Organometallics
Article
= 7.0 Hz), 7.85−7.86 (m, 3H), 8.26−8.28 (m, 2H). 13C NMR (126
MHz, CDCl3): δ 127.30, 127.35, 127.49, 128.7, 130.9, 132.8, 133.2,
136.7, 144.3, 144.4. 29Si NMR (119 MHz, CDCl3): δ −38.5, −36.8. IR
(KBr): 3040, 2180, 1430, 1120, 1100, 750, 740, 730 cm−1. MS (EI, 70
eV): m/z 362 (M+, 87), 284 (100), 257 (29). Anal. Calcd for
C24H18Si2: C, 79.50; H, 5.00. Found: C, 79.21; H, 5.30.
and evaporated. The residue was recrystallized from benzene to give
12 (0.068 g, 83%) as colorless crystals.
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12. Mp: >300 °C. H NMR (500 MHz, CDCl3): δ 7.21−7.25 (m,
6H), 7.72−7.76 (m, 6H), 7.80−7.83 (m, 6H), 8.32−8.36 (m, 4H). 13C
NMR (126 MHz, CDCl3): δ 127.3, 127.7, 128.9, 131.0, 133.0, 136.9,
145.3. 29Si NMR (99 MHz, CDCl3): δ −38.8. IR (KBr): 3040, 1430,
1110, 1100, 730, 700, 670 cm−1. MS (EI, 70 eV): m/z 438 (M+, 71),
360 (100). Anal. Calcd for C30H22Si2: C, 82.14; H, 5.06. Found: C,
82.21; H, 5.20.
Coupling of 1 with Magnesium on Conventional Heating
and Hydrolysis with D2O. The reaction of 1 (0.503 g, 1.47 mmol)
with magnesium turnings (0.080 g, 3.3 mmol) in THF (3 mL) was
carried out according to the similar procedure described above. After
the reaction was completed, the reaction mixture was hydrolyzed with
D2O. Compounds 2-d (0.092 g, 34%) and cis-3-d2 (0.068 g, 25%) were
obtained. Incorporation of deuterium atoms was confirmed by mass
Synthesis of 9-tert-Butyl-10-phenyl-9,10-disilatriptycene
(13). A solution of tert-butyllithium in pentane (1.60 mol L−1, 0.45
mL) was added dropwise to a solution of 2 (0.051 g, 0.14 mmol) in
THF (20 mL) at −40 °C, and the mixture was allowed to warm
gradually to room temperature. After the solvents were evaporated, the
residue was passed through a short column on silica gel (eluent:
hexane−dichloromethane (1:1)). The eluate was evaporated. The
residue was washed with a small amount of hexane and recrystallized
from benzene to give 13 (0.024 g, 41%) as colorless crystals.
13. Mp: 283 °C. 1H NMR (500 MHz, CDCl3): δ 1.84 (s, 9H), 7.18
(td, 3H, J = 7.2, 1.3 Hz), 7.22 (td, 3H, J = 7.2, 1.3 Hz), 7.68−7.69 (m,
3H), 7.74 (m, 3H), 8.01 (d, 3H, J = 7.2 Hz), 8.26−8.28 (m, 2H). 13C
NMR (126 MHz, CDCl3): δ 17.3, 28.8, 126.99, 127.03, 127.8, 128.8,
130.9, 133.16, 133.18, 137.0, 144.8, 146.2. 29Si NMR (99 MHz,
CDCl3): δ −39.1, −31.8. IR (KBr): 3030, 1520, 1120, 1040, 830, 760,
730 cm−1. MS (EI, 70 eV): m/z 418 (M+, 56), 361 (100), 257 (64).
HRMS (EI, 70 eV): calcd for C28H26Si2 418.1571, found 418.1567.
Synthesis of 9-Hydroxy-10-phenyl-9,10-disilatriptycene
(14). A mixture of 2 (0.051 g, 0.14 mmol), aqueous sodium hydroxide
(5.0 mol L−1, 1 mL), and THF (10 mL) was stirred at room
temperature for 1 h. Aqueous ammonium chloride was added, and the
mixture was extracted with diethyl ether. The organic layer was dried
over anhydrous magnesium sulfate and evaporated. The residue was
recrystallized from benzene to give 14 (0.042 g, 79%) as colorless
crystals.
