Montmorillonite clay catalysis. Part 14. A facile synthesis of 2-substituted and 2,2-disubstituted 1,3-benzodioxoles

Article abstract of DOI:10.1039/a805464i

A series of 2-substituted and 2,2-disubstituted 1,3-benzodioxoles have been synthesised by reaction of catechol and pyrogallol with corresponding aldehydes and ketones catalysed by montmorillonite KSF or K-10. The reactions are completed within 2.7-24 h to give satisfactory yields. Ketones give better yields than aldehydes, although highly sterically hindered ketones and diaryl ketones fail to react at all.

Full text of DOI:10.1039/a805464i

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1
Montmorillonite clay catalysis. Part 14. A facile synthesis of
-substituted and 2,2-disubstituted 1,3-benzodioxoles
2
Tong-Shuang Li,* Li-Jun Li, Bo Lu and Feng Yang
Department of Chemistry, Hebei University, Baoding 071002, Hebei Province, China
Received (in Cambridge) 14th July 1998, Accepted 9th September 1998
A series of 2-substituted and 2,2-disubstituted 1,3-benzodioxoles have been synthesised by reaction of catechol
and pyrogallol with corresponding aldehydes and ketones catalysed by montmorillonite KSF or K-10. The reactions
are completed within 2.7–24 h to give satisfactory yields. Ketones give better yields than aldehydes, although highly
sterically hindered ketones and diaryl ketones fail to react at all.
Introduction
from catechol 1 and ketones 2 in benzene or toluene with azeo-
tropic distillation (Scheme 1). The reactions were completed
within 2.7–24 h to give satisfactory yields in most cases. The
crude products 3 could be easily obtained by filtration of the
catalyst followed by evaporation of the solvent. The present
procedure gives reproducibly high yields but needs much shorter
The 1,3-benzodioxole ring system is an integral part of many
2
–5
natural products, such as sesamol and piperine. Recently, 1,3-
benzodioxoles with various substituents at the 2-position have
received more and more attention. 1,3-Benzodioxole derivatives
6
are inhibitors of mono-oxygenase enzymes, and have been
6
reaction times than with toluene-p-sulfonic acid catalyst. For
example, with toluene-p-sulfonic acid catalyst and heating for
7
–10
widely used in pesticides or pesticide intermediates,
herbi-
11
12–13
14
15,16
cides, antioxidants,
antimicrobials and medicines.
7
2, 24 and 120 h, 3b, 3l and 3s were obtained in 83, 90 and 76%
The synthesis of 1,3-benzodioxole derivatives is also useful
for the protection of catechols
organic synthesis and thus their synthesis assumes great
importance in biological chemistry and organic synthesis. The
acetal ring is stable to HNO , Pb(OAc) and BuLi
6
yield respectively. However, our procedure with KSF catalyst
1
7–20
21
or carbonyl compounds in
and heating for 7, 2.7 and 24 h gave 3b, 3l and 3s in 94, 93 and
7
3% respectively.
6
2
18,22
for
3
4
example while the cleavage of 1,3-benzodioxoles has been
23
reported by several reagents, such as NaI–AcCl, boron tri-
24
25
bromide, and NaN(SiMe ) or Li(i-Pr).
3
2
1
,3-Benzodioxoles can be synthesised from catechols and
12a,26–27
gem-dihalides.
However, there are few gem-dihalides
commercially available and they are usually expensive. Trans-
acetalisation of ketone dimethyl acetals with catechol has also
Scheme 1
24
been developed in the presence of boron tribromide. Another
obvious synthetic route is the condensation of catechols with
carbonyl compounds with acid catalysts such as phosphorus
The structure of ketones 2 have a strong influence on the
reaction. As shown in Table 1, acyclic aliphatic ketones (entries
a–2f) gave good to excellent yields of the corresponding 2,3-
disubstituted 1,3-benzodioxoles 3a–2f, while β-keto ester 2h
gave a very poor yield (9%) of the corresponding product 3h,
2
28,29
pentoxide.
