Synthesis of 2-Aminochromene Derivatives Catalyzed by KF/Al 203

Article abstract of DOI:10.1081/SCC-120027291

A series of 2-aminochromene derivatives include 2-aminobenzo-[h]chromene, and naphtha[1,2-b;6,5-b′]dipyrans derivatives were synthesized from arylaldehyde, malononitrile or ethyl cyanoacetate with 1-naphthol or 1,5-naphthalenediol in refluxing ethyl alcohol catalyzed by KF-A1 ₂0₃. The structure of the products was confirmed by X-ray analysis.

Full text of DOI:10.1081/SCC-120027291

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Synthesis of 2‐Aminochromene Derivatives Catalyzed
by KF/Al2O3
Xiang‐shan Wang a , Da‐qing Shi a , Hui‐zhen Yu a , Gao‐feng Wang a & Shu‐jiang Tu a
a Department of Chemistry , Xuzhou Normal University , Xuzhou Jiangsu, 221116, China
Published online: 16 Aug 2006.
To cite this article: Xiang‐shan Wang , Da‐qing Shi , Hui‐zhen Yu , Gao‐feng Wang & Shu‐jiang Tu (2004) Synthesis of
2‐Aminochromene Derivatives Catalyzed by KF/Al2O3 , Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 34:3, 509-514, DOI: 10.1081/SCC-120027291
To link to this article: http://dx.doi.org/10.1081/SCC-120027291
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 3, pp. 509–514, 2004
Synthesis of 2-Aminochromene Derivatives
Catalyzed by KF/Al2O3
*
Xiang-shan Wang, Da-qing Shi, Hui-zhen Yu,
Gao-feng Wang, and Shu-jiang Tu
Department of Chemistry, Xuzhou Normal University,
Xuzhou Jiangsu, China
ABSTRACT
A series of 2-aminochromene derivatives include 2-aminobenzo-[h]chro-
mene and naphtha[1,2-b;6,5-b0]dipyrans derivatives were synthesized
from arylaldehyde, malononitrile or ethyl cyanoacetate with 1-naphthol
or 1,5-naphthalenediol in refluxing ethyl alcohol catalyzed by KF-Al2O3.
The structure of the products was confirmed by X-ray analysis.
Key Words: 2-Aminochromene; Naphtho[1,2-b;6,5-b0]dipyrans; Syn-
thesis.
2-Aminochromene is an important class of compounds found as the main
compounds of many naturally occurring products employed as cosmetics and
*
Correspondence: Da-qing Shi, Department of Chemistry, Xuzhou Normal University,
Xuzhou Jiangsu, 221116, China; E-mail: xswang@xznu.edu.cn.
509
DOI: 10.1081/SCC-120027291
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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Wang et al.
pigments and utilized as potential biodegradable agrochemicals.[1–3] The
utility of fluoride salts as potential base in variety of synthetic reactions has
been recognized in recent years. Especially alumina coated with potassium
fluoride (KF-alumina) as a catalyst resulting in higher selectivity, milder
reaction conditions and easier work-up has been reported as a useful catalyst
for many reactions.[4–6] In our previous paper, we have reported that alumina
coated with potassium fluoride (KF-alumina) is a versatile solid-supported
reagent for Knoevenagel reaction,[7] Michael addition condensation[8] and any
other reactions.[9–11] Herein we report the synthesis of 2-aminochromene
derivatives catalyzed by KF-Al2O3.
When arylaldehyde, malononitrile or ethyl cyanoacetate and 1-naphthol
were treated with KF-Al2O3 in refluxing ethyl alcohol, the 2-amino-4-aryl-4H-
benzo[h]chromene derivatives were obtained in slightly high yields (72–90%)
(Table 1), if 1,5-naphthalenediol was added instead of 1-naphthol, the
naphtho[1,2-b;6,5-b0] dipyrans derivatives were isolated in the same reaction
condition in high yields (Sch. 1).
The structure of 1a was confirmed by X-ray analysis,[12] and the crystal
structure of 1a was shown in Fig. 1. In the structure of 1a, the pyran rings
adopt boat conformation. In the structure of 1a, the atoms C(1), C(2), C(4) and
C(5) are on one plane, the atom O(1) and C(3) deviate from the plane by
˚
20.0717 and 20.0710 A, the dihedral angle between the plane and phenyl
ring (C(14)–C(19)) is 88.558.
Table 1. The yields of the products.
Entry
Ar
R
Yield (%)
1a
1b
1c
1d
1e
2a
2b
2c
2d
2e
2f
2-ClC6H4
4-FC6H4
CO2Et
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
72
76
78
90
74
83
93
91
86
96
92
91
94
4-CH3OC6H4
3,4-(CH3O)2C6H3
3,4-OCH2OC6H3
C6H5
4-ClC6H4
4-FC6H4
4-BrC6H4
4-CH3OC6H4
3-NO2C6H4
3,4-(CH3O)2C6H3
2,4-Cl2C6H3
2g
2h

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511
Scheme 1.
EXPERIMENTAL
Melting points were determined in open capillaries and are uncorrected.
1
IR spectra were recorded on a TENSOR 27 spectrometer in KBr. H NMR
spectra were obtained for solution in DMSO-d6 with Me4Si as internal
standard using an Inova-400 spectrometer. Elemental analyses were carried
out using Carlo Erba 1110 analyzer. X-ray diffraction was measured on a
Siemens P4 diffractometer.
Figure 1. Structure of the compound 1a.

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Wang et al.
General Procedure
A dry 50 mL flask was charged with arylaldehyde (5 mmol), malononitrile
(5 mmol) or ethyl cyanoacetate (5 mmol), 1-naphthol (5 mmol) or 1,5-
naphthalenediol (3 mmol), KF-alumina (500 mg) and ethyl alcohol (15 mL),
The mixture was stirred at 808C for 5–6 h, then cooled to room temperature.
The mixture was poured into 200 mL water; the yellow solid was filtered off
and washed with water. The crude product was purified by recrystallization
from DMF and water to give 1 or 2.
1a. 72%, m.p. 161–1638C; 1H NMR (DMSO-d6) d: 1.00 (t, J ¼ 7.2 Hz,
3H, CH3), 3.92 (q, J ¼ 7.2 Hz, 2H, OCH2), 5.60 (s, 1H, CH), 7.12–7.25
(m, 4H, ArH), 7.38 (d, J ¼ 8.4 Hz, 1H, ArH), 7.54–7.65 (m, 3H, ArH), 7.83
(s, 2H, NH2), 7.86 (d, J ¼ 7.2 Hz, 1H, ArH), 8.30 (d, J ¼ 9.6 Hz, 1H, ArH); IR
(KBr, n, cm21): 3403, 3291, 3030, 2977, 1667, 1612, 1518, 1462, 1447, 1401,
1307, 1276, 1220, 1158, 1047, 1036, 827, 815, 776, 741, 699 cm21. Anal.
calcd for C22H18ClNO3: C 69.57, H 4.78, N 3.69; Found C 69.45, H 4.89,
N 3.63.
1
1b. 76%, m.p. 235–2378C; H NMR (DMSO-d6) d: 4.95 (s, 1H, CH),
7.09–7.12 (m, 2H, ArH), 7.15 (s, 2H, NH2), 7.21–8.23 (m, 8H, ArH); IR
(KBr, n, cm21): 3465, 3356, 2191, 1659, 1590, 1529, 1410, 1349, 1260,
1217, 1178, 1081, 1028, 903, 859, 812, 762, 738, 725 cm21. Anal. calcd
for C20H13FN2O: C 75.94, H 4.14, N 8.86; Found C 76.12, H 4.11, N
8.77.
1
1c. 78%, m.p. 192–1948C, (Lit.:[13] 1828C); H NMR (DMSO-d6) d:
3.71 (s, 3H, CH3O), 4.84 (s, 1H, CH), 6.87 (d, J ¼ 8 Hz, 2H, ArH), 7.08–7.10
(m, 3H, NH2 þ ArH), 7.16–8.23 (m, 7H, ArH); IR (KBr, n, cm21): 3426,
3336, 2187, 1642, 1591, 1509, 1407, 1233, 1214, 1181, 1141, 1081, 1035,
817, 797, 763, 748, 731cm21
.
1d. 90%, m.p. 209–2118C; 1H NMR (DMSO-d6) d: 3.71 (s, 6H, 2CH3O),
4.84 (s, 1H, CH), 6.73 (d, J ¼ 8 Hz, 1H, ArH), 6.90 (s, 2H, NH2), 7.09–8.23
(m, 8H, ArH); IR (KBr, n, cm21): 3470, 3324, 2194, 1649, 1583, 1517, 1465,
1410, 1286, 1263, 1235, 1184, 1142, 1099, 1083, 1045, 968, 861, 844, 812,
743, 728 cm21. Anal. calcd for C22H18N2O3: C 73.73, H 5.06, N 7.82; Found
C 73.59, H 5.14, N 7.73.
1e. 74%, m.p. 244–2458C; 1H NMR (DMSO-d6) d: 4.84 (s, 1H,
CH), 5.97 (s, 2H, OCH2O), 6.74 (d, J ¼ 8 Hz, 2H, ArH), 6.84 (d,
J ¼ 8 Hz, 1H, ArH), 7.11–7.13 (m, 3H, NH2 þ ArH), 7.55 þ 8.22 (m,
5H, ArH); IR (KBr, n, cm21): 3433, 3339, 2183, 1639, 1590, 1492, 1453,
1411, 1283, 1261, 1184, 1070, 1027, 834, 814, 751, 717 cm21. Anal.
calcd for C21H14N2O3: C 73.68, H 4.12, N 8.18; Found C 73.55, H 4.32,
N 8.07.

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513
2a. 83%, m.p. .3008C, 1H NMR (DMSO-d6) d: 4.91 (s, 2H, 2CH), 7.11
(s, 4H, 2NH2), 7.24–7.91 (m, 14H, ArH); IR (KBr, n, cm21): 3452, 3332,
3230, 3017, 2848, 2196, 1649, 1589, 1493, 1450, 1382, 1118, 1040, 759,
707 cm21, Anal. calcd for C30H20N4O2: C 76.91, H 4.30, N 11.96; Found C
76.85, H 4.32, N 11.87.
2b. 93%, m.p. .3008C (Lit.:[14] .3008C), 1H NMR (DMSO-d6) d: 4.96
(s, 2H, 2CH), 7.17 (s, 4H, 2NH2), 7.22–7.91 (m, 12H, ArH); IR (KBr, n,
cm21): 3450, 3330, 3057, 2220, 1634, 1561, 1472, 1440, 1380, 1250, 1140,
1016, 840 cm21
.
1
2c. 91%, m.p. .3008C, H NMR (DMSO-d6) d: 4.95 (s, 2H, 2CH),
7.13–7.17 (m, 8H, 2NH2 þ ArH), 7.22–7.91(m, 8H, ArH); IR (KBr, n,
cm21): 3460, 3355, 3210, 3080, 2212, 1663, 1618, 1518, 1398, 1233, 1189,
1085, 837 cm21, Anal. calcd for C30H18F2N4O2: C 71.42, H 3.60, N 11.11;
Found C 71.38, H 3.82, N 11.03.
1
2d. 86%, m.p. .3008C, H NMR (DMSO-d6) d: 4.95 (s, 2H, 2CH),
7.17–7.24 (m, 10H, 2NH2 þ ArH), 7.52 (d, J ¼ 8.4 Hz, 4H, ArH), 7.89
(d, J ¼ 8.4 Hz, 2H, ArH); IR (KBr, n, cm21): 3460, 3324, 3205, 2195, 1648,
1605, 1501, 1253, 1050, 863 cm21, Anal. calcd for C30H18Br2N4O2: C 57.53,
H 2.90, N 8.95; Found C 57.48, H 3.01, N 8.86.
1
2e. 96%, m.p. .3008C, H NMR (DMSO-d6) d: 3.73 (s, 6H, 2CH3O),
4.85 (s, 2H, 2CH), 6.88 (d, J ¼ 8.4 Hz, 4H, ArH), 7.06 (s, 4H, 2NH2), 7.15
(d, J ¼ 8.8 Hz, 4H, ArH), 7.21 (d, J ¼ 8.8 Hz, 2H, ArH),; 7.87 (d, J ¼ 8.4 Hz,
2H, ArH), IR (KBr, n, cm21): 3452, 3332, 3189, 2203, 1648, 1597, 1477,
1394, 1282, 1186, 1094, 827 cm21, Anal. calcd for C32H24N4O4: C 72.72, H
4.58, N 10.60; Found C 72.59, H 4.62, N 10.37.
2f. 92%, m.p. .3008C, 1H NMR (DMSO-d6) d: 5.22 (s, 2H, 2CH), 7.29–
7.33 (m, 6H, ArH), 7.61–7.75 (m, 4H, ArH), 7.93 (d, J ¼ 8.4 Hz, 2H, ArH),
8.13 (s, 4H, 2NH2); IR (KBr, n, cm21): 3400, 3316, 3196, 3050, 2187, 1665,
1605, 1513, 1401, 1253, 1094, 843, 775 cm21, Anal. calcd for C30H18N6O6:
C 64.52, H 3.25, N 15.05; Found C 64.59, H 3.21, N 15.23.
1
2g. 91%, m.p. .2608C, H NMR (DMSO-d6) d: 3.71 (s, 6H, 2CH3O),
4.85 (s, 2H, 2CH), 6.72–6.90 (m, 6H, ArH), 7.08 (s, 4H, 2NH2), 7.28
(d, J ¼ 8.8 Hz, 2H, ArH), 7.88 (d, J ¼ 8.4 Hz, 2H, ArH); IR (KBr, n, cm21):
3444, 3340, 3197, 2187, 1649, 1588, 1521, 1382, 1341, 1293, 1074, 914, 811,
723 cm21, Anal. calcd for C34H28N4O6: C 69.38, H 4.79, N 9.52; Found C
69.27, H 4.85, N 9.39.
2h. 94%, m.p. .3008C, 1H NMR (DMSO-d6) d: 5.43 (s, 2H, 2CH), 7.13
(d, J ¼ 8.4 Hz, 2H, ArH), 7.24 (s, 4H, 2NH2), 7.28 (d, J ¼ 8.4 Hz, 2H, ArH),
7.40 (d, J ¼ 8.4 Hz, 2H, ArH), 7.63 (s, 2H, ArH), 7.90 (d, J ¼ 8.4 Hz, 2H,
ArH); IR (KBr, n, cm21): 3460, 3325, 3189, 2204, 1672, 1597, 1485, 1394,
1283, 1082, 1083, 826, 759 cm21, Anal. calcd for C30H16Cl4N4O2: C 59.43,
H 2.66, N 9.24; Found C 59.37, H 2.78, N 9.11.

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ACKNOWLEDGMENT
We are grateful to the Foundation of the “Surpassing Project” of Jiangsu
Province for financial support.
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12. X-ray crystallography for 1a: Empirical formula C22H18ClNO3,
FW ¼ 379.82, T ¼ 294(2) K, monoclinic, space group C2/c,
˚
˚
˚
a ¼ 25.168(4) A, b ¼ 9.584(1) A, c ¼ 16.503(3) A, a ¼ 908, b ¼
3
3
˚
111.14(1)8, g ¼ 908, V ¼ 3712.8(10) A , Z ¼ 8, Dc ¼ 1.359 Mg/m ,
l(MoKa) ¼ 0.71073 A, m ¼ 0.228 mm21, F(000) ¼ 1584. 1.748 , u
˚
, 25.018, R ¼ 0.0565, wR ¼ 0.1320. S ¼ 0.885, Largest diff. Peak and
23
˚
hole: 0.491 and 20.204 e A
.
.
13. Elagamey, A.G.A.; Sawllim, S.Z.; El-Taweel, F.M.A.A.; Elnagdi, M.H.
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Received in Japan June 9, 2003

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