N.H. Tran Huy et al. / Journal of Organometallic Chemistry 730 (2013) 63e68
67
silica gel with hexane/dichloromethane (4:1 as the eluent). The
3.5. 1-(2-Furyl)-3,4-dimethylphosphole 6
orange compound 3 was obtained in 60% yield. 31P NMR (CD2Cl2):
d
30.04. 1H NMR (CD2Cl2):
d
1.64 (d, 2JHP ¼ 11.4 Hz, 3H, PeMe), 2.18
To a solution of furan (2.5 mL, 34.4 mmol) in THF (20 mL), BuLi
(12.5 mL of 1.5 M in hexanes) was added dropwise at 0 ꢂC. The
mixture was stirred for 1 h at room temperature, cooled at ꢁ78 ꢂC,
and then a solution of cyanophosphole (2.5 g, 13.2 mmol) in THF
(25 mL) was added. After stirring for 0.5 h at ꢁ78 ꢂC and for 1 h at
room temperature, the solution was evaporated under vacuum, and
the crude product was chromatographed on silica gel with hexane/
dichloromethane 9:1 as the eluent. 1.4 g of white crystals of 6 were
obtained (yield: 60%).
(d, 4JHP ¼ 1.4 Hz, 3H, Me); 2.31 (s, 3H, Me), 6.21 (d, 2JHP ¼ 38.0 Hz,
1H, ]CHP), 7.03, 7.11, 7.15, 7.37 (m, 7H, Th H). 13C NMR (CD2Cl2):
d
12.28 (d, 1JCP ¼ 34.4 Hz, PeMe), 15.60 (d, 3JCP ¼ 11.4 Hz, Me), 19.19
3
1
(d, JCP ¼ 11.4 Hz, Me), 119.0 (d, JCP ¼ 55.0 Hz, ]CHP), 124.56e
1
129.40 (CH Th), 131.46 (d, JCP ¼ 57.3 Hz, ]CeP), 134.88e140.75
2
(C Th), 146.75 (d, JCP ¼ 18.3 Hz, ]CeMe), 157.98 (s, ]CeMe).
Mass: m/z 697 (M ꢁ Hþ, 100%). HRMS: Calcd. for C19H18PS3IAu:
696.9013; Found: 696.9026. Anal. Calcd for C19H17PS3IAu: C,
32.77; H, 2.46. Found: C, 32.88; H, 2.45.
d
31P (CDCl3) ꢁ30.2; 1H NMR (CDCl3):
d
2.12 (d, 4JHP ¼ 2.7 Hz, 6H,
Me), 6.37 (d, 2JHP ¼ 38.5 Hz, 2H, ]CHeP), 6.35, 6.73, 7.53 (3ꢀ s.br.,
3.3. 2-(Terthienyl)-5-benzoyl-1,3,4-trimethylphosphole sulfide 4
3ꢀ 1H, furan); 13C NMR (CDCl3):
d
17.89 (d, 3JCP ¼ 4.8 Hz, Me),110.88
(d, 2JCP ¼ 7.6 Hz, furan),122.06 (d, 1JCP ¼ 27.6 Hz, ]CHeP), 126.69 (s,
furan), 146.15 (d, 1JCP ¼ 25.7 Hz, furan ]C), 147.21 (s, furan ]CH),
150.25 (d, 2JCP ¼ 9.6 Hz, phosphole ]C); HRMS: Calcd. for C10H11OP
179.0626; Found 179.0630.
