Synthesis of cross-conjugated heterocyclic mesomeric betaines

Article abstract of DOI:10.1081/SCC-100104328

Reaction of (chlorocarbonyl)phenyl ketene with several oximes such as p-chlorobenzaldehyde oxime, 2,4-dichlorobenzaldehyde oxime, p-N,N-dimethylbenzaldehyde oxime, 9-anthracene carboxaldehyde oxime and benzophenone oxime resulted in a series of cross-conj

Full text of DOI:10.1081/SCC-100104328

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SYNTHESIS OF CROSS-CONJUGATED HETEROCYCLIC
MESOMERIC BETAINES
K. Saidi a & H. Sheibani a
a Department of Chemistry , Shahid Bahonar University of Kerman , Kerman, 76175, Iran
Published online: 16 Aug 2006.
To cite this article: K. Saidi & H. Sheibani (2001) SYNTHESIS OF CROSS-CONJUGATED HETEROCYCLIC MESOMERIC BETAINES,
Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 31:12,
1809-1814, DOI: 10.1081/SCC-100104328
To link to this article: http://dx.doi.org/10.1081/SCC-100104328
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SYNTHETIC COMMUNICATIONS, 31(12), 1809–1814 (2001)
SYNTHESIS OF CROSS-CONJUGATED
HETEROCYCLIC MESOMERIC BETAINES
K. Saidi* and H. Sheibani
Department of Chemistry, Shahid Bahonar University of
Kerman, Kerman 76175, Iran
ABSTRACT
Reaction of (chlorocarbonyl)phenyl ketene with several
oximes such as p-chlorobenzaldehyde oxime, 2,4-dichloro-
benzaldehyde oxime, p-N,N-dimethylbenzaldehyde oxime,
9-anthracene carboxaldehyde oxime and benzophenone
oxime resulted in a series of cross-conjugated heterocyclic
mesomeric betaines CCMB.
We have recently reported on the cycloaddition of (chlorocarbonyl)-
1
phenylketene (1) with carbonylcompounds
and C ¼ N linkages.2,3
Reaction of thiolactam with (1) to produce a stable betaines has been
reported by Padwa and his co-workers.4 There is also a report on the reac-
tion of pyrazoles such as 1,2,3-triazoles and 1,2,4-triazoles with (chloro-
carbonyl)aryl ketenes which results in formation of a series of betaines
characterized by the presence of distinct cationic and anionic segments. It
has been reported that some of these betaines are unstable and immediate
decomposition of product occured in solution.5
* Corresponding author.
1809
Copyright & 2001 by MarcelDekker, Inc.
www.dekker.com

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1810SAIDI AND SHEIBANI
We now wish to describe an investigation of the facile cycloaddition
of this isolable and stable ketene with oximes (a 1,2-binucleophile)
such as p-chlorobenzaldehyde oxime, 2,4-dichlorobenzaldehyde oxime,
p-N,N-dimethylbenzaldehyde oxime, 9-anthracene carboxaldehyde oxime
and benzophenone oxime to yield anhydro-2-(arylmethylene)-4-phenyl-
3-hydroxy-5-oxoisoxazolium hydroxide. A series of quite stable cross-
conjugated heterocyclic mesomeric betaines (CCMB) are easily prepared
from these reactions in good yields. The importance of such a reaction in
organic synthesis is derived from its ability to generate a five-membered
heterocyclic rings, which can undergo 1,3-dipolar cycloaddition reactions.6
When a ketene such as (chlorocarbonyl)phenyl ketene is allowed to
unite with an oxime a zwitterionic system results in which the positive and
negative charges are delocalized within the ꢀ-electron system.7
As anticipated the addition of (1) and P-chlorobenzaldehyde oxime
resulted in a loss of all the ketene band in IR and instant formation of a red
precipitate of anhydro-2-(P-chlorophenylmethylene)-4-phenyl-3-hydroxy-
5-oxoisoxazolium hydroxide (IIIa) which is characteristic of CCMB
compounds.
The infrared spectrum of (IIIa) revealed the carbonyl bands at 1790
and 1730 cmÀ1. The 1H NMR spectrum of (IIIa) showed a singlet at

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HETEROCYCLIC MESOMERIC BETAINES
1811
d 9.98 ppm which belongs to CH proton and phenyl protons revealed a mul-
tiplet at d 7.11–8.01 ppm. Only one singlet is observed at 9.98 ppm.
Apparently one isomer is formed, because the oxygen with a negative
charge on this compound prefers cis configuration with respect to
hydrogen than the larger Ar groups. The tautomer form has a s-cis config-
uration and in this case the Ar group also to be further away from the
carbonyl oxygen (anti). Therefore it was concluded that only the Z isomer
Table 1. Yield Data for All Compounds
aYield of isolated products.

