BOUALIA ET AL.
7 of 10
|
−
room temperature and evaporated. The final product was used in the
next step without further purification.
116.5, 113.9, 82.8, 55.5, 29.5, and 29. HRMS (APCI ) m/z 555.14636
+
[M−H] . Anal. calcd for C27
H
23 8
N O
S
2 2
: 555.13685.
Propane‐1,3‐diyldicarbamimidothioate dihydrobromide (3a)
2,2′‐(Propane‐1,3‐diylbis(sulfanediyl))bis(4‐amino‐6‐(4‐methoxyphe-
1
Compound 3a was obtained as a white solid (95%). Mp: 218°C.
NMR (300 MHz, DMSO‐d ) δ (ppm): 9.11 (s, 8H, 4NH
H
nyl)pyrimidine‐5‐carbonitrile) (7d)
1
6
2
), 3.28
Compound 7d was obtained as a white solid (64%). Mp: >250°C.
NMR (400 MHz, DMSO‐d
(dd, J = 6.8, 2 Hz, 4H), 3.79 (s, 6H, 2CH
H
1
3
(t, J = 7.3 Hz, 2H, CH
2
), and 1.94 (q, J = 7.3 Hz, 4H, 2CH
2
). C NMR
6
) δ (ppm): 7.85 (dd, J = 6.8, 2 Hz, 4H), 7.03
(
75 MHz, DMSO‐d ) δ (ppm): 170.0, 29.2, and 29.0.
6
3
‐O), 3.23 (t, J = 6.8 Hz, 4H,
1
3
2CH
2
), and 2.09 (qt, J = 6.8 Hz, 2H, CH
2
). C NMR (100 MHz, DMSO‐
Butane‐1,4‐diyldicarbamimidothioate dihydrobromide (3b
Compound 3b was obtained as a white solid (97%). Mp: 232°C.
NMR (300 MHz, DMSO‐d ) δ (ppm): 9.08 (s, 8H, 4NH ), 3.24–3.21 (m,
H, 2CH ), and 1.70–1.68 (m, 4H, 2CH ). C NMR (75 MHz, DMSO‐
) δ (ppm): 170.3, 29.9, and 27.7.
)
6
d ) δ (ppm): 173.4, 166.7, 163.9, 162.1, 130.7, 128.4, 117.1, 114.3,
1
+
+
H
81.9, 55.9, and 29.6. HRMS (ESI ) m/z 595.1121 [M+K] . Anal. calcd
for C27 K: 595.1101.
6
2
24 8 2 2
H N O S
1
3
4
2
2
d
6
2,2′‐(Propane‐1,3‐diylbis(sulfanediyl))bis(4‐amino‐6‐(4‐nitrophenyl)‐
pyrimidine‐5‐carbonitrile) (7e
Compound 7e was obtained as a brown solid (64%). Mp: >250°C.
NMR (250 MHz, DMSO‐d ) δ (ppm): 8.28 (d, J = 8.7 Hz, 4H), 8.05 (d,
J = 8.7 Hz, 4H), 5.79 (s, 4H, 2NH ), 3.20 (t, J = 6.1 Hz, 4H, 2CH ), and
). C NMR (62.9 MHz, DMSO‐d ) δ
(ppm): 173.9, 165.2, 163.2, 148.7, 141.9, 129.9, 123.5, 119.5, 115.8,
)
1
H
4
.1.3 | General procedure for the preparation of bis
6
(
4‐amino‐5‐cyano‐pyrimidines) (7)
2
2
1
3
In a 100 ml flask were introduced 2‐alkylthiouronium (1 mmol) and 2‐
arylidene)malononitrile derivative (2 mmol) in the presence of
CO (2 mmol). The mixture was refluxed in 10 ml of isopropanol.
2.11 (qt, J = 6.1 Hz, 2H, CH
2
6
(
−
+
K
2
3
83.3, 29.4, and 29.1. HRMS (APCI ) m/z 585.09539 [M−H] . Anal.
calcd for C25 : 585.09021.
The progress of the reaction was monitored by TLC. After completion
of the reaction, the mixture was cooled to room temperature and was
poured into 100 ml of water. The precipitate was obtained by vacuum
filtration. The resulting solid residue was recrystallized from ethanol.
17 10 4 2
H N O S
2,2′‐(Propane‐1,3‐diylbis(sulfanediyl))bis(4‐amino‐6‐(3‐nitrophenyl)‐
pyrimidine‐5‐carbonitrile) (7f
Compound 7f was obtained as a brown solid (79%). Mp: 238°C.
