under reduced pressure: mp >227-228 °C (lit.81 mp 206-208 °C); 1H
NMR (300 MHz, DMSO-d6) δ 7.04-7.08 (m, 1H), 7.28-7.31 (m,
2H), 7.33-7.51 (m, 1H), 12.16 (s, 1H); 13C NMR (75.5 MHz, DMSO-
d6) δ 136.3 (s), 127.0 (s), 124.9 (s), 124.6 (d), 120.3 (d), 120.2 (d),
119.3 (s), 112.2 (d).
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: jan.bergman@ki.se.
Present Addresses
§School of Chemical Science and Engineering, Royal Institute of
Technology, Teknikringen 30, 100 44 Stockholm, Sweden.
Cyclodisulfide 23 by Thionation of Oxindole at 160 °C
(Table 3, Entry 13). Oxindole (1.33 g, 10 mmol) and the reagent 3
(1.52 g, 4 mmol) were warmed with dimethyl sulfone (4. 0 g) and then
heated at 160 °C for 5 min. The melt was allowed to cool and then
heated with water. The solid formed was crystallized from acetonitrile-
DMF 4:1 yielding 1.37 g (92%): mp >227-228 °C. This material was
identical with that obtained via reductive cleavage of the tetrasulfide 25.
3,30-Bithio-oxindole, 27. The solution obtained from reductive
cleavage of the tetrasulfide 25 was acidified with AcOH, which resulted
in quick formation of the title compound as a yellow precipitate, 2.52 g
(85%). The precipitate was recrystallized from acetonitrile, mp 180 °C
dec. This molecule is sensitive toward aerial oxidation: 1H NMR (300
MHz, DMSO-d6) δ 4.66 (s, 2H), 6.85-6.91 (m, 4H), 6.96-6.98 (m,
2H), 7.07-7.13 (m, 2H), 13.06 (s, 2H); 13C NMR (75.5 MHz, DMSO-
d6) δ 60.8 (d), 110.4 (d), 123.0 (d), 123.4 (d), 128.6 (d), 130.2 (s),
144.2 (s), 204.3 (s). Anal. Calcd for C16 H12N2S2: C, 64.60; H, 4.08; N,
9.43. Found: C, 64.26; H, 3.99; N, 9.31.
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1H NMR (300 MHz, DMSO-d6) δ 2.43 (s, 3H), 3.17 (s, 2H), 3.38 (s,
1H), 3.49 (s, 3H), 3.64 (s, 3H), 11.90 (s 1H); 13C NMR (75.5 MHz,
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126.9 (s), 139.9 (s), 164.4 (s), 171.1 (s)Anal. Calcd for C10 H13NO4S: C,
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3-(1H-Indol-3-yl)-3,30-biindoline-2-thione (Table 3, Entry 9).
3-(1H-Indol-3-yl)-3,30-biindolin-2-one105 (728 mg, 2 mmol), the reagent 3
(228 mg, 0.6 mmol), and dimethyl sulfone (3.05 g) were heated (165-
170 °C) for 20 min. The melt was allowed to cool and then heated in water
for 10 min. The solid formed was collected, 713 mg (94%): mp >260 °C;
1H NMR (300 MHz, DMSO-d6) δ 7.09-7.15 (m, 2H), 7.18-7.20 (m,
5H), 7.24-7.30 (m, 7H), 13.00 (s, 1H); 13C NMR (75.5 MHz, DMSO-d6)
δ 72.7 (s), 111.2 (d), 124.4 (d), 126.5 (d), 127.5 (d), 128.6 (d), 128.7 (d),
129.0 (d), 129.1 (d), 129.1 (d), 139.2 (s), 143.0 (s), 143.5 (s), 145.3 (s,
2C), 208.4 (s). Anal. Calcd for C24H17N3S: C, 75.96; H, 4.51; N, 11.07.
Found: C, 76.10; H, 4.46; N, 11.00.
ꢀ
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’ ASSOCIATED CONTENT
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S
Supporting Information. The crystal structural data of 3
b
and 11a have been deposited at Cambridge Data Centre and
allocated the deposition numbers CCDC 789665 and CCDC
789666. CIFs for compounds 3 and 11a are included. Experi-
mental details for 6H-indolo[2,3-b]quinolin-11-one and com-
pounds 13a and 33a (Table 1, entries 2, 3, and 8). Compound
characterization data for 6H-indolo[2,3-b]quinolin-11-one and
compounds 13a and 33a (Table 1, entries 2, 3, 8, and 11; Table 3,
entries 3, 7, and 10). Copies of 1H and 13C NMR spectra for all
1
new compounds. Copies of H NMR are provided for most
compounds in the tables. This material is available free of charge
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dx.doi.org/10.1021/jo101865y |J. Org. Chem. 2011, 76, 1546–1553