Design of postmetallocene Schiff base-like catalytic systems for polymerization of olefins: XII. Synthesis of tetradentate bis-salicylaldehyde imine ligands

Article abstract of DOI:10.1134/S1070428009040101

Reactions of salicylaldehyde, 3-tert-butylsalicylaldehyde, and 3,5-di-tert-butylsalicylaldehyde with 1,4-diaminobutane, 1,6-diaminohexane, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′,5,5′- tetramethyldiphenylmethane, 4,4′-diamino-5,5′-dicyclopentyl-3, 3′-dimethyldiphenylmethane, 4,4′-diamino-5,5′-dicyclohexyl-3, 3′-dimethyldiphenylmethane, bis(4-aminophenyl) sulfone, o,o′- and p,p′-diaminodiphenyl ethers, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy) phenyl]propane, and 4,4″-diamino-p-terphenyl gave a series of the corresponding Schiff bases which can be used as tetradentate ligands for the synthesis of titanium and zirconium complexes.

Full text of DOI:10.1134/S1070428009040101

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 4, pp. 528–535. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © I.I. Oleinik, I.V. Oleinik, S.S. Ivanchev, G.A. Tolstikov, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45, No. 4,
pp. 543–550.
Design of Postmetallocene Schiff Base-Like Catalytic Systems
for Polymerization of Olefins: XII.* Synthesis of Tetradentate
Bis-salicylaldehyde Imine Ligands
I. I. Oleinika, I. V. Oleinika, S. S. Ivanchevb, and G. A. Tolstikova
a Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: oleynik@nioch.nsc.ru
b St. Petersburg Branch, Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences,
St. Petersburg, Russia
Received April 8, 2008
Abstract—Reactions of salicylaldehyde, 3-tert-butylsalicylaldehyde, and 3,5-di-tert-butylsalicylaldehyde with
1,4-diaminobutane, 1,6-diaminohexane, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′,5,5′-tetramethyldi-
phenylmethane, 4,4′-diamino-5,5′-dicyclopentyl-3,3′-dimethyldiphenylmethane, 4,4′-diamino-5,5′-dicyclo-
hexyl-3,3′-dimethyldiphenylmethane, bis(4-aminophenyl) sulfone, o,o′- and p,p′-diaminodiphenyl ethers,
1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 4,4″-diamino-p-terphenyl
gave a series of the corresponding Schiff bases which can be used as tetradentate ligands for the synthesis of
titanium and zirconium complexes.
DOI: 10.1134/S1070428009040101
Despite striking advances in the field of studying
postmetallocene catalytic systems for polymerization
of olefins, achievement of maximal control over the
structure and properties of the resulting polymers
remains an important problem [2]. Phenoxy–imine
complexes of Group IV transition metals were found
[3] to catalyze living polymerization which makes it
possible to obtain polymers with required molecular
weight and block copolymer structure. Therefore,
design of new phenoxy–imine catalysts seems to be
quite promising.
large excess in the catalytic system [5] and insertion of
alkyl ligand into the C=N bond via 1,2-migration [6].
Moreover, cationic centers tend to undergo dimeriza-
tion through formation of μ-alkyl bridges, which is
referred to as bimolecular deactivation [7]; as a result,
inactive species become to predominate in the catalytic
system. Insofar as the above processes are sensitive
to the ligand environment, the structure of available
transition metal complexes which catalyze olefin
polymerization at elevated temperature suggests that
their modification should give rise to new promising
catalysts.
The main disadvantages of such catalysts include
loss of activity and “living” character of the process
and formation of low-molecular weight oligomers at
elevated temperature [4]. The existing views on the
mechanism of olefin polymerization over metallocene
and postmetallocene catalysts imply that the reasons
are increased contribution of chain transfer and
β-hydride transfer processes and stronger deactivation
of the catalyst as the temperature rises.
We believe that a challenging method for modifica-
tion of α-diimine, diiminopyridine, and bis(salicylalde-
hyde imine) complexes may be bonding of the imino
groups through various bridges. In other words, mod-
ified ligands can be synthesized using diamines instead
of primary alkyl- or arylamines. We also anticipated
that complexes with linked imino groups would be
more stable toward deactivation. These views are sup-
ported by the data of [8], according to which 1,2-bis-
(p-phenylene)ethane bridge connecting the arylimino
substituents in [1,2-bis(arylimino)acenaphthene]-
nickel(II) dibromide makes the modified complex
Processes inducing deactivation of catalysts are li-
gand transfer to aluminum cocatalyst present in a very
* For communication XI, see [1].
528

