April 2008
4H, m). ESI-MS m/z: 327 [Calcd for C H IN O: 327 (MꢁH)]. Anal.
609
(
11) Lee E.-S., Park J. G., Jahng Y., Tetrahedron Lett., 44, 1883—1886
(2003).
1
2
11
2
Calcd for C H IN O: C, 44.19; H, 3.40; N, 8.59. Found: C, 44.21; H, 3.42;
12
11
2
N, 8.61.
12) Yadav J. S., Reddy B. V. S., Tetrahedron Lett., 43, 1905—1907 (2002).
2
-Hydroxy-6,7,8,9-tetrahydro-11H-pyrido[2,1-b]quinazolin-11-one 13) Nishiyama Y., Hirose M., Kitagaito W., Sonoda N., Tetrahedron Lett.,
1
(
1
7
1be) White needles: mp 257—259 °C. H-NMR (DMSO-d , 250 MHz) d:
43, 1855—1858 (2002).
6
0.67 (br s, OH), 7.69 (d, 1H, Jꢀ8.3 Hz, H4), 7.45 (d, 1H, Jꢀ0.8 Hz, H1),
.43 (dd, 1H, Jꢀ8.3, 0.8 Hz, H3), 3.95 (t, 2H, Jꢀ5.6 Hz), 3.11 (d, 2H,
14) Akazone M., Kondo T., Watanabe Y., J. Org. Chem., 58, 310—312
(1993).
Jꢀ5.6 Hz), 1.92 (quintet, 2H, Jꢀ5.6 Hz), 1.87 (quintet, 2H, Jꢀ5.6 Hz). ESI-
MS m/z: 217 [Calcd for C H N O : 217 (MꢁH)]. Anal. Calcd for
15) Mhsaske S. B., Argade N. P., J. Org. Chem., 66, 9038—9040 (2001).
16) Takeuchi H., Matsushita Y., Eguchi S., J. Org. Chem., 56, 1535—1537
(1991).
1
2
12
2
2
C H N O : C, 66.65; H, 5.59; N, 12.96. Found: C, 66.62; H, 5.61; N,
12
12
2
2
1
2.97.
Luotonin A (3) The crude product was recrystallized from CHCl to
17) Dunn A. D., Kinnear K. I., J. Heterocycl. Chem., 23, 53—57 (1986).
18) Kamal A., Ramana K. V., Rao M. V., J. Org. Chem., 66, 997—1001
(2001).
19) Kametani T., Loc C. V., Higa T., Koizumi M., Ihara M., Fukumoto K.,
J. Am. Chem. Soc., 99, 2306—2309 (1977).
3
23)
yield pale yellow needles (78%): mp 281—283 °C (dec.) (lit. mp 252 °C
51)
(dec.), lit. mp 281—283 °C). Spectral data were identical to those reported
23)
previously.
Tryptanthrin (4) The crude product was recrystallized from EtOH to
20) Onaka T., Tetrahedron Lett., 1971, 4387—4390 (1971).
yield 4 (85%) as yellow needles: mp 266—267 °C (lit. mp 267—268 °C). 21) Amin A. H., Mehta D. R., Nature (London), 183, 1317 (1959).
26)
11)
Spectral data were identical to those reported previously.
Rutaecarpine (5) The crude product was recrystallized from CH OH to
22) Wu X., Qin G., Cheung K. K., Cheng K. F., Tetrahedron, 53, 13323—
13328 (1997).
3
27)
yield 5 (82%) as white needles: mp 259—260 °C (lit. mp 258 °C). Spectral
data were identical to those reported previously.
0b: A solution of anthranilic acid (13.72 g, 0.10 mol) and SOCl (50 g) in
23) Ma Z. Z., Hano Y., Nomura T., Chen Y.-J., Heterocycles, 46, 541—546
(1997).
24) Brufani M., Fedeli W., Mazza F., Gerhard A., Keller-Schierlein W., Ex-
perientia, 27, 1249—1250 (1971).
52)
1
2
dry benzene (500 ml) was refluxed for 2 h. The solvent was then evaporated
under reduced pressure at room temperature to afford iminoketene as an oily 25) Schindler F., Zähner H., Arch. Microbiol., 79, 187—203 (1971).
liquid, to which a solution of 2-pyrrolidinone (7.20 g, 0.085 mol) in dry ben-
zene (100 ml) was added. After setting overnight at room temperature, the
26) Bergman J., Egestad B., Lindström J. O., Tetrahedron Lett., 1977,
2625—2626 (1977).
precipitate formed was collected. Recrystallization from EtOH gave 20.0 g 27) Asahina Y., Kashiwaki K., J. Pharm. Soc. Jpn., 405, 1293 (1915).
ꢂ1
(
1
8
91%) of white needles: mp 180 °C. IR (KBr) cm : 3200—2500, 1702,
28) Bergman J., “The Alkaloids, Chemistry and Pharmacology,” Vol. XXI,
1
644. H-NMR (250 MHz, CDCl ) d: 10.92 (br s, D O exchangeable, OH),
ed. by Brossi A., Academic Press, New York, 1983, pp. 29—54.
3
2
.22 (1H, dd, Jꢀ7.5, 1.3 Hz, H6), 8.19 (1H, d, Jꢀ7.8 Hz, H3), 7.78 (1H, td, 29) von Niementowski S., J. Prakt. Chem., 51, 564—572 (1895).
