Rapid and efficient synthesis of 2-[3-cyano-4-(2-aryliden)-5,5-dimethyl-5H-furan-2-ylidene]-malononitrile under focused microwave irradiation

Article abstract of DOI:10.1081/SCC-100104407

New biological potential furan-2-ylidenemalononitriles (IIIa-j) were synthetised efficiently by one-pot condensation under focused microwave from starting and easy available compounds.

Full text of DOI:10.1081/SCC-100104407

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RAPID AND EFFICIENT
SYNTHESIS OF 2-[3-
CYANO-4-(2-ARYLIDEN)-5,
5-DIMETHYL-5H-FURAN-2-
YLIDENE]-MALONONITRILE
UNDER FOCUSED MICROWAVE
IRRADIATION
Didier Villemin & Liang Liao
Published online: 09 Nov 2006.
To cite this article: Didier Villemin & Liang Liao (2001) RAPID AND EFFICIENT
SYNTHESIS OF 2-[3-CYANO-4-(2-ARYLIDEN)-5, 5-DIMETHYL-5H-FURAN-2-
YLIDENE]-MALONONITRILE UNDER FOCUSED MICROWAVE IRRADIATION, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 31:11, 1771-1780, DOI: 10.1081/SCC-100104407
To link to this article: http://dx.doi.org/10.1081/SCC-100104407
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SYNTHETIC COMMUNICATIONS, 31(11), 1771–1780 (2001)
RAPID AND EFFICIENT SYNTHESIS OF
2-[3-CYANO-4-(2-ARYLIDEN)-5,
-DIMETHYL-5H-FURAN-2-YLIDENE]-
5
MALONONITRILE UNDER FOCUSED
MICROWAVE IRRADIATION
1,* 1,2
Didier Villemin
Ecole Nationale Supe
ISMRA, UMR CNRS 6507, F-14050 Caen Cedex, France
and Liang Liao
1
´
rieure d’Ingenieurs de Caen,
´
2
Guangxi Teachers University, Dept of Chemistry and
Chemical Engineering, Guilin, 541004, Guangxi, China
ABSTRACT
New biological potential furan-2-ylidenemalononitriles
(IIIa-j) were synthetised efficiently by one-pot condensation
under focused microwave from starting and easy available
compounds.
1
Butenolides are important biologically active compounds. The sub-
stitution of oxygen for a carbonyl group by a ylidenemalononitrile group is
2
known to modify biological properties, in particularly benzylidenemalono-
nitriles were studied as cytotoxic agents against tumour and as riot control
agents. So we are interested in the furan-2-ylidenemalononitriles (III)
derivatives of the butenolid (I) containing a ylidenemalononitrile group.
*
Corresponding author.
1
771
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

1
772
VILLEMIN AND LIAO
The synthesis and the chemistry of these compounds (III) in spite of their
3
potential biological applications was poorly studied.
4
Melikian and al has described the synthesis of 2-dicyanomethylen-3-
cyano-4,5,5-trimethyl-2,5-dihydrofurane (II), by the reaction of 3-hydroxy-
3
-methylbutan-2-one with two equivalents of malononitrile in presence of
sodium ethoxide. He have described also the condensation with four differ-
ent aromatic aldehydes into their substituted compounds 2-dicyanomethy-
len-3-cyano-4,5-dimethyl-4-alkylidene-2,5-dihydrofurans (III).
The wide applicability of focused microwave in chemical reaction
enhancement is due to high reaction rates with formation of cleaner
5
products and the operational simplicity.
We report herein an efficient and rapid synthesis of dicyanomethylen-
dihydrofuran (II) and the one-pot condensation of (II) into their substituted
compounds 2-dicyanomethylen-3-cyano-4,5-dimethyl-4-alkylidene-2,5-dihy-
5
drofurans (IIIa-j) under focused microwave irradiation. The mixture of 3-
6
hydroxy-3-methyl-butan-2-one (1 eq.), malononitrile (2 eq.) and a solution
7
of sodium ethoxide in a flask was placed in the cavity MES irradiated at
2
0 W for 10 minutes. Then the corresponding aldehyde (1 eq) was added and
the reaction mixture was irradiated again at 20 W for 20 minutes. The
overall yields of 2-dicyanomethylen-3-cyano-4,5-dimethyl-4-alkylidene-2,5-
dihydrofurans (IIIa-j) were 65–84% according the Scheme I.
