Chemistry of iminofurans. New example of unusual aza-Wittig reaction at lactone carbonyl group

Full text of DOI:10.1134/S1070428010060291

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 6, pp. 936–937. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © N.Yu. Lisovenko, A.E. Rubtsov, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 6, pp. 935–936.
SHORT
COMMUNICATIONS
Chemistry of Iminofurans. New Example of Unusual Aza-Wittig
Reaction at Lactone Carbonyl Group
N. Yu. Lisovenko and A. E. Rubtsov
Perm State University, ul. Bukireva 15, Perm, 614990 Russia
e-mail: rubtsov@psu.ru
Received December 15, 2009
DOI: 10.1134/S1070428010060291
Aza-Wittig reaction provides a convenient method
for building up a new carbon–nitrogen double bond
[1, 2]. Three examples of the aza-Wittig reaction in-
volving lactone carbonyl group were reported, where
the substrates were substituted 3-methylidene-5-phen-
yloxazol-2-ones [3] and 5-aryl-2,3-dihydrofuran-2,3-
diones [4, 5]. In the present work we used as substrate
5-aryl-2,3-dihydrofuran-2,3-diones Ia–Ic having
a bulky substituent in position 4 of the furan ring.
Presumably, initial nucleophilic attack by phospha-
zine II at the lactone carbonyl group in the furan ring
gave zwitterionic intermediate which underwent rear-
rangement into spiro-fused oxazaphosphetidine A.
Elimination of triphenylphosphine oxide from struc-
ture A afforded compound III. The classical Wittig re-
action of compound Ia with methyl phosphanylidene-
acetate was also reported to give product of addition at
the lactone carbonyl group despite the presence of
other carbonyl groups in the substrate molecule [6].
Prolonged storage of a solution of IIIa in toluene
resulted in the formation of 4-benzoyl-1-(9H-fluoren-
9-ylideneamino)-5-phenyl-2,3-dihydro-1H-pyrrole-
2,3-dione (IV) whose spectral parameters were con-
sistent with published data for structurally related com-
pounds synthesized previously by other methods [7].
The reactions of 4-benzoyl-5-phenyl-2,3-dihydro-
furan-2,3-dione (Ia) and 5-aryl-4-(3-arylquinoxalin-2-
yl)-2,3-dihydrofuran-2,3-diones Ib and Ic with
9H-fluoren-9-one (triphenyl-λ5-phosphanylidene)hy-
drazone (II) gave 4-benzoyl-5-phenyl-2,3-dihydro-
furan-2,3-dione 2-(9H-fluoren-9-ylidene)hydrazone
(IIIa) and 5-aryl-4-(3-arylquinoxalin-2-yl)-2,3-dihy-
drofuran-2,3-dione 2-(9H-fluoren-9-ylidene)hydra-
zones IIIb and IIIc.
4-Benzoyl-2-[N′-(9H-fluoren-9-ylidene)hydra-
zono]-5-phenyl-2,3-dihydrofuran-3-one (IIIa). A so-
O
O
PPh3
Ar
R
O
N
+
N
N
R
O
N
PPh3
Ar
O
O
Ia–Ic
II
A
O
Ph
O
Ph
O
Ar
N
N
N
N
–Ph3P=O
Ar = Ph, R = Bz
O
R
O
IIIa–IIIc
IV
Ar = Ph, R = Bz (a), 3-phenylquinoxalin-2-yl (b); Ar = 4-MeC6H4, R = 3-(4-methylphenyl)quinoxalin-2-yl (c).
936

CHEMISTRY OF IMINOFURANS. NEW EXAMPLE OF UNUSUAL AZA-WITTIG
937
lution of 2.78 g (10 mmol) of compound Ia [8] and
4.54 g (10 mmol) of phosphorane II in 30 ml of anhy-
drous toluene was kept for 24 h at room temperature,
and the precipitate was filtered off and recrystallized
from toluene. Yield 4.04 g (89%), yellow crystals,
mp 170–171°C (from toluene). IR spectrum, ν, cm–1:
1693 (C3=O), 1646 (PhCO), 1601, 1589, 1565 (C=C,
tals, decomposition point 176–177°C (from toluene).
IR spectrum, ν, cm–1: 1766 (C2=O), 1706 (C3=O), 1654
1
(PhCO), 1596, 1579 (C=C, C=N). H NMR spectrum:
δ 7.2–8.2 ppm, m (18H, Harom). Found, %: C 79.30;
H 3.96; N 6.20. C30H18N2O3. Calculated, %: C 79.28;
H 3.99; N 6.16.
The IR spectra were recorded on an FSM-1201
spectrometer from samples dispersed in mineral oil.
1
C=N). H NMR spectrum: δ 7.27–8.38 ppm, m (18H,
1
H
arom). Found, %: C 79.24; H 4.00; N 6.17.
The H NMR spectra were measured on a Varian
C30H18N2O3. Calculated, %: C 79.28; H 3.99; N 6.16.
Mercury Plus-300 instrument at 300 MHz using
DMSO-d6 as solvent and HMDS as internal reference.
The purity of the isolated compounds was checked,
and the progress of reactions was monitored, by TLC
on Silufol UV-254 plates using diethyl ether–benzene–
acetone (10:9:1) as eluent.
5-Phenyl-4-(3-phenylquinoxalin-2-yl)-2-[N′-(9H-
fluoren-9-ylidene)hydrazono]-2,3-dihydrofuran-3-
one (IIIb). A solution of 0.76 g (2 mmol) of furan-
dione Ib [9] and 0.9 g (2 mmol) of phosphorane II in
30 ml of anhydrous benzene was kept for 24 h at room
temperature. The mixture was evaporated, and the resi-
due was recrystallized from acetonitrile. Yield 0.80 g
(72%), orange crystals, mp 216–218°C (from aceto-
nitrile). IR spectrum, ν, cm–1: 1704 (C3=O), 1622
(C=N). 1H NMR spectrum, δ, ppm: 7.27–8.25 m (22H,
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 08-03-00448).
REFERENCES
H
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oxalin-2-yl]-2-[N′-(9H-fluoren-9-ylidene)hydra-
zono]-2,3-dihydrofuran-3-one (IIIc) was synthesized
in a similar way from compounds Ic and II. Yield
0.88 g (75%), orange crystals, mp 208–210°C (from
acetonitrile). IR spectrum, ν, cm–1: 1692 (C3=O), 1600
1
(C=N). H NMR spectrum, δ, ppm: 2.34 s (3H, Me),
2.35 s (3H, Me), 7.09–8.26 m (20H, Harom). Found, %:
C 80.41; H 4.51; N 9.60. C39H26N4O2. Calculated, %:
C 80.39; H 4.50; N 9.62.
4-Benzoyl-1-(9H-fluoren-9-ylideneamino)-
5-phenyl-2,3-dihydro-1H-pyrrole-2,3-dione (IV).
A solution of 2.27 g (5 mmol) of compound IIIa in
20 ml of toluene was kept for 10 days at room tem-
perature. It was then cooled to –20°C, and the precip-
itate was filtered off. Yield 1.8 g (79%), dark red crys-
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010