In this procedure, a large amount of phosphorus
pentoxide is used as both acid catalyst and dehydrating agent
and the work-up is tedious and inconvenient. Toluene-p-
(
this may be due to facile tautomerisation to the enol form, thus
6,12c,30,31
sulfonic acid is widely employed in this reaction,
and if
reducing the electrophilicity of the carbonyl group). The degree
of steric hindrance in ketones 2 had a large effect on the
reaction. Dibenzyl ketone 2i provided only 30% yield of
,2-dibenzyl-1,3-benzodioxole 3i, whereas 2,4-dimethylpentan-
-one 2j, 4,4-dimethylcholest-5-en-3-one 2p, benzophenone
w and anthrone 2x could not provide the corresponding
,3-benzodioxoles. α,β-Unsaturated ketones show very little
tendency to undergo this reaction, for example, 4-phenylbut-3-
en-2-one 2u gave 3u only in 9% yield with KSF and 18% yield
with K-10, while others such as cholest-4-en-3-one 2q and
cholest-4-ene-3,6-dione 2r failed to react at all.
Five and six-membered ring ketones gave excellent yields of
products. For example, cyclohexanone 2l gave 93% of spiro-
the water formed is removed by azeotropic distillation, only
catalytic amounts of toluene-p-sulfonic acid are needed. How-
ever, the disadvantage of this method is the long reaction time
2
3
2
1
(
8–120 h, ref. 6) and unsatisfactory yield. In recent years, other
32
catalysts, such as trimethylsilyl chloride (TMSCl) and phos-
phorus trichloride have also been used to catalyse the conden-
sation of catechol with carbonyl compounds.
3
3
Solid acids have been recently used as efficient catalysts for a
34,35
variety of organic reactions.
We have developed an efficient
and convenient preparation of acetals catalysed by montmoril-
36
lonite clay. This prompted us to use montmorillonite clays to
catalyse the synthesis of 2-substituted and 2,2-disubstituted 1,3-
benzodioxoles from catechol and the corresponding aldehydes
and ketones. We report here a facile synthesis of substituted
[
1,3-benzodioxole-2,1Ј-cyclohexane] 3l, and 5α-cholestan-3-
one 2m provided 3m in 99% yield. However, cyclooctanone 2o
provided only 24% of spiro[1,3-benzodioxole-2,1Ј-cyclooctane]
o, and only 56% with K-10; this might relate to its ring tension.
Hexane-2,5-dione 2g, when the molar ratio of 2g:1 was 3.7,
1
,3-benzodioxoles from catechol and pyrogallol with carbonyl
compounds catalysed by montmorillonite KSF or K-10.
3
gave 2-methyl-2-(3-oxobutyl)-1,3-benzodioxole 3g (57%) as the
major product with only 2.3% of 2,2Ј-dimethyl-2,2Ј-ethylene-
bis(1,3-benzodioxole) 3ga (Scheme 2). This illustrates that 1,4-
dicarbonyl compounds could be selectively protected as mono-
Results and discussion
As shown in Table 1, in the presence of montmorillonite KSF,
a series of 2,2-disubstituted 1,3-benzodioxoles were prepared
J. Chem. Soc., Perkin Trans. 1, 1998, 3561–3564
3561

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Table 1 Preparation of 2,2-disubstituted 1,3-benzodioxoles catalysed by KSF
Bp(Torr) or Mp/ЊC
a
b
Ketone 2
Catalyst/solvent/t (h)
Ratio
Product
Yield (%)
Found
Reported
c
2
2
2
a Acetone
b Butanone
c Hexan-2-one
KSF/benzene/10
KSF/benzene/7
KSF/toluene/12
K-10/toluene/6
KSF/benzene/7
KSF/toluene/12
KSF/toluene/9
KSF/toluene/11
1:10
1:7.3
2:1
2:1
1:2.8
1:2
3a
3b
3c
3c
3d
3e
3f
70
94
80
91
83
80–82(30)
95–97(30)
125–127(30)
50–51(2.5)
64–65(2.5)
84–86(1.5)
c
d
c
d
c
2
2
2
2
d Methyl isobutyl ketone
126–129(32)
146–147(35)
156–159(32)
—
120–121
—
96–97(5)
c
e Heptan-2-one
97
114–116(4.5)
c
f Octan-2-one
g Hexane-2,5-dione
1:2
1:3.7
92e
100–101(1)
3g
57
f
3
ga
2.3
9
30
no reaction
71
93
99
64
c
2
2
2
2
2
2
2
2
h Ethyl acetoacetate
i Dibenzyl ketone
j 2,4-Dimethylpentan-3-one
k Cyclopentanone
l Cyclohexanone
m 5α-Cholestan-3-one
n Cycloheptanone
o Cyclooctanone
KSF/toluene/11.5
KSF/toluene/12
KSF/toluene/9
KSF/toluene/3
KSF/benzene/2.7
KSF/benzene/3
KSF/toluene/12
KSF/toluene/12
K-10/toluene/7
KSF/toluene/7
KSF/toluene/8
KSF/toluene/6
KSF/toluene/24
KSF/toluene/15
K-10/toluene/6
KSF/toluene/12
K-10/toluene/10
KSF/toluene/13
KSF/xylenes/10
KSF/xylenes/10
1:2
1:2.1
1:2
3h
3i
130–132(5)
—
c
1:1
3k
3l
3m
3n
3o
3o
147–150(35)
49–49.5
155–156
57–59
68–70
68–70
114–115(4.5)
c
1:3.3
2.9:1
1:2
1:2
1:2
2:1
2:1
2:1
1:2.1
1:2
1:2
1:2
1:2
1:2.5
2:1
45–48
d
—
55–57
c
24
56
—
2
2
2
2
2
p 4,4-Dimethylcholest-5-en-3-one
q Cholest-4-en-3-one
r Cholest-4-ene-3,6-dione
s Acetophenone
t p-Methoxyacetophenone
no reaction
no reaction
no reaction
73
67
94
9
18
3s
3t
3t
3u
3u
3v
67–68
67–68
—
—
49–50
—
—
2
u 4-Phenylbut-3-en-2-one
2v 2-Chloroacetophenone
2w Benzophenone
2x Anthrone
64
—
no reaction
no reaction
2:1
a
b
c
d
e
Catechol:ketone (mol:mol). Isolated yield based on catechol. Ref. 6. Isolated yield based on ketone. The product is 2-methyl-2-(3-oxobutyl)-
f
1
,3-benzodioxole 3g. The product is 2,2Ј-dimethyl-2,2Ј-ethylenebis(1,3-benzodioxole) 3ga.
Table 2 Formation of 2-substituted 1,3-benzodioxoles catalysed by montmorillonites
Bp(Torr) or Mp/ЊC
a
b
Aldehyde 4
Catalyst/solvent/t (h)
Ratio
Product Yield (%)
Found
Reported
c
d
n-Butyraldehyde 4a
KSF/toluene/12
K-10/benzene/7
KSF/toluene/12
KSF/toluene/9
KSF/toluene/8.5
KSF/benzene/15
K-10/benzene/6
KSF/benzene/11
2.4:1
1:4
2:1
5a
5a
5b
5c
5d
5e
5e
5f
44
110–112(30)
110–112(30)
—
60–61
50–51
57–58
57–58
88–89
75–80(3.5)d
62c
75–80(3.5)
n-Heptaldehyde 4b
Cinnamaldehyde 4c
Benzaldehyde 4d
p-Tolualdehyde 4e
28
41
65
67
1:2
—
54–56
d
1:3.1
1:2.7
1:2.7
2.9:1
d
148–150(2.5)
70c
—
—
3
-Nitrobenzaldehyde 4f
38
a
b
c
d
Catechol:aldehyde (mol:mol). Isolated yield based on catechol. Isolated yield based on aldehyde. Ref. 6.
benzodioxoles in the presence of KSF by using on excess of
ketone.
K-10 worked better than KSF for acetalisation of ketones
in terms of reaction time and yield (Table 1, entries 2c, 2o,
We have also investigated the condensation of aldehydes 4
with catechol 1 under catalysis of KSF or K-10 (Scheme 3). The
results are shown in Table 2. In contrast with ketone com-
pounds, aldehydes gave an intractable mixture of complex
by-products in this reaction and the acetals were obtained in
only moderate yields (28–70%). This might be due to the alde-
hyde group being too reactive in the competing aldol reaction to
give, for aliphatic aldehydes, cyclic trimerisation, oxidation and
polymerisation as side reactions.
2
t and 2u). This may be due to the structure of K-10 which
retains more acidic sites after treatment with mild acid, hence
giving higher activity than the more strongly acid activated
KSF.
Pyrogallol 6, shows higher reactivity than catechol 1 for this
reaction. When 2e and 2l were treated with 6 under montmoril-
lonite KSF catalysis, 2-methyl-2-pentyl-4-hydroxy-1,3-benzo-
dioxole 7e and 4-hydroxyspiro[1,3-benzodioxole-2,1Ј-cyclo-
Scheme 2
Scheme 3
3
562
J. Chem. Soc., Perkin Trans. 1, 1998, 3561–3564

View Article Online
a bed of silica gel, and washed with diethyl ether. After evapor-
ation of the solvent, the crude products were chromatographed
on silica gel (200–300 mesh), eluted with petroleum ether (bp
6
0–90 ЊC) and diethyl ether.
2
-Methyl-2-hexyl-1,3-benzodioxole 3f. δ (80 MHz) 0.87 (3H,
H
Scheme 4
t, J 5.6, 6Ј-H), 1.20–1.50 (8H, m, 2Ј,3Ј,4Ј,5Ј-CH ), 1.60 (3H, s,
2
2
2
8
-CH ), 1.88 (2H, t, J 3.1, 1Ј-CH ) and 6.74 (4H, s, Ar-H); m/z
3 2
ϩ
Table 3 Synthesis of 2,2-disubstituted 4-hydroxy-1,3-benzodioxoles
catalysed by KSF
20 (M , 19%), 205 (7), 163 (2), 135 (100), 121 (2), 110 (13) and
1 (2).
Pyrogallol:
substrate
Product
(Yield %)
1
2
2-Methyl-2-(3-oxobutyl)-1,3-benzodioxole 3g. Colorless oil;
Entry
R
R
Solvent
t/h
Ϫ1
νmax/cm 3050, 2984, 1714, 1487, 1380, 1240, 1128, 950, 844
and 741; δ (300 MHz) 1.62 (3H, s, 2-Me), 2.12 (3H, s, 4Ј-H ),
2
2
e
l
Me
-(CH ) -
Pentyl
5
Benzene 1:2
Benzene 1:2
12
12
7e (99)
7l (99)
H
3
2
2.26 (2H, t, J 7.8, 1Ј-H), 2.61 (2H, t, J 7.8, 2Ј-H) and 6.73–6.81
ϩ
(
(
4H, m, 4,5,6,7-H ); m/z 206 (M , 30%), 191 (5), 163 (14), 145
4
4), 135 (100), 121 (6), 110 (15), 97 (22) and 81 (4).
hexane] 7l were obtained in quantitative yield (99%) (Scheme 4,
Table 3).
The montmorillonite catalysts can be reused several times
without any significant decrease in activity after being washed
with ethanol and activated at 120 ЊC.
2
,2Ј-Dimethyl-2,2Ј-ethylenebis(1,3-benzodioxole) 3ga. Mp
Ϫ1
1
2
20–121 ЊC, colorless needles from acetone; νmax/cm 3063,
929, 1485, 1379, 1316, 1238, 1121, 1038, 870 and 741; δ (300
H
MHz) 1.61 (6H, s, 2,2Ј-di-Me), 2.13 (4H, s, 2 × CH ) and 6.71–
2
ϩ
6
.79 (8H, m, Ar-H); m/z 298 (M , 22%), 283 (1), 189 (4), 174
Conclusions
(4), 147 (2), 135 (100) and 110 (3).
In summary, we have developed an alternative method for the
preparation of a variety of 2-substituted and 2,2-disubstituted
2
-Methyl-2-ethoxycarbonylmethyl-1,3-benzodioxole 3h. Col-
orless oil; δ (80 MHz) 1.20 (3H, t, J 7.1, -OCH CH ), 1.99 (3H,
s, 2-Me), 2.94 (2H, s, 1Ј-CH ), 4.14 (2H, q, J 7.1, -OCH CH )
and 6.78 (4H, s, Ar-H ); m/z 222 (M , 19%), 176 (6), 149 (69),
35 (100), 121 (7) and 110 (22).
H
2
3
1
,3-benzodioxoles catalysed by montmorillonite KSF and
2
2
3
K-10. Aldehydes give moderate yields while ketones give good
to excellent yields. Dicarbonyl compounds can selectively pro-
vide mono-benzodioxole compounds by using an excess of the
ketone. Highly sterically hindered ketones, diaryl ketones and
α,β-unsaturated ketones fail to react in this reaction. Pyrogallol
shows a higher reactivity than catechol. Compared with the
ϩ
4
1
Ϫ1
2
,2-Dibenzyl-1,3-benzodioxole 3i. Colorless oil; νmax/cm
3
(
063, 3031, 2923, 1602, 1485, 1239, 1099, 847, 737 and 699; δH
300 MHz) 3.17 (4H, s, 1Ј,1Љ-di-CH ), 6.66 (4H, s, 4,5,6,7-H )
2 4
ϩ
and 7.18–7.295 (10H, m, Ph-H ); m/z 302 (M , 19%), 245 (2),
6
reported method, our procedure needs much shorter reaction
10
times and gives higher yields for most ketones. The present
method has the additional advantages of mild conditions, easy
set-up and work-up and non-corrosive, inexpensive, reusable
and environmentally friendly catalysts.
2
11 (100), 157 (2), 135 (9) and 115 (4).
Spiro[1,3-benzodioxole-2,1Ј-cyclohexane] 3l. Mp 49–49.5 ЊC,
colorless platelets from diethyl ether (lit., 45–48 ЊC).
6
Experimental
Boiling and melting points are uncorrected. Infrared (IR)
spectra were recorded on Perkin-Elmer 983G, BTO-RAD and
FTS-40 spectrometers (film). H NMR spectra were measured
on Bruker AC-80, Varian VXR-300 and INOVA-500 spectro-
meters, using CDCl as solvent and tetramethylsilane (TMS) as
internal reference. Mass spectra were obtained on a VG-7070E
spectrometer, EI, 70 eV.
Montmorillonite KSF and K-10 were purchased from
Aldrich and activated at 120 ЊC for 3 h prior to use. The ratio
of montmorillonite KSF (or K-10):catechol was 1:1 (w/w).
Carbonyl compounds (2 and 4) and catechol (1) and pyrogallol
Spiro[1,3-benzodioxole-2,3Ј-cholestane] 3m. Mp 155–156 ЊC,
colorless needles from petroleum ether–ethyl acetate; νmax/cm
Ϫ1
3
055, 2925, 2860, 1485, 1360, 1240, 1172, 1050 and 730; δ (80
H
MHz) 0.67 (3H, s, 18Ј-H ), 0.87 (3H, s, 19Ј-H ), 0.87 (6H, d,
1
3
3
J 5.9, 26Ј, 27Ј-H ), 0.92 (3H, d, J 6.0, 21-H) and 6.74 (4H, s,
6
ϩ
Ar-H ); m/z 478 (M , 100%), 462 (2), 369 (6), 215 (6), 162 (24),
4
3
1
47 (91), 134 (24), 121 (15) and 107 (28).
Spiro[1,3-benzodioxole-2,1Ј-cycloheptane] 3n. Colorless oil;
δH (80 MHz) 0.88–2.20 (12H, m, 6 × CH ) and 6.73 (4H, s,
2
ϩ
Ar-H ); m/z 204 (M , 46%), 189 (5), 175 (7), 161 (28), 147 (100),
4
1
34 (15), 125 (57), 121 (14), 120 (22) and 110 (35).
(
6) are commercially available. Aldehydes 4 were freshly
Spiro[1,3-benzodioxole-2,1Ј-cyclooctane] 3o. Mp 68–70 ЊC,
distilled or recrystallised prior to use. All reactions were carried
out under anhydrous conditions with removal of water by azeo-
tropic distillation. For the cases of low-boiling point ketones,
such as acetone or butanone, molecular sieves (3 Å) were
employed for removal of water.
colorless needles from diethyl ether; δH (80 MHz) 0.88–2.16
ϩ
(
2
(
14H, m, 7 × CH ) and 6.73 (4H, s, Ar-H ); m/z 218 (M , 63%),
2
4
03 (2), 189 (14), 175 (14), 161 (11), 147 (100), 134 (56), 121
11), 110 (56) and 109 (65).
