The Journal of Organic Chemistry
Note
H), 7.67−7.62 (m, 5 H), 7.58−7.54 (m, 2 H), 7.49−7.45 (m, 4 H).
13C NMR (100 MHz, CDCl3): δ 148.1 (d, J = 14.1 Hz), 137.7 (d, 9.5
Hz), 136.0 (d, J = 100.8 Hz), 132.6 (d, J = 2.8 Hz), 132.0 (d, J = 9.9
Hz), 131.1 (d, J = 106.0 Hz), 129.9 (d, J = 11.7 Hz), 128.9 (d, J = 12.6
Hz), 126.7 (d, J = 12.0 Hz), 126.6. 31P NMR (162 MHz, CDCl3): δ
27.3. MS-ESI: m/z 324.1, [M + H]+.
11.9 Hz), 118.0 (d, J = 115.5 Hz), 111.1 (d, J = 12.5 Hz), 39.8. 31P
NMR (162 MHz, CDCl3): δ 29.7. MS-ESI: m/z 365.1, [M + H]+.
Bis(benzo[d][1,3]dioxol-5-yl)(phenyl)phosphine Oxide (3u). Col-
orless oil; 172 mg, 94% yield. IR (film): 3427, 2901, 1479, 1422, 1242,
1036, 930, 704. 1H NMR (400 MHz, CDCl3): δ 7.66−7.44 (m, 4 H),
7.28−7.03 (m, 5 H), 6.87−6.85 (m, 2 H), 5.99 (s, 4 H). 13C NMR
(100 MHz, CDCl3): δ 150.9 (d, J = 2.4 Hz), 148.0 (d, J = 18.2 Hz),
132.8 (d, J = 105.4 Hz), 132.0 (d, J = 10.3 Hz), 128.5 (d, J = 12.1 Hz),
127.6 (d, J = 11.0 Hz), 127.5 (d, J = 11.4 Hz), 125.8 (d, J = 108.5 Hz),
111.5 (d, J = 12.6 Hz), 108.7 (d, J = 15.0 Hz), 101.7. 31P NMR (162
MHz, CDCl3): δ 29.4. HRMS calcd for C20H15O5P(M + Na)+,
389.0554; found, 389.0555.
3-(Diphenylphosphoryl)benzoic Acid (3m) (CAS no: 2129-29-5).
1
White solid; 134 mg, 83% yield. H NMR (400 MHz, DMSO): δ
8.22−8.19 (m, 2 H), 7.83−7.81 (m, 1 H), 7.63−7.60 (m, 7 H), 7.58−
7.49 (m, 4 H). 13C NMR (100 MHz, DMSO): δ 166.9, 136.1 (d, J =
11.2 Hz), 134.0 (d, J = 101.4 Hz), 133.1, 132.7 (d, J = 2.6 Hz), 132.5
(d, J = 10.6 Hz), 132.1, 132.0 (d, J = 10.0 Hz), 131.6 (d, J = 11.5 Hz),
129.8 (d, J = 11.7 Hz), 129.3 (d, J = 11.9 Hz). 31P NMR (162 MHz,
DMSO): δ 25.3. MS-ESI: m/z 323.1, [M + H]+.
Diphenyl(thiophen-2-yl)phosphine Oxide (3n) (CAS no: 56966-
27-9). Colorless oil; 115 mg, 81% yield. 1H NMR (400 MHz, CDCl3):
δ 7.74−7.69 (m, 5 H), 7.55−7.51 (m, 2 H), 7.47−7.43 (m, 5 H),
7.18−7.16 (m, 1 H). 13C NMR (100 MHz, CDCl3): δ 137.0 (d, J =
10.3 Hz), 134.1 (d, J = 112.0 Hz), 134.0 (d, J = 5.9 Hz), 133.0 (d, J =
110.5 Hz), 132.2 (d, J = 2.6 Hz), 131.8 (d, J = 10.5 Hz), 128.6 (d, J =
12.5 Hz),128.3 (d, J = 13.8 Hz). 31P NMR (162 MHz, CDCl3): δ 21.7.
MS-ESI: m/z 285.1, [M + H]+.
