Organometallics
Article
133.2, 134.1, 134.2, 134.8, 134.9, 135.8, 141.3, 141.5, 145.0, 146.1,
EXPERIMENTAL SECTION
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146.8, 158.9, 159.0, 160.5; 31P NMR (162.0 MHz, CDCl3) δ 22.8,
General Considerations. The manipulations were performed
under an atmosphere of dry nitrogen using vacuum line and standard
Schlenk techniques. Solvents were dried by standard methods and
distilled under nitrogen before use. Hexane and CH2Cl2 were distilled
from CaH2, diethyl ether and THF were distilled from sodium
benzophenone ketyl, and methanol was distilled from Mg/I2. All
reagents were obtained from commercial suppliers and used without
further purification. The ruthenium complex (η5-C5H7)(PPh3)2RuCl
was prepared by following the method reported in the literature.26
NMR spectra were recorded at room temperature and are reported in
units of δ with residual protons in the solvents as a standard. Proton
and carbon chemical shifts are referenced to δ 7.26 and 77.1,
respectively, in CDCl3. The 31P NMR spectra were measured relative
to external 85% phosphoric acid. Both 13C and 31P spectra were
proton-decoupled spectra. Electrospray ionization mass spectrometry,
elemental analysis, and X-ray diffraction studies were carried out at the
Regional Center of Analytical Instrument located at the National
Taiwan University.
−
−144.2 (PF6 ); HRMS (ESI) calcd for C48H38O3P (M+) 657.2559,
found 657.2543.
1
Compound 6h (68% NMR yield): brown powder; H NMR (400
MHz, CDCl3) δ 6.43−6.45 (2H, m), 6.52−6.54 (2H, m), 6.98−7.00
(2H, m), 7.06−7.08 (2H, m), 7.34 (6H, m), 7.58−7.66 (9H, m),
7.72−7.75 (3H, m), 7.91 (1H, m), 8.06 (1H, m); 13C NMR (100
MHz, CDCl3) δ 20.7, 21.1, 21.3, 117.4, 118.3, 118.7, 119.6, 124.0,
126.4, 127.3, 127.5, 127.7, 127.8, 127.9, 128.4, 128.5, 128.7, 129.2,
129.4, 130.0, 130.2, 131.6, 131.9, 132.0, 132.1, 133.9, 134.0, 134.6,
135.8, 137.0, 137.3, 137.9, 138.9, 139.0, 141.5, 141.6, 145.6, 146.6,
−
146.7; 31P NMR (162.0 MHz, CDCl3) δ 23.2, −144.0 (PF6 ); HRMS
(ESI) calcd for C42H29Cl3P (M+) 669.1072, found 669.1078.
1
Compound 6i (66% NMR yield): brown powder; H NMR (400
MHz, CDCl3) δ 6.37−6.40 (2H, m), 6.66−6.68 (2H, m), 6.92−6.97
(3H, m), 7.27−7.29 (3H, m), 7.41−7.44 (2H, m), 7.48−7.52 (4H, m),
7.59−7.62 (9H, m), 7.73 (3H, m), 7.90 (1H, m); 13C NMR (100
MHz, CDCl3) δ 117.7, 118.5, 119.4, 121.9, 122.6, 123.2, 128.0, 128.4,
128.5, 128.9, 130.3, 130.4, 130.6, 131.1, 131.2, 132.0, 132.2, 132.3,
134.1, 134.2, 134.4, 134.8, 135.9, 137.0, 137.7, 141.2, 141.3, 144.3,
General Procedure for Synthesis of Arylphosphonium Salts
by (η5-C5H7)Ru(PPh3)2Cl. Under a dry nitrogen atmosphere, 1 (72.8
mg, 0.1 mmol) and KPF6 (18.4 mg, 0.1 mmol) were placed in a
reaction vessel. Phenylacetylene (2a; 31.1 mg, 0.3 mmol) in 6 mL of
dry THF was transferred to the reaction vessel under nitrogen, and the
resulting solution was stirred at room temperature for 24 h. Then the
solvent was removed under vacuum and CH2Cl2 (3 × 5 mL) was used
to extract the product. The extract was concentrated to ca. 5 mL and
was added to a 100 mL stirred mixture of diethyl ether and hexane (1/
1) to produce precipitates. This brown powder was collected and dried
under vacuum. The powder was further purified by passing through a
neutral Al2O3 column with acetone/ether as eluent to give 6a (44.9
mg, 63% yield).
