The Journal of Organic Chemistry
Article
(2-Methylbenzyl)diphenylphosphine Oxide (3e). The title
compound was prepared according to the general experimental
procedure I, purified by column chromatography on silica gel, and
eluted with PE/EA = 1:1 (v/v) to afford a white solid in 93% yield (57.0
mg). 1H NMR (400 MHz, CDCl3): δ 7.62−7.57 (m, 4H), 7.46−7.42
(m, 2H), 7.37−7.33 (m, 4H), 7.01−7.00 (m, 2H), 6.93−6.86 (m, 2H),
3.59 (d, J = 14.0 Hz, 2H), 2.06 (s, 3H). 13C {1H} NMR (100 MHz,
CDCl3): δ 137.4 (d, JC−P = 5.2 Hz), 132.3 (d, JC−P = 98.8 Hz), 131.8 (d,
(d, J = 13.6 Hz, 2H). 13C {1H} NMR (100 MHz, CDCl3): δ 133.2 (d,
C−P = 2.3 Hz), 132.2 (d, JC−P = 98.4 Hz), 132.1 (d, JC−P = 2.1 Hz), 131.8
(d, JC−P = 2.7 Hz), 131.1 (d, JC−P = 9.0 Hz), 128.9 (d, JC−P = 6.7 Hz),
128.7 (d, JC−P = 8.2 Hz), 128.5 (d, JC−P = 11.7 Hz), 128.1 (d, JC−P = 4.2
J
Hz), 127.9 (d, JC−P = 1.9 Hz), 127.6 (d, JC−P = 0.9 Hz), 127.5 (d, JC−P
1.1 Hz), 125.9, 125.6 (d, JC−P = 0.9 Hz), 38.3 (d, JC−P = 65.9 Hz). 31
{1H} NMR (162 MHz, CDCl3): δ 29.5. This compound is known.8l
=
P
(4-Fluorobenzyl)diphenylphosphine Oxide (3k). The title
compound was prepared according to the general experimental
procedure I, purified by column chromatography on silica gel, and
eluted with PE/EA = 1:1 (v/v) to afford a white solid in 71% yield (44.1
mg). 1H NMR (400 MHz, CDCl3): δ 7.63−7.58 (m, 4H), 7.46−7.42
(m, 2H), 7.39−7.34 (m, 4H), 7.01−6.97 (m, 2H), 6.81−6.77 (m, 2H),
3.54 (d, J = 13.2 Hz, 2H). 13C {1H} NMR (100 MHz, CDCl3): δ 161.8
(dd, J1C−P = 244.0 Hz, J2C−P = 3.4 Hz), 132.0 (d, JC−P = 98.5 Hz), 131.9
(d, JC−P = 2.7 Hz), 131.5 (dd, J1C−P = 8.0 Hz, J2C−P = 5.3 Hz), 131.0 (d,
J
C−P = 2.4 Hz), 131.2 (d, JC−P = 8.9 Hz), 130.7 (d, JC−P = 4.4 Hz), 130.4
(d, JC−P = 2.5 Hz), 129.6 (d, JC−P = 8.1 Hz), 128.4 (d, JC−P = 11.5 Hz),
126.9 (d, JC−P = 2.9 Hz), 125.7 (d, JC−P = 2.6 Hz), 35.2 (d, JC−P = 66.3
Hz), 20.0. 31P {1H} NMR (162 MHz, CDCl3): δ 29.7. This compound
is known.8l
(4-Methoxybenzyl)diphenylphosphine Oxide (3f). The title
compound was prepared according to the general experimental
procedure I, purified by column chromatography on silica gel, and
eluted with PE/EA = 1:1 (v/v) to afford a white solid in 92% yield (59.3
mg). 1H NMR (400 MHz, CDCl3): δ 7.63−7.58 (m, 4H), 7.44−7.40
