The first synthesis of 1,1-dinitrocyclopropane

Article abstract of DOI:10.1055/s-2004-831221

1,1-Dinitrocyclopropane was prepared in 62% yield. This high energetic compound was previously unknown. Herein its preparation via tandem reaction between nitroform and diazomethane in benzene is described.

Full text of DOI:10.1055/s-2004-831221

SHORT PAPER
2609
The First Synthesis of 1,1-Dinitrocyclopropane
S
ynthesisof 1,1
k
-Dinitrocycl
a
opropane terina M. Budynina, Elena B. Averina, Olga A. Ivanova, Nikolai V. Yashin, Tamara S. Kuznetsova,*
Nikolai S. Zefirov
Moscow State University, Department of Chemistry, Leninskie Gory, Moscow 119992, Russia
Fax +7(095)9390290; E-mail: kuzn@org.chem.msu.ru
Received 25 May 2004; revised 12 July 2004
alkenes as 1,3-dipole to give 3-nitroisoxazoline N-oxide
Abstract: 1,1-Dinitrocyclopropane was prepared in 62% yield.
This high energetic compound was previously unknown. Herein its
preparation via tandem reaction between nitroform and diazo-
methane in benzene is described.
in only 1–15% yield.7
In the course of our study of the reactions of acetylenes
and nitronates8 we obtained 1,1-dinitrocyclopropane (1)
Key words: 1,1-dinitrocyclopropane, trinitromethane, diazo- as a by-product. Because it was evident that the formation
methane, tandem reactions, alicyclic nitro compounds
of 1 was due to the reaction of nitroform and diazo-
methane, we have examined this reaction in detail. We
have found that the treatment of nitroform with diazo-
methane (in the ratio 1:4) in benzene at 5 °C gave 1,1-
dinitrocyclopropane (1) as a major product together with
isoxazoline N-oxide (2) (ratio 7:3, NMR data). The reac-
tion products were isolated after distillation or column
chromatographic purification.
Strained-ring compounds substituted with multiple nitro
groups are of considerable interest as high-energy and
high-density materials.1 Polynitrocyclopropanes are of
particular interest as compounds with heightened energy,
molecular compactness, high ratio of nitro groups to car-
bon atoms and a remarkable synthetic potential.2 Howev-
er, even the synthesis of dinitrocyclopropanes is still
complicated problem.3 Thus, the simplest representative
of gem-dinitrocyclopropanes, namely 1,1-dinitrocyclo-
propane, which is expected to have unusual chemical re-
activity and useful properties has not been synthesized yet
while at least three unsuccessful attempts of its synthesis
were documented in the literature.4–6
1
The H NMR spectrum of 1 shows one singlet at d 2.29
ppm; its 13C NMR spectrum exhibits two signals at d 19.1
ppm (JC–H = 172 Hz) and d 94.9 ppm, which are typical
values for cyclopropane rings. Mass spectrum and mi-
croanalysis also confirm the structure and composition for
1. 1,1-Dinitrocyclopropane (1) is a stable compound.
Heating of 1 to 150 °C (40 min) did not lead to any change
of its NMR spectrum.
For example, the cyclization reaction of 1-bromo-3,3-
dinitropropane under the action of bases leads exclusively
to the product of intramolecular O-alkylation, namely 3-
nitroisoxazoline N-oxide.4 Attempts of electrophilic nitra-
tion of nitrocyclopropanes at the a-carbon atom were not
successful and only dimeric coupling products were ob-
served after cyclopropyl anion generation.5 Dinitrocar-
bene generation from different precursors also did not
bring positive results.6 There exists only one brief report7
declaring the fact of generation of the dinitrocarbene from
trinitromethane salts. However, this carbene reacted with
It is necessary to emphasize that the reaction of nitroform
with diazomethane in benzene, as it has been reported pre-
viously,9 proceeded to give the O-methyl ether of nitro-
form (this pathway has been proven by the formation of
corresponding adducts with olefins). However, the forma-
tion of gem-1,1-dinitrocyclopropane (1) was not observed
in all these experiments.
Taking into consideration the literature data7,9 and our re-
sults, the scheme of the formation of 1 may be represented
in the following way (Scheme 1). The key step of the re-
action of nitroform with diazomethane (in the absence of
NO2
NO2
C-alkylation
NO2
NO2
+
NO2
CH2N2
H2C
N
N
1, 62%
–N2
HC(NO2)3
NO2
N
O-alkylation
NO2
N
A
B
N
O
O
2, 23%
Scheme 1
SYNTHESIS 2004, No. 16, pp 2609–2610
x
x.
x
x
.
2
0
0
4
Advanced online publication: 16.09.2004
DOI: 10.1055/s-2004-831221; Art ID: Z10104SS
© Georg Thieme Verlag Stuttgart · New York

2610
E. M. Budynina et al.
SHORT PAPER
Anal. Calcd for C3H4N2O4: C, 27.28; H, 3.05; N, 21.21. Found: C,
27.20; H, 3.23; N 21.22.
unsaturated compounds) is the transient formation of 1,1-
dinitroethylene (A) as the principle intermediate (for dif-
ferent possible pathways of its formation see ref.10). Dini-
troethylene (A) can add diazomethane as 1,3-
dipolarophile yielding the intermediate dinitropyrazoline
(B) which, in turn, eliminates nitrogen to give either the
product of intermolecular C-alkylation, namely 1,1-dini-
trocyclopropane (1), or the product of O-alkylation,
namely 3-nitroisoxazoline N-oxide (2).
3-Nitroisoxazoline N-Oxide (2)
1H NMR (300 MHz, CDCl3): d = 3.82 (t, 2 H, J = 9.0 Hz, CH2), 4.73
(t, 2 H, J = 9.0 Hz, CH2).
13C NMR (75 MHz, CDCl3): d = 28.57 (CH2), 64.60 (CH2), 127.32
(CNO2).
Acknowledgment
In summary, we have demonstrated that the reaction of
trinitromethane with diazomethane under mild conditions
provides the first synthesis of gem-dinitrocyclopropane
(1). The study of this reaction in detail is in a progress
now.
We thanks the Division of Chemistry and Materials Science RAS
(Grant No 1.5) for financial support of this work.
References
(1) Chemistry of energetic materials; Olah, G. A.; Squire, D. R.,
Eds.; Academic Press, Inc.: New York, 1991.
(2) Carbocyclic Three- and Four-Membered Ring Compounds:
In Houben-Weyl Methods of Organic Chemistry, Vol. E 17c;
de Meijere, A., Ed.; Thieme: Stuttgart, 1997.
NMR spectra were performed on a Varian VXR-400 (400 MHz for
1H, 100 MHz for 13C) and a Bruker DPX-300 (300 MHz for 1H, 75
MHz for 13C) spectrometer using CDCl3 as solvent. Melting points
were determined on a Electrotermal apparatus and are uncorrected.
Mass spectra were obtained on a Varian MAT 311 (electron impact)
spectrometer. Merck silica gel 60 (0.063–0.200 mm) was used for
column chromatography. Analytical TLC was performed on Silufol
silica gel plates.
(3) Wade, P. A.; Daily, W. P.; Carroll, P. J. J. Am. Chem. Soc.
1987, 109, 5452.
(4) Tartakovski, V. A.; Gribov, B. G.; Savost’yanova, I. A.;
Novikov, S. S. Izv. Akad. Nauk, Ser. Khim. 1965, 9, 1644;
Chem. Abstr. 1966, 64, 2080c.
(5) Kai, Y.; Knochel, P.; Kwiatkowski, S.; Dunitz, J. D.; Oth, J.
F. M.; Seebach, D.; Kalinowski, H. O. Helv. Chim. Acta
1982, 65, 137.
(6) O’Bannon, P. E.; Dailey, W. P. Tetrahedron 1990, 46, 7341.
(7) Chlenov, I. E.; Kashutina, M. V.; Ioffe, S. L.; Novikov, S. S.;
Tartakovski, V. A. Izv. Akad. Nauk, Ser. Khim. 1969, 9,
2085; Chem. Abstr. 1970, 72, 12627j.
Reaction of Diazomethane with Trinitromethane; Typical Pro-
cedure
The solution of diazomethane obtained from N-nitroso-N-methyl-
urea (1.03 g, 10 mmol) in benzene (10 mL) was added over 1 h to a
solution of trinitromethane (380 mg, 2.5 mmol) in benzene (10 mL)
at 5 °C and the resulting mixture was stirred at 5 °C for additional
30 min. Then the mixture was concentrated to give 1.30 g of a yel-
low oil consisting of 1 and 2 in the ratio 7:3 (as shown by 1H NMR).
N-Oxide 2 was isolated from the reaction mixture by freezing at
–20 °C to give 300 mg (23%) of the product; mp 92 °C (EtOH).4
Distillation of the residue gave pure 1 (820 mg, 62%); bp 80 °C (9
mm); d420 1.423 g/cm3; Rf = 0.66 (CHCl3).11
(8) To be reported separately.
(9) (a) Onischenko, A. A.; Chlenov, I. E.; Makarenkova, L. M.;
Tartakovski, V. A. Izv. Akad. Nauk, Ser. Khim. 1971, 7,
1560; Chem. Abstr. 1971, 75, 98480c. (b) Tartakovski, V.
A.; Chlenov, I. E.; Lagodzinskaya, G. V.; Novikov, S. S.
Dokl. Akad. Nauk. 1965, 161, 136; Chem. Abstr. 1967, 67,
53206m. (c) Onischenko, A. A.; Tartakovski, V. A. Izv.
Akad. Nauk, Ser. Khim. 1970, 4, 948; Chem. Abstr. 1970, 73,
34718n.
Caution: Although we have not experienced any problems in han-
dling these compounds, full safety precautions should be taken due
to their potential explosive nature.
(10) (a) Zeldin, L.; Shechter, H. J. Am. Chem. Soc. 1957, 79,
4708. (b) Fridman, A. L.; Gabitov, F. A.; Surkov, V. D. Zh.
Org. Khim. 1972, 8, 2457; Chem. Abstr. 1973, 78, 83543p.
(11) Separation of the reaction mixture by column
chromatography (silica gel, n-hexane–CHCl3, 3:1) led to
partial decomposition of 1.
1,1-Dinitrocyclopropane (1)
1H NMR (300 MHz, CDCl3): d = 2.29 (s, 4 H).
13C NMR (75 MHz, CDCl3): d = 19.11 (2 × CH2, J = 172 Hz), 94.92
[C(NO2)2].
MS (EI, 70 eV): m/z (%) = 133 [M + 1]+ (0.1), 132 [M]+ (0.1), 86
[M – NO2]+ (0.4), 56 [M – NO2 – NO]+ (6.4), 46 [NO2]+ (12.3), 40
[M – 2NO2]+ (32.5), 31 (100.0), 30 (87.3).
Synthesis 2004, No. 16, 2609–2610 © Thieme Stuttgart · New York