−
145.4. 31P NMR (162.0 MHz, CDCl3) δ 23.3, −144.0 (PF6 ); HRMS
(ESI) calcd for C42H29Br3P (M+) 802.9537, found 802.9569.
General Procedure for Dimerization of Phenylacetylene by
(η5-C5H7)(PPh3)2RuCl. Under a dry nitrogen atmosphere, 1 (7.3 mg,
0.01 mmol) was placed in a reaction vessel. Phenylacetylene (2a; 102.2
mg, 1.0 mmol) in 6 mL of dry THF was transferred to the reaction
vessel under nitrogen, and the resulting solution was stirred under a
dry nitrogen atmosphere at room temperature for 24 h. The solvent
was removed under vacuum, the solid residue was extracted with a
small amount of hexane, and the mixture was filtered through a short
aluminum oxide pad (1−2 cm), which was washed with hexane until
the eluent was colorless. The filtrate was evaporated to dryness and the
crude product purified by column chromatography eluted with hexane
to give a mixture of 3a and 4a (80.1 mg, 14:86 in 78% total yield).
(Z)-1,4-Diphenylbut-1-en-3-yne (4a):13 yellow liquid; 1H NMR
(400 MHz, CDCl3) δ 5.93 (1H, d, J = 11.8 Hz), 6.70 (1H, d, J = 11.8
Hz), 7.30−7.42 (6H, m), 7.48−7.51 (2H, m), 7.93 (2H, d, J = 7.5
Hz); 13C NMR (100 MHz, CDCl3) δ 88.2, 95.8, 107.4, 123.5, 128.3,
128.4, 128.5, 128.6, 128.8, 131.5, 136.6, 138.7. The spectroscopic data
of 4b−e are consistent with those in previous literature.13
1
Compound 6a: brown powder; H NMR (400 MHz, CDCl3) δ
6.46−6.48 (1H, m), 6.58−6.62 (1H, m), 6.82−6.86 (2H, m), 7.02−
7.03 (2H, m), 7.10−7.11 (3H, m), 7.40−7.47 (8H, m), 7.58−7.70
(14H, m), 8.05 (1H, m); 13C NMR (100 MHz, CDCl3) δ 117.5,
118.4, 118.7, 119.6, 127.1, 127.3, 127.6, 127.8, 127.9, 128.8, 129.3,
129.5, 130.3, 130.4, 130.8, 133.7, 133.8, 134.0, 134.1, 134.8, 135.5,
136.0, 138.0, 139.1, 141.7, 141.8, 145.5, 145.6, 146.8, 146.9; 31P NMR
−
(162.0 MHz, CDCl3) δ 23.2, −144.0 (PF6 ); HRMS (ESI) calcd for
C42H32P (M+) 567.2242, found 567.2332. Anal. Calcd for C42H32F6P2:
C, 70.79; H, 4.53. Found: C, 70.42; H, 4.46.
(Z)-1,4-Bis(p-trifluoromethylphenyl)but-1-en-3-yne (4f):25a yellow
liquid; 1H NMR (400 MHz, CDCl3) δ 6.05 (1 H, d, J = 12.0 Hz), 6.77
(1 H, d, J = 12.0 Hz), 7.55−7.67 (6 H, m), 7.98 (d, J = 8.2 Hz, 2 H);
13C NMR (100 MHz, CDCl3) δ 89.6, 95.2, 109.4, 123.8, 124.0, 125.2,
1
Compound 6c (67% yield): brown powder; H NMR (400 MHz,
CDCl3) δ 1.74 (3H, s), 2.17 (3H, s), 2.37 (3H, s), 6.52−6.56 (1H, m),
6.96−7.00 (2H, m), 7.21−7.23 (2H, m), 7.30−7.32 (2H, m), 7.46−
7.77 (21H, m), 8.03 (1H, m); 13C NMR (100 MHz, CDCl3) δ 20.7,
21.1, 21.3, 117.4, 118.3, 118.7, 119.6, 124.0, 126.4, 127.3, 127.5, 127.7,
127.8, 127.9, 128.4, 128.5, 128.7, 129.2, 129.4, 130.0, 130.2, 131.6,
131.9, 132.0, 132.1, 133.9, 134.0, 134.6, 135.8, 137.0, 137.3, 137.9,
138.9, 139.0, 141.5, 141.6, 145.6, 146.6, 146.7; 31P NMR (162.0 MHz,
125.3, 126.7, 128.8, 130.2, 130.3, 131.6, 138.0, 139.4. The
spectroscopic data of 4h,i are consistent with those in previous
literature.25a
1,2,4-Tris(p-trifluoromethylphenyl)benzene (5f):31 1H NMR (400
MHz, CDCl3) δ 7.22−7.28 (4H, m) 7.49−7.53 (5H, m) 7.64 (1H, s),
7.71−7.78 (5H, m); 13C NMR (100 MHz, CDCl3): δ 122.7, 125.2,
125.3, 125.4, 125.9, 127.1, 127.4, 12.9, 130.0, 130.1, 131.0, 131.4,
139.0, 139.9, 143.5, 144.0, 144.3; 19F NMR (470.6 MHz, CDCl3) δ
−62.47, −62.48.
