E
V. K. Gopinatha et al.
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Synlett
Yield: 88%; off-white solid; mp 240–242 °C. 1H NMR (DMSO-d6,
400 MHz): = 12.64 (s, 1 H), 12.14 (s, 1 H), 7.94 (d, J = 8 Hz,
2 H), 7.49–7.58 (m, 3 H), 7.10 (d, J = 8.8 Hz, 2 H), 6.86 (d, J =
9.2 Hz, 2 H), 4.08 (t, J = 9.6 Hz, 1 H), 3.02 (s, 3 H), 3.54–3.59 (m,
2 H). 13C NMR (DMSO-d6, 400 MHz): = 180.3, 169.6, 166.2,
159.3, 133.5, 132.2, 129.2, 129.1, 128.6, 127.3, 114.4, 85.5, 55.5,
55.2, 40.8. HRMS (ESI): m/z [M + H]+ calcd for C20H17N3O3S:
380.1024; found: 380.1026.
4.8, 4 Hz, 1 H), 7.17 (d, J = 8.4 Hz, 2 H), 4.16 (t, J = 9.4 Hz, 1 H),
3.51–3.64 (m, 2 H). 13C NMR (DMSO-d6, 400 MHz): = 179.1,
174.5, 169.2, 166.2, 137.4, 134.8, 133.4, 133.0, 132.6, 130.1,
129.1, 128.8, 85.5, 54.8, 41.3. HRMS (ESI): m/z [M + H]+ calcd for
C
17H12ClN3O2S2: 390.0059; found: 390.0063.
4-(4-Fluorophenyl)-2-phenyl-8-thioxo-1,7,9-tri-
azaspiro[4,5]dec-1-ene-6,10-dione (3h)
Yield: 88%; off-white solid; mp 208–210 °C. 1H NMR (DMSO-d6,
400 MHz): = 12.69 (s, 1 H), 12.19 (s, 1 H), 7.96 (d, J = 7.2 Hz,
2 H), 7.51–7.59 (m, 3 H), 7.14–7.24 (m, 4 H), 4.17 (t, J = 9.4 Hz,
1 H), 3.54–3.68 (m, 2 H). 13C NMR (DMSO-d6, 400 MHz): =
180.2, 179.1, 169.3, 166.1, 133.2, 132.3, 130.2, 130.1, 129.1,
128.6, 115.9, 115.7, 85.5, 54.7, 40.9. HRMS (ESI): m/z [M + H]+
calcd for C19H14FN3O2S: 368.0791; found: 368.0795.
4-(4-Chlorophenyl)-2-phenyl-8-thioxo-1,7,9-tri-
azaspiro[4,5]dec-1-ene-6,10-dione (3b)
Yield: 85%; off-white solid; mp 155–157 °C. 1H NMR (DMSO-d6,
400 MHz): = 12.67 (s, 1 H), 12.18 (s, 1 H), 7.94 (d, J = 7.2 Hz,
2 H), 7.49–7.59 (m, 3 H), 7.37 (d, J = 8.4 Hz, 2 H), 7.19 (d, J =
8.4 Hz, 2 H), 4.17 (t, J = 9.2 Hz, 1 H), 3.53–3.67 (m, 2 H). 13C NMR
(DMSO-d6, 400 MHz): = 180.1, 179.1, 169.3, 166.0, 134.9,
133.1, 132.9, 132.3, 130.0, 129.1, 128.9, 128.6, 85.4, 54.4, 40.8.
HRMS (ESI): m/z [M + H]+ calcd for C19H14ClN3O2S: 384.0495;
found: 384.0498.
2-Phenyl-4-(thiophen-2-yl)-8-thioxo-1,7,9-tri-
azaspiro[4,5]dec-1-ene-6,10-dione (3i)
Yield: 89%; off-white solid; mp 166–168 °C. 1H NMR (DMSO-d6,
400 MHz): = 12.78 (s, 1 H), 12.31 (s, 1 H), 7.92 (d, J = 7.2 Hz,
2 H), 7.56 (t, J = 7.4 Hz, 1 H), 7.49 (t, J = 7.4 Hz, 2 H), 7.44 (t, J =
3 Hz, 1 H), 6.97 (d, J = 2.4 Hz, 2 H), 4.36 (t, J = 9.4 Hz, 1 H), 3.76
(dd, J = 16.6, 8.6 Hz, 1 H), 3.51 (dd, J = 16.4, 10.8 Hz, 1 H). 13C
NMR (DMSO-d6, 400 MHz): = 180.0, 179.2, 169.3, 165.8, 138.1,
133.0, 132.4, 129.1, 128.6, 127.7, 126.7, 126.1, 84.8, 50.6, 42.4.
HRMS (ESI): m/z [M + H]+ calcd for C17H13N3O2S2: 356.4340;
found: 356.4344.
4-(4-Methoxyphenyl)-2-(thiophen-2-yl)-8-thioxo-1,7,9-tri-
azaspiro[4,5]dec-1-ene-6,10-dione (3c)
Yield: 87%; off-white solid; mp 205–207 °C. 1H NMR (DMSO-d6,
400 MHz): = 12.74 (s, 1 H), 12.27 (s, 1 H), 7.86 (d, J = 8.8 Hz,
2 H), 7.44 (dd, J = 5, 1.4 Hz, 1 H), 7.03 (d, J = 8.8 Hz, 2 H), 6.96–
6.98 (m, 2 H), 4.34 (dd, J = 11.2, 8.8 Hz, 1 H), 3.81 (s, 3 H), 3.73
(dd, J = 16.6, 8.6 Hz, 1 H), 3.47 (dd, J = 16.6, 11 Hz, 1 H). 13C NMR
(DMSO-d6, 400 MHz): = 179.1, 169.4, 166.1, 166.0, 162.6,
138.3, 130.5, 127.6, 126.6, 126.0, 125.7, 114.5, 84.7, 55.8, 50.5,
2,4-Bis(4-methoxyphenyl)-8-thioxo-1,7,9-tri-
azaspiro[4,5]dec-1-ene-6,10-dione (3j)
42.4. HRMS (ESI): m/z [M
+
H]+ calcd for C18H15N3O3S2:
Yield: 88%; off-white solid; mp 224–226 °C. 1H NMR (DMSO-d6,
400 MHz): = 12.62 (s, 1 H), 12.12 (s, 1 H), 7.88 (d, J = 8.8 Hz,
2 H), 7.07 (d, J = 8.8 Hz, 2 H), 7.03 (d, J = 8.8 Hz, 2 H), 6.84 (d, J =
8.4 Hz, 2 H), 4.04 (t, J = 9.4 Hz, 1 H), 3.81 (s, 3 H), 3.69 (s, 3 H),
3.46–3.55 (m, 2 H). 13C NMR (DMSO-d6, 400 MHz): = 179.3,
179.1, 169.9, 166.5, 162.4, 159.2, 130.4, 129.2, 127.4, 126.0,
114.4, 114.3, 85.3, 55.8, 55.5, 55.2, 40.7. HRMS (ESI): m/z [M +
H]+ calcd for C21H19N3O4S: 410.4583; found: 410.4587.
4-(Naphthalen-1-yl)-2-phenyl-8-thioxo-1,7,9-tri-
386.4600; found: 386.4606.
2-(4-Methoxyphenyl)-4-(thiophen-2-yl)-8-thioxo-1,7,9-tri-
azaspiro[4,5]dec-1-ene-6,10-dione (3d)
Yield: 86%; off-white solid; mp 230–232 °C. 1H NMR (DMSO-d6,
400 MHz): = 12.61 (s, 1 H), 12.12 (s, 1 H), 7.84–7.85 (m, 1 H),
7.70 (d, J = 2.8 Hz, 1 H), 7.22 (dd, J = 5, 3.8 Hz, 1 H), 7.06 (d, J =
8.8 Hz, 2 H), 6.84 (d, J = 8.4 Hz, 2 H), 4.06 (t, J = 9.6 Hz, 1 H), 3.69
(s, 3 H), 3.51–3.55 (m, 2 H). 13C NMR (DMSO-d6, 400 MHz): =
178.5, 174.1, 169.0, 165.8, 158.8, 137.1, 132.7, 131.9, 128.7,
128.1, 126.6, 114.4, 84.6, 55.1, 40.8. HRMS (ESI): m/z [M + H]+
calcd for C18H15N3O3S2: 386.4600; found: 386.4606.
azaspiro[4,5]dec-1-ene-6,10-dione (3k)
Yield: 89%; off-white solid; mp 130–132 °C. 1H NMR (DMSO-d6,
400 MHz): = 12.50 (s, 1 H), 12.95 (s, 1 H), 7.98–8.00 (m, 2 H),
7.84–7.92 (m, 3 H), 7.44–7.61 (m, 7 H), 5.05 (t, J = 9.2 Hz, 1 H),
3.74–3.79 (m, 2 H). 13C NMR (DMSO-d6, 400 MHz): = 180.3,
178.6, 169.9, 166.2, 133.8, 133.3, 132.3, 132.1, 131.4, 129.3,
129.2, 128.9, 128.7, 127.0, 126.1, 125.8, 125.7, 122.7, 85.2, 50.2,
42.3. HRMS (ESI): m/z [M + H]+ calcd for C23H17N3O2S: 400.4650;
found: 400.4656.
2,4-Diphenyl-8-thioxo-1,7,9-triazaspiro[4,5]dec-1-ene-6,10-
dione(3e)
Yield: 89%; off-white solid; mp 230–232 °C. 1H NMR (DMSO-d6,
400 MHz): = 12.69 (s, 1 H), 12.16 (s, 1 H), 7.96 (d, J = 5.6 Hz,
2 H), 7.51–7.61 (m, 3 H), 7.27–7.33 (m, 3 H), 7.18 (d, J = 5.2 Hz,
2 H), 4.17 (t, J = 8 Hz, 1 H), 3.58–3.67 (m, 2 H). 13C NMR (DMSO-
d6, 400 MHz): = 180.4, 179.1, 169.7, 166.2, 133.7, 132.4, 129.2,
129.1, 128.7, 128.4, 128.2, 85.5, 55.6, 39.9. HRMS (ESI): m/z [M +
H]+ calcd for C19H15N3O2S: 350.4063; found: 350.4067.
4-(4-Chlorophenyl)-2-(4-methoxyphenyl)-8-thioxo-1,7,9-
triazaspiro[4,5]dec-1-ene-6,10-dione (3f)
2,4-Bis(4-chlorophenyl)-8-thioxo-1,7,9-triazaspiro[4,5]dec-
1-ene-6,10-dione (3l)
Yield: 84%; off-white solid; mp 223–225 °C. 1H NMR (DMSO-d6,
400 MHz): = 12.71 (s, 1 H), 12.21 (s, 1 H), 7.98 (d, J = 8 Hz,
2 H), 7.61 (d, J = 4 Hz, 2 H), 7.40 (d, J = 8 Hz, 2 H), 7.21 (d, J =
4 Hz, 2 H), 4.19 (t, J = 8 Hz, 1 H), 3.60–3.64 (m, 2 H). 13C NMR
(DMSO-d6, 400 MHz): = 179.3, 179.2, 169.3, 166.0, 137.0,
134.9, 133.0, 132.0, 130.5, 130.1, 129.4, 129.1, 85.6, 54.7, 40.8.
HRMS (ESI): m/z [M + H]+ calcd for C19H13Cl2N3O2S: 418.2964;
found: 418.2968.
Yield: 84%; off-white solid; mp 225–227 °C; 1H NMR (DMSO-d6,
400 MHz): = 12.67 (s, 1 H), 12.17 (s, 1 H), 7.88 (d, J = 8.8 Hz,
2 H), 7.36 (d, J = 8.4 Hz, 2 H), 7.17 (d, J = 8.4 Hz, 2 H), 7.04 (d, J =
8.4 Hz, 2 H), 4.13 (t, J = 9.4 Hz, 1 H), 3.80 (s, 3 H), 3.48–3.62 (m,
2 H). 13C NMR (DMSO-d6, 400 MHz): = 179.3, 179.2, 169.6,
166.4, 162.6, 132.9, 130.6, 130.1, 129.0, 125.9, 114.5, 85.5, 54.4.
54.1, 40.7. HRMS (ESI): m/z [M + H]+ calcd for C20H16ClN3O3S:
414.8773; found: 414.8778.
2-(4-Chlorophenyl)-4-(4-fluorophenyl)-8-thioxo-1,7,9-tri-
azaspiro[4,5]dec-1-ene-6,10-dione (3m)
Yield: 84%; off-white solid; mp 184–186 °C. 1H NMR (DMSO-d6,
400 MHz): = 12.67 (s, 1 H), 12.16 (s, 1 H), 7.94 (d, J = 8 Hz,
2 H), 7.58 (d, J = 8 Hz, 2 H), 7.12–7.20 (m, 4 H), 4.14 (t, J = 9.2 Hz,
1 H), 3.55–3.60 (m, 2 H). 13C NMR (DMSO-d6, 400 MHz): =
179.3, 179.0, 169.2, 166.0, 137.1, 132.0, 131.7, 130.4, 130.2,
130.1, 129.3, 115.9, 85.5, 54.8, 40.8. HRMS (ESI): m/z [M + H]+
4-(4-Chlorophenyl)-2-(thiophen-2-yl)-8-thioxo-1,7,9-tri-
azaspiro[4,5]dec-1-ene-6,10-dione (3g)
Yield: 86%; off-white solid; mp 210–212 °C. 1H NMR (DMSO-d6,
400 MHz): = 12.65 (s, 1 H), 12.17 (s, 1 H), 7.85 (d, J = 4.4 Hz,
1 H), 7.70 (d, J = 2.8 Hz, 1 H), 7.36 (d, J = 8.4 Hz, 2 H), 7.22 (dd, J =
© 2019. Thieme. All rights reserved. Synlett 2019, 30, A–F