Month 2015
Synthesis and Biological Activity of 4-[(Substituted Phenoxyacetoxy)methyl]-2,6,7-
trioxa-1-phosphabicyclo[2.2.2]octane-1-one
4-[(4-Chlorophenoxy)acetyloxymethyl]-2,6,7-trioxa-1-
phosphabicyclo[2.2.2]octane-1-one (4d). White solid; yield,
67%; mp, 182–183°C; IR (KBr, cmÀ1): ν 1779, 1325,
yield, 78%; mp, 148–151°C; IR (KBr, cmÀ1): ν 1766,
1325, 1229, 1190, 1040, 963, 851. H NMR (400MHz,
DMSO-d6) δ 4.08 (s, 2H, CH2O), 4.63 (d, J= 6.8Hz, 6H,
(CH2O)3), 4.99 (s, 2H, CH2CO), 7.17–7.50 (m, 3H, Ar-
H); MS (70 eV): m/z: 366 (M+); Anal. Calcd for
C13H13ClFO7P: C, 42.58; H, 3.57. Found: C, 42.51; H,
3.57.
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1209, 1164, 1044, 965, 851, 803. H NMR (400 MHz,
DMSO-d6) δ 4.07 (s, 2H, CH2O), 4.63 (d, J = 6.4 Hz,
6H, (CH2O)3), 4.88 (s, 2H, CH2CO), 7.00–7.35 (m,
4H, Ar-H); MS (70 eV): m/z: 348 (M+); Anal. Calcd
for C13H14ClO7P: C, 44.78; H, 4.05. Found: C, 44.60;
4-[(2-Chloro-5-methylphenoxyl)acetyloxymethyl]-2,6,7-trioxa-
H, 3.90.
1-phosphabicyclo[2.2.2]octane-1-one (4k).
White solid;
yield, 38%; mp, 170–173°C; IR (KBr, cmÀ1): ν 1766,
1321, 1202, 1176, 1039, 966, 852, 804. 1H NMR
(400MHz, DMSO-d6) δ 2.33 (s, 3H, CH3), 4.01 (s, 2H,
CH2O), 4.48 (d, J=6.4Hz, 6H, (CH2O)3), 4.76 (s, 2H,
CH2CO), 6.64–7.31 (m, 3H, Ar-H); MS (70eV): m/z: 362
(M+); Anal. Calcd for C14H16ClO7P: C, 46.36; H 4.45.
Found: C, 46.35; H, 4.47.
4-[(2-Fluorophenoxy)acetyloxymethyl]-2,6,7-trioxa-1-
phosphabicyclo[2.2.2]octane-1-one (4e). White solid; yield,
73%; mp, 147–148°C; IR (KBr, cmÀ1): ν 1767, 1324,
1234, 1199, 1043, 961, 850. 1H NMR (400MHz,
DMSO-d6) δ 4.08 (s, 2 H, CH2O), 4.62 (d, J= 6.8 Hz,
6H, (CH2O)3), 4.96 (s, 2H, CH2CO), 6.99–7.28 (m, 4H,
Ar-H); MS (70eV): m/z: 332 (M+); Anal. Calcd for
C13H14FO7P: C, 47.00; H, 4.25. Found: C, 46.69; H, 4.41.
4-[(3-Trifluoromethylphenoxy)acetyloxymethyl]-2,6,7-trioxa-
1-phosphabicyclo[2.2.2]octane-1-one (4f).
yield, 69%; mp, 137–139°C; IR (KBr, cmÀ1): ν 1766,
1325, 1212, 1082, 1043, 962, 851, 827. 1H NMR
(400 MHz, DMSO-d6) δ 4.09 (s, 2H, CH2O), 4.62 (d,
J =6.0 Hz, 6H, (CH2O)3), 5.01 (s, 2H, CH2CO),
7.29–7.55 (m, 4H, Ar-H); MS (70 eV): m/z: 382 (M+);
Anal. Calcd for C14H14F3O7P: C, 43.99; H, 3.69. Found:
C, 43.78; H, 4.28.
4-[(4-Methylphenoxy)acetyloxymethyl]-2,6,7-trioxa-1-
phosphabicyclo[2.2.2]octane-1-one (4g). White solid; yield,
71%; mp, 158–159°C; IR (KBr, cmÀ1): ν 1766, 1326,
4-[(2,3-Dimethylphenoxyl)acetyloxymethyl]-2,6,7-trioxa-1-
phosphabicyclo[2.2.2]octane-1-one (4l). White solid; yield,
24%; mp, 183–184°C; IR (KBr, cmÀ1): ν 1769, 1309,
1193, 1131, 1038, 970, 855. 1H NMR (400MHz,
DMSO-d6) δ 2.21 (s, 3H, CH3), 2.29 (s, 3H, CH3), 3.98
(s, 2H, CH2O), 4.43 (d, J= 6.4Hz, 6H, (CH2O)3), 4.71 (s,
2H, CH2CO), 6.52–7.06 (m, 3H, Ar-H); MS (70 eV): m/z:
342 (M+);Anal. Calcd for C15H19O7P: C, 52.64; H, 5.60.
