6
T. Horaguchi, T. Oyanagi, E. C. Creencia, K. Tanemura and T. Suzuki
Vol. 41
3360 cm-1 (NH and OH); H nmr (deuteriochloroform): δ 5.28
1
of calcium oxide (Nakalai Tesque, Inc.) and collecting particles that
passed through the 5 mm sieve and were retained by the 2 mm
sieve. A quartz tube (66 cm in length, 12 mm i.d.) was packed to a
height of 28 cm with the calcium oxide granules (18.0 g). The tube
was positioned in horizontal stationary furnace with heating coils
(broad s, 1H, OH or NH), 5.85 (broad s, 1H, NH or OH), 6.77 (d,
J=8.0 Hz, 2H, Ar-H ), 6.87 (dd, J=8.0 and 8.0 Hz, Ar-H), 6.88
2
(dd, J=8.0 and 8.0 Hz, 1H, Ar-H), 6.97 (d, J=8.0 Hz, 1H, Ar-H),
7.07 (dd, J=8.0 and 8.0 Hz, 1H, Ar-H), 7.17 (d, J=8.0 Hz, 1H, Ar-
H), 7.21 (dd, J=8.0 and 8.0 Hz, 2H, Ar-H2); 13C nmr (deuteri-
ochloroform): δ 115.3 (d), 115.8 (d), 120.2 (d), 120.9 (d), 124.5
(d), 126.0 (d), 129.1 (s), 129.4 (d), 145.3 (s), 150.9 (s).
(
38 cm in length). The column was then purged with N gas at a rate
2
of about 19 mL/min and kept at this condition throughout the exper-
iment. The stationary furnace was kept at the reaction temperature
(450-650 °C). Starting material (1.77 mmoles) was weighed into a
Anal. Calcd. for C H NO: C, 77.82; H, 5.99; N, 7.56. Found:
1
2 11
quartz boat and placed inside the reaction tube at 3 cm from the sta-
tionary furnace and vaporized by the traveling furnace under N2
carrier gas. When the reaction temperature was 500 °C, the station-
ary furnace was kept at 500 °C while the traveling furnace was kept
at 560 °C. When the reaction temperatures were 560 °C and 600 °C
C, 77.64; H, 6.08; N, 7.65.
Acknowledgement.
We thank Mr. Yoshiaki Matsuda for the elemental analyses.
(temperatures of the stationary furnace), the traveling furnace was
REFERENCES AND NOTES
raised to reaction temperature plus 50 °C. In the case of reaction
temperature of 650 °C, the travelling furnace was kept at 650 °C.
The travelling furnace moved gradually and reached to the station-
ary furnace in 35 minutes and kept for 5 minutes at this state.
Products which came from the outlet (5 mm i.d.) of quartz tube
were collected in a vessel cooled with ice-water. The products were
extracted with acetone. After removal of the acetone the residue
was chromatographed on silica gel and eluted with benzene, ben-
zene-hexane or benzene-ethyl acetate to give a variety of products.
The structure of products were determined from their spectra.
Compounds 4, 7, 8, 9, 1 0, 11, 1 2, 1 6 were identified by comparison
of the ir, H nmr and 13C nmr spectra with those of comercially
[
1a] H. C. Waterman and D. L. Vivian, J. Org. Chem., 14, 289
(
(
1949): [b] H. C. Waterman and D. L. Vivian, U. S. Patent 2,292,808
1943); Chem. Abstr., 37, 892 (1943).
[2a] J. I. G. Cadogan and M. Cameron-Wood, Proc. Chem. Soc.
361 (1962); [b] J. I. G. Cadogan, M. Cameron-Wood, R. K. Mackie and
R. J. G. Searle, J. Chem. Soc., 4831 (1965); [c] J. I. G. Cadogan, Quart.
Rev., 22, 222 (1968).
[
3] P. A. S. Smith and B. B. Brown, J. Am. Chem. Soc., 73, 2435
1951).
4] J. S. Swenton, T. J. Ikeler and B. H. Williams, J. Am. Chem.
Soc., 92, 3103 (1970).
5a] R. A. Abramovitch, Y. Ahmad and D. Newman, Tetrahedron
Lett., 752 (1961); [b] R. A. Abramovitch and B. A. Davis, Chem. Rev.,
4, 149 (1964); [c] J. M. Lindley, I. M. McRobbie, O. Meth-Cohn and H.
Suschitzky, J. Chem. Soc., Perkin Trans. 1, 2194 (1977).
6] G. T. Morgan and L. P. Walls, J. Soc. Chem. Ind., 57, 358
(1938).
[7] V. Menmayr, U. S. Patent 2,351,171 (1944); Chem. Abstr.,
38, 5228 (1944).
(
[
1
[
1
13
available samples. The ir , H nmr and C nmr spectra of com-
pound 15 were identical with that of an authentic sample [9].
6
4-Aminocarbazole (6b).
