532
S. Sasaki et al. / Journal of Organometallic Chemistry 751 (2014) 525e533
JPC ¼ 4.7 Hz, m-Tip), 122.08 (d, JPC ¼ 4.6 Hz, m-Tip), 34.08 (s, CH-p),
32.17 (d, JPC ¼ 17.9 Hz, CH-o), 32.11 (d, JPC ¼ 17.8 Hz, CH-o), 24.64 (s,
CH(CH3)2-o), 24.55 (s, CH(CH3)2-o), 23.92 (s, CH(CH3)2-o), 23.26 (s,
CH(CH3)2-o), 23.01 (s, CH(CH3)2-p-Tip), 22.87 (s, CH(CH3)2-o); 31P
2.94 (5H, m, CH-p), 1.26 (9H, d, JHH ¼ 7.20 Hz, CH(CH3)2-o), 1.24
(12H, d, JHH ¼ 6.40 Hz, CH(CH3)2-o), 1.23 (30H, d, JHH ¼ 6.80 Hz,
CH(CH3)2-p), 1.22 (12H, d, JHH ¼ 6.80 Hz, CH(CH3)2-o), 0.96 (6H, d,
JHH ¼ 6.00 Hz, CH(CH3)2-o), 0.95 (6H, d, JHH ¼ 6.40 Hz, CH(CH3)2-
o), 0.91 (12H, d, JHH ¼ 6.80 Hz, CH(CH3)2-o), 0.76 (3H, d,
JHH ¼ 6.40 Hz, CH(CH3)2-o), 0.72 (12H, d, JHH ¼ 6.40 Hz, CH(CH3)2-
NMR (162.06 MHz, CDCl3, 293 K)
d
ꢀ50.7 (s); IR (KBr) 1675
n
(C]O)
cmꢀ1; UVeVis (CH2Cl2, c ¼ 5.62 ꢂ 10ꢀ6 mol Lꢀ1
) lmax (ε) 464 (7800),
349 (34,000), 286 (58,000) nm; FT-ICReMS (ESI) Calcd For:
[C98H130O2P2 þ H]þ: 1401.9619. Found: 1401.9629; Anal. Calcd for
o), 0.71 (12H, d, JHH
¼
6.40 Hz, CH(CH3)2-o); 13C NMR
(100.67 MHz, CDCl3, 293 K)
d
184.90 (s, C]O), 184.87 (s, C]O),
C
98H130O2P2$0.35CHCl3: C, 81.81; H, 9.10%, Found: C, 81.79; H,
153.72 (d, JPC ¼ 18.2 Hz, o-arom), 153.62 (d, JPC ¼ 16.6 Hz, o-Tip),
153.45 (d, JPC ¼ 18.1 Hz, o-Tip), 153.26 (d, JPC ¼ 19.2 Hz, o-Tip),
153.16 (d, JPC ¼ 18.3 Hz, o-Tip), 149.95 (s, p-Tip), 149.70 (s, p-Tip),
144.20 (s, quinone), 144.13 (s, quinone), 141.62 (s, quinone), 141.36
(s, quinone), 137.17 (s, quinone), 137.15 (s, quinone), 136.71 (s,
8.95%.
4.2.3. [2,6-Diisopropyl-4-(5-bromoanthraquinon-1-yl)phenyl]
bis(2,4,6-triisopropylphenyl)phosphine (9)
To a solution of 8 (1.01 g, 1.49 mmol) in tetrahydrofuran (15 mL)
was added butyllithium (1.58 M in n-hexane, 1.13 mL, 1.79 mmol)
at ꢀ78 ꢁC. The resultant mixture was stirred for 30 min, and tri-
methyl borate (0.25 mL, 2.23 mmol) was added. The mixture was
warmed, refluxed for 3 h, and concentrated under reduced
pressure. To the residue was added 1,5-dibromoanthraquinone
(1.42 g, 3.88 mmol), dichlorobis(triphenylphosphine)palladium(II)
(93.0 mg, 0.133 mmol), sodium carbonate (606 mg, 5.72 mmol),
toluene (15 mL), and degassed water (4 mL). The mixture was
refluxed for 14 h, extracted with toluene, dried over anhydrous
magnesium sulfate, concentrated under reduced pressure, and
purified by column chromatography (Al2O3/n-hexane, chloroform)
to give crude 9 (460 mg, 0.520 mmol, 35%). The product was
contaminated with 5 and the debrominated anthraquinon-1-yl
derivative, but was used in the next step without further
purification.
