May 2012
Facile Catalyzed Preparation of 14-Aryl- or Alkyl-14-H-dibenzo[a,j]xanthenes
673
by Dodecylphosphonic Acid and Dodecylsulfamic Acid: Environmentally Benign Methods
Scheme 6
Table 5
Comparison among the efficiencies of various Brønsted acid catalysts used in the synthesis of 14-(4-nitrophenyl)-14-H-dibenzo[a, j]xanthene.
Catalyst
Solvent
Temp. (ꢀC)
Time (h)
Yield (%)
NH4H2PO4/SiO2 [29]
Montmorilonite K10 [14]
NaHSO4 [30]
H2O
Solvent-free
Solvent-free
1,2-Dichloroethane
1,2-Dichloroethane
Solvent-free
Solvent-free
Solvent-free
Solvent-free
AcOH
40
120
90
82—84
82—84
100
100
80
110
80
0.70
2
0.70
3
3
2
94
80
88
91
90
84
94
94
92
60
94
90
90
94
95
90
NaHSO4 [21]
Amberlyst-15 [21]
Dowex-50w [31]
Heteropoly acid [17]
Silica sulfuric acid [32]
Indion-130 [15]
H2SO4 [8]
Sulfamic acid [10]
p-TSA [9]
Cellulose sulfuric acid [18]
[MIMPS]HSO4 [19]
DPA
1
1
0.20
73
11
2.5
2.0
0.1
1
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
125
125
110—115
100
85
85
DSA
0.25
14-(3-Methylphenyl)-14H-dibenzo[a,j]xanthene (entry 12,
Table 3). White solid, m.p.198.5ꢀC, IR (KBr, cmÀ1): 3036,
2912, 1593, 1512, 1431, 1249, 806, 748. 1H-NMR (250MHz,
CDCl3): d = 2.19 (s, 3H, —CH3), 6.47 (s, 1H), 6.84 (m, 1H),
7.09 (t, J = 7.6 Hz, 1H), 7.53 (m, 7H), 7.82 (m, 5H), 8.45 (d,
J = 8.5 Hz, 2H). 13C-NMR (63 MHz, CDCl3): d = 21.50,
37.98, 117.24, 117.84, 122.54, 124.00, 125.19, 126.53, 127.09,
127.94, 128.56, 128.78, 130.11, 130.85, 131.27, 137.92,
144.69, 148.47. EIMS: m/z (%): 372 (M+, 15.3), 282 (100.0),
281 (90.4), 253.
14-Benzyl-14H-dibenzo[a,j]xanthene (entry 14, Table 3). Yellow
solid, m.p.159ꢀC, IR (KBr, cmÀ1): 3028, 2931, 1589, 1454,
1246, 856, 741. 1H-NMR (250MHz, CDCl3): d = 3.29 (d,
J = 3.64 Hz, 2H, —CH2), 5.80 (s, 1H), 6.14 (m, 2H), 7.03–7.91
(m 13H), 8.26 (d, J = 8.23 Hz, 2H). 13C-NMR (63MHz, CDCl3):
d = 32.99, 41.29, 115.10, 117.20, 121.98, 123.82, 125.19,
126.47, 126.98, 128.12, 128.66, 129.54, 130.62, 131.10,
137.33, 149.87. EIMS: m/z (%): 372 (M+, 0.1), 371 (0.2), 348
(0.6), 282 (26.8), 281 (100.0), 152 (12.2), 57 (2.0).
Anal. Calcd for C28H20O: C, 90.32; H, 5.37%. Found: C, 89.95,
H, 5.41%.
130.86, 131.15, 141.61, 149.80. EIMS: m/z (%): 386 (M+, 1.2),
282 (30.2), 281 (100.0), 252 (10.4), 57 (23.5). Anal. Calcd for
C29H22O: C, 90.15; H, 5.69%. Found: C, 89.99; H, 5.69%.
14-(4-Nitrophenyl)-14H-dibenzo[a,j]xanthene (entry 16,
Table 3). Light-brown solid, m.p.315ꢀC (Lit. 312ꢀC).8 IR
(KBr, cmÀ1): 3066, 1589, 1512, 1332, 1238, 1138, 806, 741.
1H-NMR (250MHz, CDCl3): d = 6.60 (s, 1H), 7.52 (m, 8H),
7.84 (m, 4H), 7.87 (d, J =8.8 Hz, 2H), 8.30 (d, J =8.4 Hz, 2H).
13C-NMR (63 MHz, CDCl3): d = 37.78, 111.16, 117.34, 117.84,
121.80, 123.63, 124.35, 126.95, 128.72, 128.83, 129.35, 130.84,
148.50, 149.48, 151.73. EIMS: m/z (%): 403 (M+, 8.9), 374 (7.7),
282 (70.7), 281 (100.0), 253 (11.7), 122 (3.7), 111 (15.2), 83
(33.6), 57 (91.7). Anal. calcd. for C27H17NO3: C, 80.40; H, 4.22;
N, 3.47%. found: C, 80.16; H, 4.30; N, 3.24%.
Acknowledgment. The authors gratefully acknowledge the
support of this work by Shiraz university research council.
REFERENCES AND NOTES
[1] Henkel, B.; Zeng, W.; Bayer, E. Tetrahedron Lett 1997, 38,
3511.
14-(2-Phenylethyl)-14H-dibenzo[a,j]xanthene (entry 15,
Table 3). White solid, m.p.164ꢀC, IR (KBr, cmÀ1): 3039,
1
[2] (a) McWilliams, K.; Kelly, J. W. J Org Chem 1996, 61, 7408;
(b) Bennett, G. J.; Lee, H. H. Phytochemistry 1989, 28, 967.
[3] (a) Menchen, S. M.; Benson, S. C.; Lam, J. Y. L.; Zhen, W.;
Sun, D.; Rosenblum, B.; Khan, S. H.; Taing, M. U. S. Pat.
6,583,168, 2003; Chem Abstr 2003,139, 54287; (b)Banerjee, A.;
Mukherjee, A. K. Stain Technol 1981, 56, 83; (c) Reynolds, G. A.;
2921, 1591, 1450, 1238, 800. H-NMR (250MHz, CDCl3): d =
2.41 (m, 4H), 5.68 (s, 1H), 6.28 (m, 2H), 7.07 (m, 3H), 7.48
(m, 4H), 7.63 (m, 2H), 7.83 (m, 4H), 8.29 (d, J = 8.45 Hz, 2H).
13C-NMR (63 MHz, CDCl3): d = 30.94, 37.22, 115.88, 117.40,
122.16, 123.97, 125.28, 126.51, 127.78, 127.90, 128.22, 128.68,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet