Synthesis, structure, and properties of new phosphorus Schiff bases

Article abstract of DOI:10.1134/S1070363208040099

A series of new Schiff bases has been synthesized on the basis of (2-aminophenyl)triphenyl-phosphonium chloride and substituted salicylaldehydes. The structure of the prepared compounds has been established by means of IR, UV, and ¹H NMR spectroscopy, as well as DFT B3LYP/6-31G(d,p) quantum-chemical simulation. The possible tautomerism and certain properties of the azomethines, including complex formation, have been studied.

Full text of DOI:10.1134/S1070363208040099

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 4, pp. 567–574. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © L.D. Popov, S.A. Borodkin, I.N. Shcherbakov, Yu.N. Tkachenko, V.A. Kogan, 2008, published in Zhurnal Obshchei Khimii, 2008,
Vol. 78, No. 4, pp. 586–593.
Synthesis, Structure, and Properties
of New Phosphorus Schiff Bases
L. D. Popov, S. A. Borodkin, I. N. Shcherbakov, Yu. N. Tkachenko, and V. A. Kogan
Southern Federal University,
ul. Zorge 7, Rostov-on-Don, 344090 Russia
e-mail: saborod@list.ru
Received August 13, 2007
Abstract—A series of new Schiff bases has been synthesized on the basis of (2-aminophenyl)triphenyl-
phosphonium chloride and substituted salicylaldehydes. The structure of the prepared compounds has been
1
established by means of IR, UV, and H NMR spectroscopy, as well as DFT B3LYP/6-31G(d,p) quantum-
chemical simulation. The possible tautomerism and certain properties of the azomethines, including complex
formation, have been studied.
DOI: 10.1134/S1070363208040099
The goal of the present work was to synthesize new
phosphorus-containing azomethines and to study their
structure and some properties, including complex
formation. (2-Aminophenyl)triphenylphosphonium
chloride was reacted with substituted salicylaldehydes
to obtain phosphonium anils IIIa−IIIg.
Schiff bases are unique compounds due the
possibility of easily varying fragments at the exocyclic
C=N bond, which allows exploring such important
aspects as tautomerism, conformational equilibria,
acid&3base and donor–acceptor properties, etc. But,
probably, the most important property of azomethines
is their high complex-forming ability [1–4]. The
interest in azomethines and their metal complexes is
caused by their practical importance. Among them,
luminophores, lubricant and fuel additives, photo-
chromic materials, biologically active compounds, etc.,
were found [5]. Azomethines often serve as precursors
for synthesis of other compounds, including
heterocycles [6]. The number of papers on Schiff bases
does not reduce, and the last review [7] contains about
700 references which cover the period since 2000 until
present. In this connection we considered it of interest
to synthesize new azomethines on the basis of
aminophosphonium salts. Organophosphorus azome-
thines containing a P(III) atom, like I [8–17] and II
[18–32] and their metal complexes, have been
described in the literature, while ortho-hydroxy-
azomethines including a charged triarylphosphonium
group have never been reported.
R1
3'
OH
2'
4'
3
4
1'
5'
2
R2
5
CH=N
6'
1
6
Cl− P+Ph3
IIIа−ΙΙΙg
R1 = R2 = H (а); R1 = H, R2 = NO2 (b); R1 = H, R2 = Br (c);
R1 = H, R2 = OCH3 (d); R1 = OCH3, R2 = Br (e); R1 = R2 =
Br (f); R1 = R2 = Cl (g).
1
The H NMR spectra of compounds IIIa−IIIg in
DMSO-d6 show a hydroxyl proton signal as a singlet
at δ 10.10−12.42 ppm, which disappears upon deutera-
tion. As expected, the most downfield OH proton
signal (δ 12.42 ppm) is characteristic of nitro
derivative IIIb. The azomethine CH proton gives a
singlet at δ 8.77−9.18 ppm, the largest chemical shifts
are observed in dichloro and dibromo derivatives IIIf
P
P
N=CH−R
CH=N−R
I
II
567

568
POPOV et al.
and IIIg. The spectra also contain P+Ph3 signals at δ
system at δ 7.00−8.23 ppm. These signals overlap with
7.6−7.85 ppm, as a complex 15-proton multiplet.
PPh3 signals and, therefore, are difficult to assign.
The phosphorus-containing substituent complicates
the shape of signals of its connected aromatic ring.
