Journal of Agricultural and Food Chemistry
ARTICLE
(d, 1Hb, OCH2CO), 6.26ꢀ6.29 (d, 1H, OCHP), 6.88ꢀ7.45 (m, 10H,
C6H5 þ C6H5). Anal. Calcd for C17H19O6P: C, 58.29; H, 5.47. Found:
C, 57.92; H, 5.13.
O,O-Dimethyl R-(2,3-dichlorophenoxyacetoxy)-3-nitrobenzylpho-
sphonate (I-24): colorless solid; yield, 68%; mp 111.7ꢀ113.1 ꢀC; IR
(KBr, cmꢀ1) ν 3081 (Ar—H), 2959, 2852 (C—H), 1745 (CdO),
1581, 1459 (ArC—C), 1084 (C—O—C), 1053 (P—O—C), 777
(P—C), 1178 (—C), 1264 (PdO), 1027 (ArC—Cl), 1534, 1353
O,O-Dimethyl R-(3-methylphenoxyacetoxy)benzylphosphonate
(I-12): yellow liquid; yield, 88%; n2D0 1.5273; H NMR (400 MHz,
1
1
CDCl3) δ 2.18 (s, 3H, CH3), 3.63ꢀ3.72 (dd, 6H, 2 ꢁ OCH3), 4.73
(d, 1Ha, OCH2CO), 4.76 (d, 1Hb, OCH2CO), 6.25ꢀ6.28 (d, 1H,
CHP), 6.77ꢀ7.47 (m, 9H, C6H4 þ C6H5). Anal. Calcd for C18H21O6P:
C, 59.34; H, 5.81. Found: C, 59.09; H, 5.50.
O,O-Dimethyl R-(4-methylphenoxyacetoxy)benzylphosphonate (I-13):
white solid; yield, 84%; mp 80.3ꢀ81.0 ꢀC; 1H NMR (400 MHz, CDCl3)
δ 2.27 (s, 3H, CH3), 3.62ꢀ3.70 (dd, 6H, 2 ꢁ OCH3), 4.71 (d, 1Ha,
OCH2CO), 4.74 (d, 1Hb, OCH2CO), 6.25ꢀ6.28 (d, 1H, OCHP),
6.77ꢀ7.47 (m, 9H, C6H4 þ C6H4). Anal. Calcd for C18H21O6P: C,
59.34; H, 5.81. Found: C, 59.16; H, 5.49.
O,O-Dimethyl R-(2,3-dimethylphenoxyacetoxy)benzylphosphonate
(I-14): yellow liquid; yield, 84%; n2D0 1.5270; IR (KBr, cmꢀ1) ν 3015
(Ar—H), 1772 (CdO), 1264 (Ar—O—C), 1177 (C—O—C), 1032
(P—O—C), 770 (P—C); 1H NMR (400 MHz, CDCl3) δ 2.20ꢀ2.27 (d,
6H, 2 ꢁ CH3), 3.63ꢀ3.70 (dd, 6H, 2 ꢁ OCH3), 4.75 (d, 1Ha, OCH2CO),
4.77 (d, 1Hb, OCH2CO), 6.25ꢀ6.28 (d, 1H, CHP), 6.54ꢀ7.46 (m, 8H,
C6H3 þ C6H5). Anal. Calcd for C19H23O6P: C, 60.31; H, 6.13. Found: C,
60.38; H, 6.29.
O,O-Dimethyl R-(2-nitrophenoxyacetoxy)benzylphosphonate (I-19):
light yellow solid; yield, 61%; mp 157ꢀ158 ꢀC; IR (KBr, cmꢀ1) ν 3072
(Ar—H), 2961, 2858 (C—H), 1770 (CdO), 1591, 1448 (ArC—C), 1173
(C—O), 1048, 922 (P—O—C), 748 (P—C), 1267 (PdO), 1507, 1346
(ArC—NO2); 1H NMR (400 MHz, CDCl3) δ 3.58ꢀ3.66 (dd, 6H,
2 ꢁ OCH3), 4.82 (s, 2H, OCH2CO), 6.19 (d, 1H, CHP), 6.84ꢀ8.16
(m, 9H, C6H4 þ C6H5). Anal. Calcd for C17H18O8NP: C, 51.65; H, 4.56;
N, 3.54. Found: C, 51.60; H, 4.57; N, 3.47.
O,O-Dimethyl R-(3-methyl-4-chlorophenoxyacetoxy)-3-nitroben-
zylphosphonate (I-21): colorless solid; yield, 71%; mp 72.0ꢀ73.2 ꢀC;
IR (KBr, cmꢀ1) ν 3071 (Ar—H), 2957, 2856 (C—H), 1766 (CdO),
1530, 1485 (ArC—C), 1087 (C—O—C), 1033 (P—O—C), 724
(P—C), 1161 (Ar—O—C), 1272 (PdO), 1048 (ArC—Cl), 1530,
1352 (ArC—NO2); 1H NMR (400 MHz, CDCl3) δ 2.43 (s, 3H, CH3),
3.65ꢀ3.68 (m, 6H, 2 ꢁ OCH3), 4.71 (s, 2H, OCH2CO), 6.25 (d, 1H,
CHP), 6.58ꢀ8.23 (m, 7H, C6H4 þ C6H3); EI-MS m/z (%) 443
(Mþ, 48.55), 290 (33.44), 244 (98.01), 199 (62.38), 174 (68.29), 109
(100), 93 (92.39), 77 (43.73). Anal. Calcd for C18H19O8ClNP: C,
48.72; H, 4.32; N, 3.16. Found: C, 48.67; H, 4.14; N, 2.96.
(ArC—NO2); H NMR (400 MHz, CDCl3) δ 3.72ꢀ3.76 (m, 6H,
2 ꢁ OCH3), 4.90 (s, 2H, OCH2CO), 6.33 (d, 1H, CHP), 6.74ꢀ8.29
(m, 7H, C6H4 þ C6H3); EI-MS m/z (%) 465 (Mþ þ 1, 30.88), 464
(Mþ, 21.78), 260 (24.84), 199 (3.27), 175 (76.09), 109 (79.63), 93
(100), 777 (29). Anal. Calcd for C17H16O8Cl2NP: C, 43.99; H, 3.47; N,
3.02. Found: C, 43.57; H, 3.17; N, 2.95.
O,O-Dimethyl R-(2,6-dichlorophenoxyacetoxy)-3-nitrobenzylphos-
phonate (I-25): colorless solid; yield, 75%; mp 86.2ꢀ87.6 ꢀC; IR
(KBr, cmꢀ1) ν 3087 (Ar—H), 2952, 2863 (C—H), 1753 (CdO),
1562, 1456 (ArC—C), 1076 (C—O—C), 1033 (P—O—C), 718
(P—C), 1219 (Ar—O—C), 1252 (PdO), 1013 (ArC—Cl), 1529,
1358 (ArC—NO2); 1H NMR (400 MHz, CDCl3) δ 3.78ꢀ3.82 (m, 6H,
2 ꢁ OCH3), 4.81 (s, 2H, OCH2CO), 6.40 (d, 1H, CHP), 7.04ꢀ8.37
(m, 7H, C6H4 þ C6H3); EI-MS m/z (%) 556 (Mþ þ 93, 4.36), 464
(Mþ, 12.76), 260 (50.64), 175 (55.18), 109 (85.08), 93 (100), 77
(33.71). Anal. Calcd for C17H16O8Cl2NP: C, 43.99; H, 3.47; N, 3.02.
Found: C, 44.33; H, 3.22; N, 2.94.
O,O-Dimethyl R-(4-chlorophenoxyacetoxy)-3-nitrobenzylphos-
phonate (I-26): light yellow solid; yield, 80%; mp 79.8ꢀ83.9 ꢀC; IR
(KBr, cmꢀ1) ν 3072 (Ar—H), 2959, 2857 (C—H), 1769 (CdO),
1595, 1492 (ArC—C), 1172 (C—O—C), 1037 (P—O—C), 733
(P—C), 1233 (Ar—O—C), 1223 (PdO), 1095 (ArC—Cl), 1534,
1354 (ArC—NO2); 1H NMR (400 MHz, CDCl3) δ 3.72ꢀ3.82
(m, 6H, 2 ꢁ OCH3), 4.79 (s, 2H, OCH2CO), 6.34 (d, 1H, CHP),
6.81ꢀ8.29 (m, 8H, C6H4 þ C6H4); EI-MS m/z (%) 429 (Mþ, 80.71),
262 (46.91), 244 (91.98), 186 (98.14), 166 (70.08), 141 (100), 109
(99.22), 75 (99.47). Anal. Calcd for C17H17O8ClNP: C, 47.51; H, 3.99;
N, 3.26. Found: C,47.01; H, 3.97; N, 3.02.
O,O-Dimethyl R-(2,4-dichlorophenoxyacetoxy)-3-bromobenzyl-
phosphonate (I-33): yellow liquid; yield 53%; n2D0 1.4529; IR
(KBr, cmꢀ1) ν 3028 (Ar—H), 1750 (CdO), 1580, 1480 (CdC),
1225 (PdO), 1050 (P—O), 800 (Ar—Cl),748 (PꢀC); 1H NMR (200
MHz, CDCl3) δ 3.7ꢀ3.8 (d, 6H, 2 ꢁ OCH3), 4.75 (s, 2H, OCH2CO),
6.20 (d, 1H, CHP), 6.7ꢀ7.5 (m, 7H, C6H3 þ C6H4). Anal. Calcd for
C17H16BrCl2O6P: C, 40.99; H, 3.24. Found: C, 41.14; H, 3.25.
