Heterocyclic thiones and their analogs in 1,3-dipolar cycloaddition reactions: IV. Reactions of 4-aryl-2-phenyl-1,2-dihydrophthalazine-1-thiones with nitrile imides

Article abstract of DOI:10.1007/s11178-005-0187-x

4-Aryl-2-phenyl-1,2-dihydrophthalazine-1-thiones react with nitrile imides according to the [3 + 2]-cycloaddition pattern to give phthalazinespirothiadiazoles. The reaction occurs regioselectively at the exocyclic C=S bond.

Full text of DOI:10.1007/s11178-005-0187-x

Russian Journal of Organic Chemistry, Vol. 41, No. 3, 2005, pp. 455–460. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 3, 2005,
pp. 462–467.
Original Russian Text Copyright © 2005 by Budarina, Plotnikov, Labeish, Bel’skii, Galishev.
Heterocyclic Thiones and Their Analogs in 1,3-Dipolar
Cycloaddition Reactions: IV.* Reactions of 4-Aryl-2-phenyl-
1,2-dihydrophthalazine-1-thiones with Nitrile Imides
E. V. Budarina1, V. F. Plotnikov1, N. N. Labeish1, V. K. Bel’skii2, and V. A. Galishev1
1 St. Petersburg State Institute of Technology, Moskovskii pr. 26, St. Petersburg, 190013 Russia
e-mail: vlad@orgchem.spb.ru
2 “Karpov Research Physicochemical Institute” State Scientific Center of the Russian Federation,
Vorontsovo pole 10, Moscow, 103064 Russia
Received March 22, 2004
Abstract—4-Aryl-2-phenyl-1,2-dihydrophthalazine-1-thiones react with nitrile imides according to the [3+2]-
cycloaddition pattern to give phthalazinespirothiadiazoles. The reaction occurs regioselectively at the exocyclic
C=S bond.
Compounds possessing a C=S bond are highly reac-
tive as dipolarophiles in 1,3-dipolar cycloadditions [2].
Reactions of various thiocarbonyl compounds with
nitrile imides are known to give substituted thiadi-
azoles [3]. There are only fragmentary published data
on reactions of cyclic thioxo derivatives with nitrile
imides. For example, pyrimidinethiones were reported
to react with nitrile imides to afford pyrimidinespiro-
thiadiazoles [4]. We previously showed that substituted
3H-2-benzothiophene-1-thiones exhibit a high reactiv-
ity as dipolarophiles toward C,N-disubstituted nitrile
imides [5, 6]. We also reported on the behavior of
substituted phthalazinethiones in 1,3-dipolar cycload-
dition reactions [7].
The present work continues our studies on 1,3-di-
polar cycloaddition reactions of heterocyclic thiones.
Here, we report the results of our more detailed study
on the reaction of 2,4-disubstituted 1,2-dihydrophthal-
azines Ia–Ic with C,N-disubstituted nitrile imides
which were generated in situ by the action of triethyl-
amine on the corresponding benzohydrazonoyl chlo-
rides. 1,3-Dipolar cycloaddition reactions were carried
out in boiling benzene with equimolar amounts of
dihydrophthalazinethione Ia–Ic and benzohydrazonoyl
chloride IIa–IIg. The progress of the reactions was
monitored by TLC. The reactions occurred in a regio-
selective fashion at the exocyclic C=S bond and
resulted in formation of previously unknown 2,4,3',5'-
Scheme 1.
R1
R1
R2
Et3N
N
N
N
N
C
N
NHR3
+
–Et3N·HCl
Cl
Ph
Ph
R2
S
N
S
N
R3
Ia–Ic
IIa–IIg
IIIa–IIIk
I, R1 = Ph (a), p-MeC6H4 (b), p-ClC6H4 (c); II, R2 = R3 = Ph (a), R2 = Ph, R3 = MeCO (b), R2 = Ph, R3 = PhCO (c), R2 = Ph, R3 =
p-O2NC6H4 (d), R2 = Ph, R3 = EtOCO (e), R2 = p-O2NC6H4, R3 = EtOCO (f), R2 = p-MeOC6H4, R3 = EtOCO (g); III, R1 = R2 = R3 =
Ph (a), R1 = p-MeC6H4, R2 = R3 = Ph (b), R1 = p-ClC6H4, R2 = R3 = Ph (c), R1 = R2 = Ph, R3 = MeCO (d), R1 = p-MeC6H4, R2 = Ph,
R3 = MeCO (e), R1 = p-ClC6H4, R2 = Ph, R3 = MeCO (f), R1 = R2 = Ph, R3 = PhCO (g), R1 = R2 = Ph, R3 = p-O2NC6H4 (h), R1 = R2 =
Ph, R3 = EtOCO (i), R1 = Ph, R2 = p-O2NC6H4, R3 = EtOCO (j), R1 = Ph, R2 = p-MeOC6H4, R3 = EtOCO (k).
