Clean procedure for synthesis of chromeno[4,3-b]benzo [f]quinolin-6-one derivatives: Reaction of N-arylidenenaphthalen-2-amine with 4-hydroxycoumarin in aqueous media

Article abstract of DOI:10.1080/00397910600634449

A short and simple synthesis of chromeno[4,3- b ]benzo[ f ]quinolin-6-one derivatives was accomplished in good to high yields via the reaction of N -arylidenenaphthalen-2-amine with 4-hydroxycoumarin in aqueous media catalyzed by TEBAC. The structures wer

Full text of DOI:10.1080/00397910600634449

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Clean Procedure for Synthesis
of Chromeno[4,3‐b]benzo
[f]quinolin‐6‐one Derivatives: Reaction
of N‐arylidenenaphthalen‐2‐amine with
4‐Hydroxycoumarin in Aqueous Media
Xiang‐Shan Wang a b , Mei‐Mei Zhang a , Zhao‐Sen Zeng a , Da‐Qing Shi a b
Shu‐Jiang Tu a b
&
a Department of Chemistry , Xuzhou Normal University , Xuzhou Jiangsu,
China
b Key Laboratory of Biotechnology on Medical Plant of Jiangsu Province ,
Xuzhou, China
Published online: 20 Aug 2006.
To cite this article: Xiang‐Shan Wang , Mei‐Mei Zhang , Zhao‐Sen Zeng , Da‐Qing Shi & Shu‐Jiang Tu
(2006) Clean Procedure for Synthesis of Chromeno[4,3‐b]benzo [f]quinolin‐6‐one Derivatives: Reaction of
N‐arylidenenaphthalen‐2‐amine with 4‐Hydroxycoumarin in Aqueous Media, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 36:14, 2047-2057
To link to this article: http://dx.doi.org/10.1080/00397910600634449
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Synthetic Communicationsw, 36: 2047–2057, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910600634449
Clean Procedure for Synthesis of
Chromeno[4,3-b]benzo [ f ]quinolin-6-one
Derivatives: Reaction of
N-arylidenenaphthalen-2-amine with
4-Hydroxycoumarin in Aqueous Media
Xiang-Shan Wang
Department of Chemistry, Xuzhou Normal University, Xuzhou Jiangsu,
China and Key Laboratory of Biotechnology on Medical Plant of Jiangsu
Province, Xuzhou, China
Mei-Mei Zhang and Zhao-Sen Zeng
Department of Chemistry, Xuzhou Normal University, Xuzhou Jiangsu,
China
Da-Qing Shi and Shu-Jiang Tu
Department of Chemistry, Xuzhou Normal University, Xuzhou Jiangsu,
China and Key Laboratory of Biotechnology on Medical Plant of Jiangsu
Province, Xuzhou, China
Abstract: A short and simple synthesis of chromeno[4,3-b]benzo[ f ]quinolin-6-one
derivatives was accomplished in good to high yields via the reaction of N-arylidene-
naphthalen-2-amine with 4-hydroxycoumarin in aqueous media catalyzed by
TEBAC. The structures were established by spectroscopic data and further
confirmed by X-ray analysis. In addition, water was chosen as a green solvent.
Keywords: Aqueous medium, chromene, quinoline, Schiff base, TEBAC
Heteroaromatic rings containing nitrogen atoms often play important roles as
the scaffolds of bioactive substances. Quinoline is one of the most popular
Received in China September 25, 2003
Address correspondence to Xiang-Shan Wang, Department of Chemistry, Xuzhou
Normal University, Xuzhou Jiangsu, 221116, China. E-mail: xswang1974@yahoo.com
2047

2048
X.-S. Wang et al.
N-heteroaromatics incorporated into the structure of many pharmaceuticals. It
is known that many quinoline-containing compounds exhibit a wide spectrum
of pharmacological activities such as antiasthmatic, antiinflammatory, and
antimalarial activities.[1] In addition, it was reported that chromenes and
their derivatives are also important compounds, which are found to possess
antiestrogenic activity and are devoid of any agonistic activity,[2] and are
evaluated for potassium channel opening and hypotensive activities,[3] vasodi-
lator and antihypertensive activies,[4] b-adrenolytic activity,[5] antimicrobial
activity,[6] and biological activity of high-affinity retinoic acid receptor antag-
onist.[7] To the best of our knowledge, only a few examples of heteroaromatic
rings containing quinoline and chromene at the same time have been
mentioned in the literature.[8] Because of the toxic and volatile nature of
many organic solvents, water as reaction medium was considered a very
promising and attractive substitute for volatile organic solvents and was
widely used in the green chemistry area since Breslow,[9] who showed that
hydrophobic effects could strongly enhance the rate of several organic
reactions, rediscovered the use of water as a solvent in organic chemistry in
1980s. There has been growing recognition that water is an attractive
medium for many organic reactions resulting in less expensive, less
dangerous, and environmentally friendly reactions, such as Diels–Alder
reactions,[10] Claisen rearrangement reactions,[11] Reformatsky reactions,[12]
and pinacol-coupling reactions.[13] As part of our current studies on the devel-
opment of new routes to heterocyclic systems,[14] we now report an efficient
and clean synthetic route to 7-aryl-7,14-dihydro-6H-benzo[ f ]chromeno[4,3-
b]quinolin-6-one derivatives in aqueous medium catalyzed by TEBAC
(triethylbenzyl ammonium chloride) by the reaction of N-arylidenenaphthalen-
2-amine with 4-hydroxycoumarin.
When the reaction of N-arylidenenaphthalen-2-amine 1 and 4-hydroxy-
coumarin 2 was performed in water in the presence of TEBAC at 1008C,
high yields of 7-aryl-7,14-dihydro-6H-benzo[ f ]chromeno[4,3-b]quinolin-6-
one derivatives were obtained (Scheme 1).
To apply this reaction to a library synthesis, various kinds of N-arylidene-
naphthalen-2-amine and 4-hydroxycoumarins were subjected to give the
corresponding 7-aryl-7,14-dihydro-6H-benzo[ f ]chromeno[4,3-b]quinolin-6-
one derivatives 3, and representative examples are shown in Table 1. All of
Scheme 1.

Chromeno[4,3-b]benzo[ f]quinolin-6-one Derivatives
2049
Table 1. Results of the reaction of 1 and 2 in water at 1008Ca
Entry
Ar
Products
Time (h)
Yields (%)b
1
2
4-BrC6H4
2-ClC6H4
3a
3b
3c
3d
3e
3f
8
12
12
12
10
10
12
12
8
93.3
94.0
90.2
87.8
90.9
95.0
92.3
95.2
90.5
92.7
95.0
88.9
92.8
3
3-ClC6H4
4-ClC6H4
4
5
2,4-Cl2C6H3
3,4-Cl2C6H3
4-OHC6H4
6
7
3g
3h
3i
8
4-(CH3)2NC6H4
2-NO2C6H4
9
10
11
12
13
4-CH3OC6H4
3,4-(CH3)2C6H3
3,4-(CH3O)2C6H3
3-OH-4-CH3OC6H3
3j
10
10
8
3k
3l
3m
12
aReaction condition: 10 mL water and 0.1 g TEBAC, 2 mmol 1 and
2 mmol 2.
the N-arylidenenaphthalen-2-amine gave expected products in excellent yields
and purity. The isolated 7-aryl-7,14-dihydro-6H-benzo[ f ]chromeno[4,3-b]
quinolin-6-one derivatives 3 were completely characterized by IR, 1H
NMR, and elemental analyses. The analyses were in agreement with their
structures. The IR spectra for 3a exhibited sharp bands at 3310 cm21 (NH),
1657 cm21 (C55O). The 1H NMR spectrum of 3a exhibited a singlet identified
methine (5.91) and multiplets (7.28–8.40) for aromatic protons. The NH
proton resonance at 10.18 disappeared after addition of D2O to the DMSO-
d6 solution of 3a. To further confirm the structure of the product, the
X-ray analysis (Crystal data for 3a: C26H16BrNO2; M ¼ 454.31, orange-
yellow block crystals, 0.59 ꢀ 0.34 ꢀ 0.15 mm, monoclinic, space group P
˚
21/c, a ¼ 7.3681(8), b ¼ 13.5483(14), c ¼ 19.662(3) A, b ¼ 100.372(4)8,
3
V ¼ 1930.7(4) , Z ¼ 4, Dc ¼ 1.563 g cm23. F(000) ¼ 920, m(MoKa) ¼
.
