J. CHEM. RESEARCH (S), 1999 619
Reaction 5. Mp 296 8C (decomp.) (lit.15 300 8C), brown. 1H NMR
60 MHz, DMSO-d6): d 2.47 (s, 3 H), 7.00±7.17 (m, 6 H). IR (KBr):
3040, 2960, 1620, 1600, 1585, 1470, 1250, 1140, 1120, 1105, 1050,
Cl
(
H
N
O
�
1
1
020, 1000, 770, 700 cm . UV (DMF): lmax�nm 508. Calc. for
R
R
C10H6ClNO: C, 62.66; H, 3.13; N, 7.31. Found: C, 62.64; H, 3.07; N,
7.26%.
O
N
H
2
PhI(OAc)2, MeOH/DMF (2 : 1)
Reaction 6. Mp 313 8C (decomp.) (lit.6 316 8C), purple. 1H NMR
Cl
2
2NaOAc•3H2O
Cl
(60 MHz, DMSO-d6): d 3.83 (s, 3 H), 7.07±7.23 (m, 4 H) 7.58 (m, 2
H) IR (KBr): 3040, 2980, 2960, 1630, 1600, 1560, 1480, 1440, 1250,
N
O
O
N
�
1
1
220, 1150, 1120, 1100, 1050, 1020, 850, 830, 725, 700, 690 cm . UV
R
R
(
N, 6.74. Found: C, 57.80; H, 2.82; N, 6.69%.
Reaction7. Mp � 360 8C (lit. � 360 8C), green. H NMR (60 MHz,
DMSO-d6): d 2.17 (s, 3 H), 7.13±7.33 (m, 4 H), 7.60 (2 H), 8.20 (s, 1
H). IR (KBr): 3280, 3030, 1650, 1620, 1600, 1570, 1480, 1440, 1250,
DMF): lmax�nm 540. Calc. for C10H6ClNO : C, 57.83; H, 2.89;
2
6
1
Cl
1
Scheme 2
�
1
1210, 1170, 1120, 1105, 1070, 1030, 840, 825, 750, 720, 700 cm . UV
(
N, 11.94. Found: C, 56.26; H, 2.91; N, 11.87%.
DMF): lmax�nm 560. Calc. for C11H7ClN2O2: C, 56.29; H, 3.00;
Table 1 Oxidative cyclization of BADClBQ 2 to DClTADO 1 by
DIB
a
15
Reaction 8. Mp 298 8C (decomp.) (lit. 300 8C), reddish brown.
H NMR (60 MHz, DMSO-d6: d 7.07±7.17 (m, 6 H). IR (KBr): 3060,
1
Entry
R
t/h
T/8C
Isolated yield(%)
1620, 1595, 1575, 1470, 1440, 1260, 1210, 1160, 1140, 1105, 1050,
1020,
�
1
1b
750, 690 cm
.
UV (DMF): lmax�nm 487. Calc. for
H
H
2
2
1
1
1
0.5
3
3
3
25
25
25
25
25
25
25
35
35
60
51
87
57
92
81
88
76
74
81
ö
C11H7ClN2O2: C, 50.94; H, 1.41; N, 6.60. Found: C, 50.92; H,
2
3
1
.34; N, 6.53%.
Reaction 9. Mp � 360 8C (lit.16 � 360 8C), reddish blue. 1H NMR
b
p-CH3
p-CH3
o-CH3
p-CH3O
p-NHAc
o-Cl
4
5
6
7
8
9
(
60 MHz, DMSO-d6): d 7.03±7.14 (m, 4 H), 7.53 (m, 2 H). IR (KBr):
3
1
030, 1625, 1600, 1555, 1480, 1440, 1265, 1230, 1205, 1160, 1120,
�
1
100, 1060, 1030, 850, 830, 725, 700, 690 cm . UV (DMF):
lmax�nm 517. Calc. for C11H7ClN2O2: C, 50.94; H, 1.41; N,
6.60. Found: C, 50.91; H, 1.31; N, 6.57%.
p-Cl
p-O2N
1
0
5
a
Received, 22nd April 1999; Accepted, 24th June 1999
Paper E/9/03221E
The reaction was carried out with 2 mmol DIB, 1 mmol BADClBQ
b
and 2 mmol NaOAc�3H2O in 15 ml MeOH^DMF (2:1). The
reaction was carried out under the same conditions as a except for
the absence of NaOAc�3H2O.
References
1
2
A. H. M. Renfrews, Rev. Prog. Color Relat. Top., 1985, 15, 15.
S. L. Chen, Z. H. Zhu and K. C. Chen, Opt. Commun., 1989,
74, 84.
advantages of reaction at room temperature for a short time
with good yields instead of re£uxing for a long time with
considerable amounts of by-products.
3
K. W. Bortz, B. L. Justus and G. W. Scott, J. Phys. Chem.,
1
983, 87, 2578.
4
5
6
7
8
9
R. C. Harris and G. C. Newland, Brit. Pat., 1 034 181, 1966.
R. L. Mital and S. K. Jain, J. Chem. Soc. C, 1971, 1875.
K. Kitahara and H. Nishi, Nippon Kagaku Kaishi, 1984, 1870.
J. Horst, L. Klaus and H. K. Josef, DE, 3 439 755, 1985.
H. Walter and H. Reinhard, EP, 292 906, 1988.
Experimental
General
Procedure
for
the
Preparation
of
6,13-
Dichlorotriaryldioxazines 1.öAt room temperature, 2.0 mmol DIB
were added in one portion to a mixture of 1.0 mmol BADClBQ 2
and 2.0 mmol NaOAcÁ3H2O in 15 ml MeOH^DMF (2:1). The result-
ing mixture was stirred at the appropriate temperature. After reaction
for the required time, the mixture was ¢ltered and the ¢ltrate poured
into 30 ml water to give the colored solid which was dissolved in
S. J. Walter and H. Wolfgang, DE, 3 720 477, 1988.
10 H. Hahn and R. Blattner, EP, 298 916, 1988.
11 P. J. Stang, Angew. Chem., Int. Ed. Engl., 1992, 31, 274; R. M.
Moriarty and R. K. Vaid, Synthesis, 1990, 431; M. Ochiai,
Rev. Heteroatom. Chem., 1989, 292; P. J. Stang, Chem. Rev.,
1996, 96, 1123; T. Kitamura and Y. Fujiwara, Org. Prep. Proc.
Int., 1997, 4, 409.
12 L. W. Deady and N. H. Quazi, Aust. J. Chem., 1993, 46, 411;
R. M. Moriarty, B. A. Berglund and M. S. C. Rao, Synthesis,
1993, 318; D. H. R. Barton, J. C. Jaszberenyi and T. Sinada,
Tetrahedron, 1993, 45, 7191; G. C. Reddy, Tetrahedron Lett.,
1995, 36, 1001; D. Kumar, O. Prakash and S. P. Singh, J.
Chem. Res. (S), 1993, 204.
13 R. Y. Yang and L. X. Dai, J. Org. Chem., 1993, 58, 3381.
14 H. Nishi and M. Murayama, Nippon Kakaku Kaishi, 1979,
432.
15 S. K. Jain, K. G. Ojha and R. R. Gupta, Indian J. Chem., Sect.
B, 1979, 17, 278.
3
ml DMF. The solution was subjected to TLC (silica gel) with
n-hexane^ethylacetate (3:7) as eluent to a¡ord the product which
was puri¢ed by recrystallization from acetone.
1
4
Reactions 1 and 2 (see Table 1). Mp � 360 8C (lit. � 360 8C),
1
reddish violet. H NMR (60 MHz, DMSO-d6): d 6.83±6.97 (m, 6 H),
7
1
.50 (m, 2 H). IR (KBr): 3040, 1620, 1600, 1570, 1480, 1440, 1260,
�
1
210, 1130, 1110, 1070, 1010, 750 cm . UV (DMF): lmax�nm 520.
Calc. for C9H4ClNO: C, 60.84; H, 2.25; N, 7.88. Found: C, 60.79; H,
.12; N, 7.79%.
Reactions 3 and 4. Mp � 360 8C (lit. � 360 8C), red. H NMR
60 MHz, DMSO-d6): d 2.40 (s, 3 H), 6.96±7.10 (m, 4 H) 7.46 (m,
2
5
1
(
2
1
H). IR (KBr): 3030, 2980, 1625, 1605, 1570, 1480, 1440, 1245, 1150,
120, 1110, 1070, 1020, 850, 830, 730, 700 cm . UV (DMF):
�
1
lmax�nm 532. Calc. for C10H6ClNO: C, 62.66; H, 3.13; N, 7.31.
16 H. Nishi, M. Kabo and S. Tokita, Nipon Kagaku Kaishi, 1977,
588.
Found: C, 62.63; H, 3.04; N, 7.24%.