(m, 2H), 7.37−7.33 (m, 4H), 6.95−6.93 (m, 2H), 6.65 (d, J = 8.4 Hz,
2H), 3.65 (s, 3H), 3.51 (d, J = 13.6 Hz, 2H). 13C {1H} NMR (100 MHz,
CDCl3): δ 158.4 (d, JC−P = 2.7 Hz), 132.3 (d, JC−P = 97.9 Hz), 131.7 (d,
J
J
C−P = 9.0 Hz), 128.5 (d, JC−P = 11.6 Hz), 126.7 (dd, J1C−P = 8.0 Hz,
2C−P = 3.1 Hz), 115.2 (dd, J1C−P = 21.2 Hz, J2C−P = 2.3 Hz), 37.1 (d, JC−P
= 66.4 Hz). 31P {1H} NMR (162 MHz, CDCl3): δ 29.4. This
compound is known.8l
(4-Chlorobenzyl)diphenylphosphine Oxide (3l). The title
compound was prepared according to the general experimental
procedure I, purified by column chromatography on silica gel, and
eluted with PE/EA = 1:1 (v/v) to afford a white solid in 68% yield (44.4
mg). 1H NMR (400 MHz, CDCl3): δ 7.64−7.59 (m, 4H), 7.48−7.44
(m, 2H), 7.40−7.36 (m, 4H), 7.09 (d, J = 8.4 Hz, 2H), 6.98−6.95 (m,
2H), 3.54 (d, J = 13.6 Hz, 2H). 13C {1H} NMR (100 MHz, CDCl3): δ
132.8 (d, JC−P = 3.6 Hz), 132.0 (d, JC−P = 2.6 Hz), 131.9 (d, JC−P = 99.0
J
C−P = 2.5 Hz), 131.1 (d, JC−P = 9.1 Hz), 131.0 (d, JC−P = 4.9 Hz), 128.4
(d, JC−P = 11.6 Hz), 122.8 (d, JC−P = 8.0 Hz), 113.8 (d, JC−P = 2.3 Hz),
55.1, 37.0 (d, JC−P = 67.0 Hz). 31P {1H} NMR (162 MHz, CDCl3): δ
29.6. This compound is known.8l
(3-Methoxybenzyl)diphenylphosphine Oxide (3g). The title
compound was prepared according to the general experimental
procedure I, purified by column chromatography on silica gel, and
eluted with PE/EA = 1:1 (v/v) to afford a white solid in 91% yield (58.6
mg). 1H NMR (400 MHz, CDCl3): δ 7.66−7.61 (m, 4H), 7.47−7.43
(m, 2H), 7.40−7.35 (m, 4H), 7.02 (t, J = 8.0 Hz, 1H), 6.66−6.61 (m,
2H), 6.56 (s, 1H), 3.57 (s, 3H), 3.57 (d, J = 8.0 Hz, 2H). 13C {1H}
Hz), 131.4 (d, JC−P = 5.3 Hz), 131.1, (d, JC−P = 9.1 Hz), 129.6 (d, JC−P
=
8.0 Hz), 128.6 (d, JC−P = 11.7 Hz), 128.5 (d, JC−P = 2.2 Hz), 37.4 (d,
JC−P = 65.8 Hz). 31P {1H} NMR (162 MHz, CDCl3): δ 29.3. This
compound is known.8l
(2-Chlorobenzyl)diphenylphosphine Oxide (3m). The title
compound was prepared according to the general experimental
procedure I, purified by column chromatography on silica gel, and
eluted with PE/EA = 1:1 (v/v) to afford a white solid in 83% yield (54.2
mg). 1H NMR (400 MHz, CDCl3): δ 7.65−7.60 (m, 4H), 7.48−7.40
(m, 3H), 7.37−7.32 (m, 4H), 7.14 (d, J = 8.0 Hz, 1H), 7.10−7.01 (m,
2H), 3.79 (d, J = 13.6 Hz, 2H). 13C {1H} NMR (100 MHz, CDCl3): δ
