W. Wang et al. / Journal of Fluorine Chemistry 193 (2017) 8–16
13
4.6. General procedure for synthesis compounds III-1–24
113.72, 114.03 (d, J = 8.9 Hz), 117.29 (d, J = 25.9 Hz), 123.35, 150.64,
1
156.31(d, JC-F = 240.5 Hz), 171.67; 19FNMR (376 MHz, CDCl3):
d
Following the procedure described for II-1–II-4, compounds III-
1–III-24 were obtained. Their structures were confirmed by 1H
NMR, 13C NMR, 31P NMR, 19F NMR, IR, MS and elemental analysis.
And the physicochemical properties and spectroscopic data for all
of the title compounds III-1–24 are as follows.
ꢂ122.44; 31P NMR (160 MHz, CDCl3):
d 22.48; MS (EI) (m/z): 368
(M+); Anal. Calcd for C14H19ClFO6P: C, 45.60; H, 5.19; Found: C,
45.87; H, 5.30.
4.6.5. O,O-Dimethyl(4-fluorophenoxybutyryloxy)(phenyl)
methylphosphonate (III-5)
20
4.6.1. O,O-Dimethyl(4-fluorophenoxybutyryloxy)(methyl)
Oil; nD 1.5228; yield 74%; IR (KBr): 3365, 2955, 1743(C O),
¼
methylphosphonate (III-1)
1656, 1603, 1571, 1506, 1452, 1248, 1208, 1046, 948, 830 cmꢂ1;1H
NMR (600 MHz, CDCl3): 2.11–2.14 (m, 2H, CO2CH2CH2CH2), 2.63–
20
Oil; yield 81%; nD 1.5110; IR (KBr): 3396, 2962, 1744(C
¼
O),
d
1656, 1567, 1442, 1378, 1326, 1291, 1242, 1174, 1126, 1037, 939,
2.70 (m, 2H, CO2CH2CH2CH2), 3.63 (d, 3H, J = 10.8 Hz, PꢂꢂOꢂꢂCH3),
762 cmꢂ1 1H NMR (400 MHz, CDCl3):
;
d
1.47 (dd, 3H, J = 8.6 Hz,
3.70 (d, 3H, J = 10.8 Hz, PꢂꢂOꢂꢂCH3), 3.94 (m, 2H, CO2CH2CH2CH2),
J = 20.6 Hz, PꢂꢂCHꢂꢂCH3), 2.08–2.14 (m, 2H, CO2CH2CH2CH2), 2.59
(t, 2H, J = 7.2 Hz, CO2CH2CH2CH2), 3.77 (d, 3H, J = 6.4 Hz,
PꢂꢂOꢂꢂCH3), 3.80 (d, 3H, J = 6.0 Hz, PꢂꢂOꢂꢂCH3), 3.97 (t, 2H,
J = 6.0 Hz, CO2CH2CH2CH2), 5.30–5.35 (m,1H, PꢂꢂCH), 6.80-6.83 (m,
2H, 2,6H-Ph), 6.94–6.98 (m, 2H, 3,5H-Ph); 13CNMR (100 MHz,
6.19 (d, 1H, J = 13.2 Hz, PꢂꢂCH), 6.76–7.48 (m, 9H); 13CNMR
1
(100 MHz, CDCl3):
d
24.50, 30.59, 53.74, 66.86, 69.99 (d, JC-
P = 168.8 Hz), 115.27 (d, J = 7.7 Hz), 115.69 (d, J = 22.9 Hz), 127.72 (d,
J = 5.2 Hz), 128.59, 128.84, 133.02, 154.74, 157.15 (d, 1JC-F = 236.6 Hz),
171.51; 19FNMR (376 MHz, CDCl3):
d
ꢂ124.94; 31P NMR (160 MHz,
CDCl3):
d
14.94, 24.39, 30.45, 53.15, 63.90 (d,1JC-P = 169.8 Hz), 66.82,
CDCl3): d 18d
18.68; MS (EI) (m/z): 396 (M+); Anal. Calcd for
1
115.18 (d, J = 7.6 Hz), 115.61 (d, J = 22.8 Hz), 154.68, 156.44 (d, JC-
C19H22FO6P: C, 57.58; H, 5.59; Found: C, 57.14; H, 5.42.
F = 236.6 Hz), 171.76; 19FNMR (376 MHz, CDCl3):
NMR (160 MHz, CDCl3):
d
ꢂ124.94; 31P
d
22.54; MS (EI) (m/z): 334 (M+); Anal.