O,O-Dimethyl
sphonate (I-34): yellow liquid; yield, 78%; n2D0 1.4955; IR (KBr, cmꢀ1
R-(4-chlorophenoxyacetoxy)-2-hydroxybenzylpho-
)
O,O-Dimethyl R-(5-methyl-2-chlorophenoxyacetoxy)-3-nitrobenzyl-
phosphonate (I-22): light yellow solid; yield, 69%; mp 109.7ꢀ109.9 ꢀC;
IR(KBr, cmꢀ1) ν3087 (Ar—H), 2957, 2885 (C—H), 1776 (CdO), 1599,
1495 (ArC—C), 1094 (C—O—C), 1040 (P—O—C), 728 (P—C), 1172
(Ar—O—C), 1268 (PdO), 1057 (ArC—Cl), 1530, 1351 (ArC—NO2);
1H NMR (400 MHz, CDCl3) δ 2.56 (s, 3H, CH3), 3.72ꢀ3.77 (m, 6H, 2 ꢁ
OCH3), 4.86 (s, 2H, OCH2CO), 6.33 (d, 1H, CHP), 6.63ꢀ8.30 (m, 7H,
C6H4 þ C6H3); EI-MS m/z (%) 443 (Mþ, 41.79), 333 (41.05), 261
(13.07), 229 (86.81), 199 (95.60), 109 (78.41), 93 (100), 77 (72.39). Anal.
Calcd for C18H19O8ClNP: C, 48.72; H, 4.32; N, 3.16. Found: C, 49.37; H,
4.23; N, 3.16.
O,O-Dimethyl R-(2-methyl-4-chlorophenoxyacetoxy)-3-nitrobenzyl-
phosphonate (I-23): light yellow solid; yield, 61%; mp 132.2ꢀ133.1 ꢀC;
IR(KBr, cmꢀ1) ν 3075 (Ar—H), 2958, 2856 (C—H), 1759 (CdO), 1598,
1492 (ArC—C), 1095 (C—O—C), 1036 (P—O—C), 732 (P—C), 1186
(Ar—O—C), 1265 (PdO), 1138, 384 (ArC—Cl), 1533, 1353
(ArC—NO2); 1H NMR (400 MHz, CDCl3) δ 2.27 (s, 3H, CH3),
3.71ꢀ3.79 (m, 6H, 2 ꢁ OCH3), 4.81 (s, 2H, OCH2CO), 6.32 (d, 1H,
CHP), 6.59ꢀ8.29 (m, 7H, C6H4 þ C6H3); EI-MS m/z (%) 443
(Mþ, 51.09), 260 (6.18), 245 (85.69), 155 (79.07), 125 (86.24), 109
(92.30), 93 (100), 77 (70.47). Anal. Calcd for C18H19O8ClNP: C, 48.72; H,
4.32; N, 3.16. Found: C, 48.69; H, 4.16; N, 2.93.
ν 3473 (O—H), 2957 (R—H), 1774 (CdO), 1598 (Ar C—C), 1051
1
(C—Cl); H NMR (400 MHz, CDCl3) δ 3.49ꢀ3.86 (dd, 6H, 2 ꢁ
OCH3), 4.64 (d, 1Ha, OCH2CO), 4.74 (d, 1Hb, OCH2CO), 4.96
(s, 1H, OH), 6.48ꢀ6.51 (d, 1H, CHP), 6.78ꢀ7.59 (m, 8H, C6H4 þ
C6H4). Anal. Calcd for C17H18ClO7P: C, 50.95; H, 4.53. Found: C, 50.46;
H, 4.82.
General Procedure for the Preparation of O,O-Dialkyl
r-(Fluorophenoxyacetoxy)alkylphosphonates I-6ꢀI-8, I-15ꢀ
I-17, I-27ꢀI-29, and I-35. A solution of fluorophenoxyacetyl chloride 6
(0.011 mol) in trichloromethane (15 mL) was added to a stirred mixture of
R-hydroxyalkylphosphonate 2 (0.01 mol) and triethylamine (0.011 mol) in
trichloromethane (15 mL) at 2ꢀ4 ꢀC. The resultant mixture was stirred at
ambient temperature for 2ꢀ3 h, then washed with 0.1 M HCl, saturated
NaHCO3, and brine successively, dried, and concentrated. The residue was
chromatographed on silica with 20% acetone in petroleum ether as eluent to
give the compounds I-6ꢀI-8, I-15ꢀI-17, I-27ꢀI-29, and I-35. Their
structures were confirmed by IR, MS, and 1H NMR spectra and elemental
analysis. Physicochemical and spectroscopic data for compounds are as
follows.
O,O-Dimethyl R-(2-fluorophenoxyacetoxy)ethylphosphonate
(I-6): colorless crystal; yield, 59%; mp 62ꢀ63 ꢀC; IR (KBr, cmꢀ1
)
ν 3074 (ArC—H), 2965 (R—H), 2840 (R—H), 1769 (CdO), 1614
4803
dx.doi.org/10.1021/jf104247w |J. Agric. Food Chem. 2011, 59, 4801–4813