[
Compound 6b was obtained as colorless crystals, mp 188-192
°
3
C from ethanol (lit. [21] mp 188-192 °C); ir (potassium bromide):
-1
1
410 (NH ), 3340 (NH ), 3190 cm (NH); H nmr (deuterioace-
2 2
[
[
8] O. Kruber and G. Grigoleit, Chem. Ber., 87, 1895 (1954).
9] T. Horaguchi, R. Yamazaki and T. Abe, Bull. Chem. Soc. Jpn.,
tone): δ 5.10 (broad s, 2H, NH ), 6.49 (d, J=8.0 Hz, 1H, Ar-H),
2
6.80 (d, J=8.0 Hz, 1H, Ar-H), 7.10 (dd, J=8.0 and 8.0 Hz, 1H, Ar-
5
3, 494 (1980).
H), 7.12 (dd, J=8.0 and 8.0 Hz, 1H, Ar-H), 7.28 (dd, J=8.0 and 8.0
Hz, 1H, Ar-H), 7.43 (d, J=8.0 Hz, 1H, Ar-H), 8.13 (d, J=8 Hz, 1H,
Ar-H), 10.24 (broad s, 1H, NH); 13C nmr (deuterioacetone): δ
[10] R. Kreher and W. Koehler, Angew. Chem. Int. Ed. Engl., 14,
2
64 (1975).
[11] T. Horaguchi, L. H. Klemm and E. S. Norris, J. Heterocyclic
101.1 (d), 106.2 (d), 111.3 (d), 111.4 (s), 119.8 (d), 122.3 (d), 124.4
Chem., 32, 797 (1995).
(s), 125.0 (d), 127.9 (d), 140.8 (s), 142.9 (s), 145.4 (s).
[12] E. Ibuki, S. Ozasa and K. Murai, Bull. Chem. Soc. Jpn. 48,
Anal. Calcd. for C H N : C,79.10; H,5.53; N,15.37. Found:
1868 (1975).
1
2 10 2
[13] A. E. S. Fairfull, D. A. Peak, W. F. Short and T. I. Watkins, J.
C, 79.06; H, 5.64; N, 15.26.
-Hydroxycarbazole (6e).
Compound 6e was obtained as colorless crystals, mp 169-170
C from ethanol (lit. [22] mp 169-170 °C); ir (potassium bro-
Chem. Soc., 4700 (1952).
4
[14] I. Mori, Bull. Chem. Soc. Jpn., 48, 911 (1975).
[
15] G. Jones, B. D. Long and M. P. Thorne, J. Chem. Soc., Perkin
Trans. 2, 903 (1992).
16] T. E. A. Nieminen and T. A. Hase, Tetrahedron Lett. , 28, 4725
1987).
17] D. D. Laskar, D. Prajapati and J. S. Sandhu, J. Chem. Soc.,
°
[
1
mide): 3430 (NH), 3300 cm-1 (OH); ); H nmr (deuteriochloro-
(
form): δ 5.47 (broad s, 1H, OH), 6.58 (d, J=8.0 Hz, 1H, Ar-H),
[
7
7
1
.01 (d, J=8.0 Hz, 1H, Ar-H), 7.22-7.27 (m, 2H, Ar-H ), 7.39-
Perkin Trans. 1, 67 (2000).
[18] J. I. G. Cadogan, C. L. Hickson, H. S. Hutchison and H.
MacNab, J. Chem. Soc., Perkin Trans. 1, 377 (1991).
2
.41 (m, 2H, Ar-H ), 8.06 (broad s, 1H, NH), 8.27 (d, J=8.0 Hz,
2
H, Ar-H); 13C nmr (deuteriochloroform): δ 103.3 (d), 105.1 (d),
[
19] M. G. Hicks and G. Jones, J. Chem. Soc., Chem. Commun.,
277 (1983).
20] J. I. G. Cadogan, H. S. Hutchison and H. McNab, J. Chem.
Soc., Perkin Trans. 1, 1407 (1987)
21] J. H. Boyer and G. I. Mikol, J. Chem. Soc., Chem. Commun.,
34 (1969).
22] J. A. Cummins and M. L. Tomlinson, J. Chem. Soc., 3475
(1955).
[23] S. Gambarjan, Ber. Dtsch. Chem. Ges., 42, 4003 (1909).
1
1
10.0 (d), 111.8 (s), 119.7 (d), 122.3 (s), 122.7 (d), 125.1 (d),
26.5 (d), 138.8 (s), 141.4 (s), 151.9 (s).
Anal. Calcd. for C H NO: C, 78.67; H, 4.95; N, 7.65. Found:
1
[
1
2 9
C, 78.56; H, 5.03; N, 7.69.
[
7
2
-Hydroxydiphenylamine (13).
[
Compound 13 was obtained as colorless crystals, mp 67-68 °C
from ethanol (lit. [23] mp 69-70 °C); ir (potassium bromide):