The efficient synthesis of new sydnones containing fused ring

Article abstract of DOI:10.1081/SCC-120005430

Sydnones 2a-f were prepared by the reaction of the corresponding sydnones 1a-f with acetone in the presence of concentrate sulfuric acid or BF₃-Et₂O.

Full text of DOI:10.1081/SCC-120005430

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THE EFFICIENT SYNTHESIS OF NEW SYDNONES
CONTAINING FUSED RING
Zhan Bin Zhang a , Yong Ren Wu a & Cheng Lie Yin a
a Department of Chemistry, Beijing Normal University, Beijing, 100875, P.R. China
Version of record first published: 18 Oct 2011.
To cite this article: Zhan Bin Zhang , Yong Ren Wu & Cheng Lie Yin (2002): THE EFFICIENT SYNTHESIS OF NEW SYDNONES
CONTAINING FUSED RING, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic
Chemistry, 32:14, 2203-2207
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 14, pp. 2203–2207, 2002
THE EFFICIENT SYNTHESIS OF NEW
SYDNONES CONTAINING FUSED RING
*
Zhan Bin Zhang, Yong Ren Wu, and Cheng Lie Yin
Department of Chemistry, Beijing Normal University,
Beijing, 100875, P.R. China
ABSTRACT
Sydnones 2a–f were prepared by the reaction of the corre-
sponding sydnones 1a–f with acetone in the presence of
concentrate sulfuric acid or BF3–Et2O.
Key Words: Sydnone; Intramolecular Friedel–Crafts reac-
tion; Acetone
Since their first syntheses sydnones have received much attention and
have been reviewed by several authors.[l,2] Many of substituted sydnones
and their derivatives have proved to possess valuable biological activity
and their pharmacological activities in some instance were found high for
practical purposes. So many sydnone compounds are known, but deriva-
tives containing fused sydnone rings are less common[3,4] and their synthesis
are difficult.[5,6] In an effort to prepare new fused ring sydnones we turned
our attention to the preparation of 3-(3-hydroxylpropyl)sydnones and their
intramolecular electrophilic aromatic substitution.
*Corresponding author. E-mail: zzbbnu@sina.com
2203
DOI: 10.1081/SCC-120005430
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

2204
ZHANG, WU, AND YIN
In our previous work, we reported that 3-(aroylethyl)sydnones[7] were
reduced by sodium borohydride to produce 3-(3-aryl-3-hydroxylpropyl)syd-
nones.[8] We report here the preparation and identification of sydnones con-
taining a seven-membered fused ring. Sydnones undergo a variety of reactions
including electrophilic aromatic substitution (when unsubstituted at the
4-position), 1,3-dipolar cycloaddition (e.g. with alkynes) and acid induced
cleavage, etc. As 3-(3-aryl-3-hydroxylpropyl)sydnones have a hydroxyl group
in their side chains, they would undergo intramolecular Friedel–Crafts reac-
tion. However the reaction did not take place under different conditions.
In the presence of H2SO4 or BF3–Et2O, 3-3-(aryl-3-hydroxylpropyl)-
sydnones reacted with acetone to give sydnones containing a seven-
membered fused ring. These compounds were identified on the basis of
1
UV, IR, and HNMRspectral data presented in Tables 1 and 2. The UV
spectral data demonstrated that the sydnone ring was not decomposed. In
the IRspectrum the very strong ring carbonyl stretching band falls in the
range of 1750–1710 cmÀ1, but the C–H of sydnone ring and the O–H
stretching bands were absent. The proton NMRspectra of these compounds
show the presence of two methyl groups as two singlets, but no character-
istic singlet of the 4-proton on the sydnone ring at 6.5 ppm.
In summary, the procedure reported here represents an efficient
synthetic entry to the fused-ring sydnones.