A solution of 1-(terthienyl)-3,4-dimethylphosphole (0.36 g,
1 mmol), tBuOK (0.15 g) in diglyme (5 mL) was heated in a pressure
tube at 150 ꢂC for 5 h. The mixture was cooled at ꢁ70 ꢂC, and
a solution of benzoyl chloride (0.15 mL) was added, then further
t
stirred at room temperature for 0.25 h. Then, BuOK (0.15 g) was
3.6. Borane complex 7
added and heated at 40 ꢂC for 0.5 h. The 31P NMR showed two
t
signals at
d
142.0 (major) and
d
133 (minor). A solution of MeI
A solution of 6 (0.20 g, 1.12 mmol), BuOK (0.12 g) in diglyme
(0.06 mL) in THF (2 mL) was added while staying at ꢁ20 ꢂC for 0.5 h,
and then stirred at room temperature for 0.25 h. S8 (0.26 g) was
then added to the reaction mixture, stirred at room temperature
overnight. The solvent was evaporated under vacuum, and the
crude product was purified by chromatography on silica gel with
hexane/dichloromethane (4:1 as the eluent). Compound 4 was
(2 mL) was heated in a pressure tube at 150 ꢂC for 5 h. The
formation of the phospholide anion was monitored by 31P NMR
d
75.6 ppm (diglyme). A solution of MeI (0.07 mL) in THF (1 mL) was
added at 0 ꢂC to this solution, which was further stirred at room
temperature for 0.5 h. The 31P NMR showed a signal at
d
ꢁ11.8. A
solution of BH3$SMe2 (2 M, 0.4 mL) was added to the reaction
mixture at 0 ꢂC. After stirring for 0.5 h, the solvent was evaporated
under vacuum, and the product was purified by chromatography on
silica gel with hexane/dichloromethane. The complex was isolated
as yellow crystals (0.09 g, 40% yield).
isolated as a red solid. 31P NMR (CDCl3):
d
54.6. 1H NMR (CDCl3):
d
1.92 (s, 3H, Me), 2.11 (d, 2JHP ¼ 14.05 Hz, 3H, PeMe); 2.31 (s, 3H,
Me), 7.18, 7.20, 7.58, 7.91 (m, 12H, Th and Ph CH). 13C NMR (CDCl3):
d
15.45 (d, 3JCP ¼ 13.3 Hz, Me), 17.60 (d, 3JCP ¼ 12.4 Hz, Me), 20.93 (d,
1JCP ¼ 50.5 Hz, PeMe), 124.10e139.56 (Th and Ph CH and
d
31P (CDCl3) 31.6; 1H NMR (CDCl3):
d
1.52 (d, 2JHP ¼ 10.9 Hz, 3H,
2
4
C þ phosphole C
a
), 140.95(d, JCP ¼ 22.0 Hz, ]CMe), 153.45 (d,
MeeP), 2.14 (d, JHP ¼ 0.4 Hz, 3H, Me), 2.33 (s, 3H, Me), 6.13 (d,
2JCP ¼ 19.1 Hz, ]CMe), 193.09 (d, 2JCP ¼ 10.4 Hz, CO). Mass: m/z 509
(MeHþ, 100%). HRMS: Calcd. for C26H21OPS4: 509.0291; Found:
509.0294. Anal. Calcd for C26H21OPS4: C, 61.39; H, 4.16. Found: C,
61.25; H, 4.15.
2JHP ¼ 34.0 Hz, 1H, ]CHeP), 6.49, 6.65, 7.50 (3ꢀ m., 3ꢀ 1H, furan);
13C NMR (CDCl3):
d
9.75 (d, JCP ¼ 34.3 Hz, PeMe), 15.49 (d,
1
3JCP ¼ 9.6 Hz, Me), 18.68 (d, JCP ¼ 12.6 Hz, Me), 110.73, 111.86 (2s,
3
1
furan ]CH), 120.24 (d, JCP ¼ 56.2 Hz, ]CHeP), 126.91 (d,
1JCP
¼
56.2 Hz, ]CeP), 142.74 (s, furan ]CH), 144.20 (d,
3.4. 2-(Terthienyl)-5-benzoyl-1,3,4-trimethylphosphol-2-ene
borane complex 5
2JCP ¼ 13.3 Hz, furan ]C),149.63 (d, 2JCP ¼ 21.9 Hz, phosphole ]C
b),
2
156.23 (d, JCP ¼ 7.6 Hz, phosphole ]C
b); HRMS: Calcd. for
C10H16BOP 207.1110; Found 207.1112.