This is explained by the fact that proton–phosphorus
spin-spin coupling can reveal itself through 4–5 bonds.
Thus, the H3 signals appear as a doublet of doublets at
δ 7.8−8.1 ppm (2JHH 7.8 Hz, JHP 6 Hz) and usually
occur in the same field as triphenylphos-phonium
proton signals. The H4 signals at δ 7.9−8.1 ppm have a
complex shape due to spin–spin coupling with H5
which is meta to H4 and long-range coupling with
To assess the effect of the triphenylphosphonium
group on the positions of H NMR signals, we syn-
thesized and explored model compound V.
1
3'
OH
2'
4'
3
4
1'
5'
2
5
CH=N
NO2
6'
1
6
Cl
V
2
phosphorus. The observed coupling constants are JHH
3
7.5–8.0 and JHH 1.3 Hz. The H5 signals are doublets at
Compared to phosphonium derivative IIIb, nitro
δ 7.40−7.60 ppm (2JHH 7.4–7.7 Hz, JHP 3.0−3.7 Hz).
The H6 proton gives a doublet of doublets at δ 7.12−
7.25 ppm (JHP 14 Hz, 2JHH 7−8 Hz).
1
substitution exerts a stronger impact on the H NMR
spectrum of chloro derivative V. Thus, for example,
the OH proton signal appears as a very downfield
singlet (δ 14.23 ppm). The H4' (doublet of doublets, δ
8.24 ppm) and H6' (doublet, δ 8.69 ppm) signals in the
1H NMR spectrum of compound V are also shifted
downfield compared to compound IIIb. It is
noteworthy that the H4 signal in the spectrum of
compound V is shifted upfield from the H6 signals (δ
7.42 and 7.52 ppm, respectively). In the spectra of
derivatives III, an opposite mutual location of these
signals is observed (about 8.0 and 7.2 ppm, respec-
tively). The H3 and H5 signals in the spectra of
compounds III and V have a similar mutual location. It
follows from the above data that the substitution of the
chlorine atom by the positively charged triphenylphos-
phonium group exerts the strongest effect on the
positions of the ortho- and para-proton signals.
The shape and location of signals of the phenolic
fragment are substitution-dependent. In the case of
dichloro- and dibromo derivatives, the H4' and H6'
protons give, as expected, doublets at δ 6.54−6.76 and
7.32−7.57 ppm , respectively (3JHH 2.4−2.6 Hz). In the
1H NMR spectrum of the compound with R1 = OCH3
and R2 = Br, the same protons again appear as doublets
at δ 6.31 and 6.94 ppm, respectively (3JHH 2.3 Hz).
The H6' signals of monosubstituted compounds appear
as a doublet at δ 6.20−7.51 ppm (3JHH 2.5−2.9 Hz). In
this case, electronic effects of substituents are well-
pronounced. Thus, the electron-donor methoxy group
shifts the H6' signal upfield (to 6.20 ppm), while the
electron-acceptor nitro group shifts the same signal
downfield (to 7.51 ppm). The H4' signal is complicated
and looks like a doublet of doublets at δ 6.75−8.0 ppm
The UV spectra of compounds IIIa in ethanol
contain a strong π→π* transition band of the aromatic
rings at λmax 207 nm (log εmax 4.80), a strong π→π*
transition band (E band) at λmax 276 nm (log εmax 4.00),
and a π→π* band (K band) at λmax 358 nm (log εmax
3.95). Addition of excess acid (HCl) to the solution of
compound IIIa, the electronic spectrum changes
insignificantly, which implies weak proton-acceptor
properties of the imine nitrogen atom. In an alkaline
medium (KOH), the spectrum changes significantly.
The aromatic π→π* transition band undergoes a
bathochromic shift of 20 nm and appears at λmax 227 nm
(log εmax 4.62). The E band shifts bathochromically by
30 nm and appears at λmax 306 nm (log εmax 4.02). The
K band undergoes the strongest bathochromic shift (by
87 nm) and increases in intensity (λmax 435 nm, log εmax
4.13), implying ionization of compound IIIa. The
effect of the pH of the medium on the UV absorption
3
(2JHH 9.0 Hz, JHH 3 Hz). The largest chemical shift,
too, is observed for the nitro derivative. The H3' proton
is detected as a doublet at δ 6.81−7.24 ppm (2JHH
8.3−9.2 Hz).
