5
4.1.1.8 2-(4-chlorophenyl)-2-oxoethyl dimethyl phosphate (2h):
Greenish oil; yield 82% (82.2 mg); Rf (40% EtOAc/Hex) 0.22;
1H NMR (400 MHz, CDCl3) δ 7.84 (d, J = 8.0 Hz, 2xAr-H), 7.47
(d, J = 8.4 Hz, 2xAr-H), 5.28 (d, J = 10.4 Hz, CH2), 3.86 (d, J =
11.2 Hz, 2xCH3). 31P NMR (162 MHz, CDCl3) δ 1.29. 13C NMR
(101 MHz, CDCl3) δ 191.07 (d, J = 4.6 Hz), 155.28, 140.62,
132.17, 129.32, 129.17, 68.81 (d, J = 5.0 Hz), 54.83 (d, J = 6.2
Hz); 13C NMR (101 MHz, CDCl3) δ 129.32, 129.17, 68.81 (d, J =
5.4 Hz), 54.84 (d, J = 6.2 Hz); IR (CHCl3) ῡ[cm-1]: 2987, 2924,
2853, 1765 1621, 1583, 1523, 1442, 1306, 1267,1117, 1021, 978,
4.1.1.13. Dimethyl (2-oxo-2-(p-tolyl)ethyl) phosphate (2m): Oil;
ACCEPTED MANUSCRIPT
yield 70% (70.1 mg); Rf (40% EtOAc/Hex) 0.24; 1H NMR (400
MHz, CDCl3) δ 7.80 (d, J = 8.0 Hz, 2xAr-H), 7.29 (d, J = 8.0 Hz,
2xAr-H), 5.32 (d, J = 9.6 Hz, CH2), 3.88 (d, J = 11.6 Hz,
2xOCH3), 2.42 (s, CH3); 31P NMR (162 MHz, CDCl3) δ 1.39; 13
C
NMR (101 MHz, CDCl3) δ 191.66 (d, J = 4.8 Hz), 145.02,
129.59, 127.82, 68.83 (d, J = 5.0 Hz), 54.73 (d, J = 6.2 Hz),
21.72.; 13C NMR (101 MHz, CDCl3) δ 129.59, 127.82, 68.83 (d,
J = 5.0 Hz), 54.73 (d, J = 6.2 Hz), 21.72; IR (CHCl3) ῡ[cm-1]:
2957, 2925, 2855, 1704, 1607, 1573, 1452, 1376, 1272, 1115,
1043, 998, 852, 779; HRMS (TOF) m/z [M + Na]+ Calcd for
C11H15NaO5P 281.2020, found 281.2028.
840, 749;
C10H12ClNaO5P 301.6100, found 301.6110.
HRMS (TOF) m/z [M +
Na]+ Calcd for
4.1.1.9 2-(4-chlorophenyl)-2-oxoethyl diethyl phosphate (2i):
Greenish oil; yield 81% (81.3 mg); Rf (40% EtOAc/Hex) 0.35;
1H NMR (400 MHz, CDCl3) δ 7.85 (d, J = 8.5 Hz, 2xAr-H), 7.47
(d, J = 8.5 Hz, 2xAr-H), 5.26 (d, J = 9.9 Hz, CH2), 4.32 (q, J =
7.2 Hz, 2xCH2), 1.37 (t, J = 6.9 Hz, 2xCH3); 31P NMR (162
MHz, CDCl3) δ -0.95.; 13C NMR (126 MHz, CDCl3) δ 191.26 (d,
J = 5.3 Hz), 140.54, 132.25, 129.30, 129.23, 68.63 (d, J = 5.3
Hz), 64.49 (d, J = 5.8 Hz), 16.09 (d, J = 6.7 Hz); 13C NMR (126
MHz, CDCl3) δ 130.03, 114.11, δ 68.63 (d, J = 5.3 Hz), 64.50 (d,
J = 6.2 Hz), 16.09 (d, J = 7.2 Hz); IR (CHCl3) ῡ[cm-1]: 2992,
2922, 2851, 1767, 1633, 1591, 1463, 1246, 1093, 1029, 979,
827,755; HRMS (TOF) m/z [M + Na]+ Calcd for C12H16ClNaO5P
329.6700, found 329.6710.
