196 Letters in Organic Chemistry, 2011, Vol. 8, No. 3
Khomenko et al.
Transformation of 6a to 5a
(17%, M+), 221 (100, M+-2S), 189 (13, M+-3S), 157 (15, M+-
4S), 145 (10), 64 (9).
NaHS (0.102 g, 70%, 1.3 mmol) was added to a solution
of 6a (0.077 g, 0.3 mmol) in DMSO (1 ml). The mixture was
stirred for 24 h, and then H2O was added. The mixture was
extracted with CHCl3 and dried (Na2SO4) to obtain a mixture
Data of 6-chloro-4-nitrobenzo[d][1,2,3]trithiole (6c)
M.p. 86-88 °C. 1H-NMR: 7.57 (d, J (7,5) = 2.0, H-C(7));
7.95 (d, J (5,7) = 2.0, H-C(5)). 13C-NMR: 140.0 (s, C(3a));
145.6 (br.s, C(4)); 123.0 (d, C(5)); 133.1 (s, C(6)); 127.7 (d,
C(7)); 145.8 (s, C(7a)). HR-MS: 250.8930 (M+,
1
of 5a and 6a (ratio ~3.4:1, H-NMR); then the aq. layer was
acidified to pH 5 with concentrated HCl, extracted with
CHCl3, extract was dried (Na2SO4), and evaporated to obtain
a mixture of 5a and 6a ~3:2 (1H NMR).
+
C6H2ClNO2S3 ; calc. 250.8931).
Reaction of 4d with NaHS
Reaction of 4b with NaHS
Compounds 5d (0.014 g, 2 %) and 6d (0.088 g, 15%)
were obtained from NaHS (0.430 g, 70%, 5.4 mmol) and 4d
(0.587 g, 2.47 mmol) in DMSO (12 ml) in accordance with
the procedure of reaction of 4b with NaHS. Compounds 5d
and 6d were isolated in the pure form by column
NaHS (0.369 g, 70%, 4.6 mmol) was added to a solution
of 4-nitro-6-fluorobenzo[d]dithiol-2-one 4b (0.489 g, 2.1
mmol) in DMSO (6 ml). The mixture was stirred at r.t. for
24 h. Then H2O (20 ml) was added; the solution was
acidified with HCl, extracted with CH2Cl2 (3x20 ml), the
mixture was washed with H2O (3x10 ml), and dried
(Na2SO4). The residue obtained after solvent evaporation
was separated by column chromatography (SiO2, hexane-
benzene 1:1). This gave 5b (0.028 g, 5%) and 6b (0.208 g,
42%).
chromatography (SiO2,
hexane/benzene
1:1,
then
hexane/benzene/CHCl3 1:1:1).
Data of 9-aminobenzo[f][1,2,3,4,5]pentathiepin-7-
carbonitrile (5d)
1H-NMR: 4.89 (br.s, NH2); 6.92 (d, J (8,6) = 1.7, H-
C(8)); 7.32 (d, J (6,8) = 1.7, H-C(6)). 13C-NMR: 146.9 (s,
C(5a)); 126.5 (d, C(6)); 114.4 (s, C(7)); 119.7 (d, C(8));
150.5 (s, C(9)); 129.2 (s, C(9a)); 116.9 (s, CN). Anal. Found:
C, 30.59; H, 1.54%. Calcd. for C7H4N2S5: C, 30.41; H,
Data of 8-fluorobenzo[f][1,2,3,4,5]pentathiepin-6-amine
(5b)
1H-NMR: 4.75 (br. s, NH2); 6.37 (dd, J (7,F) = 9.8, J
(7,9) = 2.6, H-C(7)); 6.82 (dd, J (9,F) = 7.9, J (9,7) = 2.6, H-
+
1.46%. HR-MS: 275.8972 (M+, C7H4N2S5 ; calc. 275.8973).
4
C(9)). 13C-NMR: 120.6 (d, J (C,F) = 3.1, C(5a)); 151.4 (d,
EI-MS: 276 (11%, M+), 212 (100, M+-2S), 180 (18, M+-3S),
148 (16, M+-4S), 136 (12), 121 (9), 64 (15).
3J (C,F) = 12.4, C(6)); 103.2 (d, 2J (C,F) = 24.8, C(7)); 162.5
1
(d, J (C,F) = 254.0, C(8)) 112.7 (d, 2J (C,F) = 23.6, C(9));
3
Data of 7-nitrobenzo[d][1,2,3]trithiole-5-carbonitrile (6d)
147.7 (d, J (C,F) = 10.2, C(9a)). Anal. Found: C, 26.89; H,
1H-NMR: 7.78 (d, J (4,6) = 1.5, H-C(4)); 8.24 (d, J (6,4)
= 1.5, H-C(6)). 13C-NMR: 146.4 (s, C(3a)); 128.9 (d, C(4));
111.6 (s, C(5)); 127.0 (d, C(6)); 145.6 (br.s, C(7)); 147.3 (s,
1.60%. Calcd. for C6H4FNS5: C, 26.75; H, 1.50%. HR-MS:
+
268.8917 (M+, C6H4FNS5 ; calc. 268.8926). EI-MS: 269
(6%, M+), 205 (100, M+-2S), 173 (18, M+-3S), 141 (38, M+-
4S), 129 (28), 64 (63).
+
C(7a)); 115.4 (s, CN). HR-MS: 241.9257 (M+, C7H2N2O2S3 ;
calc. 241.9270).
Data of 6-fluoro-4-nitrobenzo[d][1,2,3]trithiole (6b)
M.p. 75-77 °C (EtOH). 1H-NMR: 7.38 (dd, 3J (7,F) = 7.1,
J (7,5) = 2.5, H-C(7)); 7.68 (dd, 3J (5,F) = 7.7, J (5,7) = 2.5,
ACKNOWLEDGEMENT
4
H-C(5)). 13C-NMR: 137.0 (d, J (C,F) = 3.5, C(3a)); 145.5
(br. d, 3J (C,F) = 8.4, C(4)); 110.2 (d, 2J (C,F) = 27.4, C(5));
The authors are grateful to the Presidium of Siberian
Branch of Russian Academy of Sciences for financial
support (programs N 18, 78).
1
2
160.3 (d, J (C,F) = 254.8, C(6)); 116.4 (d, J (C,F) = 25.7,
3
C(7)); 146.2 (d, J (C,F) = 7.5, C(7a)). HR-MS: 234.9232
+
(M+, C6H2FNO2S3 ; calc. 234.9226).
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Reaction of 4c with NaHS
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Compounds 5c (0.043 g, 4 %) and 6c (0.368 g, 40%)
were obtained from NaHS (0.674 g, 70%, 8.4 mmol) and 4-
nitro-6-chlorobenzo[d]dithiol 4c (0.910 g, 3.7 mmol) in
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of 4b with NaHS.
[2]
[3]
[4]
[5]
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(5c)
1H-NMR: 4.73 (br.s, NH2); 6.67 (d, J (7,9) = 2.1, H-
C(7)); 7.07 (d, J (9,7) = 2.1, H-C(9)). 13C-NMR: 123.0 (s,
C(5a)); 151.0 (s, C(6)); 116.5 (d, C(7)); 136.2 (s, C(8));
124.6 (d, C(9)); 146.8 (s, C(9a)). Anal. Found: C, 25.34; H,
1.50%. Calcd. for C6H4ClNS5: C, 25.21; H, 1.41%. HR-MS:
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–
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+
284.8633 (M+, C6H4ClNS5 ; calc. 284.8630). EI-MS: 285