The shapes and positions of the H3–H6 signals in
1
the H NMR spectrum of naphthyl derivative IV are
similar to those in the spectra of azomethines III. The
only distinguishing feature of the spectrum of this
compound is that it contains signals of the naphthalene
3'
OH
2'
4'
3
4
1'
5'
2
5
6'
7'
CH=N
10'
9'
1
6
8'
Cl− P+Ph3
IV
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 4 2008

SYNTHESIS, STRUCTURE, AND PROPERTIES OF NEW PHOSPHORUS SCHIFF BASES
569
bands of nitro derivative IIIb is similar to that in
unsubstituted compound IIIa: The aromatic π→π*
transition band in a strongly alkaline medium (excess
KOH) undergoes a 15-nm bathochromic shift com-
pared to a neutral medium, and the E band is shifted
bathochromically by 10 nm. The longest wave band
corresponding to formation of a monodeprotonated
structure is observed at λmax 435 nm with log εmax 3.93
(in neutral medium, λmax 350 nm and log εmax 3.85).
The π→π* transition band of the nitro group (in a
neutral medium, λmax 302 nm and log εmax 3.90)
undergoes a 80-nm bathochromic shift as the solution
is made alkaline (λmax 382 nm, log εmax 4.01).
Noteworthy, this equilibrium in the solution is
reversible, since adding acid to the alkaline solution (to
pH 7) restores the spectrum of the neutral form.
the relative stability of the tautomers, we accomplished
DFT B3LYP/6-311G(d,p) quantum-chemical calcula-
tions of model anils IIIa and IV in which the
triphenylphosphonium fragment of the synthesized
azomethines is replaced by trimethylphosphonium.
Figure 1 shows the steric models and calculated total
energies (au) of the most stable conformations of the
two tautomeric forms (benzoid and quinoid) and their
relative stabilities (ΔE, kcal mol–1).
Like azomethine IIIa, compound IV prefers the
benzoid tautomeric form, but the difference in the total
energies in the case of naphthyl derivative IV is much
smaller that in the case of compound IIIa, on account
of a stronger stabilization of the quinoid tautomer due
to π conjugation of the C=O bond with the more
extended aromatic system of the naphthyl fragment.
1
Compounds like III and IV can undergo benzoid–
quinoid tautomerism due to proton transfer from
oxygen to the azomethine nitrogen [33–36]. To assess
This conclusion is consistent with the H NMR data
for compounds III and IV which prefer the benzoid
form in a polar solvent (DMSO).
H
H
H
C
H
C H
H
P
C
H
H
H
H
H
H
H
C
H
H
C
H
O
C
H
H
P
C
C
N
C
H
H
H
H
H
O
H
H
C
C
C
C
C
C
C
H
C
N
C
H
C
C
H
C
C
C
C
C
C
C
C
C
H
C
H
C
H
H
C
H
H
H
H
H
H
–1092.502624 au
–1092.491342 au
ΔE 0 kcal mol–1
ΔE 7.1 kcal mol–1
H
H
H
C
H
H
H
H
H
H
C
H
H
O
H
C
H
H
H
C
H
P
P
H
C
C
H
H
H
H
C
C
C
H
H
H
O
C
H
C
C H
C
N
C
C
C
C
H
H
C
C
C
C
N
C
C
H
C
C
C C
H
C
C
C
C
H
H
C
H
C
C
C
C
H
C
H
C
C
H
H
H
H
H
H
H
–1246.1789249 au
–1246.1737251 au
ΔE 0 kcal mol–1
ΔE 3.3 kcal mol–1
Fig. 1. Steric models and calculated total energies of the most stable conformers of the two tautomeric forms (benzoid and quinoid)
and their relative stabilities (ΔE).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 4 2008

570
POPOV et al.
H
H
C
C
C
H
H
C
H
H
C
C
H
H
C
H
C
C
H
H
H
C
H
C
C
C
P
C
H
H
C
C
C
C
C
N
O
C
C
H
C
C
C
C
C
H
C
C
C
Zn
H
C
C
C
H
H
H H
C
C
C
C
H
C
H
H
C
H
N
H
O
C
H
H
C
P
C
C
C
H
H
H
C
C
C
H
H C
C
H
C
C
H
H
C
C
H
H
C
C
C
C
C
H
H
H
H
H
Fig. 2. Optimal geometry of zinc complex VI, obtained by the B3LYP/6-311G(d,p) method.
