KUZNETSOV et al.
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[M]+, 389 (12), 357 (43), 302 (57), 297 (100), 270 (62),
239 (23), 210 (12), 166 (12), 130 (14), 104 (18), 76 (16),
59 (25). Found, %: C 53.62; H 4.54; N 6.15.
C20H20N2O10. Calculated, %: C 53.57; H 4.50; N 6.25.
Pyrrolidine Va2 in the mixture with compound Va1.
1H NMR spectrum (CDCl3), δ, ppm: 3.62 s (6H, 2MeO),
3.71 s (6H, 2MeO), 4.15 m (2H, H3,4), 4.82 m (2H, H2,5),
7.70–7.90 m (4H, Pi). 13C NMR spectrum (CDCl3), δ,
ppm: 45.80 (C3,4), 52.69 (4MeO), 63.46 (C2,5), 123.82
(Cb), 129.91 (Ca), 134.77 (Cc), 166.24 (CON), 169.35
(2COO), 170.27 (2COO).
(IIIc) in 10 ml of anhydrous benzene was heated for 3 h
in a sealed ampoule at 220°C. On completion of the
reaction the solvent was distilled off in a vacuum on
a rotary evaporator. The obtained dry residue was
subjected to chromatography on a column packed with
45 g of silica gel (eluent a mixture CH2Cl2–dioxane, 70 :
3 v/v). We obtained 30 mg (20%) of phthalimide (Rf 0.25,
CH2Cl2) and 230 mg (48%) of compound IVc (Rf 0.20,
1
CH2Cl2), mp 237–239°C. H NMR spectrum (CDCl3),
δ, ppm: 3.76 s (6H, 2MeO), 4.18 m (2H, H1,5), 4.57 m
(2H, H2,4), 7.40–7.48 m (3H, Hm,p), 7.48–7.55 m (2H,
HO), 7.75–7.95 m (4H, Pi). 13C NMR spectrum (CDCl3),
δ, ppm: 46.38 (C1,5), 53.35 (2MeO), 67.61 (C2,4), 124.03
(Cb), 126.78 and 129.42 (Co,m), 129.11 (Cp), 129.70 (Ca),
131.72 (Ci), 134.92 (Cc), 169.07 (COO), 174.86 (CON).
Signal of NC=O was not seen due to slow rotation of
phthalimide fragment. Mass spectrum, m/z (Irel, %): 477
(4) [M]+, 447 (62), 445 (74), 419 (21), 418 (79), 390 (100),
389 (52), 333 (58), 239 (100), 152 (33), 119 (25), 104
(42), 76 (35), 59 (31). Found, %: C 60.25; H 4.03; N 8.67.
C24H19N3O8. Calculated, %: C 60.38; H 4.01; N 8.80.
1
Oxazole (VII). H NMR spectrum (CDCl3), δ, ppm:
3.96 s (3H, MeO), 4.00 s (3H, MeO), 6.35 s (1H, CH).
13C NMR spectrum (CDCl3), δ, ppm: 53.02 (MeO), 59.00
(MeO), 102.0 (CH), 143.12 (C=N), 155.79 (COO), 162.11
(COO). Mass spectrum, m/z (Irel, %): 157 (38) [M]+, 126
(15), 68 (28), 59 (89), 55 (23), 54 (38), 43 (100). Found,
%: C 46.20; H 4.70; N 8.81. C6H7NO4. Calculated, %:
C 45.86; H 4.46; N 8.92.
Tetramethyl rel-(2R,3R,4S,5R)-1-phthalimido-
pyrrolidine-2,3,4,5-tetracarboxylate (Vb). A solution
of 304 mg (1 mmol) of aziridine II and 0.19 ml (216 mg,
1.5 mmol) of dimethyl maleate (IIIb) in 10 ml of
anhydrous chlorobenzene was heated for 3 h in a thick-
walled glass reactor at 220°C. On completion of the
reaction the solvent was distilled off in a vacuum on
a rotary evaporator. The obtained dry residue was
subjected to chromatography on a column packed with
40 g of silica gel (gradient elution with a mixture CH2Cl2–
Et2O, from 1:0 to 9:1 v/v). We obtained 30 mg (10%) of
initial aziridine II (Rf 0.27, CH2Cl2), 60 mg (41%) of
phthalimide (Rf 0.25, CH2Cl2), and 154 mg (34%) of oily
product Vb (Rf 0.15, CH2Cl2). 1H NMR spectrum
(CDCl3), δ, ppm: 3.57 s (3H, MeO), 3.68 s (3H, MeO),
3.74 s (3H, MeO), 3.76 s (3H, MeO), 3.86 d.d (1H, H4,
J 8.0, 6.5 Hz), 4.05 d.d (1H, H3, J 8.0, 8.0 Hz), 4.89 d
(1H, H5, J 6.5 Hz), 5.08 d (1H, H2, J 8.0 Hz). 7.70–7.90
m (4H, Pi). 13C NMR spectrum (CDCl3, 20–25°C), δ,
ppm: 45.43 (C3,4), 52.38, 52.65, 52.94 (4MeO), 62.84 and
64.71 (C2,5), 123.67 (Cb), 129.94 (Ca), 134.61 (Cc),
166.51 (CON), 168.90 (COO), 169.51 (COO), 169.55
(COO), 169.81 (COO). Mass spectrum, m/z (Irel, %):
448 (3) [M]+, 389 (51), 313 (12), 302 (100), 297 (73), 270
(27), 242 (17), 239 (46), 236 (17), 198 (15), 166 (12), 130
(22), 104 (29). Found, %: C 52.09; H 4.55; N 5.92.
C20H20N2O10. Calculated, %: C 53.57; H 4.50; N 6.25.
Reactions of dimethyl cis-1-phthalimidoaziridine-
2,3-dicarboxylate II with dimethyl fumarate. A solu-
tion of 304 mg (1 mmol) of aziridine II and 216 mg
(1.5 mmol) of dimethyl fumarate (IIIa) in 10 ml of
anhydrous benzene in a sealed ampule was heated at
220°C for 3 h. On completion of the reaction the solvent
was distilled off in a vacuum on a rotary evaporator. The
obtained dry residue was subjected to chromatography
on a column packed with 45 g of silica gel (gradient elution
with a mixture CH2Cl2–Et2O, from 1 : 0 to 9 : 1 v/v). We
obtained 35 mg (22%) of methyl 5-methoxy-1,3-
oxazole-2-carboxylate (VII) (Rf 0.35, CH2Cl2), 55 mg
(37%) of phthalimide (Rf 0.25, CH2Cl2), 50 mg (11%)
tetramethyl rel-(2R,3R,4R,5R)-1-phthalimidopyr-
rolidine-2,3,4,5-tetra-carboxylate (Va1) (Rf 0.15,
CH2Cl2), and 50 mg (11%) of a mixture of compound
Va1 and tetramethyl rel-(2R,3S,4S,5R)-1-phthal-
imidopyrrolidine-2,3,4,5-tetracarboxylate (Va2)
(Rf 0.13, CH2Cl2) in a ratio 7:4 (according to 1H NMR
data). Overall yield of adduct Va1 18%, of its stereoisomer
Va2 4%.
Pyrrolidine Va1. mp 115–117°C. 1H NMR spectrum
(CDCl3), δ, ppm: 3.63 s (6H, 2MeO), 3.82 s (6H, 2MeO),
4.00 m (2H, H3,4), 4.87 m (2H, H2,5), 7.70–7.90 m (4H,
Pi). 13C NMR spectrum (CDCl3), δ, ppm: 46.93 (C3,4),
52.92 (2MeO), 53.09 (2MeO), 64.37 (C2,5); 123.74 (Cb),
130.01 (Ca), 134.67 (Cc), 166.49 (CON), 169.32 (2COO),
171.02 (2COO). Mass spectrum, m/z (Irel, %): 448 (2)
Dimethyl rel-(1R,2R,4R,5S)-6,8-dioxo-7-phenyl-
3-phthalimido-3,7-diazabicyclo-[3.3.0]octane-2,4-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 8 2009