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New Journal of Chemistry
Page 6 of 9
ARTICLE
Journal Name
(E)-Diisopropyl 4-(trifluoromethoxy)styrylphosphonate (3l, Table 2) 23c
(158 mg, 90%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.51-7.37 (m, 3H),
:
P
DOI: 10.1039/C6NJ02247B
7.21-7.19 (m, 2H), 6.23 (t, J = 17.1 Hz, 1H), 4.73-4.66 (m, 2H), 1.35 (d, J = JC-P = 9.7 Hz), 128.5 (d, JC-P = 12.0 Hz), 124.6 (d, JC-P = 18 Hz), 120.0 (d,
6.3 Hz, 6H), 1.30 (d, J = 5.7 Hz, 6H); 13C NMR (75 MHz, CDCl3): δ (ppm) JC-P = 103.5 Hz), 116.6, 113.5, 112.5, 56.0, 55.8; 31P NMR (162 MHz,
150.3, 146.0 (d, JC-P = 6.7 Hz), 133.8 (d, JC-P = 24 Hz), 129.2, 122.2,
121.2, 118.8, 117.1 (d, JC-P = 191.2 Hz), 70.7 (d, JC-P = 5.2 Hz), 24.1 (d, JC-
P = 4.5 Hz); 31P NMR (162 MHz, CDCl3) δ 16.4.
CDCl3) δ 25.0.
(E)-Diethyl 4-(benzyloxy)-3-methoxystyrylphosphonate (3t, Table 2):
(144 mg, 77%). Gummy liquid. IR (neat)/cm-1: 3458, 2981, 1598, 1512,
1267, 1244, 1139, 1026; 1H NMR (300 MHz, CDCl3): δ (ppm) 7.38-7.27 (m,
(E)-Diisopropyl 2-bromostyrylphosphonate (3m, Table 2): (148 mg,
86%). Gummy Liquid. IR (neat)/cm-1 : 3456, 2977, 1612, 1247, 1107, 983; 3H), 7.25-7.17 (m, 2H), 6.94-6.88 (m, 2H), 6.76 (d, J = 8.1 Hz, 1H), 5.98 (t,
1H NMR (400 MHz, CDCl3): δ (ppm) 7.75 (dd, J = 17.6Hz, 22.4 Hz, 1H),
J = 17.4 Hz, 1H), 5.07 (s, 2H), 4.08-3.95 (m, 4H), 3.80 (s, 3H), 1.24 (t, J =
7.58-7.53 (m, 2H), 7.32-7.16 (m, 2H), 6.24 (t, J = 17.2 Hz, 1H), 4.72 7.2 Hz, 6H) ; 13C NMR (75 MHz, CDCl3): δ (ppm) 150.0 (d, JC-P = 27.7 Hz),
(sextet, J = 6.4 Hz, 2H), 1.37-1.32 (m, 12H); 13C NMR (100 MHz, CDCl3): δ 148.6 (d, JC-P = 6.7 Hz), 136.7, 128.7, 128.5, 128.1, 128.0, 127.2, 121.9,
(ppm) 145.6 (d, JC-P = 8 Hz), 135.3 (d, JC-P = 23 Hz), 133.4, 131.0, 130.1, 113.1 (d, JC-P = 60 Hz), 110.1, 70.9, 61.8 (d, JC-P = 5.2 Hz), 56.0, 16.4 (d,
128.9, 127.7 (d, JC-P = 10 Hz), 124.9, 119.5 (d, JC-P = 190 Hz), 70.9, 70.8,
JC-P =
6 Hz); 31P NMR (202 MHz, CDCl3) δ 20.8. HRMS: m/z calcd for
70.6, 24.2, 24.2, 24.1, 24.1; 31P NMR (202 MHz, CDCl3) δ 17.1. HRMS: C20H26O5P: 377.1512 [M+H]+; found: 377.1038.
m/z calcd for C14H20BrO3P: 369.0226 [M+Na]+; found: 369.0232.
(E)-Dec-1-en-1-yldiphenylphosphine oxide (3u, Table 2) : (60%) Gummy
(E)-Diisopropyl 4-bromostyrylphosphonate (3n, Table 2) 23a: (138 mg, Liquid. IR (neat/cm-1) : 3415, 2872, 2822, 2715, 1514, 1433; 1H NMR(500
80%). 1H NMR (500 MHz, CDCl3): δ (ppm) 7.47 (d, J = 8 Hz, 2H), 7.41- MHz, CDCl3 ): δ (ppm) 7.73-7.68 (m, 4H), 7.52-7.43 (m, 4H), 6.73-6.62 (m,
7.31 (m, 3H), 6.23 (t, J = 17 Hz, 1H), 4.71-4.66 (m, 2H), 1.33 (d, J = 6.5 1H), 6.10 (dd, J = 12.5 Hz, 51.5 Hz, 1H), 2.51 (q, J = 7.5 Hz, 2H), 2.26-
Hz, 6H), 1.29 (d, J = 6 Hz, 6H); 13C NMR (125 MHz, CDCl3): δ(ppm) 146.2 2.14 (m, 1H), 1.40-1.16 (m, 21H), 0.86 (t, J = 7 Hz, 4H); 13 C NMR (100
(d, JC-P = 6.2 Hz), 134.0 (d, JC-P = 23.7 Hz), 132.1, 129.2, 124.2, 116.7 (d,
MHz, CDCl3 ): δ (ppm) 155.3, 134.7 (d, J
= 103 Hz), 131.7, 131.6,
C-P
JC-P = 191.2 Hz), 70.6 (d, JC-P = 6.2 Hz), 24.1 (d, JC-P = 3.7 Hz), 24.0 (d, JC- 131.6, 131.5, 131.4, 131.1, 131.0, 128.7, 128.6, 121.4 (d, JC-P = 100 Hz),
P = 3.7 Hz); 31P NMR (202 MHz, CDCl3) δ 17.2.
32.0, 31.1, 31.0, 29.9, 29.8, 29.6, 29.5, 29.5, 29.4, 29.3, 28.9, 22.8, 14.2;
31P NMR (202 MHz,CDCl3 ) δ 21.8. HRMS: m/z calcd for C22H29OP:
341.2029 [M+H] + ; found: 341.2024.
(E)-(4-(Tert-butyl)styryl)diphenylphosphine oxide (3o, Table 2) 23a: (160
mg, 89%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.78-7.71 (m, 4H), 7.54-
7.37 (m, 11H), 6.79 (dd, J = 17.4 Hz, 22.5 Hz, 1H), 1.30 (s, 9H); 13C NMR
(75 MHz, CDCl3): δ (ppm) 153.7, 147.5 (d, JC-P = 4.5 Hz), 133.2 (d, JC-P
94.5 Hz), 132.4 (d, JC-P = 7.5 Hz), 131.8 (d, JC-P = 2.2 Hz), 131.4 (d, JC-P
(4-Methoxyphenyl)diphenylphosphine oxide (4a, Table 3) 23k: (120 mg,
78%). 1H NMR (300 MHz, CDCl3): (ppm) 7.68-7.60 (m, 4H), 7.58-7.50
(m, 4H), 7.47-7.41 (m, 4H), 6.96 (dd, J = 8.8 Hz, 2.1 Hz, 2H), 3.83 (s, 3H);
=
=
2.2 Hz), 128.6 (d, JC-P = 12 Hz), 127.6, 125.8, 118.1 (d, JC-P = 105Hz),
34.8, 31.2 ; 31P NMR (202 MHz, CDCl3) δ 25.5.
13C NMR (100 MHz, CDCl3): δ (ppm) 162.6 (d, JC-P = 3 Hz), 134.0 (d, JC-P
=
12 Hz), 133.0 (d, JC-P = 104 Hz), 132.1 (d, JC-P = 10 Hz), 131.9 (d, JC-P = 2
Hz), 128.5 (d, JC-P = 12.0 Hz), 123.6 (d, JC-P = 110.0 Hz), 114.2 (d, JC-P
14 Hz); 31P NMR (162 MHz, CDCl3): δ(ppm) 29.1.
=
Diethyl ((1E, 3E)-4-(4-fluorophenyl)buta-1,3-dien-1-yl)phosphonate
(3p, Table 2): (123 mg, 87%). Gummy liquid, IR (neat)/cm-1: 3514, 3454,
3267, 2983, 2933, 1218, 771; 1H NMR (300 MHz, CDCl3): δ (ppm) 7.42- Diphenyl(pyridin-2-yl)phosphine oxide (4b, Table 3) 23f: (118 mg, 85%).
7.37 (m, 2H), 7.25-7.17 (m, 1H), 7.05-6.99 (m, 2H), 6.81-6.67 (m, 2H), 5.77 1H NMR (300 MHz, CDCl3): δ (ppm) 8.62 (d, J = 4.8 Hz, 1H), 8.20-8.16 (m,
(dd, J = 16.8 Hz, 18.9 Hz, 1H), 4.08 (quintet, J = 6.9 Hz, 4H), 1.32 (t, J = 1H), 7.83-7.76 (m, 4H), 7.70-7.64 (m, 1H), 7.39-7.22 (m, 7H); 13C NMR (75
7.5 Hz, 6H); 13C NMR (75 MHz, CDCl3): δ (ppm) 164.8, 161.5, 148.5 (d, JC- MHz, CDCl3): δ (ppm) 156.0 (d, JC-P = 130.5 Hz), 149.8 (d, JC-P = 18.7 Hz),
= 6 Hz), 138.4, 132.2, 128.9, 128.8, 127.0 (d, JC-P = 24.7 Hz), 118.4,
135.9 (d, JC-P = 8.2 Hz), 132.6, 132.3 (d, JC-P = 2.2 Hz), 131.8 (d, JC-P = 9
P
116.1, 115.8, 115.8, 61.8 (d, JC-P = 5.2 Hz), 16.4 (d, JC-P = 6 Hz); 31P NMR Hz), 131.6 (d, JC-P = 2.2 Hz), 131.2, 130.4 (d, JC-P = 10.5 Hz), 128.6 (d, JC-P
(202 MHz, CDCl3) δ 19.7. HRMS: m/z calcd for C14H19FO3P: 285.1050 = 13.5 Hz), 128.1 (d, JC-P = 12 Hz), 127.9, 125.0 (d, JC-P = 2.2 Hz); 31P
[M+H]+; found: 285.1053.
NMR (202 MHz, CDCl3): δ(ppm) 21.5.
(E)-Diphenyl(2-(thiophen-3-yl)vinyl)phosphine oxide (3q, Table 2): (108 Diisopropyl pyridin-3-ylphosphonate (4c, Table 3) 23g: (100 mg, 83%).
mg, 88%). Brownish solid, m.p 158 -160 oC, IR (KBr)/cm-1 : 3434, 2997,
1H NMR (500 MHz, CDCl3): δ (ppm) 8.97 (d, J = 4.8 Hz, 1H), 8.75 (s, 1H),
2923, 1436, 1180; 1H NMR (300 MHz, CDCl3): δ (ppm) 7.75-7.68 (m, 4H), 8.16-8.08 (m, 1H), 7.42-7.39 (m 1H), 4.79-4.69 (m, 2H), 1.38 (d, J = 6.3
7.52-7.37 (m, 8H), 7.28-7.27 (m, 2H), 6.60 (dd, J = 17.1 Hz, 22.3 Hz, 1H); Hz, 6H), 1.25 (d, J = 6.3 Hz, 6H); 13C NMR (75 MHz, CDCl3): δ (ppm)
13C NMR (75 MHz, CDCl3): δ (ppm) 141.1 (d, JC-P = 3.7 Hz), 138.5 (d, JC-P 152.7, 152.3 (d, JC-P = 12 Hz), 139.5 (d, JC-P = 8 Hz), 127.7, 125.7, 123.4
= 18.7 Hz), 133.0 (d, JC-P = 105 Hz), 131.8 (d, JC-P = 2.2 Hz), 131.4 (d, JC-P (d, JC-P = 11 Hz), 71.5 (d, JC-P = 5 Hz), 24.2 (d, JC-P = 5 Hz); 31P NMR (202
= 10.5 Hz), 128.6 (d, JC-P = 12 Hz), 127.4, 126.9, 125.1, 118.6 (d, JC-P
=
MHz, CDCl3): δ(ppm) 13.0.
105 Hz); 31P NMR (162 MHz, CDCl3) δ 24.7. HRMS: m/z calcd for
C18H16OPS: 311.0654 [M+H]+; found: 311.0653.
(E)-Tetraisopropyl
(diazene-1,2-diylbis(4,1-
phenylene))bis(phosphonate) (4d, Table 3): (193 mg, 76 %). Orange
(E)-(2-(Furan-2-yl)vinyl)diphenylphosphine oxide (3r, Table 2)23b: (132 liquid. IR (neat)/cm-1: 3413, 2979, 2917, 1735, 1248, 1177, 998, 772; 1H
mg, 90%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.73-7.69 (m, 4H), 7.53- NMR (400 MHz, CDCl3): δ (ppm) 7.99-7.97 (m, 8H), 4.74 (q, J = 6.4 Hz,
7.41 (m, 7H), 7.33-7.20 (m, 1H), 6.71 (dd, J = 17.1 Hz, 23.1 Hz, 1H), 6.51 4H), 1.39 (d, J = 6.4 Hz, 12H), 1.25 (d, J = 6.4 Hz, 12H); 13C NMR (100
(d, J = 3.6 Hz, 1H), 6.43 (dd, J = 1.8 Hz, 3.6 Hz, 1H); 13C NMR (75 MHz,
CDCl3): δ (ppm) 151.5 (d, JC-P = 20.2 Hz), 144.4, 134.0 (d, JC-P = 4.5 Hz),
MHz, CDCl3): δ (ppm) 133.0, 132.8, 123.0, 122.8, 71.3, 71.2, 24.2, 24.2,
24.0, 23.9; 31P NMR (202 MHz, CDCl3) δ 15.2. . HRMS: m/z calcd for
133.8, 132.4, 131.6 (d, JC-P = 3 Hz), 131.4 (d, JC-P = 10.5 Hz), 128.6 (d, JC- C24H36N2O6P2: 533.1941 [M+Na]+; found: 533.4996.
= 12 Hz), 116.6 (d, JC-P = 105.7 Hz), 113.8, 112.2; 31P NMR (162 MHz,
P
Diisopropyl (4-nitrophenyl)phosphonate (4e, Table 3) 23h: (127 mg,
CDCl3) δ 24.3.
89%). 1H NMR (300 MHz, CDCl3): δ(ppm) 8.26 (dd, J = 3 Hz, 8.8 Hz, 2H),
7.98 (dd, J = 8.7 Hz, 12.6 Hz, 2H), 4.76-4.70 (m, 2H), 1.37 (d, J = 6.3 Hz,
(E)-(2,5-Dimethoxystyryl)diphenylphosphine oxide (3s, Table 2)23b
(160 mg, 88%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.79-7.66 (m, 5H), 6H), 1.22 (d, J = 6.3 Hz, 6H); 13C NMR (75 MHz, CDCl3): δ (ppm) 150.2,
:
7.51-7.39 (m, 6H), 7.03 (d, J = 3 Hz, 1H), 6.97-6.77 (m, 3H), 3.73 (s, 3H),
137.5 (d, JC-P = 186.7 Hz), 133.4 (d, JC-P = 9.7 Hz), 123.3 (d, JC-P = 15 Hz),
6 | J. Name., 2012, 00, 1-3
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