Toullec et al.
3-(4′-Meth oxyph en yl)-6-ph en yl-4,5-dim eth yl-1-ph osph a-
2-oxa n or bor n -5-en e Su lfid e 5. 1-Phenyl-3,4-dimethylphos-
phole (940 mg, 5 mmol) and freshly distilled 4-methoxybenz-
aldehyde (610 µL, 5 mmol) were placed via a septum in a 20-
mL Schlenk tube containing distilled xylene (4 mL). The tube
was closed and heated to 150 °C for 2 h. The complete
consumption of the starting materials and the quantitative
formation of the 2 diastereoisomers of the adduct was moni-
tored by 31P NMR spectroscopy: δ (p-xylene) ) +111.7 (minor)
and δ ) +112.0 (major). Sulfur (160 mg, 5 mmol) was added,
and the solution was heated to 60 °C for 3 h. The solvents
were removed under reduced pressure to give a yellow solid.
Chromatography over silica gel with a hexane/ether (90/10)
eluent yielded an impure fraction of the major isomer. A
recrystallization using a hexane/ether solution gave 900 mg
products was monitored by 31P NMR spectroscopy: δ (p-xylene)
) +110.2 (20%), δ ) +109.3 (55%) and δ ) -8.8 (25%). Sulfur
(160 mg, 5 mmol) was added, and the solution was heated at
60 °C for 3 h. The solvents were removed under reduced
pressure to give a yellow solid. Chromatography on silica gel
with a hexane/ether (90/10 then 75/25) eluent yielded succes-
sively 8 (220 mg) as a beige oil and 7 (340 mg) as white
crystals. Total yield: 32%.
2-F or m yl-3,6-d ip h en yl-4,5-d im eth ylp h osp h a n or bor n -
5-en e su lfid e 7: 1H NMR (CDCl3) δ 1.46 (s, 3H), 1.84 (s, 3H),
3
3
2.07 (m, 2H), 4.64 (d, J H-H ) 6.5 Hz, 1H), 5.52 (dd, J H-H
)
16 Hz, 3J H-H ) 6.5 Hz, 1H), 6.60 (d, 3J H-H ) 16 Hz, 1H), 7.15-
7.35 (m, 10H); 13C{1H} NMR (CDCl3) δ 15.66 (d, J C-P ) 13
3
Hz), 17,46 (s, 3J C-P ) 19 Hz), 51.59 (d, 2J C-P ) 17.5 Hz), 52.15
(d, 1J C-P ) 70 Hz), 86.26 (d, 2J C-P ) 3.5 Hz), 123.00 (s), 127.67
(s), 127.84 (d, J C-P ) 1 Hz), 128.38 (s), 128.42 (s), 128.83 (s),
1
of white crystals. Yield: 51%. H NMR (CDCl3) δ 1.38 (d, J )
2
2
2 Hz, 3H), 1.54 (s, 3H), 2.25 (s, 1H), 2.27 (d, J H-P ) 2.5 Hz,
129.30 (d, J C-P ) 6 Hz), 131.85 (d, J C-P ) 10.5 Hz), 133.87
3
1
2
1H), 3.80 (s, 3H), 5.13 (d, J H-P ) 2 Hz, 1H), 6.85 (d, AB
(s′), 135.85 (s), 138.25 (d, J C-P ) 83 Hz), 154.64 (d, J C-P )
3
3
system, J H-H ) 8.5 Hz, 2H), 7.12 (d, AB system, J H-H ) 8.5
Hz, 2H), 7.30-7.55 (m, 5H); 13C{1H} NMR (CDCl3) δ 15.35 (d,
3J C-P ) 13 Hz), 17.83 (s, 3J C-P ) 19 Hz), 52.53 (d, 2J C-P ) 17.5
15 Hz); 31P{1H} NMR (CDCl3) δ +98.8; MS m/z 352 (M+, 100),
220 (M+ - C9H8O, 93), 205 (M+ - C7H6O - 15, 37); HRMS for
7 + 1 calcd 353.1129, found 353.1127.