* For communication III, see [1].
1070-4280/05/4103-0455 © 2005 Pleiades Publishing, Inc.

BUDARINA et al.
456
1
The H NMR spectra of spiro heterocycles IIIa,
IIId, IIIg, IIIh, IIIj, and IIIk contained signals from
aromatic protons and those corresponding to substit-
uents in position 5 of the thiadiazole ring. Compound
IIId showed in the spectrum a singlet at δ 1.57 ppm
due to protons of the acetyl group, and in the spectra of
IIIj and IIIk signals from the ethoxycarbonyl group
were present at δ 1.31 (t) and 4.28 ppm (q) and 1.27 (t)
and 4.24 ppm (q), J = 7 Hz. In the 13C NMR spectra of
IIIa, IIId, IIIg, IIIh, IIIj, and IIIk, the spiro carbon
atom linked to three heteroatoms appeared at δC 113–
119 ppm, and the C5' signal was located at δC 141–
144 ppm; the other 13C NMR parameters were con-
sistent with the assumed structures.
tetrasubstituted 1,2,2',3'-tetrahydrophthalazine-1-spiro-
2'-[1,3,4]thiadiazoles IIIa–IIIk (Scheme 1). Com-
pounds IIIa–IIIk are crystalline substances which can
be stored in air for a long time. The IR spectra of
adducts IIIa–IIIk lack absorption bands in the region
1260–1270 cm–1 (which is typical of C=S stretching
vibrations) but contain those at 1590–1595 and 1329–
1366 cm–1 due to stretching vibrations of the C=N and
C–N bonds in the thiadiazole ring. Vibrations of the
carbonyl group in the 5'-substituent in compounds
IIId–IIIg and IIIi–IIIk appear at 1635–1708 cm–1,
and the aromatic nitro groups in IIIh and IIIj give rise
to absorption at 1340–1342, 1549, and 1558 cm–1.
Compounds IIIa–IIIk displayed in the ultraviolet
region of the electron absorption spectra two maxima
with approximately equal intensities at λ 220–230 and
240–250 nm, and a less intense band was present in the
visible region (λmax 339–389 nm; logε 4.04–4.29). The
position of the latter almost does not depend on the
nature of the substituent in position 4 of the phthala-
zine ring and is determined mainly by the nature of
substituents in the thiadiazole fragment. Character-
istically, the red shift of the long-wave maximum
increases in the series IIIa–IIIc ≈ IIIj < IIId–IIIf <
IIIg < IIIh. Substituent in position 5 of the thiadiazole
ring exerts a stronger effect on the position of the long-
wave absorption maximum than does that attached
to N3. For example, the red shift of the long-wave
absorption maximum ∆λ, induced by introduction of
a nitro group into the benzene ring at C5' (compound
IIIh), is equal to 84 nm (relative to IIIa), while the
effect of a nitro group introduced into the benzene ring
on N3 is almost twice as low (cf. compounds IIIj and
IIIi, ∆λ = 49 nm). Electron-donor substituents (e.g.,
methoxy group) in the para position of the aromatic
ring in position 3' insignificantly affect the position
of the long-wave absorption maximum (cf. IIIk and
IIIi, ∆λ = 5 nm).
