G
V. V. Baranov et al.
Paper
Synthesis
1-(1-Hydroxy-2-methylpropan-2-yl)-5-thioxohexahydroimidazo-
[4,5-d]imidazol-2(1H)-one (1j)
13C NMR (75 MHz, DMSO-d6): = 42.70 (CH2), 55.11 (OMe), 66.30,
70.55 (CH–CH), 113.95, 129.40, 128.49 (CH(PMB)), 119.04 (C(PMB)),
158.44, 158.62 (C=O+C-OMe), 182.83 (C=S).
Beige powder; yield: 0.24 g (41%) (approach 1), 2.07 g (45%) (ap-
proach 2); mp 264–266 °С (MeOH).
HRMS (ESI): m/z [M + H]+ calcd for C12H14N4O2S + H: 279.0910; found:
279.0912.
IR (KBr): 3200, 2065, 1693, 1533, 1489, 1339, 1249, 1203, 1061, 888
cm–1
.
1-Phenethyl-5-thioxohexahydroimidazo[4,5-d]imidazol-2(1H)-
one (1n)
2
1H NMR (300 MHz, DMSO-d6): = 1.26 (s, 6 Н, Me), 3.37 (d, J = 10.9
Hz, 1 Н, CH2), 3.64 (d, 2J = 10.7 Hz, 1 Н, CH2), 4.77–5.14 (br. s, 1 Н, OH),
5.28 (d, 3J = 8.4 Hz, 1 Н, CH), 5.67 (d, 3J = 8.4 Hz, 1 Н, CH), 7.38 (s, 1 H,
NH), 8.83 (s, 1 H, NH), 9.00 (s, 1 H, NH).
Beige powder; yield: 3.20 g (61%) (approach 2); mp 259–260 °С
(MeOH).
13C NMR (75 MHz, DMSO-d6): = 24.21, 24.29 (Me), 57.55 (CH2),
66.92, 73.16 (CH–CH), 67.82 (CMe2), 160.16 (C=O), 183.93 (C=S).
IR (KBr): 3331, 3164, 1677, 1527, 1487, 1340, 1252, 1024, 1123, 1096,
885, 751, 702, 580 cm–1
.
1H NMR (300 MHz, DMSO-d6): = 2.69–2.90 (m, 2 Н, CH2), 3.19–3.48
(m, 2 Н, CH2), 5.38 (d, 3J = 8.4 Hz, 1 Н, CH), 5.47 (d, 3J = 8.3 Hz, 1 Н,
CH), 7.18–7.33 (m, 5 H, Ph), 7.44 (s, 1 H, NH), 8.92 (s, 1 H, NH), 9.20 (s,
1 H, NH).
13C NMR (75 MHz, DMSO-d6): = 23.38, 41.96 (CH2), 66.36, 71.55
(CH–CH), 126.19, 128.36, 128.71 (CH(Ph)), 139.03 (C(Ph)), 158.52
(C=O), 182.70 (C=S).
HRMS (ESI): m/z [M + H]+ calcd for C8H14N4O2S + H: 231.0910; found :
231.0905.
1-Allyl-5-thioxohexahydroimidazo[4,5-d]imidazol-2(1H)-one (1k)
Beige powder; yield: 0.20 g (40%) (approach 1); white powder; yield:
2.45 g (62%) (approach 2); mp 245–247 °С (MeOH).
IR (KBr): 3200, 2879, 1719, 1529, 1490, 1340, 1294, 1245, 1201, 1115,
HRMS (ESI): m/z [M + Na]+ calcd for C12H14N4OS + Na: 285.0781;
found: 285.0777.
1049, 885, 678 cm–1
.
1H NMR (300 MHz, DMSO-d6): = 3.49 (dd, 2J = 15.9 Hz, 3J = 6.8 Hz, 1
H, CH2), 3.92 (dd, 2J = 15.5 Hz, 3J = 3.7 Hz, 1 H, CH2), 5.08–5.25 (m, 2 H,
CH2), 5.37 (q, 3J = 8.3 Hz, 2 H, CH–CH), 5.63–5.78 (m, 1 H, CH), 7.6 (s, 1
H, NH), 9.05 (s, 1 H, NH), 9.17 (s, 1 H, NH).
1-Phenyl-5-thioxohexahydroimidazo[4,5-d]imidazol-2(1H)-one
(1o)
Violet powder; yield: 0.20 g (34%) (approach 1); mp >300 °С (MeOH).
13C NMR (75 MHz, DMSO-d6): = 42.46 (CH2), 66.32, 71.02 (CH–CH),
IR (KBr): 3345, 3177, 1689, 1529, 1503, 1422, 1328, 1266, 1142, 1102,
117.49 (CH2), 133.06 (CH), 158.31 (C=O), 182.78 (C=S).
HRMS (ESI): m/z [M + H]+ calcd for C7H10N4OS + H: 199.0654; found:
199.0646
887, 748, 691 cm–1
.
1H NMR (300 MHz, DMSO-d6): = 5.54 (d, 3J = 8.4 Hz, 1 H, CH), 6.09
(d, 3J = 8.5 Hz, 1 H, CH), 7.08 (t, 3J = 7.3 Hz, 1 H, Ph), 7.33 (t, 3J = 7.8 Hz,
2 H, Ph), 7.56 (d, 3J = 8.1 Hz, 2 H, Ph), 8.18 (s, 1 H, NH), 9.29 (d, 1 H,
NH), 9.42 (s, 1 H, NH).
13C NMR (75 MHz, DMSO-d6): = 65.77, 71.79 (CH–CH), 119.10,
123.06, 128.63 (CH(Ph)), 138.01 (C(Ph)), 156.35 (C=O), 183.47 (C=S).
1-Benzyl-5-thioxohexahydroimidazo[4,5-d]imidazol-2(1H)-one
(1l)
Beige powder; yield: 0.27 g (45%) (approach 1), 3.00 g (63%) (ap-
proach 2); mp 259–261 °С (MeOH).
HRMS (ESI): m/z [M + Na]+ calcd for C10H10N4OS + Na: 257.0468;
found: 257.0465.
IR (KBr): 3350, 3143, 3006, 2871, 1675, 1528, 1484, 1334, 1250, 1122,
1081 cm–1
.
1H NMR (300 MHz, DMSO-d6): = 4.01 (d, 2J = 15.5 Hz, 1 Н, CH2), 4.61
(d, 2J = 15.4 Hz, 1 Н, CH2), 5.22 (d, 3J = 8.3 Hz, 1 Н, CH), 5.42 (d, 3J = 8.3
Hz, 1 Н, CH), 7.27–7.39 (m, 5 H, Ph), 7.72 (s, 1 H, NH), 9.12 (s, 1 H, NH),
9.31 (s, 1 H, NH).
4-[2-Oxo-5-thioxohexahydroimidazo[4,5-d]imidazol-1(2H)-yl]-
butanoic Acid (1p)
Beige powder; yield: 0.22 g (36%) (approach 1); mp 215–216 °С (H2O).
13C NMR (75 MHz, DMSO-d6): = 43.31 (CH2), 66.33, 70.77 (CH–CH),
127.25, 127.82, 128.49 (CH(Ph)), 137.25 (C(Ph)), 158.48 (C=O), 182.83
(C=S).
HRMS (ESI): m/z [M + Na]+ calcd for C11H12N4OS + Na: 271.0624;
found: 271.0625.
IR (KBr): 3405, 3331, 3181, 1715, 1651, 1500, 1337, 1243, 1205, 1129,
1083, 933, 887, 812 cm–1
.
1H NMR (300 MHz, DMSO-d6): = 1.60–1.80 (m, 2 Н, CH2), 2.16 (t,
3J = 7.5 Hz, 2 Н, CH2), 3.00 (dt, 2J = 13.9 Hz, 3J = 6.8 Hz, 1 Н, CH2), 3.19
(dt, 2J = 14.0 Hz, 3J = 7.6 Hz, 1 Н, CH2), 5.37 (d, 3J = 8.4 Hz, 1 Н, CH),
5.44 (d, 3J = 8.4 Hz, 1 Н, CH), 7.53 (s, 1 H, NH), 9.04 (s, 1 H, NH), 9.14 (s,
1 H, NH), 11.81–12.32 (br s, 1 H, COOH).
1-(4-Methoxybenzyl)-5-thioxohexahydroimidazo[4,5-d]imidazol-
2(1H)-one (1m)
13C NMR (75 MHz, DMSO-d6): = 22.64, 31.01, 39.78 (CH2), 66.34,
71.44 (CH–CH), 158.72 (C=O), 174.05 (COOH), 182.74 (C=S).
HRMS (ESI): m/z [M + Na]+ calcd for C8H12N4O2S + Na: 267.0522;
Beige powder; yield: 0.32 g (46%) (approach 1), 3.61 g (65%) (ap-
proach 2); mp 264–265 °С (MeOH).
found: 267.0524.
IR (KBr): 3348, 3133, 3003, 2871, 1673, 1518, 1483, 1334, 1246, 1178,
1101, 1023 cm–1
.
1-(4-Methoxybenzyl)urea (2m)
2
1H NMR (300 MHz, DMSO-d6): = 3.76 (s, 3 H, Me), 3.91 (d, J = 15.1
2
3
Urea (200 mmol, 12.00 g) was dissolved in H2O (50 mL); then, (4-me-
thoxyphenyl)methanamine (5.2 mL, 40 mmol) and 35% aq HCl (2.5
mL) were added. The reaction mixture was refluxed for 4 h and then
cooled to r.t. The resulting precipitate was collected by filtration,
washed with H2O (50 mL), and dried in air.
Hz, 1 Н, CH2), 4.56 (d, J = 15.1 Hz, 1 Н, CH2), 5.17 (d, J = 8.4 Hz, 1 Н,
3
3
CH), 5.39 (d, J = 8.4 Hz, 1 Н, CH), 6.91 (d, J = 8.5 Hz, 2 Н, CH(PMB)),
7.23 (d, 3J = 8.5 Hz, 2 Н, CH(PMB)), 7.07 (s, 1 H, NH), 9.10 (s, 1 H, NH),
9.31 (s, 1 H, NH).
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–I