Synthesis of nitrosubstituted triangulanes

Article abstract of DOI:10.1023/A:1015045216923

The [1+2] cycloaddition of ethyl nitrodiazoacetatc to various methylenecyclopropanes afforded 1-ethoxycarbonyl-1-nitropolyspirocyclopropanes. These compounds were used in the synthesis of first representatives of nitrosubstituted triangulanes. Nitrospirop

Full text of DOI:10.1023/A:1015045216923

«
O. A. Ivanova, N. V. Yashin, E. B. Averina, Yu. K. Grishin, T. S. Kuznetsova, and N. S. Zefirov
Russian Chemical Bulletin, International Edition, Vol. 50, No. 11, pp. 2101—2105, November, 2001
2101
Synthesis of nitrosubstituted triangulanes
Department of Chemistry, M. V. Lomonosov Moscow State University,
Leninskie Gory, 119899 Moscow, Russian Federation.
Fax: +7 (095) 939 0290. E-mail: kuzn@org.chem.msu.ru
The [1+2] cycloaddition of ethyl nitrodiazoacetate to various methylenecyclopropanes
afforded 1-ethoxycarbonyl-1-nitropolyspirocyclopropanes. These compounds were used in
the synthesis of first representatives of nitrosubstituted triangulanes. Nitrospiropentane was
prepared also by dehydrohalogenation of 1-bromomethyl-1-(nitromethyl)cyclopropane.
Key words: nitrocyclopropanes, ethyl nitrodiazoacetate, 1-ethoxycarbonyl-1-nitropoly-
spirocyclopropanes, nitrosubstituted triangulanes.
As part of our continuing studies devoted to
triangulanes,1,2 we carried out research on the synthesis
of their functional derivatives among which nitro-
substituted triangulanes are of considerable interest as
novel high-energy compounds. However, the synthesis
of these nitro compounds is an experimentally compli-
cated problem. Presently, nitro and polynitro derivatives
of cyclopropanes and polyspirocyclopropanes are diffi-
The starting nitrobromide 2 was synthesized in
22% yield by the reaction of 1,1-bis(bromomethyl)cyclo-
propane (3) with 1 equiv. of AgNO in ether. On the
2
contrary, the reaction of dibromide 3 with NaNO in
2
DMSO afforded the only product, viz., nitrospirocyclo-
propylisoxazoline 4, regardless of the ratio of the start-
ing reagents. Cyclization of nitrobromide 2 under the
action of K CO in DMSO gave rise to nitrospiropen-
2
3
cultly accessible. Only a few examples of compounds of
tane 1 in 50% yield. The structure of the latter was
this series are known: nitrocyclopropanes,3
—8
1,2-di-
confirmed by the data from H and C NMR spectros-
1
13
9
10
1
nitrocyclopropanes, 1,2-dinitrospiropentane, and their
functional derivatives.9—13
copy and mass spectrometry. In the H NMR spectrum
of compound 1 (see the Experimental section), the
In the present study, we examined synthetic ap-
proaches to the preparation of nitro derivatives of the
simplest triangulanes.
One conventional procedure for the synthesis of
substituted cyclopropanes involves 1,3-dehydrohalo-
genation of the corresponding halonitropropanes. In
particular, this procedure has been used for the prepara-
tion of nitrocyclopropane starting from 1-iodo-3-nitro-
propane.7
Yet another representative of nitrocyclopropanes, viz.,
nitrospiro[2.2]pentane (1), has been previously unavail-
able. We examined the possibility of the synthesis of 1
based on 1,3-dehydrohalogenation of 1-bromomethyl-
proton of the CHNO group gives a low-field signal at
δ 4.52 as a doublet of doublets ( J = 2.8 and 6.5 Hz) due
2
3
to spin-spin coupling with the protons of the methylene
group of the substituted three-membered ring. Due to
the effect of the electronegative substituent, these pro-
tons are also noticeably deshielded (δ 1.66 and 2.15) and
2
have the geminal constant ( J = 5.4 Hz) typical of
cyclopropane compounds. The protons of the unsub-
stituted ring give high-field signals with a developed
multiplet structure at δ 0.95—1.24. The 13C NMR spec-
trum has a signal for the C atom bound to the nitro
group at δ 60.6 with the large spin-spin coupling con-
1
stant J
= 191 Hz. The signals for the nonsubstituted
C,H
1
-(nitromethyl)cyclopropane (2) (Scheme 1).
C atoms are observed in the high-field region typical of
spiropentanes, the methylene groups possessing the char-
acteristic constants (1JC,H = 164—167 Hz).
Scheme 1
Apparently, the use of 1,3-dehydrohalogenation of
halonitropropanes in the synthesis of nitropolyspirocyclo-
propanes with more complex structures is a prepara-
tively complicated problem. The procedure for their
preparation based on the [1+2] cycloaddition of
nitrosubstituted carbenes to methylenecyclopropanes
seems to be more efficient.
