Regioselectivity in the addition of 1,3-dipolarophiles to 6-aryl-1,5-diazabicyclo[3.1.0]hexanes

Article abstract of DOI:10.1023/B:RUJO.0000034912.48684.d4

Thermolysis of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes in the presence of 1,3-dipolarophiles having an unsymmetrically substituted double C=C bond (such as N-arylimides derived from 2-aryl-substituted maleic, citraconic, and itaconic acids, ethyl propynoate, aryl isocyanates, and aryl isothiocyanates) leads to formation of the corresponding 1,3-dipolar cycloaddition products. The reaction is regioselective, and in most cases only one regioisomer is obtained. The addition direction depends on the 1,3-dipolarophile structure, i.e., electronic and steric factors determining the most effective orbital interaction upon approach of the reagent to substrate.

Full text of DOI:10.1023/B:RUJO.0000034912.48684.d4

Russian Journal of Organic Chemistry, Vol. 40, No. 1, 2004, pp. 67-78. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 1, 2004,
pp. 76-87.
Original Russian Text Copyright Ó 2004 by Molchanov, Sipkin, Koptelov, Kopf, Kostikov.
Regioselectivity in the Addition of 1,3-Dipolarophiles
to 6-Aryl-1,5-diazabicyclo[3.1.0]hexanes
A. P. Molchanov1, D. I. Sipkin1, Yu. B. Koptelov1, J. Kopf2, and R. R. Kostikov1
1 St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504 Russia
..
2 Institut fur anorganische Chemie, Martin-Luter-King Platz 6, Hamburg, D-20146 Germany
Received December 18, 2002
Abstract—Thermolysis of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes in the presence of 1,3-dipolarophiles having an
unsymmetrically substituted double C=C bond (such as N-arylimides derived from 2-aryl-substituted maleic,
citraconic, and itaconic acids, ethyl propynoate, aryl isocyanates, and aryl isothiocyanates) leads to formation of
the corresponding 1,3-dipolar cycloaddition products. The reaction is regioselective, and in most cases only one
regioisomer is obtained. The addition direction depends on the 1,3-dipolarophile structure, i.e., electronic and steric
factors determining the most effective orbital interaction upon approach of the reagent to substrate.
diazabicyclo[3.1.0]hexanes Ia and Ib with unsaturated
compounds having an unsymmetrically substituted double
C=C bond, specifically with N-arylimides derived from
2-arylmaleic (IIa–IIh), citraconic (IIIa–IIIg), and ita-
conic acids (IVa and IVb), with compounds possessing a
triple carbon–carbon bond (dimethyl acetylene
dicarboxylate and ethyl 2-propynoate), and also with aryl
isocyanates Va–Vc and aryl isothiocyanates Vd–Vf which
have a double C=N bond.
In the preceding studies we have found that azo-
methine imines generated by thermal cleavage of the
carbon–nitrogen bond in 6-aryl-1,5-diazabicyclo-
[3.1.0]hexanes react with N-arylmaleimides to give 1,3-di-
polar cycloaddition products, substituted perhydropyr-
azolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-diones as mixtures
of trans and cis isomers [1]. The reactions with N-aryl-
maleimides having a substituent in the ortho position of
the aromatic ring are characterized by increased
stereoselectivity, while the same diazabicyclohexanes react
with fumaric acid diesters and fumaronitrile in a
stereoselective fashion, yielding products with a
trans,trans configuration [2].
By heating 6-aryl-1,5-diazabicyclo[3.1.0]hexanes Ia
and Ib with N-aryl-2-arylmaleimides IIa–IIh in boiling
toluene or p-xylene we obtained 20–80% of the corre-
sponding perhydropyrazolo[1,2-a]pyrrolo-[3,4-c]pyrazole-
1,3-diones as mixtures of trans (VIa–VIj) and cis iso-
mers (VIIa–VIIj) (Scheme 1). In some cases,
In the present work we tried to elucidate factors de-
termining the regioselectivity in reactions of 6-aryl-1,5-
Scheme 1.
I, IX, Ar = Ph (a), 4-MeOC6H4 (b); II, R = Ph, R1 = H (a), 4-F (b), 4-OEt (c), 4-Me (d), 4-Cl (e), 4-MeO (f), 3-NO2 (g); R =
4-O2NC6H4, R1 = H (h); VI, VII, VIII,Ar = R = Ph, R1 = H (a), 4-F (b), 4-OEt (c);Ar = Ph, R = 4-O2NC6H4, R1 = H (d), Ar =
4-MeOC6H4, R = Ph, R1 = H (e), 4-Me (f), 4-Cl (g), 4-MeO (h), 3-O2N (i);Ar = 4-MeOC6H4, R = 4-O2NC6H4, R'= H (j).
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MOLCHANOV et al.
Scheme 2.
Ar = Ph (a), 4-MeC6H4 (b), 4-MeOC6H4 (c), 4-EtOC6H4 (d), 3-ClC6H4 (e), 3,4-Cl2C6H4 (f), 3-O2NC6H4 (g).
Scheme 3.
I,Ar = Ph, R = H (a);Ar = 4-MeOC6H4, R = Me (c); IV,Ar' = Ph (a), 4-ClC6H4 (b); XII, XIII,Ar =Ar'= Ph, R = H (a);Ar = Ph,
Ar' = 4-ClC6H4, R = H (b);Ar = 4-MeOC6H4,Ar' = Ph, R = Me (c);Ar = 4-MeOC6H4,Ar' = 4-ClC6H4, R = Me (d).
regioisomeric products VIIIc, VIIIe, and VIIIg were
isolated. According to the H NMR data, the ratio of
actions were regioselective, and the corresponding sub-
stituted perhydropyrazolo[1,2-a]pyrrolo-[3,4-c]pyrazole-
1,3-diones were obtained as mixtures of trans (Xa–Xg)
and cis (XIa–XIg) isomers (Scheme 2). According to the
1H NMR spectra of the reaction mixtures, the trans:cis
isomer ratio (X:XI) was equal to 1 (a), 2.2 (b), 2.1 (c),
1.5 (d), 3.2 (e), and 1.1 (g). The diastereoisomers were
separated by fractional crystallization, and their relative
configurations were determined on the basis of spectral
1
regioisomers (VI + VII):VIII was 16 : 1 (b), 18 : 1 (c),
11:1 (d), 14 :1 (e), 15:1 (h), and 10.4 : 1 (i), and the ratio
of stereoisomers VI : VII, 0.63 (b), 0.79 (c), 1.2 (d), 0.68
(e), 0.74 (h), and 0.36 (i). The isomeric products were
separated by column chromatography, and their struc-
ture was determined by spectral methods. The configu-
ration of diastereoisomers VIa–VIj and VIIa–VIIj was
established on the basis of chemical shifts of the 9-H
proton and the respective spin–spin coupling constants.
The adducts characterized by smaller coupling constants
were assigned trans configuration (VI), while those char-
acterized by greater coupling constants were assumed to
have cis configuration (VII). In the 1H NMR spectra of
trans isomers VIa–VIj we observed two doublets in
the regions d 3.75–3.84 and 4.47–4.64 ppm (J = 4.4–
4.9 Hz), while the corresponding signals from cis iso-
mers VIIa–VIIj appeared at d 4.09–4.18 and 4.43–
4.51 ppm (J = 8.9–10.0 Hz). Regioisomers VIII which
lack vicinal CH protons showed in the 1H NMR spec-
tra two singlets at d 4.23–4.32 and 4.80–4.84 ppm. It
should be noted that 2-arylmaleimides are less reactive
than their unsubstituted analogs; therefore, in some cases
the reactions mixtures contained appreciable amounts
of the corresponding 1-arylmethyldihydropyrazoles IXa
and IXb which were formed from 6-aryldiazabicyclo-
hexanes Ia and Ib via concurrent thermal isomerization.
1
data. In the H NMR spectra of trans isomers Xa–Xg
two characteristic doublets were present at d 3.36–3.44
and 4.28–4.39 ppm (J = 4.4–5.1 Hz), while the corre-
sponding signals in the spectra of cis isomers XIa–XIg
apeared at d 3.48–3.56 and 4.35–4.46 ppm (J = 8.9–
9.8 Hz).
The structure of the products was established on the
basis of their elemental compositions and spectral param-
eters. Compound XIIb showed in the 1H NMR spec-
trum a doublet of doublets at d 4.18 ppm (J = 7.1, 9.3
Hz), which belongs to the 3'-H proton coupled with
nonequivalent protons of the neighboring methylene group
(C2'H2); signals from the latter are located at d 2.18 (d.d,
J = 7.1, 13.2 Hz) and 3.35 ppm (d.d, J = 9.3, 13.2 Hz).
Signals from methylene protons in the pyrrolidine ring
appear at d 3.00 (d, J = 18.5 Hz) and 3.48 ppm (d, J =
18.5 Hz). The corresponding proton signals of diastereo-
isomer XIIIb were observed in the 1H NMR spectrum
at d, ppm: 4.00 t (3'-H, J = 8.4 Hz); 2.72 d.d (J = 8.4,
13.2 Hz) and 2.86 d.d (J = 8.4, 13.2 Hz) (C2'H2), 3.09 d
(CH2, pyrrolidine, J= 18.1 Hz), and 3.26 d (CH2, pyrrolidine,
Diazabicyclohexane Ia reacted with citraconic acid
N-arylimides IIIa–IIIg on heating in toluene. These re-
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REGIOSELECTIVITYINTHEADDITIONOF1,3-DIPOLAROPHILES
69
J = 18.1 Hz). The relative configuration of the chiral cen-
ters (3R,3'S) in molecules XIIa and XIIb was assigned
on the basis of the X-ray diffraction data for adduct XIIa
(see figure); correspondingly, stereoisomers XIIIa and
XIIIb were assigned (3R,3'R) structure.
