9
58
A. R. Khosropour et al.
LETTER
Several functionalities present in the aryl aldehydes such
as halogen, methoxy and nitro group were tolerated. In all
the cases the corresponding benzoxanthenes were ob-
tained in good to excellent yields. These results were also
obtained in the case of the aliphatic aldehydes (Table 2,
entries 12, 13).
(5) (a) Saint-Ruf, G.; De, A.; Hieu, H. T. Bull. Chim. Ther.
972, 7, 83. (b) Saint-Ruf, G.; Hieu, H. T.; Poupelin, J. P.
1
Naturwissenschaften 1975, 62, 584.
(6) (a) Banerjee, A.; Mukherjee, A. K. Stain Technol. 1981, 56,
83. (b) Menchen, S. M.; Benson, S. C.; Lam, J. Y. L.; Zhen,
W.; Sun, D.; Rosenblum, B. B.; Khan, S. H.; Taing, M. U. S.
Patent, US 6583168, 2003.
(
(
7) Knight, C. G.; Stephens, T. Biochem. J. 1989, 258, 683.
8) (a) Sirkecioglu, O.; Talinli, N.; Akar, A. J. Chem. Res.,
Synop. 1995, 502. (b) Ahmad, M.; King, T. A.; Ko, Do.-K.;
Cha, B. H.; Lee, J. J. Phys. D: Appl. Phys. 2002, 35, 1473.
9) Quintas, D.; Garcia, A.; Dominguez, D. ChemInform 2004,
35 (14), 154.
In summary, a novel and highly efficient methodology for
the synthesis of 14-alkyl- or -aryl-14-H-dibenzo[a,j]xan-
thenes by condensation reaction of aldehydes and b-naph-
thol in the presence of catalytic amounts of pTSA under
organic solvent (method A) and solvent-free conditions
(
(
method B) was reported. In addition to the efficiency and
(10) (a) Knight, D. W.; Little, P. B. Synlett 1998, 1141.
b) Knight, D. W.; Little, P. B. J. Chem. Soc., Perkin Trans.
2001, 14, 1771.
(
1
simplicity provided by method B, this protocol describes
a very fast, ‘green’ and low cost procedure for the synthe-
sis of these products.
(11) Jha, A.; Beal, J. Tetrahedron Lett. 2004, 45, 8999.
(12) Kuo, C.-W.; Fang, J.-M. Synth. Commun. 2001, 31, 877.
(13) (a) Van Allan, J. A.; Giannini, D. D.; Whitesides, T. H. J.
Org. Chem. 1982, 47, 820. (b) Ohishi, T.; Kojima, T.;
Matsuoka, T.; Shiro, M.; Kotsuki, H. Tetrahedron Lett.
Typical Experimental Procedure (Method A)
A mixture of aldehyde (1 mmol), b-naphthol (2 mmol) and pTSA
2
001, 42, 2493. (c) Khoramabadizad, A.; Kazemi, Z.; Amiri
Rudbari, H. J. Korean Chem. Soc. 2002, 46, 541.
d) Sarma, R. J.; Baruah, J. B. Dyes Pigm. 2005, 64, 91.
(0.1 mmol) in 1,2-dichloroethane was stirred at reflux for the appro-
(
priate time according to Table 2. The progress of the reaction was
monitored by thin layer chromatography. After completion of the
reactions, the organic solvent was evaporated and a mixture of
EtOH–H O (1:3) was added to it. The suspension was stirred for 5
min and the precipitate filtered. The crude products were purified by
recrystallization from EtOH.
(14) Papini, P.; Cimmarusti, R. Gazz. Chim. Ital. 1947, 77, 142.
(15) Ota, K.; Kito, T. Bull. Chem. Soc. Jpn. 1976, 49, 1167.
(16) Sen, R. N.; Sarkar, N. N. J. Am. Chem. Soc. 1925, 47, 1079.
(17) (a) Khosropour, A. R.; Khodaei, M. M.; Kookhazadeh, M.
Tetrahedron Lett. 2004, 45, 1725. (b) Khodaei, M. M.;
2
Khosropour, A. R.; Kookhazadeh, M. Synlett 2004, 1980.
(
c) Khodaei, M. M.; Khosropour, A. R.; Beygzadeh, M.
Typical Experimental Procedure (Method B)
To a mixture of aldehyde (1 mmol) and b-naphthol (2 mmol), pTSA
Synth. Commun. 2004, 34, 1551. (d) Khosropour, A. R.;
Khodaei, M. M.; Ghozati, K. Chem. Lett. 2004, 33, 1378.
(
Lett. 2004, 33, 304. (f) Khosropour, A. R.; Khodaei, M. M.;
Ghozati, K. Russ. J. Org. Chem. 2004, 40, 1332.
(
(0.02 mmol) was added. The reaction mixture stirred magnetically
e) Khosropour, A. R.; Khodaei, M. M.; Ghozati, K. Chem.
at 125 °C for the appropriate time as shown in Table 2. The reaction
was followed by TLC. When the reaction was completed, the mix-
ture was washed with EtOH–H O (1:3). The crude products were
2
g) Khodaei, M. M.; Khosropour, A. R.; Hoseini Jomor, S. J.
purified by recrystallization from EtOH.
J. Chem. Res., Synop. 2003, 638.
(
18) Selected Characterization Data of:
Acknowledgement
14-(3-Nitrophenyl)-14-H-dibenzo[a,j]xanthene (Table 2,
Entry 7): yellow solid; mp 211 °C. IR (KBr): 3040, 1612,
We are thankful to the Razi University Research Council for partial
support of this work
–1 1
1
584, 1516, 1248, 812, 803 cm . H NMR (200 MHz,
13
CDCl ): d = 6.65 (s, 1 H), 7.15–8.6 (m, 17 H). C NMR (50
3
MHz, CDCl ): d = 38.1, 116.3, 118.5, 122.1, 122.4, 123.1,
3
1
1
25.0, 127.7, 129.5, 129.9, 130, 131.5, 131.8, 134.7, 147.4,
48.6, 149.2. Anal. Calcd for C H NO : C, 80.38; H, 4.25;
References
2
7
17
3
(
1) Lambert, R. W.; Martin, J. A.; Merrett, J. H.; Parkes, K. E.
B.; Thomas, G. J. PCT Int. Appl. WO 9706178, 1997.
2) Hideo, T. Jpn. Tokkyo Koho JP 56005480, 1981.
3) Poupelin, J. P.; Saint-Ruf, G.; Foussard-Blanpin, O.;
Marcisse, G.; Uchida-Ernouf, G.; Lacroix, R. Eur. J. Med.
Chem. 1978, 13, 67.
4) (a) Ion, R. M. Progr. Catal. 1997, 2, 55. (b) Ion, R. M.;
Frackowiak, D.; Planner, A.; Wiktorowicz, K. Acta Biochim.
Pol. 1998, 45, 833.
N, 3.47. Found: C, 80.27; H, 4.08; N, 3.56.
14-(4-Methoxyphenyl) -14-H-dibenzo[a,j]xanthene
(Table 2, Entry 11): yellow solid; mp 204 °C. IR (KBr):
(
(
–
1 1
3040, 2912, 1616, 1580, 1248, 823, 806 cm . H NMR (200
MHz, CDCl ): d = 3.67 (s, 3 H), 6.52 (s, 1 H), 6.71 (d,
J = 9.5 Hz, 2 H), 7.38–7.95 (m, 14 H), 8.43 (d, J = 9.5 Hz, 2
3
1
3
(
H). C NMR (50 MHz, CDCl
117.9, 118.4, 123.1, 124.6, 127.2, 129.1, 129.2, 131.5,
133.7, 137.8, 149.1, 158.3. Anal. Calcd for C28 : C,
6.57; H, 5.19. Found: C, 86.32; H, 5.31.
3
): d = 37.5, 53.9, 114.3,
H O
20 2
8
Synlett 2005, No. 6, 955–958 © Thieme Stuttgart · New York