Synthesis of cyclopropane-1,1,2,2-tetracarboxylic acid derivatives from aldehydes and CH-acids in the K2CO3/Bun 4NPF6/toluene heterogeneous system

Article abstract of DOI:10.1007/s11172-011-0349-7

A one-pot method for the synthesis of cyclopropane-1,1,2,2-tetracarboxylic derivatives was developed starting from aldehydes and cyanoacetic and 2-bromomalonic esters under heterogeneous conditions (K₂CO ₃/PhMe) in the presence of re

Full text of DOI:10.1007/s11172-011-0349-7

2286
Russian Chemical Bulletin, International Edition, Vol. 60, No. 11, pp. 2286—2290, November, 2011
Synthesis of cyclopropaneꢀ1,1,2,2ꢀtetracarboxylic acid derivatives
n
from aldehydes and CHꢀacids in the K CO /Bu NPF /toluene
2
3
4
6
heterogeneous system*
G. V. Kryshtal, G. M. Zhdankina, and S. G. Zlotin
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
4
7 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328. Eꢀmail: zlotin@ioc.ac.ru
A oneꢀpot method for the synthesis of cyclopropaneꢀ1,1,2,2ꢀtetracarboxylic derivatives was
developed starting from aldehydes and cyanoacetic and 2ꢀbromomalonic esters under heteroꢀ
geneous conditions (K CO /PhMe) in the presence of recoverable phaseꢀtransfer catalyst
2
3
n
Bu 4NPF6.
Key words: cyclopropanation, phaseꢀtransfer catalysis, ionic liquids.
Cyclopropanecarboxylic acid derivatives possess bioꢀ
logical activities (antibacterial, insecticide, acaricide, funꢀ
Scheme 1
1
,2
2b,3
gicide, etc.) and are used in medicine,
and agriꢀ
culture.2 In addition, a possibility of modification of
c,e
functional groups and the presence strained small ring
1
,4,5
make them important synthons in organic synthesis.
A baseꢀpromoted domino reaction between CHꢀacids conꢀ
taining a halogen atom at the nucleophilic carbon atom
and electronꢀdeficient alkenes is a convenient method for
their preparation. This reaction, commonly known as the
Michael initiated ring closure (MIRC),6 includes 1,4ꢀaddiꢀ
tion of αꢀhalogenated CHꢀacid anion A to alkene B and
subsequent intramolecular substitution for the halogen
atom (bromine or chlorine) in the intermediate C with the
formation of cyclopropane D (see Ref. 6, Scheme 1). Such
an approach has been used for the synthesis of cycloproꢀ
panes bearing various electronꢀwithdrawing substituents
a
i. The Michael reaction. ii. Cyclization.
8
its application limited. Recently, cyclopropanecarboxylic
(
EWG = CHO, COR, CO R, CN, C(O)NR , NO , etc.).
2 2 2
7
derivatives have been successfully obtained by a sequence of
the Knoevenagel reaction and MIRC involving two differꢀ
ent CHꢀacids, however this required prolonged heating the
The Knoevenagel adducts obtained from aldehydes
and malonic, acetoacetic, cyanoacetic, or nitroacetic deꢀ
rivatives are usually used as electrophiles B. In some casꢀ
es, the Knoevenagel reaction and MIRC can be carried
out in one vessel as a threeꢀcomponent process involving
one carbonyl component and two CHꢀacids (one of them
should bear a halogen atom). Thus, electrolysis of two
equivalents of malononitrile (or ethyl cyanoacetate) and
a ketone (aldehyde) in ethanolic NaBr in EtOH leads to
cyclopropanepolycarboxylic derivatives (in this case, the
bromo derivative A is generated in situ from a CHꢀacid
and NaBr), however, in such a procedure one cannot use
a mixture of different CHꢀacids, which makes the range of
9
10
components in the presence of piperidine or pyridine.