Actually, the cycloaddition of nitrocarbene to olefins
of the polyspirocyclopropane series afforded directly the
target polycyclic nitro compounds. However, the gen-
eration of nitrocarbene is a rather intricate and danger-
ously explosive procedure.14 More stable ethyl nitrodiazo-
AgNO2
1 equiv.)
NO2
NO2
Br
(
K CO3
2
Et O
DMSO
2
Br
Br
2
1
NO2
NaNO2
DMSO
3
N
O
4
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2008—2012, November, 2001.
066-5285/01/5011-2101 $25.00 © 2001 Plenum Publishing Corporation
1

2
102
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 11, November, 2001
Ivanova et al.
acetate (5) has been synthesized earlier and its reactions
(>80%) to give isomeric 1-ethoxycarbonyl-1-nitro-
with sterically nonhindered olefins in the presence of
dispiro[2.0.2.1]heptanes (13) (Scheme 4).
1
4—17
Rh (OAc) have been described.
2
4
We studied an analogous reaction of ester 5 with
olefins of the methylenecyclopropane series, viz., with
methylenecyclopropane (6), methylenespiro[2.2]pentane
Scheme 4
CO Et
NO2
(
7), bicyclopropylidene (8), and methyl 2-methylene-
2
5
+
cyclopropanecarboxylate (9).
RhII
Ethyl nitrodiazoacetate (5) was prepared by nitration
NO2
CO2Et
7
of ethyl diazoacetate with N O in CCl . Previously,14
1
4
2
5
4
13
it has been noted that this reaction gave rise to
nitroacetate 10 as a by-product. However, we found that
nitration afforded yet another by-product, viz., 3,4-di-
ethoxycarbonylfuroxan (11) (Scheme 2).
1) NaOH/EtOH
) DMSO/H O, ∆
2
2
H
NO2
H
+
NO2
Scheme 2
14
NO2
The H and 13C NMR spectra of nitrospirane 13
have two sets of signals corresponding to two isomers in
a ratio of 3 : 1 (see the Experimental section). The
1H NMR spectrum of the stereoisomers of 13 shows
well-resolved signals of three cyclopropane fragments at
high field. Thus the multiplets of the AB systems at
1
N O
2
5
N CHCO Et
N CCO Et
+
2
2
–30 °C
2
2
5
EtO C
CO Et
2
2
+
O NOCH CO Et
+
2
2
2
N
N
δ 2.0—2.4 and 1.5—1.6 correspond to the CH groups of
2
O
O
1
0
the substituted and central rings, respectively, and the
ABCD systems of the methylene protons of the third
ring are observed at δ 0.8—1.0. The presence of three
spiro-fused rings in compound 13 was confirmed by the
13C NMR spectra. This fact is supported by strong
shielding of the carbon atoms and the rather large spin-
spin coupling constant (1JC,H = 163—168 Hz). The
shielding of the signals for the quaternary C atoms
bound to the nitro and ethoxycarbonyl groups is identi-
cal with that observed for compound 12 (δ 70.0 and
1
1
The resulting three-component mixture (5 : 10 : 11 =
: 2 : 1) was separated by preparative column flash
2
chromatography.
The reaction of compound 5 with methylene-
cyclopropane (6) in the presence of catalytic amounts of
Rh (OAc) afforded ethyl 1-nitrospiro[2.2]pentane-1-
2
4
carboxylate (12) in 85% yield (Scheme 3).
7
0.1). The composition of dispiroheptane 13 was also
Scheme 3
confirmed by the data from elemental analysis.
Saponification followed by decarboxylation of nitro
ester 13 afforded 1-nitrodispiro[2.0.2.1]heptane (14) as
a mixture of two stereoisomers in a ratio of 7 : 5 in
56% yield (see Scheme 4). The structures of these
stereoisomers were confirmed by the data from H and
13C spectroscopy and mass spectrometry.
Bicyclopropylidene (8) belongs to tetrasubstituted
olefins whose reactions with ethyl nitrodiazoacetate (5),
according to the data published in the literature,16 did
not give rise to three-membered rings. However, we
succeeded in preparing ethyl 7-nitrodispiro[2.0.2.1]hep-
tane-7-carboxylate (15) in 13% yield by the reaction of
olefin 8 with ester 5 (Scheme 5).
CO Et
2
5
RhII
1) NaOH/EtOH
2) DMSO/H O,
1
NO2
2
80 °C
1
6
12
The 1H NMR spectrum of spiropentane 12 has
signals of the CH group of the substituted cyclopro-
pane fragment as an AB system at δ 2.13 and 2.38
J = 5.7 Hz). The C NMR spectrum shows a charac-
teristic signal at δ 70.3 corresponding to the quaternary
C atom, which is bound simultaneously to the nitro and
ethoxycarbonyl groups.
2
2
13
(
Hydrolysis followed by decarboxylation of nitro de-
rivative 12 upon heating in wet DMSO afforded
nitrospiropentane 1 in 20% yield. The H and 13C NMR
spectral data for 1 are in complete agreement with the
above-mentioned data for this compound prepared by
Scheme 5
1
O N
CO Et
2
2
1
,3-dehydrohalogenation of bromonitropropane 2.
Cyclopropanation of methylenespiropentane 7 with
5
RhII
ethyl nitrodiazoacetate (5) also proceeded in high yield
8
15

Nitrosubstituted triangulanes
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 11, November, 2001 2103
Scheme 6
O N
EtO C
2
2
CO Et
NO2
2
5
RhII
+
+
+
MeO C
NO2
MeO C
CO Et
MeO C
MeO C
2
MeO C
2
2
2
2
2
EtO C
O N
2
9
2
1
6a—d
Nitro ester 15 was isolated in the individual state by
column chromatography and was completely character-
ized by the data from H and 13C spectroscopy and mass
spectrometry.
The symmetry of molecule 15 is responsible for the
isochronism of the atoms of the corresponding groups in
two external three-membered rings observed in the NMR
spectra (see the Experimental section). The quaternary
C atom of the central ring has a typical chemical
shift (δ 73.2).
Experimental
1
The H and 13C NMR spectra were recorded on Varian
VXR-400 (400 and 100 MHz, respectively) and Bruker
DPX-300 (300 and 75 MHz, respectively) instruments. The
mass spectra were obtained on Varian MAT-311A and
MX-1321A spectrometers (the energy of ionizing electrons was
0 eV). The course of the reactions and the purities of the
compounds were monitored by TLC on Silufol UV-254 plates.
Preparative column chromatography was carried out using
1
7
SiO (Merck, 40/60). The GLC analysis was performed on a
2
The reactions of ethyl nitrodiazoacetate (5) with
substituted methylenecyclopropanes are of particular in-
terest because they can be considered as an approach to
the synthesis of functionally substituted nitropoly-
spirocyclopropanes. Thus, the reaction of compound 5
with ester 9 gave rise to 1-ethyl 4-methyl 1-nitro-
spiro[2.2]pentane-1,4-dicarboxylate as a mixture of four
diastereomers 16a—d in 36% yield (Scheme 6).
Most likely, the low yield of adduct 16 is associated
with a somewhat lower activity of the double bond of
methylenecyclopropane 9 in the [1+2] cycloaddition
due to the presence of the electron-withdrawing ester
group in the adjacent small ring. It should be noted that
derivative 16 is a precursor of 1-aminospiro[2.2]pentane-
Chrom-5 chromatograph equipped with a flame ioniza-
tion detector and a 3000½5-mm column (10% SE-30 on
Inerton AW) at 130—180 °C. The products were separated by
preparative GLC on a PAVKh-08 instrument equipped with a
katharometer as a detector and a 3000½5-mm column
(
10% SÅ-30 on Inerton AW) using He as the carrier gas (the
flow rate was 80—120 mL min–1).
Silver nitrite and N O were prepared according to a
2
4
1
9
procedure reported previously. The reagent Rh (OAc) was
2
4
purchased from Merck. The starting compounds, viz.,
2
0
21
1,1-di(bromomethyl)cyclopropane (3), ethyl diazoacetate,
2
2
23
methylenespiro[2.2]pentane (7), bicyclopropylidene (8), and
methyl 4-methylenespiro[2.2]pentane-1-carboxylate (9), were
synthesized according to known procedures.
2
4
Compounds 1, 2, and 14—16 were not studied by elemen-
tal analysis because of their low stability.
1
,4-dicarboxylic acid, which should, apparently, exhibit
1
-Bromomethyl-1-(nitromethyl)cyclopropane (2). Di-
high biological activity.18
bromide 3 (3.00 g, 13.2 mmol) was added to a stirred suspen-
sion of AgNO2 (2.63 g, 16.5 mmol) in anhydrous ether (7 mL)
at 0 °C for 1 h. The reaction mixture was stirred at 0 °C for
4 h and then at ∼ 20 °C for 2 h. The precipitate that formed
was filtered off and washed with ether. The combined ethereal
Nitro diester 16 can exist as four diastereomers
(
a—d) due to the presence of two asymmetric centers
2
and the possible manifestation of the geometric isomer-
ism. Unfortunately, we failed to make the assignment in
the series of diastereomers of diester 16 based on the
NMR spectral data; however, the ratio of the isomers
fractions were dried with MgSO . The solvent was distilled off
4
and the residue was purified by column chromatography (a 3 : 1
light petroleum ether—benzene mixture as the eluent). Product
2 was isolated in a yield of 0.5 g (22%), R 0.4. 1H NMR
(
a : b : c : d ≈ 50 : 45 : 5 : 1) indicates that the addition
f
of ethyl nitrodiazoacetate (5) to substituted olefins pro-
ceeded with high diastereoselectivity.15 Chromatographic
separation of the reaction mixture afforded two frac-
tions. One of these fractions contained a mixture of two
major diastereomers (16a and 16b), whereas another
fraction contained a mixture of two minor (16c and 16d)
diastereomers. The NMR spectra of all diastereomers
have signals similar in multiplicity and chemical
shifts. The 13C NMR spectra of all diastereomers
(CDCl ), δ: 0.82 (m, 2 H); 1.00 (m, 2 H); 3.42 (s, 2 H,
CH2Br); 4.38 (s, 2 H, CH2NO2). C NMR (CDCl3), δ: 15.38
3
13
(
2 CH ); 22.38 (C); 40.05 (CH Br); 80.00 (CH NO ). MS,
2 2 2 2
+
+
m/z (Irel (%)): 193, 195 [M] (2), 147, 149 [M – NO ] (20),
2
1
19, 121 (5), 107, 109 (5), 93, 95 (5), 67 [M – NO
–
2
+
Br] (100).
-Nitrospiro[2.2]pentane (1). 1-Bromomethyl-1-(nitro-
1
methyl)cyclopropane (2) (0.35 g, 1.8 mmol) was added with
stirring to a suspension of K CO (0.50 g, 3.6 mmol) in
2
3
DMSO (5 mL). The reaction mixture was stirred at ∼ 20 °C for
—4 h, poured into ice water (5 mL), and extracted with ether
4½5 mL). The ethereal extract was washed with water (2½5 mL)
3
(
1
6a—d have a characteristic signal for the qua-
ternary ethoxycarbonylnitro-substituted C atom at
δ 69—73.
and dried with MgSO . The solvent was distilled off under
4
reduced pressure and the residue was purified by preparative
GLC. Nitrospiropentane 1 was obtained in a yield of 0.10 g
Hence, the [1+2] cycloaddition of ethyl nitrodiazo-
acetate to methylenecyclopropanes in the presence of
Rh (OAc) can be used as a general procedure for the
1
(
49%). H NMR (CDCl ), δ: 0.95—1.06 (m, 2 H); 1.12—1.24
3
(m, 2 H); 1.66 (dd, 1 H, H(2a), 3J
5.4 Hz); 2.15 (dd, 1 H, H(2b), 2J2a,b = 5.4 Hz, 3J1,2b
= 6.5 Hz, 2J
2
4
1,2a
2a,b
=
=
preparation of nitro derivatives of triangulanes.

2
104
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 11, November, 2001
Ivanova et al.
2
.8 Hz); 4.52 (dd, 1 H, H(1), 3J1,2b = 2.8 Hz, 3J1,2a = 6.5 Hz).
C NMR (CDCl ), δ: 5.93 (CH , 1JC,H = 164 Hz); 8.4 (CH2,
(AB system, 2 H, C(2)H , 2J = 5.7 Hz); 4.28 (q, 2 H, OCH2,
2
1
3
3J = 7.1 Hz). 13C NMR (CDCl ), δ: 7.13 (CH ); 7.92 (CH );
3
2
3
2
2
1J
= 165 Hz); 17.9 (C(2), JC,H = 167 Hz); 21.3 (Cspiro);
1
14.09 (Me); 22.45 (CH ); 25.72 (C
); 62.70 (CH O); 70.33
2
C,H
2
spiro
0.6 (C(1), 1JC,H = 191 Hz). MS, m/z (I (%)): 114 [M + 1]+
(C); 164.93 (CO). MS, m/z (I (%)): 168 [M – OH] (8)*,
rel
+
6
rel
+
+
+
+
(
2), 67 [M – NO ] (22), 65 [C H ] (37), 55 (28), 53 (40),
156 [M – C H ] (2), 140 [M – OC H ] (16), 129 (3), 111
2 5 2 5
2
5
5
+
+
+
+
4
6 [NO2] (14), 42 (68), 39 [C H ] (100).
(68), 65 [C H ] (75), 53 (30), 39 [C H ] (62), 29
5 5 3 3
3
-Nitrospiro[4,5-dihydroisoxazole-4,1´-cyclopropane] (4).
3
+
3
[C H ] (100).
2 5
Sodium nitrite (3.37 g, 48.8 mmol) was added in one portion
to a solution of 1,1-bis(bromomethyl)cyclopropane (3) (5.30 g,
Ethyl 1-nitrodispiro[2.0.2.1]heptane-1-carboxylate (13).
The yield was 81%. R 0.50 (light petroleum ether—AcOEt as
f
2
3.2 mmol) in DMF (20 mL) at 0—5 °C. The reaction mixture
was slowly heated to ∼ 20 °C and stirred at this temperature for
5 h. Then DMF was distilled off under reduced pressure
18 Torr) and the residue was diluted with water (10 mL) and
the eluent, 4 : 1), the ratio of the isomers was 3 : 1. Found
(%): C, 57.08; H, 6.30. C H NO . Calculated (%): C, 56.87;
H 6.16. MS, m/z (Irel (%)): 194 [M – OH] (2), 183
1
0
13
4
+
1
(
+
+
+
[M – C H ] (3), 182 [M – C H ] (2), 166 [M – OC H ]
2 4 2 5 2 5
+
+
extracted with benzene (3½10 mL). The extract was dried with
MgSO , the solvent was distilled off, and the residue was
purified by column chromatography (SiO , a 3 : 1 light
petroleum ether—AcOEt mixture as the eluent). Compound 4
was obtained in 43% yield, m.p. 37—38 °C (from light petro-
(3), 155 (4), 91 [C H ] (86), 92 (18), 77 (34), 65 [C H ]
7 7 5 5
(41), 53 (31), 39 [C H ] (47), 29 [C H ] (100). Major
3 3 2 5
isomer. H NMR (CDCl ), δ: 0.82—0.86 (m, 2 H); 0.91—0.97
(m, 2 H); 1.30 (t, 3 H, Me, J = 7.1 Hz); 1.47 and 1.58
+
+
4
1
2
3
3
2
(AB system, 2 H, CH , J = 5.0 Hz); 2.15 and 2.26 (AB system,
2
2 H, CH , J = 6.0 Hz); 4.29 (q, 2 H, CH O, 3J = 7.1 Hz);
2
leum ether), R 0.6. Found (%): C, 42.19; H, 3.94; N, 19.67.
f
2
2
1
3
C NMR (CDCl ), δ: 3.2 (CH , 1JC,H = 164 Hz); 5.5 (CH2,
C H N O . Calculated (%): C, 42.25; H, 4.23; N, 19.72.
5
6
2
3
3 2
1
1J
1J
= 163 Hz); 12.8 (CH2, 1JC,H = 163 Hz); 14.0 (Me,
= 125 Hz); 15.6 (Cspiro); 22.1 (CH2, 1JC,H = 168 Hz);
H NMR, (CDCl ), δ: 1.09 (m, 2 H); 1.70 (m, 2 H); 4.77 (s,
3
C,H
C,H
1
3
2
8
H, CH O). C NMR (CDCl ), δ: 13.64 (CH ); 24.62 (C);
2
3
2
1.96 (CH O); 165.7 (CNO ).
29.6 (Cspiro); 62.6 (CH O, 1JC,H = 149 Hz); 70.0 (C); 164.3
2
2
2
1
5
1
Synthesis of ethyl nitrodiazoacetate (5).
methane (25 mL), which was pre-cooled to –25 °C, was added
to solid N O , which was prepared from N O (4 g), with
cooling to –40 °C. The resulting transparent solution was
transferred into a cooled dropping funnel at –25 °C under a
stream of argon and added to a solution of ethyl diazoacetate
Tetrachloro-
(CO). Minor isomer. H NMR (CDCl ), δ: 0.84—0.98
(m, 4 H); 1.25 (t, 3 H, Me, J = 7.1 Hz); 1.54 and 1.55
3
3
2
5
2
(AB system, 2 H, CH , J = 5.1 Hz); 2.02 and 2.40 (AB system,
2
5
2
4
2
2
3
2 H, CH , J = 5.9 Hz); 4.20 (q, 2 H, CH O, J = 7.1 Hz);
2
2
1
3
C NMR (CDCl ), δ: 5.0 (CH , 1JC,H = 164 Hz); 5.6 (CH2,
3
2
1
JC,H = 163 Hz); 12.6 (CH2, 1JC,H = 163 Hz); 13.9 (Me,
1J
= 125 Hz); 16.5 (Cspiro); 21.9 (CH , JC,H = 168 Hz);
30.4 (Cspiro); 62.5 (CH O, 1JC,H = 149 Hz); 70.1 (C);
1
(
4 g, 35 mmol) in CCl (25 mL) at the temperature from –25
4
C,H
2
to –30 °C. The completion of the reaction was judged from
2
cessation of N evolution. The solvent was distilled off under
164.8 (CO).
2
reduced pressure (the temperature was no higher than 35 °C)
and ethyl nitrodiazoacetate (5) was isolated by column flash
chromatography (ether—light petroleum ether as the eluent,
1-Nitrodispiro[2.0.2.1]heptane (14). The yield was 56%,
R 0.30 (light petroleum ether—AcOEt as the eluent, 4 : 1), the
f
ratio of the isomers was 7 : 5. MS, m/z (I (%)): 139 [M]+
rel
+
+
0
—30%). Ester 5 was obtained in a yield of 0.81 g (28%),
(2), 93 [M – NO ] (11), 91 [C H ] (100), 77 (90), 65
2 7 7
[C H ] (43), 53 (83), 39 [C H ] (77). Major isomer.
R 0.25 (light petroleum ether—AcOEt, 4 : 1). 13C NMR
+
+
f
5
5
3
3
1
(
CDCl ), δ: 13.74 (Me); 62.63 (CH O); 101.4 (C—N );
H NMR (CDCl ), δ: 0.84—1.04 (m, 4 H); 1.39 and 1.61
3
3
2
2
2
1
54.36 (CO).
Addition of ethyl nitrodiazoacetate (5) to olefins (general
(AB system, 2 H, C(3)H , J = 4.9 Hz); 1.54 (dd, 1 H, H(2a),
2
2J2a,b = 5.6 Hz, 3J1,2a = 6.5 Hz); 2.19 (dd, 1 H, 3J1,2b
3.0 Hz, 2J2a,b = 5.6 Hz); 4.31 (dd, 1 H, H(1), 3J1,2a = 6.5 Hz,
=
procedure). Ethyl nitrodiazoacetate 5 (0.30 g, 1.89 mmol) was
slowly added to a stirred mixture of alkene (5—10 equiv.) and
Rh (OAc) (3 mol.%) at 0—5 °C. Then the reaction mixture
3
13
1
J1,2b = 3.0 Hz); C NMR (CDCl ), δ: 5.8 (CH ,
J
C,H
=
=
3
2
163 Hz); 6.0 (CH2, JC,H = 162 Hz); 12.8 (CH , 1JC,H
1
2
4
2
was stirred at ∼ 20 °C for 1 h. An excess of alkene was removed
under reduced pressure and the product (a colorless oil) was
isolated by column flash chromatography (ether—light petro-
leum ether as the eluent, 0—30%).
164 Hz); 16.9 (Cspiro); 17.53 (CH , 1JC,H = 166 Hz);
2
27.2 (C
); 59.7 (CHNO2, 1JC,H = 193 Hz). Minor isomer.
spiro
1
H NMR (CDCl ), δ: 0.70—0.80 (m, 4 H); 1.32 and 1.44
3
2
(AB system, 2 H, C(3)H , J = 4.4 Hz); 1.65 (dd, 1 H,
2
2
J2a,b = 5.5 Hz, 3J1,2a = 6.4 Hz); 1.95 (dd, 1 H, J1,2b
=
3
Saponification of 1-nitrocyclopropanecarboxylates and de-
carboxylation of sodium 1-nitrocyclopropanecarboxylates (gen-
eral procedure). A 1 M solution of NaOH in EtOH (1.3 mL)
was added with stirring to a solution of ethyl 1-nitrocyclo-
propanecarboxylate (1.28 mmol) in anhydrous EtOH (1.5 mL).
After 30 min, the solvent was distilled off under reduced
pressure. The residue was dissolved in a 10 : 1 DMSO—water
mixture (3.3 mL) and heated at 80 °C for 0.5 h. The solution
was cooled, diluted with an equal volume of water, and
extracted with ether (4½15 mL). The organic layer was washed
3.0 Hz, 2J2a,b = 5.5 Hz); 4.59 (dd, 1 H, H(1), 3J1,2a = 6.4 Hz,
3J1,2b = 3.0 Hz); C NMR (CDCl ), δ: 2.8 (CH , 1J
13
=
=
3 2 C,H
164 Hz); 5.4 (CH2, JC,H = 163 Hz); 12.9 (CH , 1JC,H
1
2
1
164 Hz); 14.7 (Cspiro); 17.0 (CH , J
60.9 (CHNO2, 1JC,H = 195 Hz).
Ethyl 7-nitrodispiro[2.0.2.1]heptane-7-carboxylate (15).
= 166 Hz); 24.7 (Cspiro);
C,H
2
The yield was 13%, R 0.50 (light petroleum ether—AcOEt as
f
1
the eluent, 4 : 1). H NMR (CDCl ), δ: 1.04 (m, 2 H); 1.10
3
3
(m, 2 H); 1.29 (t, 3 H, Me, J = 7.1 Hz); 1.34 (m, 2 H, CH );
1.40 (m, 2 H, CH ); 4.29 (q, 2 H, CH O, J = 7.1 Hz).
2
3
with water (4½10 mL) and dried with MgSO . The solvent was
4
2
2
1
3
distilled off under reduced pressure and the residue was puri-
fied by column flash chromatography (ether—light petroleum
ether as the eluent, 0—10%).
C NMR (CDCl ), δ: 6.7 (2 CH ); 7.0 (2 CH ); 13.7 (Me);
3 2 2
28.5 (2 Cspiro); 62.0 (CH O); 73.20 (C); 164.32 (CO). MS,
2
+
+
m/z (Irel (%)): 211 [M] (1), 183 (1), 182 [M – C H ] (4),
166 [M – OC H ] (9), 153 (29), 137 (52), 121 (24), 119 (28),
2 5
2
5
+
Ethyl 1-nitrospiro[2.2]pentane-1-carboxylate (12). The
yield was 83%, R 0.45 (light petroleum ether—AcOEt, 4 : 1).
f
Found (%): C, 51.71; H, 6.12. C H NO . Calculated (%):
8
11
4
1
* The [M – OH]+ fragments were observed in nitro com-
pounds bearing protons at the adjacent carbon atom.
C, 51.89; H, 5.95. H NMR (CDCl ), δ: 1.12—1.26 (m, 4 H,
3
3
26
CH CH ); 1.30 (t, 3 H, Me, J = 7.1 Hz); 2.13, 2.38
2
2

Nitrosubstituted triangulanes
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 11, November, 2001 2105
+
1
6
08 (42), 106 (58), 93 (72), 92 (70), 91 [C H ] (89), 77 (77),
3. B. Hass and H. Shechter, J. Am. Chem. Soc., 1953, 75, 1382.
4. US Pat. 3769355; Chem. Abstrs., 1973, 80, 3162.
5. US Pat. 3100805; Chem. Abstrs., 1963, 60, 2800.
6. G. M. Lampman, D. A. Home, and G. D. Hager, J. Chem.
Eng. Data, 1969, 14, 396.
7
7
+
+
5 [C H ] (80), 53 (69), 39 [C H ] (67).
5
5
3
3
-Ethyl 4-methyl 1-nitrospiro[2.2]pentane-1,4-dicarboxy-
1
late (16). The yield was 36%, Rf 0.50 (light petroleum
ether—AcOEt as the eluent, 4 : 1), the ratio of the isomers
a : b : c : d ≈ 50 : 45 : 5 : 1. MS, m/z (I
(%)): 212
7. Y. Kai, P. Knochel, S. Kwiatkowski, J. D. Dunitz,
D. Seebach, and H.-O. Kalinowski, Helv. Chim. Acta,
1982, 65, 137.
8. P. A. Wade, W. P. Dailey, and P. J. Carrol, J. Am. Chem.
Soc., 1987, 109, 5452.
9. P. A. Wade, P. A. Kondracki, and P. J. Carroll, J. Am.
Chem. Soc., 1991, 113, 8807.
10. E. P. Kohler and S. F. Darling, J. Am. Chem. Soc., 1930,
52, 424.
11. E. P. Kohler and P. Alien, Jr., J. Am. Chem. Soc., 1928,
50, 884.
12. G. A. Russell, M. Makosza, and J. Hershberger, J. Org.
Chem., 1979, 44, 1195.
13. W. G. Brown and F. H. Greenberg, J. Org. Chem.,
1966, 31, 394.
14. P. E. O´Bannon and W. P. Dailey, Tetrahedron Lett., 1989,
30, 4197.
15. P. E. O´Bannon and W. P. Dailey, J. Org. Chem., 1989,
54, 3096.
16. P. E. O´Bannon and W. P. Dailey, Tetrahedron, 1990,
46, 7341.
17. P. E. O´Bannon and W. P. Dailey, Tetrahedron Lett., 1988,
29, 5719.
18. Ch. H. Stammer, Tetrahedron, 1990, 46, 2231.
19. Yu. V. Karyakin and I. I. Angelov, Chistye khimicheskie
veshchestva [Pure Chemical Compounds], Khimiya, Mos-
cow, 1974, 407 pp. (in Russian).
rel
+
+
+
[
(
(
M – OCH3] (6), 198 [M – OC H ] (7), 197 [M – NO ]
2 5 2
+
8), 169 (45), 167 [M – OC H – OCH ] (63), 156 (30), 137
2
5
3
+
+
42), 123 (37), 65 [C H ] (42), 53 (71), 39 [C H ] (80).
5
5
3
3
1
Isomer 16a. H NMR (CDCl ), δ: 1.22 (t, 3 H, Me,
3
3
2
3
J = 7.1 Hz); 1.67 (dd, 1 H, CH CH, J = 5.2 Hz, J = 8.0 Hz);
2
1
2
.76 (dd, 1 H, CH CH, 2J = 5.2 Hz, 3J = 5.6 Hz); 2.10 and
2
.43 (AB system, 2 H, C(2)H , 2J = 6.7 Hz); 2.30 (dd, 1 H,
2
C(4)H, 3J = 5.6 Hz, 3J = 8.0 Hz); 3.64 (s, 3 H, OMe); 4.23
(
(
(
3
1
q, 2 H, CH O, 3J = 7.1 Hz); 13C NMR (CDCl ), δ: 13.4
2
3
Me, 1JC,H = 127 Hz); 14.2 (C(3)H2, JC,H = 168 Hz); 21.0
1
CH, 1J
= 172 Hz); 21.2 (C(2)H , 1JC,H = 170 Hz);
1.0 (Cspiro); 52.0 (OMe, JC,H = 147 Hz); 63.0 (OCH2,
C,H
2
1
JC,H = 149 Hz); 69.6 (C(NO )); 163.9 (CO Et); 171.0
2
2
1
(
3
CO Me). Isomer 16b. H NMR (CDCl ), δ: 1.23 (t, 3 H, Me,
2 3
J = 7.1 Hz); 1.65—1.70 (m, 2 H, CH CH); 2.21 and 2.33
2
(
AB system, 2 H, C(2)H , 2J = 6.7 Hz); 2.33 (m, 1 H,
2
3
C(4)H); 3.63 (s, 3 H, OMe); 4.22 (q, 2 H, CH O, J = 7.1 Hz);
2
1
3
1
C NMR (CDCl ), δ: 13.8 (Me,
J
= 127 Hz); 14.9
C,H
3
1
(
(
C(3)H2, 1JC,H = 167 Hz); 20.2 (CH, JC,H = 171 Hz); 21.3
C(2)H2, 1J
= 170 Hz); 30.9 (Cspiro); 52.1 (OMe, 1JC,H
=
C,H
1
1
(
1
2
47 Hz); 62.9 (OCH2, JC,H = 149 Hz); 69.4 (C(NO )); 163.6
CO Et); 171.2 (CO Me). Isomer 16c. H NMR (CDCl ), δ:
2 2 3
.33 (t, 3 H, Me, J = 7.1 Hz); 1.58 (dd, 1 H, CH CH,
J = 5.2 Hz, J = 8.2 Hz); 1.84 (dd, 1 H, CH CH, J = 5.2 Hz,
2
1
3
2
3
2
2
3
J = 5.4 Hz); 2.23 and 2.37 (AB system, 2 H, C(2)H ,
2
2J = 6.2 Hz); 2.51 (dd, 1 H, C(4)H, 3J = 5.4 Hz, 3J = 8.2 Hz);
3
1
.64 (s, 3 H, OMe); 4.35 (q, 2 H, CH O, 3J = 7.1 Hz);
20. J. A. Arvin and R. Adams, J. Am. Chem. Soc., 1928,
50, 1983.
2
3
C NMR (CDCl ), δ: 14.0 (Me); 14.3 (C(3)H ); 21.7 (CH);
3
2
2
2.3 (C(2)H ); 30.5 (C
); 51.9 (OMe); 62.8 (OCH ); 72.3
21. Org. Synth., Coll. Vol. III, Eds. C. F. H. Allen, N. J.
Drake, C. S. Hamilton, R. L. Shriner, L. I. Smith, and
H. R. Snyder, Wiley and Sons, Inc., New York, 1955,
392 pp.
22. N. S. Zefirov, K. A. Lukin, S. I. Kozhushkov,
T. S. Kuznetsova, and V. A. Piven´, Zh. Org. Khim.,
1988, 24, 1644 [J. Org. Chem. USSR, 1988, 24 (Engl.
Transl.)].
2
spiro
2
(
C(NO )); 163.3 (CO Et); 170.5 (CO Me). Isomer 16d.
2 2 2
1
H NMR (CDCl ), δ: 1.34 (t, 3 H, Me, 3J = 7.1 Hz); 1.74
3
dd, 1 H, CH CH, J = 5.2 Hz, 3J = 8.1 Hz); 1.87 (dd, 1 H,
2
(
2
CH CH, J = 5.2 Hz, 3J = 5.5 Hz); 2.22 and 2.39 (AB system,
2
2
2
H, C(2)H2, 2J = 6.3 Hz); 2.34 (dd, 1 H, C(4)H, 3J = 5.5 Hz,
3
J = 8.1 Hz); 3.66 (s, 3 H, OMe); 4.31 (q, 2 H, CH O,
2
3J = 7.1 Hz); 13C NMR spectrum (CDCl ), δ: 13.9 (Me); 14.2
3
(
6
C(3)H ); 21.6 (CH); 21.9 (C(2)H ); 30.6 (Cspiro); 51.9 (OMe);
23. A. de Mejere, S. I. Kozhushkov, T. Spaeth, and N. S.
Zefirov, J. Org. Chem., 1993, 58, 502.
2
2
2.3 (OCH ); 67.9 (C(NO )); 164.3 (CO Et); 171.1 (CO Me).
2
2
2
2
2
2
4. E. Sternberg and P. Binger, Tetrahedron Lett., 1985, 26, 301.
5. T. E. Stevenes and W. P. Emmons, J. Am. Chem. Soc.,
References
1
957, 79, 6008.
2
6. N. S. Vul´fson, V. G. Zaikin, and A. I. Mikaya, Mass-
spektrometriya organicheskikh soedinenii [Mass Spectrometry
of Organic Compounds], Khimiya, Moscow, 1986, 147 pp.
(in Russian).
1
2
. N. S. Zefirov, T. S. Kuznetsova, and A. N. Zefirov, Izv.
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995, 44, 1543 (Engl. Transl.)].
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997, 33, 916 [Russ. J. Org. Chem., 1997, 33, 849 (Engl.
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