Article
Eshghi et al.
NCH2CH3), 3.69–3.77 (m, 1H, OCH2CH3), 3.93-4.02 (m, 1H,
OCH2CH3), 4.08-4.20 (m, 2H, OCH2CH3), 4.66 (d, JPH = 23.3 Hz,
1H, CHP), 4.67 (br, 1H, NH), 6.45 (d, J = 8.0 Hz, 1H, Ar-H), 6.51
(s, 1H), 6.53 (t, J = 7.2 Hz, 1H, Ar-H), 6.65 (d, J = 8.0 Hz, 2H,
Ar-H), 7.02 (t, J = 7.6 Hz, 1H, Ar-H), 7.30 (d, J = 7.2 Hz, 2H,
Ar-H). 13CNMR (100.64 MHz, CDCl3): d 12.5, 16.3 (d, 3JPC = 6.0
Hz), 16.5 (d, 3JPC = 6.0 Hz), 21.6, 44.3, 55.2 (d, 1JPC = 153.5 Hz),
63.0 (d, 2JPC = 17.2 Hz), 63.1, 110.0, 111.8, 114.8, 119.0, 121.8,
128.0 (d, 2JPC = 6.1 Hz), 129.0, 138.8, 146.7 (d, 3JPC = 16.2 Hz),
147.5. 31P (162.03 MHz, CDCl3): d 23.58, m/z (ESI) 404 [45%,
M+]. Anal. Calc. for C22H33N2O3P: C, 65.33; H, 8.22; N, 6.93.
Found: C, 65.02; H, 8.10; N, 6.82.
Diethyl (((4-chlorophenyl)amino) (4-(dimethylamino)
phenyl) methyl) phosphon (4i): Yield 95%; m.p = 130-131 °C;45
IR (KBr, cm-1) u: 3293 (NH), 2982, 1612, 1597, 1525, 1492, 1230
(P=O), 1062 (P-OEt); 1H NMR (100 MHz, CDCl3): d 1.15 (t, J =
7.8 Hz, 3H, OCH2CH3), 1.31 (t, J = 7.8 Hz, 3H, OCH2CH3), 2.92
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(s, 6H, NCH3), 3.50-4.20 (m, 4H, OCH2CH3), 4.60 (dd, JPH
=
24.0 Hz, 2JPH = 7.1 Hz, 1H, CHP), 4.7 (br, 1H, NH), 6.55 (d, J =
8.4 Hz, 2H, Ar-H), 6.70 (d, J = 8.2 Hz, 2H, Ar-H), 7.05 (d, J = 8.4
Hz, 2H, Ar-H), 7.30 (d, J = 8.2 Hz, 2H, Ar-H); m/z (ESI) 396
[15%, M+], 398 [10%, M++2]. Anal. Calc. for C19H26ClN2O3P: C,
57.50; H, 6.60; N, 7.06. Found: C, 57.01; H, 6.25; N, 6.78.
Diethyl (((4-bromophenyl) amino) (4-(dimethylamino)
phenyl)methyl)phosphonate (4j): Yield 96%; m.p = 135-136
°C; IR (KBr, cm-1): 3294 (NH), 2982, 1613, 1592, 1522, 1488,
1231 (P=O), 1063 (P-OEt); 1H NMR (400 MHz, CDCl3): d 1.15
(t, J = 7.2 Hz, 3H, OCH2CH3), 1.31 (t, J = 7.2 Hz, 3H, OCH2CH3),
2.94 (s, 6H, NCH3), 3.65–3.73 (m, 1H, OCH2CH3), 3.90-4.01 (m,
1H, OCH2CH3), 4.07-4.18 (m, 2H, OCH2CH3), 4.62 (d, JPH = 22.4
Hz, 1H, CHP), 4.81 (br, 1H, NH), 6.50 (dd, 1J = 8.8 Hz, 2J = 2.2
Hz, 2H, Ar-H), 6.70 (d, J = 8.4 Hz, 2H, Ar-H), 7.18 (d, J = 8.8 Hz,
2H, Ar-H), 7.30 (d, 1J = 8.4 Hz, 2J = 2.4 Hz, 2H, Ar-H); 13CNMR
(100.64, CDCl3): d 16.3 (d, 3JPC =6.3 Hz), 16.5 (d, 3JPC= 6.2 Hz),
40.5, 55.3 (d, 1JPC = 152.1 Hz), 63.1 (d, 2JPC = 7.0 Hz), 63.4 (d,
2JPC = 7.0 Hz), 109.9, 112.5, 115.5, 122.3, 128.6 (d, 2JPC = 5.0 Hz),
Diethyl ((4-(diethylamino)phenyl) (phenylamino) me-
thyl) phosphonate (4f): Yield 90%; m.p = 101-102 °C; IR (KBr,
cm-1) u: 3301 (NH), 3022, 2973, 1611, 1603, 1524, 1497, 1232
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(P=O), 1061 (P-OEt); H NMR (100 MHz,CDCl3): d 1.01-1.40
(m, 6H, OCH2CH3, 6H, NCH2CH3), 3.23 (q, J = 8.0 Hz, 4H,
NCH2CH3), 3.71-4.01 (m, 4H, OCH2CH3), 4.30 (dd, 1JPH = 23.0
Hz, 2JPH = 7.2 Hz, 1H, CHP), 4.50 (br, 1H, NH), 6.60-7.30 (m, 9H,
Ar-H). m/z (ESI) 390 [55%, M+]. Anal. Calc. for C21H31N2O3P: C,
64.60; H, 8.00; N, 7.17. Found: C, 64.20; H, 7.74; N, 7.10.