4.1.1.14. Diethyl (2-oxo-2-(p-tolyl)ethyl) phosphate (2n): Oil;
yield 76% (76.1 mg); Rf (40% EtOAc/Hex) 0.37; H NMR (400
1
MHz, CDCl3) δ 7.80 (d, J = 8.1 Hz, 2xAr-H), 7.28 (d, J = 8.9 Hz,
2xAr-H), 5.29 (d, J = 9.9 Hz, CH2), 4.22 (q, J = 7.2 Hz, 2xCH2),
2.42 (s, CH3), 1.37 (t, J = 7.0 Hz, 2xOCH3); 31P NMR (162
MHz, CDCl3) δ -0.86; 13C NMR (126 MHz, CDCl3) δ 191.85 (d,
J = 5.3 Hz), 145.02, 131.44, 129.60, 127.84, 68.64 (d, J = 5.3
Hz), 64.39 (d, J = 5.8 Hz), 21.79, 16.11 (d, J = 7.2 Hz); 13C NMR
(126 MHz, CDCl3) δ 129.60, 127.84, δ 68.64 (d, J = 5.5 Hz),
64.39 (d, J = 6.0 Hz), 21.78, 16.10 (d, J = 6.9 Hz); IR (CHCl3)
ῡ[cm-1]: 2954, 2923, 2853, 1705, 1607, 1457, 1400, 1376, 1237,
1115, 1031, 976, 859, 772;HRMS (TOF) m/z [M + Na]+ Calcd
for C13H19NaO5P 309.2500, found 309.2520.
4.1.1.10. Dibenzyl(2-(4-chlorophenyl)-2-oxoethyl)phosphate(2j):
4.1.1.15. 2-(4-methoxyphenyl)-2-oxoethyl dimethylphosphate (2o)
: Greenish oil; yield 75% (75.2 mg); Rf (40% EtOAc/Hex) 0.23;
1H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.8 Hz, 2xAr-H), 6.96
(d, J = 8.8 Hz, 2xAr-H), 5.29 (d, J = 10.4 Hz, CH2), 3.87(d, J =
10.8Hz, 3xOCH3); 13C NMR (126 MHz, CDCl3) δ 190.54 (d, J =
4.6 Hz), 164.15, 130.04, 126.77, 114.11, 68.68 (d, J = 5.3 Hz),
55.55, δ 54.78 (d, J = 5.8 Hz); 13C NMR (126 MHz, CDCl3) δ
130.03, 114.11, 68.68 (d, 5.3 Hz), 55.55, 54.78 (d J = 5.8 Hz); IR
(CHCl3) ῡ[cm-1]: 2958, 2924, 2852, 1697, 1601, 1576, 1513,
1462, 1315, 1264, 1243, 1115,1041, 979, 848, 779; HRMS
(TOF) m/z [M + Na]+ Calcd for C11H15NaO6P 297.2000, found
297.2012.
Greenish viscous oil; yield 79% (79.1 mg); Rf (30% EtOAc/Hex)
1
0.65; H NMR (400 MHz, CDCl3) δ 7.75 (d, J = 8.4 Hz, 2xAr-
H), 7.42 (d, J = 8.4 Hz, 2xAr-H), 7.38 – 7.10 (m, 10xAr-H), 5.21
– 5.06 (m, 2xCH2), 5.00 (d, J = 8.1 Hz, CH2). 31P NMR (162
MHz, CDCl3) δ -0.90. 13C NMR (101 MHz, CDCl3) 193.97 (d, J
= 5.4 Hz), 143.38, 138.55, 138.48, 135.11, 132.13, 131.55,
131.52, 131.03, 72.78 (d, J = 5.4 Hz), 71.56 (d, J = 5.4 Hz); 13C
NMR (101 MHz, CDCl3) δ 129.23, 128.66, 128.63, 128.13,
69.88 (d, J = 5.4 Hz), 68.67 (d, J = 5.4 Hz); IR (CHCl3) ῡ[cm-1]:
3034, 2925, 2852, 1709, 1649, 1591, 1455, 1403, 1269, 1232,
1117, 1034, 979, 882, 739; HRMS (TOF) m/z [M + Na]+ Calcd
for C22H20ClNaO5P 453.8100, found 453.8140.
4.1.1.16 Diethyl (2-(4-methoxyphenyl)-2-oxoethyl)phosphate (2p)
: Greenish oil; yield 78% (78.1 mg); Rf (40% EtOAc/Hex) 0.37;
1H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.9 Hz, 2xAr-H), 6.95
(d, J = 8.9 Hz, 2xAr-H), 5.25 (d, J = 9.8 Hz, CH2), 4.33 (q, J =
7.2 Hz, 2xCH2), 3.87 (s, OCH3), 1.36 (t, J = 7.3 Hz, 2xOCH3);
31P NMR (162 MHz, CDCl3) δ -0.87; 13C NMR (126 MHz,
CDCl3) δ 192.12 (d, J = 5.8 Hz), 165.54, 131.52, 128.43, 115.52,
), 69.89 (d, J = 5.5 Hz), 65.77 (d, J = 5.8 Hz), 56.96, 17.51 (d, J
= 6.7 Hz); 13C NMR (126 MHz, CDCl3) δ 130.10, 114.10, 68.47
(d, J = 5.5Hz), 64.35(d, J = 5.8 Hz), 55.54, 16.10 (d, J = 6.9 Hz);
IR (CHCl3) ῡ[cm-1]: 2954, 2920, 2849, 1697, 1601, 1576, 1462,
1373, 1260, 1173, 1115, 1030, 978, 834, 746; HRMS (TOF) m/z
[M + Na] + Calcd for C13H19NaO6P 325.2500, found 325.2508.