quinone), 135.24 (d, JPC
¼
26.2 Hz, ipso-arom), 134.78 (d,
JPC ¼ 25.4 Hz, ipso-arom), 132.93 (s, quinone), 132.32 (s, p-arom),
132.25 (s, quinone), 132.24 (s, quinone), 132.09 (s, p-arom), 131.77
(d, JPC ¼ 22.7 Hz, ipso-Tip), 126.45 (s, quinone), 126.40 (s,
quinone), 125.11 (br, m-arom), 125.00 (d, JPC ¼ 3.9 Hz, m-arom),
122.47 (d, JPC ¼ 4.5 Hz, m-Tip), 122.42 (d, JPC ¼ 6.9 Hz, m-Tip),
34.53 (s, CH-p), 32.30e32.80 (m, CH-o), 25.16 (s, CH(CH3)2-o),
25.07 (s, CH(CH3)2-o), 25.00 (s, CH(CH3)2-o), 24.41 (s, CH(CH3)2-
o), 23.85 (s, CH(CH3)2-o), 23.80 (s, CH(CH3)2-o), 23.60 (s,
CH(CH3)2-p-Tip), 23.50 (s, CH(CH3)2-p-Tip), 23.30 (s, CH(CH3)2-o),
23.26 (s, CH(CH3)2-o); 31P NMR (162 MHz, CDCl3, 293 K)
d
ꢀ50.5
(C]O) cmꢀ1; UVeVis (CH2Cl2,
) lmax (ε) 333 (49,000), 256 (140,000) nm;
(s), ꢀ51.1(s); IR (KBr) 1681
n
c ¼ 1.76 ꢂ 10ꢀ5 mol Lꢀ1
FT-ICReMS (ESI) Calcd for [C151H191O4P]þ: 2161.3950. Found:
2161.3941, Calcd for [C151H191O4P3 þ H]þ: 2162.4028. Found:
2162.4009, Calcd for [C151H191O4P3 þ Na]þ: 2184.3847. Found:
2184.3862; Anal. Calcd for C151H191O4P3$0.5CHCl3: C, 81.86; H,
8.68%, Found: C, 81.73; H, 8.66%.
9: Reddish brown solid; mp 182e194 ꢁC; 1H NMR (400.33 MHz,
CDCl3, 293 K)
d
8.31 (1H, dd, JHH ¼ 8.00 Hz, JHH ¼ 1.20 Hz, arom),
8.04 (1H, dd, JHH ¼ 7.60 Hz, JHH ¼ 1.20 Hz, arom), 7.97 (1H, dd,
JHH ¼ 8.00 Hz, JHH ¼ 1.20 Hz, arom), 7.75 (1H, t, JHH ¼ 8.00 Hz, arom),
7.64 (1H, dd, JHH ¼ 7.60 Hz, JHH ¼ 1.20 Hz, arom), 7.51 (1H, t,
JHH ¼ 8.00 Hz, arom), 7.00 (2H, d, JPH ¼ 3.20 Hz, arom), 6.96e6.97
(2H, bm, arom), 6.90e6.92 (2H, bm, arom), 3.52e3.68 (6H, m, CH-
o), 2.86 (2H, sept, JHH ¼ 6.80 Hz, CH-p), 1.24 (12H, d, JHH ¼ 7.20 Hz,
CH(CH3)2-p), 1.24 (18H, d, JHH ¼ 7.20 Hz, CH(CH3)2-p, o), 0.91 (6H, d,
JHH ¼ 6.80 Hz, CH(CH3)2-o), 0.71 (6H, d, JHH ¼ 6.40 Hz, CH(CH3)2-o);
4.2.5. Triarylphosphineenaphthoquinone oligomer 7
To a solution of 10 (356 mg, 0.500 mmol) in tetrahydrofuran
(10 mL) was added butyllithium (1.59 M in n-hexane, 0.70 mL,
1.11 mmol) at ꢀ78 ꢁC. The resultant mixture was stirred for 30 min,
and trimethyl borate (0.17 mL, 1.50 mmol) was added. The mixture
was warmed, refluxed for 3 h, cooled to 20 ꢁC, and concentrated
under reduced pressure. To the residue was added 2b (1.13 g,
31P NMR (162.06 MHz, CDCl3, 293 K)
d
ꢀ51.1 (s); IR (KBr) 1680 (C]
1.20
mmol),
dichlorobis(triphenylphosphine)palladium(II)
O) cmꢀ1; FT-ICReMS (ESI) Calcd For: [C56H68BrO2P]þ: 882.4135.
Found: 882.4116; Calcd For: [C56H68BrO2P þ Na]þ: 905.4033.
Found: 905.4039.
(40.0 mg, 0.06 mmol), sodium carbonate (342 g, 3.28 mmol),
toluene (20 mL), and degassed water (10 mL). The mixture was
heated at 80 ꢁC for 12 h, cooled to 20 ꢁC, extracted with ether, dried
over anhydrous magnesium sulfate, concentrated under reduced
pressure, and purified by column chromatography (Al2O3/n-hex-
ane, n-hexane/ethyl acetate ¼ 20/1) and GPC (CHCl3) to give 7
(57.0 mg, 0.016 mmol, 5%).
4.2.4. Bis[2,6-diisopropyl-4-[5-[3,5-diisopropyl-4-bis{(2,4,6-
triisopropylphenyl)phosphino}phenyl]-anthraquinon-1-yl]
phenyl](2,4,6-triisopropylphenyl)phosphine (11)
To a solution of 10 (98.0 mg, 0.137 mmol) in tetrahydrofuran
(5 mL) was added butyllithium (1.58 M in n-hexane, 0.21 mL,
0.332 mmol) at ꢀ78 ꢁC. The resultant mixture was stirred for
30 min, and trimethyl borate (0.06 mL, 0.537 mmol) was added. The
mixture was warmed, refluxed for 3 h, and concentrated under
reduced pressure. To the residue was added dichlorobis(-
triphenylphosphine)palladium(II) (21.0 mg, 0.0299 mmol), sodium
carbonate (155 mg, 1.46 mmol), and 9 (250 mg, 0.283 mmol) in
toluene (5 mL), and degassed water (2 mL). The mixture was
refluxed for 13 h, extracted with toluene, dried over anhydrous
magnesium sulfate, concentrated under reduced pressure, and
purified by column chromatography (Al2O3/n-hexane, chloroform)
and GPC to give 11 (50 mg, 0.0231 mmol, 18%).
7: purple solid; mp 284e285 ꢁC; 1H NMR (400.33 MHz, CDCl3)
d
8.25e8.06 (8H, m, quinone), 7.81e7.68 (8H, m, quinone), 7.10e
6.80 (18H, m, m-arom), 3.74e3.24 (18H, m, CH(CH3)2-o), 2.90e2.72
(3H, m, CH(CH3)2-p), 1.33e0.90 (72H, m, CH(CH3)2), 0.86e0.40
(54H, m, CH(CH3)2); 13C NMR (100.67 MHz, CDCl3, 293 K)
d 184.72
(C]O), 184.68 (C]O), 182.04 (C]O), 182.03 (C]O), 178.43 (C]O),
153.8e152.0 (m, o-Tip), 149.86 (s, p-Tip), 146.28 (naphthoquinone),
144.82 (s, p-arom), 144.64 (s, p-arom), 142.49 (s, p-arom), 137.69
(dm, J ¼ 26.0 Hz, ipso), 134.27 (brs), 134.00e133.75 (m), 133.35
(brs), 132.30 (brs), 132.05 (brs), 131.81 (s), 131.38 (s), 131.10 (d,
J ¼ 21.3 Hz, ipso), 128.02 (brs), 127.52 (brs), 127.75 (brs), 127.19 (s)
127.07 (s), 126.95 (s), 126.91e126.64 (m), 126.42 (brs, m-arom),
125.7e125.9 (m, m-arom), 122.5e122.0 (m, m-Tip)), 34.05 (s, CH-p),
32.7e31.3 (m, CH-o), 25.1e22.3 (m, CH(CH3)2); 31P NMR
11: Reddish brown solid; mp 228e234 ꢁC; 1H NMR
(400.33 MHz, CDCl3, 293 K)
d
8.03 (4H, dd, JHH ¼ 7.60 Hz,
(162.06 MHz, CDCl3)
e48.52 (s), e48.58 (s), e48.62 (s); UVeVis (CH2Cl2) lmax (ε) nm 531
d
ꢀ47.31 (s), e47.60 (s), e47.91 (s), e48.00 (s),
JHH ¼ 1.20 Hz, arom), 7.50e7.80 (8H, m, arom), 7.07e7.13 (4H, m,
arom), 7.05 (4H, d, JPH ¼ 3.20 Hz, arom), 7.00 (2H, d, JPH ¼ 3.60 Hz,
arom), 6.92e9.98 (8H, m, arom), 3.50e3.77 (18H, m, CH-o), 2.80e
(11,800),
335
(64,600);
FT-ICR-MS
(ESI)
Calcd
for
[C157H181O8P3Cl2 þ Na]þ: 2380.2239. Found: 2380.2262; Anal.