Chemistry Letters 2000
615
(1988). c) J. Harmenberg, B. Wahren, and J. Bergman, Antimicrob.
Agents Chemother., 32, 1720 (1988).
3
a) P. Chaudhuri, T. Weyhermüller, E. Bill, and K. Wieghardt, Inorg.
Chim. Acta, 252, 195 (1996). b) C. J. Fahrni, A. Pfaltz, M.
Neuburger, and M. Zehnder, Helv. Chim. Acta, 81, 507 (1998). c)
Y. Hosokawa, H. Yamane, Y. Nakao, K. Matsumoto, S.
Takamizawa, W. Mori, S. Suzuki, and H. Kimoto, Inorg. Chim.
Acta, 283, 118 (1998). d) T. Koga, H. Furutachi, T. Nakamura, N.
Fukita, M. Ohba, K. Takahashi, and H. Okawa, Inorg. Chem., 37,
989 (1998). e) B. Kersting, G. Steinfeld, and J. Hausmann, Eur. J.
Inorg. Chem., 1999, 179. f) B. Kersting and D. Siebert, Eur. J.
Inorg. Chem., 1999, 189. g) A. Aukauloo, X. Ottenwaelder, R. Ruiz,
S. Poussereau, Y. Pei, Y. Journaux, P. Fleurat,, F. Volatron, B.
Cervera, and M. C. Muñoz, Eur.J. Inorg. Chem., 1999, 1067.
Compound 1 was prepared according to the modified Schunck's
method:1a Reaction of isatin (300 mg, 2.0 mmol) with a 1.1 molar
amount of o-phenylenediamine (250 mg, 2.3 mmol) in ethanol (25
mL) at reflux temperature (82 °C) for 24 h under argon quantitative-
ly gave compound 1 (210 mg, 1.0 mmol, 67% yield)7 (the recov-
ered isatin: 90 mg, 0.6 mmol, conversion: 71%). 1: yellow needles,
mp > 212 °C (sublimation, determined by the TGA/DTA) (lit:1b mp
295–296 °C), Rf = 0.45 on silica-gel TLC (AcOEt/hexane = 2/1,
4
vol/vol); UV-visible λ
(CH2Cl2) nm (log ε), 260sh(4.70),
267(4.82), 337(4.32), 351m(4ax.38), and 382(3.85); IR (KBr) νmax 1616
cm-1 (C=N, st), 3067 (NH, st); EI-MS m/z 219(M+, 100%); Found:
m/z 219.0799, Calcd for C14H9N3: M+, 219.0796; 1H-NMR
(CD2Cl2) δ 7.41(1H, ddd, J = 7.5, 7.5, 1.0 Hz, H-9), 7.56(1H, ddd, J
= 8.0, 1.0, 0.5 Hz, H-7), 7.69(1H, ddd, J = 8.0, 7.5, 1.0 Hz, H-8),
7.72(1H, ddd, J = 8.5, 7.0, 1.5 Hz, H-2), 7.78(1H, ddd, J = 8.0, 7.0,
1.5 Hz, H-3), 8.09(1H, ddd, J = 8.0, 1.5, 0.5 Hz, H-4), 8.28(1H,
ddd, J = 8.5, 1.5, 0.5 Hz, H-1), 8.42(1H, ddd, J = 7.5, 1.0, 0.5 Hz,
H-10), and 8.76(1H, brds, NH-6).
5
6
Reactions of various alcohols with NaBH4 are well known,6 giving
a respective sodium salt of (RO)4B−. In this reaction the generated
sodium salt of (EtO)4B− served as a base for deprotonation of N-6
position of 1, affording the reactive anion species 2, quantitatively.
2: reddish-orange color; visible λmax (EtOH) nm, 480; exact FAB-
MS(negative) (Found: m/z 218.0720; Calcd for C14H8N3: M−, m/z
218.0718).
a) H. J. Schlesinger, H. C. Broun, H. R. Hoekstra, and L. R. Papps,
J. Am. Chem. Soc., 75, 199 (1953). b) J. C. Norrild and H. Eggert, J.
Am. Chem. Soc., 117, 1479 (1995). c) S. Takekuma, H. Takekuma,
T. Matsumoto, and Z. Yoshida, Tetrahedron Lett., 41, 2929 (2000).
The yield of the product is based on the consumed starting material.
The parameters were confirmed by a computer-assisted simulation
analysis.
a) The sample dried well in a vacuum desiccator was used for the
thermal, elemental and spectroscopic analyses. b) The freshly
recrystallized sample, which was not dried in a vacuum desiccator,
was used for the X-ray crystallographic analysis.
7
8
9
10 Crystallographic data for complex 3: C56H32N12Ni2·4CH2Cl2 (FW =
1330.08), dark reddish-orange block (the crystal size, 0.28 × 0.15 ×
0.05 mm), monoclinic, P21/c (#14), a = 9.271(1) Å, b = 15.950(2) Å,
We are grateful to Prof. M. Munakata (Kinki Univ.) and
Dr. K. Sugimoto (Kinki Univ.) for technical assistance of the
X-ray crystallographic analysis and Assistant Prof. T. Kuroda-
Sowa (Kinki Univ.) for discussion. This work was supported
by a Grant-in-Aid for Scientific Research (No.10146102) from
the Ministry of Education, Science, Sports and Culture, Japan.
c = 18.812(1) Å, β = 92.436(2)°, V = 2779.1(5) Å3, Z = 2, Dcalcd
=
1.589 g/cm3, µ(Mo Kα) = 11.16 cm-1, measured reflections = 6555,
observed reflections = 6317, R1 = 0.0798, wR2 = 0.2284. The X-ray
measurement of complex 3 was made with graphite monochromated
Mo Kα radiation (λ = 0.71069 Å) on a Quantum CCD area detector
coupled with a Rigaku AFC-7 diffractometer at 200 K. The structure
was solved by direct methods (SIR92) and expanded using Fourier
techniques. The non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were included but not refined. The final cycle of
full-matrix least-squares refinement was based on F2 using the pro-
gram SHELXL 97. All calculations were performed using the
teXsan crystallographic software package.
References and Notes
1
a) E. Schunck and L. Marchlewski, Ber, 28, 2528 (1895). b) G. M.
Badger and P. J. Nelson, J. Chem. Soc., 1962, 3926 (1962). c) G. P.
de Gaudemaris and B. J. Sillion, J. Polym. Sci. B, 2, 203 (1964). d)
J.K. Stille and J. R. Williamson, J. Polym. Sci. B, 2, 209 (1964). e)
G. P. de Gaudemaris, B. Sillion, and J. Prévé, Bull. Soc. Chim.,
France, 1964, 1793 (1964). f) J. K. Stille, J. R. Williamson, and F.
Arnold, J. Polym. Sci. A, 3, 1013 (1965). g) I. Schopov and N.
Popov, J. Polym. Sci., Part A-1, 7, 1803 (1969). h) G. Y. Sarkis and
H. T. Al-Badri, J. Heterocyclic Chem., 17, 813 (1980). i) K. Niume,
S. Kurosawa, F. Toda, M. Hasegawa, and Y. Iwakura, Bull. Chem.
Soc. Jpn., 55, 2293 (1982). j) J. Waluk and S. J. Komorowski,
Chem. Phys. Lett., 133, 368 (1987). k) J. Harmenberg, B. Wahren,
and J. Bergman, Antimicrob. Agents Chemother., 32, 1720 (1988). l)
B. M.-Andrieu and J.-Y. Mérour, Tetrahedron, 54, 11095 (1998).
a) V. K. Kansal and P. Potier, Tetrahedron, 42, 2389 (1986). b) A.
Rajesh, A. Chapla, and S. Charanjeet, Acta Pharm. Jugosl., 38, 11
11 a) F. A. Cotton, M. Matusz, and R. Poli, Inorg. Chem., 26, 1474
(1987).b) L. Sacconi, C. Mealli, and D. Gatteschi, Inorg. Chem., 13,
1985(1974). c) S-Y. Lai, T-W. Lin, Y-H. Chen, C-C. Wang, G-H.
Lee, M-h. Yang, M-k. Leung, and S-M. Peng, J. Am. Chem. Soc.,
121,250 (1999).
12 It should be noted that the absorption maximum (λ
470 nm) of
complex 3 is near to the maximum wavelength of themsaoxlar spectrum
(ca. 500 nm). Thus, the basic studies on physical and chemical func-
tions of complex 3 are of interest from a viewpoint of potential utili-
ty of functional delocalized electron system such as photosensitive
dyes.
2