4.1.1.11. 2-(4-bromophenyl)-2-oxoethyl diethyl phosphate (2k):
Brownish oil; yield 75% (75.1 mg); Rf (40% EtOAc/Hex) 0.36;
1H NMR (400 MHz, CDCl3) δ 7.77 (d, J = 8.5 Hz, 2xAr-H), 7.63
(d, J = 8.5 Hz, 2xAr-H), 5.27 (d, J = 10.0 Hz, CH2), 4.33 (q, J =
7.2 Hz, 2xCH2), 1.37 (t, J = 7.0 Hz, 2xCH3); 31P NMR (162
MHz, CDCl3) δ -0.98; 13C NMR (126 MHz, CDCl3) δ 191.46 (d,
J = 5.3 Hz), 171.23, 132.64, 132.28, 129.28, 68.62 (d, J = 5.3
Hz), 64.51 (d, J = 6.2 Hz), 16.09 (d, J = 7.1 Hz); 13C NMR (126
MHz, CDCl3) δ 132.28, 129.28, δ 68.62 (d, J = 5.3 Hz), 64.51 (d,
J = 5.8 Hz), 16.09 (d, J = 7.2 Hz); IR (CHCl3) ῡ[cm-1]: 2957,
2925, 2854, 1710, 1587, 1569, 1454, 1399, 1234, 1118, 1040,
980, 857, 759; HRMS (TOF) m/z [M + Na]+ Calcd for
C12H16BrNaO5P 374.1200, found 374.1206.
4.1.2 One-pot direct synthesis of 2-(4-fluorophenyl)-2-oxoethyl
diphenyl phosphate (2q). A mixture of 2-oxoaldehyde (3) (100
mg,0.746 mmol) and diaryl phosphate (4) (174 mg, 0.746 mmol)
was stirred in neet conditions for 10-15 minutes at 80 oC.
Reaction mixture was cooled to room temperature, volatile
impurities were evaporated in vacuo. To this reaction mixture,
dry toluene (1.5 mL) and potassium tert-butoxide (100mg, 0.895
mmol) was added at room temperature under Nitrogen
atmosphere. The reaction mixture was stirred for 4-6 hours at 80
°C. The completion of reaction was monitored by TLC and the
solvent was evaporated in vacuo to give the crude product, which
was purified by column chromatography (40% ethylacetate/
hexane) to give title compound (2q) (67%, 170 mg) as a viscous
4.1.1.12. Dimethyl (2-(3-nitrophenyl)-2-oxoethyl) phosphate (2l):
Brownish oil; yield 40% (40.2 mg); Rf (40% EtOAc/Hex) 0.34;
1H NMR (400 MHz, CDCl3) δ 8.21 (s, Ar-H), 7.99 (d, J = 8.2 Hz,
Ar-H), 7.69 (d, J =8.1 Hz, Ar-H), 7.34 (t, J = 8.0 Hz, Ar-H), 5.25
– 5.17 (m, CH2), 3.67 (d, J = 11.4 Hz, 2xOCH3); 31P NMR (162
MHz, CDCl3) δ -4.02; 13C NMR (126 MHz, CDCl3) δ 152.99 (d,
J = 7.5 Hz), 151.43, 138.86 (d, J = 7.1 Hz), 133.86, 132.60,
126.81, 123.14, 102.94 (d, J = 3.8 Hz), 58.13 (d, J = 5.8 Hz); 13
C
NMR (126 MHz, CDCl3) δ 130.88, 129.61, 123.82, 120.18,
99.96 (d, J = 3.8 Hz, 55.13 (d, J = 5.8 Hz); IR (CHCl3) ῡ[cm-1]:
2958, 2922, 2852, 1708, 1592, 1589, 1454, 1366, 1256, 1175,
1021, 987, 882, 756; HRMS (TOF) m/z [M + Na]+ Calcd for
C10H16NNaO7P 312.1710, found 312.1740.
1
oil; Rf (40% EtOAc/Hex) 0.61; H NMR (400 MHz, CDCl3) δ