The reaction occurs in two successive steps: formation of (II) and
condensation of (II) with aldehyde into (IIIa-j). The mechanism of the
formation of (II) is not clear because Melikian and al has proposed two
4
,7
different mechanisms for the condensation of 3-hydroxy-3-methylbutan-
-one with nitriles in presence of sodium ethoxide.
2

FURAN-2-YLIDENEMALONONITRILES
1773
Scheme I. One-pot two steps formation of 2-dicyanomethylen-3-cyano-4,5-
dimethyl-4-alkylidene-2,5-dihydrofurans (IIIa-j). R ¼ 2-furanyl (a); 2-thiophenyl (b);
3-thiopenyl (c); 3,4-dichlorophenyl (d); s,6-dichlorophenyl (e); 3-nirophenyl (h); E-
cinnamyl (i); 3-aminophenyl (j).
We performed the reaction of one molecule of malononitrile with one
molecule of 3-hydroxy-3-methylbutan-2-one and we have isolated an imi-
nolactone (IV). This iminolactone (IV) was hydrolysed easily in described
lactone (I). The reaction of malononitrile with this iminolactone (IV) con-
duct to (II). The reaction of imine instead of carbonyl group with nucleo-
9
phile is well known in particularly in heterocyclic synthesis but the reaction
of (IV) is not general and the condensation of the iminolactone (IV) with
phenylacetonitrile is not observed perhaps for steric reasons. Although
Thorpe reaction type between two molecules of malononitrile yields 2-
1
0
amino-1,1,3-tricyano-3-propene, this molecule in conditions of reaction
4
with 3-hydroxy-3-methylbutan-2-one does not conduct to (II).
Two isomers of (III) can be obtained in the condensation of (II) with
3
J
aldehydes. The coupling constant of olefin proton HH between 15 to 17Hz
correspond to a E stereochemistry.
In conclusion, new biologically potential E-furan-2-ylidenemalono-

1
774
VILLEMIN AND LIAO
nitriles (IIIa-j) were conveniently synthesized by one-pot rapid condensa-
tions under focused microwave irradiation from starting and easy available
compounds.
EXPERIMENTAL
1
The C NMR spectra were recorded with a Bruker AC 250 spectro-
3
meter at 62.89 MHz, in CDCl using TMS as internal standard (proton
3
decoupled, JCP given in Hz). The IR spectra were recorded as KBr pellets
on Perkin Elmer 16 PC FT-IR spectrometer and frequencies are given in
ꢀ
1
cm . The mass spectra were obtained on a Nermag Riber R10-10H with a
0 eV electron impact ionization. Uncorrected melting points were deter-
mined with a Kofler hot-stage apparatus and are Microwave irradiations
7
7
were carried out with a focused microwave cavity (cavity EO13 of MES ).
2
-Imino-4,5,5-trimethyl-2,5-dihydrofurane (IV)
A mixture of 3-hydroxy-3-methylbutan-2-one (3 mmol, 0.306 g), mal-
ononitrile (3 mmol, 0.198 g), and sodium ethoxide (0.3 mmol) in ethanol
(
0.3 mL) was irradiated under focused microwaves 20 W for 8 minutes.
The product was chromatographied on silica gel with EtOH/CH Cl ¼ 2/
2
2
9
8. The product obtained after evaporation of the solvent was a yellow oil.
Yield 76%. Anal. Found: H 6.82, C 64.01. C H N O requires H 6.71 C,
8
10
2
6
3.98.
