Five-membered 2,3-dioxo heterocycles: LXVI. Reactions of (2Z,5Z)-1-aryl-3-hydroxy-5-[3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene] pent-2-ene-1,4-diones with o-phenylenediamine and hydrazine. Crystalline and molecular structure of 2-{(Z)-8,8-dimethyl

Article abstract of DOI:10.1134/S1070428009100169

(2Z,5Z)-1-Aryl-3-hydroxy-5-[3,3-dimethyl-3,4-dihydroisoquinolin-1(2H) -ylidene]pent-2-ene-1,4-diones reacted with o-phenylenediamine and hydrazine to give 3-[(Z)-2-aryl-2-oxoethylidene]-1,2,3,4-tetrahydroquinoxalin-2-ones and 1-(3-aryl-1H-pyrazol-5-yl)-2-

Full text of DOI:10.1134/S1070428009100169

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 10, pp. 1519–1522. © 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. 1535–1538.
Five-Membered 2,3-Dioxo Heterocycles:
LXVI.* Reactions of (2Z,5Z)-1-Aryl-3-hydroxy-5-[3,3-dimethyl-
3,4-dihydroisoquinolin-1(2H)-ylidene]pent-2-ene-1,4-diones
with o-Phenylenediamine and Hydrazine. Crystalline
and Molecular Structure of 2-{(Z)-8,8-Dimethyl-2,3,8,9-tetra-
hydro[1,4]dioxino[2,3-g]isoquinolin-6(7H)-ylidene}-1-(3-phenyl-
1H-pyrazol-5-yl)ethanone
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 November 13, 2008
Abstract—(2Z,5Z)-1-Aryl-3-hydroxy-5-[3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]pent-2-ene-1,4-
diones reacted with o-phenylenediamine and hydrazine to give 3-[(Z)-2-aryl-2-oxoethylidene]-1,2,3,4-tetra-
hydroquinoxalin-2-ones and 1-(3-aryl-1H-pyrazol-5-yl)-2-[(Z)-3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-
ylidene]ethanones, respectively. The crystalline and molecular structure of 2-{(Z)-8,8-dimethyl-2,3,8,9-tetra-
hydro[1,4]dioxino[2,3-g]isoquinolin-6(7H)-ylidene}-1-(3-phenyl-1H-pyrazol-5-yl)ethanone was determined by
X-ray analysis.
DOI: 10.1134/S1070428009100169
We previously reported on the reaction of 5-aryl-
furan-2,3-diones with 3,3-dialkyl-1-methyl-3,4-dihy-
droisoquinolines, which occurred as β-CH-acylation of
enamino tautomer of isoquinolines with carbonyl
group in position 2 of 5-arylfuran-2,3-diones and was
accompanied by opening of the furan ring. The prod-
ucts were the corresponding (2Z,5Z)-1-aryl-3-hydroxy-
5-[3,3-dialkyl-3,4-dihydroisoquinolin-1(2H)-ylidene]-
pent-2-ene-1,4-diones I whose structure was proved by
X-ray analysis [2]. These compounds were formerly
assigned the structure of NH-acylation products of
tautomeric N-aroylpyruvoyl-3,3-dimethyl-1,2,3,4-
tetrahydro-2-methylideneisoquinolines [3], taking into
account mainly easy elimination of isoquinoline by the
action of o-phenylenediamine, which is typical of
N-aroylpyruvoylamines [4]. With a view to rationalize
the observed pattern we examined reactions of com-
pounds I with difunctional nitrogen-centered nucleo-
philes, o-phenylenediamine and hydrazine.
The reactions of compounds Ia–Ic with o-phen-
ylenediamine were carried out by heating equimolar
amounts of the reactants in boiling ethanol or acetic
acid over a period of 1–1.5 h (the progress of the reac-
tions was monitored by chromatography). As a result,
we isolated the corresponding 3-[(Z)-2-oxo-2-phenyl-
ethylidene]-1,2,3,4-tetrahydroquinoxalin-2-ones IIa–
IIc (Scheme 1) which were identified by comparing
with samples obtained independently from aroyl-
pyruvic acid esters and o-phenylenediamine [5]. Pre-
sumably, in the first step amino group in o-phenylene-
diamine attacks side-chain carbonyl carbon atom (C4)
in compounds I to form cyclic hemiaminal A; next
follows rupture of the C4–C5 bond with hydrolytic
elimination of isoquinoline molecule. This scheme is
analogous to the reaction of 1,6-diarylhexane-1,3,4,6-
tetraones with difunctional nucleophiles (o-aminoben-
* For communication LXV, see [1].
1519

KHALTURINA et al.
1520
Scheme 1.
H2N
Me Me
N
Me Me
H
O
NH HN
HO
NH2
NH2
O
O
+
H
O
H
O
R
R
R
Ar
R
Ar
Ia–Id
A
O
Ar
Me
H
N
R
R
N
+
Me
Me
N
H
O
IIa–IIc
IIIa, IIIb
Me
Me
Me
Me
N
H
·
H
·
·
·
·
·
N
O
O
H
N
N
Ia, Id
+
N2H4
N
NH
Ar
R
R
Ar
R
R
B
IVa, IVb
C
I, RR = OCH2CH2O, Ar = Ph (a); R = H, Ar = 4-MeC6H4 (b), 4-ClC6H4 (c), 4-BrC6H4 (d); II, Ar = Ph (a), 4-MeC6H4 (b),
4-ClC6H4 (c); III, RR = OCH2CH2O (a); R = H (b); IV, RR = OCH2CH2O, Ar = Ph (a); R = H, Ar = 4-BrC6H4 (b).
zenethiol [6] and pyridine-2,3-diamine [7]), which also
involves cleavage of the C2–C3 bond and hydrolytic
elimination of aryl methyl ketones.
Compounds Ia and Id reacted with an equimolar
amount of hydrazine in boiling ethanol (reaction time
30 min) to produce the corresponding 1-(3-aryl-1H-
pyrazol-5-yl)-2-[(1Z)-3,3-dimethyl-3,4-dihydroiso-
quinolin-1(2H)-ylidene]ethanones IVa and IVb
(Scheme 1) via successive attack by amino groups in
hydrazine molecule on carbon atoms in the enolized
β-diketone fragment of Ia and Id. The structure of
compound IVa was proved by X-ray analysis.
Compounds IVa and IVb are colorless crystalline
substances with high melting points (they melt with
decomposition), which are readily soluble in DMSO
and DMF, poorly soluble in other organic solvents, and
insoluble in water and saturated hydrocarbons. Their
IR spectra contained absorption bands due to stretch-
ing vibrations of the NH groups and carbonyl group
involved in intramolecular hydrogen bond at 3100–
3120 and 1605–1608 cm–1, respectively (broad bands).
C13
O3
C12
O2
C5
C6
C4
C3
C7
C2
C8
C21
C20
C1
1
Compounds IVa and IVb displayed in the H NMR
C14
C15
C17
N1
H1
C9
C19
C22
C18
spectra signals from protons in the aromatic rings and
substituents therein, a six-proton singlet from two
methyl groups in position 3 of the isoquinoline frag-
ment (δ 1.28 and 1.34 ppm for IVa and IVb, respect-
ively), a two-proton singlet from the endocyclic meth-
ylene group (δ 2.81 and 2.99 ppm for IVa and IVb),
singlets from the side-chain 2-H proton (δ 6.28–
C10
C23
C11
C16
C24
N3
O1
N2
Fig. 1. Structure of the molecule of 2-[(6Z)-8,8-dimethyl-
2,3,8,9-tetrahydro[1,4]dioxino[2,3-g]isoquinolin-6(7H)-
ylidene}-1-(3-phenyl-1H-pyrazol-5-yl)ethanone (IVa).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 10 2009