The ratios of adducts XIIa/XIIIa and XIIb/XIIIb
are close to 1.5, whereas thermolysis of diazabicyclo-
hexane Ic having two methyl groups in position 3 gives
rise to only one isomer which was identified as rel-
Structure of rel-(3R,3'S)-1,3'-diphenylspiro[pyrrolidine-
3,1'-tetrahydro-1H,5H-pyrazolo[1,2-a]pyrazole]-2,5-
dione (XIIa) according to the X-ray diffraction data.
1
(3R,3'S)-XIId on the basis of the H NMR data. The
1H NMR spectrum of XIId contained signals at d, ppm:
4.38 t (J = 8.4 Hz), 2.25 d.d (J = 8.4, 12.8 Hz), and
3.24 d.d (J = 8.4, 12.8 Hz); the observed chemical
shifts are fairly similar to those found for compound
XIIb.
imine. However, although such an approach seems to be
the most probable, there are no unambiguous proofs for its
configuration. Likewise, the reduced reactivity of
maleimides containing substituents at the double bond is
likely to result from steric interactions in the transition state.
No cycloaddition products were formed when the
thermolysis of 6-aryldiazabicyclohexanes was performed
in the presence of styrene or cinnamic acid esters, pre-
sumably because of insufficient reactivity of these
dipolarophiles. Heating of diazabicyclohexane Ia in p-xy-
lene in the presence of dimethyl acetylenedicarboxylate
or of diazabicyclohexane Ib in the presence of ethyl 2-
propynoate resulted in formation of substituted
pyrazolo[1,2-a]pyrazolecarboxylates XIV and XV in 56
and 43% yield, respectively (Scheme 5). The structure
of XIV and XV was established on the basis of analytical
and spectral data. The stereoisomeric configuration of
1
XV was assigned using H NMR spectroscopy. In the
1H NMR spectrum we observed singlets from the methine
proton at d 5.12 ppm and proton at the double bond at d
7.12 ppm.
The regioselectivity in the addition of N-arylimides
derived from 2-arylmaleic, citraconic, and itaconic acids
to azomethine imines generated from 6-aryldiazabicyclo-
hexanes Ia–Ic does does not corresponds to that expected
under charge or orbital control of the process. The re-
sults of MNDO calculations showed that the maximal
electron density in imides II is localized on the
unsubstituted carbon atom at the double bond, and in imi-
des III and IV, on the quaternary carbon atom. Both
double-bonded carbon atoms in imides II and III are char-
acterized by almost equal coefficients in the lowest un-
occupied molecular orbital (LUMO). Therefore, we be-
lieve that the regioselectivity in the addition is controlled
mainly by steric interactions in the transition state. Scheme
4 illustrates different modes of reactant approach, which
are characterized by the least steric interactions in the
case of trans configuration of intermediate azomethine
Published data on the regioselectivity of reactions of
azomethine imines with propynoates and acrylates are
contradictory. Azomethine imine generated in situ from
5-phenyl-1,3,4-oxadiazin-2-one and benzaldehyde reacts
with methyl acrylate to give product with vicinal aryl and
ester groups [3], whereas reactions of methyl propynoate
with 5,5-dimethyl-1-(arylmethylene)-3-oxopyrazolidin-1-
ium-2-ides generated from 5,5-dimethylpyrazolidin-3-one
and aromatic aldehydes lead mainly to formation of mix-
tures of regioisomeric aducts or sterically less hindered
regioisomer (in the case of 2,6-disubstituted benzaldehydes
[4]. In the adducts formed by allyl propynoate with
azomethine imines having no aryl substituent, e.g., those
generated from pyrazolidin-3-ones and formaldehyde, the
methylene and ester groups occupy 1,3-positions [5].
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MOLCHANOV et al.
EXPERIMENTAL
As we already reported [6], thermolysis of diazabi-
cyclohexanes Ia–Ih in the presence of aryl isocyanates
Va–Vc or aryl isothiocyanates Vd–Vf occurs in a
regioselelective fashion to give substituted per-
hydropyrazolo[1,2-a][1,2,4]triazoles XVIa–XVIj in high
yields (Scheme 6). The structure of adducts XVIa–
XVIj was confirmed by their analytical and spectral
data.
The IR spectra were obtained on a UR-20 spectro-
photometer from 2% solutions in chloroform. The 1H NMR
spectra were recorded on a Bruker DPX-300 spectrom-
eter (300 MHz) from 5% solutions in CDCl3.
Initial 6-aryl-1,5-diazabicyclo[3.1.0]hexanes Ia–Ih
were synthesized by condensation of 1,3-propanediamine
with the corresponding aldehyde, followed by oxidation
of the resulting hexahydropyrimidine according to the
procedure reported in [1, 9].
The regioselectivity in this reaction corresponds to
that observed previously for 1-arylmethylene-3-oxo-1-
pyrazolidin-1-ium-2-ides [7] and azomethine imines gen-
erated from 2-alkyl-3,3-pentamethylene-1-(p-tolyl-
sulfonyl)diaziridines [8]: in all cases, 1,2,4-triazole deriva-
tives were obtained.
6-(2-Methoxyphenyl)-1,5-diazabicyclo[3.1.0]-
hexane (Ih). A solution of 13.6 g (0.1 mol) of
2-methoxybenzaldehyde in 60 ml of methanol and 30 ml
of water was added dropwise with stirring over a period
of 3 h to 9.2 ml (0.11 mol) of 1,3-propanediamine, main-
taining the temperature not exceeding 45°C (the mixture
was cooled with ice water). When the entire amount of
the aldehyde was added, the mixture was stirred at room
Scheme 4.
Scheme 5.
Scheme 6.
I, R = H, Ar = Ph (a), Ar = 4-MeOC6H4 (b); R = Me, Ar = 4-
MeOC6H4 (c), R = H, Ar = 4-MeC6H4 (d), 4-ClC6H4 (e), 4-
NCC6H4 (f), 4-BrC6H4 (g), 2-MeOC6H4 (h); V, Y = O, R' = Ph
(a), 1-naphthyl (b), 3,4-Cl2C6H3 (c); Y = S, R' = Me (d), Et (e),
Ph (f); XVI, Y = O, R = H, R' = 1-naphthyl, Ar = 4-MeC6H4
(a), 4-MeOC6H4 (b), 4-ClC6H4 (c); R' = Ph, Ar = 4-NCC6H4
(d), 2-MeOC6H4 (e); R' = 3,4-Cl2C6H3, Ar = 4-BrC6H4 (f); R =
Me, R' = Ph, Ar = 4-MeOC6H4 (g); Y = S, R = H, Ar = Ph, R' =
Me (h), Et (i); Ar = 4-NCC6H4, R’ = Ph (j).
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REGIOSELECTIVITYINTHEADDITIONOF1,3-DIPOLAROPHILES
71
temperature (18–20°C). Methanol was distilled off un-
der reduced pressure at a temperature not exceeding
45°C, a 2.5 N alkaline solution of sodium hypochlorite
(53 ml, 0.133 mol) was added dropwise to the residue
over a period of 20 min under stirring and cooling with ice
water, and the mixture was stirred for 1 h at 18–20°C.
The organic layer was separated, and the aqueous layer
was shaken with benzene. The combined extracts were
washed over sodium sulfate, and the solvent was distilled
off on a rotary evaporator at a temperature not exceed-
ing 50°C. The residue was recrystallized first from ether
containing a small amount of benzene and then from a
mixture of benzene, ether, and hexane to obtain 8.4 g
(44%) of diazaalkane Ih. mp 83–84°C. IR spectrum,
5.56; N 9.88, 9.85. C26H23N3O2. Calculated, %: C 76.26;
H 5.66; N 10.26.
2-(4-Fluorophenyl)-3a,9-diphenylperhydro-
pyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-dione
(VIb/VIIb) and 2-(4-fluorophenyl)-9,9a-diphenylper-
hydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-
dione (VIIIb) were synthesized from 0.96 g (6 mmol)
of diazabicyclohexane Ia and 0.80 g (3 mmol) of imide
IIb in 7 ml of toluene. The products were isolated by
column chromatography, followed by recrystallization
from ether. Yield 0.33 g (26%) of trans isomer VIb,
mp 139°C, and 0.50 g (39%) of cis isomer VIIb, mp
137°C. 1H NMR spectrum, d, ppm (J, Hz): trans isomer
VIb: 2.22–2.32 m (2H), 2.70–2.81 m (1H), 3.19–3.34 m
(2H), 3.49–3.59 m (1H), 3.84 d (1H, 4.9), 4.55 d (1H,
4.9), 7.20–7.43 (10H), 7.51 d (2H, 7.1), 7.62 d (2H, 7.1);
cis isomer VIIb: 2.19–2.30 m (2H), 2.58–2.67 m (1H),
2.83–2.92 m (1H), 3.15 t. d (1H, 9.3, 3.5), 3.33–3.42 m
(1H), 4.18 d (1H, 9.7), 4.51 d (1H, 9.7), 7.00–7.09 (4H),
–1
n, cm : 880, 980, 1040, 1050, 1090, 1120, 1160, 1180,
1260, 1290, 1305, 1340, 1400, 1440, 1465 s, 1495, 1590,
1605, 2840, 2880, 2990 s, 3040. 1H NMR spectrum, d,
ppm (J, Hz): 1.88–2.02 m (2H), 3.09–3.23 m (2H), 3.55-
3.65 m (2H), 3.62 s (1H), 3.86 s (3H), 6.86 d (1H, 8.0),
6.96 t (1H, 7.3), 7.22–7.28 (1H), 7.36 d (1H, 7.3). Found,
%: C 69.32; H 7.27; N 14.89. C11H14N2O. Calculated,
%: C 69.45; H 7.42; N 14.73.
–1
7.33–7.53 (8H), 7.65–7.78 (2H). IR spectrum, n, cm :
cis isomer VIIa: 1120, 1160, 1240, 1300, 1380, 1450, 1510,
1730 s, 2870, 2980, 3040. Found (for trans isomer VIb),
%: C 72.86, 72.98; H 5.12, 5.33; N 9.61, 9.76.
C26H22FN3O2. Calculated, %: C 73.05; H 5.19; N 9.83.
Thermolysis of 1,5-diazabicyclo[3.1.0]hexanes in
the presence of dipolarophiles. A mixture of 1,5-di-
azabicyclo[3.1.0]hexane and dipolarophile in p-xylene was
stirred at 135–140°C over a period of 25 min for com-
pound Ia or 20 min for Ib. The reactions with the other
diazabicyclohexanes were carried out in toluene at 110°C
(2 h). The solvent was distilled off, and the residue was
either recrystallized from appropriate solvent or subjected
to column chromatography on silica gel L 100/160 mm
(gradient elution with hexane–ethyl acetate, from 6 : 1
do 1 : 1).
Characteristic proton signals of isomer VIIIb in
the 1H NMR spectrum of the reaction mixture, d, ppm
(J, Hz): 4.35 s (1H), 4.84 s (1H). Yield of dihydropyrazole
IXb 0.18 g (19%).
2-(4-Ethoxyphenyl)-3a,9-diphenylperhydro-
pyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-dione
(VIc/VIIc) and 2-(4-ethoxyphenyl)-9,9a-diphenyl-
perhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-
dione (VIIIc) were obtained from 1.28 g (8 mmol) of
diazabicyclohexane Ia and 1.17 g (4 mmol) of imide IIc
in 9 ml of toluene. The products were isolated by column
chromatography; trans isomer VIc was then recrystal-
lized from ether, and cis isomer VIIc and regioisomer
VIIIc, from acetone–ether–hexane. Yield 0.66 g (36%)
of trans isomer VIc, mp 182°C, 0.78 g (43%) of cis iso-
mer VIIc, mp 148°C, and 0.07 g (4%) of isomer VIIIc,
2,3a,9-Triphenylperhydropyrazolo[1,2-a]pyr-
rolo[3,4-c]pyrazole-1,3-dione (VIa/VIIa) was synthe-
sized from 1.54 g (9.6 mmol) of diazabicyclohexane Ia
and 1.2 g (4.8 mmol) of imide IIa in 7 ml of toluene. The
product was isolated by column chromatography, followed
by recrystallization from ether. Yield 0.19 g (10%) of trans
isomer VIa, mp 148°C, and 0.29 g (15%) of cis isomer
1
1
VIIa, mp 173°C. H NMR spectrum, d, ppm (J, Hz):
mp 135°C. H NMR spectrum, d, ppm (J, Hz): trans
trans isomer VIa: 2.20–2.32 m (2H), 2.74–2.86 m (1H),
3.21-3.38 m (2H), 3.54–3.65 m (1H), 3.83 d (1H, 4.4),
4.60 d (1H, 4.4), 7.30–7.65 (15H); cis isomer VIIa:
2.23–2.35 m (2H), 2.60–2.71 m (1H), 2.81–2.91 m (1H),
3.16 t.d (1H, 9.4, 4.4), 3.33–3.44 m (1H), 4.18 d (1H,
10.0), 4.50 d (1H, 10.0), 7.07 d (2H, 7.0), 7.30–7.78
(13H). IR spectrum, cm : cis isomer VIIa: 1120, 1160,
1240, 1380, 1510, 1600, 1730 s, 2880, 2990, 3040. Found
(for isomer mixture VIa/VIIa), %: C 76.20, 76.19; H 5.65,
isomer VIc: 1.46 t (3H, 6.9), 2.18–2.35 m (2H), 2.74–
2.84 m (1H), 3.22–3.37 m (2H), 3.54–3.64 m (1H), 3.80
d (1H, 4.4), 4.09 q (2H, 6.9), 4.58 d (1H, 4.4), 7.04 d (2H,
8.8), 7.26–7.44 (8H), 7.52 d (2H, 7.1), 7.62 d (2H, 7.1);
cis isomer VIIc: 1.41 t (3H, 7.0), 2.17–2.35 m (2H), 2.57–
2.68 m (1H), 2.81–2.92 m (1H), 3.14 t.d (1H, 9.4,
4.0), 3.32–3.44 m (1H), 3.99 q (2H, 7.0), 4.16 d (1H,
9.8), 4.50 d (1H, 9.8), 6.83 d (2H, 9.0), 6.95 d (2H, 9.0),
7.38–7.75 (10H); isomer VIIIc: 1.44 t (3H, 7.0), 2.13–
–1
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MOLCHANOV et al.
2.28 m (2H), 2.75–2.87 m (1H), 3.12–3.28 m (2H), 3.47–
3.58 m (1H), 4.04 q (2H, 7.0), 4.32 s (1H), 4.80 s (1H),
6.95 d (2H, 8.0), 7.23 d (2H, 8.0), 7.35–7.68 (10H). IR
7.37–7.58 (10H), 7.65 d (2H, 7.1); cis isomer VIIe: 2.18–
2.31 m (2H), 2.62 q (1H, 8.8), 2.80–2.92 m (1H), 3.14 t.d
(1H, 9.3, 4.0), 3.31–3.42 m (1H), 3.83 s (3H), 4.15 d (1H,
9.7), 4.47 d (1H, 9.7), 6.95 d (2H, 8.8), 7.08 d (2H, 7.1),
7.30–7.75 (10H); isomer VIIIe: 2.15–2.30 m (2H), 2.76–
2.85 m (1H), 3.11–3.26 m (2H), 3.49–3.59 m (1H), 3.81
s (3H), 4.27 s (1H), 4.82 s (1H), 6.89 d (2H, 8.0), 7.30–
–1
spectrum, n, cm : cis isomer VIIc: 1050, 1120, 1170,
1180, 1260, 1300, 1390, 1450, 1510, 1620, 1730 s, 2880,
2890, 3040; isomer VIIIc: 1050, 1120, 1170, 1260, 1310,
1395, 1520, 1620, 1730 s, 2880, 2990, 3040. Found (for
cis isomer VIIc), %:C74.02, 74.19;H6.23, 6.15; N 9.48,
9.48. C28H27N3O3. Calculated, %: C 74.15; H 6.00;
N 9.27.
–1
7.50 (10H), 7.62 d (2H, 8.0). IR spectrum, n, cm : trans
isomer VIe: 1040, 1115, 1130, 1180, 1260, 1305, 1380,
1465, 1520, 1620, 1725 s, 2840, 2970, 3040; isomer VIIIe:
1040, 1115, 1130, 1185, 1260, 1305, 1385, 1520, 1625, 1730
s, 2830, 2890, 2970, 3040. Found (for trans isomer VIe),
%: C 73.82, 73.83; H 5.87, 5.76; N 9.22, 9.22.
C27H25N3O3. Calculated, %: C 73.78; H 5.73; N 9.56.
3a-(4-Nitrophenyl)-2,9-diphenylperhydro-
pyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-dione
(VId/VIId) and 9a-(4-nitrophenyl)-2,9-diphenylper-
hydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-
dione (VIIId) were synthesized from 0.32 g (2 mmol)
of diazabicyclohexane Ia and 0.29 g (1 mmol) of imide
IIh in 6 ml of p-xylene. Recrystallization from benzene–
hexane and then from acetone–hexane gave 0.11 g
(24%) of trans isomer VId, mp 171°C, and 0.13 g (29%)
9-(4-Methoxyphenyl)-2-(4-methylphenyl)-3a-
phenylperhydropyrazolo[1,2-a]pyrrolo[3,4-c]-
pyrazole-1,3-dione (VIf/VIIf) was synthesized from
0.83 g (4.37 mmol) of diazabicyclohexane Ib and 0.5 g
(1.9 mmol) of imide IId in 5 ml of toluene. The product
was isolated by column chromatography, followed by re-
crystallization from ether. Yield 0.07 g (8%) of trans iso-
mer VIf, mp 112°C, and 0.1 g (12%) of cis isomer VIIf,
mp 138°C. 1H NMR spectrum, d, ppm (J, Hz): trans
isomer VIf: 2.15–2.32 m (2H), 2.42 s (3H), 2.71–2.81 m
(1H), 3.16–3.35 m (2H), 3.48–3.59 m (1H), 3.77 d (1H,
4.4), 3.81 s (3H), 4.51 d (1H, 4.4), 6.90 d (2H, 8.8), 7.20–
7.68 (11H); cis isomer VIIf: 2.15–2.28 m (2H), 2.33 s
(3H), 2.56–2.66 m (1H), 2.79–2.88 m (1H), 3.14 t.d (1H,
9.3, 3.4), 3.30–3.41 m (1H), 3.83 s (3H), 4.12 d (1H, 9.7),
1
of cis isomer VIId, mp 180°C. H NMR spectrum, d,
ppm (J, Hz): trans isomer VId: 2.20–2.40 m (2H),
2.77–2.92 m (1H), 3.25–3.41 m (2H), 3.47–3.57 m
(1H), 3.79 d (1H, 4.9), 4.64 d (1H, 4.9), 7.20–7.60
(10H), 7.80 d (2H, 8.5), 8.25 d (2H, 8.5); cis isomer
VIId: 2.21–2.40 m (2H), 2.60–2.72 m (1H), 2.76–
2.87 m (1H), 3.13 t.d (1H, 9.1, 4.4), 3.26–3.42 m (1H),
4.12 d (1H, 9.7), 4.47 d (1H, 9.7), 7.09 d (2H, 6.6), 7.30–
7.60 (8H), 7.91 d (2H, 8.8), 8.32 d (2H, 8.8). IR spec-
–1
trum, n, cm : trans isomer VId: 1080, 1120, 1130, 1180,
–1
4.45 d (1H, 9.7), 6.90–7.75 (13H). IR spectrum, n, cm :
1240, 1310, 1350 s, 1370, 1500, 1530, 1600, 1730 s, 2860,
2980, 3040. Found (for cis isomer VIId), %: C 68.57,
68.96; H 4.96, 5.02; N 12.23, 12.38. C26H22N4O4. Calcu-
lated, %: C 68.71; H 4.82; N 12.33.
cis isomer VIIf: 1040, 1120, 1180, 1260, 1305, 1380, 1520,
1625, 1730 s, 2870, 2970, 3030. Found, %: for trans iso-
mer VIf: C 73.90, 74.29; H 6.18, 6.08; N 9.04, 9.09; for
cis isomer VIIf: C 74.14, 74.30; H 6.00, 6.23; N 9.11,
9.10. C28H27FN3O3. Calculated, %: C 74.15; H 6.00; N
9.27.
Characteristic proton signal of isomer VIIId in the
1H NMR spectrum of the reaction mixture: d 4.84 ppm
(s, 1H).
2-(4-Chlorophenyl)-9-(4-methoxyphenyl)-3a-
phenylperhydropyrazolo[1,2-a]pyrrolo[3,4-c]-
pyrazole-1,3-dione (VIg/VIIg) and 2-(4-
chlorophenyl)-9-(4-methoxyphenyl)-9a-
phenylperhydro-pyrazolo[1,2-a]pyrrolo[3,4-
c]pyrazole-1,3-dione (VIIIg) were synthesized from
1.21 g (6.37 mmol) of diazabicyclohexane Ib and 0.91 g
(3.2 mmol) of imide IIe in 9 ml of toluene. The products
were isolated by column chromatography, followed by
recrystallization from acetone–ether–hexane. Yield 0.3 g
(20%) of trans isomer VIg, mp 139°C, 0.64 g (42%) of
cis isomer VIIg, mp 130°C, and 0.03 g (1.6%) of
regioisomer VIIIg, mp 110°C. 1H NMR spectrum, d, ppm
(J, Hz): trans isomer VIg: 2.15–2.38 m (2H), 2.66–2.79 m
(1H), 3.13–3.30 m (2H), 3.42–3.53 m (1H), 3.81 s (4H),
9-(4-Methoxyphenyl)-2,3a-diphenylperhydro-
pyrazolo[1,2-a]pyrrolo[3,4-c]pyrazol-1,3-dione (VIe/
VIIe) and 9-(4-methoxyphenyl)-2,9a-diphenylper-
hydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-
dione (VIIIe) were synthesized from 1.9 g (10 mmol)
of diazabicyclohexane Ib and 1.25 g (5 mmol) of imide
IIa in 12 ml of toluene. The products were isolated by
column chromatography, followed by recrystallization
from ether. Yield 0.55 g (25%) of trans isomer VIe, mp
134°C, 0.61 g (28%) of cis isomer VIIe, mp 143°C, and
0.11 g (5%) of regioisomer VIIIe, mp 141°C. 1H NMR
spectrum, d, ppm (J, Hz): trans isomer VIe: 2.22–2.35 m
(2H), 2.73–2.83 m (1H), 3.20–3.32 m (2H), 3.47–3.55 m
(1H), 3.81 s (4H), 4.52 d (1H, 4.9), 6.90 d (2H, 8.8),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 1 2004

REGIOSELECTIVITYINTHEADDITIONOF1,3-DIPOLAROPHILES
73
4.47 d (1H, 4.9), 6.89 d (2H, 8.8), 7.33–7.45 (7H), 7.51 d
(2H, 8.8), 7.61 d (2H, 7.1); cis isomer VIIg: 2.18–2.31 m
(2H), 2.54–2.68 m (1H), 2.79–2.92 m (1H), 3.12 t.d (1H,
9.3, 4.0), 3.29–3.43 m (1H), 3.83 s (3H), 4.15 d (1H, 9.9),
4.47 d (1H, 9.9), 6.91 d (2H, 8.8), 7.03 d (2H, 8.8), 7.25–
7.75 (9H); isomer VIIIg: 2.15–2.28 m (2H), 2.75–2.84
m (1H), 3.11–3.25 m (2H), 3.48–3.56 m (1H), 3.82 s (3H),
4.23 s (1H), 4.81 s (1H), 6.89 d (2H, 8.4), 7.22–7.49
2.96 m (1H), 3.14 t.d (1H, 9.3, 3.5), 3.32–3.45 m (1H),
3.87 s (3H), 4.19 d (1H, 9.7), 4.52 d (1H, 9.7), 6.98 d
(2H, 8.4), 7.40–7.75 (9H), 7.97 s (1H), 8.13 d (1H, 7.9).
–1
IR spectrum, n, cm : 1040, 1120, 1175, 1260, 1305, 1350 s,
1380, 1520, 1540, 1620, 1735 s, 2880, 2990, 3040. Found,
%: C 66.88, 66.69; H 5.33, 5.16; N 11.30, 11.31.
C27H24N4O5. Calculated, %: C 66.93; H 4.99; N 11.56.
Characteristic signals of isomers VIi and VIIIi in the
1H NMR spectrum of the reaction mixture, d, ppm (J,
Hz): trans isomer VIi: 3.10–3.23 m (1H), 3.32–3.45 m
(1H), 3.83 s (3H), 4.45 d (1H, 5.1); regioisomer VIIIi:
4.32 s (1H), 4.87 s (1H). Yield of dihydropyrazole IXb
0.48 g (42%).
–1
(10H), 7.61 d (2H, 7.1). IR spectrum, n, cm : trans iso-
mer VIg: 1040, 1100, 1130, 1180, 1260, 1305, 1375, 1460,
1495, 1520, 1620, 1730 s, 2840, 2975, 3040. Found (for
trans isomer VIg), %: C 68.74; H 5.14; N 8.72.
C27H24ClN3O3. Calculated, %: C 68.42; H 5.10; N 8.87.
Yield of dihydropyrazole IXb 0.63 g (52%).
9-(4-Methoxyphenyl)-3a-(4-nitrophenyl)-2-
phenylperhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyr-
azole-1,3-dione (VIIj) was synthesized from 0.38 g
(2 mmol) of diazabicyclohexane Ib and 0.29 g (1 mmol)
of imide IIh in 3 ml of toluene. Recrystallization from
benzene–hexane gave 0.23 g (47%) of cis isomer VIIj,
2,9-Bis(4-methoxyphenyl)-3a-phenyl-
perhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-
dione (VIh/ VIIh) and 2,9-bis(4-methoxyphenyl)-9a-
phenylperhydropyrazolo[1,2-a]pyrrolo[3,4-
c]pyrazole-1,3-dione (VIIIh) were synthesized from
1.71 g (9 mmol) of diazabicyclohexane Ib and 1.26 g (4.5
mmol) of imide IIf in 11 ml of toluene. The products were
isolated by column chromatography; trans isomer VIh
was then recrystallized from ether, and cis isomer VIIh,
from acetone–ether–hexane. Yield 0.7 g (33%) of trans
isomer VIh, mp 125°C, and 0.93 g (44%) of cis isomer
VIIh, mp 135°C. 1H NMR spectrum, d, ppm (J, Hz): trans
isomer VIh: 2.15–2.34 m (2H), 2.72–2.82 m (1H), 3.18–
3.31 m (2H), 3.46–3.57 m (1H), 3.75 d (1H, 4.4), 3.80 s
(3H), 3.87 s (3H), 4.50 d (1H, 4.4), 6.86 d (2H, 8.8), 7.50
d (2H, 8.8), 7.31–7.45 (7H), 7.57–7.67 (2H); cis isomer
VIIh: 2.17–2.38 m (2H), 2.61 q (1H, 8.8), 2.79–2.90 m
(2H), 3.12 t.d (1H, 9.3, 3.5), 3.78 s (3H), 3.83 s (3H),
4.13 d (1H, 9.7), 4.45 d (1H, 9.7), 6.86 d (2H, 9.3), 6.92 d
(2H, 8.8), 7.00 d (2H, 8.8), 7.40–7.50 (5H), 7.65–7.75
1
mp 183°C. H NMR spectrum, d, ppm (J, Hz): 2.20–
2.40 m (2H), 2.58–2.80 m (1H), 2.75–2.85 m (1H), 3.08–
3.17 m (1H), 3.27–3.39 m (1H), 3.83 s (3H), 4.10 d (1H,
8.9), 4.43 d (1H, 8.9), 6.94 d (2H, 8.1), 7.11 d (2H, 8.1),
7.31–7.47 (5H), 7.91 d (2H, 8.1), 8.33 d (2H, 8.1). IR
–1
spectrum, n, cm : 1040, 1120, 1180, 1260, 1300, 1350 s,
1380, 1530, 1620, 1730 s, 2840, 2970, 3020, 3040. Found,
%: C 67.10, 66.99; H 5.13, 4.98; N 11.13, 11.47.
C27H24N4O5. Calculated, %: C 66.93; H 4.99; N 11.56.
3a-Methyl-2,9-diphenylperhydropyrazolo[1,2-
a]pyrrolo[3,4-c]pyrazole-1,3-dione (Xa/XIa) was syn-
thesized from 0.48 g (3 mmol) of diazabicyclohexane Ia
and 0.42 g (2.25 mmol) of imide IIIa in 5 ml of toluene.
The product was recrystallized from a mixture of acetone
(3 ml) with ether (1.5 ml) to isolate 0.24 g (31%) of trans
isomer Xa, mp 140°C, and 0.29 g (37%) of cis isomer
XIa, mp 184°C. 1H NMR spectrum, d, ppm (J, Hz): trans
isomer Xa: 1.66 s (3H), 2.13–2.27 m (2H), 2.55–2.66 m
(1H), 3.12–3.25 m (2H), 3.38 d (1H, 4.6), 3.41–3.53 m
(1H), 4.39 d (1H, 4.6), 7.29–7.59 (10H); cis isomer XIa:
1.73 s (3H), 2.15–2.36 m (2H), 2.74–2.85 m (1H), 2.97 q
(1H, 8.8), 3.22–3.34 m (2H), 3.51 d (1H, 9.7), 4.40 d
–1
(2H). IR spectrum, n, cm : cis isomer VIIh: 1040, 1115,
1175, 1260, 1305, 1390, 1450, 1470, 1520, 1620, 1730 s,
2845, 2870, 2940, 2970, 2990, 3040. Found (for cis iso-
mer VIIh), %: C 71.56, 71.67; H 6.11, 5.74; N 8.69, 8.85.
C28H27N3O4. Calculated, %: C 71.62; H 5.80; N 8.95.
Characteristic signal of isomer VIIIh in the 1H NMR
spectrum of the reaction mixture: d 4.83 ppm (s, 1H).
–1
(1H, 9.7), 7.12–7.45 (10H). IR spectrum, n, cm : trans
9-(4-Methoxyphenyl)-2-(3-nitrophenyl)-3a-
phenylperhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyr-
azole-1,3-dione (VIIi/VIIIi) and 9-(4-methoxy-phe-
nyl)-2-(3-nitrophenyl)-9a-phenylperhydropyrazolo-
[1,2-a]-pyrrolo[3,4-c]pyrazole-1,3-dione (VIIIg)
were synthesized from 1.14 g (6 mmol) of diazabicyclo-
hexane Ib and 0.88 g (3 mmol) of imide IIg in 9 ml of
toluene. cis Isomer VIIi was recrystallized from ether.
Yield 0.7 g (48%), mp 172°C. 1H NMR spectrum, d,
ppm (J, Hz): 2.14–2.38 m (2H), 2.55–2.69 m (1H), 2.84–
isomer Xa: 1080, 1120, 1140, 1250, 1310, 1370, 1380, 1460,
1510, 1610, 1730 s, 2870, 2980, 3040; cis isomer XIa:
1120, 1160, 1240, 1290, 1305, 1375, 1390, 1455, 1505, 1610,
1730 s, 2870, 2990, 3040. Found, %: for trans isomer Xa:
C 72.83, 72.76; H 6.16, 6.03; N 12.04, 12.12; for cis iso-
mer XIa: C 72.86, 72.44; H 6.12, 6.01; N 11.94, 11.98.
C21H21N3O2. Calculated, %: C 72.60; H 6.09; N 12.10.
3a-Methyl-2-(4-methylphenyl)-9-phenylper-
hydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 1 2004

74
MOLCHANOV et al.
–1
dione (Xb/XIb) was synthesized from 0.62 g (3.9 mmol)
of diazabicyclohexane Ia and 0.6 g (3 mmol) of imide
IIIb in 7 ml of toluene. Recrystallization from benzene–
ether gave 0.55 g (45%) of trans isomer Xb with mp
143°C. 1H NMR spectrum, d, ppm (J, Hz): 1.66 s (3H),
2.14–2.25 m (2H), 2.42 s (3H), 2.56–2.67 m (1H), 3.13–
3.24 m (2H), 3.36 d (1H, 4.4), 3.40–3.50 m (1H), 4.40 d
(1H, 4.4), 7.20 d (2H, 8.1), 7.29–7.44 (5H), 7.58 d (2H,
7.47 (5H). IR spectrum, n, cm : cis isomer XId: 915,
1050, 1120, 1160, 1170, 1245, 1305, 1375, 1390, 1450, 1520,
1620, 1715 s, 2880, 2940, 2990, 3030. Found, %: for trans
isomer Xd: C 70.35, 70.74; H 6.43, 6.53; N 10.81, 10.80;
for cis isomer XId: C 70.58, 70.85; H 6.45, 6.53; N 10.76,
10.73. C23H25N3O3. Calculated, %: C 70.57; H 6.44; N
10.73.
2-(3-Chlorophenyl)-3a-methyl-9-phenylper-
hydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-
dione (Xe/XIe) was synthesized from 0.62 g (3.9 mmol)
of diazabicyclohexane Ia and 0.67 g (3 mmol) of imide
IIIe in 7 ml of toluene. Fractional crystallization of a mix-
ture of cis and trans isomers from acetone–ether gave
0.52 g (46%) of trans isomer Xe, mp 164°C, and 0.21 g
(18%) of cis isomer XIe, mp 180°C. 1H NMR spectrum,
d, ppm (J, Hz): trans isomer Xe: 1.66 s (3H), 2.15–2.25
m (2H), 2.49–2.62 m (1H), 3.10–3.22 m (2H), 3.28–3.35
m (1H), 3.38 d (1H, 4.4), 4.33 d (1H, 4.4), 7.23–7.62
(9H); cis isomer XIe: 1.72 s (3H), 2.21–2.35 m (2H),
2.74–2.85 m (1H), 2.92–3.03 m (1H), 3.23–3.33 m (2H),
3.50 d (1H, 9.8), 4.35 d (1H, 9.8), 7.05–7.48 (9H). IR
–1
7.5). IR spectrum, n, cm : 915, 1140, 1250, 1370, 1380,
1450, 1520, 1725 s, 2870, 2940, 2980, 3040. Found, %:
C 73.30, 73.12; H 6.50, 6.42; N 11.70, 11.60. C22H23N3O2.
Calculated, %: C 73.11; H 6.41; N 11.63. Characteristic
signals of cis isomer XIb in the 1H NMR spectrum of the
reaction mixture, d, ppm (J, Hz): 1.72 s (3H), 2.35 s (3H),
2.73–2.84 m (1H), 3.49 d (1H, 9.8), 4.40 d (1H, 9.8).
2-(4-Methoxyphenyl)-3a-methyl-9-phenylper-
hydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-
dione (Xc/XIc) was synthesized from 0.32 g (2 mmol)
of diazabicyclohexane Ia and 0.33 g (1.5 mmol) of imide
IIIc in 5 ml of toluene. By fractional crystallization from
ether we isolated 0.31 g (55%) of trans isomer Xc, mp
132°C, and 0.13 g (24%) of cis isomer XIc, mp 182°C.
1H NMR spectrum, d, ppm (J, Hz): trans isomer Xc:
1.68 s (3H), 2.15–2.25 m (2H), 2.56–2.64 m (1H), 3.12–
3.24 m (2H), 3.36 d (1H, 4.9), 3.38–3.49 m (1H), 3.86 s
(3H), 4.39 d (1H, 4.9), 7.02 d (2H, 8.1), 7.21–7.40 (5H),
7.58 d (2H, 7.3); cis isomer XIc: 1.72 s (3H), 2.14–2.37 m
(2H), 2.73–2.83 m (1H), 2.92–3.02 m (1H), 3.23–3.24 m
(2H), 3.49 d (1H, 8.9), 3.81 s (3H), 4.40 d (1H, 8.9), 6.92
d (2H, 8.1), 7.10 d (2H, 8.1), 7.30–7.47 (5H). IR spec-
–1
spectrum, n, cm : cis isomer XIe: 1120, 1150, 1240, 1370,
1385, 1455, 1485, 1600, 1735 s, 2870, 2990, 3040. Found
(for cis isomer XIe), %: C 65.90, 65.85; H 5.54, 5.49;
N 10.74, 10.92. C21H20ClN3O2. Calculated, %: C 66.05;
H 5.28; N 11.00.
2-(3,4-Dichlorophenyl)-3a-methyl-9-phenylper-
hydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-
dione (Xf/XIf) was synthesized from 0.62 g (3.9 mmol)
of diazabicyclohexane Ia and 0.77 g (3 mmol) of imide
IIIf in 7 ml of toluene. Fractional crystallization from
acetone–ether–hexane gave 0.35 g (28%) of trans iso-
mer Xf, mp 152°C, and 0.33 g (27%) of cis isomer XIf,
mp 159°C. 1H NMR spectrum, d, ppm (J, Hz): trans iso-
mer Xf: 1.65 s (3H), 2.16–2.29 m (2H), 2.51 q (1H, 8.8),
3.07–3.17 m (2H), 3.27–3.34 m (1H), 3.38 d (1H, 4.4),
4.28 d (1H, 4.4), 7.26–7.61 (8H); cis isomer XIf: 1.72 s
(3H), 2.20–2.35 m (2H), 2.73–2.84 m (1H), 2.91–3.03 m
(1H), 3.27–3.33 m (2H), 3.50 d (1H, 9.5), 4.41 d (1H,
9.5), 7.05–7.15 (1H), 7.30–7.52 (7H). IR spectrum, n,
–1
trum, n, cm : cis isomer XIc: 1040, 1120, 1160, 1170,
1180, 1260, 1305, 1390, 1460, 1520, 1620, 1730 s, 2840,
2870, 2940, 2990, 3040. Found (for cis isomer XIc), %:
C 70.11, 69.91; H 6.14, 6.37; N 10.97, 11.04. C22H23N3O3.
Calculated, %: C 70.01; H 6.14; N 11.13.
2-(4-Ethoxyphenyl)-3a-methyl-9-phenylper-
hydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-
dione (Xd/XId) was synthesyzed from 0.62 g (3.9 mmol)
of diazabicyclohexane Ia and 0.69 g (3 mmol) of imide
IIId in 7 ml of toluene. Fractional crystallization from ac-
etone–ether gave 0.26 g (22%) trans isomer Xd,
mp 118°C, and 0.66 g (57%) of cis isomer XId, mp 187°C.
1H NMR spectrum, d, ppm (J, Hz): trans isomer Xd:
1.45 t (3H, 7.1), 1.65 s (3H), 2.12–2.28 m (2H), 2.60 q
(1H, 8.8), 3.12–3.25 m (2H), 3.36 d (1H, 4.4), 3.38–
3.53 m (1H), 4.08 q (2H, 7.1), 4.39 d (1H, 4.4), 7.00 d
(2H, 8.8), 7.22 d (2H, 8.8), 7.30–7.43 d (3H), 7.57 d
(2H, 7.5); cis isomer XId: 1.41 t (3H, 7.1), 1.71 s (3H),
2.18–2.34 m (2H), 2.73–2.84 m (1H), 2.97 q (1H, 8.8),
3.22–3.33 m (2H), 3.48 d (1H, 9.5), 4.01 q (2H, 7.1),
4.39 d (1H, 9.5), 6.90 d (2H, 8.6), 7.08 d (2H, 8.6), 7.30–
–1
cm : cis isomer XIf: 1040, 1120, 1135, 1155, 1240, 1370,
1385, 1455, 1480, 1730 s, 2870, 2990, 3040. Found, %: for
trans isomer Xf: C 60.65, 60.41; H 4.47, 4.62; N 9.83,
9.80; [dlya tsis-izomera (XIe)]: C 60.34, 60.55; H 4.61,
4.62; N 10.04, 10.00. C21H19Cl2N3O2. Calculated, %:
C 60.59; H 4.60; N 10.09.
3a-Methyl-2-(3-nitrophenyl)-9-phenylper-
hydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-
dione (Xg/XIg) was synthesized from 0.52 g (3.25 mmol)
of diazabicyclohexane Ia and 0.69 g (2.5 mmol) of imide
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 1 2004

REGIOSELECTIVITYINTHEADDITIONOF1,3-DIPOLAROPHILES
75
IIIg in 7 ml of toluene. Recrystallization from acetone–
ether gave colorless crystals of trans isomer Xg with mp
191°C. The mother liquor was evaporated, and the residue
was recrystallized from benzene–ether to obtain 0.4 g (41%)
of cis isomer XIg with mp 188°C. 1H NMR spectrum, d,
ppm (J, Hz): trans isomer Xg: 1.69 s (3H), 2.20–2.30 m
(2H), 2.47–2.58 m (1H), 3.07–3.17 m (2H), 3.26–3.35 m
(1H), 3.44 d (1H, 5.1), 4.29 d (1H, 5.1), 7.32–7.80 (7H),
8.28–7.31 (2H); cis isomer XIg: 1.76 s (3H), 2.19–2.38 m
(2H), 2.75–2.89 m (1H), 2.93–3.05 m (1H), 3.22–3.37 m
(2H), 3.56 d (1H, 9.7), 4.46 d (1H, 9.7), 7.33–7.67 (7H),
2.89–3.01 m (2H), 3.01 d (1H, 18.5), 3.08–3.16 m (1H),
3.17–3.28 m (1H), 3.35 d.d (1H, 13.2, 9.3), 3.48 d (1H,
18.5), 4.18 d.d (1H, 9.3, 7.1), 7.23–7.51 (9H); isomer
XIIIb: 2.07–2.22 m (1H), 2.23–2.38 m (1H), 2.72 d.d
(1H, 13.2, 8.4), 2.75–2.85 m (1H), 2.86 d.d (1H, 13.2,
8.4), 2.96–3.13 m (3H), 3.10 d (1H, 18.1), 3.27 d (1H,
18.1), 4.0 t (1H, 8.4), 7.26–7.40 (5H), 7.47 d (2H, 8.8),
7.61 d (2H, 7.1). 13C NMR spectrum, dC, ppm: isomer
XIIb: 26.09 (CH2), 45.73 (CH2), 46.84 (CH2), 47.58
(CH2), 50.33 (CH2), 67.76 (CH), 68.88, 127.82, 128.04,
128.07, 129.13, 129.79, 130,69, 134.93, 141.91, 173.95,
176.36; isomer XIIIb: 25.40 (CH2), 41.28 (CH ), 46.18
–1
8.10 s (1H), 8.18–8.24 (1H). IR spectrum, n, cm : cis
2
isomer XIg: 1020, 1100, 1120, 1140, 1160, 1240, 1315,
1355 s, 1380, 1460, 1490, 1540, 1735 s, 2850, 2880, 2980,
3040. Found, %: for trans isomer Xg: C 64.44, 64.15; H
5.33, 5.23; N 14.14, 14.34; for cis isomer XIg: C 64.54,
64.54; H 5.19, 5.29; N 14.18, 14.25. C21H20N4O4. Calcu-
lated, %: C 64.28; H 5.14; N 14.28.
(CH2), 47.90 (CH2), 49.39 (CH2), 66.45 (CH), 68.37,
128.04, 128.28, 128.81, 129.00, 129.69, 130.68, 134.75,
–1
140.42, 173.35, 177.39. IR spectrum, n, cm : isomer
XIIIb: 1040, 1100, 1180, 1270, 1300, 1380, 1495, 1520,
1620, 1730 s, 2840, 2870, 2960, 3040. Found, %: for iso-
mer XIIb: C 65.97, 66.20; H 5.38, 5.25; N 10.93, 10.99;
for isomer XIIIb: C 66.33, 66.19; H 5.30, 5.24; N 11.07,
11.08. C21H20ClN3O2. Calculated, %: C 66.05; H 5.28;
N 11.00.
rel-(3R,3'S)-1,3'-Diphenylspiro[pyrrolidine-3,1'-
tetrahydro-1H,5H-pyrazolo[1,2-a]pyrazole]-2,5-dione
(XIIa) and rel-(3R,3'R)-1,3'-diphenylspiro-[pyrrolidine-
3,1'-tetrahydro-1H,5H-pyrazolo[1,2-a]-pyrazole]-2,5-
dione (XIIIa) were synthesized from 0.48 g (3mmol) of
diazabicyclohexane Ia and 0.56 g (3 mmol) of itaconic
acid imide IVa in 7 ml of toluene. Recrystallization of the
residue from acetone–ether gave 0.18 g (17%) of stere-
oisomer XIIa, mp 167°C, and 0.12 g (12%) of isomer mix-
ture XIIa/XIIIa. 1H NMR spectrum, d, ppm (J, Hz): iso-
mer XIIa: 2.05–2.23 m (1H), 2.20 d.d (1H, 13.2, 7.0),
2.29–2.43 m (1H), 2.90–3.03 m (2H), 3.02 d (1H, 18.5),
3.08–3.19 m (1H), 3.19–3.30 m (1H), 3.35 d.d (1H, 13.2,
9.3), 3.48 d (1H, 18.5), 4.20 d.d (1H, 9.3, 7.0), 7.29–7.56
rel-(3R,3'S)-3'-(4-Methoxyphenyl)-6',6'-dim-
ethyl-1-phenylspiro[pyrrolidine-3,1'-tetrahydro-
1H,5H-pyrazolo[1,2-a]pyrazole]-2,5-dione (XIIc)
was synthesized from 0.33 g (1.5 mmol) of
diazabicyclohexane Ic and 0.26 g (1.5 mmol) of itaconic
acid imide IVa in 6 ml of toluene. Recrystallization from a
mixture of acetone (3 ml), ether (2 ml), and hexane (2 ml)
gave 0.08 g (14%) of isomer XIIc with mp 142°C. An
additional amount of adduct XIIc was isolated from the
mother liquor by column chromatography. Overall yield
0.2 g (34%). 1H NMR spectrum, d, ppm (J, Hz): 1.25 s
(3H), 1.28 s (3H), 2.25 d.d (1H, 12.8, 8.4), 2.68 d (1H,
8.4), 2.71 d (1H, 10.1), 2.86 d (1H, 10.1), 2.97 d (1H,
18.1), 3.09 d (1H, 8.4), 3.24 d.d (1H, 12.8, 8.4), 3.40 d
(1H, 18.1), 3.83 s (3H), 4.38 t (1H, 8.4), 6.91 d (2H,
–1
(10H). IR spectrum, n, cm : isomer XIIa: 1075, 1110,
1130, 1190, 1240, 1380, 1450, 1500, 1595, 1730 s, 2890,
2960, 2980, 3040. Found (for isomer XIIa), %: C 72.93,
72.81; H 6.24, 6.27; N 12.32, 12.19. C21H21N3O2. Cal-
culated, %: C 72.60; H 6.09; N 12.10. Characteristic
1H NMR signals of isomer XIIIa, d, ppm (J, Hz): 3.28 d
(1H, 18.1), 3.95–4.12 m (1H).
–1
8.4), 7.29–7.56 (7H). IR spectrum, n, cm : 1040,
1120, 1190, 1250, 1300, 1460, 1520, 1620, 1730 s, 2840,
2870, 2960, 3040. Found, %: C 72.93, 72.81; H 6.24, 6.27;
N 12.32, 12.19. C24H27N3O3. Calculated, %: C 72.60;
H 6.09; N 12.10.
rel-(3R,3'S)-1-(4-Chlorophenyl)-3'-phenyl-
spiro[pyrrolidine-3,1'-tetrahydro-1H,5H-pyrazolo-
[1,2-a]pyrazole]-2,5-dione (XIIb) and rel-(3R,3'R)-
1-(4-chlorophenyl)-3'-phenylspiro[pyrrolidine-3,1'-
tetrahydro-1H,5H-pyrazolo[1,2-a]pyrazole]-2,5-
dione (XIIIb) were synthesized from 0.64 g (4 mmol)
of diazabicyclohexane Ia and 0.44 g (2 mmol) of itaconic
acid imide IVb in 5 ml of toluene. Recrystallization of the
residue from acetone gave 0.26 g (34%) of isomer XIIb,
mp 168°C, and 0.12 g (16%) of isomer XIIIb, mp 182°C.
1H NMR spectrum, d, ppm (J, Hz): isomer XIIb: 2.06–
2.24 m (1H), 2.19 d.d (1H, 13.2, 7.1), 2.29–2.42 m (1H),
rel-(3R,3'S)-1-(4-Chlorophenyl)-3'-(4-methoxy-
phenyl)-6',6'-dimethylspiro[pyrrolidine-3,1'-
tetrahydro-1H,5H-pyrazolo[1,2-a]pyrazole]-2,5-
dione (XIId) was synthesized from 0.65 g (3 mmol)
of diazabicyclohexane Ic and 0.66 g (3 mmol) of ita-
conic acid imide IVb in 7 ml of toluene. Recrystalliza-
tion from acetone–ether–hexane gave 0.39 g (30%)
of stereoisomer XIId with mp 168°C. An additional
amount of adduct XIId was isolated from the mother
liquor by column chromatography. Overall yield 0.69 g
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 1 2004

76
MOLCHANOV et al.
(53%). 1H NMR spectrum, d, ppm (J, Hz): 1.24 s (3H),
1.29 s (3H), 2.23 d.d (1H, 13.1, 8.5), 2.65 d (1H, 8.5), 7.05 d (2H, 7.8), 7.07–7.16 m (1H), 7.22 d (2H, 7.8),
(3H), 3.35–3.63 m (2H), 4.06 br.s (1H), 5.82 br.s (1H),
2.71 d (1H, 10.0), 2.86 d (1H, 10.0), 2.96 d (1H, 18.5),
3.08 d (1H, 8.5), 3.24 d.d (1H, 13.1, 8.5), 3.40 d (1H,
18.5), 3.83 s (3H), 4.37 t (1H, 8.5), 6.91 d (2H, 8.5), 7.30
d (2H, 8.5), 7.34 d (2H, 8.5), 7.48 d (2H, 8.5). IR spec-
7.32–7.40 m (1H), 7.46–7.57 (2H), 7.77 d (1H, 8.1), 7.83–
7.91 (2H). IR spectrum, n, cm : 1015, 1035, 1075, 1095,
1115, 1155, 1250, 1280, 1295, 1330, 1345, 1380, 1410, 1470,
1595, 1720 s, 2860, 2925, 2980, 3010, 3035. Found, %: C
76.64, 77.03; H 6.03, 6.04; N 12.20, 12.29. C22H21N3O.
Calculated, %: C 76.94; H 6.16; N 12.24.
–1
–1
trum, n, cm : 1040, 1100, 1180, 1250, 1300, 1380, 1490,
1520, 1620, 1730 s, 2840, 2870, 2960, 3040. Found, %:
C 65.72, 65.74; H 6.26, 6.06; N 9.27, 9.55.
C24H26ClN3O3. Calculated, %: C 65.52; H 5.96; N 9.55.
3-(4-Methoxyphenyl)-2-(1-naphthyl)perhydro-
pyrazolo[1,2-a][1,2,4]triazol-1-one (XVIb) was synthe-
sized from 0.67 g (3.5 mmol) of diazabicyclohexane Ib
and 0.59 g (3.5 mmol) of isocyanate Vb in 7 ml of toluene.
Recrystallization from benzene–hexane gave 1.13 g (90%)
of adduct XVIb with mp 149°C. 1H NMR spectrum, d,
ppm (J, Hz): 2.22–2.44 m (2H), 3.06–3.30 m (1H), 3.33–
3.62 m (2H), 3.74 s (3H), 3.93–4.18 m (1H), 5.80 br.s
(1H), 6.77 d (2H, 8.1), 7.03–7.07 m (1H), 7.26 d (2H,
8.1), 7.32–7.40 m (1H), 7.47–7.58 (2H), 7.77 d (1H,
Dimethyl 5-phenyl-2,3-dihydro-1H,5H-pyr-
azolo[1,2-a]pyrazole-6,7-dicarboxylate (XIV) was
synthesized from 0.18 g (1.1 mmol) of diazabicyclohexane
Ia and 0.14 g (1 mmol) of dimethyl acetylenedicarboxylate
in 6 ml of p-xylene. The product was isolated from the
reaction mixture by preparative thin-layer chromatog-
raphy on silica gel 5/40 mm using hexane–ethyl acetate
(3 : 1) as eluent. Yield 0.17 g (56%), mp 80°C. 1H NMR
spectrum, d, ppm (J, Hz): 2.05–2.25 m (2H), 2.85–
2.95 m (1H), 3.14-3.25 m (1H), 3.30–3.41 m (1H), 3.45–
3.56 m (1H), 3.63 s (3H), 3.95 s (3H), 5.21 s (1H), 7.24–
–1
8.1), 7.83–7.91 (2H). IR spectrum, n, cm : 1040, 1070,
1095, 1115, 1150, 1180, 1260, 1290, 1305, 1340, 1375,
1410, 1465, 1520, 1605, 1610, 1720 s, 2840, 2910,
2940, 2970, 3005, 3040. Found, %: C 73.46, 73.60;
H 5.57, 5.57; N 11.59, 11.53. C22H21N3O2. Calcu-
lated, %: C 73.59; H 5.89; N 11.69.
–1
7.48 (5H). IR spectrum, n, cm : 1070, 1100, 1140, 1270,
1340, 1440, 1620, 1700 s, 1755 s, 2860, 2960, 3040. Found,
%: C 63.77, 63.33; H 6.00, 5.96; N 9.48, 9.29.
C16H18N2O4. Calculated, %: C 63.57; H 6.00; N 9.27.
3-(4-Chlorophenyl)-2-(1-naphthyl)per-
hydropyrazolo[1,2-a][1,2,4]triazol-1-one (XVIc) was
synthesized from 0.68 g (3.5 mmol) of diazabicyclohexane
Ie and 0.59 g (3.5 mmol) of isocyanate Vb in 7 ml of
toluene. Recrystallization from benzene–hexane gave
Ethyl 5-(4-methoxyphenyl)-2,3-dihydro-1H,5H-
pyrazolo[1,2-a]pyrazole-6-carboxylate (XV). A mix-
ture of 0.29 g (1.5 mmol) of diazabicyclohexane Ib
and 0.18 g (1.8 mmol) of ethyl 2-propynoate in 5 ml of
p-xylene containing a small amount of hydroquinone was
stirred for 2 h at 110°C. The product was isolated from
the reaction mixture by column chromatography on silica
gel 40/60 mm (substrate-to-sorbent ratio 1:50; gradient
elution with petroleum ether (bp 40–70°C)–diethyl ether,
3 : 1). Yield 0.2 g (43%), oily substance. 1H NMR spec-
trum, d, ppm (J, Hz): 1.22 t (3H, 7.1), 2.01–2.21 m (2H),
2.76–2.88 m (1H), 3.08–3.17 m (1H), 3.36–3.53 m (2H),
3.79 s (3H), 4.10 q (2H, 7.1), 5.12 s (1H), 6.85 d (2H,
1
1.21 g (95%) of compound XVIc with mp 126°C. H
NMR spectrum, d, ppm (J, Hz): 2.24–2.45 m (2H), 3.10–
3.29 m (1H), 3.35–3.63 m (2H), 3.94–4.20 m (1H), 5.83
br.s (1H), 7.02–7.60 (8H), 7.79 d (2H, 8.1), 7.85–7.94 m
–1
(1H). IR spectrum, n, cm : 1020, 1070, 1095, 1130, 1150,
1235, 1270, 1290, 1345, 1380, 1410, 1465, 1495, 1520,
1540, 1605, 1720 s, 2850, 2915, 2980, 3040. Found, %:
C 69.33; H 5.05; N 11.61. C21H18ClN3O. Calculated, %:
C 69.32; H 4.99; N 11.55.
–1
8.8), 7.12 s (1H), 7.35 d (2H, 8.8). IR spectrum, n, cm :
4-(3-Oxo-2-phenylperhydropyrazolo[1,2-a]-
[1,2,4]triazol-1-yl)benzonitrile (XVId) was synthe-
sized from 0.24 g (1.3 mmol) of diazabicyclohexane If
and 0.15 g (1.3 mmol) of isocyanate Va in 3 ml of tolu-
ene. Recrystalization from ether containing a small amount
of acetone gave 0.36 g (92%) of adduct XVId with mp
200°C. 1H NMR spectrum, d, ppm (J, Hz): 2.14–2.30 m
(2H), 2.65–2.82 m (1H), 3.14–3.28 m (1H), 3.31–3.45 m
(1H), 3.92–4.07 m (1H), 5.89 s (1H), 7.05–7.49 (5H),
910, 1040, 1080, 1100, 1165, 1180, 1260 s, 1305, 1320,
1380, 1460, 1520, 1610, 1695 s, 2840, 2910, 2940, 2990,
1
3040. According to the H NMR data, no other
regioisomer was present in the reaction mixture.
3-(4-Methylphenyl)-2-(1-naphthyl)perhydro-
pyrazolo[1,2-a][1,2,4]triazol-1-one (XVIa) was synthe-
sized from 0.44 g (2.5 mmol) of diazabicyclohexane Id
and 0.42 g (2.5 mmol) of isocyanate Vc in 6 ml of toluene.
Recrystallization from benzene–hexane gave 0.75 g (87%)
of adduct XVIa with mp 150°C. 1H NMR spectrum, d,
ppm (J, Hz): 2.21–2.42 m (2H), 2.10–2.30 m (1H), 2.28 s
–1
7.54 d (2H, 8.4), 7.69 d (2H, 8.4). IR spectrum, n, cm :
1040, 1085, 1115, 1150, 1245, 1295, 1330, 1350, 1385 s,
1460, 1505, 1610, 1730 s, 2240, 2855, 2885, 2990, 3040.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 1 2004

REGIOSELECTIVITYINTHEADDITIONOF1,3-DIPOLAROPHILES
77
Found, %: C 71.02, 71.27; H 5.28, 5.50; N 18.38, 18.29.
C18H16N4O. Calculated, %: C 71.04; H 5.30; N 18.41.
Recrystallization from acetone–ether–hexane gave 0.58
g (83%) of compound XVIh with mp 115°C. 1H NMR
spectrum, d, ppm (J, Hz): 2.10–2.23 m (2H), 2.50–2.64
m (1H), 3.09 s (3H), 3.12–3.24 m (1H), 3.52–3.68 m
(1H), 4.22–4.40 m (1H), 5.48 s (1H), 7.30–7.47 (5H). IR
3-(2-Methoxyphenyl)-2-phenylperhydropyr-
azolo[1,2-a][1,2,4]triazol-1-one (XVIe) was synthe-
sized from 0.57 g (3 mmol) of diazabicyclohexane Ih and
0.36 g (3 mmol) of isocyanate Va in 7 ml of toluene. Re-
crystallization from acetone–ether gave 0.84 g (90%) of
adduct XVIe with mp 129°C. 1H NMR spectrum, d, ppm
(J, Hz): 2.12–2.25 m (2H), 2.68 q (1H, 9.3), 3.18–3.28 m
(1H), 3.36–3.45 m (1H), 3.96 s (3H), 3.97–4.06 m (1H),
6.34 s (1H), 6.90 t (1H, 7.5), 6.98 d (1H, 8.4), 7.02–7.09
m (1H), 7.22–7.35 m (4H), 7.53 d (2H, 7.9). IR spec-
–1
spectrum, n, cm : 880, 910, 990, 1010, 1050, 1095, 1120,
1170, 1250, 1290, 1305, 1325 s, 1340, 1400, 1460, 1495,
1540, 1605, 2860, 2885, 2915, 2980, 3030. Found, %: C
61.61, 61.73; H 6.67, 6.59; N 18.04, 18.00. C12H15N3S.
Calculated, %: C 61.77; H 6.48; N 18.01.
2-Ethyl-3-phenylperhydropyrazolo[1,2-
a][1,2,4]triazole-1-thione (XVIi) was synthesized from
0.48 g (3 mmol) of diazabicyclohexane Ia and 0.26 g (3
mmol) of isothiocyanate Ve in 5 ml of toluene. Recrys-
tallization from ether containing a small amount of hex-
ane gave 0.66 g (89%) of compound XVIi with mp 107°C.
1H NMR spectrum, d, ppm (J, Hz): 1.14 t (3H, 7.1), 2.10–
2.24 m (2H), 2.48–2.60 m (1H), 3.13 sext (1H, 7.1), 3.14–
3.25 m (1H), 3.43–3.59 m (1H), 4.13 sext (1H, 7.1), 4.29–
4.47 m (1H), 5.52 s (1H), 7.30–7.47 (5H). IR spectrum,
n, cm–1: 1015, 1060, 1085, 1120, 1160, 1265 s, 1320, 1340,
1380, 1340, 1455, 1480, 1520, 1600, 2850, 2880, 2940,
2980, 3040. Found, %: C 62.85, 62.96; H 6.80, 6.93; N
17.13, 17.11. C13H17N3S. Calculated, %: C 63.12; H 6.93;
N 16.99.
–1
trum, n, cm : 1035, 1055, 1080, 1105, 1110, 1160, 1250,
1280, 1330, 1390 s, 1440, 1465, 1505, 1610, 1720 s, 2845,
2910, 2945, 2980, 3040. Found, %: C 69.32; H 7.27;
N 14.89. C18H19N3O2. Calculated, %: C 69.45; H 7.42;
N 14.73.
3-(4-Bromophenyl)-2-(3,4-dichlorophenyl)per-
hydropyrazolo[1,2-a][1,2,4]triazol-1-one (XVIf) was
synthesized from 0.6 g (2.5 mmol) of diazabicyclohexane
Ig and 0.47 g (2.5 mmol) of isocyanate Vc in 6 ml of tolu-
ene. Recrystallization from benzene–ether gave 1.01 g
(94%) of compound XVIf with mp 165°C. 1H NMR spec-
trum, d, ppm (J, Hz): 2.13–2.27 m (2H), 2.56–2.76 m
(1H), 3.14–3.48 m (2H), 3.82–4.08 m (1H), 5.76 s (1H),
7.22–7.30 (3H), 7.34 d (1H, 9.1), 7.53 d (2H, 8.4), 7.75 s
4-(2-Phenyl-3-thioxoperhydropyrazolo[1,2-
a][1,2,4]triazol-1-yl)benzonitrile (XVIj) was synthe-
sized from 0.24 g (1.3 mmol) of diazabicyclohexane If
and 0.18 g (1.3 mmol) of isothiocyanate Vf in 3 ml of
toluene. Recrystallization from ether containing a small
amount of acetone gave 0.34 g (81%) of compound XVIj
with mp 160?C. 1H NMR spectrum, d, ppm (J, Hz):
12.23–2.37 m (2H), 2.77–2.90 m (1H), 3.31–3.40 m (1H),
3.49–3.63 m (1H), 4.51–4.64 m (1H), 5.89 s (1H), 7.25–
7.42 (5H), 7.45 d (2H, 8.2), 7.63 d (2H, 8.2). IR spec-
trum, n, cm–1: 1015, 1055, 1090, 1120, 1260, 1280, 1310,
1315 s, 1405 s, 1460, 1505, 1605, 2240, 2855, 2990, 3040.
Found, %: C 67.72, 67.72; H 5.23, 5.26; N 17.56, 17.37.
C18H16N4S. Calculated, %: C 67.47; H 5.03; N 17.49.
–1
(1H). IR spectrum, n, cm : 1015, 1035, 1085, 1105, 1140,
1285, 1360, 1380, 1410, 1480 s, 1600, 1730 s, 2850, 2980,
3040. Found, %: C 48.01, 48.21; H 3.26, 3.39; N 9.72,
9.73. C17H14BrCl2N3O. Calculated, %: C 47.80; H 3.30;
N 9.84.
3-(4-Methoxyphenyl)-6,6-dimethyl-2-
phenylperhydropyrazolo[1,2-a][1,2,4]triazol-1-one
(XVIg) was synthesized from 0.33 g (1.5 mmol) of
diazabicyclohexane Ic and 0.18 g (1.5 mmol) of isocyan-
ate Va in 4 ml of toluene. Recrystallization from acetone–
hexane gave 0.39 g (76%) of adduct XVIg with mp 170°C.
1H NMR spectrum, d, ppm (J, Hz): 1.22 s (3H), 1.26 s
(3H), 2.62 br.s (1H), 3.02 br.s (2H), 3.62–3.85 m (1H),
3.79 s (3H), 5.74 br.s (1H), 6.88 d (2H, 8.8), 7.03–7.11 m
X-Ray analysis of compound XIIa. C21H21N3O2,
M 347.41; crystal habit 0.3´0.1´0.1 mm; monoclinic crys-
tals, space group P21/c (no. 14); unit cell parameters
(120°C): a = 13.5737 (10), b = 7.1974 (5), c = 20.6403
(11) A°; b = 120.796(3)°; V = 1732.1 (2) A°3; Z = 4; dcalc
–1
(1H), 7.03–7.58 (6H). IR spectrum, n, cm : 1040, 1075,
1090, 1105, 1120, 1145, 1180, 1260, 1305, 1340, 1380 s,
1460, 1505, 1520, 1600, 1610, 1720 s, 2840, 2875, 2910,
2940, 2965, 3010, 3040. Found, %: C 71.40, 70.94; H
6.81, 6.85; N 12.48, 12.33. C20H23N3O2. Calculated, %:
C 71.19; H 6.87; N 12.45.
–3
–1
= 1.332 g/cm ; m = 0.087 mm ; F (000) = 736.0; MoKa
radiation, l = 0.71073A, graphite monochromator, qmax
=
27.45°. Selected bond lengths and bond angles: N1–C2
1.485(3), N1–N5 1.467(4), C2–C3 1.537(3), C3–C4
1.537(4), N5–C4 1.497(3), C2–C12 1.531(4), C2–C9
1.532(4) A; C9C2C12 102.86(18), N1C2C3 105.90(16),
2-Methyl-3-phenylperhydropyrazolo[1,2-a]-
[1,2,4]triazole-1-thione (XVIh) was synthesized
from 0.48 g (3 mmol) of diazabicyclohexane Ia and
0.22 g (3 mmol) of isothiocyanate Vd in 5 ml of toluene.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 1 2004

78
MOLCHANOV et al.
C3C2C12C11 –143.0(2), C3C2C9N10 142.6(2), N1C2C12C11
98.4(2), N1C2C9N10 –98.6(2). An additional information
is available from the Cambridge Crystal Structure Data-
base (CCDC-208216).
2. Molchanov,A.P., Sipkin, D.I., Koptelov,Yu.B., Kopf, J., and
Kostikov, R.R., Russ. J. Org. Chem., 2003, vol. 39,
p. 1338.
3. Roussi, F., Bonin, M., Chiaroni, A., Micouin, L., Riche, C.,
and Husson, H.-P., Tetrahedron Lett., 1999, vol. 40,
p. 3727.
4. Turk, C., Svete, J., Stanovnik, B., Goli, L., Goli-Grdadolnik, S.,
Golobi, A., and Seli, L., Helv. Chim. Acta, 2001,
vol. 84, p. 146.
This study was financially supported by the Ministry
of Education of the Russian Federation (project no. E00-
5-263).
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