134.2 (d, JC−P = 7.0 Hz), 132.0 (d, JC−P = 99.2 Hz), 131.9 (d, JC−P = 4.4
NMR (100 MHz, CDCl3): δ 159.4 (d, JC−P = 2.2 Hz), 132.5 (d, JC−P
7.9 Hz), 132.2 (d, JC−P = 98.7 Hz), 131.8 (d, JC−P = 2.1 Hz), 131.2 (d,
C−P = 8.9 Hz), 129.3 (d, JC−P = 2.0 Hz), 128.5 (d, JC−P = 11.6 Hz), 122.6
(d, JC−P = 5.2 Hz), 115.2 (d, JC−P = 5.0 Hz), 113.0 (d, JC−P = 2.6 Hz),
55.1, 38.2 (d, JC−P = 66.8 Hz). 31P {1H} NMR (162 MHz, CDCl3): δ
29.6. This compound is known.15
(Benzo[d][1,3]dioxol-5-ylmethyl)diphenylphosphine Oxide
(3h). The title compound was prepared according to the general
experimental procedure I, purified by column chromatography on silica
gel, and eluted with PE/EA = 1:1 (v/v) to afford a white solid in 85%
yield (57.2 mg). 1H NMR (400 MHz, CDCl3): δ 7.65−7.60 (m, 4H),
7.43 (d, J = 6.8 Hz, 2H), 7.38 (d, J = 6.8 Hz, 4H), 6.57−6.53 (m, 2H),
6.45 (d, J = 7.2 Hz, 1H), 5.80 (s, 2H), 3.49 (d, J = 13.2 Hz, 2H), 1.98 (s,
1H). 13C {1H} NMR (100 MHz, CDCl3): δ 147.5 (d, JC−P = 1.8 Hz),
146.5 (d, JC−P = 2.8 Hz), 132.2 (d, JC−P = 98.1 Hz), 131.8 (d, JC−P = 2.3
=
J
Hz), 131.8 (d, JC−P = 2.7 Hz), 131.0 (d, JC−P = 9.2 Hz), 129.6 (d, JC−P
7.3 Hz), 129.3 (d, JC−P = 2.2 Hz), 128.4 (d, JC−P = 11.7 Hz), 128.2 (d,
C−P = 2.7 Hz), 126.8 (d, JC−P = 2.5 Hz), 34.5 (d, JC−P = 66.2 Hz). 31
{1H} NMR (162 MHz, CDCl3): δ 29.5. This compound is known.8l
=
J
P
(4-Bromobenzyl)diphenylphosphine Oxide (3n). The title
compound was prepared according to the general experimental
procedure I, purified by column chromatography on silica gel, and
eluted with PE/EA = 1:1 (v/v) to afford a white solid in 61% yield (45.3
mg). 1H NMR (400 MHz, CDCl3): δ 7.74−7.69 (m, 4H), 7.56−7.48
(m, 6H), 7.33 (d, J = 7.6 Hz, 2H), 7.01 (d, J = 7.6 Hz, 2H), 3.63 (d, J =
Hz), 131.1 (d, JC−P = 9.0 Hz), 128.5 (d, JC−P = 11.5 Hz), 124.4 (d, JC−P
=
8.1 Hz), 123.3 (d, JC−P = 6.1 Hz), 110.5 (d, JC−P = 4.7 Hz), 108.1 (d,
J
C−P = 2.2 Hz), 100.9, 37.6 (d, JC−P = 67.0 Hz). 31P {1H} NMR (162
MHz, CDCl3): δ 29.5. This compound is known.8l
13.6 Hz, 2H). 13C {1H} NMR (100 MHz, CDCl3): δ 132.0 (d, JC−P
=
2.4 Hz), 131.8 (d, JC−P = 98.9 Hz), 131.7 (d, JC−P = 5.1 Hz), 131.4 (d,
C−P = 2.3 Hz), 131.1 (d, JC−P = 9.1 Hz), 130.1 (d, JC−P = 8.0 Hz), 128.6
([1,1′-Biphenyl]-4-ylmethyl)diphenylphosphine Oxide (3i).