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analysis. Deuterated positions were determined by H and 13C NMR
spectroscopy as follows: (1) decrease of integration compared with
those of 2 or cis-3 (ca. 1/2) was observed in the 2-protons of the
1
phenyl groups; (2) JC−D splitting was observed in the 13C NMR
spectra.
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2-d. Mp: 275 °C. H NMR (500 MHz, CDCl3): δ 5.62 (s, 1H,
1JSi−H = −218.5 Hz), 7.20−7.27 (m, 6H), 7.70−7.71 (m, 3H), 7.76 (d,
3H, J = 7.0 Hz), 7.87−7.89 (m, 3H), 8.28−8.30 (m, 1H). 13C NMR
(126 MHz, CDCl3): δ 127.4, 127.5, 127.6, 128.8 (d, 1JC−D = 15.6 Hz),
131.0, 132.9, 133.3, 136.8, 144.5, 144.6. MS (EI, 70 eV): m/z 363 (M+,
100), 284 (92), 258 (23), 85 (49), 83 (74). HRMS (EI, 70 eV): calcd
for C24H17DSi2 363.1009, found 363.1006.
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cis-3-d2. 1H NMR (500 MHz, CDCl3): δ 5.58 (s, 2H, JSi−H
=
−200.5 Hz), 7.33−7.36 (m, 4H), 7.41−7.44 (m, 2H), 7.46−7.48 (m,
4H), 7.56−7.57 (m, 2H), 7.76−7.77 (m, 4H). 13C NMR (126 MHz,
1
CDCl3): δ 128.1 (d, JC−D = 15.5 Hz), 128.3, 129.1, 129.9, 134.0,
135.9, 140.6. MS (EI, 70 eV): m/z 366 (M+, 34), 288 (55), 287 (100),
286 (59), 258 (28). HRMS (EI, 70 eV): calcd for C24H18D2Si2
366.1228, found 366.1227.
Coupling of 1 with Magnesium at Room Temperature. A
mixture of 1 (2.03 g, 5.93 mmol), magnesium turnings (0.301 g, 12.4
mmol), and THF (15 mL) was stirred at room temperature for 1 day.
The reaction mixture was hydrolyzed with water and extracted with
diethyl ether. The organic layer was dried over anhydrous magnesium
sulfate and evaporated. The residue was recrystallized from toluene to
give 2 (0.258 g, 24%) as colorless crystals. The filtrate was separated
by column chromatography on silica gel (eluent: hexane−diethyl ether
(1:1)) to give cis-3 (0.324 g, 30%) as a colorless oil.
Coupling of 1 with Magnesium on Microwave Irradiation.
Compound 1 (5.00 g, 14.6 mmol), magnesium turnings (0.750 g, 30.9
mmol), and THF (8 mL) were placed in a glass tube, and the glass
tube was sealed. The mixture was heated at 100 °C for 1 h and then at
180 °C for 1 h with stirring during microwave irradiation. The reaction
mixture was hydrolyzed with aqueous ammonium chloride and washed
with aqueous sodium chloride. The organic layer was dried over
anhydrous magnesium sulfate and evaporated. The residue was
recrystallized from toluene to give 2 (1.88 g, 71%).
Theoretical Calculations of the Reaction Pathways. All
theoretical calculations were performed using Gaussian 09 (revision
A.0221 for trans-4, cis-4, trans-7, and cis-7 and revision C.0122 for other
compounds). The optimized structures and frequencies were
calculated at the B3LYP/6-31+G(d) level. The intrinsic reaction
coordinate (IRC) calculations were carried out to confirm the
connectivity of the transition state and two minima, the reactant and
the product, for each reaction. All calculations were carried out on
Prime Monarch and Galleria computers and a PRIMERGY system of
the Research Center for Computational Science, Japan. For details, see
the Supporting Information.