The azomethine nitrogen atom is involved into a
strong hydrogen bond, which, together with the steric
shielding by the bulky triphenylphosphonium sub-
stituent, is likely to prevent protonation of the
investigated azomethines in an acid medium
(experimental finding).
The possibility of existence of a tetrahedral zinc
complex VI, even though it contains the bulky
triphenylphosphonium substituent, was additionally
confirmed by DFT calculations of its equilibrium
geomety (Fig. 1).
The six-membered chelate rings are almost planar,
except that they are folded by an angle of 11° along the
line connecting the donor nitrogen and oxygen atoms.
The pseudo-tetrahedral configuration of bonds around
the complex-forming metal is slightly distorted: The
angle between the chelate ring planes is 81°C. The
Zn−O and Zn−N distances are 1.930 and 2.055 Å,
respectively, that is typical of structurally similar zinc
complexes.
To study the complex-forming properties of these
compound, we explored reaction of azomethines
IIIa−IIIg and IV with Zn(II) and Cd(II) ions. The
choice of these metals is primarily explained by the
fact that many Zn(II) and Cd(II) azomethine
complexes possess interesting and important
luminescent properties and are used as organic light-
emitting diodes [37–40]. The presence of a labile
proton in the molecules of these ligands allowed us to
prepare ML2 chelate metal complexes VI. Let us note
immediately that we could isolate and purify only three
complexes: two zinc (with IIIb and IIIc as ligands)
and one cadmium (with IIIb). Comparison of the IR
spectra of these complexes with those of the free
ligands reveals disappearance of the OH absorption
band and a 10−15-nm bathochromic shift of the C=N
group with simultaneous 10−15-nm hypsochromic
shift the aldehyde Ph−O stretching vibration band,
which suggests chelate formation. The 1H NMR
spectra of the complexes no longer show the OH
proton signal, and the H3' signal is shifted upfield by
about 1.0 ppm, which provides further evidence for
chelate formation.
Preliminary tests for photochemical activity showed
that these complexes in the solid state possess
luminescent properties. Detailed investigation of the
photophysical properties of the complexes will be
reported elsewhere.
EXPERIMENTAL
The IR spectra were recorded on a Varian Scimitar
1000 FT-IR spectrophotometer for suspensions in
1
mineral oil. The Н NMR spectra were measured on a
Bruker AM-300 spectrometer, internal reference TMS.
The UV spectra were obtained on a Unicam Helious
Gamma instrument for solutions in ethanol in the range
195−500 nm.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 4 2008

SYNTHESIS, STRUCTURE, AND PROPERTIES OF NEW PHOSPHORUS SCHIFF BASES
571
Quantum-chemical calculations. The electronic
and steric structures of the compounds were calculated
nonempirically in the framework of the density
functional theory (DFT). The hybrid exchange
correlation functional B3LYP [41], with Becke’s
exchange part [42] and Lee−Yang−Parr’s correlation
part [43] was applied. The molecular geometry was
preliminary optimized over all natural variables
without any symmetry constraints. Minima on the
potential energy surface (PES) were found for each
structure by calculating force constant matrix and
normal mode frequencies. The calculations were
performed using the PCGAMESS V.7.0 program [44].
For data treatment, visualization of the results, and
presentation graphics the ChemCraft program was
used [45].
ОН), 8.89 s (1Н, СН=N), 7.6–7.8 m [15Н, Р(С6Н5)3],
8.0 m (3Н, Н3, Н4 и Н4’), 7.58 t.d (1Н, Н5, partially
5
4(6)
5
obscured by (С6Н5)3 signals, JН ,Н 7.5, JН ,Р 3.2), 7.24
d.d (1Н, Н6, partially obscured by the Н3’ signal), 7.24
d (1Н, Н3', partially obscured by the Н6 signal, JН ,Н
3' 4'
9.2), 7.51 d (1Н, Н6', JН ,Н 2.9). Found, %: С 68.78; Н
6' 4'
4.47; N 4.93; Р 5.79. С31Н24ClN2O3P. Calculated, %:
С 69.08; Н 4.49; N 5.20; Р 5.75.
[2-(1E)-(5-Bromo-2-hydroxyphenyl)methylene-
aminophenyl]triphenylphosphonium chloride (IIIc)
was prepared by the same procedure from 0.50 g of (2-
aminophenyl)triphenylphosphonium chloride and
0.258 g of 5-bromo-2-hydroxybenzaldehyde. Yield
57%, mp >300°C. IR spectrum, cm−1: 2750 (ОН),
1608 (C=N), 1291 (Ph−O). 1Н NMR spectrum
(DMSO-d6), δ , ppm (J, Hz): 10.95 s (1Н, ОН), 8.83 s
(1Н, СН=N), 7.6 – 7.85 m [15Н, Р(С6Н5)3], 7.88 d.d
[1Н, Н3, partially obscured by (С6Н5)3 signals], 8.03 t
(2-Aminophenyl)triphenylphosphonium chloride
was prepared by the reaction of triphenylphosphine
with anhydrous NiCl2 by the procedure in [46].
(1Н, Н4, JН ,Н 7.9), 7.56 t.d (1Н, Н5, JН ,Н 7.7, JН ,Р
3.3), 7.20 d.d (1Н, Н6, partially obscured by the Н4''
4
3(5)
5
4(6)
5
[2-(1E)-(2-Hydroxyphenyl)methyleneamino-
phenyl]triphenylphosphonium chloride (IIIa). To a
solution of 0.50 g of (2-aminophenyl)triphenylphos-
phonium chloride in 10 ml of ethanol, 0.13 ml of
salicylaldehyde was added, and the mixture was heated
under reflux for 4 h. The ethanol solution was then
reduced by 2/3, and ethyl acetate was added until
precipitation began. The yellow precipitate obtained
after cooling was filtered off, washed with ethyl
acetate, and recrystallized from ethanol−ethyl acetate,
1:4. Yield 67%, mp >300°C (EtOH). IR spectrum,
cm−1: 3350 (ОН), 1604 (C=N), 1278 (Ph−O). 1Н NMR
spectrum (DMSO-d6), δ , ppm (J, Hz): 10.56 s (1Н,
ОН), 8.80 s (1Н, СН=N), 7.6–7.8 m [15Н, Р(С6Н5)3],
7.8 m [1Н, Н3, obscured by (С6Н5)3 signals], 8.03 t.t
signal), 6.91 d (1Н, Н3', JН ,Н 8.8), 7.23 d.d (1Н, Н4',
3' 4'
partially obscured by the Н6 signal), 6.67 d (1Н, Н6',
6' 4'
JН ,Н 2.5). Found, %: С 65.28; Н 4.20; N 2.17; Р 5.29.
С31Н24BrClNOP. Calculated, %: С 65.00; Н 4.22; N
2.45; Р 5.41.
[2-(1E)-(2-Hydroxy-5-methoxyphenyl)methyle-
neaminophenyl]triphenylphosphonium chloride
(IIId) was prepared by the same procedure from 0.50 g
of (2-aminophenyl)triphenylphosphonium chloride and
0.195 g of 2-hydroxy-5-methoxybenzaldehyde. Yield
62%, mp >300°C. IR spectrum, cm−1: 2750 (ОН),
1598 (C=N), 1270 (Ph−O). 1Н NMR spectrum
(DMSO-d6), δ , ppm, (J, Hz): 10.10 s (1Н, ОН), 8.77 s
(1Н, СН=N), 7.6–7.8 m [15Н, Р(С6Н5)3], 7.8 m [1Н,
(1Н, Н4, JН ,Н 7.9), 7.54 t.d (1Н, Н5, JН ,Н 7.5, JН ,Р
3.7), 7.20 d.d (1Н, Н6, partially obscured by the Н4'
4
3(5)
5
4(6)
5
Н3, obscured by (С6Н5)3 signals], 8.03 t.t (1Н, Н4,
5
4
3(5)
5
4(6)
5
signal), 6.87 d.d (1Н, Н3’, JН ,Н 8.3, JН ,Н 0.8), 7.23
t.d (1Н, Н4', partially obscured by the Н6 signal), 6.47
JН ,Н 7,7), 7.53 t.d (1Н, Н , JН ,Н 7,5, JН ,Р 3,3), 7.17
3' 4'
3' 5'
d.d (1Н, Н6, JН ,Р 14,3, JН ,Н 6,9), 6.81 d (1Н, Н3',
6
6
5
JН ,Н 9,0), 6.75 d.d (1Н, Н4', JН ,Н 9,0, JН 3,0), 6.20
3' 4'
4' 3'
4',6'
t.d (1Н, Н5', JН ,Н 7.2, JН ,Н 0.8), 6.71 d.d (1Н, Н6',
5' 4'(6')
5' 3'
d (1Н, Н6', JН ,Н 2,9), 3.19 s (ОСН3). Found, %: С
6' 4'
6' 5'
6' 4'
JН ,Н 7.9, JН ,Н 1.7). Found, %: С 75.40; Н 5.00; N
2.84; Р 6.29. С31Н25ClNOP. Calculated, %: С 75.38; Н
5.10; N 2.84; Р 6.27.
