Transalkenylation of Geminally Activated Nitroethenes

Full text of DOI:10.1023/A:1026094220537

Russian Journal of Organic Chemistry, Vol. 39, No. 5, 2003, pp. 744 746. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 5, 2003,
pp. 790 792.
Original Russian Text Copyright
2003 by Aboskalova, Fel’gendler, Sheremet, Trukhin, Berestovitskaya.
SHORT
COMMUNICATIONS
Dedicated to Prof. G.I. Koldobskii
on the 70th Anniversary of His Birth
Transalkenylation of Geminally Activated Nitroethenes
N. I. Aboskalova, A. V. Fel’gendler, E. A. Sheremet,
E. V. Trukhin, and V. M. Berestovitskaya
Gertsen Russian State Pedagogical University, nab. r. Moiki 48, St. Petersburg, 191186 Russia
e-mail:chemis@herzen.spb.ru
Received March 14, 2003
Geminally activated nitroethenes of the aromatic
series, which contain a nitro or a carbonyl group as
the second electron-acceptor function, are readily
accessible compounds [1 4]. They exhibit high reac-
tivity with respect to nucleophiles [2, 5 10]. Increased
interest in the chemistry of such polyfunctional elec-
tron-deficient compounds is explained by the pos-
sibility for their ready modification via introduction
of biologically active fragments (e.g., indole and sub-
stituted indole moieties [7, 8]), as well as for design
on their base of new heterocyclic structures with
useful properties (e.g., pyrazoles, 1,2,3-triazoles, etc.
triethylamine, or piperidine) to afford benzylidene-
malononitriles VII X and benzylidenecyanoacetates
XI XIV (Scheme 1). The reaction with ethyl cyano-
acetate in methanol using sodium methoxide as a base
is accompanied by transesterification. The yield of
compounds VII XIV reaches 94%.
Presumably, CH acids having a cyano group react
with nitroethenes I VI at the double C C bond, but
the process does not stop at the stage of formation of
addition product. In the presence of a base, elimina-
tion of dinitromethyl or acetyl(benzoyl)nitromethyl
anion or so-called arylmethylene transfer [11] occurs.
Our attempts to suppress the latter process and isolate
primary nucleophilic addition products were unsuc-
cessful. According to [11], exchange process in the
transalkenylation reaction is governed by thermo-
dynamic rather than kinetic factor. In fact, the ef-
ficiency of the reaction under study is determined
primarily by thermodynamic stability of the resulting
, -dicyano- and -alkoxycarbonyl- -cyanostyrenes.
A significant role is likely to be played by the stabil-
ity of the departing functionalized nitrocarbanion.
[
9, 10]). Furthermore, a combination of two reaction
centers in molecules of geminal acylnitroethenes,
activated double bond and carbonyl group, makes
them convenient models for studying regioselectivity
problems in reactions with nucleophiles.
We have found that 2-aryl-1,1-dinitroethenes I and
II and 2-aryl-1-acetyl(benzoyl)-1-nitroethenes III VI
readily react with CH acids having a cyano group,
malononitrile and ethyl cyanoacetate, in alcoholic
solution in the presence of a base (sodium methoxide,
Scheme 1.
I, X = NO , R = H; II, X = NO , R = Cl; III, X = MeCO, R = Me N; IV, X = MeCO, R = MeO; V, X = PhCO, R = Me N;
2
2
2
2
VI, X = PhCO, X = MeO; VII, XI, R = H; VIII, XII, R = Cl; IX, XIII, R = Me N; X, XIV, R = MeO; R = Me, Et.
2
1
070-4280/03/3905-0744$25.00 2003 MAIK Nauka/Interperiodica

TRANSALKENYLATION OF GEMINALLY ACTIVATED NITROETHENES
745
Rappoport and Ladkani [6] reported on a similar
reaction of 1,1-dinitro-2,2-diphenylethene with
malonodinitrile in the presence of triethylamine,
which however required more severe conditions.
The structure of transalkenylation products VII
XIV was proved by independent synthesis from the
corresponding aldehydes and cyano group-containing
CH acids; no depression of the melting point was
observed on mixing samples obtained by the two
methods.
(1 mmol) of 4-(4-methoxyphenyl)-3-nitro-3-buten-2-
one (IV) and 0.2 g (3 mmol) of malononitrile in 3 ml
of anhydrous methanol. The mixture was heated to
the boiling point and was then left to stand for 1 h
at room temperature. The precipitate was filtered off.
Yield 0.07 g (36%), yellow crystals, mp 107 108 C
(from carbon tetrachloride); published data [15b]:
mp 110 C (from ethanol).
Following an analogous procedure, compound X
was obtained from 3-(4-methoxyphenyl)-2-nitro-1-
phenyl-2-propen-1-one (VI) and malononitrile in the
presence of piperidine. Reaction time 30 min; yield
Thus, the reaction of , -dinitrostyrenes and
acetyl(benzoyl)- -nitrostyrenes with malononitrile
-
and ethyl cyanoacetate takes the transalkenylation
path and leads to formation of the corresponding
benzylidenemalonodinitriles and benzylidenecyano-
acetates.
7
0%, mp 107 108 C (from carbon tetrachloride).
Methyl 2-cyano-3-phenylpropenoate (XI). A so-
lution of methyl cyanoacetate sodium salt, prepared
from 0.1 ml (0.1 g, 1 mmol) of methyl cyanoacetate
and 0.023 g (1 mmol) of metallic sodium in 5 ml of
anhydrous methanol, was added dropwise at 0 3 C
under continuous stirring to 0.194 g (1 mmol) of
Initial 2-aryl-1,1-dinitroethenes I and II [3, 4] and
-aryl-1-acetyl(benzoyl)-1-nitroethenes III VI [2, 12]
2
were synthesized by known methods.
Benzylidenemalononitrile (VII). Three drops of
triethylamine were added to a suspension of 0.194 g
1
,1-dinitro-2-phenylethene (I). The mixture was
stirred for 1 h at 0 3 C and for 4 h at room tempera-
ture and was poured onto finely crushed ice contain-
ing acetic acid. The precipitate was filtered off. Yield
(
(
1 mmol) of 1,1-dinitro-2-phenylethene (I) and 0.07 g
1 mmol) of malononitrile in 3 ml of anhydrous
ethanol. The mixture was stirred for 1.5 h at room
temperature and poured onto finely crushed ice con-
taining acetic acid. The precipitate was filtered off.
Yield 0.145 g (94%); light yellow crystals, mp 77
0
.123 g (66%), light yellow crystals, mp 86 87 C
(
(
from methanol); published data [16]: mp 88 89 C
from methanol).
Methyl 2-cyano-3-(4-chlorophenyl)propenoic
7
8
8 C (from ethanol); published data [13]: mp 83.5
4 C (from 2-methylbutan-2-ol).
acid (XII) was synthesized from 2-(4-chlorophenyl)-
,1-dinitroethene (II) and methyl cyanoacetate by
1
4
-Chlorobenzylidenemalononitrile (VIII) was
synthesized in a similar way from 1,1-dinitro-2-
4-chlorophenyl)ethene (II) and malononitrile. Yield
3%, colorless crystals, mp 164 165 C (from
the procedure described above for compound XI.
Yield 90%, colorless crystals, mp 121 122 C (from
ethanol); published data [17]: mp 121 C.
(
3
ethanol); published data [14]: mp 162 163 C (from
ethanol.
Methyl 2-cyano-3-(4-dimethylaminophenyl)pro-
penoate (XIII) was synthesized from 4-(4-dimethyl-
aminophenyl)-3-nitro-3-buten-2-one (III) and methyl
cyanoacetate by the procedure described above for
compound XI. Yield 53%, orange crystals, mp 134
135 C (from ethanol); published data [18]: mp 141
142 C (from ethanol).
Following an analogous procedure, compound XIII
was obtained from 3-(4-dimethylaminophenyl)-2-
nitro-1-phenyl-2-propen-1-one (V) and methyl cyano-
acetate. Reaction time 12 h. Yield 30%, mp 134
135 C (from ethanol).
4
-Dimethylaminobenzylidenemalononitrile (IX).
Three drops of piperidine were added to a suspension
of 0.23 g (1 mmol) of 4-(4-dimethylaminophenyl)-3-
nitro-3-buten-2-one (III) and 0.07 g (1 mmol) of
malononitrile in 3 ml of ethanol, and the mixture was
left to stand for 1 h at room temperature. The precip-
itate was filtered off. Yield 0.16 g (83%), orange
crystals, mp 173 174 C (from ethanol); published
data [15a]: mp 179 180 C (from anhydrous ethanol).
Following an analogous procedure, compound IX
was obtained from 3-(4-dimethylaminophenyl)-2-
nitro-1-phenyl-2-propen-1-one (V) and malononitrile.
Yield 83%, mp 173 174 C (from ethanol).
Methyl 2-cyano-3-(4-methoxyphenyl)propenoate
(XIV) was synthesized from 4-(4-methoxyphenyl)-3-
nitro-3-buten-2-one (IV) and ethyl cyanoacetate by
the procedure described above for compound XI.
Yield 80%, yellow crystals, mp 97 99 C (from
ethanol); published data [18]: mp 100 101 C (from
ethanol).
4
-Methoxybenzylidenemalononitrile (X). A solu-
tion of sodium methoxide, prepared from 0.023 g
1 mmol) of metallic sodium and 2 ml of anhydrous
methanol, was added to a suspension of 0.22 g
(
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 5 2003

7
46
ABOSKALOVA et al.
Following an analogous procedure, compound XIV
9. Bakhareva, S.V., Aboskalova, N.I., and Berestovits-
kaya, V.M., Russ. J. Gen. Chem., 2001, vol. 71,
p. 1493.
was obtained from 3-(4-methoxyphenyl)-2-nitro-1-
phenyl-2-propen-1-one (VI) and ethyl cyanoacetate.
Yield 78%, mp 98 99 C (from ethanol).
1
0. Aboskalova, N.I., Berestovitskaya, V.M., Bakhare-
va, S.V., and Fel’gendler, A.V., Khim. Geterotsikl.
Soedin., 2002, p. 1462.
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