Stereoselectivity 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.0000010225.29775.d3

Thermolysis of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes in the presence of N-arylmaleimides having a substituent in the ortho position of the aromatic ring leads to predominant formation of the corresponding trans-9- arylperhydropyrazolo[1,2-a]pyrrolo[3,4-c]

Full text of DOI:10.1023/B:RUJO.0000010225.29775.d3

Russian Journal of Organic Chemistry, Vol. 39, No. 9, 2003, pp. 1338 1345. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 9, 2003,
pp. 1410 1417.
Original Russian Text Copyright
2003 by Molchanov, Sipkin, Koptelov, Kopf, Kostikov.
Stereoselectivity 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, D-20146 Hamburg, Germany
Received December 18, 2002
Abstract Thermolysis of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes in the presence of N-arylmaleimides having
a substituent in the ortho position of the aromatic ring leads to predominant formation of the corresponding
trans-9-arylperhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-diones. 6-Aryl-1,5-diazabicyclo[3.1.0]hexanes
react with fumaric acid derivatives in a stereoselective fashion, affording perhydropyrazolo[1,2-a]pyrazoles
with a trans,trans configuration.
We previously showed that thermolysis of 6-aryl-
1,5-diazabicyclo[3.1.0]hexanes involves cleavage of
the nitrogen carbon bond with formation of azo-
methinimine which is then converted into dihydro-
pyrazole [1] or trapped by active dipolarophiles, e.g.,
N-arylmaleimides [2]. In the present work we tried
to elucidate factors determining stereoselectivity of
the cycloaddition. For this purpose, we examined the
reaction of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes Ia
Id with ortho-substituted N-arylmaleimides IIa IIh,
fumaric acid esters, and fumaronitrile. According to
the X-ray diffraction data, crystalline 6-phenyl- (Ia,
Fig. 1) and 6-(4-methoxyphenyl)-1,5-diazabicyclo-
[3.1.0]hexanes (Ib), as well as previously reported
6-(4-chlorophenyl)-1,5-diazabicyclo[3.1.0]hexane (Ic)
[3], exist as exo isomers in which the six-membered
ring has a boat conformation and the benzene ring
is located in the bisector plane of the diaziridine ring.
By heating of exo-6-aryl-1,5-diazabicyclo[3.1.0]-
hexanes Ia Id with N-arylmaleimides IIa IIh we
obtained the corresponding perhydropyrazolo[1,2-a]-
pyrrolo[3,4-c]pyrazole-1,3-diones as mixtures of trans
(IIIa IIIs) and cis isomers (IVb, IVc, IVi IVl, IVo,
IVp, IVs) (Scheme 1). Their structure was established
on the basis of their spectral parameters and elemental
analyses.
While studying the reaction of diazabicyclohexanes
with para-substituted N-arylmaleimides we showed
that the ratio of trans and cis isomers in the products
depends on the nature of substituents in the aryl ring
of both diazabicyclohexane and maleimide [2]. The
results of the present study indicate that introduction
Scheme 1.
I, V, Ar = Ph (a), 4-MeOC6H4 (b), 4-ClC6H4 (c), 4-MeC6H4 (d); II, Ar = 2,4,6-Me3C6H2 (a), 2,5-Me2C6H3 (b), 2,6-Cl2C6H3
(c), 2,4-Cl2C6H3 (d), 1-naphthyl (e), 2,4-Me2C6H3 (f), 2-BrC6H4 (g), 2-ClC6H4 (h); III, IV, Ar = Ph, Ar = 2,4,6-Me3C6H2 (a),
2,5-Me2C6H3 (b), 2,6-Cl2C6H3 (c), 2,4-Cl2C6H3 (d), 1-naphthyl (e), 2,4-Me2C6H3 (f), 2-BrC6H4 (g); Ar = 4-MeOC6H4, Ar =
2,4,6-Me3C6H2 (h), 2,6-Cl2C6H3 (i), 2,4-Cl2C6H3 (j), 1-naphthyl (k), 2-BrC6H4 (n), 2-ClC6H4 (m); Ar = 4-ClC6H4, Ar =
2,4,6-Me3C6H2 (n), 2,6-Cl2C6H3 (o), 2,4-Cl2C6H3 (p), 1-naphthyl (q), 2-BrC6H4 (r); Ar = 4-MeC6H4, Ar = 2,6-Cl2C6H3 (s).
1070-4280/03/3909-1338$25.00 2003 MAIK Nauka/Interperiodica

STEREOSELECTIVITY IN THE ADDITION OF 1,3-DIPOLAROPHILES
of substituents into the ortho position of the aromatic
1339
ring of N-arylmaleimide considerably increases the
fraction of the corresponding trans isomer III. The
isomer ratios III:IV are as follows: 5:1 (b), 7:1 (c),
11:1 (i), 6:1 (j), 12:1 (k), 7:1 (l), 13:1 (o), 5:1 (p),
and 15:1 (s). In the other cases, no cis isomer IV
was detected.
It should be noted that the reaction of diazabicyclo-
hexanes with ortho-substituted maleimides gives two
rotamers of each trans- (III) and cis-adduct (IV) due
to restricted rotation of the aryl group in the pyrroli-
dine ring; the rotamers can be distinguished by the
1H NMR spectra [4]. These results support the pre-
vious assumption that dipolarophile approaches inter-
mediate trans-azomethinimine (formed via thermally
allowed conrotatory opening of nonplanar 6-aryl-1,5-
diazabicyclohexane) preferentially from the exo side,
giving rise to trans isomer III. The trans/cis isomer
ratio does not change on temperature variation from
110 to 140 C.
The reaction of diazabicyclohexanes Ia If with
fumaric acid derivatives VIa VIc at 110 140 C gave
substituted perhydropyrazolo[1,2-a]pyrazoles VIIa
VIIh (Scheme 2). Their structure was derived from
their spectral parameters and elemental composition.
The 1H NMR spectrum of VIIb contained two
doublets from aromatic protons at 7.41 (2H, J =
8.5 Hz) and 6.94 ppm (2H, J = 8.5 Hz), a doublet
Fig. 1. Structure of 6-phenyl-1,5-diazabicyclohexane (Ia)
according to the X-ray diffraction data.
The relative configuration of the substituents in
positions 2 and 3 was established by analysis of the
two-dimensional 1H NMR spectrum of compound
VIIb, as well as by NOE experiments. In the 2D
spectrum of VIIb (Fig. 2), ortho-protons of the
methoxyphenyl group in position 3 give cross peaks
with protons in positions 3 and 2. This is possible
only when the methoxyphenyl and cyano groups are
arranged trans. The lack of nuclear Overhauser effect
on successive irradiation of each of the three protons
(1-H, 2-H, and 3-H) also supports the trans,trans
configuration of the adducts.
Thus we presume that the reaction with fumaric
acid derivatives involves formation of a transition
state like A:
from the 1-H proton at
a doublet from 3-H at
4.35 ppm (J = 4.2 Hz),
3.97 ppm (J = 7.5 Hz),
a singlet from the methoxy group at
3.84 ppm,
a doublet of doublets from 2-H at 3.52 ppm (J = 7.5
and 4.2 Hz), and multiplet signals from protons of
the trimethylene group in the regions 2.60 3.27 ppm
(NCH2) and 2.20 2.81 ppm (NCH2CH2). Magnetic
nonequivalence of the methylene protons results from
their pseudoaxial or pseudoequatorial orientation.
In this case, steric interactions between the elec-
tron-acceptor group in fumaric acid derivative and aryl
group of azomethinimine are stronger than interaction
with the trimethylene bridge, so that the trans,trans-
adduct is obtained.
Scheme 2.
EXPERIMENTAL
The IR spectra were recorded on a UR-20 spectro-
1
photometer from 2% solutions in chloroform. The H
NMR spectra were measured on a Bruker DPX-300
instrument (300 MHz) from 5% solutions in CDCl3.
Initial 6-aryl-1,5-diazabicyclo[3.1.0]hexanes Ia Id
were prepared by condensation of the corresponding
aromatic aldehyde with 1,3-diaminopropane, followed
by oxidation of intermediate hexahydropyrimidine
according to the procedure reported in [2].
4-(1,5-Diazabicyclo[3.1.0]hex-6-yl)benzonitrile
(Ie). A solution of 6.6 g (0.05 mol) of 4-cyanobenz-
I, X = H (a), MeO (b), Cl (c), Me (d), CN (e), Br (f);
VI, Y = CN (a), CO2Ph (b), CO2Me (c); VII, Y = CN,
X = H (a), MeO (b), Me (c), CN (d), Cl (e), Br (f); X = H,
Y = CO2Ph (g), CO2Me (h).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

1340
MOLCHANOV et al.
C 71.39; H 5.95; N 22.81. C11H11N3. Calculated, %:
C 71.33; H 5.99; N 22.69.
6-(4-Bromophenyl)-1,5-diazabicyclo[3.1.0]-
hexane (If). A solution of 18.5 g (0.1 mol) of
4-bromobenzaldehyde in a mixture of 140 ml of
methanol and 20 ml of water was added over a period
of 3 h under stirring and cooling with ice water to
10 ml (0.12 mol) of 1,3-diaminopropane, maintaining
the temperature below 45 C. The mixture was stirred
for 1 h at 20 C, methanol was distilled off under
reduced pressure at a temperature not exceeding 45 C,
50 ml (0.125 mol) of a 2.5 N solution of sodium
hypochlorite 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 20 C.
The organic phase was separated, and the aqueous
phase was extracted with benzene. The extracts were
combined with the organic phase and dried over
sodium sulfate, and the solvent was distilled off on
a rotary evaporator at a temperature not exceeding
50 C. Recrystallization of the residue from ether con-
taining small amounts of benzene and hexane gave
16.7 g (70%) of diazabicyclohexane If as colorless
Fig. 2. Two-dimensional 1H NMR spectrum of rel-
(1R,2R,3S)-3-(4-methoxyphenyl)perhydropyrazolo[1,2-a]-
pyrazole-1,2-dicarbonitrile (VIIb).
1
crystals with mp 99 101 C. IR spectrum, , cm :
880, 965, 980, 1020, 1075, 1095, 1190, 1255, 1300,
1340, 1380, 1430, 1455, 1490, 1605, 1640, 2885,
aldehyde in a mixture of 70 ml of methanol and 35 ml
of water was added dropwise under stirring and
cooling with ice water to 8.3 ml (0.1 mol) of 1,3-di-
aminopropane, maintaining the temperature below
45 C. When the addition was complete, the mixture
was stirred for 3.5 h at 20 C, methanol was distilled
under reduced pressure at a temperature not exceeding
45 C, 74 ml (0.17 mol) of a 2.3 N solution of sodium
hypochlorite 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 20 C.
The organic phase was separated, and the aqueous
phase was extracted with benzene. The extracts were
combined with the organic phase and dried over
sodium sulfate, and the solvent was distilled off on
a rotary evaporator at a temperature not exceeding
50 C. The product was isolated by column chromato-
graphy on silica gel (L 100/200; substrate-to-sorbent
weight ratio 1:16; eluent diethyl ether), followed
by recrystallization from diethyl ether. Yield 3.94 g
1
2990 s, 3040 s. H NMR spectrum, , ppm (J, Hz):
1.82 2.03 m (2H), 3.09 s (1H), 3.12 3.23 m (2H),
3.52 3.66 m (2H), 7.23 d (2H, 7.9), 7.47 d (2H, 7.9).
Found, %: C 50.19, 50.12; H 4.41, 4.60; N 11.82,
11.68. C10H11BrN2. Calculated, %: C 50.23; H 4.64;
N 11.72.
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 Ia If and the corresponding
dipolarophile in p-xylene was stirred for 20 min (Ib,
Id), 25 min (Ia), or 30 min (Ic) at 135 140 C (or in
toluene, for 2 h at 110 C). The solvent was distilled
off, and the residue was either recrystallized from
appropriate solvent or purified by chromatography.
The products were colorless crystalline substances.
rel-(3aS,9S,9aR)-2-Mesityl-9-phenylperhydro-
pyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-dione
(IIIa) was synthesized from 0.64 g (4 mmol) of diaza-
bicyclohexane Ia and 0.86 g (4 mmol) of imide IIa
in 8 ml of p-xylene. Recrystallization from acetone
diethyl ether petroleum ether (bp 40 70 C) gave 0.6 g
(40%) of trans isomer IIIa. mp 174 175 C. IR spec-
1
(43%), mp 102 103 C. IR spectrum, , cm : 880,
960, 975 s, 1025, 1110, 1190, 1260, 1290, 1310,
1340, 1380, 1430, 1455, 1470, 1510, 1610, 2240 s,
1
1
trum, , cm : 1040, 1240, 1310, 1340, 1380, 1455,
2885, 2955, 2990 s, 3030 s. H NMR spectrum, ,
1490, 1620, 1730 s, 1795, 2860, 2930, 2990, 3040.
1H NMR spectrum, , ppm (J, Hz): 2.09 s (3H), 2.17 s
(3H), 2.19 2.30 m (2H), 2.32 s (3H), 2.44 2.56 m
(1H), 2.62 2.73 m (1H), 3.20 3.22 m (1H), 3.38
ppm (J, Hz): 1.85 2.03 m (2H), 3.05 3.22 m (3H),
3.58 3.65 m (2H), 7.37 d (2H, 8.5), 7.52 d (2H, 8.5).
13C NMR spectrum, C, ppm: 21.36, 52.16, 55.42,
111.90, 118.62, 128.01, 131.83, 142.49. Found, %:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

STEREOSELECTIVITY IN THE ADDITION OF 1,3-DIPOLAROPHILES
1341
1
3.50 m (1H), 3.97 4.12 m (2H), 4.73 br.s (1H), 6.98 s
(2H), 7.32 7.67 (5H). Found, %: C 73.50, 73.38;
H 6.60, 6.78; N 10.98, 10.90. C23H25N3O2. Calcu-
lated, %: C 73.57; H 6.71; N 11.19. When the reac-
tion was carried out in toluene, the yield of compound
IIIa was 89%.
isomer IIId. mp 169 170 C. IR spectrum, , cm :
1065, 1105, 1150, 1185, 1240, 1375, 1390, 1480,
1610, 1735 s, 2850, 2890, 3040. H NMR spectrum,
1
, ppm (J, Hz): 1.16 2.35 m (2H), 2.44 2.80 m (2H),
3.19 3.35 m (1H), 3.39 3.54 m (1H), 4.02 4.16 m
(2H), 4.73 br.s and 4.82 br.s (1H), 7.17 7.64 (8H).
Found, %: C 59.46, 59.66; H 4.48, 4.42; N 10.68,
10.49. C20H17Cl2N3O2. Calculated, %: C 59.71;
H 4.26; N 10.45.
rel-(3aS,9S,9aR)-2-(1-Naphthyl)-9-phenylper-
hydropyrazolo[1,2-a]pirrolo[3,4-c]pyrazole-1,3-
dione (IIIe) was synthesized from 0.40 g (2.5 mmol)
of compound Ia and 0.61 g (2.5 mmol) of imide IIe
in 6 ml of toluene. Recrystallization from acetone
diethyl ether gave 0.8 g (84%) of trans isomer IIIe.
rel-(3aS,9S,9aR)-2-(2,5-Dimethylphenyl)-9-
phenylperhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyra-
zole-1,3-dione (IIIb) and rel-(3aS,9R,9aR)-2-(2,5-di-
methylphenyl)-9-phenylperhydropyrazolo[1,2-a]-
pyrrolo[3,4-c]pyrazole-1,3-dione (IVb) were synthe-
sized from 0.4 g (2.5 mmol) of compound Ia and
0.5 g (2.5 mmol) of imide IIb in 12 ml of p-xylene.
Recrystallization from diethyl ether containing a small
amount of acetone gave 0.55 g (61%) of trans isomer
1
1
IIIb. mp 161 162 C. IR spectrum, , cm :
mp 178 179 C. IR spectrum, , cm : 1190, 1220,
1240, 1345, 1370, 1405, 1730 s, 2860, 2880, 2980,
3040, 3060. H NMR spectrum, , ppm (J, Hz): 2.18
1
1240, 1370, 1715 s, 2990, 3040. H NMR spectrum,
1
, ppm (J, Hz): 2.12 s and 2.20 s (3H), 2.22 2.30 m
(2H), 2.35 s (3H), 2.44 2.75 m (2H), 3.15 3.34 m
(1H), 3.37 3.53 m (1H), 3.93 4.09 m (2H), 4.73 br.s
(1H), 6.92 s and 6.98 s (1H), 7.14 7.65 (7H). Found,
%: C 73.27, 72.96; H 6.53, 6.64; N 11.72, 11.69.
C22H23N3O2. Calculated, %: C 73.11; H 6.41;
2.35 m (2H), 2.42 2.81 m (2H), 3.22 3.38 m (1H),
3.42 3.56 m (1H), 4.00 4.22 m (2H), 4.83 br.s and
4.95 br.s (1H), 7.33 8.20 (12H). Found, %: C 75.33;
H 5.57; N 11.27. C24H21N3O2. Calculated, %:
C 75.18; H 5.52; N 10.96.
rel-(3aS,9S,9aR)-2-(2,4-Dimethylphenyl)-9-
phenylperhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyra-
zole-1,3-dione (IIIf) was synthesized from 0.32 g
(2 mmol) of compound Ia and 0.40 g (2 mmol) of
imide IIf in 4 ml of toluene. Recrystallization from
a minimal amount of acetone with addition of diethyl
ether gave 0.52 g (72%) of trans isomer IIIf. mp 165
1
N 11.63. Characteristic H signals of cis isomer IVb,
, ppm (J, Hz): 4.37 d (1H, 8), 6.73 s and 6.77 s (1H).
When the reaction was carried out in toluene, the
yield of IIIb was 83%.
rel-(3aS,9S,9aR)-2-(2,6-Dichlorophenyl)-9-
phenylperhydropyrazolo[1,2-a]pirrolo[3,4-c]pyra-
zole-1,3-dione (IIIc) and rel-(3aS,9R,9aR)-2-(2,6-di-
chlorophenyl)-9-phenylperhydropyrazolo[1,2-a]-
pyrrolo[3,4-c]pyrazole-1,3-dione (IVc) were ob-
tained from 0.32 g (2 mmol) of compound Ia and
0.48 g (2 mmol) of imide IIc in 6 ml of p-xylene.
Recrystallization from a mixture of 28 ml of acetone
and 2 ml of diethyl ether gave 0.61 g (76%) of trans
1
166 C. IR spectrum, , cm : 1195, 1240, 1380, 1510,
1610, 1730 s, 2860, 2890, 2930, 2990, 3040. H
1
NMR spectrum, , ppm (J, Hz): 2.10 s and 2.20 s
(3H), 2.19 2.34 m (2H), 2.37 s (3H), 2.45 2.74 m
(2H), 3.19 3.33 m (1H), 3.37 3.52 m (1H), 3.93
4.09 m (2H), 4.70 br.s (1H), 6.95 7.65 (8H). Found,
%: C 72.83, 72.91; H 6.56, 6.49; N 11.61, 11.62.
C22H23N3O2. Calculated, %: C 73.11; H 6.41;
N 11.63.
rel-(3aS,9S,9aR)-2-(2-Bromophenyl)-9-phenyl-
perhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-
dione (IIIg) was synthesized from 0.48 g (3 mmol) of
compound Ia and 0.76 g (3 mmol) of imide IIg in
12 ml of p-xylene. Recrystallization from a small
amount of acetone with addition of diethyl ether gave
0.6 g (49%) of trans isomer IIIg. mp 154 155 C.
1
isomer IIIc. mp 198 199 C. IR spectrum, , cm :
1240, 1370, 1445, 1465, 1730 s, 2990, 3040. 1H
NMR spectrum, , ppm (J, Hz): 2.13 2.32 m (2H),
2.45 2.60 m (1H), 2.70 2.82 m (1H), 3.25 3.39 m
(1H), 3.43 3.56 m (1H), 4.15 4.19 m (2H), 4.88 br.s
(1H), 7.32 7.50 (6H), 7.64 d (2H, 7.5). Found, %:
C 59.94, 59.82; H 4.42, 4.45; N 10.48, 10.50.
C20H17Cl2N3O2. Calculated, %: C 59.71; H 4.26;
1
N 10.45. Characteristic H signals of cis isomer IVc,
, ppm (J, Hz): 3.99 d.d (1H, 9, 8), 4.40 d (1H, 9),
4.50 d (1H, 8).
1
IR spectrum, , cm : 1040, 1060, 1120, 1190, 1240,
rel-(3aS,9S,9aR)-2-(2,4-Dichlorophenyl)-9-
phenylperhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyra-
zole-1,3-dione (IIId) was synthesized from 0.40 g
(2.5 mmol) of compound Ia and 0.61 g (2.5 mmol)
of imide IId in 6 ml of toluene. Recrystallization from
acetone ether hexane gave 0.79 g (79%) of trans
1310, 1340, 1380, 1450, 1480, 1600, 1665, 1740 s,
2850, 2890, 2990, 3040. H NMR spectrum, , ppm
(J, Hz): 2.14 2.34 m (2H), 2.42 2.82 m (2H), 3.22
3.37 m (1H), 3.41 3.55 m (1H), 4.02 4.15 m (2H),
4.71 br.s and 4.92 br.s (1H), 7.22 7.76 (9H). Found,
%: C 58.19, 57.97; H 4.51, 4.61; N 9.85, 10.03.
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

1342
MOLCHANOV et al.
C20H18BrN3O2. Calculated, %: C 58.26; H 4.40;
N 10.19.
2.56 2.75 m (1H), 3.20 3.32 m (1H), 3.37 3.50 (1H),
3.84 s (3H), 3.98 4.12 m (2H), 4.67 br.s and 4.76 br.s
(1H), 6.85 7.62 (7H). Found, %: C 58.57, 58.45;
H 4.53, 4.58; N 9.55, 9.71. C21H19Cl2N3O3. Calcu-
lated, %: C 58.34; H 4.43; N 9.72. Characteristic H
signals of cis isomer IVj, , ppm (J, Hz): 3.85 s (3H),
rel-(3aS,9S,9aR)-2-Mesityl-9-(4-methoxyphenyl)-
perhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-
dione (IIIh) was synthesized from 0.57 g (3 mmol) of
compound Ib and 0.65 g (3 mmol) of imide IIa in
7 ml of toluene. Recrystallization from benzene ether
gave 0.88 g (72%) of trans isomer IIIh. mp 134
1
4.36 d (1H, 9), 4.48 d (1H, 8).
rel-(3aS,9S,9aR)-9-(4-methoxyphenyl)-2-(1-naph-
thyl)perhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyra-
zole-1,3-dione (IIIk) and rel-(3aS,9R,9aR)-9-(4-
methoxyphenyl)-2-(1-naphtyl)perhydropyrazolo-
[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-dione (IVk) were
obtained from 0.38 g (2 mmol) of compound Ib and
0.45 g (2 mmol) of imide IIe in 5 ml of toluene.
Recrystallization from a mixture of 3 ml of acetone
and 3 ml of ether gave 0.71 g (90%) of trans isomer
1
135 C. IR spectrum, , cm : 1040, 1195, 1260, 1310,
1380, 1470, 1490, 1615, 1715 s, 2840, 2960, 2970,
1
3030. H NMR spectrum, , ppm (J, Hz): 2.09 s (3H),
2.17 s (3H), 2.19 2.30 m (2H), 2.32 s (3H), 2.44
2.56 m (1H), 2.62 2.73 m (1H), 3.20 3.22 m (1H),
3.38 3.50 m (1H), 3.97 4.12 m (2H), 4.73 br.s (1H),
6.98 s (2H), 7.32 7.67 (5H). Found, %: C 70.99,
70.77; H 6.55, 6.65; N 10.27, 10.09. C24H27N3O3.
Calculated, %: C 71.09; H 6.71; N 10.36.
1
IIIk. mp 188 C. IR spectrum, , cm : 1040, 1190,
1230, 1260, 1305, 1345, 1370, 1405, 1465, 1520,
1620, 1720 s, 2840, 2910, 2970, 2980, 3040. H
rel-(3aS,9S,9aR)-2-(2,6-Dichlorophenyl)-9-(4-
methoxyphenyl)perhydropyrazolo[1,2-a]pyrrolo-
[3,4-c]pyrazole-1,3-dione (IIIi) and rel-(3aS,9R,9aR)-
2-(2,6-dichlorophenyl)-9-(4-methoxyphenyl)per-
hydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-
dione (IVi) were obtained from 0.48 g (2.5 mmol) of
compound Ib and 0.61 g (2.5 mmol) of imide IIc in
6 ml of toluene. Recrystallization from acetone with
addition of a small amount of ether gave 0.94 g (87%)
of trans isomer IIIi. mp 196 197 C. IR spectrum, ,
1
NMR spectrum, , ppm (J, Hz): 2.15 2.38 m (2H),
2.46 2.57 m (1H), 2.60 2.79 m (1H), 3.21 3.39 m
(1H), 3.42 3.55 m (1H), 3.84 s (3H), 4.01 4.20 m
(2H), 4.75 br.s and 4.89 br.s (1H), 6.95 d (2H, 8.4),
7.34 8.01 (9H). Found, %: C 72.98, 72.80; H 5.69,
5.75; N 10.28, 10.26. C25H23N3O3. Calculated, %:
1
C 72.62; H 5.65; N 10.16. Characteristic H signals
of cis isomer IVk, , ppm (J, Hz): 3.79 s (3H),
4.57 d (1H, 8).
1
cm : 1040, 1110, 1185, 1240, 1260, 1300, 1370,
1440, 1460, 1520, 1620, 1740 s, 2840, 2970, 3040.
1H NMR spectrum, , ppm (J, Hz): 2.15 2.31 m (2H),
2.44 2.57 m (1H), 2.68 2.77 m (1H), 3.25 3.36 m
(1H), 3.43 3.54 m (1H), 3.83 s (3H), 4.07 4.17 m
(2H), 4.85 br.s (1H), 6.95 d (2H, 8.4), 7.3 7.40 m
(1H), 7.45 d (2H, 7.5), 7.55 d (2H, 8.4). Found,
%: C 58.57, 58.42; H 4.55, 4.61; N 9.65, 9.64.
C21H19Cl2N3O3. Calculated, %: C 58.34; H 4.43;
rel-(3aS,9S,9aR)-2-(2-Bromophenyl)-9-(4-meth-
oxyphenyl)perhydropyrazolo[1,2-a]pyrrolo[3,4-c]-
pyrazole-1,3-dione (IIIl) and rel-(3aS,9R,9aR)-2-(2-
bromophenyl)-9-(4-methoxyphenyl)perhydropyra-
zolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-dione (IVl)
were obtained from 0.48 g (2.5 mmol) of compound
Ib and 0.63 g (2.5 mmol) of imide IIg in 6 ml of
toluene. Recrystallization from a benzene ether mix-
ture gave 0.6 g (72%) of trans isomer IIIl. mp 160
1
N 9.72. Characteristic H signals of cis isomer IVi,
, ppm (J, Hz): 3.78 s (3H), 3.94 d.d (1H, 8, 8),
1
161 C. IR spectrum, , cm : 1020, 1050, 1180, 1230,
4.35 d (1H, 8), 4.48 d (1H, 8).
1260, 1380, 1480, 1520, 1560, 1580, 1620, 1630,
1720 s, 1730 s, 2850, 2940, 2970, 3040. H NMR
1
rel-(3aS,9S,9aR)-2-(2,4-Dichlorophenyl)-9-(4-
methoxyphenyl)perhydropyrazolo[1,2-a]pyrrolo-
[3, 4-c]pyrazole-1,3-dione (IIIj) and rel-
(3aS,9R,9aR)-2-(2,4-dichlorophenyl)-9-(4-methoxy-
phenyl)perhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyra-
zole-1,3-dione (IVj) were obtained from 0.38 g
(2 mmol) of compound Ib and 0.48 g (2 mmol) of
imide IId in 12 ml of p-xylene. Recrystallization from
acetone containing a small amount of hexane gave
0.49 g (56%) of trans isomer IIIj. mp 145 146 C.
spectrum, , ppm (J, Hz): 1.15 2.32 m (2H), 2.41
2.77 m (2H), 3.21 3.35 m (1H), 3.38 3.53 m (1H),
3.83 s (3H), 3.96 4.13 m (2H), 4.71 br.s and 4.87 br.s
(1H), 6.95 d (2H, 8.4), 7.21 7.56 (5H), 7.72 d (2H,
8.4). Found, %: C 56.70, 57.17; H 4.75, 4.75; N 9.47,
9.30. C21H20BrN3O3. Calculated, %: C 57.02; H 4.56;
1
N 9.50. Characteristic H signals of cis isomer IVl,
, ppm (J, Hz): 3.79 s (3H), 4.35 d (1H, 10), 4.50 d
(1H, 8).
rel-(3aS,9S,9aR)-2-(2-Chlorophenyl)-9-(4-meth-
oxyphenyl)perhydropyrazolo[1,2-a]pyrrolo[3,4-c]-
pyrazole-1,3-dione (IIIm) was synthesized from
0.48 g (2.5 mmol) of compound Ib and 0.52 g
1
IR spectrum, , cm : 1040, 1060, 1110, 1150, 1180,
1250, 1310, 1380, 1390, 1460, 1480, 1520, 1620,
1
1740 s, 2840, 2920, 2960, 3040. H NMR spectrum,
, ppm (J, Hz): 2.12 2.29 m (2H), 2.41 2.55 m (1H),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

STEREOSELECTIVITY IN THE ADDITION OF 1,3-DIPOLAROPHILES
1343
(2.5 mmol) of imide IIh in 6 ml of toluene. Recrystal-
lization from benzene hexane gave 0.77 g (77%) of
(3aS,9R,9aR)-9-(4-chlorophenyl)-2-(2,4-dichloro-
phenyl)perhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyra-
zole-1,3-dione (IVp) were obtained from 0.39 g
(2 mmol) of compound Ic and 0.48 g (2 mmol) of
imide IId in 4 ml of toluene. Recrystallization from
benzene hexane gave 0.5 g (57%) of trans isomer
trans isomer IIIm. mp 150 151 C. IR spectrum,
,
1
cm : 1040, 1070, 1090, 1240, 1260, 1310, 1340,
1380, 1450, 1460, 1480, 1520, 1560, 1580, 1620,
1
1730 s, 2860, 2940, 2970, 3040. H NMR spectrum,
1
, ppm (J, Hz): 2.15 2.35 m (2H), 2.45 2.77 m (2H),
3.21 3.34 m (1H), 3.39 3.52 m (1H), 3.83 s (3H),
3.95 4.11 m (2H), 4.71 br.s and 4.79 br.s (1H), 6.94 d
(2H, 8.4), 7.23 7.58 (6H). Found, %: C 63.50, 63.53;
H 5.27, 5.30; N 10.57, 10.64. C21H20ClN3O3. Calcu-
lated, %: C 63.40; H 5.07; N 10.56.
IIIp. mp 157 158 C. IR spectrum, , cm : 890,
1020, 1070, 1100, 1110, 1150, 1190, 1230, 1340,
1380, 1395, 1490, 1590, 1730 s, 2855, 2990, 3040.
1H NMR spectrum, , ppm (J, Hz): 2.18 2.35 m (2H),
2.45 2.75 m (2H), 3.16 3.32 m (1H), 3.37 3.54 m
(1H), 3.90 4.09 m (2H), 4.63 br.s and 4.70 br.s (1H),
7.16 7.59 (7H). Found, %: C 55.01, 54.74; H 3.96,
3.82; N 9.47, 9.40. C20H16Cl3N3O2. Calculated, %:
rel-(3aS,9S,9aR)-9-(4-Chlorophenyl)-2-mesityl-
perhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyrazole-1,3-
dione (IIIn) was synthesized from 0.49 g (2.5 mmol)
of compound Ic and 0.54 g (2.5 mmol) of imide IIa
in 6 ml of toluene. Recrystallization from benzene
diethyl ether gave 0.94 g (92%) of trans isomer IIIn.
1
C 55.00; H 3.69; N 9.62. Characteristic H signals of
cis isomer IVp, , ppm (J, Hz): 4.38 d (1H, 9),
4.48 d (1H, 8).
rel-(3aS,9S,9aR)-9-(4-Chlorophenyl)-2-(1-naph-
thyl)perhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyra-
zole-1,3-dione (IIIq) was synthesized from 0.58 g
(3 mmol) of compound Ic and 0.67 g (3 mmol) of
imide IIe in 7 ml of toluene. Recrystallization from
benzene diethyl ether gave 1.18 g (94%) of trans
1
mp 157 158 C. IR spectrum, , cm : 1040, 1070,
1090, 1240, 1260, 1310, 1340, 1380, 1450, 1460,
1480, 1520, 1560, 1580, 1620, 1730 s, 2860, 2940,
2970, 3040. 1H NMR spectrum, , ppm (J, Hz): 2.08 s
(3H), 2.17 s (3H), 2.20 2.31 m (2H), 2.32 s (3H),
2.42 2.55 m (1H), 2.60 2.70 m (1H), 3.16 3.30 m
(1H), 3.35 3.45 m (1H), 3.93 4.05 m (2H), 4.65 br.s
(1H), 6.97 s (2H), 7.38 d (2H, 7.5), 7.58 (2H, 7.5).
Found, %: C 67.14, 66.98; H 5.84, 6.05; N 9.94,
10.04. C23H24ClN3O2. Calculated, %: C 67.39;
H 5.90; N 10.25.
1
isomer IIIq. mp 190 191 C. IR spectrum, , cm :
1020, 1095, 1190, 1240, 1350, 1370, 1405, 1490,
1
1610, 1730 s, 2850, 2980, 3040. H NMR spectrum,
, ppm (J, Hz): 2.22 2.38 m (2H), 2.45 2.80 m (2H),
3.22 3.35 m (1H), 3.44 3.55 m (1H), 4.01 4.21 m
(2H), 4.70 br.s and 4.81 br.s (1H), 7.34 8.02 (11H).
Found, %: C 68.92, 68.68; H 4.84, 4.81; N 10.06,
9.82. C24H20ClN3O2. Calculated, %: C 68.98; H 4.82;
N 10.06.
rel-(3aS,9S,9aR)-9-(4-Chlorophenyl)-2-(2,6-di-
chlorophenyl)perhydropyrazolo[1,2-a]pyrrolo-
[3, 4-c]pyrazole-1,3-dione (IIIo) and rel-
(3aS,9R,9aR)-9-(4-chlorophenyl)-2-(2,6-dichloro-
phenyl)perhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyra-
zole-1,3-dione (IVo) were obtained from 0.49 g
(2.5 mmol) of compound Ic and 0.61 g (2.5 mmol) of
imide IIc in 6 ml of toluene. Recrystallization from
benzene with addition of a small amount of diethyl
ether gave 0.9 g (82%) of trans isomer IIIo. mp 178
rel-(3aS,9S,9aR)-2-(2-Bromophenyl)-9-(4-chloro-
phenyl)perhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyra-
zole-1,3-dione (IIIr) was synthesized from 0.49 g
(2.5 mmol) of compound Ic and 0.63 g (2.5 mmol) of
imide IIg in 6 ml of toluene. Recrystallization from
acetone hexane gave 0.84 g (75%) of trans isomer
1
IIIr. mp 148 149 C. IR spectrum, , cm : 1020,
1
179 C. IR spectrum, , cm : 1020, 1100, 1190, 1240,
1060, 1100, 1195, 1240, 1380, 1450, 1480, 1595,
1
1340, 1370, 1450, 1470, 1500, 1575, 1730 s, 2990,
3040. 1H NMR spectrum, , ppm (J, Hz): 2.18
2.29 m (2H), 2.44 2.58 m (1H), 2.68 2.78 m (1H),
3.23 3.35 m (1H), 3.43 3.54 m (1H), 4.01 4.16 m
(2H), 4.88 br.s (1H), 7.35 7.49 (5H), 7.58 d (2H, 8.4).
Found, %: C 55.02, 55.01; H 3.89, 3.95; N 9.65, 9.79.
C20H16Cl3N3O2. Calculated, %: C 55.00; H 3.69;
1630, 1735 s, 2850, 2990, 3040. H NMR spectrum,
, ppm (J, Hz): 1.16 2.38 m (2H), 2.43 2.79 m (2H),
3.16 3.33 m (1H), 3.40 3.53 m (1H), 3.91 4.10 m
(2H), 4.65 br.s and 4.81 br.s (1H), 7.25 7.60 (7H),
7.73 d (1H, 7.9). Found, %: C 53.71, 53.65; H 4.00,
4.02; N 9.28, 9.12. C20H17BrClN3O2. Calculated, %:
C 53.77; H 3.84; N 9.41.
rel-(3aS,9S,9aR)-2-(2,6-Dichlorophenyl)-9-(4-
tolyl)perhydropyrazolo[1,2-a]pyrrolo[3,4-c]pyra-
zole-1,3-dione (IIIs) and rel-(3aS,9R,9aR)-2-(2,6-di-
chlorophenyl)-9-(4-tolyl)perhydropyrazolo[1,2-a]-
pyrrolo[3,4-c]pyrazole-1,3-dione (IVs) were obtained
from 0.52 g (3 mmol) of compound Id and 0.73 g
1
N 9.62. Characteristic H signals of cis isomer IVo,
, ppm (J, Hz): 3.98 d.d (1H, 9, 8), 4.38 d (1H, 9),
4.48 d (1H, 8).
rel-(3aS,9S,9aR)-9-(4-chlorophenyl)-2-(2,4-di-
chlorophenyl)perhydropyrazolo[1,2-a]pyrrolo-
[3, 4-c]pyrazole-1,3-dione (IIIp) and rel-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

1344
MOLCHANOV et al.
(3 mmol) of imide IIc in 7 ml of toluene. Recrystal-
lization from benzene with addition of a small amount
of diethyl ether gave 1.03 g (82%) of trans isomer
(1H, 8.2, 4.1), 3.99 d (1H, 8.2), 4.35 d (1H, 4.1),
7.23 d (2H, 7.7), 7.37 d (2H, 7.7). Found, %: C 71.55,
71.61; H 6.24, 6.34; N 22.14, 22.42. C15H16N4.
Calculated, %: C 74.40; H 6.34; N 22.20. When the
reaction was carried out in toluene, the yield of
product VIIc was 62%.
1
IIIs. mp 197 198 C (decomp.). IR spectrum, , cm :
1115, 1190, 1240, 1340, 1370, 1445, 1470, 1575,
1730 s, 2860, 2900, 2930, 2990, 3040. 1H NMR spec-
trum, , ppm (J, Hz): 2.13 2.25 m (2H), 2.39 s (3H),
2.45 2.55 m (1H), 2.68 2.77 m (1H), 3.24 3.38 m
(1H), 3.40 3.53 m (1H), 4.05 4.40 m (2H), 4.87 br.s
(1H), 7.20 d (2H, 7.9), 7.30 7.40 (1H), 7.45 d (2H,
8.8), 7.52 d (2H, 7.9). Found, %: C 60.81; H 4.84;
N 10.11. C21H19Cl2N3O2. Calculated, %: C 60.59;
rel-(1R,2R,3S)-3-(4-Cyanophenyl)perhydropyra-
zolo[1,2-a]pyrazole-1,2-dicarbonitrile (VIId) was
obtained from 0.24 g (1.3 mmol) of compound Ie and
0.1 g (1.3 mmol) of fumaronitrile (VIa) in 3 ml of
toluene. Recrystallization from acetone ether hexane
gave 0.22 g (64%) of dinitrile VIId. mp 144 145 C.
1
1
H 4.60; N 10.09. Characteristic H signals of cis
IR spectrum, , cm : 910, 950, 975, 1025, 1110,
isomer IVs, , ppm (J, Hz): 2.32 s (3H), 3.95 d.d
(1H, 9, 8), 4.35 d (1H, 9), 4.47 d (1H, 8).
1150, 1250, 1280, 1300, 1360, 1420, 1460, 1510,
1620, 2240 s, 2865, 2975, 2990, 3040. 1H NMR spec-
trum, , ppm (J, Hz): 2.27 2.51 m (2H), 2.75 t.d
(1H, 9.7, 6.2), 3.10 3.29 m (3H), 3.51 d.d (1H, 7.1,
4.4), 4.13 d (1H, 7.1), 4.37 d (1H, 4.4), 7.64 d (2H,
8.4), 8.24 d (2H, 8.4). Found, %: C 68.27; H 5.06;
N 26.90. C15H13N5. Calculated, %: C 68.42; H 4.98;
N 26.60.
rel-(1R,2R,3S)-3-Phenylperhydropyrazolo[1,2-a]-
pyrazole-1,2-dicarbonitrile (VIIa) was synthesized
from 0.4 g (2.5 mmol) of compound Ia and 0.2 g
(2.5 mmol) of fumaronitrile (VIa) in 8 ml of p-xylene.
The product was isolated by flash chromatography
using gradient elution with hexane, hexane ether
(1:1), and ether. Yield 0.3 g (50%), undistillable
rel-(1R,2R,3S)-3-(4-Chlorophenyl)perhydropyra-
zolo[1,2-a]pyrazole-1,2-dicarbonitrile (VIIe) was
obtained from 0.58 g (3 mmol) of compound Ic and
0.23 g (3 mmol) of fumaronitrile (VIa) in 7 ml of
toluene. Recrystallization from acetone ether gave
0.6 g (74%) of dinitrile VIIe. mp 153 155 C. IR spe-
1
oily substance. H NMR spectrum, , ppm (J, Hz):
2.25 2.50 m (2H), 2.77 t.d (1H, 9.8, 5.0), 3.05
3.28 m (3H), 3.53 d.d (1H, 7.5, 4.0), 4.03 d (1H, 7.5),
4.36 d (1H,4.0), 7.36 7.55 m (5H).
rel-(1R,2R,3S)-3-(4-Methoxyphenyl)perhydro-
pyrazolo[1,2-a]pyrazole-1,2-dicarbonitrile (VIIb)
was synthesized from 0.38 g (2 mmol) of compound
Ib and 0.16 g (2 mmol) of fumaronitrile (VIa) in 8 ml
of p-xylene. Recrystallization from 2-propanol ether
hexane gave 0.4 g (75%) of dinitrile VIIb. mp 100
1
ctrum, , cm : 910, 950, 1020, 1090 s, 1150, 1295,
1320, 1350, 1490 s, 1610, 2255, 2865, 2990, 3030.
1H NMR spectrum, , ppm (J, Hz): 2.25 2.48 m (2H),
2.74 t.d (1H, 9.8, 5.6), 3.05 3.27 m (3H), 3.50 d.d
(1H, 7.7, 4.2), 4.03 d (1H, 7.7), 4.35 d (1H, 4.2),
7.35 7.48 (4H). Found, %: C 61.89, 61.46; H 4.83,
4.73; N 20.38, 20.68. C14H13ClN4. Calculated, %:
C 61.65; H 4.80; N 20.54.
1
101 C. IR spectrum, , cm : 910, 950, 980, 1040 s,
1110, 1150, 1180, 1260 s, 1305, 1360, 1370, 1440,
1460, 1520, 1585, 1620, 2260, 2840, 2870, 2890,
1
2920, 2940, 2970, 2990, 3040. H NMR spectrum, ,
rel-(1R,2R,3S)-3-(4-Bromophenyl)perhydropyra-
zolo[1,2-a]pyrazole-1,2-dicarbonitrile (VIIf) was
obtained from 0.91 g (3.8 mmol) of compound If and
0.3 g (3.8 mmol) of fumaronitrile VIa in 7 ml of
toluene. Recrystallization from acetone ether hexane
gave 0.83 g (69%) of dinitrile VIIf. mp 155 157 C
ppm (J, Hz): 2.20 2.48 m (2H), 2.75 t.d (1H, 9.9,
5.2), 3.04 3.21 m (3H), 3.52 d. d (1H, 7.5, 4.2),
3.84 s (3H), 3.97 d (1H, 7.5), 4.35 d (1H, 4.2), 6.94 d
(2H, 8.6), 7.41 d (2H, 8.6). Found, %: C 67.18, 67.45;
H 5.95, 5.91; N 20.62, 20.86. C15H16N4O. Calculated,
%: C 67.15; H 6.01; N 20.88.
1
(decomp.). IR spectrum, , cm : 910, 950, 1020,
rel-(1R,2R,3S)-3-(4-Tolyl)perhydropyrazolo-
[1,2-a]pyrazole-1,2-dicarbonitrile (VIIc) was syn-
thesized from 0.52 g (3 mmol) of compound Id and
0.23 g (3 mmol) of fumaronitrile (VIa) in 12 ml of
p-xylene. Recrystallization from acetone hexane gave
0.41 g (54%) of dinitrile VIIc. mp 144 145 C. IR
1090 s, 1150, 1295, 1320, 1350, 1490 s, 1610, 2255,
2865, 2990, 3030. H NMR spectrum, , ppm (J, Hz):
1
2.25 2.48 m (2H), 2.74 t.d (1H, 9.8, 6.0), 3.05
3.28 m (3H), 3.50 d.d (1H, 7.7, 4.2), 4.01 d (1H, 7.7),
4.35 d (1H, 4.2), 7.38 d (2H, 8.0), 7.56 d (2H, 8.0).
Found, %: C 53.05, 52.92; H 4.05, 4.03; N 17.66,
17.28. C14H13BrN4. Calculated, %: C 53.01; H 4.13;
N 17.66.
Diphenyl rel-(1R,2R,3S)-3-phenylperhydropyra-
zolo[1,2-a]pyrazole-1,2-dicarboxylate (VIIg) was
synthesized from 0.53 g (3.3 mmol) of compound Ia
1
spectrum, , cm : 870, 910, 950, 975, 1030 s, 1050,
1110 s, 1150, 1250, 1290, 1310, 1350, 1360, 1465,
1520, 2255, 2870, 2930, 2990 s, 3040. 1H NMR spec-
trum, , ppm (J, Hz): 2.22 2.48 m (2H), 2.39 s (3H),
2.75 t. d (1H, 10.2, 5.5), 3.04 3.27 m (3H), 3.54 d.d
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

STEREOSELECTIVITY IN THE ADDITION OF 1,3-DIPOLAROPHILES
1345
and 0.8 g (3 mmol) of diphenyl fumarate (VIb) in
12 ml of p-xylene. Recrystallization from diethyl ether
gave 0.8 g (62%) of diester VIIg. mp 100 101 C. IR
105.68 (0.25), N1C8C9C10 26.10 (0.33) . The overall
set of crystallographic parameters of compound Ia
was included into the Cambridge Crystal Structure
Database (CCDC-179633).
1
spectrum, , cm : 960, 1080, 1110, 1170 s, 1240 s,
1500, 1600, 1760 s, 2890, 2990, 3040. 1H NMR spec-
trum, , ppm (J, Hz): 2.08 2.23 m (1H), 2.31 2.45 m
(1H), 2.93 3.04 (1H), 3.18 3.35 m (2H), 3.50 t.d
(1H, 9.5, 4.6), 4.18 d.d (1H, 8.2, 5.6), 4.32 d (1H,
8.2), 4.57 d (1H, 5.6), 7.06 d (2H, 8.2), 7.20 7.48
(11H), 7.59 d (2H, 7.2). Found, %: C 72.88, 73.19;
H 5.63, 5.55; N 6.61, 6.70. C26H24N2O4. Calculated,
%: C 72.88; H 5.65; N 6.54.
Dimethyl rel-(1R,2R,3S)-3-phenylperhydropyra-
zolo[1,2-a]pyrazole-1,2-dicarboxylate (VIIh) was
obtained from 0.58 g (3.6 mmol) of 6-phenyl-1,5-di-
azabicyclo[3.1.0]hexane (Ia) and 0.5 g (3.5 mmol) of
dimethyl fumarate (VIc). The product was isolated by
preparative thin-layer chromatography on silica gel
(5/40 m) using diethyl ether as eluent. Yield 0.53 g
6-(4-Methoxyphenyl)-1,5-diazabicyclo[3.1.0]hexane
(Ib). C11H14N2O; M 190.25; crystal habit 0.8 0.6
0.5 mm; rhombic crystals, space group Pbca (no. 61);
unit cell parameters at 20 C: a = 8.450(1), b =
3
9.236(1), c = 26.103(1) ; V = 2037.19(34)
;
Z = 8; dcalc = 1.240 g/cm3; = 0.65 mm ; F(000) =
816.0; CuK irradiation, = 1.54178 , graphite
monochromator, = 76.41 . Some bond lengths
1
max
and angles: C1 N1 1.447 (0.002), C1 N2 1.456
(0.002), N1 N2 1.505 (0.002), N2 C10 1.483 (0.002),
N1 C8 1.477 (0.002), C1 H1 0.980, C1 C2 1.485
(0.002) ; N1C1N2 62.48 (0.08), C1N2N1 58.46 (0.07),
N2N1C1 59.05 (0.07); C1N1N2C10 105.81 (0.12),
N1C8C9C10 26.49 (0.15) . The overall set of crystallo-
graphic parameters of compound Ib was included into
the Cambridge Crystal Structure Database (CCDC-
179634).
(50%), undistillable oily substance. IR spectrum,
,
1
cm : 1020, 1085, 1110, 1130, 1240, 1330, 1360,
1380, 1440, 1460, 1600, 1750 s, 2860, 2890, 2960,
1
2990, 3040. H NMR spectrum, , ppm (J, Hz): 2.00
2.13 m (1H), 2.22 2.39 m (1H), 2.82 2.93 (1H),
3.08 3.18 m (2H), 3.35 t.d (1H, 9.6, 4.4), 3.69 s (3H),
3.83 s (3H), 3.87 d.d (1H, 8.4, 5.1), 4.10 d (1H, 8.4),
4.19 d (1H,5.1), 7.24 7.48 (5H).
X-Ray analysis. 6-Phenyl-1,5-diazabicyclo[3.1.0]-
hexane (Ia). C10H12N2; M 160.22; rhombic crystals,
space group Pna21 (no. 33); unit cell parameters at
REFERENCES
1. Trofimov, V.V., Koptelov, Yu.B., Molchanov, A.P.,
and Kostikov, R.R., Zh. Org. Khim., 1994, vol. 30,
p. 1389.
2. Koptelov, Yu.B., Kim, M.Kh., Molchanov, A.P., and
Kostikov, R.R., Russ. J. Org. Chem., 1999, vol. 35,
p. 110; Molchanov, A.P., Sipkin, D.I., Kopte-
lov, Yu.B., and Kostikov, R.R., Russ. J. Org. Chem.,
2001, vol. 37, p. 841.
20 C: a = 8.845(1), b = 8.798(1), c = 11.327(1)
;
=
=
V = 881.45(16) 3; Z = 4; dcalc = 1.207 g/cm3;
1
0.57 mm ; F(000) = 344.0; CuK iradiation,
3. Kuznetsov, V.V., Kutepov, S.A., Makhova, N.N., and
Lysenko, K.A., Azotistye geterotsikly i alkaloidy
(Nitrogen-Containing Heterocycles and Alkaloids),
Kartsev, V.G. and Tolstikov, G.A., Eds., Moscow:
Iridium, 2001, vol. 2, p. 173.
1.54178 , graphite monochromator;
= 76.58 .
max
Some bond lengths and angles: C1 N1 1.452 (0.003),
C1 N2 1.459 (0.003), N1 N2 1.494 (0.003), N2 C10
1.486 (0.004), N1 C8 1.470 (0.004), C1 H1 0.980,
C1 C2 1.481 (0.003) ; N1C1N2 61.73 (0.17), C1N2N1
58.91 (0.16), N2N1C1 59.36 (0.17); C1N1N2C10
4. Molchanov, A.P., Stepakov, A.V., and Kostikov, R.R.,
Russ. J. Org. Chem., 2000, vol. 36, p. 1139.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003