2-Hydroxybenzaldehyde (2-phenylquinazolin-4-yl)hydrazones and their Zn II complexes: Synthesis and photophysical properties

Article abstract of DOI:10.1007/s11172-011-0360-z

N-(2-Phenylquinazolin-4-yl)-N′-salicylidenehydrazines and their Zn^II complexes were obtained. The structures and luminescent properties of these new quinazoline derivatives were examined.

Full text of DOI:10.1007/s11172-011-0360-z

Russian Chemical Bulletin, International Edition, Vol. 60, No. 11, pp. 2347—2353, November, 2011
2347
2ꢀHydroxybenzaldehyde (2ꢀphenylquinazolinꢀ4ꢀyl)hydrazones
and their ZnII complexes: synthesis and photophysical properties*
T. V. Trashakhova,a E. V. Nosova,a P. A. Slepukhin,b M. S. Valova,b G. N. Lipunova,b and V. N. Charushinb
aFirst President of Russia B. N. El´tsin Ural Federal University,
19 ul. Mira, 620002 Ekaterinburg, Russian Federation.
Eꢀmail: emily74@rambler.ru
bI. Ya. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences,
22 ul. S. Kovalevskoi, 620219 Ekaterinburg, Russian Federation.
Eꢀmail: lipunova@ios.uran.ru
Nꢀ(2ꢀPhenylquinazolinꢀ4ꢀyl)ꢀN´ꢀsalicylidenehydrazines and their ZnII complexes were
obtained. The structures and luminescent properties of these new quinazoline derivatives were
examined.
Key words: salicylidenehydrazine, 4ꢀhydrazinoꢀ2ꢀphenylquinazoline, zinc(II) complexes,
photoluminescence.
Nitrogen heterocyclic derivatives containing a phenolic
OH group are widely known as ligands. For instance, metꢀ
al complexes with 2ꢀbenzimidazolylꢀ8ꢀhydroxyquinolines
have an N,N,Oꢀenvironment around the central metal
atom and exhibit intense luminescence.1 Systems that
combine the structural elements of oꢀhydroxy azomethines
and heterocycles are of particular attention because many
complexes based on oꢀhydroxy azomethines show lumiꢀ
nescent properties.2 Nitrogenꢀcontaining πꢀdeficient
heterocycles such as pyridine, pyrimidine, quinoline, quiꢀ
noxaline, etc. have already been used successfully as fragꢀ
ments of electron transport layers in electroluminescent
materials.3 Zinc(II) chelate complexes with ligands
of the quinoline series are employed in the design of
OLEDꢀoriented materials.4
Here we extended the synthesis of fluorineꢀcontaining
quinazoline derivatives5—7 to 2ꢀhydroxybenzaldehyde
(2ꢀphenylquinazolinꢀ4ꢀyl)hydrazones and their ZnII comꢀ
plexes and studied their photophysical properties. Earlier,
complexation reactions of hydrazones prepared from saliꢀ
cylaldehyde and 4ꢀhydrazinoquinazolines have not been
examined; nor have the corresponding fluoroquinazoline
ligands been documented. We used the phenyl substituent
in position 2 because 2ꢀphenylquinazolines containing
a long chain of conjugated bonds in a substituent in posiꢀ
tion 4 are known8 to exhibit luminescent properties. The
presence of a F atom in the ligand enhances both its therꢀ
mal and chemical stability and its solubility in organic
solvents and, consequently, widens the scope of its techniꢀ
cal applications (e.g., preparation of superior quality films
from materials with unique physicochemical properties9).
That is why fluorineꢀcontaining quinazolines were chosen
as objects of our investigations.
5ꢀFluoroꢀ2ꢀphenylquinazolinone (1a) was obtained as
described earlier;6 the same method was employed in the
synthesis of its nonfluorinated analog 1b.
To introduce a hydrazino group into position 4, first
we obtained 4ꢀchlorinated derivatives 2a—c from quinꢀ
azolinones 1a—c in boiling POCl3 by analogy with 4ꢀchloroꢀ
2ꢀethylthioꢀ6,7,8ꢀtrifluoroquinazoline.5 Heating of
4ꢀhydrazinoꢀ2ꢀphenylquinazolines 3a,b with appropriate
aldehydes in ethanol afforded hydrazones 4a—h (Scheme 1).
To study the photophysical properties of fluorineꢀconꢀ
taining hydrazones in which the F atom is not hydrogenꢀ
bonded to the NH fragment of the substituent in position 4
but can still exert the electronic influence on the system, we
obtained 6,7ꢀdifluorinated derivatives 4g,h from earlier10
described 6,7ꢀdifluoroꢀ3Hꢀ2ꢀphenylquinazolinꢀ4ꢀone (1c)
1
(see Scheme 1). The H NMR spectra of ligands 4a—h
show multiplets for the fluorobenzene (or benzene), pheꢀ
nyl, and hydroxyphenyl fragments and singlets for the OH
and –CH=N groups. The signal for the NH group appears
as a doublet for 5ꢀfluorinated derivatives 4a—c and as a
broadened singlet for the other ligands 4.
Complexes 5a—h were obtained by heating hydrazones
4a—h with zinc(II) acetate in methanol (see Scheme 1).
The 1H NMR spectra of complexes 5a—h contain multipꢀ
lets for the aromatic protons and singlets for the —CH=N
group. The spectra of complexes 5a,c,d,f—h show no sigꢀ
nals for the OH groups, while analogous signals in the
spectra of complexes 5b,e are fewer by one than for the
* Dedicated to Academician of the Russian Academy of Sciences
O. M. Nefedov on the occasion of his 80th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2302—2307, November, 2011.
1066ꢀ5285/11/6011ꢀ2347 © 2011 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 60, No. 11, November, 2011
Trashakhova et al.
Scheme 1
1–3: X = F, Y = H (a); X = Y = H (b); X = H, Y = F (c)
4, 5
a
b
X
F
F
Y
H
H
R
H
4ꢀOH
4, 5
c
d
X
F
H
Y
H
H
R
3,5ꢀBr2
H
4, 5
e
f
X
H
H
Y
H
H
R
4, 5
g
h
X
H
H
Y
F
F
R
H
4ꢀOH
3,5ꢀBr2
5ꢀNO2
corresponding hydrazones. The broadened singlets for the
NH groups are shifted downfield compared to the correꢀ
sponding signal of the ligand. According to MS data, the
ligandꢀtoꢀmetal ratio in the complexes obtained is 1 : 1.
The structure of complex 5c as an example was examꢀ
ined by Xꢀray diffraction. Structure 5c is a chain coordiꢀ
nation polymer in which the Zn atoms are bridged by
acetate groups; the complex crystallizes as a solvate with
two DMF molecules. The Zn atom is fiveꢀcoordinated to
form a distorted trigonal bipyramid with the singly charged
quinazoline ligand occupying both the apices and one verꢀ
tex of the equatorial plane (Fig. 1). The phenyl substituent
of quinazoline makes an angle of 55.5° with the plane of
the heterocycle. The formation of a conjugated metal cheꢀ
late structure causes proton transfer from the hydrazone
fragment to the N(3) atom of the heterocycle and shortꢀ
ens the CAr—N bond (N(4)—C(8), 1.309(6) Å), which
becomes close in length to the C=N bond (e.g., the
N(2)—C(17) bond length in this structure is 1.287(5) Å).
The coordination polymer is stacked along the axis 0c, the
zinc atoms being spaced in the stacks at 5.021(5) Å. The
room between the stacks is occupied by solvate DMF molꢀ
ecules. One crystallographically independent DMF moleꢀ
cule is not involved in any specific interactions, while the
second molecule forms an intermolecular hydrogen bond
between the formyl CO group and the NH group of the
quinazoline fragment (N(3)—O(2S) [x + 1, –y + 2, z + 1/2],
2.794(6) Å). A fragment of the crystal packing of the polyꢀ
mer chains is shown in Fig. 2; the hydrogen atoms and
some solvent molecules are omitted. Selected bond lengths
and bond angles in structure 5c are given in Table 1.
The Cambridge Structural Database11 contains no data
on fiveꢀcoordinate zinc(II) complexes with tridentate
ligands based on hydrazinobenzazines. Their nearest strucꢀ
tural analogs are fiveꢀcoordinate zinc(II) complexes with
Schiff bases prepared from salicylaldehyde derivatives and
2ꢀaminomethylpyridine.12—15 The formation of a sevenꢀ
coordinate zinc(II) complex with a hydrazonopyridine deꢀ
rivative has been reported.16
C(15)
Br(1)
C(12)
C(13)
C(16)
C(11)
O(2)
O(4)
O(1)
C(10)
C(20)
C(14)
C(9)
C(1)
Zn(1)
C(21)
C(19)
C(18)
N(1)
C(8)
N(2)
C(22)
N(3)
C(2)
C(23)
C(17)
N(4)
Br(2)
C(7)
C(6)
C(3)
C(4)
F(1)
C(5)
Fig. 1. Fragment of structure 5c.

ZnII complexes of new quinazolinylhydrazones
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 11, November, 2011 2349
Table 1. Selected bond lengths d and bond angles ω in comꢀ
plex 5c
Bond
d/Å
Angle
ω/deg
Zn(1)—O(1) 1.940(3)
Zn(1)—O(2) 1.986(3)
Zn(1)—O(4) 2.046(3)
Zn(1)—N(2) 2.049(4)
Zn(1)—N(1) 2.248(4)
N(2)—N(4) 1.400(5)
O(2)—C(16) 1.286(5)
O(4)—C(19) 1.281(5)
N(4)—C(8) 1.309(6)
N(2)—C(17) 1.287(5)
O(2)—Zn(1)—O(4) 194.39(12)
O(1)—Zn(1)—O(2) 108.25(13)
O(1)—Zn(1)—O(4) 192.94(13)
N(2)—Zn(1)—N(1) 161.02(13)
O(1)—Zn(1)—N(2) 134.12(14)
O(2)—Zn(1)—N(2) 117.50(14)
N(4)—N(2)—Zn(1) 120.6(3)
C(17)—N(2)—N(4) 111.8(4)
a
C(8)—N(4)—N(2)
113.2(4)
C(17)—N(2)—Zn(1) 127.6(4)
c
0
The formation of structures 5 suggest that compounds 4
act as monoanionic tridentate ligands in these complexꢀ
ation reactions. In the complex, the ligand is coordinated
to the zinc(II) atom through two N atoms and one O atom
to form fiveꢀ and sixꢀmembered chelate rings.
b
Hydrazones 4 and their complexes 5 absorb at
370—495 nm; the electronic absorption spectra of the fluꢀ
orinated derivatives and their nonfluorinated analogs are
similar. In all the cases but the transformation 4h → 5h,
the complexation results in a bathochromic shift of the
longerꢀwavelength band in the absorption spectra (Table 2).
In acetonitrile at room temperature, hydrazones 4 and
their complexes 5 exhibit dark blue or green photoꢀ
luminescence with an emission peak at 465—549 nm. The
electronic absorption and photoluminescence spectra of
ligands 4 and complexes 5 are given in Table 2.
