A new strategy of the chemical route to the cyclopropane structure: direct transformation of benzylidenemalononitriles and malononitrile into 1,1,2,2-tetracyanocyclopropanes

Article abstract of DOI:10.1016/j.tet.2007.11.027

The new reaction was found: the direct formation of cyclopropanes from activated olefins and C-H acids. The action of free halogen or active halogen containing compounds on the equal amounts of benzylidenemalononitriles and malononitrile in basic alcohol

Full text of DOI:10.1016/j.tet.2007.11.027

Available online at www.sciencedirect.com
Tetrahedron 64 (2008) 708e713
www.elsevier.com/locate/tet
A new strategy of the chemical route to the cyclopropane structure:
direct transformation of benzylidenemalononitriles and
malononitrile into 1,1,2,2-tetracyanocyclopropanes
*
Michail N. Elinson , Sergey K. Feducovich, Nikita O. Stepanov, Anatolii N. Vereshchagin,
Gennady I. Nikishin
N.D. Zelinsky Institute of Organic Chemistry, Leninsky prospect 47, 119991 Moscow, Russia
Received 23 July 2007; received in revised form 24 October 2007; accepted 8 November 2007
Available online 12 November 2007
Abstract
The new reaction was found: the direct formation of cyclopropanes from activated olefins and CeH acids. The action of free halogen or
active halogen containing compounds on the equal amounts of benzylidenemalononitriles and malononitrile in basic alcohol solutions results
in the formation of 3-aryl-1,1,2,2-tetracyanocyclopropanes in 65e95% yields. Thus, the new simple and efficient way to 3-aryl substituted tet-
racyanocyclopropanes was found directly from such simple and reasonable starting compounds as benzylidenemalononitriles and malononitrile.
Ó 2007 Elsevier Ltd. All rights reserved.
Keywords: Malononitrile; Benzylidenemalononitriles; Tetracyanocyclopropanes; Cyclopropane formation
1. Introduction
activities.3e5 Insecticidal pyrethrins (derivatives of cyclopro-
panoid chrysanthemic acid) are perhaps the best known exam-
ple of their use.3 Thus, the prevalence of cyclopropane
containing compounds with biological activity, whether iso-
lated from natural sources or rationally designed pharmaceu-
tical agents, has inspired chemists to find novel and diverse
approaches to their synthesis.
Though the methods of cyclopropanes synthesis have long
been documented, so far, all of them consist of two main
groups: (1) intramolecular cyclization or (2) interaction of
two different molecules (addition of carbenes to olefins or Mi-
chael initiated ring closure (MIRC) are the most known exam-
ples of this type).3,5 MIRC play an important role in organic
chemistry and many synthetic applications are described in
the literature so far.6
Malononitrile is a commonly known and widely used reagent
in the synthesis of heterocyclic compounds, pharmaceuticals,
pesticides, fungicides, and solvatochromic dyes. The unique
reactivity of this compound has led to its widespread application
in organic chemistry, as well as or even more than other CeH
acids such as malonate and cyanoacetic esters.1
The use of alkylidenemalononitriles, which contain an acti-
vated double bond together with two reactive CN groups, is
also quite common in organic synthesis. The ever-increasing
interest in different addition, cyclization, and condensation
reactions with alkylidenemalononitriles will undoubtedly
continue.2
The cyclopropyl group is also a vital structural unit in many
synthetic and naturally occurring compounds, exhibiting
a wide spectrum of biologic properties ranging from enzyme
inhibition to herbicidal, antibiotic, antitumor, and antiviral
The well-known method of MIRC synthesis of substituted
cyclopropanes involves addition of halogenosubstituted CeH
acid anions (A), generated by the action of a base on the cor-
responding CeH acid (AH), to the conjugated activated ole-
fins followed by cyclization with elimination of halogen
anion7 (Scheme 1).
* Corresponding author. Tel.: þ7 495 137 38 42; fax: þ7 495 135 53 28.
E-mail address: elinson@ioc.ac.ru (M.N. Elinson).