We suggest a new, mild, and efficient method for the
threeꢀcomponent synthesis of cyclopropanes under heteroꢀ
geneous conditions (K CO —toluene) in the presence
2
3
of fluorineꢀcontaining phaseꢀtransfer catalyst (PTC)
n
Bu NPF , an analog of ionic liquids. In the literature,
4
6
there are examples when ionic liquids are used as solvents
1
1,12
and acidꢀbase catalysts of the Knoevenagel reaction
1
3
and MIRC, however, they have not been used earlier in
these reactions as PTC.
First of all, we studied a K CO ꢀinduced condensation
2
3
*
Dedicated to Academician of the Russian Academy of Sciences
of benzaldehyde (1a) with ethyl cyanoacetate (2) without
O. M. Nefedov on the occasion of his 80th birthday.
PTC and in the presence of tetraalkylammonium or
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2244—2247, November, 2011.
066ꢀ5285/11/6011ꢀ2286 © 2011 Springer Science+Business Media, Inc.
1

Cyclopropanetetracarboxylates
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 11, November, 2011 2287
Scheme 2
of PTC, however, addition of an ammonium salt (5 mol.%)
to the system gives product 3a, whose yield was the highest
(
89%) in the case of tetrabutylammonium hexafluorophosꢀ
n
phate Bu NPF (see Refs 14 and 15). It is important that
4
6
this PTC, being poorly soluble in toluene and water, is easy
separated from the product and can be used no less than
three times with the same efficiency (see Table 1, entry 5).
We found that in the same heterogeneous system, the
Knoevenagel adduct 3a with diethyl bromomalonate (4)
gives cyclopropane 5a in 98% yield, exceeding the yields
reported in the literature (62% in the system K CO /
2
3
1
6
17
DMF/BTEAꢀCl, 82% during electrolysis ). The idenꢀ
tical conditions allows us to synthesize product 5a from
compounds 1a, 2, and 4 excluding the step of isolation of
the intermediate 3a. After the Knoevenagel reaction
reached completion, bromomalonate 4 was added to the
reactor to furnish 5a in 94% yield calculated from the
introduced aldehyde 1a.
Reagents, conditions, and yields: i. NCCH CO Et (2), K CO /PTC
2
2
2
3
(
5 mol.%), PhMe, 20 °C, 4 h; ii. BrCH(CO Et) (4), K CO /
2 2 2 3
n
Bu NPF (5 mol.%), PhMe, 20 °C, 4.5 h, the yield was 98%;
iii. 1) NCCH CO Et (2), 2) BrCH(CO Et) (4), K CO /Bu NPF
4
6
n
2
2
2
2
2
3
4
6
(
5 mol.%), PhMe, 20 °C, the yield was 94%.
It turned out that various (aromatic, heteroaromatic,
and aliphatic) aldehydes 1a—i, including prenylꢀcontainꢀ
ing ones 1d—f, can be involved into the tandem sequence
of the Knoevenagel reaction and MIRC under conditions
found. The corresponding cyclopropane derivatives were
obtained in high yields (Scheme 3, Table 2). Depending
on the ratio of components, dialdehyde 1g forms products
Table 1. Optimization of conditions for the synthesis of 3a
from benzaldehyde (1a) and ethyl cyanoacetate (2)
Entry
PTC
Yield (%) (cycle)
a recovered catalyst
3
1
2
3
4
5
—
0
—
0
0
55
BnEt NCl
82
86
97
3
[bmim]BF
Bu 4NBF4
Bu 4NPF6
4
Scheme 3
n
n
97 (1),
8 (2), 98 (3)
96 (1), 95 (2),
95 (3)
9
ꢀbutylꢀ3ꢀmethylimidazolium salts with the Cl , BF4–, and
–
1
–
PF6 anions. The reactions were carried out under compaꢀ
rable conditions (toluene, 20 °C, 4 h) (Scheme 2, Table 1).
It turned out that the reaction does not occur in the absence
Reagents and conditions: i. 1) NCCH CO Et (2), 2) BrCH(CO Et) (4),
2
2
2
2
n
K CO /Bu NPF (5 mol.%), PhMe, 20 °C.
2
3
4
6
Table 2. Oneꢀpot synthesis of cyclopropanetetracarboxylic acid derivatives 5a—j
Entry
1
R
τ/h
5
Yield of 5 (%)
Step 1
Step 2
1
2
3
4
5
6
7
8
9
a
b
c
d
e
f
g
h
i
Ph
4.0
3.0
30.0
2.0
2.0
8.0
2.0
2.5
9.0
10.0
3
6
8
a
b
c
d
e
f
94
89
a
4ꢀO NC H
4
2
6
b
4ꢀMeOC H
91
95
88
6
4
Me C=CH
4
2
a
Me C=CH(CH ) C(Me)=CH
12
12
7
5
6
2
2 2
Me CHCH
4ꢀOCHC H
2ꢀFuryl
2ꢀThienyl
85
91
2
2
a
g
h
i
6
4
94
91
95
c
10
g
4ꢀOCHC H
15
j
6
4
a
b
c
The reaction was carried out in the presence of PTC recovered from the preceding experiment.
The first step of the reaction was carried out at 45 °C.
Compound 5j was obtained at the molar ratio of reagents 1 : 2 : 4 = 1 : 2 : 2.

2288
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 11, November, 2011
Kryshtal et al.
n
5
g and 5j containing one or two cyclopropane rings. In
(1.0 g, 0.5 mmol), K2CO3 (0.7 g, 0.5 mmol), and Bu 4NPF6 (0.1 g,
5
mol.%) in toluene (2.0 mL) with vigorous stirring. The reꢀ
action mixture was stirred at 20 °C for 4.5 h (TLC moniꢀ
toring) and diluted with water, the catalyst was filtered off,
the filtrate was extracted with Et O (2×5 mL). The comꢀ
bined organic extract was washed with water (20 mL) and
dried with MgSO , the solvent was evaporated at reduced
pressure (40 °C, 40 Torr). A crude product was purified
this case, efficiency of the reactions do not decrease if they
are carried out in the presence of PTC recovered from the
preceding experiments (see Table 2, entries 2, 5, and 7).
The NMR data show that the process is stereoselecꢀ
tive. A mutual Eꢀarrangement of the substituent R and the
ester group in the known products1
2
4
6—19
5a,c (data for the
trimethyl ester are given in Ref. 17) and 5d,e (see Ref. 16)
on a column with SiO , eluting sequentially with nꢀhexane
2
was confirmed by comparison of chemical shifts for the
and its mixture with EtOAc to obtain 5a (1.75 g, 98%) as
a colorless oil.
1
proton of the cyclopropane ring H with the δ values for
1
Synthesis of compounds 5a—j from 1a—i. A mixture of comꢀ
pounds 1 (0.5 mmol), 2 (0.57 g, 0.5 mmol), K CO (0,7 g,
the known compounds. Thus, the value δ = 3.93 in the
H
1
product 5a agrees with the value δ
for compound
2
3
H
n
Eꢀ5a1
7,19
0.5 mmol), and Bu 4NPF6 (0.1 g, 5 mol.%) in toluene (2.0 mL)
was vigorously stirred at the indicated temperature (see Table 2,
step 1) until 1 disappeared (TLC monitoring), after which
a solution of 4 (1.2 g, 0.5 mmol) in toluene (2.0 mL) was addꢀ
ed, and the stirring was continued at the indicated temperaꢀ
ture (see Table 2, steps 2 and 3, TLC monitoring). Then, the
reaction mixture was diluted with water, the catalyst was filꢀ
tered off, the filtrate was extracted with Et2O (2×5 mL). The
combined organic extract was washed with water (20 mL) and
and differs from the corresponding value for isoꢀ
mer Zꢀ5a (δ 4.01).19 The new compounds 5b,f—j, which
1
13
were characterized by the IR, H and C NMR spectral
data and microanalytical data, were assigned the structure
of Eꢀisomers by analogy. Compound 5e consists of two
isomers differing in configuration of the double bond in
the isoprenoid group, since commercially available mixꢀ
ture of Eꢀ and Zꢀcitrals 65/35 was used for the synthesis of
the starting aldehyde 1e.