Diethyl ((4-(diethylamino)phenyl)((4-nitrophenyl) amino)
methyl) phosphonate (4g): Yield 85%; m.p = 140-141 °C; IR
(KBr, cm-1) u: 3269 (NH), 3040, 2972, 1597, 1520, 1505, 1481,
1231 (P=O), 1051 (P-OEt), 574; 1H NMR (100 MHz, CDCl3): d
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131.8, 145.6 (d, JPC = 15.2 Hz), 150.25. 31P (162.03 MHz,
1.00-1.40 (m, 6H, OCH2CH3, 6H, NCH2CH3), 3.43 (q, J = 8.1 Hz,
CDCl3): d 23.01. m/z (ESI) 440 [40%, M+], 442 [35%, M++2].
Anal. Calc. for C19H26BrN2O3P: C, 51.71; H, 5.94; N, 6.35.
Found: C, 51.50; H, 5.80; N, 6.6.21.
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4H, NCH2CH3), 3.50-4.20 (m, 4H, OCH2CH3), 4.70 (dd, JPH
=
24.0 Hz, 2JPH = 7.5 Hz, 1H, CHP), 5.75 (br, 1H, NH), 6.60 (d, J =
8.0 Hz, 2H, Ar-H), 7.10-7.30 (m, 4H, Ar-H), 8.01 (d, J = 8.0 Hz,
2H, Ar-H); m/z (ESI) 435 [45%, M+]. Anal. Calc. for
C21H30N3O5P: C, 57.92; H, 6.94; N, 9.65. Found: C, 57.24; H,
6.75; N, 9.42.
Diethyl (((3-bromophenyl) amino) (4-(dimethylamino)
phenyl) methyl)phosphonatee (4k): Yield 92%; m.p = 110-111
°C; IR (KBr, cm-1): 3294 (NH), 3018, 2974, 1612, 1594, 1523,
1479, 1235 (P=O), 1057 (P-OEt); 1H NMR (100 MHz,CDCl3): d
1.15-1.30 (m, 6H OCH2CH3), 2.88 (s, 6H, NCH3), 3.60-4.21 (m,
Diethyl ((4-(diethylamino)phenyl) ((4-methoxyphenyl)
amino) methyl) phosphonate (4h): Yield 95%; m.p = 120–121
°C; IR(KBr, cm-1): 3299 (NH), 3018, 2971, 1611, 1520, 1510,
1234 (P=O), 1031 (P-OEt); 1H NMR (400 MHz, CDCl3): d
1.10-1.30 (m, 6H, OCH2CH3, 6H, NCH2CH3), 3.31 (q, J = 8.0 Hz,
4H, NCH2CH3), 3.69 (s, 3H, OCH3), 3.65-3.80 (m, 1H,
OCH2CH3), 3.93-3.97 (m, 1H, OCH2CH3), 4.08-4.14 (m, 2H,
OCH2CH3), 4.36 (b, 1H, NH), 4.57 (dd, 1JPH = 23.0 Hz, 2JPH = 7.2
Hz, 1H, CHP), 6.57-6.70 (m, 6H, Ar-H), 7.24-7.26 (m, 2H, Ar-H),
13CNMR (100.62, CDCl3): d 12.5, 16.2 (d, 3JPC = 6.0 Hz), 16.5 (d,
3JPC = 6.0 Hz), 44.3, 55.6, 56.2 (d, 1JPC = 152.5 Hz), 63.0, 63.1,
111.8, 114.7, 115.3, 121.9, 128.8 (d, 2JPC = 5.0 Hz), 140.9 (d, 3JPC
= 1.5 Hz), 147.5, 152.5. 31P (161.99 MHz, CDCl3): d 23.99 ppm,.
m/z (ESI) 420 [30%, M+]. Anal. Calc. for C22H33N2O4P: C, 62.84;
H, 7.91; N, 6.66. Found: C, 62.43; H, 7.68; N, 6.60.
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4H, OCH2CH3), 4.32 (dd, JPH = 23.0 Hz, JPH = 7.0 Hz, 1H,
CHP), 4.7 (br, 1H, NH), 6.5-7.30 (m, 8H, Ar-H). 31P (162.03
MHz, CDCl3): d 23.70. m/z (ESI) 440 [30%, M+], 442 [28%,
M++2]. Anal. Calc. for C19H26BrN2O3P: C, 51.71; H, 5.94; N,
6.35. Found: C, 51.50; H, 5.90; N, 6.24.
Diethyl ((4-tolylamino)(4-(dimethylamino) phenyl) me-
thyl) phosphonate (4l): Yield 92%; m.p = 102-103 °C;2 IR (KBr,
cm-1) u: 3295 (NH), 3018, 2982, 1611, 1603, 1524, 1497, 1237
(P=O), 1060 (P-OEt), 1H NMR (100 MHz, CDCl3) d: 1.13-1.45
(m, 6H, OCH2CH3), 2.20 (s, 3H, CH3Ar), 2.70 (s, 6H, NCH3),
3.60-4.22 (m, 4H, OCH2CH3), 4.50-4.65 (m, 1H, CHP), 4.75 (br,
1H, NH), 6.58-7.53 (m, 8H, Ar); MS (m/z) 376 [20%, M+]. Anal.
Calc. for C20H29N2O3P: C, 63.81; H, 7.77; N, 7.44. Found: C,
63.75; H, 7.70; N, 7.26.
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© 2015 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim J. Chin. Chem. Soc. 2015, 62, 1087-1096