A facile synthesis of [E]-α-cyanocinnamic aldehydes from Baylis-Hillman adducts

Article abstract of DOI:10.1081/SCC-100104470

A facile synthesis of stereochemically pure [E]-α-cyanocinnamic aldehydes from Baylis-Hillman adducts is described.

Full text of DOI:10.1081/SCC-100104470

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A FACILE SYNTHESIS OF [E]-α-CYANOCINNAMIC
ALDEHYDES FROM BAYLIS-HILLMAN ADDUCTS
Subramanian Ravichandran a
a School of Chemistry, University of Hyderabad , Hyderabad, 500 046, India
Published online: 09 Nov 2006.
To cite this article: Subramanian Ravichandran (2001) A FACILE SYNTHESIS OF [E]-α-CYANOCINNAMIC ALDEHYDES FROM
BAYLIS-HILLMAN ADDUCTS, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 31:14, 2185-2188, DOI: 10.1081/SCC-100104470
To link to this article: http://dx.doi.org/10.1081/SCC-100104470
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SYNTHETIC COMMUNICATIONS, 31(14), 2185–2188 (2001)
A FACILE SYNTHESIS OF
[E]-a-CYANOCINNAMIC ALDEHYDES
FROM BAYLIS-HILLMAN ADDUCTS
Subramanian Ravichandran
School of Chemistry, University of Hyderabad,
Hyderabad – 500 046, India
ABSTRACT
A facile synthesis of stereochemically pure [E]-a-cyanocin-
namic aldehydes from Baylis-Hillman adducts is described.
In continuation of our research programme aimed at developing the
Baylis-Hillman reaction as a source for stereoselective process,1 I herein
report a simple and efficient methodology for synthesis of stereochemically
pure [E]-a-cyanocinnamic aldehydes from Baylis-Hillman adducts accord-
ing to the following scheme. The results were summarised in the Table 1.
Scheme 1.
2185
Copyright & 2001 by Marcel Dekker, Inc.
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Table 1. Stereoselective Synthesis of [E]-a-Cyanocinnamic Aldehydes
Allyl
bromide
Reaction
Time (h)
Ar
Product
Yield (%)
1a
1b
1c
1d
1e
1f
Phenyl
2
2
2
2
2
2
2a
2b
2c
2d
2e
2f
70
71
71
73
71
73
p-tolylphenyl
p-chlorophenyl
p-isopropylphenyl
o-tolylphenyl
l-naphthyl
The a-cyanocinnamic aldehydes were earlier prepared either by
the base catalyzed condensation of appropriate aromatic aldehydes
with 3-oxopropanenitrile, generated in situ from isoxazole2,3 or by conden-
sation of 3,3-dimethoxypropanenitrile with aldehydes followed by acid
hydrolysis.4
In conclusion, this method gives a possibility of preparing stereoche-
mically pure [E]-a-cyanocinnamic aldehydes with yields comparable to those
cited in literature.5
EXPERIMENTAL SECTION
All melting points were recorded on a Superfit (India) capillary melt-
ing point apparatus and are uncorrected. Infrared spectra (IR) were
recorded with a Perkin-Elmer 1310 spectrometer. 1H and 13C NMR spectra
were recorded at 200 and 50 MHz, respectively. Elemental analyses were
recorded on Perkin-Elmer 240C-CHN analyzer.
The compounds 1a–1f were prepared as per the procedure reported in
literature.6
General Procedure for the Synthesis of [E]-a-Cyanocinnamic
Aldehydes (2a–2f )
To a mixture of (2E)-2-(bromomethyl)alk-2-enenitrile (1a–1f) (2 mM)
and NaHCO3 (4 mM) in 3 ml of anhydrous DMSO was stirred at room
temperature for 2 hours. Then the reaction mixture was diluted with cold
water and extracted with ether. The organic layer was dried over anhyd.
Na2SO4 and the solvent was removed by using a rotory evaporator under