The structure of the cycloaddition products was
also confirmed by mass spectrometry. Compounds
IIIg–IIIk showed in the mass spectra low-intense
molecular ion peaks (M+). Only the molecular ion peak
of IIIg had a relative intensity of 44% due to strong
stabilization via delocalization of the positive charge
over the benzoyl substituent. A specific feature of the
mass spectra of these compounds is the absence of
fragment ions resulting from elimination of any sub-
stituent from the spirobicyclic framework, which is
typical of other complex molecules. The mass spectra
of IIIj and IIIk contained an ion peak with m/z 395;
however, it was difficult to rationalize the origin of that
ion. The most abundant ion in the spectra of IIIg–IIIj
(100%; 60% for IIIk) was that with m/z 313. Its
formation may be illustrated by Scheme 2. Cleavage of
the five-membered ring gives ion F1 with m/z 314, in
which the positive charge may be localized with a high
probability on the sulfur atom. The subsequent ring
closure with participation of the ortho-position of the
nearby phenyl group (SEarom) leads to formation of
cation F2 which is stabilized due to charge delocaliza-
tion over both benzene rings and heteroatoms.
The product structure was also proved by the X-ray
diffraction data obtained from a single crystal of
Scheme 2.
e–
N
N
N
N
N
N
S
N
S
S
R
N
R'
F1, m/z 314
F2, m/z 313
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 3 2005

HETEROCYCLIC THIONES AND THEIR ANALOGS ... IV.
C12
457
5'-acetyl-2,4,3'-triphenyl-1,2,2',3'-tetrahydrophthala-
C13
zine-1-spiro-2'-[1,3,4]thiadiazole (IIId). The structure
of molecule IIId is shown in figure, and the bond
lengths and bond angles therein (except for those in the
aromatic substituents) are given in table. The benzene
ring in the phthalazine fragment is almost planar; the
average deviation of atoms from the mean-square
plane is 0.0065 Å. However, the corresponding value
for the dihydropyridazine ring is 0.1388 Å; here, the
N2 atom deviates from the mean-square plane by
0.2395 Å, and the C4 atom, by –0.2514 Å. As a result,
the dihedral angle between the mean-square planes of
the benzene and pyridazine rings is 10.0° (hereinafter
the atom numbering corresponds to that shown in
figure). The C9–C14 and C15–C20 benzene rings are
turned through dihedral angles of 54.6 and 45.4°,
respectively, relative the C1C2C3C4N1N2 plane; there-
fore, no conjugation exists between the heteroring and
aromatic substituents therein. The average deviation
of atoms in the five-membered thiadiazole ring
(SC4C27N3N4) is 0.0059 Å, while the sulfur atom de-
viates from the mean-square plane by 0.0072 Å. This
means that conjugation within the thiadiazole ring is
possible. The SC4C27N3N4 plane is almost orthogonal
to the pyridazine ring plane: the corresponding di-
hedral angle is 87.4°. The dihedral angle between the
C21–C26 benzene and thiadiazole ring planes is 26.8°,
which is likely to rule out the possibility for effective
conjugation between these fragments, but the acetyl
group is almost coplanar to the thiadiazole ring (the
dihedral angle is as small as 3.4°). The average devia-
tion of atoms from the OC27C28C29 plane is 0.0037 Å.
C11
C10
C8
C14
C9
C1
C2
N1
N2
C7
C16
C15
C3
C17
C6
C4
C22
C21
S
C18
C19
C5
O
C20
C23
C24
N3
N4
C27
C25
C26
C28
C29
Structure of the molecule of 5'-acetyl-2,4,3'-triphenyl-
1,2,2',3'-tetrahydrophthalazine-1-spiro-2'-[1,3,4]thiadiazole
(IIId) according to the X-ray diffraction data (hydrogen
atoms are not shown).
X-Ray analysis of a single crystal of 5'-acetyl-
2,4,3'-triphenyl-1,2,2',3'-tetrahydrophthalazine-1-spiro-
2'-[1,3,4]-thiadiazole (IIId) was performed on a Syn-
tex P1 automatic diffractometer (MoKα irradiation, Nb
filter, θ/2θ-scanning, 2θ ≤ 45°). Monoclinic crystals,
C29H22N4OS, with the following unit cell parameters:
a = 8.787(1), b = 17.959(3), c = 15.343(1) Å; β =
99.39(1)°; V = 2388.8(1.1) Å3; space group P21/c;
Z = 4; dcalc = 1.320 g/cm3. The structure was solved by
the direct method from 2434 reflections with I > 3σ(I)
in the full-matrix anisotropic approximation for C, N,
O, and S atoms and isotropic approximation for hydro-
gen atoms; the final divergence factors were R = 0.030,
Rw = 0.035 (no correction for absorption was intro-
duced). All calculations were performed on a NOVA-3
minicomputer using SHELXTL program. The coor-
dinates of non-hydrogen and hydrogen atoms and their
equivalent temperature factors are available from the
authors.
Thus we have found that 2,4-disubstituted 1,2-di-
hydrophthalazine-1-thiones regioselectively react with
C,N-disubstituted nitrile imides at the exocyclic C=S
bond to give phthalazinespirothiadiazoles.
EXPERIMENTAL
The IR spectra of solutions of compounds IIIa–
IIIk in chloroform were recorded on a Specord 75IR
spectrometer (layer thickness 0.97 mm). The electron
absorption spectra of solutions in acetonitrile were
measured on a Specord UV-Vis spectrophotometer
1
using 1-cm cells. The H and 13C NMR spectra were
Initial dihydrophthalazine-1-thiones Ia and Ic were
synthesized by the procedure described in [7].
2-Phenyl-4-p-tolyl-1,2-dihydrophthalazine-1-
thione (Ib). A mixture of 3.1 g of 2-phenyl-4-p-tolyl-
1,2-dihydrophthalazine-1-one and 2.2 g of P2S5 in
20 ml of anhydrous o-xylene was heated for 30 min
obtained on a Bruker AM-500 instrument at 500 and
125 MHz, respectively, from 20% solutions in chloro-
form-d using HMDS as internal reference. The mass
spectra (electron impact, 70 eV) were run on an MKh-
1321 mass spectrometer; direct inlet probe temperature
120°C, ion source temperature 200°C.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 3 2005

BUDARINA et al.
458
Bond lengths d (Å) and bond angles ω (deg) in the molecule
of 5'-acetyl-2,4,3'-triphenyl-1,2,2',3'-tetrahydrophthalazine-
1-spiro-2'-[1,3,4]thiadiazole (IIId)
(C=N), 1348 (C–N), 1282 (C=S). UV spectrum, λmax
,
nm (logε): 286 (3.98), 297 (4.02), 369 (4.06). Found,
%: C 76.55; H 5.03; S 9.48. C21H16N2S. Calculated, %:
C 76.79; H 4.92; S 9.76.
Bond
S–C4
d
Bond
S–C27
d
Nitrile imides were generated in situ by the action
of triethylamine on benzohydrazonoyl chlorides IIa–
IIg, following the procedure reported in [8].
1.889(2)
1.216(3)
1.292(3)
1.454(3)
1.473(3)
1.291(2)
1.490(3)
1.396(3)
1.391(3)
1.385(3)
1.471(3)
1.740(2)
1.396(2)
1.468(3)
1.358(2)
1.428(3)
1.463(3)
1.384(3)
1.508(3)
1.375(3)
1.379(3)
1.485(3)
O–C28
N1–C1
N2–C15
N3–C4
N4–C27
C1–C9
C2–C8
C3–C5
C6–C7
C27–C28
N1–N2
N2–C4
N3–N4
N3–C21
C1–C2
C2–C3
C3–C4
C5–C6
C7–C8
C28–C29
Reactions of 1,2-dihydrophthalazine-1-thiones
Ia–Ic with nitrile imides generated from com-
pounds IIa–IIg (general procedure). A solution of
1 mmol of triethylamine in 2 ml of anhydrous benzene
was added to a solution of 0.5 mmol of 1,2-dihydro-
phthalazine-1-thione Ia–Ic and 0.5 mmol of benzo-
hydrazonoyl chloride IIa–IIg in 7 ml of dry benzene.
The mixture was heated for 0.5 h under reflux, cooled,
and filtered, the precipitate was washed with benzene,
the filtrate was evaporated under reduced pressure, and
the residue was made crystalline by grinding with
pentane and was recrystallized from acetonitrile.
Angle
C4SC27
ω
Angle
ω
089.5(1)
117.0(2)
0118.2(15)
116.6(2)
112.9(2)
116.6(2)
117.6(2)
119.5(2)
120.1(2)
111.1(1)
112.1(2)
109.4(2)
120.1(2)
120.1(2)
119.6(2)
120.3(2)
121.0(2)
117.2(2)
121.8(2)
122.4(2)
N2N1C1
N1N2C15
N4N3C4
C4N3C21
N1C1C2
C2C1C9
C1C2C8
C2C3C4
C4C3C5
SC4N3
119.0(2)
110.2(2)
118.1(1)
123.9(2)
122.6(2)
120.8(2)
122.9(2)
117.9(2)
121.7(2)
102.3(1)
108.6(1)
113.2(2)
120.2(2)
120.1(2)
121.7(2)
119.9(2)
119.1(2)
120.9(1)
118.7(2)
118.9(2)
2,4,3',5'-Tetraphenyl-1,2,2',3'-dihydrophthala-
zine-1-spiro-2'-[1,3,4]thiadiazole (IIIa). Yield 75%,
mp 184–186°C. IR spectrum, ν, cm–1: 1590 (C=N),
1329 (C–N). UV spectrum: λmax 339 nm (logε 4.27).
1H NMR spectrum, δ, ppm: 6.91–7.72 m (24H, Harom).
13C NMR spectrum, δC, ppm: 117.91 (C1(2')); 120.74,
124.76, 125.20, 126.23, 126.75, 127.35, 128.04,
128.41, 128.52, 128.70, 129.14, 129.22, 131.15,
132.89, 135.79 (Carom); 142.85 (C5'); 144.83 (C4).
Found, %: C 77.53; H 4.88; S 6.01. C33H24N4S. Calcu-
lated, %: C 77.91; H 4.76; S 6.30.
N1N2C4
C4N2C15
N4N3C21
N3N4C27
N1C1C9
C1C2C3
C3C2C8
C2C3C5
SC4N2
N2C4N3
N2C4C3
C3C5C6
C6C7C8
C1C9C10
N2C15C16
N3C21C22
SC27N4
N4C27C28
OC28C29
2,3',5'-Triphenyl-4-p-tolyl-1,2,2',3'-tetrahydro-
phthalazine-1-spiro-2'-[1,3,4]thiadiazole (IIIb).
Yield 80%, mp 192–194°C. IR spectrum, ν, cm–1: 1591
(C=N), 1329 (C–N). UV spectrum: λmax 340 nm
(logε 4.25). Found, %: C 77.83; H 5.43; S 5.98.
C34H26N4S. Calculated, %: C 78.12; H 5.02; S 6.13.
SC4C3
N3C4C3
C5C6C7
C2C8C7
C1C9C14
N2C15C20
N3C21C26
SC27C28
OC28C27
C27C28C29
4-p-Chlorophenyl-2,3',5'-triphenyl-1,2,2',3'-
tetrahydrophthalazine-1-spiro-2'-[1,3,4]thiadiazole
(IIIc). Yield 89%, mp 197–199°C. IR spectrum, ν,
cm–1: 1595 (C=N), 1332 (C–N). UV spectrum:
λmax 339 nm (logε 4.27). Found, %: C 72.55; H 4.36;
Cl 6.32; S 5.77. C33H23ClN4S. Calculated, %: C 72.97;
H 4.28; Cl 6.53; S 5.90.
5'-Acetyl-2,4,3'-triphenyl-1,2,2',3'-tetrahydro-
phthalazine-1-spiro-2'-[1,3,4]thiadiazole (IIId).
Yield 92%, mp 196–198°C. IR spectrum, ν, cm–1: 1592
(C=N), 1345 (C–N), 1670 (C=O). UV spectrum:
under reflux. After cooling, the precipitate was filtered
off, the solvent was removed from the filtrate under
reduced pressure, and the residue was recrystallized
from glacial acetic acid. Yield 2.7 g (82%). Yellow
needles, mp 158–160°C. IR spectrum, ν, cm–1: 1590
1
λmax 367 nm (logε 4.12). H NMR spectrum, δ, ppm:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 3 2005

HETEROCYCLIC THIONES AND THEIR ANALOGS ... IV.
459
1.57 s (3H, CH3CO), 7.03–7.66 m (19H, Harom).
