The Journal of Organic Chemistry
Note
6.7 Hz), 128. One (d, J = 2.9 Hz), 126.43(d, J = 2.8 Hz), 70.2 (d, J = 6.7
Hz), 34.6 (d, J = 139.2 Hz), 23.8 (d, J = 3.9 Hz), 23.5 (d, J = 4.8 Hz).
31P NMR (162 MHz, CDCl3): δ (ppm) 25.3. GC−MS (EI, 70 eV) m/z
= 256 (M+, 11), 214 (25), 199 (28), 173 (34), 172 (34), 123 (33), 119
(31), 92 (43), 91 (100), 65 (26), 59 (13). This compound is known.12
Benzyldiphenylphosphine Oxide (1d). This compound was
prepared according to general procedure A from diphenylphosphine
oxide (1.0 g, 4.95 mmol), sodium hydride (238 mg, 5.94 mmol, 60%
dispersion in mineral oil), and (bromomethyl)benzene (847 mg, 4.95
(methylsulfonyl)benzene (1.803 g, 7.24 mmol): yield 2.104 g (95%);
white solid; mp 64−65 °C. 1H NMR (400 MHz, CDCl3): δ (ppm) 7.85
(d, J = 8.0 Hz, 2H), 7.47 (dd, J1 = 8.0 Hz, J2 = 2.4 Hz, 2H), 4.02 (sextet,
J1 = 6.8 Hz, 4H), 3.20 (d, J = 22.4 Hz, 2H), 3.01 (s, 3H), 1.23 (t, J = 7.2
Hz, 6H). 13C NMR (100 MHz, CDCl3): δ (ppm) 139.0 (d, J = 3.9 Hz),
138.5 (d, J = 9.5 Hz), 130.6 (d, J = 5.7 Hz), 127.5 (d, J = 2.9 Hz), 62.3
(d, J = 6.7 Hz), 44.5, 33.8 (d, J = 136.3 Hz), 16.3 (d, J = 5.7 Hz). 31P
NMR (162 MHz, CDCl3): δ (ppm) 25.2. GC−MS (EI, 70 eV) m/z =
307 ([M + H]+, 3), 306 (M+, 22), 278 (31), 250 (18), 199 (12), 183
(9), 170 (71), 124 (71), 109 (52), 107 (100), 104 (79), 91 (45), 90
(54), 89 (43), 81 (40), 77 (21), 65 (14), 51 (5). This compound is
known.15
1
mmol): yield 1.389 g (96%); white solid; mp 190−192 °C. H NMR
(400 MHz, DMSO): δ (ppm) 7.81−7.76 (m, 4H), 7.50−7.45 (m, 6H),
7.14−7.11 (m, 5H), 3.87 (d, J = 14.0 Hz, 2H). 13C NMR (100 MHz,
DMSO): δ (ppm) 133.5 (d, J = 96.3 Hz), 132.3 (d, J = 7.6 Hz), 131.7,
130.8 (d, J = 9.6 Hz), 130.2 (d, J = 4.8 Hz), 128.6 (d, J = 11.5 Hz),
128.0, 126.4, 36.0 (d, J = 64.8 Hz). 31P NMR (162 MHz, DMSO): δ
(ppm) 28.7. GC−MS (EI, 70 eV) m/z = 293 ([M + H]+, 3), 292 (M+,
18), 291 (36), 202 (13), 201 (100), 183 (5), 152 (5), 91 (12), 77 (22),
65 (8). 51 (11). This compound is known.12
Diethyl (3-Bromobenzyl)phosphonate (1p). This compound was
prepared according to general procedure A from diethyl phosphite (1.0
g, 7.24 mmol), sodium hydride (348 mg, 8.69 mmol, 60% dispersion in
mineral oil), and 1-bromo-3-(bromomethyl)benzene (1.809 g, 7.24
1
mmol): yield 2.040 g (95%); colorless liquid. H NMR (400 MHz,
CDCl3): δ (ppm) 7.33−7.24 (m, 2H), 7.13−7.03 (m, 2H), 3.95−3.88
(m, 4H), 2.99 (d, J = 22.0 Hz, 2H), 1.14 (t, J = 7.2 Hz, 6H). 13C NMR
(100 MHz, CDCl3): δ (ppm) 133.8 (d, J = 8.6 Hz), 132.5 (d, J = 6.6
Hz), 129.8 (d, J = 2.9 Hz), 129.7 (d, J = 2.8 Hz), 128.2 (d, J = 6.7 Hz),
122.2 (d, J = 2.9 Hz), 62.0 (d, J = 6.7 Hz), 33.2 (d, J = 138.2 Hz), 16.2
(d, J = 5.7 Hz). 31P NMR (162 MHz, CDCl3): δ (ppm) 26.1. GC−MS
(EI, 70 eV) m/z = 308 (M+, 81Br, 26), 306 (M+, 79Br, 26), 280 (10), 278
(10), 252 (18), 250 (18), 227 (22), 199 (42), 198 (23), 196 (23), 171
(57), 169 (55), 124 (56), 117 (19), 109 (100), 97 (43), 96 (27), 93
(20), 91 (59), 90 (78), 89 (67), 81 (62), 65 (30), 63 (27). This
compound is known.16
Diethyl (4-Vinylbenzyl)phosphonate (1j). This compound was
prepared according to general procedure A from diethyl phosphite (1.0
g, 7.24 mmol), sodium hydride (348 mg, 8.69 mmol, 60% dispersion in
mineral oil), sodium iodide (108 mg, 0.72 mmol), and 1-
(chloromethyl)-4-vinylbenzene (1.104 g, 7.24 mmol): yield 1.711 g
(93%); colorless liquid. 1H NMR (400 MHz, CDCl3): δ (ppm) 7.33 (d,
J = 8.0 Hz, 2H), 7.23 (dd, J1 = 8.0 Hz, J2 = 2.8 Hz, 2H), 6.68 (dd, J1 =
10.8 Hz, J2 = 17.2 Hz, 1H), 5.72 (d, J = 17.2 Hz, 1H), 5.21 (d, J = 10.8
Hz, 1H), 4.04−3.94 (m, 4H), 3.12 (d, J = 22.0 Hz, 2H), 1.22 (t, J = 7.2
Hz, 6H). 13C NMR (100 MHz, CDCl3): δ (ppm) 136.3 (d, J = 1.9 Hz),
136.1 (d, J = 3.8 Hz), 131.0 (d, J = 9.6 Hz), 129.8 (d, J = 6.7 Hz), 126.3
(d, J = 2.9 Hz), 113.6, 62.1 (d, J = 6.7 Hz), 33.4 (d, J = 137.3 Hz), 16.3
(d, J = 5.7 Hz). 31P NMR (162 MHz, CDCl3): δ (ppm) 26.9. GC−MS
(EI, 70 eV) m/z = 255 ([M + H]+, 3), 254 (M+, 25), 226 (12), 198 (9),
144 (14), 131 (19), 118 (16), 117 (100), 115 (30), 109 (10), 91 (20),
81 (10). This compound is known.13
Diethyl (2-Bromobenzyl)phosphonate (1q). This compound was
prepared according to general procedure A from diethyl phosphite (1.0
g, 7.24 mmol), sodium hydride (348 mg, 8.69 mmol, 60% dispersion in
mineral oil), and 1-bromo-2-(bromomethyl)benzene (1.809 g, 7.24
1
mmol): yield 2.000 g (90%); colorless liquid. H NMR (400 MHz,
CDCl3): δ (ppm) 7.52 (d, J = 7.6 Hz, 1H), 7.43 (td. J = 2.0 Hz, J = 7.6
Hz, 1H), 7.22 (t, J = 7.6 Hz, 1H), 7.08−7.03 (m, 1H), 4.01 (sextet, J =
7.2 Hz, 4H), 3.37 (d, J = 22.0 Hz, 2H), 1.22 (t, J = 7.2 Hz, 6H). 13C
NMR (100 MHz, CDCl3): δ (ppm) 132.7 (d, J = 2.9 Hz), 131.7 (d, J =
8.6 Hz), 131.4 (d, J = 4.8 Hz), 128.3 (d, J = 2.8 Hz), 127.3 (d, J = 3.8
Hz), 124.7 (d, J = 8.6 Hz), 62.0 (d, J = 6.7 Hz), 33.3 (d, J = 138.2 Hz),
16.2 (d, J = 6.6 Hz). 31P NMR (162 MHz, CDCl3): δ (ppm) 25.8. GC−
MS m/z = 227 (M+ − Br, 58), 199 (23), 171 (100), 169 (17), 109 (11),
107 (12), 91 (15), 90 (25), 89 (23), 81 (16). This compound is
known.17
Diethyl (4-(Trifluoromethyl)benzyl)phosphonate (1k). This com-
pound was prepared according to general procedure A from diethyl
phosphite (1.0 g, 7.24 mmol), sodium hydride (348 mg, 8.69 mmol,
60% dispersion in mineral oil), and 1-(bromomethyl)-4-
(trifluoromethyl)benzene (1.730 g, 7.24 mmol): yield 2.037 g (95%);
colorless liquid. 1H NMR (400 MHz, CDCl3): δ (ppm) 7.39 (d, J = 8.0
Hz, 2H), 7.26 (d, J = 8.0 Hz, 2H), 3.91−3.83 (m, 4H), 3.03 (d, J = 22.8
Hz, 2H), 1.08 (t, J = 7.2 Hz, 6H). 13C NMR (100 MHz, CDCl3): δ
(ppm) 135.9 (d, J = 8.6 Hz), 129.9 (d, J = 6.7 Hz), 128.9 (qd, J1 = 32.4
Hz, J2 = 3.8 Hz), 125.2 (dd, J1 = J2 = 3.9 Hz), 124.0 (q, J = 270.7 Hz),
62.1 (d, J = 6.7 Hz), 33.5 (d, J = 137.2 Hz), 16.1 (d, J = 5.7 Hz). 31P
NMR (162 MHz, CDCl3): δ (ppm) 25.8. GC−MS (EI, 70 eV) m/z =
297 ([M + H]+, 3), 296 (M+, 18), 277 (12), 276 (15), 240 (30), 186
(11), 159 (81), 140 (68), 124 (40), 119 (11), 109 (100), 97 (34), 96
(27), 93 (13), 91 (28), 81 (43), 95 (16). This compound is known.12
Methyl 4-((Diethoxyphosphoryl)methyl)benzoate (1l). This com-
pound was prepared according to general procedure A from diethyl
phosphite (1.0 g, 7.24 mmol), sodium hydride (348 mg, 8.69 mmol,
60% dispersion in mineral oil), and methyl 4-(bromomethyl)benzoate
Diethyl (Naphthalen-2-ylmethyl)phosphonate (1r). This com-
pound was prepared according to general procedure A from diethyl
phosphite (1.0 g, 7.24 mmol), sodium hydride (348 mg, 8.69 mmol,
60% dispersion in mineral oil), and 2-(bromomethyl)naphthalene
1
(1.600 g, 7.24 mmol): yield 1.957 g (97%); yellow liquid. H NMR
(400 MHz, CDCl3): δ (ppm) 7.81−7.74 (m, 4H), 7.46−7.41 (m, 3H),
4.05−3.96 (m, 4H), 3.31 (d, J = 22.0 Hz, 2H), 1.23 (t, J = 7.2 Hz, 6H).
13C NMR (100 MHz, CDCl3): δ (ppm) 133.3 (d, J = 2.9 Hz), 132.3 (d,
J = 2.9 Hz), 129.1 (d, J = 9.5 Hz), 128.4 (d, J = 7.7 Hz), 128.1 (d, J = 2.0
Hz), 127.8 (d, J = 5.7 Hz), 127.6, 127.5, 126.1, 125.7, 62.2 (d, J = 7.7
Hz), 33.9 (d, J = 137.2 Hz), 16.4 (d, J = 5.7 Hz). 31P NMR (162 MHz,
CDCl3): δ (ppm) 27.0. GC−MS (EI, 70 eV) m/z = 279 ([M + H]+, 6),
278 (M+, 37), 250 (10), 168 (12), 155 (13), 142 (19), 141 (100), 139
(11), 115 (31). This compound is known.12
Diethyl ([1,1′-Biphenyl]-4-ylmethyl)phosphonate (1s). This com-
pound was prepared according to general procedure A from diethyl
phosphite (1.0 g, 7.24 mmol), sodium hydride (348 mg, 8.69 mmol,
60% dispersion in mineral oil), and 4-(bromomethyl)-1,1′-biphenyl
(1.789 g, 7.24 mmol): yield 2.131 g (97%); white solid; mp 59−60 °C.
1H NMR (400 MHz, CDCl3): δ (ppm) 7.50−7.45 (m, 4H), 7.36−7.22
(m, 5H), 4.00−3.91 (m, 4H), 3.10 (d, J = 21.6 Hz, 2H), 1.18 (t, J = 7.2
Hz, 6H). 13C NMR (100 MHz, CDCl3): δ (ppm) 140.6, 139.7 (d, J =
3.8 Hz), 130.6 (d, J = 8.6 Hz), 130.1 (d, J = 6.7 Hz), 128.7, 127.2, 127.1,
126.9, 62.2 (d, J = 6.7 Hz), 33.4 (d, J = 137.2 Hz), 16.44 (d, J = 5.7 Hz).
31P NMR (162 MHz, CDCl3): δ (ppm) 27.1. GC−MS (EI, 70 eV) m/z
= 305 ([M + H]+, 6), 304 (M+, 40), 276 (11), 181 (12), 168 (17), 167
(100), 165 (28), 152 (15). This compound is known.18
1
(1.658 g, 7.24 mmol): yield 1.950 g (94%); yellow liquid. H NMR
(400 MHz, CDCl3): δ (ppm) 7.86 (d, J = 8.0 Hz, 2H), 7.26 (dd, J1 = 2.0
Hz, J2 = 8.0 Hz, 2H), 3.94−3.88 (m, 4H), 3.78 (s, 3H), 3.09 (d, J = 22.0
Hz, 2H), 1.12 (t, J = 6.8 Hz, 6H). 13C NMR (100 MHz, CDCl3): δ
(ppm) 166.7, 137.1 (d, J = 8.6 Hz), 129.7 (d, J = 6.7 Hz), 129.6, 128.7
(d, J = 2.9 Hz), 62.2 (d, J = 6.7 Hz), 52.0, 33.9 (d, J = 136.3 Hz), 16.3
(d, J = 5.8 Hz). 31P NMR (162 MHz, CDCl3): δ (ppm) 25.9. GC−MS
(EI, 70 eV) m/z = 287 ([M + H]+, 5), (286 (m+, 33), 271 (5), 255
(33), 254 (42), 243 (13), 230 (37), 227 (24), 226 (44), 225 (11), 199
(31), 198 (15), 181 (21), 176 (31), 163 (43), 150 (68), 149 (89), 135
(22), 124 (100), 121 (53), 119 (16), 118 (94), 109 (80), 107 (24), 97
(59), 96 (11), 91 (62), 90 (82), 89 (51), 81 (52), 77 (21), 65 (20), 63
(17). This compound is known.14
Diethyl (4-(Methylsulfonyl)benzyl)phosphonate (1o). This com-
pound was prepared according to general procedure A from diethyl
phosphite (1.0 g, 7.24 mmol), sodium hydride (348 mg, 8.69 mmol,
60% dispersion in mineral oil), and 1-(bromomethyl)-4-
D
J. Org. Chem. XXXX, XXX, XXX−XXX