2
-Methyl-2-(p-methoxyphenyl)-1,3-benzodioxole 3t. Mp 67–
General procedure
Ϫ1
6
8 ЊC, colorless platelets from acetone; νmax/cm 2992, 2938,
The montmorillonite KSF (or K-10) catalyst (110 mg) was
added to a solution of catechol 1 (110 mg, 1.00 mmol) or
pyrogallol 6 (126 mg, 1.00 mmol) and ketone 2 (or aldehyde 4)
in benzene or toluene as indicated in Tables 1–3. The mixture
was stirred at refluxing temperature for the length of time as
shown in Tables 1–3 and the water was separated from the reac-
tion system by azeotropic distillation with a water separator.
The progress of the reaction was monitored by TLC (GF254).
After cooling, the catalyst was removed by filtration through
1612, 1485, 1380, 1238, 1177, 1130, 1085, 954, 836 and 743; δH
(300 MHz) 1.97 (3H, s, 2-Me), 3.80 (3H, s, 4Ј-OMe), 6.79 (4H, s,
4,5,6,7-H ), 6.89 (2H, d, J 8.6, 3Ј,5Ј-H ) and 7.52 (2H, d,
4
2
ϩ
J 8.6, 2Ј, 6Ј-H ); m/z 242 (M , 15%), 227 (17), 184 (1), 150 (1),
2
133 (100) and 118 (3).
2-Methyl-2-(2-phenylvinyl)-1,3-benzodioxole 3u. Colorless oil;
Ϫ1
νmax/cm 3065, 1660, 1603, 1485, 1364, 1237, 1195, 1100, 970,
823, 745 and 692; δH (300 MHz) 1.86 (3H, s, 2-Me), 6.33 (1H,
J. Chem. Soc., Perkin Trans. 1, 1998, 3561–3564
3563

View Article Online
d, J 15.9, 1Ј-H), 6.80 (4H, s, 4,5,6,7-H ), 6.87 (1H, d, J 15.9,
3 F. Dallacker, K. Reperich and M. Mayer, Chem.-Ztg., 1991, 115,
4
ϩ
203.
2
Ј-H) and 7.22–7.40 (5H, m, Ph-H ); m/z 238 (M , 100%), 222
5
4
E. E. Stashenko, H. S. Villa and M. Y. Combariza, Int. Symp.
Chromatogr., 35th Anniv. Res. Group Liq. Chromatogr. Jpn., 1995,
(
55), 128 (9) and 63 (9).
4
75 (Chem. Abstr., 1995, 123, 321673a).
2
-Chloromethyl-2-phenyl-1,3-benzodioxole 3v. Mp 49–50 ЊC,
5
E. Haslam and R. D. Haworth, J. Chem. Soc., 1955, 827.
6 E. R. Cole, G. Crank and H. T. H. Minh, Aust. J. Chem., 1980, 33,
675.
M. Anderson, A. G. Brinnand and R. E. Woodall, Eur. Pat.
469 686/1990 (Chem. Abstr., 1992, 116, 235642p).
A. Tozzi, Eur. Pat. 512 379/1991 (Chem. Abstr., 1993, 118, 118974d).
M. Anderson, A. G. Brinnand and R. E. Woodall, Eur. Pat. 512 379/
Ϫ1
colorless needles from chloroform; νmax/cm 3065, 2960, 1485,
236, 737 and 698; δ (300 MHz) 4.00 (2H, s, 2-CH Cl), 6.81–
.89 (4H, m, 4,5,6,7-H ) and 7.40–7.645 (5H, m, Ph-H ); m/z
46 (M , 13%), 210 (1), 197 (100), 181 (1), 169 (1), 137 (4) and
05 (19).
1
6
2
1
H
2
7
4
5
ϩ
8
9
1
991 (Chem. Abstr., 1993, 119, 95537t).
2
-(2Ј-Phenylvinyl)-1,3-benzodioxole 5c. Mp 60–61 ЊC, color-
10 C. Devakumar and V. S. Saxina, Shashpa, 1994, 1, 47.
11 F. Arndt and H. Franke, Ger. Pat. 2 624 822/1976 (Chem. Abstr.,
Ϫ1
less platelets from diethyl ether; νmax/cm 3066, 3030, 2930,
658, 1482, 1356, 1234, 1145, 917 and 734; δ (300 MHz) 6.37
1H, dd, J 16.2, 6.6, 1Ј-H), 6.60 (1H, d, J 6.6, 2-H), 6.83 (4H, s,
,5,6,7-H ), 6.92 (1H, d, J 16.2, 2Ј-H) and 7.31–7.47 (5H, m,
Ph-H ); m/z 224 (M , 100%), 197 (2), 181 (1), 165 (2), 147 (13),
31 (8), 121 (12), 115 (100) and 103 (11).
1
978, 88, 105307a).
1
(
4
H
1
2 (a) T. Isobe, H. Seino and S. Watanabe, Yukagaku, 1985, 34, 349; (b)
T. Isobe and H. Seino, Yukagaku, 1989, 38, 161; (c) T. Isobe and H.
Seino, Yukagaku, 1990, 39, 931; (d) T. Isobe and H. Seino,
Yukagaku, 1994, 43, 1017.
4
ϩ
5
1
13 T. H. Minh, E. R. Cole and G. Grank, Australian Pat. 533 866/1980
Chem. Abstr., 1984, 101, 191878d).
(
1
4 T. Isobe, Bokin Bobai, 1985, 13, 485; T. Isobe, H. Seino and
S. Watanabe, Bokin Bobai, 1985, 13, 485; T. Isobe and H. Seino,
Bokin Bobai, 1988, 16, 453.
5 H. Akimoto, K. Ootsu and F. Ito, Jap. Pat. 05 09 170/1990 (Chem.
Abstr., 1993, 119, 8798n).
2
-Phenyl-1,3-benzodioxole 5d. Mp 50–51 ЊC, colorless needles
6
from diethyl ether (lit., 54–56 ЊC).
1
2
-(p-Methylphenyl)-1,3-benzodioxole 5e. Mp 57–58 ЊC, color-
6
less needles from diethyl ether (lit., bp 148–150 ЊC/2.5 mm Hg).
16 Y. Kumagai, J. M. Fukuto and A. K. Cho, Curr. Med. Chem., 1994,
, 254.
1
1
7 T. W. Greene and P. G. M. Wuts, in Protective Groups in Organic
Synthesis, Wiley, New York, 1991, p. 170.
2
-(m-Nitrophenyl)-1,3-benzodioxole 5f. Mp 88–89 ЊC, light
Ϫ1
yellow needles from diethyl ether; νmax/cm 3060, 2981, 1536,
484, 1351, 1234, 1095, 948, 843 and 741; δH (300 MHz) 6.90
4H, s, 4,5,6,7-H), 7.045 (1H, s, 2-H), 7.64 (1H, t, J 7.7, 5Ј-H),
.93 (1H, d, J 7.7, 6Ј-H), 8.31 (1H, ddd, J 7.7, 2.4, 1.1, 4Ј-H)
and 8.46 (1H, t, J 2.1, 2Ј-H); m/z 243 (M , 61%), 224 (5), 197
11), 168 (1), 150 (5), 139 (4), 121 (100), 115 (14) and 104 (6).
1
1
2
8 G. Majetich and S. Liu, Synth. Commun., 1993, 23, 2331.
9 E. J. Corey and S. D. Hurt, Tetrahedron Lett., 1977, 45, 3923.
0 K. Ogura and G. Tsuchihashi, Tetrahedron Lett., 1971, 34,
3151.
21 U. Eder, G. Sauer, G. Haffer, J. Ruppert, R. Wiechert, A. Fuerst and
W. Meier, Helv. Chim. Acta, 1976, 59, 999.
2 S. Bengtsson and T. Hogberg, J. Org. Chem., 1989, 54, 4549.
3 L. Corda, A. M. Fadda, A. Maccioni, A. M. Maccioni and
G. Podda, J. Heterocycl. Chem., 1988, 25, 311.
24 E. Napolitano, R. Fiaschi and E. Mastrorilli, Synthesis, 1986,
122.