dried with MgSO , the solvent was evaporated at reduced presꢀ
4
sure (40 °C, 40 Torr). A crude product was purified on a column
In conclusion, we suggested simple and efficient proꢀ
cedure for the synthesis of cyclopropaneꢀ1,1,2,2ꢀtetracarꢀ
boxylic derivatives from aldehydes and cyanoacetic and
with SiO , eluting sequentially with nꢀhexane and the nꢀhexꢀ
2
ane—EtOAc solvent mixture. The yields of products 5a—j are
given in Table 2. Physicochemical properties, the IR specꢀ
2ꢀbromomalonic esters under heterogeneous conditions
1
13
tral data, H and C NMR spectral data, as well as results of
elemental analysis of the newly synthesized compounds 5 are
given below.
(
K CO /PhMe) in the presence of recoverable PTC
2
3
n
Bu NPF .
4
6
Triethyl (E)ꢀ2ꢀcyanoꢀ3ꢀphenylcyclopropaneꢀ1,1,2ꢀtricarbꢀ
oxylate (5a). A colorless oil, nD20 1.5040. H NMR, δ: 1.09, 1.31
and 1.39 (all t, 3 H each, 3 Me, J = 7.0 Hz); 3.93 (s, 1 H, CH);
1
Experimental
4
.13, 4.26 and 4.34 (all q, 2 H each, 3 OCH , J = 7.0 Hz);
2
1H and 13C NMR spectra were recorded on a Bruker AMꢀ300
spectrometer (300.13 and 75.47 MHz, respectively) in CDCl3.
IR spectra were recorded on a Specord Mꢀ82 spectrometer. Eleꢀ
mental analysis was performed on a Perkin—Elmer 2400 microꢀ
analyzer. Reaction progress was monitored by TLC on Silufol
plates (eluent: nꢀhexane—EtOAc, 8 : 2, visualization with the
7.27—7.40 (m, 5 H, Ph).
Triethyl (E)ꢀ2ꢀcyanoꢀ3ꢀ(4ꢀnitrophenyl)cyclopropaneꢀ1,1,2ꢀ
tricarboxylate (5b). A light yellow powder, m.p. 123—124 °C. IR
ꢀ
1
(KBr), ν/cm : 1352, 1556 (NO ); 1755 (C=O); 2249 (CN).
2
1
H NMR, δ: 1.16, 1.32 and 1.41 (all t, 3 H each, 3 Me, J = 7.0 Hz);
3.97 (s, 1 H, CH); 4.18, 4.29 and 4.37 (all q, 2 H each, 3 OCH2,
UV light and I vapors). Purification of products was performed
by column chromatography on silica gel (Acros, 0.060—0.200 mm).
J = 7.0 Hz); 7.60 (d, 2 H, Ar, J = 8.8 Hz); 8.25 (d, 2 H, Ar,
2
13
J = 8.8 Hz). C NMR, δ: 13.7, 13.9, 14.0, 30.8, 38.1, 47.6, 63.1,
63.4, 64.6, 112.9, 123.9, 129.9, 137.1, 147.9, 162.1, 163.3, 163.7.
Found (%): C, 56.62; H, 4.87; N, 6.85. C H N O . Calculatꢀ
Aldehydes 1a—i, ethyl cyanoacetate (2), diethyl bromomalonate
n
ester (4), catalysts Bu 4NBF , [bmim]BF , BnEt NCl, and
4
4
3
19 20
2
8
n
K CO (Acros) were used as purchased. The Bu NPF catalyst
was synthesized according to the known method.
ed (%): C, 56.43; H, 4.99; N, 6.93.
2
3
4
1
6
5
Triethyl (E)ꢀ2ꢀcyanoꢀ3ꢀ(4ꢀmethoxyphenyl)cyclopropaneꢀ
1,1,2ꢀtricarboxylate (5c). A white powder, m.p. 74—75 °C.
Optimization of the Knoevenagel reaction conditions. A mixꢀ
ture of compounds 1a (1.06 g, 1 mmol), 2 (1.13 g, 1 mmol),
K CO (1.38 g, 1 mmol), and a catalyst (5 mol.%) (see Table 1)
1
H NMR, δ: 1.15, 1.31 and 1.39 (all t, 3 H each, 3 Me, J = 7.0 Hz);
3.80 (s, 3 H, OMe); 3.87 (s, 1 H, CH); 4.17, 4.28 and 4.34 (all q,
2
3
in toluene (3.0 mL) was vigorously stirred for 4 h at 20 °C. The
2 H each, 3 OCH , J = 7.0 Hz); 6.89 (d, 2 H, Ar, J = 8.8 Hz);
7.30 (d, 2 H, Ar, J = 8.8 Hz).
2
n
n
reaction mixture was diluted with water (if Bu NPF or Bu NBF
4
6
4
4
were used, the catalyst was filtered off) and extracted with Et O
Triethyl (E)ꢀ2ꢀcyanoꢀ3ꢀ(2ꢀmethylpropenyl)cyclopropaneꢀ
1,1,2ꢀtricarboxylate (5d). A colorless oil, nD20 1.4745. H NMR,
δ: 1.25, 1.27 and 1.32 (all t, 3 H each, 3 Me, J = 7.0 Hz); 1.79
2
1
(
(
2×5 mL). The combined organic extract was washed with water
20 mL) and dried with MgSO , the solvent was evaporated at
4
reduced pressure (40 °C, 40 Torr). A crude product was purified
and 1.81 (both s, 3 H each, Me C); 3.34 (d, 1 H, CH, J = 8.1 Hz);
2
on a column with SiO , eluting sequentially with nꢀhexane and
4.17, 4.25 and 4.27 (all q, 2 H each, 3 OCH , J = 7.0 Hz); 5.19
2
2
its mixture with EtOAc. The yields of 3a and amount of recovꢀ
(m, 1 H, CH).
ered catalyst (Bun NPF was reused in two more reaction cycles)
Triethyl (E)ꢀ2ꢀcyanoꢀ3ꢀ(2,6ꢀdimethylheptaꢀ1,5ꢀdienyl)cycloꢀ
propaneꢀ1,1,2ꢀtricarboxylate (5e) (a mixture of Z/Eꢀisomers
4
6
are given in Table 1.
2
0
Synthesis of compound 5a from 3a. A solution of 4 (1.2 g,
.5 mmol) in toluene (2.0 mL) was added to a suspension of 3a
35/65 in the isoprenoid substituent R). A colorless oil, n
D
1
0
1.4800. H NMR, δ: 1.27, 1.28 and 1.34 (all t, 3 H each, 3 Me,

Cyclopropanetetracarboxylates
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 11, November, 2011 2289
J = 7.0 Hz); 1.59 and 1.69 (both s, 3 H each, Me C); 1.80
References
2
(
Zꢀisomer) and 1.82 (Eꢀisomer) (both s, Z/E = 35/65, 3 H, C(Me));
2
4
.10—2.25 (m, 4 H, 2 CH ); 3.33—3.40 (m, 1 H, CH); 4.22,
2
.26 and 4.29 (all q, 2 H each, 3 OCH , J = 7.0 Hz); 5.02—5.15
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2
13
(
1
m, 1 H, CH); 5.22 (d, 1 H, CH, J = 8.1 Hz). C NMR, δ:
3.8, 13.9, 14.0 (all MeCH O); 17.4 and 26.3 (Me C); 17.6
2
2
and 25.6 (C(Me)); 23.7 (CH ); 31.3 and 39.5 (CH ); 33.0,
3
2
2
5.3, 47.5 (all Ccycle); 62.6, 62.9, 63.8 (all OCH ); 112.6
2
(
CN); 123.2 and 123.4 ((Me)C=CH); 129.8 (Me C=CH);
2
1
32.5 (Me C); 146.7 and 146.8 (C(Me)); 162.7, 163.8, 164.3
2
(
all C=O).
Triethyl (E)ꢀ2ꢀcyanoꢀ3ꢀisobutylcyclopropaneꢀ1,1,2ꢀtricarbꢀ
43, 2286; (d) B. D. Zlatopolskiy, K. Loscha, P. Alvermann,
2
0
–1
oxylate (5f). A colorless oil, nD 1.4550. IR (neat), ν/cm
748 (C=O), 2256 (CN). H NMR, δ: 0.94 and 0.98 (both d,
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1
1
3
3
H each, 2 Me, J = 6.6 Hz); 1.23, 1.27 and 1.31 (all t, 3 H each,
Me, J = 7.0 Hz); 1.63—1.81 (m, 3 H, CH , CH); 2.59 (t, 1 H,
2
CH, J = 7.0 Hz); 4.16, 4.24 and 4.26 (all q, 2 H each, 3 OCH ,
2
13
J = 7.0 Hz). C NMR, δ: 13.6, 13.7, 13.8, 21.8, 21.9, 27.5, 30.5,
5.0, 38.1, 46.5, 62.3, 62.7, 63.5, 112.8, 163.0, 163.9, 164.2.
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3
17
25
6
ed (%): C, 60.16; H, 7.42; N, 4.13.
Triethyl (E)ꢀ2ꢀcyanoꢀ3ꢀ(4ꢀformylphenyl)cyclopropaneꢀ1,1,2ꢀ
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tricarboxylate (5g). A colorless oil, nD20 1.5125. IR (neat), ν/cm
1
–1
:
1
700 (C=O); 1748 (C=O); 2252 (CN). H NMR, δ: 1.12, 1.31
and 1.39 (all t, 3 H each, 3 Me, J = 7.0 Hz); 3.96 (s, 1 H, CH);
.15, 4.29 and 4.35 (all q, 2 H each, 3 OCH , J = 7.0 Hz); 7.57
4
(
(
6
1
2
d, 2 H, Ar, J = 8.1 Hz); 7.89 (d, 2 H, Ar, J = 8.1 Hz); 10.01
s, 1 H, CHO). 13C NMR, δ: 13.8, 13.9, 14.1, 30.7, 38.6, 47.6,
2.9, 63.2, 64.3, 112.3, 129.4, 129.6, 129.9, 136.3, 163.0, 163.9,
64.2, 191.3. Found (%): C, 61.92; H, 5.53; N, 3.55. C H NO .
20
21
7
Calculated (%): C, 62.01; H, 5.46; N, 3.62.
Triethyl (E)ꢀ2ꢀcyanoꢀ3ꢀ(2ꢀfuryl)cyclopropaneꢀ1,1,2ꢀtricarbꢀ
2
0
–1
oxylate (5h). A colorless oil, nD 1.4818. IR (neat), ν/cm
:
1
1
3
4
752 (C=O); 2256 (CN). H NMR, δ: 1.24, 1.30 and 1.37 (all t,
H each, 3 Me, J = 7.0 Hz); 3.85 (s, 1 H, CH); 4.24, 4.26 and
.31 (all q, 2 H each, 3 OCH , J = 7.0 Hz); 6.39 (dd, 1 H, CH,
2
J = 3.3 Hz, J = 3.3 Hz); 6.54 (d, 1 H, CH, J = 3.3 Hz); 7.41
s, 1 H, CH). 13C NMR, δ: 13.7, 13.9, 14.0, 30.7, 33.1, 47.0,
3.1, 63.3, 64.2, 110.5, 111.0, 112.4, 162.0, 163.1, 163.6.
Found (%): C, 58.52; H, 5.41; N, 3.95. C H NO . Calculatꢀ
(
6
17
19
7
ed (%): C, 58.45; H, 5.48; N 4.01.
