926 Bull. Chem. Soc. Jpn., 78, No. 5 (2005)
Rotational Isomerism of Di(9-anthryl)ethynes
romethylsulfonyl)oxy]anthracene (8d0): Yield 29% based on 6d;
yellow oil; 1H NMR (CDCl3) ꢀ 1.34 (6H, d, J ¼ 7:0 Hz), 3.03
(1H, septet, J ¼ 7:0 Hz), 7.38 (1H, d, J ¼ 7:3 Hz), 7.42 (1H, s),
7.46–7.50 (2H, m), 7.61–7.70 (2H, m), 7.91 (1H, d, J ¼ 8:8
Hz), 8.25 (1H, d, J ¼ 8:3 Hz), 8.27 (1H, d, J ¼ 8:3 Hz), 8.56
(1H, s); 13C NMR (CDCl3) ꢀ 24.1, 34.2, 118.9 (q, JCF ¼ 320
Hz), 120.3, 120.8, 124.2, 125.0, 125.8, 125.9, 126.7, 126.7,
127.2, 127.5, 127.8, 128.3, 128.4, 128.7, 130.7, 131.5, 139.8,
140.8, 149.1 (one signal was missing due to overlapping.); HRMS
(FAB) Found: 444.1027, Calcd for C24H19F3O3S: Mþ 444.1007.
1-(3,5-Diisopropylphenyl)-9-[(trifluoromethylsulfonyl)oxy]-
anthracene (8e). A mixture of 7e and 7e0 in ca. 6:5 ratio was
used as the starting material. The corresponding triflates 8e and
8e0 were separated by HPLC with hexane as eluent, and obtained
as the second and first fractions (elution times 23.8 and 13.4 min
at flow rate 9.5 mL minꢂ1), respectively. The desired compound
was obtained as a yellow solid in 32% yield based on 6e. mp
122.5–123.0 ꢁC; 1H NMR (CDCl3) ꢀ 1.30 (12H, br), 2.95 (2H,
septet, J ¼ 6:8 Hz), 7.12 (1H, s), 7.17 (2H, brs), 7.51–7.61 (4H,
m), 7.99 (1H, dd, J ¼ 2:4, 6.8 Hz), 8.05 (1H, d, J ¼ 8:3 Hz),
8.18 (1H, d, J ¼ 8:3 Hz), 8.55 (1H, s); 13C NMR (CDCl3) ꢀ
24.0, 24.3, 34.4, 118.2 (q, JCF ¼ 321 Hz), 121.5, 123.2, 123.8,
125.3, 125.5, 125.7, 126.1, 127.1, 127.5, 127.7, 128.0, 131.4,
131.6, 133.2, 137.6, 139.1, 141.2, 148.2; HRMS (FAB) Found:
486.1445, Calcd for C27H25F3O3S: Mþ 486.1477. 1-(3,5-Diiso-
propylphenyl)-10-[(trifluoromethylsulfonyl)oxy]anthracene (8e0):
Yield 23% based on 6e; yellow solid; mp 100.5–101.5 ꢁC;
1H NMR (CDCl3) ꢀ 1.35 (12H, d, J ¼ 6:8 Hz), 3.02 (1H, septet,
J ¼ 6:8 Hz), 7.23 (1H, s), 7.25 (2H, s), 7.47–7.52 (2H, m), 7.64
(1H, dd, J ¼ 6:8, 8.3 Hz), 7.69 (1H, dd, J ¼ 6:8, 8.8 Hz), 7.92
(1H, d, J ¼ 8:8 Hz), 8.25 (1H, d, J ¼ 8:8 Hz), 8.26 (1H, d, J ¼
8:8 Hz), 8.61 (1H, s); 13C NMR (CDCl3) ꢀ 24.2, 34.3, 118.9 (q,
JCF ¼ 320 Hz), 120.1, 120.8, 124.2, 124.4, 125.0, 125.7, 125.8,
126.6, 126.9, 127.3, 127.8, 128.7, 130.7, 131.5, 139.7, 139.8,
141.2, 149.0; HRMS (FAB) Found: 486.1503, Calcd for
C27H25F3O3S: Mþ 486.1477.
the desired product was obtained as the less easily eluted fraction.
Recrystallization from hexane–dichloromethane gave the pꢁure
compound in 36% yield as orange crystals. mp 207.0–208.0 C;
1H NMR (CD2Cl2) ꢀ 0.28 (12H, d, J ¼ 6:8 Hz), 1.88 (2H, septet,
J ¼ 6:8 Hz), 6.55 (4H, d, J ¼ 7:3 Hz), 7.22–7.25 (6H, m), 7.40–
7.53 (6H, m), 7.99–8.01 (4H, m), 8.37 (2H, d, J ¼ 8:8 Hz), 8.46
(2H, s); 13C NMR (CD2Cl2) ꢀ 22.9, 33.2, 103.7, 118.4, 124.7,
124.9, 125.9, 126.2, 128.0, 128.2, 128.4, 128.9, 129.7, 130.0,
130.2, 131.2, 132.6, 133.7, 140.3, 141.2, 146.9; UV (CHCl3) ꢂ
(log ") 271.5 (5.2), 404.0 (4.3), 428.5 nm (4.5); Anal. Found: C,
93.50; H, 6.13%. Calcd for C48H38: C, 93.77; H, 6.23%; HRMS
(FAB) Found: m=z 615.3080, Calcd for C48H38: MHþ,
615.3052. [1-(4-Isopropylphenyl)-9-anthryl][4-(4-isopropylphen-
yl)-9-anthryl]ethyne (3b0): yield 10%; red crystals; mp 182.5–
183.0 ꢁC; 1H NMR (CDCl3) ꢀ 0.23 (6H, d, J ¼ 6:8 Hz), 1.40
(6H, d, J ¼ 6:8 Hz), 1.91 (1H, septet, J ¼ 6:8 Hz), 3.07 (1H, sep-
tet, J ¼ 6:8 Hz), 6.69 (2H, d, J ¼ 7:8 Hz), 7.40–7.57 (14H, m),
7.86 (1H, d, J ¼ 8:1 Hz), 8.08 (1H, d, J ¼ 7:8 Hz), 8.09 (1H, d,
J ¼ 8:1 Hz), 8.33 (1H, d, J ¼ 8:3 Hz), 8.37 (1H, d, J ¼ 8:5
Hz), 8.43 (1H, s), 8.60 (1H, s), 8.77 (1H, d, J ¼ 8:8 Hz); 13C NMR
(CD2Cl2) ꢀ 22.6, 24.2, 32.9, 34.0, 98.4, 102.1, 117.4, 118.7, 124.8,
125.2, 125.4, 125.6, 126.0, 126.3, 126.4, 126.8, 126.9, 127.1,
127.2, 127.3, 128.4, 128.6, 128.7, 129.8, 129.8, 130.0, 130.8,
130.9, 131.0, 131.5, 132.0, 132.3, 133.3, 134.4, 138.2, 140.3,
141.0, 146.8, 147.9 (three signals were missing due to overlap-
ping.); HRMS (FAB) Found: m=z 614.2964, Calcd for C48H38:
Mþ, 614.2974.
Bis[1-(4-t-butylphenyl)-9-anthryl]ethyne (3c).
This com-
pound was similarly prepared from 8c. The product was purified
by chromatography on silica gel with hexane–dichloromethane
(5:1) as eluent to give the desired compound in 69% yield as yel-
low crystals. mp 246.0–246.5 ꢁC; 1H NMR (CDCl3) ꢀ 0.38 (18H,
s), 6.76 (4H, d, J ¼ 7:8 Hz), 7.24 (2H, dd, J ¼ 1:5, 6.8 Hz), 7.27
(4H, d, J ¼ 8:3 Hz), 7.40–7.52 (6H, m), 7.99 (2H, dd, J ¼ 1:0, 8.3
Hz), 8.00 (2H, d, J ¼ 7:8 Hz), 8.37 (2H, dd, J ¼ 1:0, 8.8 Hz), 8.47
(2H, s); 13C NMR (CD2Cl2) ꢀ 30.4, 33.7, 103.6, 118.4, 123.8,
124.7, 125.9, 126.2, 128.1, 128.2, 128.4, 128.9, 129.7, 130.0,
130.1, 131.3, 132.6, 133.8, 139.9, 141.2, 149.1; Anal. Found: C,
93.06; H, 6.70%. Calcd for C50H42: C, 93.41; H, 6.59%; HRMS
(FAB) Found: m=z 642.3266, Calcd for C50H42: Mþ, 642.3287.
Bis[1-(3-isopropylphenyl)-9-anthryl]ethyne (3d). This com-
pound was similarly prepared from 8d. The product was purified
by chromatography on silica gel with hexane–dichloromethane
(5:1) as eluent. The main fraction was purified by HPLC with hex-
ane as eluent to give the desired compound in 54% yield as yellow
Bis[1-(4-methylphenyl)-9-anthryl]ethyne (3a). To 5 mL of
acetonitrile, which was degassed by bubbling Ar gas for 1 h, were
added 37.8 mg (0.90 mmol) of LiCl, 83.3 mg (0.20 mmol) of 8a,
11.6 mg (0.010 mmol) of [Pd(PPh3)4], and 0.079 mL (0.15 mmol)
of bis(tributylstannyl)ethyne. The whole was refluxed for 15 h
under Ar atmosphere. After cooling, the reaction mixture was
quenched with water, and extracted with ether. The separated
organic solution was washed with brine, dried over MgSO4, and
evaporated. The crude product was purified by chromatography
on silica gel with hexane–dichloromethane (5:1) as eluent to give
54 mg (96%) of the desired compound as orange crystals. mp
ꢁ
1
ꢁ
crystals. mp 192.5–193.0 C; H NMR (C2D2Cl4, 110 C) ꢀ 0.64
(12H, brs), 2.19 (2H, septet, J ¼ 6:8 Hz), 6.04 (2H, d, J ¼ 8:3
Hz), 6.37 (2H, dd, J ¼ 7:3, 7.8 Hz), 6.99 (2H, d, J ¼ 7:3 Hz),
7.05 (2H, s), 7.20 (2H, d, J ¼ 6:3 Hz), 7.39–7.50 (6H, m),
7.93–7.99 (4H, m), 8.38 (2H, d, J ¼ 8:8 Hz), 8.41 (2H, s);
13C NMR (CD2Cl2) ꢀ 22.7, 22.8, 23.8, 24.0, 33.4, 33.5, 104.1,
104.2, 118.6, 123.4, 123.5, 124.8, 126.0, 126.2, 126.3, 127.0,
127.1, 127.3, 127.7, 127.7, 128.09, 128.14, 128.2, 128.7, 128.7,
129.5, 129.7, 130.4, 130.6, 131.1, 132.2, 132.6, 133.6, 133.7,
141.6, 143.1, 147.4; UV (CHCl3) ꢂ (log ") 270.0 (4.7), 404.0
(3.8), 428.5 nm (3.9); HRMS (FAB) Found: m=z 614.2990, Calcd
for C48H38: Mþ, 614.2974.
ꢁ
1
246.0–246.5 C; H NMR (CD2Cl2) ꢀ 1.11 (6H, s), 6.28 (4H, d,
J ¼ 7:8 Hz), 7.05 (4H, d, J ¼ 7:8 Hz), 7.21 (2H, d, J ¼ 6:8
Hz), 7.43–7.55 (6H, m), 8.01–8.04 (4H, m), 8.36 (2H, d, J ¼
8:8 Hz), 8.44 (2H, s); 13C NMR (CD2Cl2) ꢀ 20.1, 103.8, 118.8,
124.8, 126.0, 126.1, 127.8, 127.9, 128.1, 128.3, 128.7, 129.2,
129.5, 130.4, 131.2, 132.6, 133.4, 136.6, 140.2, 141.3; UV (cyclo-
hexane) ꢂ (log ") 268.5 (5.1), 402.5 (4.3), 427.0 nm (4.4); Anal.
Found: C, 94.16; H, 5.33%. Calcd for C44H30: C, 94.59; H, 5.41%;
HRMS (FAB) Found: m=z 558.2379, Calcd for C44H30: Mþ,
558.2347.
Bis[1-(4-isopropylphenyl)-9-anthryl]ethyne (3b). This com-
pound was similarly prepared from 8b. The products were separat-
ed by chromatography with hexane–dichloromethane (5:1) as elu-
ent. The main fraction was a mixture of 3b and its isomer 3b0,
which was then separated by GPC. After recycling several times,
Bis[1-(3,5-diisopropylphenyl)-9-anthryl]ethyne (3e). This
compound was similarly prepared from 8e. The product was puri-
fied by chromatography on silica gel with hexane–dichlorometh-
ane (10:1) as eluent to give the desired compound in 47% yield
as yellow crystals. mp 208.5–209.0 ꢁC; 1H NMR (CD2Cl2) ꢀ