Found: C, 52.86; H, 5.38.
White solid;
4-[(4-Fluorophenoxyl)acetyloxymethyl]-2,6,7-trioxa-1-
phosphabicyclo[2.2.2]octane-1-one (4m).
White solid;
yield, 84%; mp, 139–140°C; IR (KBr, cmÀ1): ν 1768,
1326, 1204, 1159, 1043, 962, 850, 833. 1H NMR
(400MHz, DMSO-d6) δ 4.02 (s, 2H, CH2O), 4.52 (d,
J =6.8 Hz, 6H, (CH2O)3), 4.66 (s, 2H, CH2CO),
6.85–7.02 (m, 4H, Ar-H); MS (70 eV): m/z: 332 (M+);
Anal. Calcd for C13H14FO7P: C, 47.00; H, 4.25. Found:
C, 47.42; H, 4.03.
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1214, 1087, 1043, 961, 850, 818. H NMR (400MHz,
DMSO-d6) δ 2.23 (s, 3H, CH3), 4.06 (s, 2H, CH2O), 4.60
(d, J=6.4Hz, 6H, (CH2O)3), 4.82 (s, 2H, CH2CO),
6.84–7.10 (m, 4H, Ar-H); MS (70eV): m/z: 328 (M+);
Anal. Calcd for C14H17O7P: C, 51.23; H, 5.22. Found: C,
50.94; H, 51.23.
4-[(4-Chloro-2-mehtyphenoxyl)acetyloxymethyl]-2,6,7-trioxa-
4-[(3-Mehthylphenoxyl)acetyloxymethyl]-2,6,7-trioxa-1-
phosphabicyclo[2.2.2]octane-1-one (4n).
Yellowish solid;
1-phosphabicyclo[2.2.2]octane-1-one (4h).
White solid;
yield, 12%; mp, 144–145°C; IR (KBr, cmÀ1): ν 1769,
yield, 71%; mp, 143–145°C; IR (KBr, cmÀ1): ν 1765,
1325, 1219, 1185, 1043, 962, 850, 822. 1H NMR
(400MHz, DMSO-d6) δ 2.19 (s, 3H, CH3), 4.07 (s, 2H,
CH2O), 4.62 (d, J=6.4Hz, 6H, (CH2O)3), 4.90 (s, 2H,
CH2CO), 6.91–7.26 (m, 3H, Ar-H); MS (70 eV): m/z:
362 (M+); Anal. Calcd for C14H16ClO7P: C, 46.36; H,
4.45. Found: C, 46.37; H, 4.57.
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1322, 1206, 1171, 1041, 966, 857. H NMR (400MHz,
DMSO-d6) δ 2.28 (s, 3H, CH3), 4.06 (s, 2H, CH2O), 4.59
(d, J = 6.4Hz, 6H, (CH2O)3), 4.84 (s, 2H, CH2CO),
6.78–7.19 (m, 4H, Ar-H); MS (70 eV): m/z: 328 (M+);
Anal. Calcd for C14H17O7P: C, 51.23; H, 5.22. Found: C,
51.09; H, 4.89.
4-[(4-Butylphenoxyl)acetyloxymethyl]-2,6,7-trioxa-1-
4-[(4-Chloro-3-methylphenoxy)acetyloxymethyl]-2,6,7-
trioxa-1-phosphabicyclo[2.2.2]octane-1-one (4i). Yellowish
solid; yield, 65%; mp, 122–123°C; IR (KBr, cmÀ1): ν
phosphabicyclo[2.2.2]octane-1-one (4o).
Yellowish solid;
yield, 21%; mp, 200–202°C; IR (KBr, cmÀ1): ν 1774,
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1325, 1204, 1188, 1047, 965, 852. H NMR (400MHz,
1766, 1324, 1244, 1168, 1044, 962, 849, 811. H NMR
DMSO-d6) δ 1.25 (s, 9H, (CH3)3), 4.05 (s, 2H, CH2O),
4.55 (d, J= 6.4Hz, 6H, (CH2O)3), 4.84 (s, 2H, CH2CO),
6.87–7.31 (m, 4H, Ar-H); MS (70 eV): m/z: 370 (M+);
Anal. Calcd for C17H23O7P: C, 55.13; H, 6.26. Found: C,
55.33; H, 5.93.
(400 MHz, DMSO-d6) δ 2.28 (s, 3H, CH3), 4.07 (s, 2H,
CH2O), 4.63 (d, J= 6.4Hz, 6H, (CH2O)3), 4.86 (s, 2H,
CH2CO), 6.75–7.33 (m, 3H, Ar-H); MS (70eV): m/z: 362
(M+); Anal. Calcd for C14H16ClO7P: C, 46.36; H, 4.45.
Found: C, 45.99; H, 4.54.
Biological activity testing. The preliminary herbicidal
activity of title compounds 4a–o was measured according
4-[(2-Chloro-4-fluorophenoxy)acetyloxymethyl]-2,6,7-trioxa-
1-phosphabicyclo[2.2.2]octane-1-one (4j). Yellowish solid;
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet