[3+2] Cycloaddition of diazocarbonyl compounds to 1,1-dinitroethenes: Synthesis of functionalized gem-dinitrocyclopropanes

Article abstract of DOI:10.1055/s-2007-983727

The synthesis of functionalized gem-dinitrocyclopropanes via [3+2] cycloaddition of diazocarbonyl compounds with 1,1-dinitroethenes [in some cases in the presence of Mo(CO)₆ as catalyst] has been developed. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2007-983727

PAPER
2009
[3+2] Cycloaddition of Diazocarbonyl Compounds to 1,1-Dinitroethenes:
Synthesis of Functionalized gem-Dinitrocyclopropanes
Synthesis of the
F
u
l
nctiona
g
lized gem
-
D
a
initrocyclopropan
A
es . Ivanova,a,b Ekaterina M. Budynina,a Elena B. Averina,a Tamara S. Kuznetsova,*a,b Yurii K. Grishin,a
Nikolai S. Zefirova,b
a
Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1-3, Moscow 119992, Russian Federation
Fax +7(495)9390290
b
IPhaC RAS, Severnyi Proezd 1, Chernogolovka, Moscow Region 142432, Russian Federation
E-mail: kuzn@org.chem.msu.ru
Received 7 March 2007; revised 30 April 2007
Z1
R1
R2
Abstract: The synthesis of functionalized gem-dinitrocyclopro-
Z2
panes via [3+2] cycloaddition of diazocarbonyl compounds with
1,1-dinitroethenes [in some cases in the presence of Mo(CO)6 as
catalyst] has been developed.
– N2
a)
Z1
Z1
Z2
Z2
Z1
R1
R2
b) R1 = H
R1
R2
+
N2
Key words: [3+2] cycloaddition, a-diazocarbonyl compound, 1,1-
dinitroethene, 1,1-dinitrocyclopropane, hexacarbonylmolybdenum
HN
N
Z2
R2
N
N
c)
– HZ1
Z2
R
Z
1 = H,
1 = NO2,
CN, Hal
Polynitrocyclopropanes are of particular interest as a new
family of compounds with increased energy content and
high potential synthetic utility.1,2 Therefore, the develop-
ment of new methods for the synthesis of these unique
polyfunctionalized cyclopropanes is important. It is
known that the direct interaction of carbenes with elec-
tron-deficient alkenes does not generally result in the for-
mation of cyclopropanes.3a The reaction of diazo
compounds with electron-deficient alkenes proceeds as a
[3+2] cycloaddition (Scheme 1),3–6 depending on the
structure of the substrate employed, the resulting 1-pyra-
zolines can undergo the following transformations: (a) ni-
trogen elimination, by thermolysis or photolysis, followed
by cyclopropane formation; (b) tautomerization to 2-pyra-
zolines (for R1 = H); (c) elimination of HZ1 (Z1 = NO2,
CN, Hal) leading to aromatic pyrazole systems.3–6
HN
R2
N
Scheme 1
dinitrocyclopropane. However, our mechanistic picture
was in obvious contrast with the data of Fridman and co-
workers,7 who had reported that the reaction of 1,1-dini-
troethene with diazocarbonyl compounds leads to substi-
tuted nitropyrazoles without the formation of 1,1-
dinitrocyclopropane derivatives.
Thus, we decided to reinvestigate this [3+2]-cycloaddi-
tion process with the goal of finding a novel synthetic
route to 1,1-dinitrocyclopropane derivatives via [3+2] cy-
cloaddition of diazocarbonyl compounds to 1,1-dinitro-
ethenes.
Two alkenes, namely 1,1-dinitroethene (1)8 and b,b-dini-
trostyrene (2)9 were chosen as model gem-dinitroalkene
substrates for the reaction with diazo compounds. Taking
into consideration the instability of alkene 1, we generated
it in situ by spontaneous dehydration of 2,2-dinitroethanol
(3) (Scheme 2).8
Recently, we reported the first synthesis of the parent 1,1-
dinitrocyclopropane by reaction of trinitromethane with
diazomethane.2b Rationalization of this process includes
the intermediacy of 1,1-dinitroethene (1), which, in turn,
reacts with diazomethane through a [3+2] cycloaddition
to yield 3,3-dinitropyrazoline as the second intermediate.
The latter eliminates a molecule of nitrogen to form 1,1-
1) HNO3
CH2Cl2
KOH/H2O
H2CO
HO2CCH2CO2Me
KC(NO2)2CO2Me
KC(NO2)2H
2) KHCO3/H2O
53%
92%
4
5
H+
NO2
NO2
– H2O
KC(NO2)2CH2OH
HC(NO2)2CH2OH
81%
6
3
1
Scheme 2
SYNTHESIS 2007, No. 13, pp 2009–2013
x
x.
x
x
.
2
0
0
7
Advanced online publication: 18.06.2007
DOI: 10.1055/s-2007-983727; Art ID: Z05707SS
© Georg Thieme Verlag Stuttgart · New York

2010
O. A. Ivanova et al.
PAPER
While the multistep synthesis of 1,1-dinitroethene (1) is 1 or 2. Previously the formation of 10 was detected after
known,10 we improved some of its stages (see the experi- heating diazoacetate in pyridine.12 Phenylcyclopropanes
mental section).
8d,e were identified as mixtures of two diastereomers in
2.3:1 and 9:1 ratio, respectively. This is due to the stereo-
selectivity of the cyclopropane formation reaction. Ac-
cording to the NMR data, the stereochemistry of the major
product has been assigned as having a trans arrangement
of the phenyl group and the functional group and the mi-
nor product has been referred to as the cis-isomer
(Figure 1).
We have found, that the reaction of both 1,1-dinitro-
ethenes 1 and 2 with diazocarbonyl compounds 7a–c,
containing a hydrogen atom in the a-position, leads to
mixtures of the corresponding 1,1-dinitrocyclopropanes
8a–e and nitropyrazoles 9a–e in various ratios (Table 1).
We also studied the influence of hexacarbonylmolybde-
num on the route of the reaction of dinitroalkenes 1 and 2
with diazocarbonyl compounds 7a–c. This catalyst was
proposed by Doyle et al. for the reactions of ethyl diazo-
acetate or a-diazoacetophenone with a,b-unsaturated
compounds to increase the yields of the corresponding cy-
clopropane derivatives.11a,b In the absence of this catalyst
2-pyrazolines are the main products of these reactions.11c
The reactions of dinitroalkenes with disubstituted diazo
compounds are less selective compared to monosubstitut-
ed diazo compounds. In fact, the reaction of 1,1-dinitro-
ethene (1) with disubstituted diazo compounds 7d–f leads
to a complex mixture of products and dinitrocyclopro-
panes 8f–h were isolated in moderate yields only after
column chromatography (Table 2).
According to the data presented in Table 1, the yields and
the ratio of the products in the reaction of 1,1-dinitro-
ethene (1) and ethyl diazoacetate (7a) do not notably de-
pend on the use of the catalyst. At the same time, the result
The molecular structures of 8a–h and 9a–e were also un-
ambiguously proved by 1H and 13C NMR spectra (see ex-
perimental section).
of the reaction of dinitroalkenes 1 and 2 with a-diazoace- The vicinal spin–spin coupling constants for rigid three-
tophenone (7b) depends dramatically on the presence of membered rings have a distinct Karplus-type dependence
the catalyst. Thus, the use of hexacarbonylmolybdenum on the dihedral angle13a as it shown previously for mono-
affords dinitrocyclopropanes 8b and 8e as main products substituted cyclopropane compounds.13b,c We have found
in good yields.
that the values of the coupling constants 3Jcis and 3Jtrans of
polysubstituted dinitrocyclopropanes 8a–e are also signif-
icantly different: J = 10.4–12.1 and 9.1–9.9 Hz, respec-
It is worth noting that tetraethyl 1H-pyrrole-2,3,4,5-tetra-
carboxylate (10) was formed as a byproduct (5–10%
yield) in the reaction of diazoacetate 7a with dinitroalkene
3
tively; thus we were able to distinguish the isomers of
Table 1 Reaction of 1,1-Dinitroethenes with Diazocarbonyl Compounds Containing an a-Hydrogen
R1
R1
O2N
NO2
NO2
H
O2N
O2N
H
+
N2
+
N
R2
R1
R2
N
R2
H
1, 2
7a–c
8a–e
9a–e
1,2
7
8,9
R1
R2
Mo(CO)6,
(mol%)
Solvent
Temp
(°C)
Time
(h)
Yielda
(%)
8
9
1
1
1
1
1
1
2
2
2
2
a
a
b
b
c
a
a
b
b
c
H
CO2Et
CO2Et
COPh
COPh
COMe
COMe
CO2Et
CO2Et
COPh
COPh
–
4
Et2O
reflux
reflux
55–60
60–65
60
19
19
6
35
37
30
71
42
54
12
41
28
70
41
40
40
25
38
38
55
44
58
15
H
Et2O
H
–
benzene
benzene
benzene
benzene
benzene
benzene
benzene
benzene
H
5
10b
6
H
–
c
c
H
5
40–45
reflux
reflux
reflux
reflux
40b
3
a
a
b
b
d
d
e
Ph
Ph
Ph
Ph
–
10
–
3
0.5c
0.5c
e
5
a Yield of isolated product (column chromatography).