1
2
Hz), 52.58 (d, J C-P ) 70.5 Hz), 55.36 (s), 85.99 (d, J C-P ) 4
Hz), 113.59 (s), 127.26 (s), 127.66 (d, J C-P ) 4 Hz), 127.82 (d,
J C-P ) 1 Hz), 128.50 (s), 129.24 (d, J C-P ) 4 Hz), 132.00 (d,
3-(2′-P h en yleth en yl)-6-p h en yl-4,5-d im eth yl-1-p h osp h a -
2-oxa n or bor n -5-en e 8: 1H NMR (CDCl3) δ 1.32 (s, 3H), 1.39
2
(d, J ) 2.5 Hz, 3H), 2.14 (m, 2H), 3.75 (dd, J H-P ) 16.5 Hz,
1
2
3
J C-P ) 11 Hz), 138.32 (d, J C-P ) 83 Hz), 154.56 (d, J C-P
)
3J H-H ) 5.5 Hz, 1H), 3.86 (d, J H-H ) 5.5 Hz, 1H), 6.95-7.50
15 Hz), 159.71 (s); 31P{1H} NMR (CDCl3) δ +98.1; MS m/z 355
(M+ - 1, 9), 219 (M+ - C7H6O - 1, 100), 205 (M+ - C7H6O -
15, 28), 187 (M+ - C7H6O - S - 1, 13); HRMS for 5 + 1 calcd
357.1078, found 357.1075. Anal. Calcd for 5: C, 67.42; H, 5.90.
Found: C, 66.91; H, 5.91.
(m, 10H), 9.99 (d, J H-P ) 1.5 Hz, 1H); 13C{1H} NMR (CDCl3)
3
3
3
δ 16.43 (d, J C-P ) 12,5 Hz), 19.70 (s, J C-P ) 17.5 Hz), 50.40
(d, 2J C-P ) 20.5 Hz), 51.68 (s), 52.48 (d, 1J C-P ) 56.5 Hz), 58.44
(d, 1J C-P ) 30 Hz), 127.88 (s), 128.22 (d, 4J C-P ) 1.5 Hz), 128.36
3
(s), 128.61 (s), 128.74 (s), 129.41 (d, J C-P ) 5 Hz), 131.81 (d,
J C-P ) 10.5 Hz), 134.00 (d, J C-P ) 68 Hz), 137.73 (d, J C-P
6 Hz), 157.85 (d, J C-P ) 15 Hz), 198.98 (d, J C-P ) 1 Hz);
31P{1H} NMR (CDCl3) δ +56.0; MS m/z 351 (M+ - 1, 9), 220
(M+ - C9H8O, 100), 205 (M+ - C7H6O - 15, 30); HRMS for 8
+ 1 calcd 353.1129, found 353.1134.
1
3-n -Non yl-6-p h en yl-4,5-d im eth yl-1-p h osp h a -2-oxa n or -
bor n -5-en e Su lfid e 6. 1-Phenyl-3,4-dimethylphosphole (940
mg, 5 mmol) and freshly distilled decanal (940 µL, 5 mmol)
were placed via a septum in a 20-mL Schlenk tube containing
distilled xylene (2 mL). The tube was closed and heated to 150
°C for 2 h. The complete consumption of the starting materials
and the formation of the two diastereoisomers of the adduct
in 50% yield, along with the formation of 2H-phosphole dimers
in 50% yield, was monitored by 31P NMR spectroscopy: δ (p-
xylene) ) +106.8 (major) and δ ) +109.5 (minor) (ratio 10:1).
Sulfur (160 mg, 5 mmol) was added, and the solution was
heated to 60 °C for 3 h. The solvents were removed under
reduced pressure to give a yellow solid. Chromatography over
silica gel with a hexane/ether (90/10) eluent yielded 730 mg
)
2
2
3,6-Dip h en yl-4,5-d im eth yl-1-p h osp h a -2-oxa n or bor n -5-
en e Oxid e 12. 1-Phenyl-3,4-dimethylphosphole (940 mg, 5
mmol) and freshly distilled benzaldehyde (510 µL, 5 mmol)
were placed via a septum in a 20-mL Schlenk tube containing
distilled xylene (4 mL). The tube was closed and heated to 150
°C for 2 h. Hydrogen peroxide (100 vol,10 mL) were added,
and the solution was stirred to room temperature for 30 min.