Fig. 2. Fragment of the molecular packing of complex 5c.
The transformations of hydrazones 4 into complexes 5
result in blue shifts of the emission peaks by 3—41 nm,
except for hydrazone 4e (see Table 2).
It is known17 that the fluorescence of oꢀhydroxy azoꢀ
methines is due to the ionization of the OH bond in the
Table 2. Absorption and emission spectra of hydrazones 4 and their complexes 5
Comꢀ
pound
X
Y
R
λ
max/nm
Photoluminescence*
Stokes shift
Δλ/nm
Quantum
yield
Absorption
4а
4b
4c
4d
4e
4f
4g
4h
5а
5b
5c
5d
5e
5f
F
F
F
H
H
H
H
H
F
Н
Н
Н
Н
Н
Н
F
Н
4ꢀОН
3,5ꢀBr2
Н
4ꢀОН
3,5ꢀBr2
Н
5ꢀNO2
Н
4ꢀОН
3,5ꢀBr2
Н
372, 354
377, 362
375, 359
370, 353
375, 360
530
490
537
492
465
549
522
**512**
489
484
510
489
484
508
491
485
158
113
109
122
90
175
151
144
46
40
48
44
40
0.003
<0.001
0.003
<0.001
<0.001
0.004
<0.001
0.004
0.092
0.002
0.01
374, 358
371, 356
F
495, 468, 368
443, 418, 399
444, 418, 397
462, 433, 413
445, 419, 398
444, 418, 397
461, 436
Н
Н
Н
Н
Н
Н
F
F
F
H
H
H
H
H
0.29
4ꢀОН
3,5ꢀBr2
Н
0.015
0.027
0.21
47
43
40
5g
5h
448, 422, 401
445, 420
F
5ꢀNO2
0.025
* Excitation at the longerꢀwavelength absorption band.
** Excitation at 368 nm.

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Russ.Chem.Bull., Int.Ed., Vol. 60, No. 11, November, 2011
Trashakhova et al.
Reagentꢀgrade solvents (carbinol, DMSO) were used as purꢀ
chased from Khimmed and Reakhim (Russia).
excited singlet state followed by proton transfer to the
N atom and the formation of the quinonoid structure.
Earlier,18 it has been illustrated with the simplest salicylꢀ
aldehyde hydrazone that the formation of a quinonoid
structure can be photoinduced as well. It is not unlikely
that the luminescence mechanism of hydrazones 4 is simꢀ
ilar to that of other oꢀhydroxy azomethines, so the hypsoꢀ
chromic shifts of the emission peak in the spectra of the
complexes with respect to its position in the spectra of the
starting hydrazones are due to the decomposition of the
lowꢀenergy quinonoid forms of the ligands during the comꢀ
plexation.
The complexation 4 → 5 considerably lowers the Stokes
shift and increases the quantum yield (see Table 2). The
more intense fluorescence of zinc complexes with oꢀhydrꢀ
oxy azomethines compared to the ligands themselves (see,
e.g., Ref. 19) has been associated with the increased rigidꢀ
ity of the system upon the complexation.
4ꢀChloroꢀ5ꢀfluoroꢀ2ꢀphenylquinazoline (2a). Phosphoryl
chloride (5 mL) was added to quinazolinone 1a (1.0 g, 4.2 mmol).
The reaction mixture was refluxed for 1.5 h, cooled to room
temperature, and poured onto ice. The colorless precipitate that
formed was filtered off, washed with water, and dried. The yield
1
was 0.48 g (45%), m.p. 140—142 °C. H NMR (DMSOꢀd6), δ:
7.15 (dd, 1 H, H(6), 3JH,F = 9.9 Hz, 3JH,H = 8.2 Hz); 7.48—7.57
(m, 3 H, H(3´)—H(5´)); 7.56 (d, 1 H, H(8), 3J = 8.2 Hz); 7.74
(td, 1 H, H(7), 3JH,H = 8.2 Hz, 4JH,F = 5.5 Hz); 8.19 (dd, 2 H,
3
4
H(2´), H(6´), J = 7.0 Hz, J = 1.5 Hz). Found (%): C, 64.96;
H, 3.09; N, 10.85. C14H8ClFN2. Calculated (%): C, 65.00;
H, 3.12; N, 10.83.
4ꢀChloroꢀ6,7ꢀdifluoroꢀ2ꢀphenylquinazoline (2c) was obtained
as described for compound 2a. Yield 56%, m.p. 94—96 °C.
1H NMR (DMSOꢀd6), δ: 7.52—7.60 (m, 3 H, Ph); 8.05 (m, 1 H,
H(5)); 8.21 (m, 1 H, H(8)); 8.50 (m, 2 H, Ph). Found (%):
C, 60.83; H, 2.59; N, 10.11. C14H7ClF2N2. Calculated (%):
C, 60.78; H, 2.55; N, 10.13.
5ꢀFluoroꢀ4ꢀhydrazinoꢀ2ꢀphenylquinazoline (3a). Hydrazine
hydrate (1.0 mL, 20 mmol) was added to a suspension of
4ꢀchloroquinazoline 2a (1.0 g, 3.9 mmol) in ethanol (20 mL).
The reaction mixture was stirred at 70 °C for 3 h and cooled. The
bright yellow precipitate that formed was filtered off, washed
with hexane, and recrystallized from acetonitrile. The yield was
In conclusion, note also that quinazolineꢀcontaining
hydrazones 4 are promising ligand systems for the design
of complexes with other metals.
Experimental
1
0.5 g (50%), m.p. 178—180 °C. H NMR (DMSOꢀd6), δ: 4.97
1
3
3
H NMR spectra were recorded on a Bruker DRXꢀ400 specꢀ
(br.s, 2 H, NH); 7.15 (dd, 1 H, H(6), JH,F = 11.5 Hz, JH,H
=
trometer (400.13 MHz) in DMSOꢀd6 with Me4Si as the internal
standard. Mass spectra were measured on a MicrOTOFꢀQ II
mass spectrometer (Bruker Daltonics, Bremen, Germany)
equipped with an ESI source, a sixꢀport valve, and a kd Scientifꢀ
ic syringe pump (flow rate 180 μL h–1). The mass spectrometer
was controlled with the micrOTOFcontrol 2.3 patch 1 and
HyStar 3.2 software (Bruker Daltonics). The operating parameꢀ
ters of the mass spectrometer were as follows: rated resolution
17 500, positive ionization mode for an m/z range of 50—800 Da,
ionꢀsource capillary voltage 4500 V, glass capillary outlet voltage
166 V, spraying gas pressure 0.8 bar, flow rate of the drying gas
4 L min–1, gas heater temperature 250 °C. Averaging and sumꢀ
mation settings were 3 and 5000, respectively, which corresponds
to one spectrum per second. The ion travel time was 70 μs; the
radio frequency of the hexapole was 100 Vpp. Prior to each
measurement, the mass spectrometer was calibrated externally
from six reference peaks of lithium formate clusters detected
upon the injection of a solution of LiOH (c = 10 mmol L–1) in
PriOH—0.2% aqueous HCOOH (1 : 1, v/v) into the instrument.
Electronic absorption spectra were recorded on a UVꢀ2401PC
spectrophotometer (Shimadzu, Japan) in acetonitrile. Emission
spectra were recorded on a Cary Eclipse spectrofluorimeter (Varian,
USA) in acetonitrile (c = ~5•10–6 mol L–1). Relative quantum
yields were determined according to a known procedure20 with
quinine bisulfate (ϕ = 0.546) for compounds 4 and fluorescein
(ϕ = 0.92) as standards. Melting points were determined on
a Stuart SMP3 instrument. The course of the reactions was monꢀ
itored by TLC on silica gel.
= 8.1 Hz); 7.45 (m, 3 H, Ph); 7.53 (d, 1 H, H(8), 3J = 8.1 Hz);
7.64 (m, 1 H, H(7)); 8.52 (m, 2 H, Ph); 8.72 (br.s, 1 H, NH).
Found (%): C, 66.07; H, 4.32; N, 22.09. C14H11FN4. Calculatꢀ
ed (%): C, 66.13; H, 4.36; N, 22.03.
6,7ꢀDifluoroꢀ4ꢀhydrazinoꢀ2ꢀphenylquinazoline (3c) was obꢀ
tained as described for compound 3a. Yield 56%, m.p.
240—243 °C. 1H NMR (DMSOꢀd6), δ: 4.76 (br.s, 2 H, NH);
7.44 (m, 3 H, Ph); 7.56 (dd, 1 H, H(5), 3J = 11.6 Hz, 4J = 8.0 Hz);
8.21 (dd, 1 H, H(8), 3J = 11.6 Hz, 4J = 9.2 Hz); 8.52 (d, 2 H, Ph);
9.61 (br.s, 1 H, NH). Found (%): C, 61.73; H, 3.65; N, 20.61.
C14H10F2N4. Calculated (%): C, 61.76; H, 3.70; N, 20.58.
Nꢀ(5ꢀFluoroꢀ2ꢀphenylquinazolinꢀ4ꢀyl)ꢀN´ꢀsalicylidenehydrꢀ
azine (4a). Salicylaldehyde (0.5 mL, 4.77 mmol) was added to
a solution of hydrazine 3a (0.45 g, 1.77 mmol) in ethanol (15 mL).
The reaction mixture was refluxed for 1.5 h and cooled. The
yellow precipitate that formed was filtered off and recrystallized
from acetonitrile. The yield was 0.4 g (63%), m.p. 202—204 °C.
1H NMR (DMSOꢀd6), δ: 6.92 (t, 1 H, H(5″), 3J = 7.4 Hz); 7.00
3
(d, 1 H, H(3″), J = 8.1 Hz); 7.28 (m, 2 H, H(6), H(4″)); 7.38
(dd, 1 H, H(6″), 3J = 7.6 Hz, 4J = 1.5 Hz); 7.53 (m, 3 H,
H(3´)—H(5´)); 7.69 (d, 1 H, H(8), 3J = 8.4 Hz); 7.78 (td, 1 H,
3
4
H(7), JH,H = 8.2 Hz, JH,F = 6.0 Hz); 8.60 (dd, 2 H, H(2´),
3
H(6´), J = 7.93 Hz, 4J = 2.1 Hz); 8.81 (s, 1 H, CH=N); 11.12
5
(d, 1 H, NH, JH,F = 9.2 Hz); 12.34 (br.s, 1 H, OH). MS, m/z
(Irel (%)): 359 [M + H] (100). Found (%): C, 70.43; H, 4.18;
N, 15.58. C21H15FN4O. Calculated (%): C, 70.38; H, 4.22;
N, 15.63.
Nꢀ(5ꢀFluoroꢀ2ꢀphenylquinazolinꢀ4ꢀyl)ꢀN´ꢀ(4ꢀhydroxysalicylꢀ
idene)hydrazine (4b) was obtained from 4ꢀhydroxysalicylaldehyde
and hydrazine 3a as described for compound 4a. Yield 56%, m.p.