−
CDCl3) δ 23.1, −144.0 (PF6 ); HRMS (ESI) calcd for C45H38P (M+)
609.2177, found 609.2703. Anal. Calcd for C45H38F6P2: C, 71.61; H,
5.07. Found: C, 71.38; H, 4.92.
1
Compound 6d (65% yield): brown powder; H NMR (400 MHz,
(Z)-1,4-Bis(o-trifluoromethylphenyl)but-1-en-3-yne (4g):32 yellow
liquid; 1H NMR (400 MHz, CDCl3) δ 6.03 (1H, d, J = 11.8 Hz), 6.91
(1H, d, J = 11.8 Hz), 7.12−7.22 (6H, m), 7.39 (1H, d, J = 7.3 Hz),
8.25−8.27 (1H, m); 13C NMR (100 MHz, CDCl3) δ 91.1, 92.2, 110.4,
121.3, 122.1, 122.8, 124.8, 125.6, 125.7, 125.9, 125.9, 127.5, 127.8,
128.2, 128.2, 130.2, 131.0, 131.3, 131.4, 131.5, 134.3, 135.7.
CDCl3) δ 2.03 (3H, s), 2.19 (3H, s), 2.34 (3H, s), 6.30−6.36 (4H, m),
6.89 (3H, m), 7.19−7.31 (4H, m), 7.52−7.63 (14H, m), 7.71−7.72
(3H, m), 7.98 (1H, m); 13C NMR (100 MHz, CDCl3) δ 20.9, 21.0,
21.1, 117.8, 118.7, 118.9, 119.8, 126.8, 128.3, 128.5, 129.3, 130.0,
130.1, 130.2, 130.6, 131.9, 132.6, 133.3, 133.4, 134.0, 134.1, 134.7,
135.1, 135.9, 136.3, 137.0, 137.7, 138.9, 141.4, 141.5, 145.4, 146.6,
−
146.7; 31P NMR (162.0 MHz, CDCl3) δ 23.2, −144.0 (PF6 ); HRMS
(ESI) calcd for C45H38P (M+) 609.2177, found 609.2746. Anal. Calcd
for C45H38F6P2: C, 71.61; H, 5.07. Found: C, 71.43; H, 4.98.
ASSOCIATED CONTENT
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1
Compound 6e (59% yield): brown powder; H NMR (400 MHz,
S
* Supporting Information
CDCl3) δ 3.94 (3H, s), 3.73 (3H, s), 3.85 (3H, s), 6.14−6.16 (1H, m),
6.37−6.39 (2H, m), 6.67−6.69 (2H, m), 6.95−6.98 (2H, m), 7.40−
7.71 (17H, m), 7.75−7.80 (3H, m), 8.00 (1H, m); 13C NMR (100
MHz, CDCl3) δ 54.0, 55.3, 55.6, 113.3, 113.5, 115.0, 119.2, 120.1,
128.4, 128.6, 128.7, 130.4, 130.6, 130.9, 131.8, 132.1, 132.2, 132.3,
Figures, a table, and a CIF file giving the solid-state structure
and crystallographic data for 6a and NMR and mass spectra.
This material is available free of charge via the Internet at
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dx.doi.org/10.1021/om500745y | Organometallics 2014, 33, 6408−6412