A solution of 1-(terthienyl)-3,4-dimethylphosphole (0.36 g,
1 mmol), tBuOK (0.15 g) in diglyme (5 mL) was heated in a pressure
tube at 150 ꢂC for 5 h. The mixture was cooled at ꢁ70 ꢂC, and
a solution of benzoyl chloride (0.15 mL) was added, then further
stirred at room temperature for 0.25 h. After stirring, tBuOK (0.15 g)
was added and heated at 40 ꢂC for 0.5 h. The 31P NMR showed
3.7. 1-(a-Terfuryl)-3,4-dimethylphosphole
To a solution of terfuran (1 g, 5 mmol) in THF (15 mL), cooled
at ꢁ70 ꢂC, BuLi (3.6 mL of 1.6 M in hexanes) was added dropwise.
The mixture was stirred for 30 min at ꢁ70 ꢂC and 2 h at room
temperature, cooled at ꢁ78 ꢂC, and then a solution of cyano-
phosphole (0.7 g, 5 mmol) in THF (10 mL) was added. After stirring
for 0.5 h at ꢁ78 ꢂC and for 1 h at room temperature, the solution
was evaporated under vacuum, and the crude product was chro-
matographed on silica gel with hexane/dichloromethane 9:1 as the
eluent: e 0.4 g of terfuran was recovered e 0.5 g of 1-terfuryl-3,4-
dimethyl phosphole was obtained as beige crystals (53% yield).
a signal at
d 142.0 ppm. A solution of MeI (0.06 mL) in THF (2 mL)
was added at ꢁ20 ꢂC for 0.5 h, and stirred at room temperature for
0.25 h. The 31P NMR spectrum showed a signal at
d 6.4 ppm. A
solution of BH3.SMe2 (2 M, 0.5 mL) was then added at 0 ꢂC to the
reaction mixture. After being stirred for 0.5 h, the solvent was
evaporated under vacuum, and the crude product was purified by
chromatography on silica gel with hexane/dichloromethane (3:2 as
the eluent). Compound 5 was isolated as an orange solid (0.07 g).
d
31P (CDCl3) ꢁ28.3; 1H NMR (CDCl3):
d
2.12 (d, 4JHP ¼ 7 Hz, 6H,
31P NMR (CD2Cl2):
d
47.5. 1H NMR (CD2Cl2):
d
1.21 (d, 2JHP ¼ 10.0 Hz,
Me), 6.37 (d, 2JHP ¼ 39.1 Hz, 2H, ]CHeP), 6.48 (m, 1H, furan), 6.60
(m, 5H, furan), 7.41 (m, 1H, furan); HRMS: Calcd. for C18H15O3P
311.0837; Found 311.0834.
3H, PeMe), 1.40 (d, 3JHH ¼ 7.0 Hz, 3H, Me); 2.18 (s, 3H, Me), 3.82 (m,
1H, b-H phospholene), 4.27(m, 1H, a-H phospholene), 7.08, 7.12,
7.56, 7.65, 8.16 (m, 12H, Th and Ph CH). 13C NMR (CD2Cl2):
d
9.11 (d,
1JCP ¼ 27.6 Hz, PeMe), 16.88 (d, JCP ¼ 10.7 Hz, Me), 19.82 (d,
3.8. 2-(a-Terfuryl)-1,3,4-trimethylphosphole borane complex 8
3
3JCP ¼ 4.6 Hz, ]CeMe), 48.11 (s,
b
-CH), 51.52 (d, JCP ¼ 26.0 Hz,
1
CHP), 123.85e137.08 (Th and Ph CH and C), 157.89 (d, 2JCP ¼ 13.8 Hz,
A solution of 1-(a-terfuryl)-3,4-dimethylphosphole (0.25 g,
2
]CMe), 195.11 (d, JCP ¼ 4.6 Hz, CO). Mass: m/z 479 (M ꢁ BH3,
0.86 mmol), tBuOK (0.12 g) in diglyme (2 mL) was heated in
a pressure tube at 160 ꢂC for 3 h. The formation of the phospholide
100%). HRMS: Calcd. for C26H24OPS3: 479.0721; Found: 479.0734.