1
(
7
ϩ
(
2
2
2
-Methyl-2-pentyl-4-hydroxy-1,3-benzodioxole 7e. Light yel-
Ϫ1
low oil; νmax/cm 3262, 3060, 3030, 2954, 2869, 1643, 1504,
478, 1389, 1315, 1255, 1058, 1026, 759 and 710; δ (500 MHz)
.88 (3H, t, J 7.3, 5Ј-H ), 1.29–1.32 (4H, m, 3Ј,4Ј-H ), 1.47–1.50
2H, m, 2Ј-H ), 1.63 (3H, s, 2-Me), 1.91–1.94 (2H, m, 1Ј-H ),
.79 (1H, br s, 4-OH), 6.39 (1H, dd, J 7.8, 1.0, 5-H), 6.44 (1H,
ϩ
dd, J 7.8, 1.0, 7-H) and 6.66 (1H, t, J 7.8, 6-H); m/z 222 (M ,
00%), 207 (17), 179 (15), 151 (100), 137 (9), 126 (100) and 108
1
0
(
H
25 J. R. Hwu, F. F. Wong, J. J. Huang and S. C. Tsay, J. Org. Chem.,
3
4
1
997, 62, 4097.
2
2
2
6 Y. Y. Zhao, H. B. Jia, X. F. Li, M. F. Liu and Y. S. Shen, Jilin Daxue
Ziran Kexue Xuebao, 1983, 92.
7 B. T. Kim, Y. K. Min, N. K. Park, K. Y. Cho and I. H. Jeong,
Heterocycles, 1995, 41, 641.
28 H. Iwagami, M. Yatagai, M. Nalazawa, H. Orita, Y. Honda,
T. Ohnuki and T. Yukawa, Bull. Chem. Soc. Jpn., 1991, 64, 175.
9 G. Tsatsas and M. A. Papadaki-Valiraki, Chem. Chron., 1972, 1,
162.
0 T. F. Buckley III and H. Rapoport, J. Am. Chem. Soc., 1980, 102,
3
31 I. M. Takais, P. M. Hadjimihalakis, G. G. Tsantali and H. Pilini,
J. Heterocycl. Chem., 1992, 29, 123.
32 Y. Nishida, M. Abe, H. Ohrui and H. Meguro, Tetrahedron:
Asymmetry, 1993, 4, 1431.
3 R. R. Bikbulatov, T. V. Timofeeva, L. N. Zorina, O. G. Safiev and
V. V. Zorin, Zh. Obshch. Khim., 1996, 66, 1854.
4 T. P. Kumar, K. R. Reddy and R. S. Reddy, J. Chem. Res. (S), 1994,
394.
4
2
1
(
5).
2
4
-Hydroxyspiro[1,3-benzodioxole-2,1Ј-cyclohexane] 7l. Mp
37
8
1
4–85 ЊC, light yellow blocks from diethyl ether (lit., mp 115–
16 ЊC); δH (500 MHz) 1.48–1.51 (2H, m, 3Ј-H ), 1.73 (4H,
3
2
056.
quintet, J 6.0, 2Ј, 4Ј-H ), 1.92 (4H, t, J 6.0, 1Ј, 5Ј-H ), 4.75 (1H,
br s, 4-OH), 6.40 (1H, dd, J 7.5, 1.0, 5-H), 6.44 (1H, dd, J 8.0,
.0, 7-H) and 6.66 (1H, t, J 7.8, 6-H).
4
2
1
3
Acknowledgements
3
This project was supported by NSFC, Natural Science Found-
ation of Hebei Province (297065) and the Science and Technol-
ogy Commission of Hebei Province. B. L. would like to thank
the Department of Chemistry, Cangzhou normal College, for
leave of absence.
35 T. S. Li and T. S. Jin, Youji Huaxue, 1996, 16, 385.
3
6 (a) T. S. Li, S. H. Li, J. T. Li and H. Z. Li, J. Chem. Res. (S), 1997, 26;
b) Z. H. Zhang, T. S. Li, T. S. Jin and J. T. Li, J. Chem. Res. (S),
998, paper 8/03046D.
(
1
3
7 G. Podda, A. M. Fadda, A. M. Maccioni, B. Pelli and P. Traldi,
J. Heterocycl. Chem., 1986, 23, 311.
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