NMR (250 MHz, DMSO‐d ) δ (ppm): 8.63 (t, J = 8.3 Hz, 2H), 8.37 (d,
J = 8.0 Hz, 2H), 8.34 (d, J = 7.7 Hz, 2H), 7.79 (t, J = 8.0 Hz, 2H), 6.02 (s,
)
1
H
2
,2′‐(Propane‐1,3‐diylbis(sulfanediyl))bis(4‐amino‐6‐phenylpyrimi-
6
dine‐5‐carbonitrile) (7a
)
Compound 7a was obtained as a white solid (65%). Mp: 228–230°C;
2
4H, 2NH ), 3.09 (t, J = 6.2 Hz, 4H, 2CH
2
), and 2.17 (qt, J = 6.2 Hz, 2H,
1
13
H NMR (400 MHz, DMSO‐d
6
) δ (ppm): 7.81 (dd, J = 6.8, 1.6 Hz, 4H),
.57–7.48 (m, 6H), 3.23 (t, J = 6.8 Hz, 4H, 2CH ), and 2.10 (qt,
) δ (ppm): 173.9,
CH
2
). C NMR (62.9 MHz, DMSO‐d
6
) δ (ppm): 173.9, 164.5, 163.2,
7
2
147.6, 137.3, 134.5, 129.1, 125.3, 116.1, 115.8, 82.8, 29.3, and
13
−
+
J = 6.8 Hz, 2H, CH
2
). C NMR (100 MHz, DMSO‐d
6
29.1. HRMS (APCI ) m/z 585.09539 [M−H] . Anal. calcd for
: 585.09214.
1
67.7, 164.0, 136.4, 131.1, 128.9, 128.8, 116.7, 83.9, and 29.7. Anal.
calcd for C25 : C, 60.46; H, 4.06; N, 22.56; S, 12.91; Found: C,
9.86; H, 4.05; N, 22.07, S, 12.30.
25 17 10 4 2
C H N O S
20 8 2
H N S
5
2,2′‐(Propane‐1,3‐diylbis(sulfanediyl))bis(4‐amino‐6‐(4‐chlorophenyl)‐
pyrimidine‐5‐carbonitrile) (7g)
1
2
,2′‐(Propane‐1,3‐diylbis(sulfanediyl))bis(4‐amino‐6‐p‐tolylpyrimi-
Compound 7g was obtained as a white solid (70%). Mp: >250°C.
NMR (400 MHz, DMSO‐d
(dd, J = 6.8, 2.0 Hz, 4H), 3.22 (t, J = 6.8 Hz, 4H, 2CH
H
dine‐5‐carbonitrile) (7b
Compound 7b was obtained as a beige solid (58%). Mp: >250°C.
NMR (250 MHz, DMSO‐d ) δ (ppm): 7.89 (d, J = 8.2 Hz, 4H), 7.23 (d,
J = 8.2 Hz, 4H), 3.23 (t, J = 5.9 Hz, 4H, 2CH ), 2.23 (s, 6H, 2CH ), and
). C NMR (62.9 MHz, DMSO‐d ) δ
)
6
) δ (ppm): 7.83 (dd, J = 6.8, 2 Hz, 4H), 7.56
), and 2.08 (qt,
) δ (ppm): 173.8,
166.4, 163.6, 136.4, 135.1, 130.8, 129.0, 116.5, 82.9, 29.7, and 29.4.
1
H
2
1
3
6
J = 6.8 Hz, 2H, CH
2
). C NMR (100 MHz, DMSO‐d
6
2
3
1
3
+
+
2
.14 (qt, J = 5.9 Hz, 2H, CH
2
6
2 8 2
HRMS (ESI ) m/z 603.0128 [M+K] . Anal. calcd for C25H18Cl N S K:
(ppm): 173.7, 167.2, 164.1, 141.3, 135.9, 135.5, 135.1, 133.4, 129.1,
603.0110.
−
1
5
28.7, 119.8, 116.9, 82.6, 29.6, 29.4, and 20.9. HRMS (APCI ) m/z
+
23.15653 [M−H] . Anal. calcd for C27
23
H N
S
8 2
: 523.15379.
2,2′‐(Propane‐1,3‐diylbis(sulfanediyl))bis(4‐amino‐6‐(4‐bromophenyl)
pyrimidine‐5‐carbonitrile) (7h)
1
2
,2′‐(Propane‐1,3‐diylbis(sulfanediyl))bis(4‐amino‐6‐(3‐methoxyphe-
nyl)pyrimidine‐5‐carbonitrile) (7c)
Compound 7c was obtained as a white solid (67%). Mp: 222°C.
NMR (250 MHz, DMSO‐d ) δ (ppm): 7.75–7.72 (m, 6H), 7.14–7.12 (m,
), 3.79 (s, 6H, 2CH ‐O), 3.23 (t, J = 6.2 Hz, 4H,
), and 2.13 (qt, J = 6.2 Hz, 2H, CH
) δ (ppm): 173.5, 167.2, 163.5, 159.2, 137.4, 129.9, 116.9,
Compound 7h was obtained as a white solid (69%). Mp: >250°C.
NMR (250 MHz, DMSO‐d
J = 8.6 Hz, 4H), 5.71 (br s, 4H, 2NH
H
6
) δ (ppm): 7.77 (d, J = 8.6 Hz, 4H), 7.61 (d,
), 3.22 (t, J = 6.8 Hz, 4H, 2CH ),
) δ
(ppm): 173.5, 165.8, 163.3, 134.9, 131.3, 130.2, 124.9, 116.0, 82.3,
1
H
2
2
1
3
6
and 2.12 (qt, J = 6.8 Hz, 2H, CH
2
). C NMR (62.9 MHz, DMSO‐d
6
2
H), 6.0 (s, 4H, 2NH
CH
2
3
1
3
−
+
2
2
2
). C NMR (62.9 MHz,
29.2, and 29. HRMS (APCI ) m/z 650.94626 [M–H] . Anal. calcd for
17Br : 650.93832.
DMSO‐d
6
25
C H
2 8 2
N S