NMR H (CDCl ) d : 1.50 (6 H, s, 2 Â CH ), 2.15 (3 H, s, C ¼ CCH ),
1
3
H
3
3
1
3
6
.75 (1H, s, NH). NMR C (CDCl ) d : 13.3 (CH ), 25.2 (2 Â CH ), 89.3
3
C
3
3
(C-O), 110.7(–CN), 12 7. 4, 165.5 (NC–C ¼ C), 170.2 (C ¼ N). MS m/z (rel.
int.) : 277 (M ., 96.9), 262 (100), 229 (10.9), 220 (10.9), 185 (17.2), 179
þ
(
17.2), 143 (12.5), 115 (10.9), 88 (25), 81 (21.9), 43 (34.4). IR (film ꢀ
max
ꢀ
1
cm : 2230 (CN), 1664 (ꢀC ¼ N), 1074, 980, 894
4
,5,5-Trimethyl-2-oxo-2,5-dihydro-furan-3-carbonitrile (I)
The product (IV) was hydrolysed by a solution of hydrochloric acid
3N). After extraction with ether, drying of magnesium sulfate and evapora-
tion of ether, we have obtained a white solid, yield 95%.
(
Anal.Found: H 6.10, C 63.48. C H NO requires: H 6.0, C 63.57. MP
8
9
2
ꢁ
ꢁ
11
ꢁ
1
6
2
2 –63 C (lit. 61.5–62.5 C). NMR H (CDCl ) d : 1.55 (6 H, s, 2 Â CH ),
3
H
3
1
3
.32 (3 H, s, C ¼ CCH ). NMR C (CDCl ) d : 13.91 (CH ), 24.42
3 3 C 3

FURAN-2-YLIDENEMALONONITRILES
1775
(
(
1
2 Â CH ), 88.37(C-O), 104.62, 110. 74 (–CN), 165.50 (NC–C ¼ C), 184.84
3
ꢀ1
C ¼ O). IR (KBr) v
cm : 2240 (CN), 1764 (C ¼ O), 1738 (C ¼ C),
max
654, 1648.
2
-Dicyanomethylen-3-cyano-4,5,5-trimethyl-2,
-dihydrofurane(II)
5
A mixture of 3-hydroxy-3-methylbutan-2-one (3 mmol, 0.306 g), mal-
ononitrile (6 mmol, 0.396 g), and sodium ethoxide (0.45 mmol) in ethanol
0.3 mL) was irradiated under focused microwaves 20 W for 8 minutes. The
(
solid obtained was crystallised in the ethanol (526 mg, 88%).
ꢁ
Yield: 88%, yellow solid, MP 196–198 C.
Anal.Found: H 4.42, C 66.23. C H N O requires: H 4.55, C 66.32. IR
1
1
9
3
ꢀ
1
KBr) vmax cm : 3084, 3056, 2992, 2228 (CN), 1620, 1588, 1560, 1432,
(
1
394, 1340, 1210, 1104, 988, 782.
Synthesis of 2-[3-cyano-4-(R-vinyl)-5,5-dimethyl-5H-furan-2-ylidene]-
malononitriles (III) from a-Cetols and Malononitrile in One-Pot
Under Microwave Irradiation
In a typical experiment a mixture of 3-hydroxy-3-methylbutan-2-one
(
3 mmol), malononitrile (6 mmol, 0.396 g), and a solution of sodium ethox-
ide (0.4 mmol) in ethanol (0.25 mL) was irradiated by focused microwave at
0 W for 20 minutes. Then furan-2-carboxaldehyde (3 mmol) was added,
and the mixture was irradiated by focused microwave at 20 W for another
0 minutes. After cooling, the product was obtained after filtration and then
recrystallised in ethanol (1.1 g, 75%).
2
2
2
-[3-Cyano-4-(2-furan-2-yl-vinyl)-5,5-dimethyl-5H-furan-2-ylidene]-
malononitrile(IIIa)
Obtained from 3-hydroxy-3-methylbutan-2-one (1 eq.), malononitrile
2 eq.) and furan-2-carboxaldehyde (1 eq.).
(
ꢁ
4
Yield 76%, brown solid, MP: 248–249 C (lit. 245–246 C).
ꢁ
Anal.Found: H 4.31, C 69.14. C H N O requires: H 4.35, C 69.06.
1
6
12
3
2
1
NMR H (CDCl ) d : 1.75 (6 H, s, 2 CH ), 6.64–6.66 (1 H, m, Harom), 6.85
3
H
3
3
(
1 H, d, J ¼ 16.1 Hz, trans HC ¼ CH), 6.97(1 H, m, Harom), 7.55 (1 H,
HH
3
13
d, JHH ¼ 16.1 Hz, trans CH ¼ CH), 7.69 (1 H, s, Harom). NMR
C
(
CDCl ) d : 26.4 (2 CH ), 97.7 (–OC(CH ) ), 98.3 (NC–C ¼ C), 110.7
3
C
3
3 2

1
776
VILLEMIN AND LIAO
(
1
(
(
1
–CN), 111.1 (–CN), 111.9 (–CN), 112.2, 114.3, 120.7, 132.2, 148.2, 150.9,
þ.
73.5 (NC–C ¼ C), 176. MS m/z (rel. int.) : 277 (M , 96.9), 262 (100), 229
10.9), 220 (10.9), 185 (17.2), 179 (172), 143 (12.5), 115 (10.9), 88 (25), 81
ꢀ1
21.9), 43 (34.4). IR (KBr) ꢀmax cm : 2234 (CN), 1612, 1586, 1568, 1460,
378, 1292, 772. Beilstein : 7384244.
2
-[3-Cyano-4-(2-thiophen-2-yl-vinyl)-5,5-dimethyl-5H-furan-
-ylidene]-malononitrile (IIIb)
2
Obtained from 3-hydroxy-3-methylbutan-2-one (1 eq.), malononitrile
2 eq.) and thiophene-2-carboxaldehyde (1 eq.).
(
ꢁ
Yield 80%, brown solid, MP: 253–255 C.
Anal.Found: H 4.05, C 65.13. C H N OS requires: H 4.11, C 65.29
1
6
12
3
1
3
NMR H (CDCl ) d : 1.78 (6 H, s, 2 CH ), 6.74 (1 H, d, J ¼ 16.1 Hz,
3
H
3
HH
CH ¼ CH), 7.18–7.22 (1 H, m, Harom), 7.51 (1 H, d, Harom), 7.68 (1 H, d,
3
13
Harom). 7.85 (1 H, d, J ¼ 16.1 Hz, CH ¼ CH). NMR C (CDCl ) d :
HH
3
C
2
1
6.5 (2 CH ), 97.6 (–OC(CH ) ), 98.7(NC– C ¼ ), 110.5 (NC–), 111.1 (–CN),
3
3 2
11.6 (–CN), 113.6, 129.6, 133.5, 135, 139.7, 140.1, 173.5, 176.5,.5 MS EI m/
þ
z (rel. int %) : 293 M ., 24.5), 292 (74.5), 277 (25.5), 276 (66), 266 (4.7), 254
(
(
1
12), 247(16), 203(15), 198 (15), 184 (18), 166 (19), 161 (19), 140 (26), 98
ꢀ
1
55), 44 (100). IR (KBr) nmax cm : 2228 (CN), 1576, 1546, 1458, 1418,
396, 1382, 1352, 1292, 1112, 960, 728.
2
-[3-Cyano-4-(2-thiophen-3-yl-vinyl)-5,5-dimethyl-5H-furan-
-ylidene]-malononitrile (IIIc)
2
Obtained from 3-hydroxy-3-methylbutan-2-one (1 eq.), malononitrile
2 eq.) and thiophene-3-carboxaldehyde (1 eq.).
(
ꢁ
Yield 89%, brown solid, MP: 242–243 C.