Synthesis of 9,10-Diphenyl-9,10-disilatriptycene (12). A
solution of phenyllithium in THF, prepared by the reaction of
bromobenzene (0.140 g, 0.89 mmol) with butyllithium in hexane (1.60
mol L−1, 0.6 mL) in THF (2 mL), was added dropwise to a solution of
2 (0.068 g, 0.19 mmol) in THF (20 mL) at −40 °C, and the mixture
was stirred at −40 °C for 2 h. After the solvent was evaporated, the
residue was dissolved in dichloromethane, and insoluble materials were
filtered off. The filtrate was dried over anhydrous magnesium sulfate
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14. Mp: >300 °C. H NMR (500 MHz, CDCl3): δ 3.55 (s, 1H),
7.21 (td, 3H, J = 7.4, 1.3 Hz), 7.27 (td, 3H, J = 7.4, 1.3 Hz), 7.68−7.71
(m, 3H), 7.72−7.74 (m, 3H), 7.87−7.89 (m, 3H), 8.27−8.29 (m, 2H).
13C NMR (126 MHz, CDCl3): δ 127.1, 127.4, 127.5, 128.9, 131.0,
131.1, 132.7, 136.9, 145.1, 145.3. 29Si NMR (99 MHz, CDCl3): δ
−40.9, −30.1. IR (KBr): 3060, 3050, 1430, 1100, 1050, 920, 880, 750,
730, 700, 680 cm−1. MS (EI, 70 eV): m/z 378 (M+, 100), 377 (100),
300 (43), 257 (19), 255 (28). Anal. Calcd for C24H18OSi2·H2O: C,
72.68; H, 5.08. Found: C, 72.69; H, 4.81.
Synthesis of 9-Chloro-10-phenyl-9,10-disilatriptycene (15).
Benzoyl peroxide (0.061 g, 0.25 mmol) was added to a solution of 2
(0.201 g, 0.554 mmol) in carbon tetrachloride (5 mL). The mixture
was refluxed for 4 days. The solvent was evaporated. The residue was
washed with a small amount of hexane and recrystallized from toluene
to give 15 (0.191 g, 87%) as colorless crystals.
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15. Mp: 169 °C. H NMR (500 MHz, CDCl3): δ 7.10−7.14 (m,
3H), 7.17−7.20 (m, 3H), 7.57−7.59 (m, 3H), 7.65−7.67 (m, 3H),
7.82−7.86 (m, 3H), 8.16−8.18 (m, 2H). 13C NMR (126 MHz,
CDCl3): δ 127.8, 128.0, 128.5, 129.0, 131.3, 131.5, 132.7, 136.8, 143.1,
144.4. 29Si NMR (99 MHz, CDCl3): δ −40.6, −14.8. IR (KBr): 3050,
1420, 1120, 1040, 860, 750, 710, 690, 590, 570 cm−1. MS (EI, 70 eV):
m/z 398 (M+(37Cl), 44), 396 (M+(35Cl), 100), 320 (37Cl, 35), 318
(35Cl, 76), 255 (33). Anal. Calcd for C24H17ClSi2: C, 72.61; H, 4.32.
Found: C, 72.62; H, 4.46.
Synthesis of 9-Bromo-10-phenyl-9,10-disilatriptycene (16).
Bromine (0.114 g, 0.713 mmol) was added dropwise to a solution of 2
(0.248 g, 0.684 mmol) in dichloromethane at room temperature. The
mixture was stirred for 8 h at room temperature. The reaction mixture
was evaporated, and the residue was recrystallized from toluene to give
16 (0.090 g, 30%) as colorless crystals.
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16. Mp: 218 °C. H NMR (500 MHz, CDCl3): δ 7.24−7.36 (m,
6H), 7.72−7.78 (m, 6H), 7.95−7.98 (m, 3H), 8.28−8.32 (m, 2H). 13C
NMR (126 MHz, CDCl3): δ 127.8, 128.2, 128.7, 130.2, 132.5, 132.7,
133.9, 136.8, 144.2, 144.3. 29Si NMR (99 MHz, CDCl3): δ −50.8,
−16.9. IR (KBr): 3050, 1410, 1180, 1030, 850, 780, 700, 680 cm−1.
MS (EI, 70 eV): m/z 442 (M+(81Br), 100), 440 (M+(79Br), 91), 364
E
dx.doi.org/10.1021/om301170r | Organometallics XXXX, XXX, XXX−XXX