13C NMR spectrum, δC, ppm: 25.17 (CH3); 118.94
(C1(2')); 122.93, 124.40, 125.30, 127.06, 127.19,
127.84, 128.20, 128.42, 128.79, 129.06, 129.13, 131.14
(Carom); 135.46 (C5'); 141.80 (C4); 178.50 (C=O).
Found, %: C 73.09; H 4.81; S 6.47. C29H22N4OS. Cal-
culated, %: C 73.38; H 4.68; S 6.75.
Found, %: C 71.34; H 4.36; S 5.68. C33H23N5O2S. Cal-
culated, %: C 71.58; H 4.20; S 5.79.
Ethyl 2,4,3'-triphenyl-1,2,2',3'-tetrahydro-
phthalazine-1-spiro-2'-[1,3,4]thiadiazole-5'-carbox-
ylate (IIIi). Yield 90%, mp 193–195°C. IR spectrum,
ν, cm–1: 1594 (C=N); 1346 (C–N); 1704 (C=O); 1140,
1084 (C–O). UV spectrum: λmax 340 nm (logε 4.09).
Mass spectrum, m/z (Irel, %): 504 (5) [M]+, 314 (24)
[C20H14N2S]+, 313 (100) [C20H13N2S]+, 190 (10)
[C10H10N2O2]+, 91 (19) [C6H5N]+, 77 (86) [C6H5]+.
Found, %: C 71.25; H 4.88; S 6.11. C30H24N4O2S. Cal-
culated, %: C 71.40; H 4.80; S 6.35.
5'-Acetyl-2,3'-diphenyl-4-p-tolyl-1,2,2',3'-tetra-
hydrophthalazine-1-spiro-2'-[1,3,4]thiadiazole
(IIIe). Yield 75%, mp 224–226°C. IR spectrum, ν,
cm–1: 1591 (C=N), 1343 (C–N), 1670 (C=O). UV
spectrum: λmax 368 nm (logε 4.09). Found, %: C 73.44;
H 5.11; S 6.39. C30H24N4OS. Calculated, %: C 73.73;
H 4.96; S 6.56.
Ethyl 3'-p-nitrophenyl-2,4-diphenyl-1,2,2',3'-
tetrahydrophthalazine-1-spiro-2'-[1,3,4]thiadiazole-
5'-carboxylate (IIIj). Yield 87%, mp 225–227°C. IR
spectrum, ν, cm–1: 1588 (C=N); 1332 (C–N); 1708
(C=O); 1139, 1087 (C–O); 1558, 1340 (NO2). UV
5'-Acetyl-4-p-chlorophenyl-2,3'-diphenyl-1,2,-
2',3'-tetrahydrophthalazine-1-spiro-2'-[1,3,4]thiadi-
azole (IIIf). Yield 72%, mp 205–207°C. IR spectrum,
ν, cm–1: 1592 (C=N), 1344 (C–N), 1670 (C=O). UV
spectrum: λmax 364 nm (logε 4.11). Found, %: C 68.26;
H 4.28; Cl 6.49; S 5.98. C29H21ClN4OS. Calculated, %:
C 68.42; H 4.17; Cl 6.96; S 6.30.
1
spectrum: λmax 389 nm (logε 4.29). H NMR spectrum,
δ, ppm: 1.31 t (3H, CH3CH2, J = 7 Hz), 4.28 q
(2H, CH3CH2, J = 7 Hz), 7.22–8.09 m (18H, Carom).
13C NMR spectrum, δC, ppm: 14.05 (CH3); 62.56
(CH2); 117.90 (C1(2')); 124.73, 125.86, 126.38, 127.13,
127.59, 128.55, 128.60, 129.10, 129.69, 131.78
(Carom); 142.24 (C5'); 147.00 (C4); 159.38 (C=O). Mass
spectrum, m/z (Irel, %): 549 (4) [M]+, 314 (30)
[C20H14N2S]+, 313 (100) [C20H13N2S]+, 235 (5)
[C10H10N2O2]+, 91 (4) [C6H5N]+, 77 (39) [C6H5]+.
Found, %: C 65.33; H 4.42; S 5.64. C30H23N5O4S. Cal-
culated, %: C 65.55; H 4.23; S 5.83.