0040-4020/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2007.11.027

M.N. Elinson et al. / Tetrahedron 64 (2008) 708e713
709
R2
R1
R2
R1
R1
R2
_
X
Y
CO2Me
CO2Me
R1
R2
electrolysis
NaHal, MeOH
X
Y
X
Y
MeO2C
MeO2C
CO2Me
CO2Me
CO2Me
CO2Me
CHalXY
+
C
C
_
-
C
C
+
Hal
(A)
Hal = I, Br
X = CO2R
Y = CO2R, CN, C(O)NR2
Hal = Br, I
Scheme 3.
Scheme 1.
The co-electrolysis of alkylidenecyanoacetic and malonic
esters carried out within the guidelines of this approach re-
sulted in the stereoselective synthesis of (E )-isomers of
trialkyl 3-substituted-2-cyanocyclopropane-1,1,2-tricarboxy-
lates17 (Scheme 4).
This method was used for the syntheses of tetracyanosubsti-
tuted cyclopropanes from alkylidene- or benzylidenemalono-
nitriles and bromomalononitrile8e12 with one exceptiondthe
base was omitted because bromomalononitrile is a reasonably
strong acid,13 which can furnish a sufficient concentration of
bromodicyanocarbanion14 for the reaction. The yields of the
tetracyanocyclopropanes were in the range of 30e90%
(Scheme 2), but the excess (1.3e3.0 equiv) of bromomalono-
nitrile was commonly used,8,9 and the usual reaction time took
10e20 h.8,9 Moreover, in some cases the reaction time was as
long as 1e6 days.8
R2
H
CN
CO2R1
R1O2C
R1O2C
CN
CO2R1
electrolysis
NaBr, R1OH
R2
+
CO2R1
CO2R1
Scheme 4.
We have recently accomplished electrocatalytic trans-
formation of alkylidenemalononitriles and malonates into
dialkyl 3-substituted-2,2-dicyanocyclopropane-1,1-dicarboxy-
lates18 and also alkylidenemalononitriles and malononitrile
into 3-substituted 1,1,2,2-tetracyanocyclopropanes in 50e90%
yields.19
R1
R2
R1
R2
_
CN
CN
NC
NC
CN
CN
CBr(CN)2
+
C
C
_
-
Br
Scheme 2.
Nevertheless, any new one-step and efficient chemical ap-
proach to substituted 1,1,2,2-tetracyanocyclopropanes starting
from simple and reasonable compounds is welcome.
3-Phenyl-1,1,2,2-tetracyanocyclopropane was obtained in
95% yield through the reaction of 3-fold excess of benzylide-
nemalononitrile with dibromomalononitrile in the presence of
equimolar quantity of rare indium powder and 0.2 equiv of
lithium iodide as catalyst in dimethylformamide.15
2. Results and discussion
The next essential step in the cyclopropane ring construc-
tion was connected with the electrochemical technique and
using halogen containing mediatory systems in an undivided
cell. Thus, the new electrochemical approach to functionally
substituted cyclopropanes was performed by the electrolysis
of alkylidenemalonates and malonate in an undivided cell
in methanol in the presence of halides as mediators16
(Scheme 3).
This communication dealswith new direct chemical transfor-
mation of alkylidenemalononitriles 1aen and malononitrile 2
into tetracyanosubstituted cyclopropanes 3aen realized under
the action of active halogen containing compounds (Scheme 5).
First, to evaluate the synthetic potential of the procedure pro-
posed and to optimize the conditions, the transformation of
benzylidenemalononitrile 1a and malononitrile 2 into 3-phenyl-
1,1,2,2-tetracyanocyclopropane 3a was studied (Table 1).
R2
R1
CN
R1
NC
NC
CN
CN
XHal
CN
_
C
+
C
3
R2
B
R OH ,
CN
CN
3a-n
1a-n
2
Hal = I, Br
X=I, Br,
O
N
O
R3 = Me, Et
a R1 = H, R2 = Ph; b R1 = H, R2 = 4-MeC6H4; c R1 = H, R2 = 2-MeOC6H4; d R1 = H, R2 = 3-MeOC6H4;
e R1 = H, R2 = 4-MeOC6H4; f R1 = H, R2 = 4-FC6H4; g R1 = H, R2 = 2-ClC6H4; h R1 = H, R2 = 3-ClC6H4;
i R1 = H, R2 = 4-ClC6H4; j R1 = H, R2 = 2-Cl(4-Cl)C6H3; k R1 = H, R2 = 3-BrC6H4; l R1 = H, R2 = 4-NO2C6H4;
m R1 = H, R2 = n-Pr; n R1 + R2 = -(CH2)5-
Scheme 5.