73.50; Н 4.98; N 2.57; Р 5.89. С32Н27ClNO2P.
Calculated, %: С 73.35; Н 5.19; N 2.67; Р 5.91.
[2-(1E)-(2-Hydroxy-5-nitrophenyl)methylene-
aminophenyl]triphenylphosphonium chloride (IIIb)
was prepared by the same procedure from 0.50 g of (2-
aminophenyl)triphenylphosphonium chloride and
0.214 g of 2-hydroxy-5-nitrobenzaldehyde. Yield 86%,
mp >300°C. IR spectrum, cm−1: 2450 (ОН), 1605
[2-(1E)-(5-Bromo-2-hydroxy-3-methoxyphenyl)
methyleneaminophenyl]triphenylphosphonium
chloride (IIIe) was prepared by the same procedure
from 0.50 g of (2-aminophenyl)triphenylphosphonium
chloride and 0.297 g of 5-bromo-2-hydroxy-3-meth-
oxybenzaldehyde. Yield 45%, mp >300°C. IR spec-
trum, cm−1: 2730 (ОН), 1602 (C=N), 1259 (Ph−O). 1Н
NMR spectrum (DMSO-d6), δ , ppm, (J, Hz): 10.06 s
1
(C=N), 1577, 1339 (NO2), 1282 (Ph−O). Н NMR
spectrum (DMSO-d6), δ , ppm (J, Hz): 12.42 s (1Н,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 4 2008

572
POPOV et al.
(1Н, ОН), 8.90 s (1Н, СН=N), 7.6–7.85 m [15Н, Р
5.87. С35Н27ClNOP. Calculated, %: С 77.27; Н 5.00;
N 2.57; Р 5.69.
(С6Н5)3], 7.91 d.d (1Н, Н3, JН ,Р 6.0, JН ,Н 7.8), 8.03 t.t
3
3
4
(1Н, Н4, JН ,Н 8.0), 7.56 t.d (1Н, Н5, JН ,Н 7.4, JН ,Р
4
3(5)
5
4(6)
5
2-(E)-(2-Chlorophenyliminomethyl)-4-nitro-
phenol (V). To a solution of 0.30 g of ortho-
chloroaniline in 5 ml of ethanol, 0.393 g of 2-hydroxy-
5-nitrobenzaldehyde in 5 ml of ethanol was added, and
the mixture was heated under reflux. Two minutes
later, a precipitate began to form. After 30 min under
reflux, the precipitate was filtered off and washed with
ethanol and recrystallized from ethanol−DMF. Yield
3.0), 7.22 d.d.d (1Н, Н6, JН ,Р 14.4, JН ,Н 6.9), 6.31 d
6
6
5
(1Н, Н4', JН 2.2), 6.94 d (1Н, Н6', JН ,Н 2.3), 3.79 s
(ОСН3). Found, %: С 63.77; Н 4.27; N 2.27; Р 5.17.
С32Н26BrClNO2P. Calculated, %: С 63.75; Н 4.35; N
2.32; Р 5.14.
