Mendeleev Commun., 2008, 18, 297–299
F(3)
F(2A)
F(2)
N(1)
HO
OH
F(3A)
F(1)
Ph Ph
N
N
Path A
Path B
O(9)
C(7)
C(8)
F(1A)
C(5)
C(4)
Ph
O
O
MeONa
[O]
C(2)
O(10)
2
C(12)
C(11)
C(17)
C(6)
C(3)
C(13)
HO
HO
O
HO
HO
O
O
Ph Ph
Ph Ph
C(15)
C(14)
N
N
N
N
N
C(16)
Figure 1 Molecular structure of 4b (CF3 group is disordered over two
Ph
Ph
O
O
O
O
O
O
O
O
positions with occupances 0.62:0.38).
1
differ from those published previously [only IR and H NMR
O
Ph Ph
Ph Ph
spectra of 2 (R = Ph, Me) were given],1 but unambiguously
prove the ascribed structure (see Online Supplementary Materials).
The structure of 4b was proven by X-ray diffraction analysis
(Figure 1).‡ Compound 4a was isolated as a mixture of Z- and
E-isomers, which were able to turn into each other in solution,
this process accelerates in the presence of silica gel. The E-isomer
N
N
N
Ph
9
Ph
10
O2
O2
1
was evolved from the mixture by recrystallization, the H and
13C NMR spectra of Z-isomer were obtained by a comparison
of spectra of a mixture with those for the individual E isomer.
HO
O
HO
O
Ph Ph
OO
Ph Ph
OO
N
N
N
N
O
OH
Ph
Ph
Ph
Ph
N
N
O
O
O
O
H2
Ph
Pd/C
Ph
O
O
Ph Ph
O
O
O
N
N
4a
5
H2 Pd/C
Ph
7
O
O
OH
Ph
Ph
Ph
N
N
NH
Scheme 3
Ph
Ph
Catalytic hydrogenation of the mixture of isomers 4a leads to
compounds 5, 6, perhaps, in the result of non-selective hydro-
genation of C=C and C=N bonds. In the latter case, the sub-
sequent reduction of the C=C bond and dehydration apparently
leads to compound 6 (Scheme 2).§
When the reaction of pyrroline 1a with benzaldehyde was
carried out in the presence of air, the oxidation products,
oxetane 7 and tetrahydrofuran derivative 8, were isolated along
with usual condensation products 2a and 4a (Scheme 1). The
structures of 7 and 8 were proven by X-ray crystallography
(Figures 2 and 3).‡
Ph
O
O
O
6
Scheme 2
‡
X-ray diffraction data.
(4Z)-4-Benzylidene-2,2-dimethyl-5-(trifluoromethyl)-2,4-dihydro-3H-
pyrrol-3-one 1-oxide 4b: C14H12F3NO2, M = 283.25, monoclinic, space
group P21/n; a = 11.8660(4), b = 8.5615(4) and c = 13.2120(6) Å,
b = 99.5340(10)°, V = 1323.68(10) Å3, T = 296 2 K, Z = 4, dcalc
= 1.421 g cm–3; m(MoKα) = 0.123 mm–1; F(000) = 584, reflections
measured/independent, 12563/4203; Rint = 0.0186; the final indexes are
S = 1.117, R1 = 0.0928, wR2 = 0.1980 for all reflections and R1 = 0.0578,
wR2 = 0.1818 for 2482 F0 > 4s.
3,3,10,10-Tetramethyl-1,8,12-triphenyl-6-oxa-2,9-diazadispiro[4.1.4.1]-
dodeca-1,8-diene-4,11-dione 2,9-dioxide 7: C31H28N2O5, M = 508.55,
orthorhombic, space group P212121; a = 10.186(3), b = 14.540(4) and c =
= 17.849(5) Å, V = 2643.7(12) Å3, T = 296 2 K, Z = 4, dcalc = 1.278 g cm–3;
m(MoKα) = 0.096 mm–1; F(000) = 1072, reflections measured/inde-
pendent, 3238/3238; the final indexes are S = 1.095, R1 = 0.1256,
wR2 = 0.1630 for all reflections and R1 = 0.0626, wR2 = 0.1380 for
1914 F0 > 4s.
3a,6a-Dihydroxy-5',5',6,6-tetramethyl-2,2',3-triphenyl-3,3a,6,6a-tetra-
hydrospiro(furo[2,3-c]pyrrole-2,3'-pyrrol)-4'(5'H)-one 1',5-dioxide 8:
C31H30N2O6, M = 526.56; monoclinic, space group P21/c; a = 14.490(6),
b = 10.932(6) and c = 17.138(8) Å, b = 101.70(4)°, V = 2658(2) Å3, T =
= 293(2) K, Z = 4, dcalc = 1.316 g cm–3; m(MoKα) = 0.092 mm–1; reflec-
tions measured/independent, 3895/3713; Rint = 0.0418; the final indexes
are R1 = 0.1354, wR2 = 0.2601 for all reflections and R1 = 0.0775, wR2 =
= 0.1883 for I > 2s(I).
=
C(35)
C(30)
C(36)
C(24)
C(23)
C(22)
C(34)
C(29)
C(31)
C(27)
C(28)
C(37)
C(32)
C(33)
C(8)
C(25)
C(26)
C(12)
C(21)
N(2)
C(38)
N(9)
O(13)
C(7)
C(1)
C(11)
C(17)
C(3)
C(5)
O(16)
O(15)
C(4)
O(6)
C(10)
C(20)
O(14)
C(18)
C(19)
Figure 2 Molecular structure of 7 (H-atoms are not shown).
§
4-Benzyl-1-hydroxy-2,2-dimethyl-5-phenyl-1,2-dihydro-3H-pyrrol-3-one
5 and 4-benzyl-2,2-dimethyl-5-phenyl-1,2-dihydro-3H-pyrrol-3-one 6.
A mixture of isomers 4a (0.08 g, 0.27 mmol) was hydrogenated in MeOH
over Pd/C for 1 h at atmospheric pressure. Then the catalyst was filtered
off and the solution was evaporated. Compounds 5 and 6 were separated
by silica gel column chromatography [hexane–Et2O (1:1), Et2O].
For characteristics of compounds 2a,b, 4a,b and 5–8, see Online
Supplementary Materials.
CCDC 622728, 675095 and 680017 contain the supplementary crystal-
lographic data for this paper. These data can be obtained free of charge from
data_request/cif. For details, see ‘Notice to Authors’, Mendeleev Commun.,
Issue 1, 2008.
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