6
T. E. ALI ET AL.
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(
1
1
C−5), 126.1 (C−6), 128.3 (C−2 ,6 Phenyl), 129.7 (C-3 ,5 Phenyl), Synthesis of 2-ethoxy-3-phenyl-2-sulfido-2,3-
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34.7 (C−7), 142.8 (C−1 Phenyl), 145.4 (CH=N), 152.8 (C−8a), dihydrochromeno[2,3-e][1,2,4,3] triazaphosphepin-
+
56.1 (C−2), 175.5 (C=Opyrone). MS (m/z): 341.09 (M ). Anal. 6-(1H)-one (7)
Calcd for C16H12N3O4P (341.25): C, 56.31; H, 3.54; N, 12.31.
A solution of phosphorus pentasulfide (2.22 g, 10 mmol) in
absolute ethanol (30 ml) was heated under reflux for 1 hour to
give O,O-diethyldithiophosphoric acid. A solution of compound
Found: C, 56.02; H, 3.18; N, 12.09%.
2
(1.39 g, 5 mmol) in dry dioxane (30 ml) was added to the pre-
Synthesis of 2,3-diphenyl-2-oxido-3-phenyl-2,3-
dihydrochromeno[2,3-e][1,2,4,3] triazaphosphepin-
vious ethanolic solution. The mixture was heated under reflux
for 8 hours. The reaction mixture was concentrated into its half
volume and left to cool. The formed solid after adding some
water, was filtered off and recrystallized from acetonitrile to give
green crystalline solid in 52% yield; mp 235–237°C. IR (KBr),
6
-(1H)-one (5)
A solution of phenyl phosphonic dichloride (0.7 ml, 5 mmol)
in dry dioxane (5 ml), was added dropwise to a solution of
compound 2 (1.39 g, 5 mmol) in dry dioxane (50 ml) in pres-
ence of a catalytic amount of triethylamine (0.7 ml, 10 mmol)
at 5–10°C for 30 min. The mixture was heated under reflux for
−1
(
νmax, cm ): 3254 (NH), 2965 (C–Haliph), 1641 (C=Opyrone),
1
1
600 (C=N), 1532 (C═C), 1077 (P–O–C), 750 (P=S). H-NMR
(
300 MHz, DMSO-d6): 1.05–1.19 (m, 3H, CH3), 3.35–3.80 (m,
H, CH2), 6.69 (t, 1H, J = 6.0 Hz, H−6), 6.88 (d, 2H, J = 6.3 Hz,
Ph–H), 7.19 (m, 2H, H−8 and H−7), 7.34−7.43 (m, 2H, Ph–H),
2
4
hours then filtered off to remove triethyl ammonium chlo-
ride. The filtrate was concentrated into its half volume and left
for 2 days. The formed solid was filtered off and recrystallized
from diluted ethanol to give the product as pale yellow solid
7
(
(
.66 (t, 1H, J = 8.0, Ph−H), 8.00 (d, 1H, J = 6.0 Hz, H−5), 8.43
s, 1H, CH=N), 10.06 (s, 1H, NH exchangeable with D2O). MS
+
m/z): 385.26 (M ). Anal. Calcd for C18H16N3O3PS (385.37):
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in 65% yield; mp 236−239°C. IR (KBr), (νmax, cm ): 3122
C, 56.10; H, 4.18; N, 10.90; S, 8.32. Found: C, 55.92; H, 4.01; N,
(
NH), 3087 (C–Harom), 1663 (C═Opyrone), 1611 (CH=N), 1567,
10.59; S, 7.93%.
1
1
6
7
535 (C=C), 1227 (P=O). H-NMR (300 MHz, DMSO-d6):
.83–6.93 (m, 1H, H−6), 7.34−7.48 (m, 6H, H−8 and Ph–H),
.54−8.11 (m, 4H, H−7 and Ph–H), 8.70 (s, 1H, H−5), 9.01
Synthesis of 3-(phenylamino)-2-sulfido-2-sulfanion-1,2-
3
1
(
s, 1H, CH=N), 10.94 (s, 1H, NH exchangeable with D2O). P-
4
dihydro-5H-3λ -chromeno [2,3-d][1,3,2]
+
NMR (160 MHz, DMSO-d6): 32.1 ppm. MS (m/z): 401.12 (M ).
Anal. Calcd for C22H16N3O3P (401.35): C, 65.84; H, 4.02; N,
diazaphosphininum-5-one (8)
A mixture of phosphorus pentasulfide (1.11 g, 5 mmol) and
compound 2 (1.39 g, 5 mmol) in dry dioxane (50 ml), was heated
under reflux for 7 hours. The reaction mixture was concentrated
into its half volume and left to cool. The formed solid was filtered
off and recrystallized from ethanol to give orange crystalline
10.47. Found: C, 65.49; H, 3.79; N, 10.12%.
Synthesis of 2-(4-methylphenyl)-3-phenyl-2-sulfido-2,3-
dihydrochromeno[2,3-e] [1,2,4,3]triazaphosphepin-
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solid in 60% yield; mp 263–265°C. IR (KBr), (νmax, cm ): 3274,
6
-(1H)-one (6)
3
1
7
7
227 (2 NH), 3055 (C–Harom), 1635 (C=Opyrone), 1617 (CH═N),
1
598, 1548 (C=C), 808 (P=S). H-NMR (300 MHz, DMSO-d6):
Lawesson’s reagent (1.6 g, 4 mmol) was added to a solution of
compound 2 (1.11 g, 4 mmol) in dry dioxane (50 ml). The mix-
ture was heated under reflux for 8 hours. The solution was con-
centrated to its half volume and left to cool. The oily product
was treated with diethyl ether to give solid which was filtered
off and recrystallized from acetonitrile to give red crystalline
.20 (t, 1H, J = 6.5 Hz, H−6), 7.37 (m, 2H, H−8 and H−7),
.53 (d, 2H, J = 6.6 Hz, Ph–H), 7.78–7.89 (m, 2H, Ph–H), 8.03
(
d, 1H, J = 6.8 Hz, Ph–H), 8.26 (s, 1H, H−5), 9.35 (s, 1H,
CH=N), 10.11 (s, 1H, NH exchangeable with D2O), 11.90 (s,
+
1
H, NH exchangeable with D2O). MS (m/z): 373.07 (M ). Anal.
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1
16 12 3 2 2
Calcd for C H N O PS (373.39): C, 51.47; H, 3.24; N, 11.25;
solid in 64% yield; mp 220−225°C. IR (KBr), (νmax, cm ): 3195
S, 17.18. Found: C, 51.13; H 2.96; N, 10.86; S, 16.84%.
(
(
(
NH), 3062 (C–Harom), 2956 (C–Haliph), 1668 (C═Opyrone), 1602
1
C=N), 1571, 1559 (C═C), 1032 (O–C), 796 (P=S). H-NMR
300 MHz, DMSO-d6): 3.77 (s, 3H, OCH3), 6.74 (t, 1H, J =
Synthesis of [(2-amino-4-oxo-4H-chromen-3-yl)(2-
phenylhydrazinyl)methyl] phosphonic acid (10)
6
.0 Hz, H−6), 6.88−6.99 (m, 2H, Ph–H), 7.05 (d, 1H, J = 6.3 Hz,
H−8), 7.19 (t, 1H, J = 6.5 Hz, H−7), 7.51 (t, 2H, J = 6.2 Hz,
Ar–H), 7.52−7.61 (m, 3H, Ph–H and Ar–H), 7.81 (t, 1H, J =
6
8
.0, Ph–H), 7.95 (s, 1H, Ph–H), 8.11 (d, 1H, J = 6.0 Hz, H−5), Phosphonic acid (0.50 g, 6 mmol) was added to a solution of
.79 (s, 1H, CH=N), 10.46 (s, 1H, NH exchangeable with D2O). compound 2 (1.39 g, 5 mmol) in dry dioxane (60 ml) in presence
C-NMR (75 MHz, DMSO-d6): 55.4 (OCH3), 119.0 (C−8), of a catalytic amount of 4-toluenesulfonic acid (0.1 g). The mix-
1
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1
(
(
19.4 (C−3), 120.0 (C−4 Phenyl), 123.7 (C−3 ,5 Aryl), 125.0 ture was heated under reflux for 12 hours. The reaction mixture
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C−2 ,6 Phenyl), 125.6 (C−4a), 126.1 (C−5), 126.9 (C−6), 129.5 was concentrated into its half volume. After adding some water,
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C−3 ,5 Phenyl), 130.0 (C−2 ,6 Aryl), 132.8 (d, JPC = 9.0 Hz, the formed solid was filtered off and crystallized from abso-
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C−1 Aryl), 134.7 (C−7), 140.4 (C−1 Phenyl), 145.4 (CH=N), lute methanol to give orange crystalline solid in 42% yield; mp
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−1
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52.7 (C−4 Aryl), 155.9 (C−8a), 161.7 (C−2), 175.4 (C=O). 117–120°C. IR (KBr), (νmax, cm ): 3389, 3247 (br, OH, NH2
3
1
P-NMR (160 MHz, DMSO-d6): 72.5 ppm. MS (m/z): 447.33 and NH), 3058 (C–Harom), 1628 (C=Opyrone), 1603 (C=C), 1279
+
1
(
4
M ). Anal. Calcd for C23H18N3O3PS (447.44): C, 61.74; H, (P=O). H-NMR (300 MHz, DMSO-d6): 3.38 (br, 2H, P–OH
.05; N, 9.39; S, 7.17. Found: C, 61.41; H, 3.79; N, 9.11; S, 6.81%. exchangeable with D2O), 4.61 (d, 1H, JPCH = 24 Hz, CH–P),