4',6'
6' 4'
[2-(1E)-(3,5-Dibromophenyl-2-hydroxy)methyle-
neaminophenyl]triphenylphosphonium chloride
(IIIf) was prepared by the same procedure from 0.50 g
of (2-aminophenyl)triphenylphosphonium chloride and
0.359 g of 3,5-dibromo-2-hydroxybenzaldehyde in
butan-1-ol. Yield 87%, mp >300°C. IR spectrum,
cm−1: 2700 (ОН), 1609 (C=N), 1280 (Ph−O). 1Н NMR
spectrum (DMSO-d6), δ , ppm, (J, Hz): 11.21 s (1Н,
ОН), 9.18 s (1Н, СН=N), 7.6–7.8 m [15Н, Р(С6Н5)3],
8.1 m (2Н, Н3 и Н4), 7.6 m [1Н, Н5, obscured by
1
92%, mp 190°C. Н NMR spectrum (DMSO-d6), δ,
ppm, (J, Hz): 14.23 s (1Н, ОН), 9.20 s (1Н, СН=N),
4
7.58 d.d (1Н, Н3, JН ,Н 8.0, JН ,Н 1.5), 7.42 t.d (1Н, Н ,
3
4
3
5
JН ,Н 7.6, JН ,Н 1.4), 7.31 t.d (1Н, Н5, JН ,Н 7.6,
4
3(5)
4
6
5
4(6)
JН ,Н 1.5), 7.52 d.d (1Н, Н6, JН ,Н 7.9, JН ,Н 1.3), 7.10
5
3
6
5
6
4
d (1Н, Н3', JН ,Н 9.2), 8.24 d.d (1Н, Н4', JН ,Н 9.2,
3' 4'
4' 3'
6'
4' 6'
6' 4'
JН ,Н 2.8), 8.69 d (1Н, Н , JН ,Н 2.8).
[2-(1E)-(2-Hydroxy-5-nitrophenyl)methylene-
aminophenyl]triphenylphosphonium chloride zinc
complex (VI). To a solution of 0.50 g of compound
IIIb in 10 ml of absolute methanol, a solution of 0.102 g
of Zn(CH3COO)2 · 2Н2О in 5 ml methanol was added.
The mixture was refluxed for 4 h, and the precipitate
that formed was filtered off and washed with
methanol. Yield 47%, mp>300°C. IR spectrum, cm−1:
(С6Н5)3 signals], 7.21 d.d (1Н, Н6, JН ,Р 14.3, JН ,Н
6
6
5
6.9), 6.76 d (1Н, Н4', JН 2.4), 7.57 d (1Н, Н6', JН ,Н
2.4). Found, %: С 56.81; Н 3.47; N 2.21; Р 4.92.
С31Н23Br2ClNOP. Calculated, %: С 57.13; Н 3.56; N
2.15; Р 4.75.
4',6'
6' 4'
[2-(1E)-(3,5-Dichloro-2-hydroxyphenyl)methyle-
neaminophenyl]triphenylphosphonium chloride
(IIIg) was prepared by the same procedure from 0.50 g
of (2-aminophenyl)triphenylphosphonium chloride and
0.245 g of 3,5-dichloro-2-hydroxybenzaldehyde. Yield
65%, mp >300°C. IR spectrum, cm−1: 2730 (ОН),
1608 (C=N), 1280 (Ph−O). 1Н NMR spectrum
(DMSO-d6), δ , ppm (J, Hz): 11.12 s (1Н, ОН), 9.18 s
(1Н, СН=N), 7.65–7.85 m [15Н, Р(С6Н5)3], 8.1 m (2Н,
Н3 и Н4), 7.59 m [1Н, Н5, partially obscured by (С6Н5)3
1
1594 (C=N), 1572, 1298 (NO2 + Ph−O). Н NMR
spectrum (DMSO-d6), δ , ppm, (J, Hz): 8.74 s (1Н,
СН=N), 7.6–7.85 m [15Н, Р(С6Н5)3], 7.8 m [1Н, Н3,
obscured by (С6Н5)3 signals], 7.96 t (1Н, Н4, JН ,Н
4
3(5)
7.6), 7.49 t.d (1Н, Н5, JН ,Н 7.7, JН ,Р 3.3), 7.14 d.d
5
4(6)
5
(1Н, Н6, JН ,Р 14.3, JН ,Н 6.9), 6.10 d (1Н, Н3', JН ,Н
9.6), 7.62 d.d [1Н, Н4', partially obscured by (С6Н5)3
6
6
5
3' 4'
signals, JН ,Н 3.2], 7.42 d (1Н, Н6', JН ,Н 3.2). Found,
%: Zn 5.54; Р 5.53. С62Н46Cl2N4O6P2Zn. Calculated,
%: Zn 5.73; Р 5.43.
4' 6'
6' 4'
signals], 7.21 d.d (1Н, Н6, JН ,Р 14.3, JН ,Н 6.9), 6.54 d
6
6
5
(1Н, Н4', JН 2.6), 7.32 d (1Н, Н6', JН ,Н 2.6). Found,
%: С 66.37; Н 3.98; N 2.41; Р 5.69. С31Н23Cl3NOP.