NEW SYDNONES CONTAINING FUSED RING
2205
Table 1. Physical, Analytical, UV, and IRData of Compounds 2a–g
Elemental
Analysis
Yield
(%)
M.P.
(ꢀC)
(calc.%)
H
UV ꢀ
(nm, " Â 10À3
IR
(cmÀ1
Compound
C
N
)
)
2a
85.7
80
176–178
175–176
161–162
169–170
218–220
142–143
64.82, 6.15, 11.08
(64.60, 6.20, 10.76)
66.06, 6.62, 10.49
(65.68, 6.61, 10.21)
57.24, 5.26, 9.78
(57.05, 5.13, 9.50)
50.02, 4.43, 8.41
(49.58, 4.46, 8.26)
55.33, 5.03, 13.48
(55.08, 4.95, 13.76)
69.38, 5.94, 9.01
(69.66, 5.85, 9.03)
296 (6.95)
207 (10.8)
298 (2.98)
207 (4.86)
299 (17.8)
220 (33.4)
295 (6.59)
220 (12.5)
274 (3.29)
208 (2.28)
286 (5.60)
224 (25.9)
1745
2b
2c
2d
2e
2f
1750
1740
1720
1720
1740
82
79
60.3
67.2
Table 2. 1H NMRSpectral Data of Compounds 2a–g
Compound
1H NMR(ppm)
2a
7.37 (m, 5H, Ar-H), 4.85 (dd, 1H, CH-O), 4.75, 4.46 (2ddd, 2H,
CH2-Syd), 2.58, 2.30 (2m, 2H, CH2), 1.69, 1.65 (2s, 6H, 2 Â CH3)
7.25, 7.19 (2d, 4H, Ar-H), 4.82 (dd, 1H, CH-O), 4.75, 4.46
(2ddd, 2H, CH2-Syd), 2.54, 2.35 (2m, 2H, CH2),
2.357 (s, 3H, CH3-Ar), 1.69, 1.63 (2s, 6H, 2 Â CH3)
7.35, 7.30 (2d, 4H, Ar-H), 4.83 (dd, 1H, CH-O), 4.73, 4.47
(2ddd, 2H, CH2-Syd), 2.56, 2.30 (2m, 2H, CH2), 1.68,
1.65 (2s, 6H, 2 Â CH3)
7.50, 7.25 (2d, 4H, Ar-H), 4.81 (dd, 1H, CH-O), 4.73, 4.47
(2ddd, 2H, CH2-Syd), 2.56, 2.24 (2m, 2H, CH2), 1.67, 1.64
(2s, 6H, 2 Â CH3)
8.25, 7.56 (2d, 4H, Ar-H), 4.97 (dd, 1H, CH-O), 4.75, 4.51
(2ddd, 2H, CH2-Syd), 2.66, 2.23 (2m, 2H, CH2), 1.687
(s, 6H, 2 Â CH3)
7.85, 7.47 (2m, 7H, Ar-H), 5.01 (dd, 1H, CH-O), 4.79, 4.49
(2ddd,2H,CH2-Syd), 2.65, 2.37 (2m, 2H, CH2), 1.73, 1.69
(2s, 6H, 2 Â CH3)
2b
2c
2d
2e
2f

2206
ZHANG, WU, AND YIN
EXPERIMENTAL
1H NMRspectra were obtained on an Advance 500 Bruker spectrom-
eter in CDCl3; chemical shifts are reported relative to TMS as an internal
standard. Ultraviolet spectra were recorded on a Shimadzu UV-240 spectro-
photometer in ethanol; Infrared spectra were obtained on a Hitachi 260-50
spectrophotometer as KBr discs; Microanalyses were performed on a
Perkin-Elmer 240C CHN instrument. All melting points were determined
with a Yanaco mp-500 melting point apparatus and are uncorrected.
Typical Procedure for Reduction of
3-Aroylethylsydnones by Using NaBH4
To an ice-cooled EtOH solution (10 mL) containing 3-aroylethylsyd-
none (2 mmol), NaBH4 (0.l g, 2.6 mmol) was added. After being stirred at
room temperature for 1 h, the resultant solution was poured into cold water
(100 mL). The crude product was recrystallized from 95% ethanol yielding
3-Aroylethylsydnone 1a–f.
The Synthesis of Sydnones 2a–f, General Procedure
To a solution of 3-(3-aryl-3-hydroxylpropyl)sydnone 1 (2.5 mmol) in
acetone (15 mL), concentrate H2SO4 (0.5 mL) or BF3–Et2O (1 mL) is added
dropwise at 0ꢀC and the stirring is continued for 24 h at r.t.. The mixture is
poured into water (50 mL) and extracted with ethyl acetate (3 Â 20 mL). The
organic layer is dried over Na2SO4. The solvent is evaporated and the crude
product is recrystallized from ethyl acetate/hexane to give colorless 2a–f.
ACKNOWLEDGMENT
We are grateful for financial support from natural science foundation
for young teachers of Beijing Normal University.
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2. Stewart, F.H.C. Chem. Rev. 1964, 64, 129.
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NEW SYDNONES CONTAINING FUSED RING
2207
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Received in Japan May 28, 2001