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[E]-a-CYANOCINNAMIC ALDEHYDES
2187
reduced pressure thus providing stereochemically pure [E]-a-cyanocinnamic
aldehydes either after crystallization from EtOAc: hexane(1:2) (2a–2c,
2e–2f) or after column chromatography (silica gel, 2% ethylacetate in
1
hexane) (2d) in good yields. All products gave satisfactory (IR, H and
13C) spectral data and elemental analyses. The purity of all title compounds
was determined to be >95% by 200 MHz proton NMR and/or elemental
analysis.
2-Cyano-3-phenylpropenal (2a): m.p: 95–96ꢀC (lit.4 96–97ꢀC). IR (KBr):
1
2224, 1690 cmÀ1. H NMR (200 MHz) (CDCl3): d 7.48–7.70 (m, 3H), 7.93
(s, 1H), 8.05–8.14 (m, 2H), 9.60 (s, 1H). 13C NMR (50 MHz) (CDCl3): d
112.40, d 114.08, 129.50, 131.32, 134.26, 159.40, 187.08. Elemental analysis
calculated for C10H7NO: C, 76.42; H, 4.49; N, 8.91 and found C, 76.50; H,
4.48; N, 8.95%.
2-Cyano-3-(4-methylphenyl)propenal (2b): m.p: 83–85ꢀC IR (KBr):
1
2227, 1695 cmÀ1. H NMR (200 MHz) (CDCl3): d 2.4 (s, 3H) 7.31–7.52
(m, 2H), 7.91 (s, 1H), 8.12–8.16 (m, 2H), 9.62 (s, 1H).13C NMR (50 MHz)
(CDCl3): d 21.57, 112.36, 118.11, 128.54, 132.30, 134.28, 159.22, 186.42.
Elemental analysis calculated for C11H9NO: C, 77.19; H, 5.26; N, 8.18
and found C, 77.16; H, 5.24; N, 8.15%.
2-Cyano-3-(4-chlorophenyl)propenal (2c): m.p: 89–91ꢀC IR (KBr):
2229, 1696 cmÀ1 1H NMR (200 MHz) (CDCl3): d 7.8 (s, 1H) 7.37–7.76
.
(m, 4H), 9.64 (s, 1H). 13C NMR (50 MHz) (CDCl3): d 111.23, 117.09,
129.32, 131.26, 134.37, 142.50, 156.48, 187.06. Elemental analysis calculated
for C10H6NClO: C, 62.82; H, 3.14; N, 7.32; Cl, 18.32 and found C, 62.81; H,
3.16; N, 7.30%.
2-Cyano-3-(4-isopropylphenyl)propenal (2d): IR (neat): 2218, 1695 cmÀ1
.
1H NMR (200 MHz) (CDCl3): d 1.26 (d, 6H), 2.97 (sept, 1H), 7.34–7.56 (m,
13
4H), 7.84 (s, 1H), 9.72 (s, 1H).
C NMR (50 MHz) (CDCl3): d 23.79,
33.97, 51.98, 121.74, 128.38, 132.87, 139.52, 141.06, 156.39, 186.62.
Elemental analysis calculated for C13H13NO: C, 78.39; H, 6.53; N, 7.03
and found C, 78.36; H, 6.54; N, 7.01%.
2-Cyano-3-(2-methylphenyl)propenal (2e): m.p: 84–87ꢀC IR (KBr):
2217, 1698 cmÀ1 1H NMR (200 MHz) (CDCl3): d 2.42 (s, 3H). 7.42–7.56
(m, 2H), 7.92 (s, 1H), 8.14–8.18 (m, 2H), 9.59 (s, 1H). 13C NMR (50 MHz)
(CDCl3): d 22.43, 113.14, 120.04, 127.59, 132.28, 133.96, 159.18, 186.24.
Elemental analysis calculated for C11H9NO: C, 77.19; H, 5.26; N, 8.18
and found C, 77.14; H, 5.28; N, 8.16%.
2-Cyano-3-(1-napthyl)propenal (2f): m.p: 171–174ꢀC. IR (KBr): 2222,
1693 cmÀ1. 1H NMR (200 MHz) (CDCl3): d 7.61–8.53 (m, 7H), 8.86 (s, 1H),
9.74 (s, 1H). 13 C NMR (50 MHz) (CDCl3): d Elemental analysis calculated
for C14H9NO: C, 81.14; H, 4.38; N, 6.76 and found C, 80.85; H, 4.46; N,
6.74%.

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RAVICHANDRAN
ACKNOWLEDGMENTS
SR thanks his brothers SS and Dr. SP for encouragement in research.
SR also thanks COSIST programme in organic synthesis in the school of
chemistry, University of Hyderabad.
REFERENCES
1. Basavaiah, D.; Krishnamacharyulu, M.; Suguna Hyma, R.; Pandiaraju,
S. Tetrahedron Lett. 1997, 38, 2141 and references cited therein.
2. Ciller, J.A.; Martin, N.; Seoane, C.; Soto, J.L. J. Chem. Soc. Perkin
Trans. 1 1985, 2581.
3. Herbert, A. Chem. Abstr. 1978, 88, 62159j.
4. Elliot, A.J.; Morris, P.E.; Petty, S.L.; Williams, C.H. J. Org. Chem.
1997, 62, 8071.
5. Basavaiah, D.; Kumaragurubaran, N.; Padmaja, K. Synlett. 1999, 1630.
6. Buchholz, R.; Hoffmann, H.M.R. Helv. Chim. Acta. 1991, 74, 1213.
Received in The Netherlands October 14, 2000

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