Di([1,1′-biphenyl]-4-yl)(phenyl)phosphine Oxide (3v) (CAS no:
1
661451-80-5). White solid; 163 mg, 76% yield. H NMR (400 MHz,
CDCl3): δ 7.81−7.73 (m, 6 H), 7.71−7.69 (m, 4 H), 7.62−7.55 (m, 5
H), 7.52−7.44 (m, 6 H), 7.40−7.37 (m, 2 H). 13C NMR (100 MHz,
CDCl3): δ 144.8 (d, J = 2.8 Hz), 140.0, 133.3, 132.7 (d, J = 10.2 Hz),
132.2 (d, J = 10.2 Hz), 132.1 (d, J = 2.5 Hz), 131.2 (d, J = 106.1 Hz),
129.0, 128.7 (d, J = 12.6 Hz), 128.2, 127.3, 127.2. 31P NMR (162
MHz, CDCl3): δ 28.9. MS-ESI: m/z 431.1, [M + H]+.
Ethyldiphenylphosphine Oxide (3w) (CAS no: 1733-57-9). White
1
solid; 108 mg, 94% yield. H NMR (400 MHz, CDCl3): δ 7.68−7.63
(m, 4 H), 7.44−7.34(m, 6 H), 2.24−2.15 (m, 2 H), 1.11 (dt, J = 17.3,
7.5 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ 132.8 (d, J = 98.5 Hz),
131.5 (d, J = 2.4 Hz), 130.7 (d, J = 8.9 Hz), 128.5 (d, J = 11.5 Hz),
22.7 (d, J = 73.9 Hz), 5.5 (d, J = 5.3 Hz). 31P NMR (162 MHz,
CDCl3): δ 33.9. MS-ESI: m/z 231.1, [M + H]+.
Phenyl-di-p-tolylphosphine Oxide (3o) (CAS no: 18957-70-5).
1
White solid; 142 mg, 93% yield. H NMR (400 MHz, CDCl3): δ
7.66−7.61 (m, 2 H), 7.55−7.49 (m, 4 H), 7.48−7.47 (m, 1 H), 7.43−
7.39 (m, 2 H), 7.26−7.22 (m, 4 H), 2.37 (s, 6 H). 13C NMR (100
MHz, CDCl3): δ 142.4 (d, J = 2.9 Hz), 133.1 (d, J = 104.1 Hz), 132.2
(d, J = 10.4 Hz), 132.1 (d, J = 10.1 Hz), 131.8 (d, J = 2.5 Hz), 129.5
(d, J = 106.5 Hz), 129.3 (d, J = 12.1 Hz), 128.5 (d, J = 12.2 Hz), 21.6.
31P NMR (CDCl3, 162 MHz): δ 29.3. MS-ESI: m/z 329.1, [M + Na]+.
Bis(3-chlorophenyl)(phenyl)phosphine Oxide (3p) (CAS no:
Dipentyl(phenyl)phosphine Oxide (3x) (CAS no: 66232-90-4).
1
Light yellow oil; 93 mg, 70% yield. H NMR (400 MHz, CDCl3): δ
7.69−7.65 (m, 2 H), 7.52−7.44 (m, 3 H), 2.00−1.89 (m, 2 H), 1.87−
1.77 (m, 2 H), 1.67−1.54 (m, 2 H), 1.46−1.21 (m, 10 H), 0.82 (t, J =
6.9 Hz, 6 H). 13C NMR (100 MHz, CDCl3): δ 132.9 (d, J = 91.6 Hz),
131.5 (d, J = 2.5 Hz), 130.5 (d, J = 9.2 Hz), 128.7 (d, J = 11.0 Hz),
33.3 (d, J = 14.3 Hz), 30.0 (d, J = 68.0 Hz), 22.2, 21.2 (d, J = 3.8 Hz),
13.9. 31P NMR (162 MHz, CDCl3): δ 40.5. MS-ESI: m/z 267.1, [M +
H]+.
Diphenyl(p-tolyl)phosphine Oxide (3y) (CAS no: 6840-28-4).