710
M.N. Elinson et al. / Tetrahedron 64 (2008) 708e713
Table 1
Table 3
Direct transformation of benzylidenemalononitrile 1a and malononitrile 2 into
3-phenyl 1,1,2,2-tetracyanocyclopropane 3a by the action of halogen or NBS
in basic alcoholsa
Direct transformation of substituted benzylidenemalononitriles 1ben and
malononitrile 2 into substituted 1,1,2,2-tetracyanocyclopropanes 3ben by
the action of bromine in EtOH/EtONa systema
No.
XHal
Base
R3OH
Yield of 3ab (%)
No.
R1
R2
Benzylidenee
malononitrile
Product, yieldb (%)
1
I2
KOH
KOH
MeOH
EtOH
EtOH
EtOH
EtOH
EtOH
MeOH
EtOH
EtOH
EtOH
25
36
51
35
48
63
44
67
93
95
2
I2
1
H
H
H
H
H
H
H
H
H
H
H
H
4-MeC6H4
2-MeOC6H4
3-MeOC6H4
4-MeOC6H4
4-FC6H4
1b
1c
1d
1e
1f
3b, 84
3c, 89
3d, 92
3e, 75
3f, 81
3g 79
3h, 72
3i, 87
3j, 65
3k, 68
3l, 71
3m, 84
3n, 75
3
I2
EtONa
NaOH
KOH
2
4
NBS
NBS
NBS
Br2
Br2
Br2
Br2
3
c
5
4
6
EtONa
KOH
KOH
5
7
6
2-ClC6H4
3-ClC6H4
4-ClC6H4
1g
1h
1i
8
7
9
10c
a
EtONa
EtONa
8
c
9
2-Cl(4-Cl)C6H3
3-BrC6H4
4-NO2C6H4
n-Pr
1j
10
11
12
13
a
1k
1l
Reagents and conditions: 10 mmol of benzylidenemalononitrile, 10 mmol
of malononitrile, 20 mL of alcohol, 12 mmol of base, 10 mmol of halogen or
NBS, time of the reactiond3 h.
1m
1n
e(CH2)5e
b
Isolated yields.
Malononitrile of 13 mmol.
c
Reagents and conditions: 10 mmol of benzylidenemalononitrile, 10 mmol
of malononitrile, 20 mL of EtOH, 12 mmol of EtONa, 10 mmol of bromine,
time of the reactiond3 h.
The second step was devoted to careful evaluation of
EtONa quantity needed for reaction (Table 2).
b
Isolated yields.
EtOH: 30 mL.
c
Table 2
Influence of EtONa quantity on 3-phenyl 1,1,2,2-tetra-cyanocyclopropane 3a
spirocyclopropane 3n. Hence the method is useful for the
synthesis of tetracyanocyclopropanes from alkylidenemalono-
nitriles and malononitrile as well as from cycloalkylidenema-
lononitriles and malononitrile (entries 12 and 13, Table 3).
Taking into consideration the data obtained, the following
reaction scheme for the transformation of benzylidene- or
alkylidenemalononitriles 1aen and malononitrile 2 into
substituted tetracyanocyclopropanes 3aen is proposed
(Scheme 6).
yielda
No.
Quantity of EtONa (equiv)
Yield of 3ab (%)
1
2
3
4
5
a
0.5
1.0
1.2
1.5
2.0
63
78
93
65
34
Reagents and conditions: 10 mmol of benzylidenemalononitrile, 10 mmol
of malononitrile, 20 mL of EtOH, 5e20 mmol of EtONa, 10 mmol of
bromine, time of the reactiond3 h.
b
R2
R1
_
Isolated yields.