Anal.Found: H 4.23, C 65.34. C H N OS requires: H 4.11, C 65.29
1
6
12
3
1
3
NMR H (CDCl ) d : 1.79 (6 H, s, 2 CH ), 6.84 (1 H, d, J ¼ 16.3 Hz,
3
H
3
HH
3
HC ¼ CHtrans), 7.47–7.48 (2 H, m, Harom), 7.68 (1 H, d, J ¼ 16.3 Hz,
HH
1
3
CH ¼ CH), 7.80 (1 H, s, Harom). NMR C (CDCl ) d : 26.6 (2 CH ), 97.7
3
C
3
(
–OC(CH ) ), 100.5, 101.3, 110.6 (NC), 111 (NC–), 111.8 (CN), 114.8,
3 2
1
int %) : 293 (M , 43), 292 (100), 277 (13), 276 (20), 266 (4.5), 203 (14),
24.9, 128.6, 133, 137.8, 140.6, 174 (NC–C ¼ C), 175.2. MS EI m/z (rel.
þ
ꢀ
1
1
86 (33), 182 (31), 164 (11), 87(25), 85 (35). IR (KBr) ꢀmax cm : 2222 (CN),
1
570, 1546, 1498, 1374, 1292, 1110, 800, 664.

FURAN-2-YLIDENEMALONONITRILES
1777
2
-[3-Cyano-4-(3,4-dichloro-styryl)-5,5-dimethyl-5H-furan-
-ylidene]-malononitrile (IIId)
2
Obtained from 3-hydroxy-3-methylbutan-2-one (1 eq.), malononitrile
2 eq.) and 3,4-dichlorobenzaldehyde (1 eq.).
(
ꢁ
Yield 67%, orange solid, MP: 253–258 C.
Anal.Found: H 3.01, C 60.43. C18H Cl N O requires: H 3.11, C
1
1
2
3
1
6
0.69 NMR H (DMSO-d ) d : 1.79 (6 H, s, 2 CH ), 7.33 (1 H, d,
6
H
3
3
JHH ¼ 16.6 Hz, HC ¼ CH), 7.76 (1 H, d, J ¼ 8.5 Hz, Harom), 7.83 (1 H, d,
3
4
J ¼ 16.6 Hz, CH ¼ CH), 7.92 (1 H, d, d,
J
¼ 8.5 Hz,
J
¼ 2 Hz,
6 C
HH
HH
4
13
Harom), 8.29 (1 H, d, J ¼ 2 Hz, Harom). NMR C (DMSO-d ) d
:
HH
2
1
5.1(2CH ),99.6(–OC(CH ) ),101.0,110.6(–CN),111.8(–CN),112.6(–CN),
3 3 2
17.5, 129.2, 131.0, 131.3, 132.1, 134.2, 135.1, 144.1, 174.4, 177.1. MS EI
þ.
m/z (rel. int %) : 359 (6.4), 357(55.3), 355 (M , 100), 340 (32), 339 (43), 263
(
45), 258 (51), 186 (28), 180 (38), 148 (60), 91 (28), 55 (32). IR (KBr)
1
ꢀ
ꢀmax cm : 2226 (CN), 1618, 1574, 1552, 1468, 1400, 1380, 1210, 1100,
028, 832, 650.
1
2
-[3-Cyano-4-(2,6-dichloro-styryl)-5,5-dimethyl-5H-furan-
-ylidene[-malononitrile (IIIe)
2
Obtained from 3-hydroxy-3-methylbutan-2-one (1 eq.), malononitrile
2 eq.) and 2,6-dichlorobenzaldehyde (1 eq.).
(
ꢁ
Yield 66%, yellow solid, MP: 259–260 C.
Anal.Found: H 3.08, C 60.55. C H Cl N O requires: H 3.11, C 60.69
1
8
11
2
3
1
3
NMR H (CDCl ) d : 1.85 (6 H, s, 2 CH ), 7.37 (1 H, d, J ¼ 16.9 Hz,
3
H
3
HH
3
HC ¼ CH), 7.44–7.47 (3 H, m, Harom), 7.76 (1 H, d, JHH ¼ 16.9 Hz,
13
CH ¼ CH). NMR C (CDCl ) d : 26.5 (2 CH ), 98.1 (OC(CH ) ), 102.7,
3
C
3
3 2
1
1
09.6 (CN), 110.5 (CN), 111.4 (CN), 123.3, 129.5, 130.9, 131.7, 135.6, 140.7,
73.4, 175.2. MS EI m/z (rel. int %) : 359 (8.6), 357(45), 355 (M , 100), 340
þ.