The solvents were removed under reduced pressure to give a
white solid. Chromatography on silica gel with ether as the
eluent yielded 1260 mg of the compound 12 as white crystals.
1
of 6 as white crystals. Yield: 39%. H NMR (CDCl3) δ 0.79 (t,
4
1
3J H-H ) 7 Hz, 3H), 1.17 (m, 16H), 1.34 (s, 3H), 1.88 (d, J H-H
Yield: 82%. H NMR (CDCl3) δ 1.27 (d, J ) 2 Hz, 3H), 1.46 (s,
2
2
3
) 2 Hz, 3H), 2.17 (d, J H-P ) 10 Hz, 1H), 2.19 (dd, J H-P ) 11
3H), 1.96 (s, 1H), 1.99 (d, J H-P ) 8.5 Hz, 1H), 5.06 (d, J H-P
)
Hz, 4J H-H ) 2 Hz, 1H), 3.99 (d, 1H, 3J H-P ) 11 Hz), 7.15-7.30
2 Hz, 1H), 7.10-7.35 (m, 10H); 13C{1H} NMR (CDCl3) δ 14.57
3 3 1
(m, 5H); 13C{1H} NMR (CDCl3) δ 14.05 (s), 15.87 (d, J C-P
)
(d, J C-P ) 15 Hz), 18.41 (s, J C-P ) 20 Hz), 46.00 (d, J C-P )
2
3
3
13 Hz), 17.17 (s, J C-P ) 19 Hz), 22.55 (s), 26.43 (s), 29.16 (s),
29.32 (s), 29.34 (s), 29.35 (s), 30.32 (d, J C-P ) 2 Hz), 31.74 (s),
88 Hz), 49.29 (d, J C-P ) 23 Hz), 85.70 (s), 126.31 (s), 128.13
3
(s), 128.52 (s), 128.79 (s), 129.15 (d, J C-P ) 2 Hz), 129.24 (s),
2
1
50.15 (d, J C-P ) 18.5 Hz), 52.70 (d, J C-P ) 71 Hz), 87.30 (d,
132.38 (d, J C-P ) 9 Hz), 136.91 (d, J C-P ) 4 Hz), 134.09 (d,
2J C-P ) 4 Hz), 127.43 (d, J ) 1 Hz), 128.08 (s), 128.97 (d, J )
1J C-P ) 110 Hz), 155.48 (d, J C-P ) 18 Hz); 31P{1H} NMR (p-
2
1
6 Hz), 131.92 (d, J ) 10.5 Hz), 138.14 (d, J C-P ) 83.5 Hz),
xylene) δ + 58.6; MS m/z 188 (M+ - C7H6O, 100). HRMS for
12 + 1 calcd 311.1201, found 311.1200.
154.63 (d, J C-P ) 15 Hz); 31P{1H} NMR (CDCl3) δ +95.2; MS
2
m/z 376 (M+, 94), 220 (M+ - C10H20O, 100), 205 (M+ - C10H20
O
-15, 26), 187 (M+ - C10H20O -S -1, 10); HRMS for 6 + 1
calcd 377.2068, found 377.2070.
Ack n ow led gm en t. The authors thank BASF for the
financial support of Patrick Toullec and of this research
program.
St u d y of t h e R ea ct ion b et w een 2-H P h osp h ole a n d
tr a n s-Cin n am aldeh yde. 1-Phenyl-3,4-dimethylphosphole (940
mg, 5 mmol) and freshly distilled trans-cinnamaldehyde (630
µL, 5 mmol) were placed via a septum in a 20-mL Schlenk
tube containing distilled xylene (2 mL). The tube was closed
and heated to 150 °C for 2 h. The complete consumption of
the starting materials and the obtention of three different
Su p p or tin g In for m a tion Ava ila ble: Crystallographic
data for 2 (endo) and 3 (endo). This material is available free
J O020720J
2806 J . Org. Chem., Vol. 68, No. 7, 2003