CN
CN
R1
R2
CN
B, -BH
CN
CN
NC
_
C
C
+
R3OH
Excellent conversions of starting compounds and 93% yield
of cyclopropane 3a were obtained when the reaction was
carried out in ethanol by the action of bromine in the presence
of 1.2 equiv of EtONa (entry 9, Table 1 and entry 3, Table 2).
The increase of malononitrile quantity had a little effect on the
3a yield (entry 10, Table 1). The increase of EtONa quantity
compared to 1.2 equiv (entries 4 and 5, Table 2) resulted
in a sufficient decrease of the reaction yield, that may be con-
nected with the activation of undesired base induced
oligomerization processes of starting malononitrile1 and
benzylidenemalononitile.2d,e
CN
CN
1
2
A
XHal
R2
R1
R2
R1
CN
Hal
NC
NC
NC
CN
CN
R3OH
CN
CN
3
4
Under the optimal conditions found i.e., bromine as active
halogen compound, 1.2 equiv of EtONa as base, and ethanol
as solvent, substituted benzylidenemalononitriles or alkylide-
nemalononitriles 1ben and malononitrile were transformed
into corresponding substituted 1,1,2,2-tetracyanocyclopro-
panes 3ben in 65e92% yields (Table 3).
O
N
R3=Me, Et
X=I, Br,
Hal = I, Br
O
Scheme 6.
In the case of benzylidenemalononitriles 1e and 1j (entries
4 and 9, Table 3) the quantity of EtOH was increased up to
30 mL because of the lower solubility of 1e and 1j in EtOH.
Thus, under conditions used, 3-substituted 1,1,2,2-tetracyano-
cyclopropanes 3aen were obtained in 65e95% yields,
among them 3-propyl substituted cyclopropane 3m and
The Michael addition of malononitrile to benzylidene- or
alkylidenemalononitrile 1 in the presence of the base results
in the anion A formation. Earlier formation of anion A from
benzylidenemalononitrile and malononitrile was observed un-
der basic conditions.20

M.N. Elinson et al. / Tetrahedron 64 (2008) 708e713
711
Then halogenation of anion A by the action of active halogen
containing compound leads to substituted 1-halogeno-1,1,3,3-
tetracyanopropane 4. The following cyclization of 4 into tetra-
cyanocyclopropane 3 in alcoholic solutions takes place in
accordance with the earlier reported data.14 It should be espe-
cially mentioned that the last step of the mechanism (Scheme 6)
is a part of the tetracyanocyclopropane synthesis suggested by
Mariella and Roth.14 This method includes bromination of
2-alkyl substituted 1,1,3,3-tetracyanopropanes 5 with instant
formation of 3-alkyl substituted 1,1,2,2-tetracyanocyclopropanes
6 in 60e90% yields (Scheme 7).14
CeH acids. The action of free halogen or active halogen con-
taining compounds on the equal amounts of benzylidene- or
alkylidenemalononitriles and malononitrile in basic alcohol
solutions results in the formation of 3-substituted 1,1,2,2-tetra-
cyanocyclopropanes in 65e95% yields. The latter are well-
known precursors for different bicyclic heterosystems, among
them containing cyclopropane ring19a,21 and possessing differ-
ent types of pharmacological activity.3,22 The new simple and
efficient way to 3-aryl substituted tetracyanocyclopropanes
was found starting from such simple and reasonable com-
pounds as benzylidenemalononitriles and malononitrile. The
procedure utilizes inexpensive reagents, it is easily carried
out and the work up is not complicated. 3-Aryl substituted-
1,1,2,2-tetracyanocyclopropanes are crystallized directly
from the reaction mixture, consequently, the isolation includes
only filtration and washing with warm water.
Compared to the MIRC method suggested by Hart and
Kim8 this new one uses equimolar amount of malononitrile
instead of the excess of bromomalononitrile. Thus, the stage
of bromomalononitrile synthesis is omitted. As compared
with the method of bromination and further intramolecular
cyclization of 2-substituted 1,1,3,3-tetracyanopropanes re-
ported by Mariella and Roth,14 it should be mentioned that
this method is known only for a few examples (only for three
2-alkyl substituted 1,1,3,3-tetracyanopropanes; alkyl¼methyl,
ethyl and n-propyl), which is connected with complexity of
the synthesis and isolation of 2-substituted 1,1,3,3-
tetracyanopropanes.