(
(
(
52), 338 (62), 320 (26), 318 (60), 263 (35), 258 (41), 184 (41), 180 (45), 170
ꢀ
1
41), 159 (48), 150 (36). 135 (31), 113 (21), 99 (36). IR (KBr) ꢀmax cm : 2230
CN), 1588, 1574, 1542, 1376, 1336, 1108, 794.
2
-[3-Cyano-4-(3-hydroxy-4-methoxy-styryl)-5,5-dimethyl-5H-furan-2-
ylidene]-malononitrile (IIIf )
Obtained from 3-hydroxy-3-methylbutan-2-one (1 eq.), malononitrile
2 eq.) and 3-hydroxy-4-methoxybenzaldehyde (1 eq.).
(

1
778
VILLEMIN AND LIAO
ꢁ
Yield 75%, brown solid, MP>265 C.
Anal.Found: H 4.63, C 68.61. C H N O requires: H 4.54, C 68.46
1
9
15
3
3
1
NMR H (DMSO-d ) d : 1.77 (6 H, s, 2 CH ), 3.85 (3 H, OCH ), 6.89 (1 H,
6
H
3
3
3
d, Harom), 7.03 (1 H, d, J ¼ 16.3 Hz, HC ¼ CH), 7.41 (1 H, d, Harom),
HH
3
13
7
(
.48 (1 H, s, Harom), 7.88 (1 H, d, J ¼ 16.3 Hz, CH ¼ CH). NMR C
6 C 3 3 3 2
HH
DMSO-d ) d : 25.4 (2 CH ), 54.9, 55.9 (OCH ), 96.3 (OC(CH ) ), 99,
1
1
3
11.3, 111.9, 112.2, 112.6, 113, 116.2, 125.6, 126.2, 148.3, 148.9, 152.2,
þ
75.9, 177.3, MS EI m/z (rel. int %) : 334 (16), 333 (M ., 74), 318 (4.7),
17(8.4), 288 (5.6), 185 (58), 181 (96), 152 (26), 87(50), 85 (100). IR (KBr)
ꢀ
1
ꢀmax cm : 3330–3500 (OH), 2246 (CN), 1584, 1548, 1472, 1444, 1418, 1296,
258, 1202, 1022.
1
2
-[3-Cyano-4-(2-hydroxy-styryl)-5,5-dimethyl-5H-furan-
-ylidene]-malononitrile (IIIg)
2
Obtained from 3-hydroxy-3-methylbutan-2-one (1 eq.), malononitrile
2 eq.) and 3-hydroxybenzaldehyde (1 eq.).
(
ꢁ
Yield 70 %, brown solid, MP>265 C.
Anal.Found: H 4.47, C 71.09. C H N O requires: H 4.32, C 71.28,
1
8
13
3
2
1
NMR H (DMSO-D ) d : 1.75 (6 H, s, 2 CH ), 2.49 (1 H, s, OH), 6.88–6.96
6
H
3
3
(
2 H, m, Harom), 7.33–7.36 (1 H, m, Harom), 7.41 (1 H, d, J ¼ 16.5 Hz,
HH
3
HC ¼ CH), 7.83 (1 H, m, Harom), 8.16 (1 H, d, J ¼ 16.5 Hz, CH ¼ CH).
HH
1
3
NMR C (DMSO-d ) d : 25.2 (2 CH ), 53.8, 97.5, (OC(CH ) ), 99.2, 111.3,
6
C
3
3 2
112.1, 112.9, 115.2, 116.6, 119.9, 121.3, 130.6, 134.2, 144, 158.5, 176.3, 177.4.
þ
MS EI m/z (rel. int %) : 303 (M .,23), 302 (14), 220 (22), 215 (24), 186 (99),
1
85 (63), 182 (66), 106 (49), 92 (74), 78 (44), 65 (74), 59 (100). IR (KBr) ꢀ
max
ꢀ
1
cm : 3150–3300 (OH), 2238 (CN), 2222 (CN), 1730, 1600, 1570, 1536,
502, 1382, 1264, 1106, 976, 758.
1
2
-[3-Cyano-5,5-dimethyl-4-(3-nitro-styryl)-5H-furan-
-ylidene]-malononitrile (IIIh)
2
Obtained from 3-hydroxy-3-methylbutan-2-one (1 eq.), malononitrile
2 eq.) and 3-nitro-benzaldehyde (1 eq.).
(
ꢁ
Yield: 73%, yellow solid, MP>265 C.
Anal.Found: H 3.70, C 64.98. C H N O requires: H 3.64, C 65.06.
1
8
12
4
3
1
3
NMR H (DMSO-d ) d : 1.83 (6 H, s, 2 CH ), 7.41 (1 H, d, J ¼ 16.6 Hz,
6
H
3
HH
3
HC ¼ CH), 7.77 (1 H, m, Harom), 7.99 (1 H, d, J ¼ 16.6 Hz, CH ¼ CH),
HH
1
3
8
:
.31–8.39 (2 H, m, Harom), 8.78 (1 H, s, Harom). NMR C (DMSO-d ) d
6
C
25.1 (2 CH ), 55.3, 99.7, 101.6, 110.5 (CN), 111.7 (CN), 112.6 (CN), 118.0,
3

FURAN-2-YLIDENEMALONONITRILES
1779
1
24.3, 125.9, 130.7, 134.5, 136.1, 144.3, 148.4, 174.4, 176.9. MS EI m/z (rel.
þ.
int%) : 333 (26), 332 (M , 89), 317(3 7) , 316 (100), 236 (40), 185 (20), 181
37), 151 (37), 135 (23), 116 (37), 106 (77), 92 (66), 85 (40), 78 (49), IR (KBr)
(
ꢀ
1
ꢀmax cm : 2232 (CN), 2212 (CN), 1582, 1546, 1530, 1396, 1384, 1350, 1110,
60, 676.
8
2
-[3-Cyano-4-(4-phenyl-buta-1,3-dienyl)-5,5-dimethyl-5H-furan-
-ylidene]-malononitrile (IIIi)
2
Obtained from 3-hydroxy-3-methylbutan-2-one (1 eq.), malononitrile
2 eq.) and trans-cinnamaldehyde (1 eq.).
(
ꢁ
Yield 81%, brown solid, MP : 221–223 C.
Anal.Found: H 4.83, C 76.72. C H N O requires: H 4.82, C 76.66.
2
0
15
3
1
NMR H (CDCl ) dH : 1.75 (6 H, s, 2 CH ), 6.57(1 H, d,
3
3
3
3
JHH ¼ 15.5 Hz, HC ¼ CH), 7.00–7.15 (2 H, m), 7.19 (1 H, d,
13
JHH ¼ 15.5 Hz, CH ¼ CH), 7.35–7.75 (5 H, m, Harom). NMR
C
(
CDCl ) d : 26.5 (2 CH ), 97.6, 98.8, 110.6, 115.1, 118.4, 127.4, 128.3,
3
C
3
1
28.6, 129.2, 129.3, 129.7, 131.0, 135.2, 146.5, 148.1, 173.7. MS EI m/z
þ.
(
1
rel. int %) : 314 (11), 313 (M , 30) 298 (8), 286 (19), 275 (23), 270 (36),
96 (29), 192 (33), 180 (47), 116 (52), 106 (30), 92 (100), 78 (52). IR (KBr)
ꢀ
1
ꢀmax cm : 2228 (CN), 1670, 1560, 1522, 1396, 1380, 1340, 1286, 1168, 1106,
54, 684.
7
2
-[4-(3-Amino-styryl)-3-cyano-5,5-dimethyl-5H-furan-
-ylidene]-malononitrile (IIIj)
2
Obtained from 3-hydroxy-3-methylbutan-2-one (1 eq.), malononitrile
2 eq.) and 3-amino-benzaldehyde (1 eq.).
(
ꢁ
Yield 78%, brown solid, MP>265 C.
