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Tyutyunov et al.
31P{1H} NMR (CDCl3), δ: 48.4. 11B NMR (CDCl3), δ: –11.84
(m, 6 B); –8.01 (d, 2 B, JBH = 150.2 Hz); –1.63 (d, 2 B,
JBH = 149.0 Hz).
Yield 0.19 g (98%). M.p. 138 °C. Found (%): C, 52.31; H, 6.02;
B, 31.76; P, 9.81. C15H23B10P. Calculated (%): C, 52.61;
H, 6.77; B, 31.57; P, 9.05. 1H NMR (CDCl3), δ: 1.3—3.1 (m,
9 H, BH); 1.57 (s, 2 H, CH2); 3.40 (s, 1 H, CH carborane); 3.43
(s, 1 H, CH carborane); 7.26 (m, 6 H, CHPh); 7.44 (m, 4 H,
CHPh). 31P{1H} NMR (CDCl3), δ: –13.0. 11B NMR (CDCl3),
δ: –14.34 (m, 6 B); –8.58 (d, 2 B, JBH = 149.7 Hz); –1.69 (d,
1 B, JBH = 147.9 Hz); 6.67 (s, 1 B).
1ꢀDicyclohexylphosphinomethylꢀ1,2ꢀdicarbaꢀclosoꢀdodecaꢀ
borane (8). An ether solution (6.5 mmol) of 1ꢀoꢀcarboranylꢀ
methylmagnesium bromide was slowly added with stirring
at 0 °C to a solution of dicyclohexylchlorophosphine (1.5 g,
6.45 mmol) in anhydrous ether (10 mL). The reaction mixture
was stirred for 1 h at 20 °C, refluxed for 5 h, cooled, carefully
quenched by water, and extracted with ether. After removal
of the solvent, the residue was recrystallized from acetone. Yield
2.1 g (91%). M.p. 160 °C (acetone). Found (%): C, 50.70; H,
9.98; B, 30.12; P, 8.49. C15H35B10P. Calculated (%): C, 50.82;
H, 9.95; B, 30.49; P, 8.74. 1H NMR (CDCl3), δ: 1.0—1.3 (m,
12 H, CH2Cy); 1.45—1.85 (m, 10 H, CH2Cy); 2.28 (d, 2 H, CH2,
2JHP = 3.0); 1.5—3.1 (m, 10 H, BH); 4.02 (s, 1 H, CH carborane).
31P{1H} NMR (CDCl3), δ: –0.3.
Suzuki—Miyaura crossꢀcoupling. The specified haloarene 15
or 16 (0.5 mmol), phenylboronic acid (73 mg, 0.6 mmol), and
the specified base (Na2CO3, K3PO4) (1—1.5 mmol) were placed
into a Schlenk flask. Then Pd(OAc)2 (1 mg, 0.005 mmol) and
specified ligand 1—9 (0.01 mmol) were added. The reactor was
purged with argon and the specified solvent (5 mL) was added.
The mixture was stirred for 1.5—3 h at 40—80 °C (see Table 1),
cooled to 20 °C, diluted with hexane (10 mL), filtered through
1
a silica gel layer, and analyzed by H NMR spectroscopy.
9ꢀBromomethylꢀ1,2ꢀdicarbaꢀclosoꢀdodecaborane (12). A
solution of PBr3 (3.0 g, 11.1 mmol) in anhydrous benzene
(10 mL) was added with stirring to a solution of 9ꢀ(hydroxyꢀ
methyl)ꢀoꢀcarborane (11) (5.7 g, 32.7 mmol) in anhydrous
benzene (60 mL). The mixture was stirred for 10 h, poured in
water, and extracted with benzene. After removal of the solvent,
the residue was distilled in vacuo. Yield 5.8 g (75%). B.p. 158 °C
(1.5 Torr), m.p. 47 °C. Found (%): C, 15.66; H, 5.61; B, 45.68.
C3H13B10Br. Calculated (%): C, 15.19; H, 5.53; B, 45.59; Br,
33.69. 1H NMR ((CD3)2CO), δ: 1.4—3.1 (m, 9 H, BH); 2.68
(s, 2 H, CH2); 4.42 (s, 1 H, CH carborane); 4.48 (s, 1 H,
CH carborane). 11B NMR ((CD3)2CO), δ: –13.96 (m, 6 B);
–9.07 (d, 2 B, JBH = 150.2 Hz); –2.56 (d, 1 B, JBH = 147.9 Hz);
5.46 (s, 1 B).
1,2ꢀDicarbaꢀclosoꢀdodecaboraneꢀ9ꢀdiphenylphosphinomethyl
oxide (13). Method А. A mixture of 9ꢀbromomethylꢀoꢀcarborane
(12) (0.10 g, 0.42 mmol) and Ph2POEt (0.3 mL) was heated for
5 h at 150 °C and evacuated for 1 h at 60 °C (1 Torr). The
residue was dissolved in 5 mL of toluene with heating and cooled,
and the precipitated crystals were filtered off and dried. The
product was recrystallized from acetonitrile. Yield 0.14 g (95%).
M.p. 240 °C (acetonitrile). Found (%): C, 50.34; H, 6.52;
B, 30.30; P, 8.44. C15H23B10OP. Calculated (%): C, 50.26;
H, 6.47; B, 30.16; O, 4.46; P, 8.64.
References
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Method B. Chlorodiphenylphosphine (10.55 g, 47.82 mmol)
was added to a cooled (0 °C) mixture of 9ꢀcarboxyꢀoꢀcarborane
(10) (3.0 g, 15.94 mmol) and water (0.57 g, 31.87 mmol).
The reaction mixture was heated for 3 h at 80 °C and for 80 h at
180 °C. After cooling, the glassy substance was triturated with
toluene (20 mL) with heating to 80 °C. The precipitate was
filtered off, washed with a 5% aqueous solution of Na2CO3,
dried, and recrystallized from acetonitrile. Yield 4.0 g (70%).
9ꢀDiphenylphosphinomethylꢀ1,2ꢀdicarbaꢀclosoꢀdodecaborane
(7). Trichlorosilane (3 mL) was added to a suspension of
(oꢀcarboranꢀ9ꢀylmethyl)diphenylphosphine oxide (13) (0.20 g,
0.56 mmol) in toluene (10 mL). The reaction mixture was heated
for 5 h at 100 °C until the white precipitate completely dissolved.
After cooling, the mixture was concentrated in vacuo. The
product was recrystallized from a heptane—toluene mixture.
11. S. E. Lyubimov, A. A. Tyutyunov, V. N. Kalinin, E. E. Saidꢀ
Galiev, A. R. Khokhlov, P. V. Petrovskii, V. A. Davankov,
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Obshch. Khim., 1983, 53, 1431 [J. Gen. Chem. USSR, 1983,
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13. L. I. Zakharkin, V. A. Ol´shevskaya, N. B. Boiko, Izv. Akad.
Nauk. Ser. Khim., 1996, 719 [Russ. Chem. Bull., 1996, 45,
680 (Engl. Transl.)].
Received April 25, 2008;
in revised form July 4, 2008