4.6.6. O,O-Dimethyl(3-trifluoromethylphenoxybutyryloxy)(phenyl)
Calcd for C14H20FO6P: C, 50.30; H, 6.03; Found: C, 50.20; H, 6.10.
methylphosphonate (III-6)
20
Oil; nD 1.5025; yield 75%; IR (KBr): 3416, 2954, 1743(C
¼
O),
1H NMR
d 2.15–2.19 (m, 2H, CO2CH2CH2CH2), 2.66–2.71
4.6.2. O,O-Dimethyl(3-trifluoromethylphenoxybutyryloxy)(methyl)
1652, 1570, 1452, 1397, 1330, 1166, 1049, 959, 884 cmꢂ1
(600 MHz, CDCl3):
;
methylphosphonate 5 (III-2)
20
Oil; yield 74%; nD 1.5231; IR (KBr): 3406, 2958, 1744(C
¼
O),
(m, 2H, CO2CH2CH2CH2), 3.63 (d, 3H, J = 10.8 Hz, PꢂꢂOꢂꢂCH3), 3.70
1656, 1592, 1452, 1378, 1330, 1291, 1242, 1168, 1126, 1037, 962,
(d, 3H, J = 10.8 Hz, PꢂꢂOꢂꢂCH3), 4.02 (m, 2H, CO2CH2CH2CH2), 6.20
786 cmꢂ1;1H NMR (400 MHz, CDCl3):
d
1.47 (dd, 3H, J = 7.2 Hz,
(d, 1H, J = 13.8 Hz, PꢂꢂCH), 6.99–7.49 (m, 9H); 13CNMR (100 MHz,
1
J = 17.2 Hz, PꢂꢂCHꢂꢂCH3), 2.12–2.19 (m, 2H, CO2CH2CH2CH2), 2.60
(t, 2H, J = 7.6 Hz, CO2CH2CH2CH2), 3.77 (d, 3H, J = 6.4 Hz,
PꢂꢂOꢂꢂCH3), 3.80 (d, 3H, J = 4.8 Hz, PꢂꢂOꢂꢂCH3ꢂꢂCH3), 4.05 (t,
2H, J = 6.4 Hz, CO2CH2CH2CH2), 5.31-5.35 (m, 1H, PꢂꢂCH), 7.04–7.41
CDCl3):
d
24.50, 30.59, 53.80, 66.56, 70.07 (d, JC-P = 169.2 Hz),
1
111.08, 117.43, 117.88, 125.56 (q, JC-F = 270.5 Hz), 127.77, 128.62,
2
128.89, 129.93 (q, JC-F = 32.3 Hz), 132.99, 155.61, 158.75, 171.49;
19FNMR (376 MHz, CDCl3):
d
ꢂ63.70; 31P NMR (160 MHz, CDCl3):
d
(m, 4H, 2,4,5,6H-Ph); 13CNMR (100 MHz, CDCl3):
d
14.80, 24.16,
18.68; MS (EI) (m/z): 446 (M+); Anal. Calcd for C20H22F3O6P: C,
30.24, 53.00, 63.86 (d, 1JC-P = 169.5 Hz), 66.43, 110.91, 117.14, 117.66,
53.82; H, 4.97; Found: C, 53.84; H, 5.02.
123.73 (q, 1JC-F = 270.5 Hz), 129.79, 131.43(q, 2JC-F = 32.0 Hz), 158.64,
171.48; 19FNMR (376 MHz, CDCl3):
d
ꢂ63.63; 31P NMR (160 MHz,
4.6.7. O,O-Dimethyl(4-chloro-2-fluorophenoxybutyryloxy)(phenyl)
CDCl3):
d
22.49; MS (EI) (m/z): 384 (M+); Anal. Calcd for
methylphosphonate (III-7)
20
C15H20F3O6P: C, 46.88; H, 5.25; Found: C, 47.05; H, 5.17.
Oil; nD 1.5319; yield 78%; IR (KBr): 3412, 2953, 1741(C O),
¼
1656, 1572, 1472, 1450, 1399, 1305, 1265, 1193, 1132, 1050, 949, 894,
4.6.3. O,O-Dimethyl(4-chloro-2-fluorophenoxybutyryloxy)(methyl)
methylphosphonate (III-3)
860, 803, 700 cmꢂ1;1H NMR (600 MHz, CDCl3):
d
2.13–2.18 (m, 2H,
CO2CH2CH2CH2), 2.65–2.73 (m, 2H, CO2CH2CH2CH2), 3.64 (d, 3H,
J = 10.8 Hz, PꢂꢂOꢂꢂCH3), 3.70 (d, 3H, J = 10.8 Hz, PꢂꢂOꢂꢂCH3), 4.03
(m, 2H, CO2CH2CH2CH2), 6.19 (d, 1H, J = 13.2 Hz, PꢂꢂCH), 6.82–7.48
20
Oil; yield 78%; nD 1.5155; IR (KBr): 3030, 2980, 2860, 1745
(C
CDCl3):
¼
O), 1580, 1260, 1170, 1060, 810 cmꢂ1 1H NMR (400 MHz,
;
d
1.47 (dd, 3H, J = 7.2 Hz, J = 10.8 Hz, PꢂꢂCHCH3), 2.13–2.20
(m, 8H); 13CNMR (100 MHz, CDCl3):
d
24.36, 30.32, 53.76, 68.04,
1
(m, 2H, CO2CH2CH2CH2), 2.65 (t, 2H, J = 7.2 Hz, CO2CH2CH2CH2),
3.77 (d, 3H, J = 8.8 Hz, PꢂꢂOꢂꢂCH3), 3.80 (d, 3H, J = 8.8 Hz,
PꢂꢂOꢂꢂCH3), 4.05 (t, 2H, J = 7.8 Hz, CO2CH2CH2CH2), 5.31–5.33
(m, 1H, PꢂꢂCH), 6.85–7.14 (m, 3H, 3,5,6H-Ph); 13CNMR (100 MHz,
70.07 (d, JC-P = 164.6 Hz), 115.54, 116.90 (d, J = 21.7 Hz), 124.16,
126.60 (d, J = 8.8 Hz), 127.72 (d, J = 5.5 Hz), 128.58, 128.84, 132.98,
143.95 (d, J = 9.8 Hz), 152.67 (d, JC-F = 249.2 Hz), 171.39; 19FNMR
1
(376 MHz, CDCl3):
d
ꢂ123.04; 31P NMR (160 MHz, CDCl3):
d 18.68;
CDCl3):
d
14.92, 24.26, 30.21, 53.14, 63.95 (d, 1JC-P = 170.3 Hz), 68.08,
MS (EI) (m/z): 430 (M+); Anal. Calcd for C19H21ClFO6P: C, 52.97; H,
113.72, 114.02 (d, J = 8.9 Hz), 117.15 (d, J = 21.7 Hz), 123.40, 150.64,
4.91; Found: C, 52.71; H, 4.88.
1
156.31 (d, JC-F = 244.1 Hz), 171.67; 19FNMR (376 MHz, CDCl3):
d
ꢂ122.51; 31P NMR (160 MHz, CDCl3):
d
22.49; MS (EI) (m/z): 368
4.6.8. O,O-Dimethyl(2-chloro-4-fluorophenoxybutyryloxy)(phenyl)
(M+); Anal. Calcd for C14H19ClFO6P: C, 45.60; H, 5.19; Found: C,
methylphosphonate (III-8)
20
45.76; H, 5.53.
Oil; nD 1.5261;yield 80%; IR (KBr): 3396, 2956, 1744(C O),
¼
1657, 1600, 1572, 1495, 1452, 1398, 1261, 1193, 1052, 950, 905, 860,
4.6.4. O,O-Dimethyl(2-chloro-4-fluorophenoxybutyryloxy)(methyl)
methylphosphonate (III-4)
803, 769 cmꢂ1 1H NMR (600 MHz, CDCl3):
;
d
2.14–2.19 (m, 2H,
CO2CH2CH2CH2), 2.69–2.77 (m, 2H, CO2CH2CH2CH2), 3.64 (d, 3H,
J = 10.8 Hz, PꢂꢂOꢂꢂCH3), 3.70 (d, 3H, J = 10.8 Hz, PꢂꢂOꢂꢂCH3), 3.99–
4.04 (m, 2H, CO2CH2CH2CH2), 6.19 (d, 1H, J = 13.2 Hz, PꢂꢂCH), 6.81-
20
Oil; yield 76%; nD 1.5161; IR (KBr): 3030, 2980, 2860, 1745
(C
CDCl3):
¼
O), 1580, 1260, 1170, 1060, 810 cmꢂ1 1H NMR (400 MHz,
;
d
1.47 (dd, 3H, J = 7.2 Hz, J = 17.2 Hz, PꢂꢂCHCH3), 2.13–2.20
7.48 (m, 8H); 13CNMR (100 MHz, CDCl3):
d 24.38, 30.32, 53.80,
(m, 2H, CO2CH2CH2CH2), 2.65 (t, 2H, J = 7.2 Hz, CO2CH2CH2CH2),
3.77 (d, 3H, J = 8.8 Hz, PꢂꢂOꢂꢂCH3), 3.80 (d, 3H, J = 8.8 Hz,
PꢂꢂOꢂꢂCH3), 4.04 (t, 2H, J = 6.0 Hz, CO2CH2CH2CH2), 5.32–5.33
(m, 1H, PꢂꢂCH), 6.85–7.14 (m, 3H, 3,5,6H-Ph); 13CNMR (100 MHz,
68.12, 70.05 (d, 1JC-P = 168.9 Hz), 113.81, 114.17 (d, J = 8.5 Hz), 117.31,
1
117.56, 127.71, 128.57, 128.82, 133.02, 150.74, 156.44 (d, JC-
F = 240.9 Hz), 171.47; 19FNMR (376 MHz, CDCl3):
d
ꢂ124.94; 31P
NMR (160 MHz, CDCl3):
d
18.63; MS (EI) (m/z): 430 (M+); Anal.
CDCl3):
d
14.92, 24.26, 30.21, 53.14, 63.95 (d, 1JC-P = 169.7 Hz), 68.08,
Calcd for C19H21ClFO6P: C, 52.97; H, 4.91; Found: C, 52.65; H, 5.08.