White solid; 66 mg, 45% yield. 1H NMR (400 MHz, CDCl3): δ
7.89−7.84 (m, 4 H), 7.78−7.70 (m, 4 H), 7.66−7.62 (m, 4 H), 7.48−
7.45 (m, 2 H), 2.59 (s, 3 H). 13C NMR (CDCl3, 100 MHz): δ 142.5
(d, J = 2.3 Hz), 133.4 (d, J = 104.1 Hz), 132.2 (d, J = 10.4 Hz), 132.1
(d, J = 10.0 Hz), 131.8 (d, J = 2.7 Hz), 129.3 (d, J = 12.3 Hz), 129.2
(d, J = 106.7 Hz), 128.5 (d, J = 11.9 Hz), 21.6. 31P NMR (CDCl3, 162
MHz): δ 29.1. MS-ESI: m/z 293.2, [M + H]+.
Diphenyl(2,4,6-triisopropylphenyl)phosphine Oxide (3z). White
solid; mp 146−147 °C; 210 mg, 99% yield. IR (film): 3409, 3054,
2959, 1601, 1436, 1383, 1181, 1101, 701. 1H NMR (400 MHz,
CDCl3): δ 7.69−7.64 (m, 4 H), 7.46−7.41(m, 6 H), 7.09 (s, 2 H),
3.57−3.52 (m, 2 H), 2.92−2.86 (m, 1 H), 1.26 (d, J = 6.8 Hz, 6 H),
0.9 (d, J = 6.5 Hz, 12 H). 13C NMR (101 MHz, CDCl3): δ 155.1 (d, J
= 10.7 Hz), 152.7, 137.3, 136.3, 131.7 (d, J = 10.0 Hz), 131.3, 128.5
(d, J = 12.2 Hz), 123.1 (d, J = 10.1 Hz), 34.2, 31.0 (d, J = 4.9 Hz),
24.5, 23.7. 31P NMR (162 MHz, CDCl3): δ 32.1. HRMS-ESI calcd for
C27H33OP(M + Na)+, 427.2166; found, 427.2163.
Dimethyl Mesitylphosphonate (4a) (CAS no: 68351-71-3). Light
yellow oil; 89 mg, 78% yield. 1H NMR (400 MHz, CDCl3): δ 6.87 (s,
2 H), 3.68 (d, J = 11.3 Hz, 6 H), 2.55 (s, 6 H), 2.25 (s, 3 H). 13C
NMR (101 MHz, CDCl3): δ 144.0 (d, J = 12.5 Hz), 142.1 (d, J = 2.4
Hz), 130.4 (d, J = 15.6 Hz), 121.0 (d, J = 182.4 Hz), 51.7 (d, J = 5.7
Hz), 23.0 (d, J = 2.3 Hz), 21.1. 31P NMR (162 MHz, CDCl3): δ 23.5.
MS-ESI: m/z 229.1, [M + H]+.
1
54300-33-3). Light yellow oil; 153 mg, 94% yield. H NMR (400
MHz, CDCl3): δ 7.66−7.60 (m, 4 H), 7.58−7.56 (m, 1 H), 7.54−7.47
(m, 6 H), 7.43−7.39 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ 135.3
(d, J = 16.3 Hz), 134.5 (d, J = 102.2 Hz), 132.6 (d, J = 2.7 Hz), 132.5
(d, J = 2.5 Hz), 132.0 (d, J = 28.5 Hz), 131.9 (d, J = 7.3 Hz), 131.1 (d,
J = 106.0 Hz), 130.1 (d, J = 13.4 Hz), 130.0 (d, J = 9.5 Hz), 128.9 (d, J
= 12.5 Hz). 31P NMR (162 MHz, CDCl3): δ 26.9. MS-ESI: m/z 347.1,
[M + H]+.
Bis(4-fluorophenyl)(phenyl)phosphine Oxide (3q) (CAS no:
1
54300-32-2). White solid; 128 mg, 82% yield. H NMR (400 MHz,
CDCl3): δ 7.66−7.62 (m, 6 H), 7.56−7.53 (m, 1 H), 7.47−7.45 (m, 2
H), 7.14 (t, J = 8.2 Hz, 4 H). 13C NMR (100 MHz, CDCl3): δ 165.2
(dd, J = 254.5, 3.8 Hz), 134.6 (dd, J = 11.9, 8.7 Hz), 132.3 (d, J = 2.0
Hz), 132.2 (d, J = 106.1 Hz), 132.0 (d, J = 10.4 Hz), 128.8 (d, J = 12.4
Hz), 128.5 (dd, J = 107.4, 4.0 Hz), 116.1 (dd, J = 21.1, 13.3 Hz). 31P
NMR (162 MHz, CDCl3): δ 27.6. MS-ESI: m/z 315.1, [M + H]+.
Bis(4-methoxyphenyl)(phenyl)phosphine Oxide (3r) (CAS no:
799-55-3). Light yellow oil; 162 mg, 96% yield. 1H NMR (400
MHz, CDCl3): δ 7.64−7.59 (m, 2 H), 7.57−7.50 (m, 4 H), 7.49−7.46
(m, 1 H), 7.42−7.38 (m, 2 H), 6.92 (dd, J = 8.9, 2.2 Hz, 4 H), 3.79 (s,
6 H). 13C NMR (101 MHz, CDCl3): δ 162.4 (d, J = 2.6 Hz), 134.0 (d,
J = 11.2 Hz), 133.0, 132.0 (d, J = 10.1 Hz), 131.7 (d, J = 2.2 Hz), 128.4
(d, J = 12.8 Hz), 124.1 (d, J = 111.2 Hz), 114.1 (d, J = 13.1 Hz), 55.3.
31P NMR (162 MHz, CDCl3): δ 28.8. MS-ESI: m/z 339.2, [M + H]+.
Dimesityl(phenyl)phosphine Oxide (3s) (CAS no: 57368-26-0).
1
White solid; 145 mg, 80% yield. H NMR (400 MHz, CDCl3): δ
7.47−7.41 (m, 4 H), 6.85−6.80 (m, 5 H), 2.26 (s, 6 H), 2.13 (m, 12
H). 13C NMR (100 MHz, CDCl3): δ 141.9 (d, J = 10.2 Hz), 141.0 (d,
J = 2.7 Hz), 137.5 (d, J = 96.5 Hz), 132.4, 131.6 (d, J = 3.0 Hz), 131.2
(d, J = 11.3 Hz), 130.1 (d, J = 100.2 Hz), 128.7 (d, J = 12.4 Hz), 23.6
(d, J = 4.4 Hz), 21.1. 31P NMR (162 MHz, CDCl3): δ 29.2. MS-ESI:
m/z 363.1, [M + H]+.
Diethyl Phenylphosphonate (4b) (CAS no: 1754-49-0). Colorless
oil; 96 mg, 90% yield. 1H NMR (400 MHz, CDCl3): δ 7.79−7.74 (m,
2 H), 7.52−7.48 (m, 1 H), 7.44−7.39 (m, 2 H), 4.15−3.98 (m, 4 H),
1.27 (t, J = 6.9 Hz, 6 H). 13C NMR (100 MHz, CDCl3): δ 132.4 (d, J
= 2.9 Hz), 131.8 (d, J = 9.8 Hz), 128.6 (d, J = 188.3 Hz), 128.5 (d, J =
14.9 Hz), 62.1 (d, J = 5.3 Hz), 16.3 (d, J = 6.4 Hz). 31P NMR (162
MHz, CDCl3): δ 18.7. MS-ESI: m/z 215.1, [M + H]+.
Bis(4-(dimethylamino)phenyl)(phenyl)phosphine Oxide (3t) (CAS
1
no: 803-20-3). White solid; 155 mg, 85% yield. H NMR (400 MHz,
CDCl3): δ 7.65−7.61 (m, 2 H), 7.45−7.38 (m, 5 H), 7.35−7.32 (m, 2
H), 6.63−6.61 (m, 4 H), 2.91 (s, 12 H). 13C NMR (100 MHz,
CDCl3): δ 152.1 (d, J = 2.0 Hz), 134.8 (d, J = 104.0 Hz), 133.3 (d, J =
11.0 Hz), 131.9 (d, J = 9.8 Hz), 130.9 (d, J = 2.6 Hz), 128.0 (d, J =
Diethyl (4-Bromophenyl)phosphonate (4c) (CAS no: 20677-12-7).
1
Colorless oil; 134 mg, 92% yield. H NMR (400 MHz, CDCl3): δ
F
dx.doi.org/10.1021/jo4012199 | J. Org. Chem. XXXX, XXX, XXX−XXX