Month 2017
New Route for Construction of Four-, Five- and Six-membered Phosphorus
Heterocycles
+
1
with D O). MS (EI, m/z): 340 (M ). Anal. Calcd for
(C═S), 703 (P═S). H‐NMR (500 MHz, DMSO‐d6):
2
C H N PS (340.42): C, 42.34; H, 3.85; N, 16.46; S,
7.53 (s, 2H, 2NH exchangeable with D O), 7.75 (s, 1H,
1
2
13
4
3
2
2
8.26%. Found: C, 42.02; H, 3.72; N, 16.21; S, 28.02%.
N ‐[phenylmethylidene]benzoicthiocarbohydrazide (4). Beige
SH exchangeable with D O), 8.54 (brs, 1H, NH
2
0
+
exchangeable with D O). MS (EI, m/z): 185 (M ). Anal.
2
crystals, mp 195–197°C [13,14], yield 81%. IR (KBr),
Calcd for CH N PS (185.23): C, 6.48; H, 2.18; N,
4
3
3
ꢀ
1
(
νmax, cm ): 3180 (NH), 3059 (C─Harom), 1620 (C═N),
22.69; S, 51.93%. Found: C, 6.23; H, 2.07; N, 22.42; S,
51.64%.
1
1
601 (C═C), 1288 (C═S). H‐NMR (500 MHz,
DMSO‐d ): 7.43–7.71 (m, 8H, Ph─H), 7.88–7.89 (m, 2H,
2‐Mercapto‐4‐oxo‐1‐{[phenylmethylidene]amino}‐1,3,2‐dia
6
Ph─H), 8.45 (s, 1H, CH═N), 11.83 (brs, 1H, NH
zaphosphetidine‐2‐sulfide (8a). Beige crystals, mp 195–
+
ꢀ1
1
97 (dec.) °C, yield 59%. IR (KBr), (νmax, cm ): 3191
exchangeable with D O). MS (EI, m/z): 240 (M ). Anal.
2
Calcd for C H N S (240.32): C, 69.97; H, 5.03; N, 11.66;
(NH), 3083 (C─Harom), 1686 (C═O), 752 (P═S).
14 12 2
1
S, 13.34%. Found: C, 69.69; H, 4.86; N, 11.39; S, 13.03%.
H‐NMR (500 MHz, DMSO‐d
6
): 7.36–7.86 (m, 5H,
2
‐Mercapto‐3‐{[phenylmethylidene]amino}‐2,3‐dihydro‐4‐
thioxo‐1,3,2‐benzoxazaphosphinine‐2‐sulfide, pyridine solvate
5a).
Ph─H), 8.15 (brs, 1H, SH exchangeable with D O),
2
8
.69 (s, 1H, CH═N), 10.63 (brs, 1H, NH exchangeable
(
Yellow crystals, mp 226–227°C, yield 68%. IR
13
with D O). C‐NMR (150 MHz, CDCl ): 121.5, 129.3,
132.8, 138.0, 147.4, 167.7. MS (EI, m/z): 257 (M ).
Anal. Calcd for C H N OPS (257.27): C, 37.35; H,
2
3
ꢀ
1
(
KBr), (νmax, cm ): 3058, 3028 (C─Harom), 1630 (C═N),
233 (C═S), 755 (P═S). H‐NMR (500 MHz, DMSO‐d ):
.94–7.07 (m, 4H, Ar─H), 7.30 (d, 1H, J = 7 Hz, β‐H),
.36–7.43 (m, 4H, Ar─H and β‐H), 7.53 (d, 1H, γ‐H),
.71 (d, 2H, J = 6.1 Hz, Ar─H), 7.85 (d, 1H, J = 7.6 Hz,
+
1
1
6
7
7
6
8
8
3
2
3
.13; N, 16.33; S, 24.93%. Found: C, 37.02; H, 3.01; N,
1
6.09; S, 24.67%.
2‐Mercapto‐1‐{[phenylmethylidene]amino}‐4‐thioxo‐1,3,2‐
α‐H), 8.01 (d, 1H, α‐H), 7.78 (brs, 1H, SH exchangeable
diazaphosphetidine‐2‐sulfide (8b).
139–140°C, yield 52%. IR (KBr), (νmax, cm ): 3253
Beige crystals, mp
13
ꢀ1
with D O), 8.44 (s, 1H, CH═N). C‐NMR (150 MHz,
2
CDCl ): 116.1, 118.9, 119.3, 121.8, 124.7, 125.6, 128.7,
(NH), 3030 (C─Harom), 1590 (C═N), 750 (P═S).
3
1
1
28.8, 128.9, 129.0, 138.4, 144.3, 148.7, 151.6, 207.0.
H‐NMR (500 MHz, DMSO‐d ): 7.36–7.40 (m, 3H,
6
+
MS (EI, m/z): 429 (M ). Anal. Calcd for C H N OPS
Ph─H), 7.75–7.77 (m, 2H, Ph─H), 7.95 (s, 1H, SH
19
16
3
3
(429.51): C, 53.13; H, 3.75; N, 9.78; S, 22.40%. Found:
exchangeable with D O), 8.20 (s, 1H, CH═N), 11.40 (s,
2
C, 52.88; H, 3.54; N, 9.59; S, 22.11%.
1H, NH exchangeable with D O). MS (EI, m/z): 273
2
+
2
‐Mercapto‐3‐{[phenylmethylidene]amino}‐4(1H)‐thioxo‐
,3‐dihydro‐1,3,2‐benzodiazaphosphinine‐2‐sulfide, pyridine
solvate (5b). Pale brown crystals, mp 154–158°C, yield
(M ). Anal. Calcd for C H N PS (273.34): C, 35.15;
8
8
3
3
2
H, 2.95; N, 15.37; S, 35.19%. Found: C, 34.82; H, 2.60;
N, 15.06; S, 34.87%.
ꢀ
1
6
7%. IR (KBr), (νmax, cm ): 3378 (NH), 3050
4‐Amino‐3‐mercapto‐5‐oxo‐1,2,4,3‐triazaphospholidine‐
1
(
C─Harom), 1636 (C═N), 1253 (C═S), 749 (P═S). H‐
3‐sulfide (9a).
64%. IR (KBr), (νmax, cm ): 3429, 3201 (br, NH ,
2
White crystals, mp 121–123°C, yield
ꢀ
1
NMR (500 MHz, DMSO‐d ): 6.35 (br, 1H, SH
6
1
exchangeable with D O), 6.54 (t, 1H, J = 6.9 Hz,
NH), 1707 (C═O), 1628 (NH2 def), 790 (P═S). H‐
2
Ar─H), 6.71–6.74 (m, 3H, Ar─H), 7.17 (t, 1H,
J = 7 Hz, Ar─H), 7.40–7.50 (m, 5H, Ar─H, and β‐H),
NMR (500 MHz, DMSO‐d ): 5.53 (br, 2H, NH2
6
exchangeable with D O), 7.34 (s, 1H, SH exchangeable
2
7
.53 (d, 1H, J = 7.5 Hz, γ‐H), 7.66–7.72 (m, 3H, Ar─H
with D O), 8.52 (brs, 1H, NH exchangeable with D O),
2
2
and α‐H), 8.36 (s, 1H, CH═N), 11.58 (s, 1H, NH
11.59 (br, 1H, NH exchangeable with D O). MS (EI,
2
+
+
exchangeable with D O). MS (EI, m/z): 428 (M ). Anal.
2
m/z): 184 (M ). Anal. Calcd for CH N OPS (184.18):
5 4 2
Calcd for C H N PS (428.53): C, 53.25; H, 4.00; N,
C, 6.52; H, 2.74; N, 30.42; S, 34.82%. Found: C, 6.29;
1
9
17
4
3
1
3.07; S, 22.45%. Found: C, 53.03; H, 3.72; N, 12.88;
H, 2.39; N, 30.12; S, 34.59%.
S, 22.08%.
4‐Amino‐3‐mercapto‐5‐thioxo‐1,2,4,3‐triazaphospholidine‐
3‐sulfide (9b). Beige crystals, mp 224–226°C, yield 69%.
3
‐Mercapto‐5‐oxo‐1,2,4,3‐triazaphospholidine‐3‐sulfide
ꢀ
1
(
6a).
Pale brown crystals, mp 262–263°C (Td), yield
IR (KBr), (νmax, cm ): 3267, 3211 (NH , NH), 1646 (NH
2 2
ꢀ
1
1
7
2%. IR (KBr), (νmax, cm ): 3410, 3310, 3206 (NH),
def.), 1157 (C═S), 754 (P═S). H‐NMR (500 MHz,
DMSO‐d ): 5.23 (br, 2H, NH exchangeable with D O),
1
1
678 (C═O), 763 (P═S). H‐NMR (500 MHz,
6
2
2
DMSO‐d ): 5.80 (brs, 2H, 2NH exchangeable with D O),
7.12 (s, 1H, SH exchangeable with D O), 8.45 (brs, 1H,
6
2
2
7
.50 (s, 1H, SH exchangeable with D O), 8.55 (brs, 1H,
2
NH exchangeable with D
2
O), 12.66 (s, 1H, NH
1
3
13
NH exchangeable with D O). C‐NMR (150 MHz,
CDCl ): 169.0. MS (EI, m/z): 169 (M ). Anal. Calcd for
CH N OPS (169.16): C, 7.10; H, 2.38; N, 24.84; S,
3
exchangeable with D O). C‐NMR (150 MHz, CDCl ):
2
2
3
+
+
3
202.0 (C═S). MS (EI, m/z): 198 (M –2H). Anal. Calcd
for CH OPS (200.24): C, 6.00; H, 2.52; N, 27.98; S,
48.04%. Found: C, 5.62; H, 2.31; N, 27.62; S, 47.79%.
4
3
2
N
5
4
3
7.91%. Found: C, 6.82; H, 2.12; N, 24.51; S, 37.64%.
3
‐Mercapto‐5‐thioxo‐1,2,4,3‐triazaphospholidine‐3‐sulfide
3
‐Mercapto‐5‐oxo‐4‐{[phenylmethylidene]amino}‐1,2,4,3‐
(
6b). Pale yellow crystals, mp 245–247 (Td) °C, yield
triazaphospholidine‐3‐sulfide (11a). Yellow crystals, mp
ꢀ
1
ꢀ1
6
6%. IR (KBr), (νmax, cm ): 3413, 3209 (NH), 1182
1
84–185°C, yield 59%. IR (KBr), (νmax, cm ): 3195
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet