1-(Substituted Phenoxyacetoxy)alkylphosphonates
J. Agric. Food Chem., Vol. 55, No. 5, 2007 1873
Rf ) 0.61 (silica gel, acetone/petroleum ether, 1:1). IR (KBr, cm-1):
3023 (ArC-H), 1777 (CdO, str), 1589 (ArC-C), 1494 (ArC-C), 1446
(m, 2H, 2 and 6-phenyl-H), 6.76 (d, 1H, J ) 3.0, 4-furanyl-H), 7.21
(d, 1H, J ) 8.8, 5-phenyl-H), 7.48 (t, 1H, J ) 1.2, 5-furanyl-H). EI-
MS m/z (%): 388 (M+ 11), 309 (57), 234 (29), 205 (49), 200 (49),
189 (100), 165 (10), 155 (86), 142 (41), 125(79), 109 (70), 94 (18), 93
(96). Anal. calcd for C16H18ClO7P: C, 49.43; H, 4.67. Found: C, 49.53;
H, 4.56.
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(ArC-C), 1255, 1171, 1037, 945. H NMR (CDCl3): δ 3.74 (d, 3H,
J ) 10.8, OCH3), 3.77 (d, 3H, J ) 10.8, OCH3), 4.80 (s, 2H, OCH2-
CO), 6.37 (d, 1H, J ) 13.8, PCHO), 6.85 (dd, 2H, J ) 6.9, J ) 2.4,
2 and 6-phenyl-H), 7.23 (dd, 2H, J ) 6.9, J ) 2.4, 3 and 5-phenyl-H),
7.26-7.29 (m, 1H, 3-furanyl-H), 7.42 (d, 1H, J ) 7.8, 4-furanyl-H),
7.71 (dd, 1H, J ) 7.8, J ) 1.4, 5-furanyl-H). EI-MS m/z (%): 374
(M+ 0.7), 258 (20), 244 (77), 201 (22), 186 (13), 148 (10), 141 (26),
109 (43), 94 (8), 93 (58). Anal. calcd for C15H16ClO7P: C, 48.08; H,
4.30. Found: C, 48.13; H, 4.37.
Data for O,O-Dimethyl (2-Chloro-5-methylphenoxyacetoxy)(furan-
2-yl)methylphosphonate (9). White solid; 0.81 g; yield, 64%; mp 97-
98 °C; Rf ) 0.60 (silica gel, acetone/petroleum ether, 1:1). IR (KBr,
cm-1): 3115, 1774 (CdO, str), 1585 (ArC-C), 1493 (ArC-C), 1448
1
(ArC-C), 1265, 1170, 1059, 930. H NMR (CDCl3): δ 2.27 (s, 3H,
Data for O,O-Dimethyl (2,4-Dichlorophenoxyacetoxy)(furan-2-yl)-
methylphosphonate (4). Yellowish solid; 1.10 g; yield, 87%; mp 62-
63 °C; Rf ) 0.60 (silica gel, acetone/petroleum ether, 1:1). IR (KBr,
cm-1): 3074 (ArC-H), 1765 (CdO, str), 1583 (ArC-C), 1483 (ArC-
C), 1439 (ArC-C), 1285, 1188, 1036, 934. 1H NMR (CDCl3): δ3.76
(d, 3H, J ) 10.8, OCH3), 3.83 (d, 3H, J ) 10.8, OCH3), 4.75, 4.78 (q,
AB system, 2H, JAB ) 16.5, OCH2CO), 6.38 (d, 1H, J ) 14.8, PCHO),
6.40-6.42 (m, 1H, 3-furanyl-H), 6.62 (t, 1H, J ) 2.4, 4-furanyl-H),
6.75 (d, 1H, J ) 8.8, 6-phenyl-H), 7.13 (dd, 1H, J ) 8.8, J ) 2.4,
5-phenyl-H), 7.37 (d, 1H, J ) 2.4, 3-phenyl-H), 7.47 (t, 1H, J ) 0.9,
5-furanyl-H). EI-MS m/z (%): 408 (M+ 13), 220 (66), 205 (53), 189
(75), 175 (61), 162 (100), 145(32), 133 (37), 109 (50), 94 (6), 93 (70).
Anal. calcd for C15H15Cl2O7P: C, 44.03; H, 3.70. Found: C, 44.08; H,
3.67.
PhCH3), 3.75 (d, 3H, J ) 10.8, OCH3), 3.82 (d, 3H, J ) 10.8, OCH3),
4.75, 4.78 (q, AB system, 2H, JAB ) 16.5, OCH2CO), 6.39 (d, 1H, J
) 11.2, PCHO), 6.39-6.42 (m, 1H, 3-furanyl-H), 6.60-6.63 (m, 2H,
4-furanyl-H and 6-phenyl-H), 6.73-6.77 (m, 1H, 4-phenyl-H), 7.23
(d, 1H, J ) 8.0, 3-phenyl-H), 7.48 (t, 1H, J ) 0.9, 5-furanyl-H). EI-
MS m/z (%): 388 (M+ 1), 205 (3), 200 (54), 189 (9), 165 (18), 155
(27), 142 (36), 125(44), 109 (12), 94 (6), 93 (12). Anal. calcd for C16H18-
ClO7P: C, 49.43; H, 4.67. Found: C, 49.23; H, 4.47.
Data for O,O-Dimethyl (3-Fluorophenoxyacetoxy)(thien-2-yl)meth-
ylphosphonate (10). Yellowish solid; 0.89 g; yield, 70%; mp 76-77
°C; Rf ) 0.64 (silica gel, acetone/petroleum ether, 1:1). IR (KBr, cm-1):
3087 (ArC-H), 1740 (CdO, str), 1596 (ArC-C), 1491 (ArC-C),
1437 (ArC-C), 1213, 1143, 1040, 940. 1H NMR (CDCl3): δ 3.70 (d,
3H, J ) 10.8, OCH3), 3.77 (d, 3H, J ) 10.8, OCH3), 4.61 (s, 2H,
OCH2CO), 6.62-6.71 (m, 4H, PCHO, 2, 4 and 6- phenyl-H), 6.99 (t,
1H, J ) 3.0, 3-thienyl-H), 7.14 (d, 1H, J ) 2.4, 5- phenyl-H), 7.19-
7.23 (m, 1H, 4-thienyl-H), 7.27-7.31 (m, 1H, 5-thienyl-H). EI-MS
m/z (%): 374 (M+ 2), 220 (11), 205 (21), 170 (36), 125 (47), 113
(50), 109 (40), 95 (100), 93 (20). Anal. calcd for C15H16FO6PS: C,
48.13; H, 4.31. Found: C, 48.48; H, 4.14.
Data for O,O-Dimethyl (2,6-Dichlorophenoxyacetoxy)(furan-2-yl)-
methylphosphonate (5). Yellowish solid; 0.76 g; yield, 60%; mp 92-
93 °C; Rf ) 0.62 (silica gel, acetone/petroleum ether, 1:1). IR (KBr,
cm-1): 3126, 1767 (CdO, str), 1567 (ArC-C), 1458 (ArC-C), 1428
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(ArC-C), 1271, 1189, 1032, 937. H NMR (CDCl3): δ 3.79 (d, 3H,
J ) 10.8, OCH3), 3.85 (d, 3H, J ) 10.8, OCH3), 4.71 (s, 2H, OCH2-
CO), 6.41 (s, 1H, 3-furanyl-H), 6.44 (d, 1H, J ) 15.9, PCHO), 6.65
(s, 1H, 4-furanyl-H), 6.98-7.03 (m, 1H, 4-phenyl-H), 7.26 (d, 2H,
J ) 8.0, 3 and 5-phenyl-H), 7.46 (s, 1H, 5-furanyl-H). EI-MS m/z
(%): 408 (M+ 20), 220 (40), 205 (11), 189 (98), 175 (32), 162 (100),
145(17), 133 (25), 109 (21), 94 (2), 93 (27). Anal. calcd for C15H15-
Cl2O7P: C, 44.03; H, 3.70. Found: C, 44.44; H, 3.48.
Data for O,O-Dimethyl (4-Fluorophenoxyacetoxy)(thien-2-yl)meth-
ylphosphonate (11). Yellowish solid; 0.85 g; yield, 67%; mp 68-
70 °C; Rf ) 0.62 (silica gel, acetone/petroleum ether, 1:1). IR (KBr,
cm-1): 3083 (ArC-H), 1762 (CdO, str), 1627 (ArC-C), 1506 (ArC-
C), 1444 (ArC-C), 1247, 1195, 1029, 941. 1H NMR (CDCl3): δ 3.70
(d, 3H, J ) 10.7, OCH3), 3.77 (d, 3H, J ) 10.7, OCH3), 4.64, 4.67 (q,
AB system, 2H, JAB ) 16.4, OCH2CO), 6.54 (d, 1H, J ) 13.5, PCHO),
6.80-6.83 (m, 2H, 2 and 6-phenyl-H), 6.91-6.93 (m, 2H, 3 and
5-phenyl-H), 6.99-7.03 (m, 1H, 3-thienyl-H), 7.27-7.31 (m, 1H,
4-thienyl-H), 7.38 (d, 1H, J ) 5.2, 5-thienyl-H). EI-MS m/z (%): 374
(M+ 51), 220 (14), 205 (100), 170 (17), 125 (84), 113 (31), 109 (51),
94 (24), 93 (85). Anal. calcd for C15H16FO6PS: C, 48.13; H, 4.31.
Found: C, 48.30; H, 4.19.
Data for O,O-Dimethyl (2,3-Dichlorophenoxyacetoxy)(furan-2-yl)-
methylphosphonate (6). Yellowish solid; 0.79 g; yield, 62%; mp 81-
82 °C; Rf ) 0.64 (silica gel, acetone/petroleum ether, 1:1). IR (KBr,
cm-1): 3081 (ArC-H), 1779 (CdO, str), 1581 (ArC-C), 1463 (ArC-
C), 1427 (ArC-C), 1270, 1172, 1054, 938. 1H NMR (CDCl3): δ 3.75
(d, 3H, J ) 10.8, OCH3), 3.83 (d, 3H, J ) 10.8, OCH3), 4.79, 4.82 (q,
AB system, 2H, JAB ) 16.5, OCH2CO), 6.38 (d, 1H, J ) 11.4, PCHO),
6.41 (s, 1H, 3-furanyl-H), 6.63 (d, 1H, J ) 1.5, 4-furanyl-H), 6.98-
7.03 (dd, 1H, J ) 5.4, J ) 1.8, 6-phenyl-H), 7.09-7.13 (m, 2H, 4 and
5-phenyl-H), 7.48 (s, 1H, 5-furanyl-H). EI-MS m/z (%): 408 (M+ 60),
377 (11), 271 (20), 249 (34), 220 (20), 205 (92), 189 (98), 175 (90),
162 (38), 145(63), 133 (22), 109 (81), 94 (25), 93 (100). Anal. calcd
for C15H15Cl2O7P: C, 44.03; H, 3.70. Found: C, 44.50; H, 3.50.
Data for O,O-Dimethyl (4-Chloro-2-methylphenoxyacetoxy)(furan-
2-yl)methylphosphonate (7). Yellowish liquid; 1.00 g; yield, 79%; nD20
1.5016; Rf ) 0.63 (silica gel, acetone/petroleum ether, 1:1). IR (KBr,
cm-1): 3078 (ArC-H), 1772 (CdO, str), 1598 (ArC-C), 1492 (ArC-
C), 1447 (ArC-C), 1235, 1171, 1039, 932. 1H NMR (CDCl3): δ 2.25
(s, 3H, PhCH3), 3.76 (d, 3H, J ) 11.0, OCH3), 3.81 (d, 3H, J ) 11.0,
OCH3), 4.70, 4.73 (q, AB system, 2H, JAB ) 16.5, OCH2CO), 6.39 (d,
1H, J ) 14.4, PCHO), 6.40-6.42 (m, 1H, 3-furanyl-H), 6.52 (s, 1H,
4-furanyl-H), 6.62-6.66 (m, 1H, 6-phenyl-H), 7.06-7.08 (m, 1H,
5-phenyl-H), 7.13 (s, 1H, 3-phenyl-H), 7.45-7.49 (m, 1H, 5-furanyl-
H). EI-MS m/z (%): 388 (M+ 17), 234 (38), 205 (23), 189 (100), 165
(1), 155 (58), 142 (19), 125(51), 109 (46), 94 (9), 93 (67). Anal. calcd
for C16H18ClO7P: C, 49.43; H, 4.67. Found: C, 49.72; H, 4.52.
Data for O,O-Dimethyl (4-Chloro-3-methylphenoxyacetoxy)(furan-
2-yl)methylphosphonate (8). White solid; 0.99 g; yield, 78%; mp 47-
48 °C; Rf ) 0.60 (silica gel, acetone/petroleum ether, 1:1). IR (KBr,
cm-1): 3081 (ArC-H), 1774 (CdO, str), 1576 (ArC-C), 1478 (ArC-
C), 1447 (ArC-C), 1269, 1170, 1055, 939. 1H NMR (CDCl3): δ2.31
(s, 3H, PhCH3), 3.75 (d, 3H, J ) 10.7, OCH3), 3.80 (d, 3H, J ) 10.7,
OCH3), 4.66, 4.69 (q, AB system, 2H, JAB ) 16.4, OCH2CO), 6.38 (d,
1H, J ) 12.8, PCHO), 6.40-6.42 (m, 1H, 3-furanyl-H), 6.61-6.67
Data for O,O-Dimethyl (2,4-Dichlorophenoxyacetoxy)(thien-2-yl)-
methylphosphonate (12). Yellowish solid; 1.15 g; yield, 91%; mp 92-
93 °C; Rf ) 0.62 (silica gel, acetone/petroleum ether, 1:1). IR (KBr,
cm-1): 3072 (ArC-H), 1763 (CdO, str), 1582 (ArC-C), 1483 (ArC-
C), 1434 (ArC-C), 1275, 1190, 1038, 946. 1H NMR (CDCl3): δ 3.70
(d, 3H, J ) 10.5, OCH3), 3.77 (d, 3H, J ) 10.5, OCH3), 4.74, 4.77 (q,
AB system, 2H, JAB ) 16.5, OCH2CO), 6.50 (d, 1H, J ) 13.5, PCHO),
6.69 (d, 1H, J ) 8.8, 6-phenyl-H), 6.98-7.01 (t, 1H, J ) 3.6, 3-thienyl-
H), 7.24 (s, 1H, 4-thienyl-H), 7.09 (dd, 1H, J ) 8.8, J ) 2.4, 5-phenyl-
H), 7.35-7.36 (m, 2H, 3-phenyl-H and 5-thienyl-H). EI-MS m/z (%):
424 (M+ 9), 220 (37), 205 (60), 175 (58), 162 (76), 145 (26), 133
(28), 109 (33), 94 (4), 93 (100). Anal. calcd for C15H15Cl2O6PS: C,
42.37; H, 3.56. Found: C, 42.47; H, 3.90.
Data for O,O-Dimethyl (4-Chlorophenoxyacetoxy)(thien-2-yl)meth-
ylphosphonate (13). Yellowish solid; 1.08 g; yield, 85%; mp 94-95
°C; Rf ) 0.61 (silica gel, acetone/petroleum ether, 1:1). IR (KBr, cm-1):
3083 (ArC-H), 1762 (CdO, str), 1596 (ArC-C), 1494 (ArC-C),
1443 (ArC-C), 1247, 1177, 1027, 939. 1H NMR (CDCl3): δ 3.71 (d,
3H, J ) 10.8, OCH3), 3.78 (d, 3H, J ) 10.8, OCH3), 4.67, 4.71 (q, AB
system, 2H, JAB ) 16.4, OCH2CO), 6.53 (d, 1H, J ) 13.5, PCHO),
6.77-6.82 (m, 2H, 2 and 6-phenyl-H), 7.00-7.04 (m, 1H, 3-thienyl-
H), 7.19-7.24 (m, 2H, 3 and 5-phenyl-H), 7.26-7.30 (m, 1H, 4-thienyl-
H), 7.39 (d, 1H, 5-thienyl-H). EI-MS m/z (%): 390 (M+ 31), 220(31),
205 (74), 186 (9), 141 (54), 128 (20), 111 (62), 109 (63), 94 (18), 93
(100). Anal. calcd for C15H16ClO6PS: C, 46.10; H, 4.13. Found: C,
46.01; H, 4.08.