R1
R1
CN
Br2
NC
NC
NC
CN
CN
EtOH
CN CN
5
6
60-90%
R
1 = Me, Et, n-Pr
Scheme 7.
Taking into consideration that anion A exists in alcoholic
solutions in equilibrium with benzylidene- or alkylidenemalo-
nonitrile 1 and anion of malononitrile B20 the following alter-
native mechanism of tetracyanocyclopropanes 3 formation
could also take place (Scheme 8).
R2
R1
CN
CN
CN
R1
R2
NC
_
CN
CN
_
C
C
+
CN CN
A
R3OH
1
B
4. Experimental section
4.1. General remarks
XHal
R2
R1
All melting points were measured with a Gallenkamp melt-
1
CN
CN
R1
R2
ing point apparatus and are uncorrected. H and 13C NMR
CN
CN
NC
NC
CN
CN
Hal
+
C
C
R3OH
spectra were recorded with Bruker AC-200, Bruker WM-
250, and Bruker AC-300 spectrometers at ambient tempera-
ture. Chemical shifts values are relative to Me4Si. IR spectra
were registered with a SPECORD M82 spectrometer in KBr
pellets. Mass-spectra (EI¼70 eV) were obtained directly
with a Finningan MAT INCOS 50 spectrometer.
1
3
O
N
R3=Me, Et
X=I, Br,
Hal = I, Br
O
Scheme 8.
4.2. Typical procedure
The last step of the Scheme 8 mechanism corresponds to
tetracyanocyclopropane synthesis reported by Hart and Kim
(Scheme 2),8,9 which includes addition of the 1.3e3.0 equiv
excess of bromomalononitrile to alkylidene-, benzylidene- and
a-arylalkylidenemalononitriles in 50e95% aqueous ethanol
with formation of substituted 1,1,2,2-tetracyanocyclopropanes
in 30e90% yields.
To a 10 mL ethanol solution of benzylidenemalononitrile 1
(10 mmol) and malononitrile 2 (10 mmol) in a 50 mL beaker,
12 mmol of base in 10 mL of ethanol was added for 1 min.
Then 10 mmol of halogen or N-bromsuccinimide was added
without cooling. The mixture was magnetically stirred at
room temperature for 3 h. Then solid phase was filtered off,
washed with warm water, and dried in desiccator over P2O5
to isolate pure 3aen.
3. Conclusions
All compounds (3aen) gave expected NMR spectra. For
new compounds (3f,k), satisfactory elemental analyses,
mass, and IR spectroscopy data were obtained.
Thus, the new reaction was found, namely the direct forma-
tion of cyclopropane structures from activated olefins and

712
M.N. Elinson et al. / Tetrahedron 64 (2008) 708e713
4.2.1. 3-Phenyl-1,1,2,2-tetracyanocyclopropane (3a)
White solid. Yield 2.07 g (95%); m p 229e230 ꢀC (ace-
toneehexane); lit. mp9 227e230 ꢀC; dH (250 MHz, DMSO-d6)
5.10 (1H, s, CH), 7.48e7.80 (5H, m, Ar).
4.2.7. 3-(2-Chlorophenyl)-1,1,2,2-tetracyanocyclo-
propane (3g)
White solid. Yield 1.99 g (79%); mp 245e247 ꢀC (ace-
toneehexane); lit. mp9 246e248 ꢀC; dH (250 MHz, DMSO-d6)
5.47 (1H, s, CH), 7.50e7.65 (2H, m, Ar), 7.72 (1H, d,
J 7.8 Hz, Ar), 8.06 (1H, d, J 7.5 Hz, Ar).
4.2.2. 3-(4-Methylphenyl)-1,1,2,2-tetracyanocyclo-
propane (3b)
White solid. Yield 1.95 g (84%); mp 226e227 ꢀC (ace-
toneehexane); lit. mp9 227e230 ꢀC; dH (250 MHz, DMSO-d6)
2.31 (3H, s, CH3), 5.20 (1H, s, CH), 7.28 (2H, d, J 8.0 Hz,
Ar), 7.65 (2H, d, J 8.0 Hz, Ar).
4.2.8. 3-(3-Chlorophenyl)-1,1,2,2-tetracyanocyclo-
propane (3h)
White solid. Yield 1.82 g (72%); mp 187e189 ꢀC (ace-
toneehexane); lit. mp9 183e185 ꢀC; dH (250 MHz, DMSO-d6)
5.37 (1H, s, CH), 7.50e7.60 (2H, m, Ar), 7.82 (1H, d,
J 3.7 Hz, Ar), 8.09 (1H, s, Ar).
4.2.3. 3-(2-Methoxyphenyl)-1,1,2,2-tetracyanocyclo-
propane (3c)23
4.2.9. 3-(4-Chlorophenyl)-1,1,2,2-tetracyanocyclo-
propane (3i)
White solid. Yield 2.20 g (87%); mp 250e251 ꢀC (acetonee
hexane); lit. mp9 248e250 ꢀC; dH (300 MHz, DMSO-d6) 5.28
(1H, s, CH), 7.59 (2H, d, J 8.5 Hz, Ar), 7.88 (2H, d, J 8.5 Hz, Ar).
White solid. Yield 2.21 g (89%); mp 240e241 ꢀC (ace-
toneehexane); dH (250 MHz, DMSO-d6) 3.89 (3H, s, OCH3),
5.04 (1H, s, CH), 7.05 (1H, t, J 7.5 Hz, Ar), 7.19 (1H, d,
J 8.3 Hz, Ar), 7.48 (1H, t, J 7.9 Hz, Ar), 7.76 (1H, d,
J 7.5 Hz, Ar); dC (75 MHz, DMSO-d6) 23.6, 38.9, 56.5,
110.1, 111.4, 112.1, 115.2, 121.1, 130.5, 132.2, 157.9; MS
(70 eV) m/z (relative intensity %): 248 ([Mþ], 100), 233
(58), 221 (57), 206 (36), 194 (17), 178 (26), 156 (28), 114
(57), 91 (67), 77 (43); IR (KBr): nmax 2262, 1604, 1436,
1253, 764 cmꢁ1; C14H8N4O: calcd (%) C 67.74, H 3.25, N
22.57, found (%): C 67.62, H 3.12, N 22.38.
4.2.10. 3-(2,4-Dichlorophenyl)-1,1,2,2-tetracyano-
cyclopropane (3j)
White solid. Yield 1.87 g (65%); mp 226e228 ꢀC (ace-
toneehexane); lit. mp9 225e228 ꢀC; dH (300 MHz, DMSO-d6)
5.48 (1H, s, CH), 7.66 (1H, dd, J1 8.5, J2 2.0 Hz, Ar),
7.93 (1H, d, J 2.0 Hz, Ar), 8.10 (1H, d, J 8.5 Hz, Ar).
4.2.11. 3-(3-Bromophenyl)-1,1,2,2-tetracyanocyclo-
propane (3k)
4.2.4. 3-(3-Methoxyphenyl)-1,1,2,2-tetracyanocyclo-
propane (3d)
White solid. Yield 2.28 g (92%); mp 227e229 ꢀC (ace-
toneehexane); lit. mp19a 227e230 ꢀC; dH (200 MHz, DMSO-
d6) 3.76 (3H, s, OCH3), 5.28 (1H, s, CH), 7.15e7.45 (4H,
m, Ar).
White solid. Yield 2.02 g (68%); mp 186e187 ꢀC (ace-
toneehexane); dH (250 MHz, DMSO-d6) 5.31 (1H, s, CH),
7.44 (1H, t, J 8.5 Hz, Ar), 7.68 (1H, d, J 8.5 Hz, Ar), 7.87
(1H, d, J 8.5 Hz, Ar), 8.22 (1H, s, Ar); dC (75 MHz, DMSO-
d6) 23.4, 40.6, 109.5, 110.9, 121.9, 128.8, 129.5, 131.1,
132.6, 132.9; MS (70 eV) m/z (relative intensity %): 298
(Mþ, 12), 296 (Mþ, 11), 234 (6), 232 (6), 217 (99), 190
(100), 153 (56), 126 (87), 100 (39), 89 (60); IR (KBr): nmax
2268, 1568, 1484, 780, 692 cmꢁ1; C13H5BrN4: calcd (%) C
52.55, H 1.70, Br 26.89, N 18.86, found (%): C 52.39, H
1.86, Br 26.72, N 18.70.