Triethyl (E)ꢀ2ꢀcyanoꢀ3ꢀ(2ꢀthienyl)cyclopropaneꢀ1,1,2ꢀtriꢀ
2
0
carboxylate (5i). A light yellow oil, n
1.5055. IR (neat),
D
–
1
1
ν/cm : 1752 (C=O); 2248 (CN). H NMR, δ: 1.20, 1.30 and
1
4
.38 (all t, 3 H each, 3 Me, J = 7.0 Hz); 3.96 (s, 1 H, CH); 4.23,
.27 and 4.33 (all q, 2 H each, 3 OCH , J = 7.0 Hz); 7.00 (dd, 1 H,
2
CH, J = 5.1 Hz, J = 3.7 Hz); 7.22 (dd, 1 H, CH, J = 3.7 Hz,
J = 1.1 Hz); 7.31 (dd, 1 H, CH, J = 5.1 Hz, J = 1.1 Hz).
C NMR, δ: 13.7, 13.9, 14.0, 31.9, 34.9, 48.4, 63.0, 63.2, 64.2,
13
7. Y.ꢀF. Han, M. Xia, Curr. Org. Chem., 2010, 14, 379.
8. (a) G. I. Nikishin, M. N. Elinson, T. L. Lizunova, B. I.
Ugrak, Tetrahedron Lett., 1991, 32, 2655; (b) M. N. Elinson,
T. L. Lizunova, B. I. Ugrak, M. O. Dekaprilevich, G. I.
Nikishin, Tetrahedron Lett., 1993, 34, 5795.
1
12.5, 126.6, 127.2, 128.0, 162.0, 163.3, 163.8. Found (%):
C, 55.81; H, 5.32; N, 3.87, S, 8.69. C H NO S. Calculatꢀ
17
19
6
ed (%): C, 55.88; H, 5.24; N, 3.83; S, 8.78.
Hexaethyl 3,3´ꢀ(1,4ꢀphenylene)bis[(E)ꢀ2ꢀcyanocyclopropꢀ
aneꢀ1,1,2ꢀtricarboxylate] (5j). A white powder, m.p. 187—188 °C.
IR (KBr), ν/cm–1: 1748 (C=O); 2252 (CN). H NMR, δ: 1.15,
9. M. F. A. Adamo, V. R. Konda, Tetrahedron Lett., 2008,
49, 6224.
1
1
.31 and 1.39 (all t, 3 H each, 3 Me, J = 7.0 Hz); 3.90 (s, 1 H,
10. C. G. Yan, X. K. Song, Q. F. Wang, J. Sun, U. Siemeling,
C. Bruhn, Chem. Commun, 2008, 1440.
11. (a) X. Xin, X. Guo, H. Duan, Y. Lin, H. Sun, Catal. Comꢀ
mun., 2007, 115; (b) F. Santamarta, P. Verdha, E. Tojo,
Catal. Commun., 2008, 1779; (c) Y. O. Sharma, M. S. Deꢀ
gani, Green Chem., 2009, 11, 526.
CH); 4.14, 4.26 and 4.34 (all q, 2 H each, 3 OCH , J = 7.0 Hz);
7
3
1
2
.42 (s, 4 H, Ar). 13C NMR, δ: 13.8, 13.9, 14.0, 30.7, 30.8, 38.7,
8.8, 47.8, 63.0, 63.2, 64.3, 112.6, 129.2, 130.4, 162.4, 163.7,
64.2. Found (%): C, 59.82; H, 5.80; N, 4.25. C H N O .
3
2
36
2
12
Calculated (%): C, 59.99; H, 5.66; N 4.37.

2290
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 11, November, 2011
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1
2. (a) Y. Liu, J. Peng, S. Zhai, J. Li, J. Mao, M. Li, H. Qiu,
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2
006, 47, 6951; (d) C. Yue, A. Mao, Y. Wei, M. Lü, Catal.
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1
1
1
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Received March 1, 2011;
in revised form July 4, 2011