2.153 mm21. Intensity data were collected on Rigaku Mercury diffractometer
˚
with graphite monochromated MoKa radiation (l ¼ 0.71070 A) using v scan
mode with 3.018 , u , 27.488. 4412 unique reflections were measured and
3827 reflections with I . 2s (I) were used in the refinement. Structure was
solved by direct methods and expanded using Fourier techniques. The final
cycle of full-matrix least squares technique was done to R ¼ 0.0446 and
wR ¼ 0.0968.) of 3a was carried out. The selected bond lengths and bond
angles are given in Table 2. The structure of 3a and packing arrangement in
a unit cell of 3a along a are shown in Figs. 1 and 2. The X-ray crystal
structure determination indicates the atoms C(1), C(2), C(3), C(4), C(5),
and N(1) form a six-membered ring, with the interatomic distances
˚
1.368(3) A for C(1)-C(2) and 1.377(3) A for C(4)-C(5), which are near to
˚
˚
that of the typical C55C double bond (1.34 A). The bond angles of

2050
X.-S. Wang et al.
˚
Table 2. Selected bond lengths (A) and selected bond angles (8) for 3a
Bond Distances Distances
Distances
Bond distances for compound 3a
Br(1)-C(24)
O(1)-C(6)
O(2)-C(6)
O(2)-C(7)
N(1)-C(1)
N(1)-C(5)
C(1)-C(2)
C(1)-C(12)
1.900(2)
C(2)-C(6)
1.432(3)
1.509(3)
1.517(3)
1.531(3)
1.377(3)
1.426(3)
1.418(3)
1.223(3)
1.370(2)
1.376(2)
1.362(3)
1.403(3)
1.368(3)
1.449(3)
C(2)-C(3)
C(3)-C(4)
C(3)-C(21)
C(4)-C(5)
C(4)-C(20)
C(5)-C(13)
Bond angles
Degree
Bond angles
Degree
Bond angles for compound 3a
121.09(16)
C(6)-O(2)-C(7)
C(1)-N(1)-C(5)
N(1)-C(1)-C(2)
N(1)-C(1)-C(12)
C(2)-C(1)-C(12)
C(1)-C(2)-C(6)
C(1)-C(2)-C(3)
C(6)-C(2)-C(3)
C(2)-C(3)-C(4)
C(2)-C(3)-C(21)
C(4)-C(3)-C(21)
C(5)-C(4)-C(20)
C(5)-C(4)-C(3)
C(20)-C(4)-C(3)
C(4)-C(5)-N(1)
C(4)-C(5)-C(13)
N(1)-C(5)-C(13)
O(1)-C(6)-O(2)
O(1)-C(6)-C(2)
117.88(18)
116.08(18)
124.95(19)
118.97(18)
116.11(19)
121.85(18)
117.25(18)
124.99(19)
120.1(2)
121.46(17)
119.83(18)
120.11(18)
120.06(18)
120.29(19)
122.73(18)
116.97(17)
110.53(16)
110.09(16)
111.29(16)
119.36(19)
120.19(18)
120.26(18)
121.16(18)
120.95(19)
O(2)-C(6)-C(2)
O(2)-C(7)-C(8)
O(2)-C(7)-C(12)
C(7)-C(12)-C(1)
C(11)-C(12)-C(1)
C(14)-C(13)-C(5)
C(19)-C(20)-C(4)
C(15)-C(20)-C(4)
C(22)-C(21)-C(3)
C(26)-C(21)-C(3)
C(23)-C(24)-Br(1)
C(25)-C(24)-Br(1)
122.09(19)
119.61(19)
120.92(19)
120.83(19)
119.59(19)
119.13(19)
C(2)-C(1)-N(1), C(1)-C(2)-C(3), C(3)-C(4)-C(5), and C(4)-C(5)-O(1) are
119.83(18), 122.73(18), 120.19(18) and 121.16(18)8 respectively, which
also illustrates that C(1), C(2), C(4), and C(5) all adopt sp2 hybrid orbit to
form C—C double bonds. The bond angle of C(1)-N(1)-C(5) [121.46(17)8]
is near to 1208, which indicates that the atom N(1) adopts sp2 hybrid orbit
to conjugate to the intercyclic C55C double bonds C(1)—C(2) and C(4)—
C(5). The X-ray crystal structure determination indicates the 1,4-dihydropyr-
idine ring of the chromenopyridine moiety is slightly distorted and adopts a
boat conformation. The atoms C(3) and N(1) deviate from the basal plane
˚
defined by the atoms C(1)/C(2)/C(4)/C(5)/by 0.254 (2) and 0.095 (2) A,
respectively. The 1,4-dihydropyridine is nearly parallel to the phenyl ring
[C(4)/C(5)/C(13)/C(14)/C(15)/C(20)], phenyl ring [C(15)ꢀC(20)], phenyl
ring [C(7)ꢀC(12)], and pyran ring [C(1)/C(2)/C(6)/C(7)/C(12)/O(2)],

Chromeno[4,3-b]benzo[ f]quinolin-6-one Derivatives
2051
Figure 1. Crystal structure of the product 3a.
forming the dihedral angles of 5.2(1), 4.2(2), 6.7(1), and 7.9(1)8, respectively,
and nearly perpendicular to phenyl ring [C(21)ꢀC(26)], forming a dihedral
angles of 82.2(2)8. The dihedral angle between the phenyl ring
[C(7)ꢀC(12)] and phenyl ring [C(15)ꢀC(20)] is 10.8(1)8.
Figure 2. Packing arrangement in a unit cell of 3a along a.

2052
X.-S. Wang et al.
Scheme 2.
Though the detailed mechanism of this reaction has not been clarified yet,
the formation of 3 can be explained by the possible mechanism presented in
Scheme 2.
Finally the reuse of the water and TEBAC was studied. At completion,
monitored by TLC, the reaction mixture was allowed to cool to room tempera-
ture, the solid of the products was isolated by filtration, and the filtrate of the
water together with TEBAC could be reused directly. Investigations by using
1a and 2 as model substrates showed that successive reuse of the recovery
water and TEBAC was feasible. A summary of the reuse of water and
TEBAC is shown in Table 3. Even in the fourth round the yield of the
product 3 is fairly high.
In conclusion, an efficient green chemistry method for the synthesis of
chromeno[4,3-b]benzo[ f ]quinolin-6-one derivatives by condensation of
4-hydroxycoumarin and N-arylidenenaphthalen-2-amine was successfully
established. In this method, the potential active compounds containing
quinoline as well as chromene heteroaromatic rings can be synthesized
easily by a one-step reaction. Compared to other methods,[8] this new
method has the advantage of good yields, mild reaction conditions, easy
workup, inexpensive reagents, and environmentally friendly procedure.
EXPERIMENTAL
Melting points were determined in open capillaries and are uncorrected. IR
spectra were recorded on a Tensor 27 spectrometer in KBr. 1H NMR

Chromeno[4,3-b]benzo[ f]quinolin-6-one Derivatives
Table 3. Study on the reuse of water and TEBACa
2053
Entry
Temperature/8C
Reaction time/h
Yields (%)b
1
2
3
4
100
100
100
100
12
12
12
12
93
93
95
92
aReaction condition: 10 mL of water and TEBAC, 2 mmol of 1a,
and 2 mmol of 2.
bIsolated yields.
spectra were obtained for solution in DMSO-d6 with Me4Si as internal
standard using a Bruker-400 spectrometer. Elemental analyses were carried
out using a Carlo Erba 1110 analyzer. X-ray diffraction was measured on a
Rigaku Mercury diffractometer.
General Procedure
A suspension of a mixture of N-arylidenenaphthalen-2-amine 1 (2 mmol),
4-hydroxycoumarin 2 (2 mmol), and TEBAC (0.1 g) was stirred in water
(10 mL) at 1008C for 8–12 h. The crystalline powder formed was collected
by filtration, washed with water, and recrystallized from DMF and water to
give pure 4-arylchromeno[4,3-b] benzo[ f ]quinoline derivatives 3.
Data
3a: mp .3008C (lit.[8a] 378–3808C). IR (KBr, n, cm21): 3310, 3056, 1657,
1621, 1588, 1570, 1527, 1511, 1478, 1430, 1404, 1321, 1251, 1203, 1185,
1089, 1056, 1010, 835, 757, 742; 1H NMR (DMSO-d6, d, ppm): 5.91
(s, 1H, CH), 7.30 (d, J ¼ 8.8 Hz, 2H, ArH), 7.37–7.40 (m, 4H, ArH), 7.46–
7.50 (m, 2H, ArH), 7.64–7.68 (m, 1H, ArH), 7.73 (d, J ¼ 8.8 Hz, 2H,
ArH), 7.88 (d, J ¼ 7.6 Hz, 1H, ArH), 7.91–7.98 (m, 2H, ArH), 8.39
(d, J ¼ 7.2 Hz, 1H, ArH), 10.18 (s, 1H, NH).
3b: mp .3008C (lit.[8a], 409–4108C). IR (KBr, n, cm21): 3297, 3056, 1673,
1
1622, 1589, 1569, 1528, 1509, 1474, 1407, 1254, 1206, 1049, 760, 701; H
NMR (DMSO-d6, d, ppm): 6.21 (s, 1H, CH), 7.06–7.16 (m, 2H, ArH), 7.31
(dd, J ¼ 7.6 Hz, J0 ¼ 1.2 Hz, 1H, ArH), 7.35–7.52 (m, 5H, ArH), 7.64–7.68
(m, 1H, ArH), 7.72 (d, J ¼ 8.8 Hz, 1H, ArH), 7.85 (d, J ¼ 8.0 Hz, 1H,
ArH), 7.89 (d, J ¼ 8.8 Hz, 1H, ArH), 8.18 (d, J ¼ 8.0 Hz, 1H, ArH), 8.43
(d, J ¼ 8.0 Hz, 1H, ArH), 10.18 (s, 1H, NH).
3c: mp .3008C. IR (KBr, n, cm21): 3305, 3065, 1656, 1620, 1589, 1510,
1
1475, 1430, 1405, 1251, 1205, 1184, 1055, 815, 754, 741, 709; H NMR

2054
X.-S. Wang et al.
(DMSO-d6, d, ppm): 5.96 (s, 1H, CH), 7.14 (d, J ¼ 8.8 Hz, 1H, ArH), 7.22
(t, J ¼ 7.6 Hz, 1H, ArH), 7.29 (d, J ¼ 7.6 Hz, 1H, ArH), 7.38–7.41 (m, 3H,
ArH), 7.46–7.51 (m, 2H, ArH), 7.64–7.68 (m, 1H, ArH), 7.74 (d,
J ¼ 8.8 Hz, 1H, ArH), 7.89 (d, J ¼ 8.0 Hz, 1H, ArH), 7.94 (d, J ¼ 8.4 Hz,
1H, ArH), 8.00 (d, J ¼ 8.4 Hz, 1H, ArH), 8.39 (d, J ¼ 8.0 Hz, 1H, ArH),
8.20 (s, 1H, NH). Anal. calcd. for C26H16ClNO2: C, 76.19; H, 3.93;
N, 3.42; found C, 76.28; H, 3.91; N, 3.49.
3d: mp .3008C. IR (KBr, n, cm21): 3310, 3055, 1659, 1621, 1588, 1569,
1527, 1510, 1477, 1430, 1404, 1321, 1250, 1204, 1187, 1089, 1053, 1015,
918, 834, 813, 782, 756, 711, 697; 1H NMR (DMSO-d6, d, ppm): 5.93
(s, 1H, CH), 7.24 (d, J ¼ 8.4 Hz, 2H, ArH), 7.36 (d, J ¼ 8.4 Hz, 2H, ArH),
7.39 (d, J ¼ 8.0 Hz, 2H, ArH), 7.48 (t, J ¼ 7.6 Hz, 2H, ArH), 7.64–7.68
(m, 1H, ArH), 7.73 (d, J ¼ 8.8 Hz, 1H, ArH), 7.88 (d, J ¼ 8.0 Hz, 1H,
ArH), 7.92 (d, J ¼ 8.8 Hz, 1H, ArH), 7.97 (d, J ¼ 8.8 Hz, 1H, ArH), 8.39
(d, J ¼ 7.6 Hz, 1H, ArH), 10.18 (s, 1H, NH). Anal. calcd. for
C26H16ClNO2: C, 76.19; H, 3.93; N, 3.42; found C, 76.31; H, 3.87; N, 3.56.
3e: mp .3008C. IR (KBr, n, cm21): 3297, 3052, 1656, 1618, 1589, 1529,
1
1474, 1407, 1320, 1252, 1205, 1107, 1046, 863, 818, 758, 741; H NMR
(DMSO-d6, d, ppm): 6.20 (s, 1H, CH), 7.23 (dd, J ¼ 8.4 Hz, J0 ¼ 2.4 Hz,
1H, ArH), 7.37–7.52 (m, 6H, ArH), 7.65–7.69 (m, 1H, ArH), 7.72
(d, J ¼ 8.8 Hz, 1H, ArH), 7.87 (d, J ¼ 8.0 Hz, 1H, ArH), 7.91
(d, J ¼ 8.8 Hz, 1H, ArH), 8.10 (d, J ¼ 8.4 Hz, 1H, ArH), 8.43
(d, J ¼ 8.0 Hz, 1H, ArH), 10.21 (s, 1H, NH). Anal. calcd. for
C26H15Cl2NO2: C, 70.28; H, 3.40; N, 3.15; found C, 70.42; H, 3.47; N, 3.28.
3f: mp .3008C. IR (KBr, n, cm21): 3300, 3067, 1657, 1621, 1588, 1528,
1
1512, 1476, 1404, 1251, 1206, 1059, 1031, 815, 754, 741, 708; H NMR
(DMSO-d6, d, ppm): 5.97 (s, 1H, CH), 7.26 (dd, J ¼ 8.4 Hz, J0 ¼ 1.6 Hz,
1H, ArH), 7.39–7.50 (m, 5H, ArH), 7.61 (d, J ¼ 1.6 Hz, 1H, ArH), 7.65–
7.69 (m, 1H, ArH), 7.74 (d, J ¼ 8.4 Hz, 1H, ArH), 7.89 (d, J ¼ 8.4 Hz, 1H,
ArH), 7.95 (d, J ¼ 8.4 Hz, 1H, ArH), 7.99 (d, J ¼ 8.4 Hz, 1H, ArH), 8.40
(d, J ¼ 8.0 Hz, 1H, ArH), 10.23 (s, 1H, NH). Anal. calcd. for
C26H15Cl2NO2: C, 70.28; H, 3.40; N, 3.15; found C, 70.33; H, 3.54; N, 3.18.
3g: mp .3008C. IR (KBr, n, cm21): 3300 (b), 1656, 1620, 1589, 1528, 1510,
1476, 1405, 1252, 1214, 1101, 1056, 1006, 836, 819, 755; 1H NMR (DMSO-
d6, d, ppm): 5.80 (s, 1H, CH), 6.55 (d, J ¼ 8.4 Hz, 2H, ArH), 7.12
(d, J ¼ 8.4 Hz, 2H, ArH), 7.35–7.39 (m, 2H, ArH), 7.45–7.49 (m, 2H,
ArH), 7.63–7.66 (m, 1H, ArH), 7.70 (d, J ¼ 8.4 Hz, 1H, ArH), 7.85–7.90
(m, 2H, ArH), 7.99 (d, J ¼ 8.0 Hz, 1H, ArH), 8.38 (d, J ¼ 8.0 Hz, 1H,
ArH), 9.20 (b, 1H, OH), 10.08 (s, 1H, OH). Anal. calcd. for C26H17NO3: C,
79.78; H, 4.38; N, 3.58; found C, 79.65; H, 4.44; N, 3.62.
3h: mp .3008C. IR (KBr, n, cm21): 3308, 3066, 2885, 1667, 1615, 1589,
1526, 1478, 1431, 1405, 1357, 1254, 1201, 1185, 1162, 1112, 1054, 947,

Chromeno[4,3-b]benzo[ f]quinolin-6-one Derivatives
2055
813, 782, 763, 744, 722; 1H NMR (DMSO-d6, d, ppm): 2.74 (s, 6H, 2NCH3),
5.77 (s, 1H, CH), 6.52 (d, J ¼ 8.8 Hz, 2H, ArH), 7.13 (d, J ¼ 8.8 Hz, 2H,
ArH), 7.35–7.39 (m, 2H, ArH), 7.45–7.49 (m, 2H, ArH), 7.62–7.66
(m, 1H, ArH), 7.70 (d, J ¼ 8.8 Hz, 1H, ArH), 7.84–7.89 (m, 2H, ArH),
8.00 (d, J ¼ 8.4 Hz, 1H, ArH), 8.37 (d, J ¼ 8.0 Hz, 1H, ArH), 10.07 (s, 1H,
NH). Anal. calcd. for C28H22N2O2: C, 80.36; H, 5.30; N, 6.69; found C,
80.52; H, 5.40; N, 6.64.
3i: mp .3008C. IR (KBr, n, cm21): 3290, 3059, 1693, 1657, 1636, 1590,
1531, 1410, 1386, 1354, 1251, 1204, 1099, 1046, 1002, 827, 810, 756, 745,
1
716; H NMR (DMSO-d6, d, ppm): 6.74 (s, 1H, CH), 7.21 (dd, J ¼ 7.6 Hz,
J0 ¼ 1.2 Hz, 1H, ArH), 7.30–7.50 (m, 7H, ArH), 7.63–7.67 (m, 1H, ArH),
7.78 (d, J ¼ 8.8 Hz, 1H, ArH), 7.88–7.91 (m, 1H, ArH), 7.99(d, J ¼ 8.8 Hz,
1H, ArH), 8.41 (d, J ¼ 8.0 Hz, 1H, ArH), 8.49 (d, J ¼ 8.8 Hz, 1H, ArH),
10.24 (s, 1H, NH). Anal. calcd. for C26H16N2O4: C, 74.28; H, 3.84; N,
6.66; found C, 74.13; H, 3.91; N, 6.70.
3j: mp .3008C (lit.[8a], 373–3758C). IR (KBr, n, cm21): 3302, 3052, 1658,
1621, 1589, 1538, 1476, 1428, 1405, 1321, 1301, 1251, 1207, 1178, 1108,
1057, 1031, 833, 814, 743; 1H NMR (DMSO-d6, d, ppm): 3.61 (s, 3H,
CH3O), 5.85 (s, 1H, CH), 6.73 (d, J ¼ 8.8 Hz, 2H, ArH), 7.24
(d, J ¼ 8.8 Hz, 2H, ArH), 7.36–7.39 (m, 2H, ArH), 7.45–7.49 (m, 2H,
ArH), 7.63–7.67 (m, 1H, ArH), 7.71 (d, J ¼ 8.0 Hz, 1H, ArH), 7.86
(d, J ¼ 8.4 Hz, 1H, ArH), 7.89 (d, J ¼ 8.0 Hz, 1H, ArH), 8.00
(d, J ¼ 8.4 Hz, 1H, ArH), 8.38 (d, J ¼ 8.0 Hz, 1H, ArH), 10.12 (s, 1H, NH).
3k: mp .3008C. IR (KBr, n, cm21): 3304, 3050, 2916, 1659, 1621, 1588,
1527, 1510, 1474, 1404, 1319, 1252, 1211, 1183, 1057, 817, 759, 740, 723;
11H NMR (DMSO-d6, d, ppm): 2.04 (s, 3H, CH3), 2.06 (s, 3H, CH3), 5.83
(s, 1H, CH), 6.92 (d, J ¼ 8.0 Hz, 1H, ArH), 7.03 (d, J ¼ 8.0 Hz, 1H, ArH),
7.10 (s, 1H, ArH), 7.38 (d, J ¼ 8.0 Hz, 2H, ArH), 7.45–7.49 (m, 2H, ArH),
7.62–7.66 (m, 1H, ArH), 7.72 (d, J ¼ 8.8 Hz, 1H, ArH), 7.86
(d, J ¼ 8.4 Hz, 1H, ArH), 7.90 (d, J ¼ 8.8 Hz, 1H, ArH), 7.99
(d, J ¼ 8.8 Hz, 1H, ArH), 8.38 (d, J ¼ 8.0 Hz, 1H, ArH), 10.12 (s, 1H, NH).
Anal. calcd. for C28H21NO2: C, 83.35; H, 5.25; N, 3.47; found C, 83.19; H,
5.31; N, 3.56.
3l: mp .3008C. IR (KBr, n, cm21): 3312, 2927, 2833, 1657, 1636, 1622,
1589, 1528, 1477, 1406, 1265, 1252, 1185, 1137, 1058, 1026, 820, 807,
1
757, 742; H NMR (DMSO-d6, d, ppm): 3.59 (s, 3H, CH3O), 3.65 (s, 3H,
CH3O), 5.87 (s, 1H, CH), 6.66 (d, J ¼ 8.4 Hz, 1H, ArH), 6.72
(d, J ¼ 8.4 Hz, 1H, ArH), 7.08 (d, J ¼ 1.2 Hz, 1H, ArH), 7.36–7.40 (m, 2H,
ArH), 7.45–7.50 (m, 2H, ArH), 7.65 (t, J ¼ 8.0 Hz, 1H, ArH), 7.72
(d, J ¼ 8.8 Hz, 1H, ArH), 7.87 (d, J ¼ 8.0 Hz, 1H, ArH), 7.90
(d, J ¼ 8.8 Hz, 1H, ArH), 8.03 (d, J ¼ 8.4 Hz, 1H, ArH), 8.38
(d, J ¼ 8.0 Hz, 1H, ArH), 10.14 (s, 1H, NH). Anal. calcd. for C28H21NO4:
C, 77.23; H, 4.86; N, 3.22; found C, 77.16; H, 4.92; N, 3.40.

2056
X.-S. Wang et al.
3n: mp .3008C. IR (KBr, n, cm21): 3312, 2928, 1656, 1618, 1590, 1528,
1476, 1448, 1430, 1407, 1382, 1281, 1253, 1225, 1183, 1146, 1125, 1103,
1
1055, 1033, 1007, 823, 759, 749, 706; H NMR (DMSO-d6, d, ppm): 3.66
(s, 3H, CH3), 5.82 (s, 1H, CH), 6.51–6.54 (m, 2H, ArH), 7.03 (s, 1H, ArH),
7.36–7.39 (m, 2H, ArH), 7.44–7.48 (m, 2H, ArH), 7.62–7.66 (m, 1H,
ArH), 7.71 (d, J ¼ 8.8 Hz, 1H, ArH), 7.87 (d, J ¼ 8.0 Hz, 1H, ArH), 7.89
(d, J ¼ 8.8 Hz, 1H, ArH), 8.03 (d, J ¼ 8.4 Hz, 1H, ArH), 8.37
(d, J ¼ 8.0 Hz, 1H, ArH), 8.78 (b, 1H, OH), 10.12 (s, 1H, NH). Anal. calcd.
for C27H19NO4: C, 76.95; H, 4.54; N, 3.32; found C, 77.05; H, 4.61; N, 3.37.
ACKNOWLEDGMENTS
We are grateful to the Foundation of the Education Committee of Jiangsu
Province (04KJB150139) for financial support.
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