Direct heterocyclization of tetrahydroisoquinolin-1-ylideneacetic acids by the action of 5-arylfuran-2,3-diones

Full text of DOI:10.1134/S1070428009100297

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 10, pp. 1576–1577. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © V.V. Khalturina, Yu.V. Shklyaev, Z.G. Aliev, A.N. Maslivets, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45,
No. 10, pp. 1587–1588.
SHORT
COMMUNICATIONS
Direct Heterocyclization of Tetrahydroisoquinolin-1-ylideneacetic
Acids by the Action of 5-Arylfuran-2,3-diones
V. V. Khalturinaa, Yu. V. Shklyaeva, Z. G. Alievb, and A. N. Maslivetsc
a Institute of Technical Chemistry, Ural Division, Russian Academy of Sciences, Perm, Russia
b Institute of Chemical Physics Problems, Russian Academy of Sciences, Chernogolovka, Moscow oblast, Russia
c Perm State University, ul. Bukireva 15, Perm, 614990 Russia
e-mail: koh2@psu.ru
Received April 2, 2009
DOI: 10.1134/S1070428009100297
We previously described acylation with 5-aryl-
furan-2,3-diones of the β-CH group in the enamino
tautomers of substituted 1-methyl-3,4-dihydroiso-
quinolines having no other functional groups. These
reactions afforded (2Z,5Z)-1-aryl-3-hydroxy-5-[3,3-di-
methyl-3,4-dihydroisoquinolin-1(2H)-ylidene]pent-
2-ene-1,4-diones [1, 2]. In the present communication
we report on the reaction of 5-arylfuran-2,3-diones
with 1-methylidene-1,2,3,4-tetrahydroisoquinolines
possessing an additional functional group at the exo-
cyclic carbon atom attached to C1.
acetamides IIa and IIb at a ratio of 1:1 on heating in
boiling anhydrous benzene (reaction time 1–2 h). The
progress of the reactions was monitored by thin-layer
chromatography, and the products were the corre-
sponding (3E,5Z)-5-(2-aryl-2-oxoethylidene)-3-[3,3-
dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]pyrro-
lidine-2,4-diones IIIa and IIIb whose structure was
determined by X-ray analysis.
Presumably, the first reaction step is acylation of
the β-CH group in the enamino fragment of isoquino-
lines IIa and IIb by the C2=O carbonyl carbon atom of
5-arylfuran-2,3-diones Ia and Ib. The subsequent
opening of the furan ring at the O1–C2 bond (as report-
5-Arylfuran-2,3-diones Ia and Ib reacted with
[3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]-
Me
Me
Me
Me
R
R
R
R
NH
NH
Me
Me
O
R
R
O
O
O
O
O
O
+
NH
Ar
O
O
NH2
H2N
NH2
O
Ar
O
O
Ar
Ia, Ib
IIa, IIb
Me Me
NH
O
–H2O
Ar
NH
R
O
O
R
IIIa, IIIb
I, Ar = Ph (a), 4-MeC6H4 (b); II, R = H (a), MeO (b); III, Ar = Ph, R = H (a), Ar = 4-MeC6H4, R = MeO (b).
1576

DIRECT HETEROCYCLIZATION OF TETRAHYDROISOQUINOLIN-...
1577
ed for the reactions of 5-arylfuran-2,3-diones with
oxygen-, sulfur-, and nitrogen-centered mono- and
binucleophiles [3]) is followed by Z,E isomerization
and intramolecular cyclization with elimination of
water molecule.
8.12 m (6H, Harom), 10.26 s (1H, NH), 11.25 s (1H,
1-H). Found, %: C 69.93; H 6.07; N 6.09. C26H26N2O5.
Calculated, %: C 69.94; H 5.87; N 6.27.
The IR spectra were recorded on an FMS-1201
spectrometer from samples dispersed in mineral oil.
1
(3E,5Z)-3-[3,3-Dimethyl-3,4-dihydroisoquinolin-
1(2H)-ylidene]-5-(2-oxo-2-phenylethylidene)pyrroli-
dine-2,4-dione (IIIa). A solution of 2.0 mmol of
5-phenylfuran-2,3-dione (Ia) and 2.0 mmol of amide
IIa in 20 ml of anhydrous benzene was heated for 2 h
under reflux. The mixture was cooled, and the precip-
itate was filtered off. Yield 0.60 g (85%), mp 166–
168°C (decomp., from EtOH). IR spectrum, ν, cm–1:
3383, 3190 br (NH), 1661 (C2=O), 1625 (C4=O), 1594
The H NMR spectra were measured on a Bruker
WP-400 instrument from solutions in DMSO-d6 using
TMS as internal reference. The purity of the isolated
compounds was checked by thin-layer chromatography
on Silufol plates using ethyl acetate–benzene (1:5) as
eluent; development with iodine vapor.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 08-03-01032, 07-03-96036, 07-03-00001).
1
(PhCO). H NMR spectrum, δ, ppm: 1.29 s (6H, Me),
3.00 s (2H, 4-H), 6.69 s (1H, CH), 7.37–8.30 m (9H,
Harom), 10.37 s (1H, NH), 11.25 s (1H, 1-H). Found, %:
C 74.03; H 5.53; N 7.33. C23H20N2O3. Calculated, %:
C 74.18; H 5.41; N 7.52.
REFERENCES
1. Shklyaev, Yu.V. and Maslivets, A.N., Russ. J. Org.
Chem., 1996, vol. 32, p. 302.
(3E,5Z)-3-[6,7-Dimethoxy-3,3-dimethyl-3,4-dihy-
droisoquinolin-1(2H)-ylidene]-5-[2-(4-methylphen-
yl)-2-oxoethylidene]pyrrolidine-2,4-dione (IIIb) was
synthesized in a similar way. Yield 87%, mp 111–
113°C (decomp., from EtOH). IR spectrum, ν, cm–1:
3336, 3180 br (NH), 1678 (C2=O), 1633 (C4=O), 1611
(=CHC=O). H NMR spectrum, δ, ppm: 1.30 s (6H,
Me), 2.35 s (3H, MeC6H4), 2.93 s (2H, 4-H), 3.82 s
(3H, OMe), 3.89 s (3H, OMe), 6.67 s (1H, CH), 6.99–
2. Khalturina, V.V., Shklyaev, Yu.V., and Maslivets, A.N.,
Enaminy v organicheskom sinteze. Doklady IV Vserossii-
skoi konferentsii (Enamines in Organic Synthesis. Proc.
IVth All-Russian Conf.), Perm, 2007, p. 307.
3. Andreichikov, Yu.S., Gein, V.L., Zalesov, V.V., Koz-
lov, A.P., Kollents, G., Maslivets, A.N., Pimenova, E.V.,
and Shurov, S.N., Khimiya pyatichlennykh 2,3-diokso-
geterotsiklov (Chemistry of Five-Membered 2,3-Dioxo
Heterocycles), Perm: Perm. Gos. Univ., 1994, p. 5.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 10 2009