Jꢀ8.5, 1.3 Hz, H5), 7.54 (1H, td, Jꢀ8.5, 1.3 Hz, H4), 4.15 (2H, t, 30) Brown D. J., “Quinazolines, Supplement I,” Interscience Publishers,
Jꢀ6.2 Hz), 3.63 (2H, t, Jꢀ6.2 Hz), 2.18 (2H, quintet, Jꢀ6.2 Hz), 2.05 (2H,
New York, 1996, pp. 1—150.
13
quintet, Jꢀ6.2 Hz). C-NMR (62.5 MHz, CDCl ) d: 160.55, 158.51,
31) Armarego W. L. F., “Fused Pyrimidines,” ed. by Brown D. J., Inter-
science Publishers, New York, 1967, pp. 89—218.
32) Morris R. S., Handford W. F., Adams R., J. Am. Chem. Soc., 57, 951—
954 (1935).
3
1
1
36.87, 136.55, 128.98, 127.49, 119.99, 117.85, 43.62, 27.82, 21.08, 17.92,
7.16. ESI-MS m/z: 219 [Calcd for C H N O (MꢁH): 219]. MS m/z: 218
1
2
14
2
2
ꢁ
ꢁ
ꢁ
(M , 12) 200 (M ꢂH O, 100), 173 (M ꢂCOOH, 4), 160 (11). Anal. Calcd
2
for C H N O : C, 66.04; H, 6.47; N, 12.84. Found: C, 66.08; H, 6.43; N, 33) Möhrle H., Seidel C. M., Chem. Ber., 106, 1595—1600 (1973).
12
14
2
2
1
2.89.
2
34) Nesterova I. N., Radkevich T. P., Granik V. G., Khim.-Farm. Zhur., 25,
28—30 (1991) [Chem. Abstr., 116, 41412 (1992)].
35) Japan Kokai Tokkyo Koho, JP 83-190614 (1984).
36) Manhas M. S., Amin S. G., J. Heterocycl. Chem., 13, 903—906
(1976).
37) Levy P. R., Stephen H., J. Chem. Soc., 1956, 985—988 (1956).
38) Mason J. J., Bergman J., Org. Biomol. Chem., 5, 2486—2490 (2007).
39) Zhou H.-B., Liu G.-S., Yao Z.-J., J. Org. Chem., 72, 6270—6272
(2007).
40) Nacro K., Zha C., Guzzo P. R., Herr R. J., Peace D., Friedrich T. D.,
Bioorg. Med. Chem., 15, 4237—4246 (2007).
,3-Tetramethylene-4(3H)-quinazolinone (6,7,8,9-Tetrahydro-11H-
pyrido[2,1-b]quinazolin-11-one, 1ba) mixture of 10b (4.36 g,
.02 mol) in polyphosphoric acid (40 ml) was heated at 100—120 °C for 1 h.
A
0
The reaction mixture was poured to ice (400 g) and the resulting mixture
was made basic with 1 N NaOH. The precipitate formed was collected and
recrystallized from EtOH to afford white needles (3.48 g, 87%): mp 98—
2)
1
99 °C (lit. mp 98.5—99.5 °C). H-NMR (250 MHz, CDCl ) d: 8.23 (1H,
3
dd, Jꢀ8.0 Hz, H1), 7.68 (1H, td, Jꢀ8.3, 1.3 Hz, H2), 7.55 (1H, d, Jꢀ8.0 Hz,
H4), 7.39 (1H, td, Jꢀ8.0, 1.0 Hz, H3), 4.05 (2H, t, Jꢀ6.2 Hz), 2.97 (2H, t,
Jꢀ6.5 Hz), 2.01—1.87 (4H, m).
41) Servais A., Azzouz M., Lopes D., Courillon C., Malacria M., Angew.
Acknowledgement Financial support from the Korean Research Foun-
dation Grant (KRF-2005-041-E00496) is gratefully acknowledged. DHK
and CSS are recipients of the BK-21 scholarship. Currently, KCJ is a student
Chem. Int. Ed. Engl., 46, 576—579 (2007).
42) Bowman W. R., Elsegood M. R. J., Stein T., Weaver G. W., Org. Bio-
mol. Chem., 5, 103—113 (2007).
at the Department of Biochemistry, University of Iowa, Iowa City, IA 52242, 43) Kamal A., Shankaraiah N., Devaiah V., Reddy K. L., Tetrahedron Lett.,
U.S.A.
47, 9025—9028 (2006).
44) Low yield of this type of reaction has been reported: see Bergman J.,
References and Notes
Bergman S., J. Org. Chem., 50, 1246—1255 (1985).
1
2
)
)
Chatterjee A., Ganguly M. G., Phytochemistry, 7, 307—311 (1968).
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Chem., 19, 151—159 (1966).
Johns S. R., Lamberton J. A., Chem. Commun., 1965, 267 (1965).
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3
4
)
)
(1935).
5)
6)
7)
Stephen T., Stephen H., J. Chem. Soc., 1956, 4694—4695 (1956).
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Kamal A., Shankaraiah N., Devaiah V., Reddy K. L., Tetrahedron Lett.,
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(1956).
4
7, 9025—9028 (2006).
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1708—1710 (1927).
51) Ma Z. Z., Hano Y., Nomura T., Chen Y.-J., Heterocycles, 51, 1593—
1596 (1999).
52) Lee S. H., Kim S. I., Park J. G., Lee E.-S., Jahng Y., Heterocycles, 55,
1555—1560 (2001).
8
9
)
(
)
(
1
0) Liu J.-F., Ye P., Sprague K., Sargent K., Yohannes D., Baldino C. M.,
Wilson C. J., Ng S.-C., Org. Lett. 7, 3363—3366 (2005).