FIVE-MEMBERED 2,3-DIOXO HETEROCYCLES: LXVI.
1521
N1A
N3
N2
H1A
O1A
H2
O1
H1
H2A
N2A
N3A
N1
Fig. 2. Centrosymmetric dimer formed by molecules IVa in crystal.
6.45 ppm) and 4-H in the pyrazole ring (δ 6.83–
6.89 ppm), and NH protons in the isoquinoline
(δ 11.50–11.57 ppm) and pyrazole rings (δ 13.39–
13.61 ppm).
tions in DMSO-d6 on a Bruker AM-400 spectrometer
operating at 400 MHz; the chemical shifts were deter-
mined relative to tetramethylsilane as internal refer-
ence. The purity of the products was checked by thin-
layer chromatography on Silufol plates using ethyl
acetate–benzene (1:5) or ethyl acetate as eluent; spots
were visualized by treatment with iodine vapor.
The structure of molecule IVa is shown in Fig. 1.
The N1–H1 and C15=O1 groups are involved in fairly
strong intramolecular hydrogen bond with the follow-
ing parameters: (N1 · · · O1 2.64, H1 · · · O1 2.01 Å,
∠N1H1O1 131.9°). The phenyl ring in position 3 of the
pyrazole ring deviates from the pyrazole ring plane as
a result of steric repulsion between hydrogen atoms on
C17, C14, and C20. The torsion angles O1C15C16N2 and
N3C18C19C24 are 17.8 and 20.9°, respectively. All bond
lengths in molecule IVa are consistent with the corre-
sponding standard values within the experimental error
(0.005–0.007 Å). Difference syntheses of electron den-
sity localized hydrogen atom on the N2 atom, indicat-
ing that molecules of IVa in crystal have tautomeric
structure B. However, bond length distribution over the
pyrazole ring is not unambiguous. The N2–C16 bond
(1.340 Å) is shorter than N3–C18 (1.360 Å). Neverthe-
less, analysis of crystal packing shows that compound
IVa exists as tautomer B. The only shortened inter-
molecular contact was revealed between the O1 and N2
atoms (2.77 Å). It may be interpreted as fairly strong
hydrogen bond N2–H2···O1, giving rise to centrosym-
metric dimers (Fig. 2).
3-[(Z)-2-Oxo-2-phenylethylidene]-1,2,3,4-tetra-
hydroquinoxalin-2-one (IIa). A solution of 0.6 mmol
of compound Ia and 0.6 mmol of o-phenylenediamine
in 20 ml of ethanol was heated for 1 h under reflux.
The mixture was cooled, and the precipitate was
filtered off. Yield 90%, mp 267–268°C (decomp.; from
ethyl acetate); published data [5]: mp 266–267°C.
IR spectrum, cm–1: 3058 br (NH), 1691 (C=O, amide),
1
1617 br (COPh). H NMR spectrum, δ, ppm: 6.83 s
(1H, CH), 7.14–8.00 m (9H, Harom), 12.04 s and
13.67 s (1H each, NH).
Compounds IIb and IIc were synthesized in a sim-
ilar way.
3-[(Z)-2-(4-Methylphenyl)-2-oxoethylidene]-
1,2,3,4-tetrahydroquinoxalin-2-one (IIb). Yield 88%,
mp 229–230°C (decomp.; from ethyl acetate); pub-
lished data [5]: mp 229–230°C.
3-[(Z)-2-(4-Chlorophenyl)-2-oxoethylidene]-
1,2,3,4-tetrahydroquinoxalin-2-one (IIc). Yield 87%,
mp 270–271°C (decomp.; from ethyl acetate); pub-
lished data [5]: mp 270–271°C.
EXPERIMENTAL
2-{(6Z)-8,8-Dimethyl-2,3,8,9-tetrahydro[1,4]di-
oxino[2,3-g]isoquinolin-6(7H)-ylidene}-1-(3-phenyl-
1H-pyrazol-5-yl)ethanone (IVa). A solution of
The IR spectra were recorded from samples dis-
persed in mineral oil on an FSM-1201 spectrophotom-
eter. The H NMR spectra were measured from solu-
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 10 2009

KHALTURINA et al.
1522
0.1 mmol of compound Ia and 0.1 mmol of hydrazine
hydrate in 10 ml of ethanol was heated for 30 min
under reflux. The mixture was cooled, and the precip-
itate was filtered off. Yield 86%, mp >244°C
(decomp.; from ethanol). IR spectrum, ν, cm–1: 3100 br
(NH), 1605 br (CO). 1H NMR spectrum, δ, ppm: 1.28 s
(6H, CH3), 2.81 s (2H, 9-H), 4.33 m (4H, CH2CH2),
6.28 s (1H, 2-H), 6.83 s (1H, 4′-H), 7.29–7.87 m (7H,
1-[3-(4-Bromophenyl)-1H-pyrazol-5-yl]-2-[(1Z)-
3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]-
ethanone (IVb). Yield 89%, mp 237–239°C (decomp.;
from ethanol). IR spectrum, ν, cm–1: 3120 br (NH),
1
1608 br (CO). H NMR spectrum, δ, ppm: 1.34 s (6H,
CH3), 2.99 s (2H, 4-H), 6.45 s (1H, 2-H), 6.89 s (1H,
4′-H), 7.37–8.12 m (8H, Harom), 11.57 s (1H, NH),
13.61 s (1H, NH). Found, %: C 62.46; H 4.84; N 9.77.
C22H20BrN3O. Calculated, %: C 62.57; H 4.77; N 9.95.
Harom), 11.50 s (1H, NH), 13.39 s (1H, NH). Found, %:
C 71.78; H 5.83; N 10.34. C24H23N3O3. Calculated, %:
C 71.80; H 5.77; N 10.47.
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).
X-Ray diffraction data for compound (IVa).
Colorless well-faceted elongated prism-like crystals,
monoclinic crystal system; unit cell parameters: a =
14.559(3), b = 9.941(2), c = 15.064(3) Å; β =
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 10 2009