271—273 °C. 1H NMR (DMSOꢀd6), δ: 5.90 (d, 1 H, H(4″),
3J = 8.3 Hz); 5.92 (s, 1 H, H(3″)); 6.69 (d, 1 H, H(5″),
3J = 8.3 Hz); 6.80 (dd, 1 H, H(6), 3JH,F = 11.5 Hz, 4J = 7.9 Hz);
Hydrazone 4d was obtained as described earlier.21 Comꢀ
pounds 4 and 5 were obtained from 2ꢀaminoꢀ6ꢀfluorobenzoꢀ
nitrile (99%), 2ꢀaminobenzonitrile (98%), salicylaldehyde (98%),
2ꢀhydroxyꢀ5ꢀnitrobenzaldehyde (98%), 4ꢀhydroxysalicylaldeꢀ
hyde (98%), and 3,5ꢀdibromosalicylaldehyde (98%) (Alfa Aesar).

ZnII complexes of new quinazolinylhydrazones
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 11, November, 2011 2351
7.00—7.05 (m, 3 H, H(3´)—H(5´)); 7.20 (d, 1 H, H(8), 3J = 8.2
Hz); 7.29 (td, 1 H, H(7), 3JH,H = 8.2 Hz, 4JH,F = 7.9 Hz); 8.13
(dd, 2 H, H(2´), H(6´), 3J = 7.8 Hz, 4J = 1.7 Hz); 8.23 (s, 1 H,
CH=N); 9.30 (br.s, 1 H, OH); 10.4 (d, 1 H, NH, 3JH,F = 10.0 Hz);
11.9 (br.s, 1 H, OH). MS, m/z (Irel (%)): 375 [M + H] (100).
Found (%): C, 67.33; H, 4.07; N, 14.93. C21H15FN4O2. Calcuꢀ
lated (%): C, 67.37; H, 4.04; N, 14.97.
Nꢀ(6,7ꢀDifluoroꢀ2ꢀphenylquinazolinꢀ4ꢀyl)ꢀN´ꢀ(5ꢀnitroꢀ
salicylidene)hydrazine (4h) was obtained from 5ꢀnitrosalicylꢀ
aldehyde and hydrazine 3c as described for compound 4a. Yield
71%, m.p. 223—225 °C. 1H NMR (DMSOꢀd6), δ: 7.17 (m, 1 H,
H(3″)); 7.51 (m, 3 H, H(3´)—H(5´)); 7.73 (m, 1 H, H(5)); 8.17
(m, 1 H, H(8)); 7.40—7.60 (m, 4 H, H(2´), H(6´), H(4″), H(6″));
8.71 (s, 1 H, CH=N); 12.20 (br.s, 1 H, NH); 13.30 (br.s, 1 H,
OH). MS, m/z (Irel (%)): 422 [M + H] (100). Found (%):
C, 59.90; H, 3.16; N, 16.59. C21H13F2N5O3. Calculated (%):
C, 59.86; H, 3.11; N, 16.62.
2ꢀ[(5ꢀFluoroꢀ2ꢀphenylquinazolinꢀ4ꢀylidene)hydrazonoꢀ
methyl]phenyloxidozinc(II) acetate (5a). Potassium hydroxide
(0.05 g, 1.25 mmol) and zinc acetate (0.2 g, 1.08 mmol) were
successively added to a stirred suspension of hydrazone 4a (0.20 g,
0.56 mmol) in methanol (20 mL). The reaction mixture was
stirred at room temperature for 48 h. The precipitate of complex
5a that formed was filtered off, washed with water, and dried
in vacuo. The yield was 0.23 g (82%), m.p. >320 °C. 1H NMR
(DMSOꢀd6), δ: 1.79 (s, 3 H, MeCO); 6.93 (t, 1 H, H(5″),
3J = 7.5 Hz); 7.02 (d, 1 H, H(3″), 3J = 8.0 Hz); 7.25—7.35
(m, 2 H, H(6), H(4″)); 7.44 (dd, 1 H, H(6″), 3J = 7.3 Hz,
4J = 1.5 Hz); 7.54 (m, 3 H, H(3´)—H(5´)); 7.69 (d, 1 H, H(8),
3J = 8.2 Hz); 7.79 (m, 1 H, H(7)); 8.54 (m, 2 H, H(2´), H(6´));
8.88 (s, 1 H, CH=N); 12.00—12.10 (br.s, 1 H, NH). MS, m/z
(Irel (%)): 421 [M – HOAc] (100). Found (%): C, 57.32; H, 3.33;
N, 11.54. C23H17FN4O3Zn. Calculated (%): C, 57.38; H, 3.54;
N, 11.64.
2ꢀ[(5ꢀFluoroꢀ2ꢀphenylquinazolinꢀ4ꢀylidene)hydrazonoꢀ
methyl]ꢀ4ꢀhydroxyphenyloxidozinc(II) acetate (5b) was obtained
from zinc acetate and hydrazone 4b as described for complex 5a.
Yield 77%, m.p. >300 °C. 1H NMR (DMSOꢀd6), δ: 3.18 (s, 3 H,
MeCO); 6.05 (m, 1 H, H(4″)); 6.10—6.20 (m, 1 H, H(3″)); 6.96
(m, 1 H, H(5″)); 7.02 (m, 1 H, H(6)); 7.18 (m, 3 H, Ph); 7.30—7.40
(m, 1 H, H(8)); 7.43 (m, 1 H, H(7)); 7.91 (m, 2 H, H(2´),
H(6´)); 8.45 (s, 1 H, CH=N); 9.60 (br.s, 1 H, OH); 12.00—13.00
(br.s, 1 H, NH). MS, m/z (Irel (%)): 437 [M – HOAc] (100).