5'-Benzoyl-2,4,3'-triphenyl-1,2,2',3'-tetrahydro-
phthalazine-1-spiro-2'-[1,3,4]thiadiazole (IIIg).
Yield 74%, mp 205–207°C. IR spectrum, ν, cm–1: 1594
(C=N), 1348 (C–N), 1635 (C=O). UV spectrum:
1
λmax 380 nm (logε 4.01). H NMR spectrum, δ, ppm:
7.02–7.83 m (24H, Harom). 13C NMR spectrum, δC,
ppm: 119.07 (C1(2')); 122.88, 125.31, 126.85, 127.19,
127.37, 127.95, 128.13, 128.26, 128.44, 128.66, 128.83,
129.03, 129.15, 129.58, 130.12, 131.16, 132.00, 132.73
(Carom); 141.94 (C5'), 147.03 (C4), 182.73 (C=O). Mass
spectrum, m/z (Irel, %): 536 (44) [C34H24N4OS]+, 314
(28) [C20H14N2S]+, 313 (100) [C20H13N2S]+, 222 (2)
[C14H10N2O]+, 91 (2) [C6H5N]+, 77 (73) [C6H5]+.
Found, %: C 75.78; H 4.66; S 5.77. C34H24N4OS. Cal-
culated, %: C 79.06; H 4.59; S 5.97.
Ethyl 3'-p-methoxyphenyl-2,4-diphenyl-1,2,2',3'-
tetrahydrophthalazine-1-spiro-2'-[1,3,4]thiadiazole-
5'-carboxylate (IIIk). Yield 78%, mp 172–173°C. IR
spectrum, ν, cm–1: 1590 (C=N); 1347 (C–N); 1703
(C=O); 1142, 1087 (C–O); 2828 (OCH3). UV spec-
1
trum: λmax 345 nm (logε 4.07). H NMR spectrum, δ,
ppm: 1.27 t (3H, CH3CH2, J = 7 Hz), 3.74 s (3H,
OCH3), 4.24 q (2H, CH3CH2, J = 7 Hz), 6.74–7.64 m
(18H, Harom). 13C NMR spectrum, δC, ppm: 14.13
(CH3); 55.36 (OCH3); 61.90 (CH2); 113.99 (C1(2'));
120.42, 124.36, 125.10, 127.04, 127.32, 127.42,
128.32, 128.41, 128.76, 128.98, 129.11, 131.12 (Carom);
144.66 (C5'); 155.44 (C4); 160.09 (C=O). Mass
spectrum, m/z (Irel, %): 534 (10) [M]+, 314 (15)
[C20H14N2S]+, 313 (100) [C20H13N2S]+, 220 (5)
[C11H12N2O3]+, 91 (8) [C6H5N]+, 77 (78) [C6H5]+.
Found, %: C 69.47; H 5.05; S 5.86. C31H26N4O3S. Cal-
culated, %: C 69.63; H 4.91; S 6.00.
5'-p-Nitrophenyl-2,4,3'-triphenyl-1,2,2',3'-tetra-
hydrophthalazine-1-spiro-2'-[1,3,4]thiadiazole
(IIIh). Yield 88%, mp 206–208°C. IR spectrum, ν,
cm–1: 1593 (C=N), 1330 (C–N), 1549, 1342 (NO2).
1
UV spectrum: λmax 423 nm (logε 4.04). H NMR spec-
trum, δ, ppm: 6.98–9.17 m (23H, Harom). 13C NMR
spectrum, δC, ppm: 118.38 (C1(2')); 121.78, 123.78,
124.79, 125.46, 126.54, 126.85, 127.13, 127.60, 128.10,
128.47, 128.71, 128.88, 129.14, 129.24, 129.60, 131.27,
132.00, 132.85, 137.49 (Carom); 142.38 (C5'); 144.62
(C4). Mass spectrum, m/z (Irel, %): 553 (5) [M]+, 314
(33) [C20H14N2S]+, 313 (100) [C20H13N2S]+, 239 (6)
[C13H9N3O2]+, 91 (70) [C6H5N]+, 77 (85) [C6H5]+.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 03-03-32919).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 3 2005

BUDARINA et al.
4. Grubert, L., Patzel, M., Jugelt, W., Riemer, B., and
460
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