Application of a thermal β-elimination reaction to N-alkoxy-3,3-dinitroisoxazolidines: Synthesis of 3-nitroisoxazolines

Article abstract of DOI:10.1055/s-2006-926312

A facile general method has been developed for the synthesis of 5-substituted 3-nitroisoxazolines by the application of a thermal β-elimination reaction to N-alkoxy-3,3-dinitroisoxazolidines in chlorobenzene. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2006-926312

706
PAPER
Application of a Thermal b-Elimination Reaction to N-Alkoxy-3,3-dinitro-
isoxazolidines: Synthesis of 3-Nitroisoxazolines
Application of
a
T
l
herma
l
g
b
-
Eliminatio
a
nReactionto
N
-A
A
lkoxy-3,3-dinitro
.
isoxazolidine
I
s
vanova, Ekaterina M. Budynina, Elena B. Averina, Tamara S. Kuznetsova,* Nikolai S. Zefirov
Moscow State University, Department of Chemistry, Leninskie Gory, Moscow 119992, Russia
Fax +7(95)9390290; E-mail: kuzn@org.chem.msu.ru
Received 2 June 2005; revised 13 September 2005
which gives 3,3-dinitroisoxazolidines with electron-with-
Abstract: A facile general method has been developed for the syn-
thesis of 5-substituted 3-nitroisoxazolines by the application of a
thermal b-elimination reaction to N-alkoxy-3,3-dinitroisoxazo-
lidines in chlorobenzene.
drawing, aromatic, and heterocyclic substituents in good
to excellent yields.12–15 Interestingly, the three-component
reactions of iodotrinitromethane with two alkenes pro-
ceed to give iododinitroisoxazolidines, which spontane-
ously undergo thermal b-elimination at room temperature
to form 3-nitroisoxazolines.15 Therefore the nitroisoxazo-
lines of a target structure can be obtained through this
synthetic sequence including the formation of dinitroisox-
azolidines followed by b-elimination of nitro and alkoxy
groups. In this reaction, in situ generated nitronates can be
formally regarded as a synthetic equivalent of nitronitrile
oxide (Scheme 1).
Key words: b-elimination, [3+2] cycloaddition, isoxazolines, isox-
azolidines, heterocycles
Nitroisoxazolines are useful synthetic intermediates1 and
precursors of a wide range of valuable materials such as
biocide protecting technical materials,2 different pharma-
cological agents,3 or crop-protecting compositions against
phytotoxic secondary effects of herbicides.4 Their high re-
activity provides the following possible functionaliza-
tions: 1) the nitro group can be displaced by a variety of
nucleophiles such as thiolate, cyanide, hydride, azide
ions, ammonia, and alkoxides;5,6 2) 3-nitro-D2-isoxazo-
lines can be transformed to 3-nitroisoxazoles by treatment
with oxidizing agents;7 3) the lability of the N–O bond af-
fords various products via ring cleavage.1a
From these standpoints, we have developed an effective
general method to obtain 3-nitroisoxazolines by b-elimi-
nation of available 3,3-dinitroisoxazolidines.
First, we examined the thermal b-elimination from the
model isoxazolidine 1a12 with heating in various solvents
under reflux (Table 1).
Boiling benzene (Table 1, entry 1) resulted in no b-elimi-
nation products. In the case of toluene or o-xylene their
methyl groups underwent radical nitration by the NO2 rad-
ical which formed during the reaction. The formation of
side-products substantially complicated the isolation of
the target isoxazoline 2. The same reaction in DMSO at
100 °C or in boiling nitromethane proceeded slower than
in pyridine or chlorobenzene. The highest yields were ob-
served when the reaction was performed using chloroben-
zene or pyridine as solvents (Table 1, entry 6, 7). Acidic
catalysts like hydrochloric acid in benzene or p-toluene-
sulfonic acid as well as basic catalysts like organic bases
did not influence the rate of the reaction and the yield of
The classical method for the synthesis of isoxazolines is
the [3+2] cycloaddition of nitrile oxides to alkenes.1,8
However, this method is not applicable to 3-nitroisoxazo-
lines since nitronitrile oxide is not yet available.
The known approaches to 3-nitroisoxazolines are com-
plex multistep procedures.6,9–11 At the same time, isoxazo-
lidine derivatives are known to undergo b-elimination
forming isoxazolines.1,8
Recently, we described the one-pot synthesis of 3,3-dini-
troisoxazolidines with various functional groups.12 This
synthetic route is based on the three-component reaction
of tetranitro- and halotrinitromethanes with two alkenes,
C(NO2)2
N
NO2
C(NO2)2
XC(NO2)3
O
O
N
N
X = NO2, Br, I
O
O
X
O
X
nitronic ester
O2N
N O
nitrile oxide
Scheme 1
SYNTHESIS 2006, No. 4, pp 0706–0710
x
x
.
x
x
.2
0
0
6
Advanced online publication: 25.01.2006
DOI: 10.1055/s-2006-926312; Art ID: T07405SS
© Georg Thieme Verlag Stuttgart · New York

PAPER
Application of a Thermal b-Elimination Reaction to N-Alkoxy-3,3-dinitroisoxazolidines
707
Table 2 Thermal b-Elimination of the Model Isoxazolidine 1a–f
Table 1 Thermal b-Elimination of Isoxazolidine 1a
NO2
NO2
O2N
O2N
O2N
O
O2N
chlorobenzene
N
N
solvent
reflux
RO
reflux
N
O
O
N
O
1a–g
2
O
Reaction time (h) Yielda of 2 (%)
2
R
1a
O2N
NO2
Entry
Solvent
Reaction time (h) Yielda of 2 (%)
1a
1b
1c
1.5
1
77
85
73
1
2
3
4
5
6
7
8
Benzene
DMSOb
2
–
NO2
9
45
68
70
traces
75
77
–
Nitromethane
Toluene
10
4.5
0.3
2
Br
0.5
o-Xylene
Ph
Pyridine
1d
1e
2
2
75
78
Chlorobenzene
H2O–NaHCO3
1.5
2
NO2
Ph
a Yield of isolated product after column chromatography.
b Reaction carried out at 100 °C.
NO2
I
1f
1
4
83
–
isoxazoline 2. For example, starting isoxazolidine 1a was
isolated unchanged after refluxing in chloroform for two
hours in the presence of triethylamine.
1g
Me
a Yield of isolated product after column chromatography.
b-Elimination of 3,3-dinitroisoxazolidines 1a–f bearing
various alkoxy substituents in boiling chlorobenzene led
to isoxazoline 2 in good yields (Table 2). Therefore, the
influence of substituents R on the yields of nitroisoxazo-
line 2 was minimal.
mation of starting isoxazolidine followed by b-elimina-
tion without its isolation and may be utilized as a
convenient synthesis of 3-nitroisoxazolines.
While nitroisoxazoline 2 was generally formed in good
yields (Table 2), in the case of starting isoxazolidine 1g, a
complex mixture of decomposition products was ob-
tained.
We have screened a number of 3,3-dinitroisoxazolidines
to expand the scope of the b-elimination method. Ther-
molysis of isoxazolidines 3a–d, obtained by the reaction
of commercially available olefins such as styrene, butyl
vinyl ether, vinyl acetate, or methylenecyclohexane with
tetranitromethane, readily led to nitroisoxazolines 4a–d in
good yields (Table 3). Conversion of isoxazolidine 3a to
isoxazoline 4a was accompanied by the formation of a
small amount of b-nitrostyrene.
In addition, we found that 3-nitroisoxazolines may be ob-
tained by a one-pot synthesis starting from olefins. Thus,
for example, nitroisoxazoline 2 was synthesized in 64%
yield from bicyclobutylidene, methylenecyclobutane, and
tetranitromethane. The one-pot reaction includes the for-
Table 3 Thermal b-Elimination 3,3-Dinitroisoxazolidines
NO2
O2N
O2N
R
petroleum ether
chlorobenzene
reflux
R
+
C(NO2)4
R
N
R
r.t.
N
O
R'
R'
O
R'
O
3a–d
O2N
R'
4a–d
Isoxazolidine
R
R¢
H
H
Reaction time (h)
Isoxazoline
Yield (%)
3a
3b
3c
3d
Ph
14
23
10
15
4a
4b
4c
4d
71
73
74
72
BuO
-(CH2)5-
OCOCH3
H
Synthesis 2006, No. 4, 706–710 © Thieme Stuttgart · New York

708
O. A. Ivanova et al.
PAPER
Table 4 Thermolysis of Isoxazolidines 5a–d
NO2
O2N
O2N
O
chlorobenzene
reflux
R
R'
N
R
R'
N
O
O
5a–d
6a–d
X
Isoxazolidine
X
R
R¢
H
H
H
Reaction time (h) Isoxazoline
Yield (%)
5a
5b
5c
5d
NO2
NO2
Br
CH(OEt)2
CN
3.5
3
6a
6b
6c
82
72
63
69
COCH3
CO2CH3
4
NO2
CH3
4
6da
a The reaction was performed in refluxing pyridine.
ppm; 13C: CDCl3, d = 77.1 ppm, DMSO-d6, d = 39.5 ppm). Mps
were recorded on a electrothermal 9100 capillary melting point ap-
paratus and are uncorrected. Column chromatography was per-
formed on silica gel 60 (230–400 mesh, Merck). Petroleum ether
(PE) used had the boiling range 40–60 °C. Tetranitromethane and
olefins were commercially available. Isoxazolidines 1a,12 1b,16
1c,15 1d,e,14 1f,15 3a,17 3b,18 3d,18 5a,b,d,12 5c,15 were prepared ac-
cording to published procedures.
Thermolysis of isoxazolidines 5a–d synthesized by the
three-component reactions of tetranitro- or bromotrini-
tromethane with alkenes12–15 allowed us to obtain isoxazo-
lines 6a–d bearing electron-withdrawing functional
groups at C-5 (Table 4).
Thermal b-elimination of isoxazolidine 715 successfully
resulted in the synthesis of the unusual 3-nitro-4,4,5,5-tet-
rasubstituted isoxazoline 8 (Scheme 2).
Caution: Although we have not experienced any problems in the
handling of these compounds, full safety precautions should be tak-
en due to their potential explosive nature.
NO2
O2N
O2N
chlorobenzene
6-Methoxy-7,7-dinitro-5-oxa-6-azaspiro[3.4]octane (1g)
A solution of CH2N2 obtained from N-methyl-N-nitrosourea (2 g, 19
mmol) in benzene (10 mL) was added to a cooled (5 °C) solution of
trinitromethane (0.76 g, 5 mmol) and methylenecyclobutane (0.34
g, 5 mmol) in benzene (5 mL). The reaction mixture was warmed to
r.t. and kept at that temperature for 1 d. The solvent was evaporated
and the residue was dissolved in CHCl3. The product was isolated
after column chromatography (CHCl3–PE, 1:2).
N
reflux
O
N
O
O
7
8 (80%)
Br
Scheme 2
It was observed that the b-elimination of 3,3-dinitroisox-
azolidines proceeded via formation of their side-chain re-
arrangement product. We isolated this product in the
Yield: 1.00 g (86%); oil; Rf 0.64 (CHCl3).
1H NMR (CDCl3): d = 1.65–1.76 (m, 1 H, c-Bu), 1.82–1.92 (m, 1 H,
reactions with compounds 1a, 5a–d, and 7, containing a c-Bu), 2.16–2.48 (m, 3 H, c-Bu), 2.59–2.67 (m, 1 H, c-Bu), 3.38 [d,
2J = 15.2 Hz, 1 H, CH2C(NO2)2], 3.66 (s, 3 H, CH3O), 3.74 [d,
bicyclobutyl substituent on the alkoxy fragment. Accord-
ing to these results and literature data, we presume the
mechanism of this reaction involves the formation of a
stable NO2 radical, homolytic cleavage of the exocyclic
2J = 15.2 Hz, 1 H, CH2C(NO2)2].
13C NMR (CDCl3): d = 13.2 (CH2), 34.2 (CH2), 38.8 (CH2), 43.2
[CH2C(NO2)2], 60.6 (CH3O), 89.7 (C), 128.0 [C(NO2)2].
N–O bond, followed by the cleavage of a small ring, and
recombination of two radicals to yield nitroketones 9
(Scheme 3).
Anal. Calcd for C7H11N3O6: C, 36.05; H, 4.72. Found: C, 36.09; H,
4.89.
3,3-Dinitro-2-{[1-(nitromethyl)cyclohexyl]oxy}-1-oxa-2-aza-
spiro[4.5]decane (3c)
Methylenecyclohexane (0.48 g, 5 mmol) was added to a cooled (0
°C) solution of tetranitromethane (0.49 g, 2.5 mmol) in hexane (5
mL). The reaction mixture was warmed to r.t. and kept at that tem-
NMR spectra were recorded on a Bruker DPX-400 spectrometer at
r.t.; the chemical shifts were measured in ppm relative to the resid-
ual solvent peak (1H: CDCl3, d = 7.24 ppm, DMSO-d6, d = 2.50
NO2
O2N
X
⋅
X
NO2
X
N
+
2
O
⋅
O
O
O
O
⋅
X
1
O2N
9a (X = NO2)
9b (X = Br)
Scheme 3
Synthesis 2006, No. 4, 706–710 © Thieme Stuttgart · New York

PAPER
Application of a Thermal b-Elimination Reaction to N-Alkoxy-3,3-dinitroisoxazolidines
709
3
perature for 7 d. The solvent was evaporated and the residue was
dissolved in CHCl3. The product was isolated after column chroma-
tography (CHCl3–PE, 1:2).
1H NMR (CDCl3): d = 1.21 (t, J = 7.1 Hz, 3 H, CH3), 1.24 (t,
3J = 7.1 Hz, 3 H, CH3), 3.42 [dd, J = 17.9, J = 11.7 Hz, 1 H,
2
3
2
CH2C(NO2)], 3.54–3.69 (m, 2 H, OCH2CH3), 3.59 [dd, J = 17.9,
3J = 7.3 Hz, 1 H, CH2C(NO2)], 3.73–3.83 (m, 2 H, OCH2CH3), 4.61
[d, 3J = 3.4 Hz, 1 H, CH(OEt)2], 5.06 (ddd, 3J = 3.4, 7.3, 11.7 Hz, 1
H, CHO).
Yield: 0.56 g (58%); oil; Rf 0.73 (CHCl3).
1H NMR (CDCl3): d = 1.31–2.05 (m, 20 H, c-Hex), 3.11 [d,
2J = 15.0 Hz, 1 H, CH2C(NO2)2], 3.63 [d, 2J = 15.0 Hz, 1 H,
CH2C(NO2)2], 4.50 (d, 2J = 12.0 Hz, 1 H, CH2NO2), 4.71 (d,
2J = 12.0 Hz, 1 H, CH2NO2).
13C NMR (CDCl3): d = 15.2 (CH3), 15.9 (CH3), 30.8 [CH2C(NO2)],
63.9 (CH2O), 65.6 (CH2O), 87.5 (CH), 101.1 (CH), 163.8 [C(NO2)].
Anal. Calcd for C8H14N2O5: C, 44.03; H, 6.47; N, 12.84. Found: C,
43.92; H, 6.48; N, 12.82.
13C NMR (CDCl3): d = 22.4 (2 × CH2), 23.7 (2 × CH2), 24.4 (CH2),
24.5 (CH2), 31.5 (CH2), 32.0 (CH2), 36.3 (CH2), 39.4 (CH2), 42.8
[CH2C(NO2)2], 79.7 (CH2NO2), 84.5 (C), 91.1 (C), 128.3
[C(NO2)2].
3-Nitro-4,5-dihydroisoxazole-5-carbonitrile (6b)9
Solid; mp 132 °C (Lit.9 mp 132 °C).
Anal. Calcd for C15H24N4O8: C, 46.39; H, 6.23. Found: C, 46.74; H,
5.97.
2
3
1H NMR (DMSO-d6): d = 3.92 [dd, J = 17.4, J = 7.1 Hz, 1 H,
CH2C(NO2)], 4.02 [dd, 2J = 17.4, 3J = 11.9 Hz, 1 H, CH2C(NO2)],
6.10 (dd, 3J = 7.1, 11.9 Hz, 1 H, CHO).
D2-Isoxazolines 2,11 4a–d, 6a–d, and 8 from Isoxazolidines; Gen-
eral Procedure
13C NMR (DMSO-d6): d = 36.6 (CH2), 73.0 (CH), 117.0 (CN),
168.2 [C(NO2)].
A solution of isoxazolidine (1 mmol) in chlorobenzene (3 mL) was
1
refluxed until the starting material had disappeared (TLC and H
NMR). The products were isolated after column chromatography or
recrystallization.
1-(3-Nitro-4,5-dihydroisoxazol-5-yl)ethanone (6c)
Solid; mp 60–61 °C (EtOH); Rf 0.31 (CHCl3).
1H NMR (CDCl3): d = 2.26 (s, 3 H, CH3), 3.50 [dd, 2J = 18.2,
3J = 12.6 Hz, 1 H, CH2C(NO2)], 3.71 [dd, 2J = 18.2, 3J = 7.4 Hz, 1
H, CH2C(NO2)], 5.32 (dd, 3J = 7.4, 12.7 Hz, 1 H, CHO).
13C NMR (CDCl3): d = 26.5 (CH3), 31.7 (CH2), 89.8 (CH), 163.2
[C(NO2)], 202.0 (CO).
3-Nitro-5-phenyl-4,5-dihydroisoxazole (4a)9,10
Solid; mp 65 °C (Lit.9,10 mp 64–65 °C); Rf 0.46 (PE–EtOAc, 4:1).
1H NMR (CDCl3): d = 3.52 (dd, 2J = 17.9, 3J = 6.8 Hz, 1 H, CH2),
3.90 (dd, 2J = 17.9, 3J = 11.7 Hz, 1 H, CH2), 6.10 (dd, 3J = 9.8, 11.7
Hz, 1 H, CHO), 7.35–7.51 (m, 5 H, Ph).
13C NMR (CDCl3): d = 38.0 (CH2), 89.5 (CH), 126.1 (2 × Ph-CH),
129.3 (2 × Ph-CH), 129.7 (Ph-CH), 137.5 (Ph-C), 163.0 [C(NO2)].
Anal. Calcd for C5H6N2O4: C, 37.98; H, 3.82; N, 17.72. Found: C,
C 37.97; H, 3.85; N, 17.55.
Methyl 5-Methyl-3-nitro-4,5-dihydroisoxazole-5-carboxylate
(6d)
Oil; Rf 0.19 (PE–EtOAc, 4:1).
5-Butoxy-3-nitro-4,5-dihydroisoxazole (4b)
Oil; Rf 0.49 (PE–EtOAc, 4:1).
1H NMR (CDCl3): d = 0.85–1.01 (m, 3 H, CH3), 1.26–1.48 (m, 2 H,
CH2), 1.51–1.72 (m, 2 H, CH2), 3.34 [dd, 2J = 18.4, 3J = 2.5 Hz, 1
H, CH2C(NO2)], 3.57 [dd, 2J = 18.4, 3J = 7.1 Hz, 1 H, CH2C(NO2)],
3.63 (dt, 2J = 9.6, 3J = 6.6 Hz, 1 H, CH2), 3.93 (dt, 2J = 9.6, 3J = 6.4
Hz, 1 H, CH2), 5.92 (dd, 3J = 2.5, 7.1 Hz, 1 H, CHO).
13C NMR (CDCl3): d = 13.7 (CH3), 19.1 (CH2), 31.4 (CH2), 36.9
[CH2C(NO2)], 69.7 (CH2O), 109.0 (CHO), 161.5 [C(NO2)].
1H NMR (CDCl3): d = 1.80 (s, 3 H, CH3), 3.38 [d, 2J = 18.1 Hz, 1
2
H, CH2C(NO2)], 3.87 (s, 3 H, CH3), 4.03 [d, J = 18.1 Hz, 1 H,
CH2C(NO2)].
13C NMR (CDCl3): d = 23.6 (CH3), 39.7 [CH2C(NO2)], 53.9
(CH3O), 92.9 (C), 162.2 [C(NO2)], 169.6 (COOCH3).
Anal. Calcd for C6H8N2O5: C, 38.30; H, 4.29. Found: C, 38.58; H,
4.45.
Anal. Calcd for C7H12N2O4: C, 44.68; H, 6.43. Found: C, 44.49; H,
6.81.
11-Nitro-9-oxa-10-azadispiro[3.0.3.3]undec-10-ene (8)
Oil; Rf 0.78 (PE–EtOAc, 4:1).
3-Nitro-1-oxa-2-azaspiro[4.5]dec-2-ene (4c)
Solid; mp 50–51 °C; Rf 0.50 (PE–EtOAc, 4:1).
1H NMR (CDCl3): d = 1.39–1.54 (m, 4 H, CH2), 1.68–1.96 (m, 6 H,
CH2), 3.18 (s, 2 H, CH2).
13C NMR (CDCl3): d = 22.7 (2 × CH2), 24.4 (CH2), 36.4 (2 × CH2),
40.3 [CH2C(NO2)], 96.6 (C), 162.5 [C(NO2)].
1H NMR (CDCl3): d = 1.76–1.87 (m, 1 H, CH2), 1.92–2.05 (m, 1 H,
CH2), 2.07–2.18 (m, 1 H, CH2), 2.23–2.33 (m, 1 H, CH2), 2.35–2.45
(m, 2 H, CH2), 2.46–2.57 (m, 2 H, CH2), 2.60–2.73 (m, 4 H, CH2).
13C NMR (CDCl3): d = 13.5 (CH2), 15.7 (CH2), 26.1 (2 × CH2),
30.0 (2 × CH2), 51.6 (CBr), 100.1 (C), 168.0 [C(NO2)].
Anal. Calcd for C9H12N2O3: C, 55.09; H, 6.16. Found: C, 54.71; H,
6.51.
Anal. Calcd for C8H12N2O3: C, 52.17; H, 6.57; N, 15.21. Found: C,
52.69; H, 6.57; N, 15.35.
4-Nitro(1-nitrocyclobutyl)butan-1-one (9a)
Yield: 0.09 g (42%); oil; Rf 0.40 (PE–EtOAc, 4:1).
3-Nitro-4,5-dihydroisoxazol-5-yl Acetate (4d)9
Oil; Rf 0.31 (CHCl3).
1H NMR (CDCl3): d = 2.16 (s, 3 H, CH3), 3.48 [dd, 2J = 18.9,
3J = 2.0 Hz, 1 H, CH2C(NO2)], 3.59 [dd, 2J = 18.9, 3J = 7.6 Hz, 1 H,
CH2C(NO2)], 6.98 (dd, 3J = 2.0, 7.6 Hz, 1 H, CHO).
13C NMR (CDCl3): d = 19.5 (CH3), 35.9 [CH2C(NO2)], 99.9
(CHO), 164.2 [C(NO2)], 169.0 (OCOCH3).
1H NMR (CDCl3): d = 1.80–1.92 (m, 1 H, CH2), 1.95–2.05 (m, 1 H,
3
3
CH2), 2.29 (q, J = 6.8 Hz, 2 H, CH2), 2.65 (t, J = 6.8 Hz, 2 H,
CH2CO) 2.69–2.84 (m, 4 H, CH2), 4.41 (t, 3J = 6.8 Hz, 2 H,
CH2NO2).
13C NMR (CDCl3): d = 13.4 (CH2), 21.0 (CH2), 30.5 (2 × CH2),
32.1 (CH2), 74.0 (CH2NO2), 92.9 (C), 198.1 (CO).
Anal. Calcd for C8H12N2O5: C, 44.44; H, 5.59. Found: C, 44.46; H,
5.76.
5-(Diethoxymethyl)-3-nitro-4,5-dihydroisoxazole (6a)
Oil; Rf 0.55 (PE–EtOAc, 4:1).
Synthesis 2006, No. 4, 706–710 © Thieme Stuttgart · New York

710
O. A. Ivanova et al.
PAPER
1-(1-Bromocyclobutyl)-4-nitrobutan-1-one (9b)
Yield: 0.08 g (32%); oil; Rf 0.52 (PE–EtOAc, 4:1).
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1H NMR (CDCl3): d = 1.71–1.86 (m, 1 H), 2.17–2.30 (m, 1 H), 2.34
(7) Diamanti, G.; Duranti, E.; Tontini, A. Synthesis 1993, 1104.
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(10) Tartakovskii, V. A.; Chlenov, I. E.; Morozova, N. S.;
Novikov, S. S. Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl.
Transl.) 1966, 346; Chem. Abstr. 1966, 64, 17567e.
(11) Ivanova, O. A.; Averina, E. B.; Grishin, Yu. K.; Kuznetsova,
T. S.; Korlyukov, A. A.; Antipin, M. Yu.; Zefirov, N. S.
Dokl. Chem. (Engl. Transl.) 2002, 382, 21; Chem. Abstr.
2002, 137, 337505.
(quint, 3J = 6.8 Hz, 2 H, CH2), 2.52–2.61 (m, 2 H), 2.78–2.88 (m, 2
3
3
H), 2.91 (t, J = 6.8 Hz, 2 H, CH2CO), 4.47 (t, J = 6.8 Hz, 2 H,
CH2NO2).
13C NMR (CDCl3): d = 16.3 (CH2), 21.9 (CH2), 32.0 (CH2), 35.4
(2 × CH2), 61.6 (CBr), 74.3 (CH2NO2), 203.2 (CO).
Anal. Calcd for C8H12BrNO3: C, 38.42; H, 4.84; N, 5.60. Found: C,
38.97; H, 5.19; N, 4.95.
7-Nitro-5-oxa-6-azaspiro[2.4]oct-6-ene (2);11 One-Pot Synthesis
Methylenecyclobutane (2.5 mmol) was added to a cooled (0 °C) so-
lution of tetranitromethane (2.5 mmol) and bicyclobutylidene (1b)
(2.5 mmol) in chlorobenzene (5 mL). The reaction mixture was
warmed to r.t. and kept at this temperature for 48 h. The reaction
mixture was refluxed for 1.5 h. The solvent was evaporated and the
residue was dissolved in CHCl3. The product was isolated after col-
umn chromatography (CHCl3–PE, 1:2).
(12) Budynina, E. M.; Ivanova, O. A.; Averina, E. B.; Grishin,
Yu. K.; Kuznetsova, T. S.; Zefirov, N. S. Dokl. Chem. (Engl.
Transl.) 2002, 382, 16; Chem. Abstr. 2003, 138, 4478.
(13) Budynina, E. M.; Ivanova, O. A.; Averina, E. B.; Grishin,
Yu. K.; Kuznetsova, T. S.; Zefirov, N. S. Dokl. Chem. (Engl.
Transl.) 2002, 387, 304; Chem. Abstr. 2003, 138, 304197.
(14) Averina, E. B.; Budynina, E. M.; Ivanova, O. A.; Grishin,
Yu. K.; Gerdov, S. M.; Kuznetsova, T. S.; Zefirov, N. S.
Russ. J. Org. Chem. (Engl. Transl.) 2004, 40, 162; Chem.
Abstr. 2005, 142, 155884.
Solid; mp 52–53 °C; Rf 0.47 (CHCl3).
Acknowledgment
We thank the Division of Chemistry and Materials Science RAS
(Grant No. 1.5) for financial support of this work.
References
(15) Budynina, E. M.; Ivanova, O. A.; Averina, E. B.; Grishin,
Yu. K.; Kuznetsova, T. S.; Zefirov, N. S. Synthesis 2005,
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Synthesis 2006, No. 4, 706–710 © Thieme Stuttgart · New York