4.2.5. 3-(4-Methoxyphenyl)-1,1,2,2-tetracyanocyclo-
propane (3e)
White solid. Yield 1.86 g (75%); mp 208e210 ꢀC (ace-
toneehexane); lit. mp22 209e210 ꢀC; dH (250 MHz, DMSO-
d6) 3.77 (3H, s, OCH3), 5.12 (1H, s, CH), 7.02 (2H, d,
J 8.9 Hz, Ar), 7.71 (2H, d, J 8.9 Hz, Ar).
4.2.12. 3-(4-Nitrophenyl)-1,1,2,2-tetracyano-
cyclopropane (3l)
4.2.6. 3-(4-Fluorophenyl)-1,1,2,2-tetracyanocyclo-
propane (3f)
White solid. Yield 1.87 g (71%); mp 232e234 ꢀC (ace-
toneehexane); lit. mp9 232e235 ꢀC; dH (250 MHz, DMSO-d6)
5.52 (1H, s, CH), 8.20 (2H, d, J 8.8 Hz, Ar), 8.35 (2H, d,
J 8.8 Hz, Ar).
White solid. Yield 1.91 g (81%); mp 216e217 ꢀC (ace-
toneehexane); dH (250 MHz, DMSO-d6) 5.23 (1H, s, CH),
7.34 (2H, t, J 8.5 Hz, Ar), 7.89 (2H, dd, J1 8.5, J2 5.4 Hz,
Ar); dC (75 MHz, DMSO-d6) 23.8, 41.5, 109.9, 111.4, 116.5
4.2.13. 3-Propyl-1,1,2,2-tetracyanocyclopropane (3m)
White solid. Yield 1.55 g (84%); mp 136e138 ꢀC (ace-
toneehexane); lit. mp19a 136e138 ꢀC; dH (200 MHz, CDCl3)
1.13 (3H, t, J 7.3 Hz, CH3), 1.60e1.85 (2H, m, CH2), 1.94
(2H, q, J 7.3 Hz, CH2) 2.78 (1H, t, J 7.3 Hz, CH).
2
4
3
(d, JCF 21.8 Hz), 123.7 (d, JCF 3.0 Hz), 132.6 (d, JCF
1
8.6 Hz), 163.3 (d, JCF 246.3 Hz); dF (282 MHz, DM
SO-d6) ꢁ111.5 to ꢁ111.6 (m); MS (70 eV) m/z (relative inten-
sity %): 236 ([Mþ], 24), 209 (66), 182 (16), 172 (34), 159
(19), 145 (46), 121 (49), 108 (100); IR (KBr): nmax 2264,
1604, 1512, 1220, 848 cmꢁ1; C13H5FN4: calcd (%) C 66.10,
H 2.13, F 8.04, N 23.72, found (%): C 65.89, H 2.28, F
7.86, N 23.41.
4.2.14. 1,1,2,2-Tetracyanospiro[2.5]octane (3n)
White solid. Yield 1.58 g (75%); mp 178e180 ꢀC (ace-
toneehexane); lit. mp8 177e179 ꢀC; dH (200 MHz, DMSO-d6)

M.N. Elinson et al. / Tetrahedron 64 (2008) 708e713
713
7. (a) Widman, O. Ber. 1918, 51, 533e541; (b) Westoo, G. Acta Chem.
Scand. 1959, 13, 683e688; (c) Warner, D. T. J. Org. Chem. 1959, 24,
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1.45e1.55 (2H, m, CH2), 1.60e1.75 (4H, m, 2CH2),
1.80e1.95 (4H, m, 2CH2).
Acknowledgements
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The authors gratefully acknowledge the financial support of
the Presidential Scholarship Program for State Support of
Leading Science Schools of Russian Federation (Project No.
5022.2006.3).
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