Month 2016
Synthesis and Antioxidant Properties of New Dioxaphosphocines
ꢀ
1
Physical and spectral data of compounds 7a–d and 6a–j.
(ZnSe, cm ): ν 3335 (NH), 1265 (P¼O), 937 (P–O–C);
1
8
-Methyl-2-phenoxy-6-phenyl-5,6-dihydro-4H-1,3,2-benzodio-
H NMR (500 MHz, DMSO-d ): δ 7.41–6.72 (m, 13H, Ar–
6
xaphosphocine-2-oxide (7a). White solid, mp: 116–118°C;
H), 5.51 (brs, 1H, NH), 4.31–4.27 (m, 1H, CH), 3.35–3.27
ꢀ
1
IR (ZnSe, cm ): ν 3048 (aromatic C–H), 1295 (P¼O),
(m, 2H, OCH ), 2.45–2.32 (m, 5H, O–CH –CH – and Ar–
2
2
2
1
13
9
44 (P–O–C); H NMR (500MHz, DMSO-d ): δ 7.25–6.97
CH3); C NMR (125MHz, DMSO-d ): δ 146.2 (2C),
6
6
(m, 13H, Ar–H), 4.41–4.38 (m, 1H, CH), 3.34–3.29 (m, 2H,
142.3, 132.7, 131.2 (2C), 130.1, 129.2 (2C), 128.7 (2C),
OCH ), 2.15–2.10 (m, 5H, O–CH –CH – and Ar–CH );
127.8 (2C), 126.3, 120.1, 119.2, 118.7 (2C), 61.2, 40.2,
2
2
2
3
13
31
C NMR (125MHz, DMSO-d ): δ 152.6, 145.3 (2C),
39.4, 20.7; P NMR (200MHz, DMSO-d ): δ 18.73;
6
6
+
1
31.2 (2C), 130.5 (2C), 128.0 (2C), 127.9 (2C), 126.9 (2C),
LCMS [m/z]: 380.32 [M+1] ˙; Anal. Calcd for
31
125.5 (2C), 121.6, 115.0 (2C), 59.2, 39.3 (2C), 20.4;
P
C H NO P: C, 69.65; H, 5.84; N, 3.69; Found C, 69.61;
22
22
3
NMR (200 MHz, DMSO-d ): δ 22.42; HRMS [m/z]:
H, 5.78; N, 3.65.
8-Methyl-6-phenyl-2-(4-toluidino)-5,6-dihydro-4H-1,3,2λ -
benzodioxaphosphocin-2-one (6b). White solid, mp: 120–
6
+
5
3
81.1827 [M + 1] ˙; Anal. Calcd for C H O P: C, 69.47;
2
2 21 4
H, 5.56; Found C, 69.38; H, 5.52.
ꢀ
1
8-Methyl-2-(4-nitrophenoxy)-6-phenyl-5,6-dihydro-4H-1,3,2-
122°C; IR (ZnSe, cm ): ν 3362 (NH), 1271 (P¼O), 943
1
benzodioxaphosphocine-2-oxide (7b). Pale yellow solid, mp:
(P–O–C); H NMR (500MHz, DMSO-d ): δ 7.39–6.63
6
ꢀ
1
1
1
04–106°C; IR (ZnSe, cm ): ν 3035 (aromatic C–H),
(m, 12H, Ar–H), 5.43 (brs, 1H, NH), 4.36–4.32 (m, 1H,
CH), 3.34–3.28 (m, 2H, OCH ), 2.35–2.15 (m, 8H, O–
1
278 (P¼O), 956 (P–O–C); H NMR (500MHz,
2
13
DMSO-d ): δ 8.10–6.98 (m, 12H, Ar–H), 4.39–4.36 (m,
CH –CH – and 2XCH3);
C
NMR (125MHz,
6
2
2
1
H, CH), 3.35–3.29 (m, 2H, OCH ), 2.17–2.09 (m, 5H,
DMSO-d ): δ 146.3 (2C), 141.7, 133.1, 131.5 (2C),
2
3
6
1
O–CH –CH – and Ar–CH );
DMSO-d ): δ 154.2, 145.5 (2C), 141.2, 131.3 (2C),
C NMR (125MHz,
130.2, 129.3 (2C), 128.5 (2C), 127.7 (2C), 126.5, 120.3,
2
2
3
31
119.5, 118.9 (2C), 55.6, 40.3, 39.6, 20.8 (2C); P NMR
6
1
1
30.7, 128.3 (2C), 128.1 (2C), 126.5, 125.4 (2C), 121.7,
(200 MHz, DMSO-d ): δ 19.21; LCMS [m/z]: 394.26 [M
6
3
1
+
16.1 (2C), 61.2, 39.4 (2C), 20.5; P NMR (200MHz,
+ 1] ˙; Anal. Calcd for C H NO P: C, 70.22; H, 6.15;
23
24
3
+
DMSO-d ): δ 18.65; LCMS [m/z]: 426.12 [M+ 1] ˙;
Anal. Calcd for C H NO P: C, 62.12; H, 4.74; N, 3.29;
Found C, 62.05; H, 4.68; N, 3.21.
N, 3.56; Found C, 70.18; H, 6.09; N, 3.52.
6
5
2
2
20
6
2-(4-Methoxyanilino)-8-methyl-6-phenyl-5,6-dihydro-4H-1,3,2λ -
benzodioxaphosphocin-2-one (6c). White solid, mp: 120–
ꢀ
1
2-(4-Chlorophenoxy)-8-methyl-6-phenyl-5,6-dihydro-4H-1,3,2-
122°C; IR (ZnSe, cm ): ν 3278 (NH), 1263 (P¼O), 956
1
benzodioxaphosphocine-2-oxide (7c).
