A convenient synthesis of 5-oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran derivatives catalyzed by KF-alumina

Article abstract of DOI:10.1081/SCC-120015567

A series of 5-oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran derivatives were prepared by the reaction of arylmethylidenemalononitriles or 2-cyano-3-aryl-1-acrylate with 5,5-dimethyl-1,3-cyclohexanedione (dimedone) in DMF at room temperature catalyzed by KF-al

Full text of DOI:10.1081/SCC-120015567

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A Convenient Synthesis of 5-Oxo-5,6,7,8-tetrahydro-4
H -benzo-[b]-pyran Derivatives Catalyzed by KF-
Alumina
a
a b
a
a
Xiang-Shan Wang , Da-Qing Shi
, Shu-Jiang Tu & Chang-Sheng Yao
a
Department of Chemistry, Xuzhou Normal University, Xuzhou, P.R., China
b
Department of Chemistry, Xuzhou Normal University, Xuzhou, 221009, P.R., China
Version of record first published: 20 Aug 2006.
To cite this article: Xiang-Shan Wang , Da-Qing Shi , Shu-Jiang Tu & Chang-Sheng Yao (2003): A Convenient Synthesis
of 5-Oxo-5,6,7,8-tetrahydro-4 H -benzo-[b]-pyran Derivatives Catalyzed by KF-Alumina, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 33:1, 119-126
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Õ
SYNTHETIC COMMUNICATIONS
Vol. 33, No. 1, pp. 119–126, 2003
A Convenient Synthesis of
-Oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran
Derivatives Catalyzed by KF-Alumina
5
Xiang-Shan Wang, Da-Qing Shi,* Shu-Jiang Tu,
and Chang-Sheng Yao
Department of Chemistry, Xuzhou Normal University,
Xuzhou, P.R. China
ABSTRACT
A series of 5-oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran derivatives
were prepared by the reaction of arylmethylidenemalononitriles or
2
-cyano-3-aryl-l-acrylate with 5,5-dimethyl-1,3-cyclohexanedione
dimedone) in DMF at room temperature catalyzed by KF-alumina.
(
The structure of the product was confirmed by X-ray analysis.
Key Words: 4H-benzo-[6]-pyran; Arylmethylidenemalononitriles;
2
-cyano-3-aryl-1-acrylate; Synthesis.
*Correspondence: Da-qing Shi, Department of Chemistry, Xuzhou Normal
University, Xuzhou, 221009, P.R. China. E-mail: wxs2001z@sina.com.cn.
1
19
DOI: 10.1081/SCC-120015567
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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1
20
Wang et al.
Scheme 1.
The utility of fluoride salts as potential base in variety of synthetic
1,2]
[
reactions has been recognized in recent years.
However, low solubility
of fluoride salts in ordinary solvents hamper their wide applications in
organic synthesis. On the other hand, there has been increasing use of
inorganic solid supports as catalyst resulting in higher selectivity, milder
reaction conditions and easier work-up, which has been reported as a
[
3,4]
[5,6]
useful catalyst for many reactions.
In our previous paper,
we have
reported that alumina coated with potassium fluoride (KF-alumina) is a
versatile solid-supported reagent for Knoevenagel reaction and Michael
addition condensation. In this paper, we would like to report that
preparation of 5-oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran derivatives
catalyzed by KF-alumina.
When arylmethylidenemalononitriles or 2-cyano-3-aryl-1-acrylate (1)
and 5,5-dimethyl-1,3-cyclohexanedione (dimedone) (2) were treated with
KF-alumina in DMF at room temperature (Sch. 1). The desired 5-oxo-
5,6,7,8-tetrahydro-4H-benzo-[b]-pyran derivatives (3) were obtained in
good yields (60–89%) (Table 1) within very short reaction time (1–3 h).
The structures of the products (X-ray crystal structures of 3c and 3n
shown in Figs. 1 and 2) were established on the basis of spectroscopic data
[7]
[8]
and confirmed by X-ray diffraction studies on monocrystal of 3c and 3n.
The reactions also can be catalyzed by potassiumfluoride (not
alumina), only 41% yield of 3a was obtained, when the same reaction
ꢀ
was carried out in DMF at 80 C using potassiumfluoride as the catalyst.
In conclusion, with good yields and mild conditions, we think that the
present work described here in provide a useful method for the preparation
of 5-oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran derivatives.
EXPERIMENTAL
Melting points were determined in open capillaries and are uncor-
rected. IR spectra were recorded on a FT IR-8101 spectrometer.

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5
-Oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran Derivatives
Table 1. The yields of the products.
121
Entry
Ar
R
Isolated yield (%)
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
a
b
c
d
e
f
g
h
i
C
6
H
5
CN
71
80
79
70
81
75
70
72
72
78
73
80
66
63
89
70
60
70
4-CH C H
6
CN
CN
CN
CN
CN
CN
CN
CN
3
4
3,4-OCH
2
6 3
OC H
3,4-(OCH
4-ClC H
4-CH OC
3
2 6 3
) C H
6
4
3
6
H
4
6 4
2-ClC H
4-NO C H
2-furyl
2
6
4
j
k
l
C
6
H
5
2
CO Me
C H
6
CO Et
2
5
4-CH C H
3
CO Me
2
6
4
m
n
o
p
q
r
4-CH
4-ClC
4-ClC H
2-ClC
2-ClC
3
C
6
H
4
CO
CO
2
Et
Me
6
H
4
2
CO Et
2
6
4
4
4
6
H
H
CO
CO
2
Me
Et
6
2
3,4-OCH OC H
2
CO Et
2
6
3
Figure 1. X-ray crystal structure of 3c.

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22
Wang et al.
Figure 2. X-ray crystal structure of 3n.
1
H NMR spectra were measured on a R-1500A spectrometer using TMS
as internal standard. Mass spectra were determined on Micromass
OA-TOFMS instrument. Elemental analyses were carried out using
Carlo Erba 1110 analyzer. X-ray diffraction were measured on a
Siemens P4 diffractometer.
GeneralProcedure
A dry 50-mL flask was charged with arylmethylidene malononitriles
or 2-cyano-3-aryl-1-acrylate (1) (2 mmol), 5,5-dimethyl-1,3-cyclohexane-
dione (dimedone) (2.5 mmol), KF-alumina (250 mg) and DMF (10 mL).
The mixture was stirred at room temperature for 1–3 h. Then the solid
material was filtered off and washed with a little DMF. The filterate was
poured into 200 mL water. The white solid was filtered off, then washed
with water. The crude solid was purified by recrystallization from95%
EtOH to give (3).
ꢀ
ꢁ1
3
a: M.p. 226–228 C; IR (KBr, ꢀ, cm ): 3280, 3250, 3040, 2990, 2980,
1
2
245, 1650, 1600, 1480, 740, 700; H NMR (CD COCD , ꢁ, ppm): 1.01
3 3

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5
-Oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran Derivatives
123
(
3H, s, CH ), 1.10 (3H, s, CH ), 2.21 (2H, s, CH ), 2.56 (2H, s, CH ), 3.06
2
3
3
2
(
2H, br., s, NH ), 4.28 (1H, s, CH), 7.27 (5H, s, ArH); MS: m/e (%) 294
2
þ
(
M , 8), 227 (100), 217 (15), 171 (19), 102 (17); Elemental analysis: Found
(
N, 9.52.
%): C, 73.60; H, 6.07; N, 9.38. Calcd. for C H N O : C, 73.45; H, 6.16;
1
8
18
2
2
ꢀ
ꢁ1
3b: M.p. 208–210 C; IR (KBr, ꢀ, cm ): 3320, 3280, 3040, 2990,
1
2
1
980, 2240, 1680, 1600, 1510, 850; H NMR (CD COCD , ꢁ, ppm):
3 3
.06 (3H, s, CH ), 1.11 (3H, s, CH ), 2.25 (5H, d, CH , CH ), 2.54
3
3
2
3
(
2H, s, CH ), 3.05 (2H, br., s, NH ), 4.25 (1H, s, CH), 7.13 (4H, s,
2 2
þ
ArH); MS: m/e (%) 308 (M , 7), 241 (27), 227 (100), 171 (21), 115
19); Elemental analysis: Found (%): C, 74.12; H, 6.41; N, 8.97. Calcd.
for C H N O : C, 74.00; H, 6.54; N, 9.09.
(
1
9
20
2
2
ꢀ
ꢁ1
3
c: M.p. 212–214 C; IR (KBr, ꢀ, cm ): 3280, 3200, 3040, 2990,
970, 2240, 1680, 1600, 1500, 1490, 870, 790; H NMR (CD COCD , ꢁ,
1
2
3 3
ppm): 0.98 (3H, s, CH ), 1.06 (3H, s, CH ), 2.19 (2H, s, CH ), 2.51 (2H,
3
3
2
s, CH ), 3.28 (2H, br., s, NH ), 4.12 (1H, s, CH), 6.00 (2H, s, OCH O),
2
2
2
þ
6
2
.69–6.93 (3H, m, ArH); MS: m/e (%) 338 (M , 8), 271 (100), 242 (9),
15 (9), 188 (15), 173 (17), 160 (16), 145 (12); Elemental analysis: Found
(
%): C, 67.61; H, 5.24; N, 8.16. Calcd. for C H N O : C, 67.44; H,
19 18 2 4
5
.36; N, 8.28.
ꢀ
ꢁ1
3d: M.p. 173–174 C; IR (KBr, ꢀ, cm ): 3300, 3250, 3040, 2990,
1
2
240, 1650, 1600, 1520, 860, 820; H NMR (CD COCD , ꢁ, ppm): 1.02
3 3
(
(
3H, s, CH ), 1.08 (3H, s, CH ), 2.21 (2H, s, CH ), 2.54 (2H, s, CH ), 3.07
3 3 2 2
2H, br., s, NH ), 3.75 (6H, s, 2 Â OCH ), 4.23 (1H, s, CH), 6.82 (3H, s,
2
3
þ
ArH); MS: m/e (%) 354 (M , 9), 323 (17), 288 (95), 273 (58), 257 (100),
2
6
17 (12), 201 (31), 176 (14); Elemental analysis: Found (%): C, 67.92; H,
.16; N, 7.83. Calcd. for C H N O : C, 67.78; H, 6.26; N, 7.91.
2
0
22
2
4
ꢀ
ꢁ1
3
e: M.p. 207–209 C; IR (KBr, ꢀ, cm ): 3300, 3200, 3040, 2990, 2970,
1
2240, 1650, 1610, 1490, 850; H NMR (CD COCD , ꢁ, ppm): 1.01 (3H, s,
3 3
CH ), 1.09 (3H, s, CH ), 2.22 (2H, s, CH ), 2.59 (2H, s, CH ), 3.07 (2H,
2
3
3
2
þ
br., s, NH ), 4.30 (1H, s, CH), 7.30 (4H, s, ArH); MS: m/e (%) 328 (M ,
2
12), 261 (62), 227 (100), 217 (25), 171 (30), 150 (22), 136 (28); Elemental
analysis: Found (%): C, 65.84; H, 5.20; N, 8.51. Calcd. for
C H ClN O : C, 65.75; H, 5.21; N, 8.52.
1
8
17
2
2
ꢀ
ꢁ1
3f: M.p. 198–200 C; IR (KBr, ꢀ, cm ): 3400, 3300, 3040, 2990, 2980,
1
2
970, 2240, 1680, 1610, 1510, 840; H NMR (CD COCD , ꢁ, ppm): 0.95
3 3
(
3H, s, CH ), 1.02 (3H, s, CH ), 2.16 (2H, s, CH ), 2.48 (2H, s, CH ), 3.28
3 3 2 2
(
2H, br., s, NH ), 3.71 (3H, s, OCH ), 4.12 (1H, s, CH), 6.87–6.99 (4H,
2
3
þ
m, ArH); MS: m/e (%) 324 (M , 9), 257 (100), 243 (20), 227 (50), 201
12), 146 (17); Elemental analysis: Found (%): C, 70.42; H, 6.13; N, 8.62.
Calcd. for C H N O : C, 70.35; H, 6.22; N, 8.64.
(
1
9
20
2
3

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Wang et al.
g: M.p. 200–202 C; IR (KBr, ꢀ, cm ): 3300, 3200, 3040, 2990,
ꢀ
ꢁ1
3
1
2
970, 2240, 1680, 1600, 1450, 770; H NMR (CD COCD , ꢁ, ppm):
3 3
1.08 (3H, s, CH ), 1.10 (3H, s, CH ), 2.20 (2H, s, CH ), 2.54 (2H, s,
CH ), 3.05 (2H, br., s, NH ), 4.86 (1H, s, CH), 7.29 (4H, s, ArH); MS:
3
3
2
2
2
þ
m/e (%) 328 (M , 4), 293 (15), 227 (100), 211 (34), 171 (80), 136 (11), 115
7); Elemental analysis: Found (%): C, 65.92; H, 5.18; N, 8.43. Calcd. for
C H ClN O : C, 65.75; H, 5.21; N, 8.52.
(
1
8
17
2
2
ꢀ
ꢁ1
3
h: M.p. 130–132 C; IR (KBr, ꢀ, cm ): 3300, 3200, 3040, 2990,
1
2
970, 2240, 1650, 1600, 1510, 830; H NMR (CD COCD , ꢁ, ppm):
3 3
1.00 (3H, s, CH ), 1.10 (3H, s, CH ), 2.20 (2H, s, CH ), 2.60 (2H, s,
CH ), 3.06 (2H, br., s, NH ), 4.49 (1H, s, CH), 7.26–8.29 (4H, m,
3
3
2
2
2
þ
ArH); MS: m/e (%) 339 (M , 20), 242 (100), 217 (35), 186 (14), 145
(
20), 117 (15); Elemental analysis: Found (%): C, 63.95; H, 4.98; N,
1
2.27. Calcd. for C H N O : C, 63.71; H, 5.05; N, 12.38.
18 17 3 4
ꢀ
ꢁ1
3
i: M.p. 218–220 C; IR (KBr, ꢀ, cm ): 3400, 3300, 3050, 2990, 2980,
1
2
240, 1680, 1600, 730; H NMR (CD COCD , ꢁ, ppm): 1.00 (3H, s,
3
3
CH ), 1.10 (3H, s, CH ), 2.28 (2H, s, CH ), 2.54 (2H, s, CH ), 3.05
3
3
2
2
(
(
2H, br., s, NH ), 4.44 (1H, s, CH), 6.18–7.37 (3H, m, ArH); MS: m/e
2
%) 284 (M , 4), 256 (11), 218 (100), 203 (30), 190 (35), 162 (69), 134 (48),
þ
1
9
20 (30), 106 (35); Elemental analysis: Found (%): C, 67.62; H, 5.54; N,
.79. Calcd. for C H N O : C, 67.59; H, 5.67; N, 9.86.
1
6
16
2
3
ꢀ
ꢁ1
3j: M.p. 146–148 C, IR (KBr, ꢀ, cm ) 3410, 3270, 3020, 2980, 1700,
1
2
660, 1610, 1500, 1450, 740, 710; ꢁ 0.96 (3H, s, CH ), 1.09 (3H, s, CH ),
H
3
3
.19 (2H, s, CH ), 2.42 (2H, s, CH ), 3.60 (3H, s, OCH ), 4.72 (1H, s,
3
2
2
CH), 6.16 (2H, br., s, NH ), 7.22 (5H, s, ArH); Elemental analysis: Found
2
(
N, 4.28.
%): C, 69.52; H, 6.57; N, 4.20. Calcd. for C H NO : C, 69.72; H, 6.42;
19 21 4
ꢀ
ꢁ1
3k: M.p. 158–160 C, IR (KBr, v, cm ) 3400, 3260, 3020, 2980, 1700,
1
660, 1610, 1520, 1460, 730, 700; ꢁH 0.93–1.23 (9H, m, 3 Â CH ), 2.15
3
(
2H, s, CH ), 2.38 (2H, s, CH ), 3.82–4.18 (2H, q, J ¼ 7.2 Hz, OCH ),
2
2
2
4.67 (1H, s, CH), 6.04 (2H, br., s, NH ), 7.17 (5H, s, ArH); Elemental
analysis: Found (%): C, 70.27; H, 6.84; N, 4.08. Calcd. for C H NO :
2
2
0
23
4
C, 70.38; H, 6.74; N, 4.11.
ꢀ
ꢁ1
3
l: M.p. 172–174 C, IR (KBr, ꢀ, cm ) 3310, 3260, 3020, 2980, 1730,
1
700, 1610, 1510, 1460, 840; ꢁ 0.97 (3H, s, CH ), 1.09 (3H, s, CH ), 2.18
H 3 3
(
2H, s, CH ), 2.26 (3H, s, CH ), 2.41 (2H, s, CH ), 3.60 (3H, s, OCH ),
2 3 2 3
4.68 (1H, s, CH), 6.10 (2H, br., s, NH ), 7.06–7.10 (4H, m, ArH);
2
Elemental analysis: Found (%): C, 70.33; H, 6.90; N, 4.05. Calcd. for
C H NO : C, 70.38; H, 6.74; N, 4.11.
2
0
23
4
ꢀ
ꢁ1
3m: M.p. 156–157 C, IR (KBr, ꢀ, cm ) 3300, 3250, 3020, 2980,
1
720, 1690, 1610, 1500, 1470, 830; ꢁH 0.98–1.29 (9H, m, 3 Â CH ), 2.19
3

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5
-Oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran Derivatives
125
(
2H, s, CH ), 2.26 (3H, s, CH ), 2.42 (2H, s, CH ), 3.87–4.22 (2H, q,
2
3
2
J ¼ 7.2 Hz, OCH ), 4.67 (1H, s, CH), 6.10 (2H, br., s, NH ), 7.06–7.10
2
2
(4H, m, ArH); Elemental analysis: Found (%): C, 70.84; H, 7.20; N, 3.89.
Calcd. for C H NO : C, 70.98; H, 7.04; N, 3.94.
2
1
25
4
ꢀ
ꢁ1
3
n: M.p. 167–168 C, IR (KBr, ꢀ, cm ) 3500, 3300, 3020, 2980, 1680,
1
670, 1600, 1520, 1450, 840; ꢁ 0.96 (3H, s, CH ), 1.09 (3H, s, CH ), 2.19
H
3
3
(
2H, s, CH ), 2.41 (2H, s, CH ), 3.59 (3H, s, OCH ), 4.68 (1H, s, CH),
2 2 3
6.19 (2H, br., s, NH ), 7.19 (4H, s, ArH); Elemental analysis: Found (%):
C, 63.04; H, 5.68; N, 3.79. Calcd. for C H NClO : C, 63.07; H, 5.53;
2
1
9
20
4
N, 3.87.
o: M.p. 150–152 C, IR (KBr, ꢀ, cm ) 3400, 3260, 3020, 2990, 1700,
660, 1620, 1520, 1480, 840; ꢁH 0.97–1.26 (9H, m, 3 Â CH ), 2.19 (2H, s,
ꢀ
ꢁ1
3
1
3
CH ), 2.42 (2H, s, CH ), 3.86–4.22 (2H, q, J ¼ 7.2 Hz, OCH ), 4.68 (1H,
2
2
2
s, CH), 6.20 (2H, br., s, NH ), 7.19 (4H, s, ArH); Elemental analysis:
2
Found (%): C, 63.97; H, 5.98; N, 3.69. Calcd. for C H NClO : C,
2
0
22
4
6
3.91; H, 5.86; N, 3.73.
ꢀ
ꢁ1
3
p: M.p. 198–200 C, IR (KBr, ꢀ, cm ) 3450, 3270, 3020, 2980, 1690,
1
650, 1610, 1500, 1460, 750; ꢁ 0.99 (3H, s, CH ), 1.09 (3H, s, CH ), 2.17
H
3
3
(
2H, s, CH ), 2.42 (2H, s, CH ), 3.57 (3H, s, OCH ), 5.02 (1H, s, CH),
2 2 3
6.15 (2H, br., s, NH ), 7.15–1.19 (4H, m, ArH); Elemental analysis:
Found (%): C, 63.31; H, 5.68; N, 3.85. Calcd. for C H NClO : C,
2
1
9
20
4
6
1
3.07; H, 5.53; N, 3.87.
ꢀ
ꢁ1
3
q: M.p. 181–183 C, IR (KBr, v, cm ) 3450, 3250, 3020, 2990, 1680,
660, 1610, 1510, 1470, 740; ꢁH 0.99–1.24 (9H, m, 3 Â CH ), 2.17 (2H, s,
3
CH ), 2.41 (2H, s, CH ), 3.84–4.20 (2H, q, J ¼ 7.2 Hz, OCH ), 5.02 (1H,
2
2
2
s, CH), 6.22 (2H, br., s, NH ), 7.06–7.16 (4H, m, ArH); Elemental ana-
2
lysis; Found (%): C, 63.68; H, 5.99; N, 3.63. Calcd. for C H NClO : C,
2
0
22
4
6
3.91; H, 5.86; N, 3.73.
ꢀ
ꢁ1
3
r: M.p. 156–158 C, IR (KBr, ꢀ, cm ) 3480, 3300, 1730, 1680; ꢁH
0
4
6
.99–1.29 (9H, m, 3 Â CH ), 2.20 (2H, s, CH ), 2.41 (2H, s, CH ), 3.88–
3
2
2
.24 (2H, q, J ¼ 7.2 Hz, OCH ), 4.63 (1H, s, CH), 5.87 (2H, s, OCH O),
2 2
.21 (2H, br., s, NH ), 6.68–6.84 (3H, m, ArH); Elemental analysis:
2
Found (%): C, 65.47; H, 6.11; N, 3.58. Calcd. for C H NO : C,
2
1
23
6
65.45; H, 5.97; N, 3.64.
ACKNOWLEDGMENT
We are grateful to the Foundation of the ‘‘Surpassing Project’’ of
Jiangsu Province for financial support.

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
1
26
Wang et al.
REFERENCES
1
2
. Clark, J.H. Fluoride ion as a base in organic synthesis. Chem. Rev.
980, 80(5), 429.
. Ando, T.; Yamawaki, J. Multiphase synthesis by fluoride anion. Yuki
1
Gosei Kaga Ku Kyokaishi., 1981, 39 (1), 14. Chem. Abstr., 94 (1981),
191060t.
3
4
5
. Yamawaki, J.; Kawate, T.; Ando, T.; Hanafusa, T. Potassium fluor-
ide on alumina. An efficient solid base for elimination, addition, and
condensation. Bull. Chem. Soc. Jpn. 1983, 56 (6), 1885.
. Villemin, D.; Ricard, M. Activation of weakly acidic carbon-
hydrogen bonds by adsorption on potassiumfluoride-alu mi na.
Tetrahedron Lett. 1984, 25 (10), 1059.
. Gao, Y.; Shi, D.Q.; Zhou, L.H.; Dai, G.Y. Condensation reaction of
carbonyl with acid methylene compound catalyzed by potassium
fluoride on alumina. Youji Huaxue (Ch) 1996, 16 (6), 548; Chem.
Abstr. 1997, 126, 171372x.
6
. Shi, D.Q.; Lu, Z.S.; Wang, S.H.; Tu, S.J.; Dai, G.Y. A convenient
synthesis of (3-oxo 1,3-diaryl) propylpropane dinitriles catalyzed by
KF-alumina. Synth. Commun. 1998, 28 (21), 4003.
7
. X-ray crystallography for 3c: Empirical formula C H N O ,
1
9
18
2
4
F ¼ 338.35, T ¼ 297(2) K, monoclinic, space group C2/c, a ¼
w
ꢀ
ꢀ
˚
˚
˚
2
6.753(5) A, b ¼ 9.409(2) A, c ¼ 16.036(2) A, ꢂ ¼ 90 , ꢃ ¼ 121.000(10) ,
ꢀ
˚
3
3
g ¼ 90 , V ¼ 3460.0(12) A , Z ¼ 8, Dc ¼ 1.299 Mg/m , ꢄ (MoKa) ¼
ꢁ
1
ꢀ
ꢀ
˚
0
.71073 A, ꢅ ¼ 0.092 mm
,
F(000) ¼ 1424. 1.78 <ꢆ<25.25 ,
R ¼ 0.0410, wR ¼ 0.0926. S ¼ 0.905, largest diff. peak and hole:
ꢁ
3
˚
0
.161 and ꢁ 0.159 eꢂA
.
. X-ray crystallography for 3n: Empirical formula C H ClNO ,
8
1
9
20
4
˚
F ¼ 361.81, T ¼ 297(2)K, triclinic, space group P-1, a ¼ 8.519(2) A,
w
ꢀ
ꢀ
˚
˚
b ¼ 10.346(2) A, c ¼ 11.481(2) A, ꢂ ¼ 108.16(1) , ꢃ ¼ 107.78(2) , g ¼
ꢀ
3
3
˚
9
0
1.83(2) , V ¼ 906.5(3) A , Z ¼ 2, Dc ¼ 1.326 Mg/m , ꢄ(MoKa) ¼
ꢁ
ꢀ ꢀ
˚
1
.71073 A, ꢅ ¼ 0.234 mm , F(000) ¼ 380. 1.98 <ꢆ<25.00 , R ¼
0
ꢁ
.0467, wR ¼ 0.1270. S ¼ 1.050, largest diff. peak and hole: 0.487 and
ꢁ
˚
0.423 e.A .
3
Received in Japan October 9, 2001