Found (%): C, 55.55; H, 3.41; N, 11.32. C23H17FN4O4Zn. Calꢀ
culated (%): C, 55.53; H, 3.40; N, 11.26.
Nꢀ(3,5ꢀDibromosalicylidene)ꢀN´ꢀ(5ꢀfluoroꢀ2ꢀphenylquinꢀ
azolinꢀ4ꢀyl)hydrazine (4c) was obtained from 3,5ꢀdibromosalicylꢀ
aldehyde and hydrazine 3a as described for compound 4a. Yield
43%, m.p. 269—271 °C. 1H NMR (DMSOꢀd6), δ: 7.27 (dd, 1 H,
H(6), 3JH,F = 11.3 Hz, 4J = 8.2 Hz); 7.51 (m, 3 H, H(3´)—H(5´));
7.56 (d, 1 H, H(4″), 3J = 1.7 Hz); 7.66 (d, 1 H, H(6″), 3J = 1.7 Hz);
7.69 (d, 1 H, H(8), 3J = 8.3 Hz); 7.79 (m, 1 H, H(7)); 8.62
(d, 2 H, H(2´), H(6´), 3J = 3.8 Hz); 8.74 (s, 1 H, CH=N); 11.45
3
(d, 1 H, NH, JH,F = 6.5 Hz); 13.6 (br.s, 1 H, OH). MS, m/z
(Irel (%)): 517 [M + H] (100). Found (%): C, 48.89; H, 2.52;
N, 10.81. C21H13Br2FN4O. Calculated (%): C, 48.87; H, 2.54;
N, 10.85.
Nꢀ(2ꢀPhenylquinazolinꢀ4ꢀyl)ꢀN´ꢀsalicylidenehydrazine (4d)
was obtained from salicylaldehyde and hydrazine 3b as described
for compound 4a. Yield 65%, m.p. 178—180 °C. 1H NMR
(DMSOꢀd6), δ: 6.91 (m, 1 H, H(5″)); 7.10 (m, 1 H, H(3″)); 7.31
(m, 1 H, H(6)); 7.45—7.65 (m, 5 H, H(3´)—H(5´), H(4″), (6″));
7.80—7.90 (m, 2 H, H(5), H(7)); 8.37 (m, 1 H, H(8)); 8.62 (m, 2 H,
H(2´), H(6´)); 8.66 (s, 1 H, CH=N); 11.9 (br.s, 1 H, NH); 12.3
(br.s, 1 H, OH). MS, m/z (Irel (%)): 341 [M + H] (100).
Found (%): C, 74.15; H, 4.78; N, 16.43. C21H16N4O. Calculatꢀ
ed (%): C, 74.10; H, 4.74; N, 16.46.
Nꢀ(4ꢀHydroxysalicylidene)ꢀN´ꢀ(2ꢀphenylquinazolinꢀ4ꢀyl)ꢀ
hydrazine (4e) was obtained from 4ꢀhydroxysalicylaldehyde and
hydrazine 3b as described for compound 4a. The reaction time
was 3 h. The reaction product was recrystallized from DMSO.
Yield 59%, m.p. 275—277 °C. 1H NMR (DMSOꢀd6), δ: 6.33
(m, 2 H, H(3″), H(5″)); 7.21 (d, 1 H, H(6″), 3J = 8.4 Hz); 7.45—7.65
(m, 4 H, H(3´)—H(5´), H(6)); 7.75—7.85 (m, 2 H, H(5), H(7));
8.32 (m, 1 H, H(8)); 8.54 (s, 1 H, CH=N); 8.60 (m, 2 H, H(2´),
H(6´)); 9.70 (br.s, 1 H, OH); 11.7 (br.s, 1 H, NH); 12.30 (br.s, 1 H,
OH). MS, m/z (Irel (%)): 357 [M + H] (100). Found (%):
C, 70.82; H, 4.56; N, 15.70. C21H16N4O2. Calculated (%):
C, 70.78; H, 4.53; N, 15.72.
Nꢀ(3,5ꢀDibromosalicylidene)ꢀN´ꢀ(2ꢀphenylquinazolinꢀ4ꢀyl)ꢀ
hydrazine (4f) was obtained from 3,5ꢀdibromosalicylaldehyde and
hydrazine 3b as described for compound 4a. The reaction time
was 3 h. Yield 57%, m.p. 255—257 °C. 1H NMR (DMSOꢀd6), δ:
7.50—7.80 (m, 5 H, H(3´)—H(5´), H(6), H(4″), H(6″)); 7.86
(m, 2 H, H(2´), H(6´)); 8.34 (m, 1 H, H(5) or H(7)); 8.61 (m, 1 H,
H(7) or H(5)); 8.64 (m, 1 H, H(8)); 9.06 (s, 1 H, CH=N);
12.0 (br.s, 1 H, NH); 13.5 (br.s, 1 H, OH). MS, m/z (Irel (%)):
499 [M + H] (100). Found (%): C, 50.68; H, 2.87; N, 11.21.
C21H14Br2N4O. Calculated (%): C, 50.63; H, 2.83; N, 11.25.
Nꢀ(6,7ꢀDifluoroꢀ2ꢀphenylquinazolinꢀ4ꢀyl)ꢀN´ꢀsalicylideneꢀ
hydrazine (4g) was obtained from salicylaldehyde and hydrazine
3c as described for compound 4a. Yield 74%, m.p. 195—197 °C.
1H NMR (DMSOꢀd6), δ: 6.93 (m, 1 H, H(5″)); 6.99 (m, 1 H,
H(3″)); 7.29 (m, 1 H, H(4″)); 7.45—7.55 (m, 4 H, H(3´)—H(5´),
H(6″)); 7.71 (dd, 1 H, H(5), 3J = 11.4 Hz, 5J = 7.5 Hz); 8.44
(m, 1 H, H(8)); 8.58 (m, 2 H, H(2´), H(6´)); 8.61 (s, 1 H, CH=N);
11.90 (br.s, 1 H, NH); 12.10 (br.s, 1 H, OH). MS, m/z (Irel (%)):
377 [M + H] (100). Found (%): C, 66.98; H, 3.70; N, 14.92.
C21H14F2N4O. Calculated (%): C, 67.02; H, 3.75; N, 14.89.
3,5ꢀDibromoꢀ2ꢀ[(5ꢀfluoroꢀ2ꢀphenylquinazolinꢀ4ꢀylidene)ꢀ
hydrazonomethyl]phenyloxidozinc(II) acetate (5c) was obtained
from zinc acetate and hydrazone 4c as described for complex 5a.
Yield 74%, m.p. >330 °C. 1H NMR (DMSOꢀd6), δ: 1.84 (s, 3 H,
3
MeCO); 6.87 (dd, 1 H, H(6), JH,F = 10.4 Hz, 4J = 8.4 Hz);
7.14 (d, 1 H, H(8), 3J = 8.1 Hz); 7.35 (d, 1 H, H(4″), 3J = 1.9 Hz);
7.40 (m, 4 H, H(3´)—H(5´), H(7)); 7.46 (d, 1 H, H(6″),
3J = 1.9 Hz); 7.86 (m, 2 H, H(2´), H(6´)); 8.45 (s, 1 H,
CH=N); 12.00—13.00 (br.s, 1 H, NH). MS, m/z (Irel (%)):
579 [M – HOAc] (100). Found (%): C, 43.21; H, 2.28;
N, 8.73. C23H15Br2FN4O3Zn. Calculated (%): C, 43.19; H, 2.34;
N, 8.76.
2ꢀ[(2ꢀPhenylquinazolinꢀ4ꢀylidene)hydrazonomethyl]phenylꢀ
oxidozinc(II) acetate (5d) was obtained from zinc acetate and
hydrazone 4d as described for complex 5a. Yield 80%, m.p.
1
>300 °C. H NMR (DMSOꢀd6), δ: 1.78 (s, 3 H, MeCO); 6.65
(m, 1 H, H(5″)); 6.89 (m, 1 H, H(3″)); 7.14 (m, 1 H, H(6)); 7.29
(m, 1 H, H(6″)); 7.38 (m, 1 H, H(7) or H(5)); 7.40—7.55 (m, 4 H,
H(3´)—H(5´), H(4″)); 7.61 (m, 1 H, H(5) or H(7)); 7.87 (m, 2 H,
H(2´), H(6´)); 8.25 (m, 1 H, H(8)); 8.66 (s, 1 H, CH=N);
12.10—12.40 (br.s, 1, NH). MS, m/z (Irel (%)): 403 [M – HOAc]
(100). Found (%): C, 59.63; H, 3.82; N, 12.07. C23H18N4O3Zn.
Calculated (%): C, 59.61; H, 3.88; N, 12.09.

2352
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 11, November, 2011
Trashakhova et al.
4ꢀHydroxyꢀ2ꢀ[(2ꢀphenylquinazolinꢀ4ꢀylidene)hydrazonoꢀ
methyl]phenyloxidozinc(II) acetate (5e) was obtained from zinc
acetate and hydrazone 4e as described for complex 5a. Yield
76%, m.p. >340 °C. 1H NMR (DMSOꢀd6), δ: 1.78 (s, 3 H,
MeCO); 6.13 (m, 2 H, H(3″), H(5″)); 7.04 (d, 1 H, H(6″),
3J = 8.0 Hz); 7.30—7.55 (m, 6 H, H(3´)—H(5´), H(5)—H(7));
7.85—8.10 (m, 2 H, H(2´), H(6´)); 8.18 (m, 1 H, H(8)); 8.49
(s, 1 H, CH=N); 9.60 (br.s, 1 H, OH); 12.00—13.00 (br.s, 1 H,
NH). MS, m/z (Irel (%)): 419 [M – HOAc] (100). Found (%):
C, 57.65; H, 3.74; N, 11.63. C23H18N4O4Zn. Calculated (%):
C, 57.62; H, 3.75; N, 11.69.
atoms were located geometrically and refined using a riding model
with dependent thermal parameters. The final R factors are
R1 = 0.0366 and wR2 = 0.0400 for reflections with I > 2σ(I) and
R1 = 0.0762 and wR2 = 0.0420 for all reflections; S = 1.001. The
maximum and minimum peaks of the residual electron density
are 0.444 and –0.337 e Å–3, respectively.
The Xꢀray diffraction data for structure 5c have been deꢀ
posited with the Cambridge Crystallographic Data Center
(CCDC No. 841489) and can be retrieved free of charge from
www.ccdc.cam.ac.uk/data_request/cif.
3,5ꢀDibromoꢀ2ꢀ[(2ꢀphenylquinazolinꢀ4ꢀylidene)hydrazonoꢀ
methyl]phenyloxidozinc(II) acetate (5f) was obtained from zinc
acetate and hydrazone 4f as described for complex 5a. Yield
73%, m.p. >340 °C. 1H NMR (DMSOꢀd6), δ: 2.53 (s, 3 H,
MeCO); 7.24 (m, 1 H, H(6″)); 7.32 (s, 1 H, H(4″)); 7.35—7.50
(m, 5 H, H(3´)—H(5´), H(6), H(5) or H(7)); 7.52 (m, 1 H, H(7)
or H(5)); 7.89 (m, 1 H, H(8)); 7.91 (s, 1 H, CH=N); 8.21 (m, 1 H,
H(2´)); 8.43 (m, 1 H, H(6´)); 12.00—13.00 (br.s, 1 H, NH). MS,
m/z (Irel (%)): 561 [M – HOAc] (100). Found (%): C, 44.48;
H, 2.53; N, 9.08. C23H16Br2N4O3Zn. Calculated (%): C, 44.44;
H, 2.57; N, 9.01.
This work was financially supported by the Ministry
of Education and Science of the Russian Federation
(State Contract 02.740.11.0260), the Council on Grants
at the President of the Russian Federation (State Supꢀ
port Program for Leading Scientific Schools of the
Russian Federation, Grant NShꢀ65261.2010.3), and the
Russian Foundation for Basic Research (Project No. 11ꢀ03ꢀ
00718).
References
2ꢀ[(6,7ꢀDifluoroꢀ2ꢀphenylquinazolinꢀ4ꢀylidene)hydrazonoꢀ
methyl]phenyloxidozinc(II) acetate (5g) was obtained from zinc
acetate and hydrazone 4g as described for complex 5a. Yield
83%, m.p. >340 °C. 1H NMR (DMSOꢀd6), δ: 2.53 (s, 3 H,
MeCO); 6.42 (m, 1 H, H(5″)); 6.57 (m, 1 H, H(3″)); 7.03 (m, 1 H,
H(4″)); 7.12 (m, 1 H, H(5)); 7.19 (m, 1 H, H(6″)); 7.40 (m, 3 H,
H(3´)—H(5´)); 7.87 (m, 2 H, H(2´), H(6´)); 7.96 (m, 1 H, H(8));
8.42 (s, 1 H, CH=N); 12.00—13.00 (br.s, 1 H, NH). MS, m/z
(Irel (%)): 439 [M – HOAc] (100). Found (%): C, 55.33; H, 3.18;
N, 11.27. C23H16F2N4O3Zn. Calculated (%): C, 55.31; H, 3.20;
N, 11.22.
2ꢀ[(6,7ꢀDifluoroꢀ2ꢀphenylquinazolinꢀ4ꢀylidene)hydrazonoꢀ
methyl]ꢀ6ꢀnitrophenyloxidozinc(II) acetate (5h) was obtained
from zinc acetate and hydrazone 4h as described for complex 5a.
Yield 85%, m.p. >320 °C. 1H NMR (DMSOꢀd6), δ: 2.54
(s, 3 H, MeCO); 6.60 (m, 1 H, H(3″)); 7.27 (m, 1 H, H(5));
7.43 (m, 3 H, H(3´)—H(5´)); 7.87 (m, 2 H, H(2´), H(6´)); 7.95
(m, 1 H, H(4″)); 8.01 (m, 1 H, H(6″)); 8.24 (m, 1 H, H(8)); 8.57
(s, 1 H, CH=N); 12.00—13.00 (br.s, 1 H, NH). MS, m/z
(Irel (%)): 484 [M – HOAc] (100). Found (%): C, 50.74; H, 2.71;
N, 12.91. C23H15F2N5O5Zn. Calculated (%): C, 50.73; H, 2.75;
N, 12.86.
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Xꢀray diffraction study of complex 5c was carried out for
a yellow crystal stub (0.29×0.16×0.09 mm) on an Xcalibur 3
automatic fourꢀcircle diffractometer equipped with a CCD deꢀ
tector according to a standard procedure (MoꢀKα radiation,
graphite monochromator, ωscan mode, scan step 1°, T = 295(2) K).
An absorption correction was applied analytically using a multiꢀ
faceted crystal model.22 The crystal is monoclinic, space group Cc;
the unit cell parameters are a = 11.4604(8) Å, b = 31.4795(19) Å,
3
c = 9.5863(5) Å, β = 107.754(5)°, V = 3293.7(3) Å ; Z = 4 for the
molecular formula C29H29Br2FN6O5Zn, dcalc = 1.585 g cm–3
,
μ = 3.223 mm–1, F(000) = 1576, scan range 3.11° < θ < 26.37°.
The measured 6914 reflections included 4666 independent ones
(Rint = 0.0357); the number of reflections with I > 2σ(I) was 2698.
The completeness of the data set was 95.7%. The structure was
solved by the direct methods and refined by the fullꢀmatrix leastꢀ
squares method on F2 with the SHELXTL program package.23 All
nonꢀhydrogen atoms were refined anisotropically; the hydrogen
12. L. Y. Zhong, Acta Crystallogr., Sect. C: Cryst. Struct. Comꢀ
mun., 2005, 61, 456.
13. L. Y. Zhong, Acta Crystallogr., Sect. C: Cryst. Struct. Comꢀ
mun., 2005, 61, 432.
14. L. Y. Zhong, Acta Crystallogr., Sect. E: Struct. Rep. Online,
2005, 61, 1571.

ZnII complexes of new quinazolinylhydrazones
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 11, November, 2011 2353
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[Organic Luminophores], Khimiya, Moscow, 1984, p. 58
(in Russian).
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Mosk. Gos. Univ., Moscow, 1985, 158 (in Russian).
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22. R. C. Clark, J. S. Reid, Acta Crystallogr., 1995, A51, 887.
23. G. M. Sheldrick, Acta Crystallogr., 2008, A64, 112.
19. T. Chattopadhyay, M. Mukherjee, K. S. Banu, A. Banerfee,
E. Suresh, E. Zangrando, D. Das, J. Coord. Chem., 2009,
62, 967.
Received March 2, 2011;
in revised form October 11, 2011