The title compound was prepared according to the general
experimental procedure I, purified by column chromatography on
silica gel, and eluted with DCM:EA = 4:1 (v/v) to afford a white solid in
87% yield (64.1 mg). 1H NMR (400 MHz, CDCl3): δ 7.75−7.70 (m,
4H), 7.54−7.50 (m, 4H), 7.47−7.38 (m, 8H), 7.33−7.29 (m, 1H), 7.17
(dd, J1 = 8.4 Hz, J2 = 2.0 Hz, 2H), 3.70 (d, J = 13.6 Hz, 2H). 13C {1H}
J
(d, JC−P = 11.7 Hz), 120.9 (d, JC−P = 3.9 Hz), 37.5 (d, JC−P = 65.8 Hz).
31P {1H} NMR (162 MHz, CDCl3): δ 29.3. This compound is known.16
(3-Bromobenzyl)diphenylphosphine Oxide (3o). The title
compound was prepared according to the general experimental
procedure I, purified by column chromatography on silica gel, and
eluted with PE/EA = 1:1 (v/v) to afford a white solid in 51% yield (37.9
mg). 1H NMR (400 MHz, CDCl3): δ 7.64−7.59 (m, 4H), 7.48−7.43
(m, 2H), 7.41−7.36 (m, 4H), 7.24−7.21 (m, 1H), 7.11 (d, J = 1.6 Hz,
1H), 7.02−6.96 (m, 2H), 3.53 (d, J = 13.6 Hz, 2H). 13C {1H} NMR
(100 MHz, CDCl3): δ 133.4 (d, JC−P = 7.9 Hz), 133.0 (d, JC−P = 5.2 Hz),
131.8 (d, JC−P = 99.2 Hz), 132.0 (d, JC−P = 2.7 Hz), 131.1 (d, JC−P = 9.0
NMR (100 MHz, CDCl3): δ 140.6 (d, JC−P = 1.2 Hz), 139.6 (d, JC−P
3.1 Hz), 132.2 (d, JC−P = 98.5 Hz), 131.8 (d, JC−P = 2.7 Hz), 131.1 (d,
C−P = 9.1 Hz), 130.5 (d, JC−P = 5.2 Hz), 130.1 (d, JC−P = 8.1 Hz), 128.7,
=
J
128.5 (d, JC−P = 11.7 Hz), 127.2, 127.1 (d, JC−P = 2.6 Hz), 126.9, 37.8
(d, JC−P = 66.0 Hz). 31P {1H} NMR (162 MHz, CDCl3): δ 29.7. This
compound is known.16
(Naphthalen-2-ylmethyl)diphenylphosphine Oxide (3j). The
title compound was prepared according to the general experimental
procedure I, purified by column chromatography on silica gel, and
eluted with PE/EA = 1:1 (v/v) to afford a white solid in 72% yield (49.3
mg). 1H NMR (400 MHz, CDCl3): δ 7.67−7.56 (m, 7H), 7.48 (s, 1H),
7.43−7.39 (m, 2H), 7.35−7.29 (m, 6H), 7.15 (d, J = 8.4 Hz, 1H), 3.72
Hz), 129.8 (d, JC−P = 2.4 Hz), 128.7 (d, JC−P = 5.0 Hz), 128.6 (d, JC−P
=
11.8 Hz), 122.2 (d, JC−P = 2.9 Hz), 37.7 (d, JC−P = 65.3 Hz). 31P {1H}
NMR (162 MHz, CDCl3): δ 29.3. This compound is known.17
Diphenyl(4-(trifluoromethyl)benzyl)phosphine Oxide (3p).
The title compound was prepared according to the general
experimental procedure I, purified by column chromatography on
4164
J. Org. Chem. 2021, 86, 4159−4170