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SAIDI AND SHEIBANI
is the predominant product. 13C NMR spectrum is consistent with the pro-
posed structure. The mass spectrum revealed the molecular ion peak at m/z
299 (64%) and base peak at m/z 139 (100%) which is due to (C7H6CIN)þ
fragment. It is pertinent to note that a phenylhydrogen from ortho position
shifts to the nitrogen atom giving the base peak.
This fragment along with an odd molecular weight (because it con-
tains nitrogen) with an odd electron is a good evidence of rearrangement.
Table 2. Analytical Data
Analysis (%)
Calcd. (Found)
Compd.
No.
Molecular
Formula
Mass Spectrum
m/z
C
H
N
(IIIa)
(IIIb)
(IIIc)
(IIId)
(IIIe)
C16H10ClNO3
C16H9Cl2NO3
C18H16N2O3
C24H15NO3
C22H15NO3
64.10 3.33 4.60
molecular ion 299 (64%, M+),
139 (100% base peak),
(63.45 3.40 4.64) 118 (81%), 89 (57%)
57.48 2.69 4.19
molecular ion 333 (22%, M+),
173 (100% base peak), 145 (52%),
(57.02 2.89 4.23) 118 (74%), 89 (62%)
molecular ion 308 (26%, M+),
175 (31%), 148 (100% base peak),
118 (19%)
molecular ion 365 (15%, M+),
221 (38%), 203 (100% base peak)
78.90 4.11 3.84
(77.92 4.30 3.90)
77.41 4.40 4.11
molecular ion 341 (10%, M+),
312 (50%), 249 (63%), 105
(100% base peak)
(76.5 4.56 4.28)
Attempts to obtain satisfactory C & H analysis were unsuccessful.

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HETEROCYCLIC MESOMERIC BETAINES
1813
Table 3. SpectralData
Compd.
No.
IR (KBr)
cmÀ1 C¼O
1H-NMR (DMSO)
13C-NMR (DMSO)
TMS d (ppm)
d (ppm)
(IIIa)
(IIIb)
(IIIc)
(IIId)
1790, 1730 9.98 [s, 1 H]
8.01–7.11 [m, 9 H]
192.5, 170.9, 170.6, 139.8, 135.3,
131.6, 129.8, 128.5, 128.1, 125.3,
125.1, 124.1
1795, 1730 10.26 [s, 1 H]
7.8–6.8 [m, 8 H]
189.3, 170.9, 170.6, 140.2, 137.6,
131.54, 131.52, 131.4, 130.7, 128.7,
128.5, 125.2, 125.0
1780, 1730 9.65 [s, 1 H]
8.09–6.77 [m, 9 H]
2.49 [S, 6 H]
190.3, 170.9, 170.6, 154.6, 147.9,
132.0, 131.5, 128.5, 128.1, 125.2,
125.0, 111.6, 40.15
1810, 1750 11.45 [s, 1 H] 194.6, 171.1, 170.7, 135.7, 131.8,
9.00–7.10 [m, 14 H] 131.7, 131.1, 129.8, 129.7, 129.2,
128.5, 126.3, 125.1, 125.0, 124.8,
123.9
(IIIe)
1795, 1730 8.35–7.10 [m, 10 H] 196.3, 171.1, 170.7, 137.4, 133.1,
131.6, 130.0, 129.0, 128.5, 125.2,
125.0
The bond cleavage occured at a similar location producing the base peaks in
their respective mass spectra.
EXPERIMENTAL
Solvent was dried over sodium and distilled prior to use. Reagents
were employed as purchased from Merck and Fluka. Melting points were
1
determined on Gallkamp (UK) apparatus and uncorrected. H NMR and
13C NMR spectra were recorded on a Bruker DRX-500 MHz FT nuclear
magnetic resonance. IR spectra were obtained using a Matson 1000 FT IR
spectrometer. (Chlorocarbonyl)phenyl ketene was prepared by a procedure
similar to that of Nakanishi.8
Typical Procedure for the Reaction of (Chlorocarbonyl)phenyl
Ketene with Oximes
A 0.2 mmol(0.36 g) portion of (1) in 20 mlof dry diethylether
was added dropwise to a stirred solution of 0.2 mmol (0.31 g) of

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SAIDI AND SHEIBANI
P-chlorobenzaldehyde oxime at 0ꢀC under a nitrogen atmosphere.
A red precipitate of anhydro-2-(P-chlorophenylmethylene)-4-phenyl-3-
hydroxy-5-oxoisoxazolium hydroxide was formed instantly. The reaction
mixture was filtered and the products were recrystalized from benzene and
further characterized.
ACKNOWLEDGMENT
The authors express appreciation to the Shahid Bahonar University of
Kerman faculty research committee for its support of this investigation.
REFERENCES
1. Saidi, K.; Shaterian, H.R.; Sheibani, H. Synth. Commun. 2000,
30(13), 2345.
2. Saidi, K.; Shaterian, H.R.; Aghaei, D. Heterocycl. Commun. 2000,
6(1), 94.
3. Saidi, K.; Darehkordi, A. J. Fluorine Chem. in press.
4. Padwa, A.; Coats, S.J.; Harring, S.R.; Hadjiarapoglou, L.; Semones,
M.A. Synthesis 1995, 973.
5. Potts, K. T.; Murphy, P. M.; Kuehnling, W. R. J. Org. Chem. 1988,
53(13), 2889.
6. Potts, K.T.; Ehlinger, R.; Nichols, W.M. J. Org. Chem. 1975, 40(18),
2596.
7. Ollis, W.D.; Stanforth, S.P.; Ramsden, C.A. Tetrahedron 1985, 2239.
8. Nakanishi, S.; Batler, K. Organic Preparations and Procedures. Int.
1975, 7(4), 155.
Received in Japan May 27, 2000

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