White solid, mp:
(P–O–C); H NMR (500MHz, DMSO-d ): δ 7.41–6.62
6
ꢀ
1
1
18–120°C; IR (ZnSe, cm ): ν 3045 (aromatic C–H),
(m, 12H, Ar–H), 5.47 (brs, 1H, NH), 4.35–4.29 (m, 1H,
1
1
287 (P¼O), 946 (P–O–C); H NMR (500MHz,
CH), 3.72 (s, 3H, OCH ), 3.34–3.27 (m, 2H, OCH ),
3
2
1
3
DMSO-d ): δ 7.43–6.92 (m, 12H, Ar–H), 4.29–4.27 (m,
2.31–2.18 (m, 5H, O–CH –CH – and Ar–CH );
C
6
2
2
3
1
H, CH), 3.31–3.27 (m, 2H, OCH ), 2.18–2.13 (m, 5H,
NMR (125MHz, DMSO-d ): δ 154.2, 146.4 (2C), 134.7,
132.2, 131.3 (2C), 129.2 (2C), 128.1 (2C), 126.5, 125.7,
2
3
6
1
O–CH –CH – and Ar–CH );
C NMR (125MHz,
2
2
3
DMSO-d ): δ 150.2, 143.6 (2C), 131.2 (2C), 129.7, 128.2
119.2, 117.3 (2C), 115.6 (2C), 62.3, 54.8, 40.2 (2C),
6
31
(
1
2C), 127.6 (2C), 126.3 (2C), 125.1 (2C), 121.8 (2C),
20.7; P NMR (200MHz, DMSO-d ): δ 20.12; LCMS
6
3
1
+
16.3, 115.2, 60.8, 40.1, 39.7, 20.6; P NMR (200MHz,
[m/z]: 410.43 [M +1] ˙; Anal. Calcd for C H NO P: C,
23
24
4
+
DMSO-d ): δ 18.73; LCMS [m/z]: 415.14 [M+ 1] ˙;
67.47; H, 5.91; N, 3.42; Found C, 67.42; H, 5.85; N, 3.37.
6
Anal. Calcd for C H ClO P: C, 63.70; H, 4.86; Found
C, 63.65; H, 4.78.
2-[4-(Dimethylamino)anilino]-8-methyl-6-phenyl-5,6-dihydro-
2
2
20
4
5
4H-1,3,2λ -benzodioxaphosphocin-2-one (6d).
White solid,
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1
2-(2-Chlorophenoxy)-8-methyl-6-phenyl-5,6-dihydro-4H-1,3,2-
mp: 126–128°C; IR (ZnSe, cm ): ν 3314 (NH), 1245
1
benzodioxaphosphocine-2-oxide (7d).
White solid, mp:
(P¼O), 973 (P–O–C); H NMR (500MHz, DMSO-d ): δ
6
ꢀ
1
1
1
17–119°C; IR (ZnSe, cm ): ν 3042 (aromatic C–H),
285 (P¼O), 941 (P–O–C); H NMR (500MHz,
7.38–6.67 (m, 12H, Ar–H), 5.56 (brs, 1H, NH), 4.31–4.24
(m, 1H, CH), 3.4–3.1 (s, 6H, N(CH ) ), 3.37–3.26 (m, 2H,
1
3
2
DMSO-d ): δ 7.42–6.94 (m, 12H, Ar–H), 4.30–4.27 (m,
OCH ), 2.28–2.19 (m, 5H, O–CH –CH – and Ar–CH );
2 2 2 3
6
13
1
H, CH), 3.33–3.27 (m, 2H, OCH ), 2.19–2.13 (m, 5H,
C NMR (125MHz, DMSO-d ): δ 150.6, 146.2 (2C),
2
3
6
1
O–CH –CH – and Ar–CH );
C NMR (125MHz,
132.3 (2C), 130.7 (2C), 129.6 (2C), 128.4 (2C), 127.2,
125.3, 119.8 (2C), 117.3 (2C), 114.2 (2C), 59.3, 41.5 (2C),
2
2
3
DMSO-d ): δ 150.5, 143.2 (2C), 130.9 (2C), 129.3, 128.0
6
3
1
(
1
2C), 127.1 (2C), 126.6 (2C), 125.3 (2C), 121.8 (2C),
40.3, 39.2, 20.7; P NMR (200MHz, DMSO-d ): δ 18.76;
6
3
1
+
15.2 (2C), 60.6, 40.5, 39.2, 20.7; P NMR (200MHz,
LCMS [m/z]: 423.24 [M+1] ˙; Anal. Calcd for
+
DMSO-d ): δ 18.75; LCMS [m/z]: 415.08 [M+ 1] ˙;
C H N O P: C, 68.23; H, 6.44; N, 6.63; Found C,
24 27 2 3
6
Anal. Calcd for C H ClO P: C, 63.70; H, 4.86; Found
C, 63.64; H, 4.81.
68.18; H, 6.41; N, 6.57.
8-Methyl-2-(4-nitroanilino)-6-phenyl-5,6-dihydro-4H-1,3,2λ -
benzodioxaphosphocin-2-one (6e). Pale yellow solid, mp:
124–126°C; IR (ZnSe, cm ): ν 3258 (NH), 1254 (P¼O),
2
2
20
4
5
8-Methyl-N,6-diphenyl-5,6-dihydro-4H-1,3,2-benzodioxaphosphocin-
ꢀ
1
2-amine-2-oxide (6a).
White solid, mp: 124–126°C; IR
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet