Spiro-heterocyclization of pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-trione by the action with cyclic enehydrazine

Full text of DOI:10.1134/S1070428008060298

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 6, pp. 937–938. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © N.L. Racheva, Z.G. Aliev, A.N. Maslivets, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 6, pp. 943–944.
SHORT
COMMUNICATIONS
Spiro-Heterocyclization of Pyrrolo[2,1-c][1,4]benzoxazine-
1
,2,4-trione by the Action with Cyclic Enehydrazine
a
b
a
N. L. Racheva , Z. G. Aliev , and A. N. Maslivets
a
Perm State University, ul. Bukireva 15, Perm, 614990 Russia
e-mail: koh2@psu.ru
b
Institute of Chemical Physics Problems, Russian Academy of Sciences,
Chernogolovka, Moscow oblast, Russia
Received June 15, 2006
DOI: 10.1134/S1070428008060298
Reactions of 2,3-dihydro-1H-pyrrole-2,3-diones,
including those fused at the [a]-side to nitrogen-con-
taining heterocycles, with cyclic enehydrazines were
not reported previously. By reaction of 3-benzoyl-2,4-
dihydro-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-tri-
one (I) with an equimolar amount of N′-(5,5-dimethyl-
1′,4,5,5′,6,7-hexahydrospiro[indole-3,2′-pyrrol]-1(2H)-
yl]-3-nitrobenzamide (III) whose structure was proved
by X-ray analysis.
Presumably, the process involves successive attacks
by the β-CH and NH groups in cyclic enehydrazine II
3
a
4
on the C and C atoms in pyrrolobenzoxazine I,
respectively (as in the reactions of I with mononucleo-
philes [1]), cleavage of the 1,4-oxazine ring at the
3
-oxocyclohex-1-en-1-yl)-3-nitrobenzohydrazide (II)
(
which may be regarded as a cyclic enehydrazine) in
4
5
boiling anhydrous m-xylene (reaction time 10–15 min)
we obtained in high yield N-[3′-benzoyl-4′-hydroxy-1′-
C –O bond, and pyrrole ring closure with participa-
tion of the hydrazine fragment. The formation of struc-
ture like A via closure of pyridazine ring did not occur,
(
2-hydroxyphenyl)-6,6-dimethyl-2,4,5′-trioxo-
O
H
N
Me
Me
O N
2
N
H
O
N
O
O
O
NO
2
O
N
O
COPh
+
H
N
O
Me
Me
N
H
O
COPh
O
I
II
O
OH
NO2
NO2
HN
N
O
O
O
OH
O
Me
N
NH
O
Me
O
Me
Me
N
N
HO
O
O
O
COPh
OH
Ph
OH
III
A
9
37

9
38
RACHEVA et al.
presumably because of reduced nucleophilicity of the
NH group neighboring to the carbonyl group.
OH), 12.03 s (1H, NH), 12.40 br.s (1H, OH, enol).
Found, %: C 62.57; H 4.01; N 9.50. C H N O . Cal-
33
26
4
9
culated, %: C 63.66; H 4.21; N 9.00.
The described reaction is a rare example of regio-
selective synthesis of difficultly accessible spiro[in-
dole-3,2′-pyrrole] system with various functional sub-
stituents in different positions of both heterocycles.
The IR spectrum was recorded on an FMS-1201
1
spectrometer. The H NMR spectrum was measured on
a Bruker WP-400 instrument using tetramethylsilane
as internal reference. The purity of compound III was
checked by TLC on a Silufol plate using ethyl acetate
as eluent (development with iodine vapor).
N-[3′-Benzoyl-4′-hydroxy-1′-(2-hydroxyphenyl)-
6
,6-dimethyl-2,4,5′-trioxo-1′,4,5,5′,6,7-hexahydro-
spiro[indole-3,2′-pyrrol]-1(2H)-yl]-3-nitrobenz-
amide (III). Yield 87%, mp 230–232°C (from metha-
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 07-03-96036, 08-03-01032).
–
1
nol). IR spectrum (mineral oil), ν, cm : 3377 br,
2
5′
3
214 br (NH, OH); 1771, 1698 (C =O, C =O); 1655,
4
′
1
620, 1605 (COPh, C =O, NHCO), 1524 (δNH).
H NMR spectrum (DMSO-d ), δ, ppm: 0.80 s (3H,
REFERENCE
1
6
Me), 0.86 s (3H, Me), 2.03 d.d and 2.14 d.d (1H each,
1
. Maslivets, A.N., Mashevskaya, I.V., Krasnykh, O.P., Shu-
rov, S.N., and Andreichikov, Yu.S., Zh. Org. Khim., 1992,
vol. 28, p. 2545.
7
-H, J =15.9 Hz), 2.26 d.d and 2.42 d.d (1H each, 5-H,
J = 18.5 Hz), 6.76–8.51 m (13H, Harom), 9.35 s (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 6 2008