699
The carbazol and diamine were obtained in 54% and 19% yields,
respectively, in the presence of 2 equiv of MnI2 in CHCl3. In the
cases of [Mn(acac)3] and [Mn(acac)2], carbazol and diamine
were not obtained or were obtained in very low yields, and the
starting material 5 was consumed. This can be attributed to the
high reactivity of [Mn(acac)3] and [Mn(acac)2] toward the
anthracene dimer 6. In contrast, MnI2 is not so reactive toward
the dimer of anthracene derivatives.
silica gel (hexane:EtOAc = 5:1) to afford yellow solid 4a
(67 mg) in 69% yield.
Reactions of 3b-3I, in 0.1 mmol scale, finished in 3 h (3c,
9 h).
Compound 4a: 1H NMR (600 MHz, CDCl3): ¤ 5.21 (brs,
2H), 7.32 (t, J = 7.8 Hz, 2H), 7.39 (t, J = 8.4 Hz, 2H), 7.47
(d, J = 9.6 Hz, 2H), 7.61 (d, J = 8.4 Hz, 2H), 7.73 (s, 2H),
7.99 (d, J = 8.4 Hz, 2H), 8.20 (d, J = 9.6 Hz, 2H), 8.52 (s,
2H); 13C NMR (CDCl3): ¤ 109.3, 119.3, 122.4, 125.2, 126.0,
127.5, 128.2, 128.2, 128.9, 130.8, 131.6, 132.2, 132.9,
152.8. HRMS m/z: calcd for C28H18O2: 386.1307. Found:
386.1307.
References and Notes
1
As for Fe, see: a) H. Egami, K. Matsumoto, T. Oguma, T.
54, 3007. d) I. S. Ioffe, L. S. Efros, Trudylkkhti, Lab,
krasyashchikh. Vwshchestv 1939, 7, 142. (Original paper is
Compound 4b: 1H NMR (600 MHz, CDCl3): ¤ 0.96 (t,
J = 7.2 Hz, 6H), 1.19 (t, J = 7.2 Hz, 6H), 1.28 (t, J = 6.6 Hz,
6H), 1.47 (t, J = 7.2 Hz, 6H), 2.7-2.85 (m, 8H), 2.88 (q,
J = 6.6 Hz, 4H), 3.29 (q, J = 7.2 Hz, 4H), 5.22 (s, 2H), 7.43
(d, J = 9.0 Hz, 2H), 8.04 (s, 2H), 8.20 (d, J = 9.0 Hz, 2H),
8.69 (s, 2H); 13C NMR (CDCl3): ¤ 14.65, 15.59, 15.71,
15.81, 21.76, 21.94, 22.86, 22.88, 109.1, 118.3, 118.9,
123.8, 127.6, 128.6, 129.6, 130.8, 131.9, 134.71, 134.74,
136.9, 137.9, 152.1. HRMS m/z: calcd for C44H50O2:
610.3811. Found: 610.3812.
2
As for Cu, see: a) J. B. Hewgley, S. S. Stahl, M. C.
Vyskočil, M. Smrčina, M. Lorenc, I. Tišlerová, R. D.
Brooks, J. J. Kulagowski, V. Langer, L. J. Farrugia, P.
As for V, see: a) S. Takizawa, T. Katayama, C. Kameyama,
K. Onitsuka, T. Suzuki, T. Yanagida, T. Kawai, H. Sasai,
As for Mn, see: a) H. Nishino, N. Itoh, M. Nagashima, K.
Representative procedure of dimerization of 2-naphthol: A
mixture of 1.3 mg of [Mn(acac)2], 17.2 mg of 6-ethylnaph-
thalen-2-ol, 1 mL of CHCl3 were stirred at 50 °C for 6 h.
After cooling at room temperature, the concentrated reaction
mixture was purified on silica gel column (hexane:EtOAc =
5:1) to affod white solid (14 mg) in 81% yield.
1
Compound 4c: H NMR (600 MHz, DMSO-d6): ¤ 2.22 (s,
6H), 2.34 (s, 6H), 7.30 (s, 2H), 7.374 (s, 2H), 7.378 (d,
J = 9.0 Hz, 2H), 7.73 (s, 2H), 8.04 (d, J = 9.0 Hz, 2H), 8.37
(s, 2H), 9.18 (s, 2H); 13C NMR (DMSO-d6): ¤ 19.78, 19.86,
113.3, 120.1, 120.4, 124.9, 126.3, 126.5, 127.6, 128.5,
129.1, 130.8, 132.3, 133.8, 135.2, 152.1. HRMS m/z: calcd
for C32H26O2: 442.1932. Found: 442.1928.
3
4
5
1
Compound 4g: H NMR (600 MHz, CDCl3): ¤ 5.57 (s, 2H),
7.33 (t, J = 11.0 Hz, 2H), 7.39-7.45 (m, 4H), 7.52 (t, J =
11.0 Hz, 4H), 7.65 (d, J = 13.2 Hz, 2H), 7.81-7.85 (m, 6H),
8.01 (d, J = 12.6 Hz, 2H), 8.28 (s, 2H), 8.57 (s, 2H);
13C NMR (CDCl3): ¤ 110.4, 122.2, 125.0, 125.7, 127.4,
127.9, 128.0, 128.1, 128.5, 128.6, 129.6, 130.7, 130.9,
131.8, 132.6, 137.4, 150.3. HRMS m/z: calcd for C40H26O2:
538.1900. Found: 538.1923.
Compound 4h: 1H NMR (600 MHz, CDCl3): ¤ 1.48 (t,
J = 7.2 Hz, 6H), 3.0 (q, J = 7.2 Hz, 4H), 5.35 (s, 2H), 7.29
(t, J = 7.8 Hz, 2H), 7.38 (t, J = 7.8 Hz, 2H), 7.60 (d,
J = 9 Hz, 2H), 7.66 (s, 2H), 7.99 (d, J = 9.0 Hz, 2H), 8.03
(s, 2H), 8.48 (s, 2H); 13C NMR (CDCl3): ¤ 13.63, 24.04,
108.7, 121.9, 124.7, 125.3, 126.3, 127.9, 128.0, 128.8,
128.8, 130.5, 132.0, 134.0, 152.1. HRMS m/z: calcd for
C32H26O2: 442.1932. Found: 442.1928.
6
7
CCDC number 909538.
Typical procedure of dimerization: To a solution of 98 mg
(0.5 mmol) of 2-hydroxyanthracene 3a in 2 mL of CHCl3,
7.7 mg (0.025 mmol) of MnI2 was added. The reaction
mixture was stirred at 50 °C in open air for 12 h. After cooled
to room temperature, the reaction mixture was concentrated,
and the residue was purified by column chromatography on
8
9
Their synthesis will be reported in somewhere else.
10 K. Niimi, E. Miyazaki, I. Osaka, K. Takimiya, Synthesis
Chem. Lett. 2013, 42, 697-699
© 2013 The Chemical Society of Japan