Calculated, %: С 66.15; Н 4.12; N 2.49; Р 5.50.
4',6'
6' 4'
[2-(1E)-(2-Hydroxy-5-nitrophenyl)methylene-
aminophenyl]triphenylphosphonium chloride
cadmium complex (VI) was prepared by the same
procedure from 0.50 g of compound IIIb and 0.124 g
of Cd(CH3COO)2 · 2Н2О. Yield 28%, mp>300°C. IR
spectrum, cm−1: 1594 (C=N), 1575, 1311 (NO2), 1299
[2-(1E)-(2-Hydroxy-1-naphthyl)methylene-
aminophenyl]triphenylphosphonium chloride (IV)
was prepared by the same procedure from 0.50 g of (2-
aminophenyl)triphenylphosphonium chloride and
0.221 g of 2-hydroxy-1-naphthaldehyde. Yield 57%,
mp >300°C. IR spectrum, cm−1: 2670 (ОН), 1592
1
(Ph−O). Н NMR spectrum (DMSO-d6), δ , ppm, (J,
Hz): 8.77 s (1Н, СН=N), 7.6–7.85 m [15Н, Р(С6Н5)3],
7.8 m [1Н, Н3, obscured by (С6Н5)3 signals], 7.90 t
1
(C=N), 1273 (Ph−O). Н NMR spectrum (DMSO-d6),
(1Н, Н4, JН ,Н 7.5), 7.4 m (1Н, Н5, obscured by the
4
3(5)
δ, ppm, (J, Hz): 11.66 s (1Н, ОН), 9.07 s (1Н, СН=N),
Н6' signal), 7.14 d.d (1Н, Н6, JН ,Р 14.0, JН4,'Н 7.6), 6.00
6
6
5
7.6–7.8 m [17Н, Р(С6Н5)3 + 2Нnaphth.], 8.23 d (1H, H9',
d (1Н, Н3', JН ,Н 9.8), 7.56 d.d [1Н, Н , JН ,Н 9.7,
3' 4'
4' 3'
JH ,H 8.5), 8.07 t.t (1Н, Н4, JН ,Н 7.7), 7.8 d.d (1Н,
Н3), 7.6 t.d [1Н, Н5, partially obscured by (С6Н5)3
signals], 7.25 d.d (1Н, Н6), 7.23 d (1Н, Н6 J 7.2), 7.01
m (2H, Hnaphth.). Found, %: С 76.93; Н 4.81; N 2.67; Р
9' 8'
4
3(5)
JН ,Н 3.2], 7.40 d (1Н, Н6', partially obscured by the
4' 6'
Н5 signal, JН ,Н 3.2). Found, %: Cd 9.72; Р 5.41.
6' 4'
С62Н46CdCl2N4O6P2. Calculated, %: Cd 9.46; Р 5.21.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 4 2008

SYNTHESIS, STRUCTURE, AND PROPERTIES OF NEW PHOSPHORUS SCHIFF BASES
573
14. Cameron, P.A., Gibson, V.C., Redshaw, C., Segal, J.A.,
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[2-(1E)-(5-Bromo-2-hydroxyphenyl)methylene-
aminophenyl]triphenylphosphonium chloride zinc
complex (VI) was prepared by the same procedure
from 0.50 g of compound IIIc and 0.096 g of Zn
(CH3COO)2 · 2Н2О. Yield 33%, mp > 300°C. IR
1
spectrum, cm−1: 1606 (C=N), 1300 (Ph−O). Н NMR
spectrum (DMSO-d6), δ , ppm, (J, Hz): 8.89 s (1Н,
СН=N), 7.6–7.85 m [15Н, Р(С6Н5)3], 7.8 m [1Н, Н3,
obscured by (С6Н5)3 signals], 7.90 br.t (1Н, Н4), 7.42
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6
6
5
6.58 d (1Н, Н3', JН ,Н 8.9), 6.96 br.d (1Н, Н4'), 6.44
3' 4'
br.s (1Н, Н6'). Found, %: Zn 5.37; Р 5.09.
С62Н46Br2Cl2N2O2P2Zn. Calculated, %: Zn 5.41; Р
5.12.
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ACKNOWLEDGMENTS
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The work was financially supported by the internal
grant of the Southern Federal University for 2007.
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