b Then reflux, 0.5 h.
c Then r.t., 2 d.
Synthesis 2007, No. 13, 2009–2013 © Thieme Stuttgart · New York

PAPER
Synthesis of the Functionalized gem-Dinitrocyclopropanes
2011
gel 60 (230–400 mesh, Merck). Ethyl diazoacetate,14 2-diazo-1-
phenylethanone,15 1-diazopropan-2-one,16 ethyl 2-diazopro-
panoate,16 methyl 2-diazo-3-phenylpropanoate,17 and diazomalonic
ester18 were prepared by published procedures.
Table 2 Reaction 1,1-Dinitroethene with Disubstituted Diazocarbo-
nyl Compounds
R1
NO2
NO2
O2N
O2N
R1
R2
+
N2
– N2
R2
7d–f
Methyl Dinitroacetate Potassium Salt (4)
1
8f–h
To a stirred soln of fuming HNO3 (77 mL, d = 1.50) in CH2Cl2 (57
mL) at –5 °C was added monomethyl malonate (23.9 g, 0.2 mol).
The mixture was stirred at 5–7 °C for 3 h, then it was quenched with
ice-water (120 mL). The organic layer was washed with ice-water
(3 × 60 mL), then sat. aq KHCO3 (170 mL) was added to the organic
layer and the resulting mixture was stirred at 5–7 °C for 20 min. The
thus-formed precipitate was filtered off and dried in air to give a
cream-colored solid; yield: 21.4 g (53%); mp 209 °C (dec.).
7
8
R1
R2
Solvent
Time Yield
(h)
16
10
4
(%)
d
e
f
f
Me
CO2Et
Et2O
56
g
h
CH2Ph CO2Me
CO2Et CO2Et
benzene
15
chlorobenzene
35
1H NMR (DMSO-d6): d = 3.69 (s, 3 H, CH3).
13C NMR (DMSO-d6): d = 52.6 (CH3O), 131.04 [C(NO2)2], 161.49
(CO2CH3).
1.5%
0%
7.0%
Potassium Dinitromethane (5)
Methyl dinitroacetate potassium salt (15.0 g, 0.074 mol) was added
to a stirred soln of KOH (5.56 g, 0.1 mol) in H2O (56 mL) and the
mixture was heated at 65–70 °C for 30 min. Then the resulting mix-
ture was allowed to cool to 0 °C, the yellow solid was filtered off,
washed with ice-water (2 × 10 mL), and dried in air; yield: 9.80 g
(92%).
1H NMR (DMSO-d6): d = 3.46 (s, 1 H, CH).
13C NMR (DMSO-d6): d = 122.7 (CH).
H
H
H
Ph
H
H
H
H
NO2
NO2
NO2
0.9%
COPh
COOEt
Ph
COOEt
NO2
NO2
NO2
8b
8d trans
8d cis
Figure 1 Representative NOE enhancements for compounds 8b,d
Potassium 2,2-dinitroethanol (6)
8d,e. The correctness of the stereochemical assignment
was unambiguously confirmed by the observation of NOE
enhancements due to dipolar interaction between the hy-
drogens of compounds 8b,d. The results of NOE measure-
ments are presented in Figure 1. It is interesting to note
that the hydrogen atoms of the three-membered rings of
A suspension of potassium dinitromethane (6 g, 0.042 mol) and
40% aq formaldehyde (6 mL) in H2O (10 mL) was heated at 90 °C
for 15 min and the resulting soln was cooled to 0–5 °C. The yellow
solid was filtered off, washed with ice-water (2 mL) and MeOH (2
mL), and dried in air; yield: 5.90 g (81%), mp 148–150 °C (Lit.8 152
°C).
the compounds studied are shifted downfield (Dd = 2.5– 1H NMR (DMSO-d6): d = 4.52 (t, J = 6.1 Hz, 1 H, OH), 4.72 (d,
3
3J = 6.1 Hz, 2 H, CH2).
1
4.9) due to the influence of substituents. The JCH con-
13C NMR (DMSO-d6): d = 57.4 (CH2OH), 136.4 [C(NO2)2].
stants have rather large values (166–174 Hz).
In general, the efficiency of the method described for the
synthesis of dinitrocyclopropanes depends on steric and
electronic factors. For example, in the reaction of b,b-
dinitrostyrene (2) with disubstituted diazocarbonyl com-
pounds 7d,e, cyclopropanes were found in small amounts
and they could not be isolated. b,b-Dinitrostyrene (2) did
not react with diethyl diazomalonate (7f). In addition, the
reaction of the dinitroethenes 1 and 2 with ethyl diazoni-
troacetate did not result in the formation of cyclopropane
derivatives.
2,2-Dinitroethanol (3)
Potassium 2,2-dinitroethanol (0.5 g, 2.9 mmol) was dissolved in
ice-water (2 mL), then soln of concd H2SO4 (0.08 mL) in H2O (2.5
mL) was added at 3 °C under stirring. The aqueous soln was extract-
ed with cold Et2O (5 × 3 mL) and the combined organic layers were
dried (anhyd MgSO4). Then benzene (5 mL) (or Et2O, chloroben-
zene) was added to the ether soln and the soln was concentrated to
5 mL in vacuo. The crude dinitroethanol was utilized without puri-
fication.
Reaction of 1,1-Dinitroethene (1) with Diazo Compounds 7a–c;
General Procedure
In conclusion, reactions of 1,1-dinitroalkenes with a-di-
azocarbonyl compounds represent a useful approach for
the synthesis of novel functionalized gem-dinitrocyclo-
propanes, readily able to undergo further chemical modi-
fications.
The mixture of the diazo compound (2.9 mmol) in benzene (or Et2O
for diazoacetate) (5 mL), Mo(CO)6 (0.030 g, 4 mol%), and 2,2-dini-
troethanol [obtained from potassium 2,2-dinitroethanol (2.9 mmol)
in benzene (5 mL)] was heated at reflux with activated 4 Å molec-
ular sieves for several hours (Table 1). After cooling the resulting
mixture was concentrated in vacuo. The products 8a–c, 9a–c, and
10 were isolated by column chromatography (n-hexane–CHCl3,
1:1).
NMR spectra (400 MHz) were recorded on a Bruker Avance-400
spectrometer at r.t. referenced to the solvent (1H: CDCl3, d = 7.26,
DMSO-d6, d = 2.50; 13C: CDCl3, d = 77.1, DMSO-d6, d = 39.5).
MS were recorded on the MALDI-TOF mass-spectrometer Bruker
Ultraflex in positive mode, dithranol was used as a matrix. Melting
points: Electrothermal 9100 capillary melting point apparatus, val-
ues uncorrected. Column chromatography was performed on silica
Ethyl 2,2-Dinitrocyclopropanecarboxylate (8a)
Oil; Rf = 0.7 (CHCl3).
1H NMR (CDCl3): d = 1.30 (t, J = 7.1 Hz, 3 H, CH3), 2.55 (dd,
3
2J = 7.8, 3J = 10.6 Hz, 1 H, CH2CHCO2Et), 2.78 (dd, J = 7.8,
2
Synthesis 2007, No. 13, 2009–2013 © Thieme Stuttgart · New York

2012
O. A. Ivanova et al.
PAPER
3
3J = 9.1 Hz, 1 H, CH2CHCO2Et), 3.41 (dd, J = 10.6, 9.1 Hz, 1 H,
CH2CHCO2Et), 4.25 (m, 2 H, CH2O).
(5 mL) for several hours (Table 1). After cooling, the resulting mix-
ture was concentrated in vacuo. The products 8d,e and 9d,e were
isolated by column chromatography (n-hexane–EtOAc, 20:1).
13C NMR (CDCl3): d = 13.7 (CH3), 22.3 (1JCH = 174 Hz, CH2), 31.3
(1JCH = 176 Hz, CH2), 63.2 (CH2O), 97.3 [C(NO2)2], 164.7 (CO2Et).
Ethyl 2,2-Dinitro-3-phenylcyclopropanecarboxylate (8d)
Oil; ratio trans/cis 70:30; Rf = 0.6 (CHCl3).
Anal. Calcd for C6H8N2O6: C, 35.30; H, 3.95; N, 13.72. Found: C,
35.25; H, 3.70; N, 13.59.
trans-Isomer
Ethyl 5-Nitro-1H-pyrazole-3-carboxylate (9a)7
3
1H NMR (CDCl3): d = 1.34 (t, J = 7.1 Hz, 3 H, CH3), 4.01 (d,
Crystals; mp 155 °C (CHCl3) [Lit.7 155–156 °C]; Rf = 0.2 (CHCl3).
3J = 9.9 Hz, 1 H, CH), 4.31 (q, J = 7.1 Hz, 2 H, CH2), 4.39 (d,
3
3J = 9.9 Hz, 1 H, CH), 7.31 (m, 2 H, Ph), 7.39 (m, 3 H, Ph).
1H NMR (DMSO-d6): d = 1.32 (t, 3J = 7.2 Hz, 3 H, CH3), 4.36 (q,
3J = 7.2 Hz, 2 H, CH2O), 7.48 (s, 1 H, CH), 15.19 (br s, 1 H, NH).
13C NMR (CDCl3): d = 13.9 (CH3), 33.9 (1JCH = 169 Hz, CH), 38.8
(1JCH = 168 Hz, CH), 63.4 (CH2), 101.0 [C(NO2)2], 127.1 (C, Ph).
128.1 (2 CH, Ph), 129.2 (2 CH, Ph), 129.7 (CH, Ph), 164.3 (C).
13C NMR (DMSO-d6): d = 14.4 (CH3), 62.2 (CH2O), 105.1 (CH),
136.3 (C), 156.4 (C), 158.2 (CO2Et).
Tetraethyl 1H-Pyrrole-2,3,4,5-tetracarboxylate (10)12
Oil; Rf = 0.5 (CHCl3).
cis-Isomer
3
1H NMR (CDCl3): d = 1.19 (t, J = 7.1 Hz, 3 H, CH3), 3.69 (d,
3J = 12.1 Hz, 1 H, CH), 4.09 (d, J = 12.1 Hz, 1 H, CH), 4.19 (q,
3
3
1H NMR (CDCl3): d = 1.31 (t, J = 7.2 Hz, 6 H, 2 CH3), 1.35 (t,
3J = 7.1 Hz, 2 H, CH2), 7.31 (m, 2 H, Ph), 7.39 (m, 3 H, Ph).
3J = 7.2 Hz, 6 H, 2 CH3), 4.36 (q, 3J = 7.2 Hz, 4 H, 2 CH2), 4.42 (q,
3J = 7.2 Hz, 4 H, 2 CH2).
13C NMR (CDCl3): d = 13.7 (CH3), 33.8 (1JCH = 173 Hz, CH), 38.5
(1JCH = 166 Hz, CH), 62.7 (CH2), 98.9 [C(NO2)2], 126.4 (C, Ph),
128.5 (2 CH, Ph), 129.0 (2 CH, Ph), 129.8 (CH, Ph), 162.8 (C).
(2,2-Dinitrocyclopropyl)phenylmethanone (8b)
Crystals; mp 89 °C; Rf = 0.6 (CHCl3).
Anal. Calcd for C12H12N2O6: C, 51.43; H, 4.32; N, 10.00. Found: C,
51.42; H, 4.20; N, 10.01.
1H NMR (CDCl3): d = 2.61 (dd, 2J = 7.6, 3J = 10.4 Hz, 1 H,
CH2CHCOPh), 3.05 (dd, 2J = 7.6, 3J = 9.2 Hz, 1 H, CH2CHCOPh),
4.36 (dd, 3J = 10.4, 9.2 Hz, 1 H, CH2CHCO2Et), 7.50–7.60 (m, 2 H,
Ph), 7.66–7.74 (m, 1 H, Ph), 7.98–8.04 (m, 2 H, Ph).
(2,2-Dinitro-3-phenylcyclopropyl)phenylmethanone (8e)
Oil; ratio trans/cis 90:10; Rf = 0.7 (CHCl3).
13C NMR (CDCl3): d = 22.3 (1JCH = 173 Hz, CH2), 33.3 (1JCH = 171
Hz, CH2), 98.8 [C(NO2)2], 128.8 (2 CH, Ph), 129.2 (2 CH, Ph),
135.0 (CH, Ph), 135.3 (C, Ph), 188.8 (CO).
trans-Isomer
3
1H NMR (CDCl3): d = 4.64 (d, J = 10.1 Hz, 1 H, CH), 4.89 (d,
3J = 10.1 Hz, 1 H, CH), 7.34 (m, 2 H, Ph), 7.42 (m, 3 H, Ph), 7.59
(m, 2 H, CH, Ph-CO), 7.73 (m, 1 H, CH, Ph-CO), 8.10 (m, 2 H, CH,
Ph-CO).
Anal. Calcd for C10H8N2O5: C, 50.85; H, 3.41; N, 11.86. Found: C,
50.82; H, 3.19; N, 11.63.
13C NMR (CDCl3): d = 36.6 (1JCH = 165 Hz, CH), 38.3 (1JCH = 167
Hz, CH), 102.2 [C(NO2)2], 127.7 (C, Ph). 128.1 (2 CH, Ph), 128.9
(2 CH, Ph), 129.3 (2 CH, Ph), 129.3 (2 CH, Ph), 129.7 (CH, Ph),
130.6 (C, Ph), 135.2 (CH, Ph), 188.1 (C=O).
(5-Nitro-1H-pyrazol-3-yl)phenylmethanone (9b)7
Crystals; mp 186 °C (CHCl3) [Lit.7 186–187 °C].
1H NMR (DMSO-d6): d = 7.45 (s, 1 H, CH), 7.52–7.60 (m, 2 H, Ph),
7.63–7.72 (m, 1 H, Ph), 7.91–7.98 (m, 2 H, Ph), 15.19 (br s, 1 H,
NH).
13C NMR (DMSO-d6): d = 106.0 (CH), 129.1 (2 CH, Ph), 129.4 (2
CH, Ph), 134.0 (CH, Ph), 136.1 (C, Ph), 141.6 (C), 156.2 (C), 183.8
(CO).
cis-Isomer
3
1H NMR (CDCl3): d = 4.25 (d, J = 12.1 Hz, 1 H, CH), 4.54 (d,
3J = 12.1 Hz, 1 H, CH), 7.34 (m, 2 H, Ph), 7.42 (m, 3 H, Ph), 7.59
(m, 2 H, m-CH, Ph-CO), 7.73 (m, 1 H, p-CH, Ph-CO), 8.10 (m, 2 H,
o-CH, Ph-CO).
1-(2,2-Dinitrocyclopropyl)ethanone (8c)
Crystals; mp 62–63 °C; Rf = 0.5 (CHCl3).
Anal. Calcd for C16H12N2O5: C, 61.54; H, 3.85; N, 8.97. Found: C,
61.38; H, 3.85; N, 8.66.
1H NMR (CDCl3): d = 2.49 (dd, 2J = 7.8, 3J = 10.4 Hz, 1 H,
CH2CHCOCH3), 2.50 (s, 3 H, CH3), 2.79 (dd, 2J = 7.8, 3J = 9.2 Hz,
1 H, CH2CHCOCH3), 3.67 (dd, 3J = 10.4, 9.2 Hz, 1 H,
CH2CHCOCH3).
Ethyl 5-Nitro-4-phenyl-1H-pyrazole-3-carboxylate (9d)
Yellow oil; Rf = 0.1 (CHCl3).
3
1H NMR (CDCl3): d = 1.26 (t, J = 7.1 Hz, 3 H, CH3), 4.23 (q,
3J = 7.1 Hz, 3 H, CH2), 7.35–7.70 (m, 5 H, Ph).
MS-MALDI-TOF: m/z = 261 [M]+.
13C NMR (CDCl3): d = 22.3 (1JCH = 173 Hz, CH2), 31.7 (CH3), 36.2
(1JCH = 172 Hz, CH), 98.6 [C(NO2)2], 197.3 (CO).
Anal. Calcd for C5H6N2O5: C, 34.49; H, 3.47; N, 16.09. Found: C,
34.52; H, 3.35; N, 16.02.
(5-Nitro-4-phenyl-1H-pyrazol-3-yl)phenylmethanone (9e)
Yellow oil; Rf = 0.1 (CHCl3).
1-(5-Nitro-1H-pyrazol-3-yl)ethanone (9c)7
1H NMR (CDCl3): d = 7.35–7.70 (m, 10 H, Ph).
Crystals; mp 131–132 °C (CHCl3) [Lit.7 136–137 °C].
Anal. Calcd for C16H11N3O3: C, 65.53; H, 3.75; N, 14.33. Found: C,
65.71; H, 3.95; N, 14.58.
1H NMR (CD3OD): d = 2.60 (s, 3 H, CH3), 7.59 (s, 1 H, CH).
13C NMR (DMSO-d6): d = 27.0 (CH3), 104.5 (CH), 142.2 (C),
156.5 (C), 188.0 (CO).
Reaction of 1,1-Dinitroethene with Disubstituted Diazo Com-
pounds 7d–f; General Procedure
A mixture of the diazo compound (2.9 mmol) in a solvent (5 mL)
and 2,2-dinitroethanol [obtained from potassium 2,2-dinitroethanol
(2.9 mmol) in the same solvent] was heated at reflux with activated
4 Å molecular sieves for several hours (Table 2). After cooling the
1-Substituted 2,2-Dinitro-3-phenylcyclopropanes 8d,e; General
Procedure
A mixture of b,b-dinitrostyrene (2, 0.5 g, 2.6 mmol), diazo com-
pound 7a or 7b (2.6 mmol), and Mo(CO)6 was refluxed in benzene
Synthesis 2007, No. 13, 2009–2013 © Thieme Stuttgart · New York

PAPER
Synthesis of the Functionalized gem-Dinitrocyclopropanes
2013
resulting mixture was concentrated in vacuo. The products were
isolated by column chromatography (n-hexane–CHCl3, 1:1).
(2) (a) Ivanova, O. A.; Yashin, N. V.; Averina, E. B.; Grishin,
Yu. K.; Kuznetsova, T. S.; Zefirov, N. S. Izv. Akad. Nauk,
Ser. Khim. 2001, 11, 2008; Russ. Chem. Bull. 2001, 50,
2101. (b) Budynina, E. M.; Averina, E. B.; Ivanova, O. A.;
Yashin, N. V.; Kuznetsova, T. S.; Zefirov, N. S. Synthesis
2004, 2609.
(3) (a) Maas, G. In Houben-Weyl; Vol. E17a, de Meijere, A.,
Ed.; Thieme: Stuttgart, 1997, 426–435. (b) Shapiro, E. A.;
Dyadkin, A. B.; Nefedov, O. M. Diazoesters; Nauka:
Moscow, 1992, 29–30; (in Russian).
(4) (a) Wulfman, D. S.; Linstrumelle, G.; Cooper, C. F. In The
Chemistry of the Diazonium and Diazo Groups, Part 2; Patai,
S., Ed.; Wiley: New York, 1978, 821. (b) Machezie, K. In
The Chemistry of the Hydrazo, Azo and Azoxy Groups, Part
1; Patai, S., Ed.; Wiley: New York, 1975, 239.
Ethyl 1-Methyl-2,2-dinitrocyclopropanecarboxylate (8f)
Oil; Rf = 0.6 (CHCl3).
1H NMR (CDCl3): d = 1.30 (t, 3J = 7.2 Hz, 3 H, CH3), 1.61 (s, 3 H,
2
2
CH3), 2.49 (d, J = 8.3 Hz, 1 H, CH2), 2.90 (d, J = 8.3 Hz, 1 H,
CH2), 4.20–4.35 (m, 2 H, OCH2).
13C NMR (CDCl3): d = 13.7 (CH3), 15.01 (CH3), 26.4 (1JCH = 171
Hz, CH2), 37.9 (C), 63.8 (CH2O), 101.2 [C(NO2)2], 166.2 (CO2Et).
Anal. Calcd for C7H10N2O6: C, 38.54; H, 4.62; N, 12.84. Found: C,
38.58; H, 4.49; N, 12.70.
Methyl 1-Benzyl-2,2-dinitrocyclopropanecarboxylate (8g)
Oil; Rf = 0.6 (CHCl3).
(5) (a) Engel, P. S. Chem. Rev. 1980, 80, 99. (b) Ye, T.;
McKervey, M. A. Chem. Rev. 1994, 94, 1143.
2
1H NMR (CDCl3): d = 2.66 (d, J = 8.6 Hz, 1 H, CH2), 2.93 (d,
(6) Regitz, M.; Heydt, H. In 1,3-Dipolar Cycloaddition
Chemistry, Vol. 1; Padwa, A., Ed.; Wiley: New York, 1984,
393.
(7) Fridman, A. L.; Gabitov, F. A.; Surkov, V. D. Zh. Org.
Khim. 1972, 8, 2457; Chem. Abstr. 1973, 78, 83543.
(8) (a) Duden, P.; Pondorff, W. Ber. Dtsch. Chem. Ges. 1905,
38, 2031. (b) Gold, M. H.; Hamel, E. E.; Klager, K. J. Org.
Chem. 1957, 22, 1665.
2J = 8.6 Hz, 1 H, CH2), 3.74 (s, 3 H, CH3), 3.83 (s, 2 H, CH2), 7.30–
7.55 (m, 5 H, Ph).
13C NMR (CDCl3): d = 25.6 (1JCH = 170 Hz, CH2), 34.8 (CH2), 44.8
(C), 51.8 (CH3), 100.5 [C(NO2)2], 128.1 (2 CH, Ph), 128.9 (2 CH,
Ph), 130.3 (CH, Ph), 134.3 (C, Ph), 167.9 (CO2CH3).
Anal. Calcd for C12H12N2O6: C, 51.43; H, 4.32; N, 10.00. Found: C,
51.09; H, 3.95; N, 10.20.
(9) Novikov, S. S.; Belikov, V. M.; Dem’yanenko, V. F.;
Lapshina, L. V. Izv. Akad. Nauk SSSR, Otdel. Khim. Nauk
1960, 7, 1295; Chem. Abstr. 1961, 55, 423d.
Diethyl 2,2-Dinitrocyclopropane-1,1-dicarboxylate (8h)
Oil; Rf = 0.8 (CHCl3).
(10) Grakauskas, V.; Guest, A. M. J. Org. Chem. 1978, 43, 3485.
(11) (a) Doyle, M. P.; Davidson, J. G. J. Org. Chem. 1980, 45,
1538. (b) Doyle, M. P.; Dorow, R. L.; Tamblyn, W. H. J.
Org. Chem. 1982, 47, 4059. (c) Doyle, M. P.; Colsman, M.
R.; Dorow, R. L. Heterocycl. Chem. 1983, 20, 943.
(12) Tomilov, Yu. V.; Platonov, D. N.; Averkiev, B. B.;
Shulishov, E. V.; Nefedov, O. M. Izv. Akad. Nauk, Ser.
Khim. 2003, 1, 176; Russ. Chem. Bull. 2003, 52, 187–191.
(13) (a) Contreras, R. H.; Peralta, J. E. Prog. Nucl. Magn. Reson.
Spectrosc. 2000, 37, 321. (b) Watt, V. S.; Goldstein, J. H.
Chem. Phys. 1967, 46, 4165. (c) Crecely, L. M.; Watt, V. S.;
Goldstein, J. H. J. Mol. Spectrosc. 1969, 30, 184.
(14) Newman, M. S.; Ottmann, G. F.; Grundmann, C. F. Org.
Synth. Coll. Vol. IV; John Wiley & Sons: London, 1963, 424.
(15) Jung, E.; Min, S.-J.; Houk, K. N.; Ess, D. J. Org. Chem.
2004, 69, 9085.
1H NMR (CDCl3): d = 1.30 (t, 3J = 7.1 Hz, 6 H, CH3), 2.99 (s, 2 H),
4.29 (q, 3J = 7.1 Hz, 4 H, CH2O).
13C NMR (CDCl3): d = 13.7 (2 CH3), 25.9 (1JCH = 174 Hz, CH2),
44.3 (C), 64.1 (2 CH2O), 98.0 [C(NO2)2], 161.8 (2 CO2Et).
Anal. Calcd for C9H12N2O8: C, 39.14; H, 4.38; N, 10.14. Found: C,
39.46; H, 4.28; N, 9.98.
Acknowledgment
We thank the Division of Chemistry and Materials Science RAS
(Program N 1.5), the President’s grant ‘Support of Leading Scienti-
fic School’ N 2552.2006.3 (academician N.S. Zefirov), and the
Russian Foundation of Basic Research (Project 07-03-00685-a) for
financial support of this work.
(16) Regitz, M.; Menz, F. Chem. Ber. 1968, 101, 2622.
(17) Barrett, A. G. M.; Braddock, D. C.; Lenoir, I.; Tone, H. J.
Org. Chem. 2001, 66, 8260.
References
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Synthesis 2007, No. 13, 2009–2013 © Thieme Stuttgart · New York