Anal.Found: H 4.60, C 71.75. C H N O requires: H 4.67, C 71.51,
1
8
14
4
1
3
NMR H (DMSO-d ) d : 1.72 (6 H, s, 2 CH ), 6.65 (2 H, d, J ¼ 8.5 Hz,
6
H
3
HH
3
3
Harom), 6.80 (1 H, d, J ¼ 16 Hz, HC ¼ CH), 7.66 (2 H, d, J ¼ 8.5 Hz,
HH
HH
3
13
Harom), 7.86 (1 H, d, J ¼ 16 Hz, CH ¼ CH). NMR C (DMSO-d ) d :
HH
6
C
2
1
5.7(2 CH ), 91.5, 98.2, 107.7, 112.2, (CN), 112.8 (CN), 113.6 (CN), 114.3,
3
22.1, 133.7, 150.0, 155.4, 175.7, 177.5. MS EI m/z (rel. int %) : 302
þ
(
M .,4.7), 280 (3), 209 (20), 204 (22), 186 (11), 182 (11), 106 (19), 92 (20),
ꢀ
1
8
NH ), 2228 (CN), 1640, 1590, 1564, 1552, 1520, 1496, 1458, 1386, 1266,
7(44), 85 (67), 65 (61), 59 (100). IR (KBr) ꢀmax cm : 3474 (–NH ), 3364 (–
2
2
1
168, 1110, 870, 698, 654.

1
780
VILLEMIN AND LIAO
ACKNOWLEDGMENTS
Thanks go to the ‘‘region Basse et Haute-Normandie’’ (Rincof) for
their generous financial support (grant for L.L.) and to Professor G.
Melikian for interesting discussion.
REFERENCES AND NOTES
1
. Knight, D.W. Contemporary Org. Synth. 1994, 1, 287; b)
Laduwahetty, T. Contemporary Org. Synt. 1996, 2, 133; c) Collins, I.
Contemporary Org. Synth. 1996, 3, 295.
2. Freeman, F. Chem. Rev. 1980, 80, 329.
3. Dmitriev, V.I. Voen-Med. Zh. 1974, 11, 88; Chem. Abstr. 1974, 81,
374; Berry, W.L.; Nisonger Jr., D.P.; Craig, P.S. US 3715379; Chem.
Abstr., 1973, 78, 124 322m.
4
5
6
. Melikian, G.; Rouessac, F.P. and Alexandre, C. Synth. Commun.
1
. For reviews on the chemistry of malononitrile, see: Freeman, F.M.
Chem. Rev. 1969, 69, 591; Fatiadi, A.J. Synthesis 1978, 165 and 241.
. For a review on focused microwave action: Loupy, A.; Petit, A.;
Hamelin, J.; Texier-Boullet, F.; Jacquault, P.; Mathe, D. Synthesis
995, 25, 3045.
1
998, 1213. For a general review on microwave activation: Kingston,
H.M.S. and Haswell, S.J. Microwave Enhanced Chemistry, ACS (1998).
. Although results were obtained with a cavity EO13 of MES described
previously (Villemin, D. and Martin, B. Synth. Commun. 1995, 25,
7
2
4
319), we obtained recently similar results with a Prolabo Synthewave
02 and with a tube of internal diameter of 10 mm as reactor.
8
. Melikian, G.; Rouessac, F.P.; Alexandre, C. Synth. Commun. 1993,
3, 2269.
2
9
. Charles, G. Bull. Soc. Chim. Fr. 1963, 1554: I.J. Flechter, A.E. Siegrist,
Adv. Heter. Chem. 1978, 23, 171.
1
1
0. Carboni, R.A.; Coffman, D.D.; Howard, E.G. J. Amer. Chem. Soc.
958, 80, 2838; Erian, A.W. Chem. Rev. 1993, 93, 1991.
1. Avetisyan, A.A.; Mangasaryan, Ts. A.; Melikyan, G.S.; Dangyan M.T.
1
and Matsoyan, S.G.; Zhur. Org. Khim. 1971, 7, 962–964; Chem. Abstr.
1
971, 75, 63047q
Received in the UK July 5, 2000