DESIGN OF POSTMETALLOCENE SCHIFF BASE-LIKE CATALYTIC SYSTEMS ... XII.
529
stable and highly active, as well as capable of promot-
ing living polymerization at a considerably higher tem-
perature (75°C) as compared to acyclic analog (0°C).
oxy–imine complexes. The synthetic procedure was
based on the reaction of substituted salicylaldehydes
with primary diamines, some examples of which have
already been reported [6, 9, 11, 14]. We have extended
this procedure to the synthesis of new bis-salicylalde-
hyde imine ligands V–VII and optimized conditions of
their synthesis.
Clarkson et al. [9] showed that deactivation of com-
plexes with bridged arylimine substituents and those
having no such bridges follow different mechanisms.
Presumably, structural variation of the bridging frag-
ment could displace the maximal catalytic activity
toward higher temperature by analogy with bridged
metallocenes [10]. Ishii et al. [11] found that the cata-
lytic activity of [6,6′-polymethylenebis(iminomethyl)-
bis(2-R-phenoxy)]zirconium(IV) dichloride A in the
polymerization of ethylene increases in parallel with
the number of methylene units in the bridge. The cata-
lytic activity also increases as the temperature rises,
though the molecular weight of the polymerization
product decreases.
Aldehydes I–III reacted with 1,4-diaminobutane
(IVa) and 1,6-diaminohexane (IVb) in methanol at
room temperature in the absence of a catalyst, and the
corresponding diimines V–VII (a, b) were formed in
5–6 min in quantitative yield (Scheme 1). The reac-
tions with diaminodiphenylmethanes IVc–IVf, 4,4′-di-
aminodiphenyl sulfone (IVg), and o,o′-diaminodi-
phenyl ether (IVh) were carried out by heating in
boiling methanol in the presence of a catalytic amount
of formic acid, the reaction time ranged from 1 to 4 h,
and the yields of diimines Vc–Vh, VIc–VIh, and
VIIc–VIIh were 91–99%. The condensation of alde-
hydes I–III at both amino groups of p,p′-diaminodi-
phenyl ether (IVi) and diamines IVj, IVk, and IVl was
possible only on prolonged heating of the reactants in
methanol–methylene chloride (1:1) in the presence of
a catalytic amount of formic acid. The yields of bis-
salicylaldehyde imines Vi–Vl, VIi–VIl, and VIIi–VIIl
ranged from 81 to 94%. When the reactions with di-
amines IVi–IVl were carried out in methanol, the proc-
ess stopped at the stage of formation of the corre-
sponding poorly soluble monoimines.
R
R
O
N
O
ZrCl2
N
( )n
A
While performing systematic studies on the effect
of structural modification of metal complexes and their
catalytic activity [12, 13] we found that bis{4,4′-meth-
ylenebis[(p-phenylene)iminomethyl]bis(2-R1-4-R2-
phenoxy)}dititanium(IV) tetrachloride (B) even at
70°C ensures very effective preparation of linear poly-
ethylene with high and ultrahigh molecular weight and
increased melting point [13]. In the present work we
examined the synthesis of tetradentate ligands con-
taining various diimine bridges with a view to make
them accessible for the preparation of bridged phen-
The structure of compounds V–VII was confirmed
by analytical and spectral data. According to the
1H NMR spectra, the isolated Schiff bases were pure
E isomers. Compounds V–VII displayed in the
1H NMR spectra singlets from the N=CH protons at
δ 8.02–9.03 ppm and broadened singlets from the hy-
droxy protons in the region δ 12.33–14.15 ppm; the
downfield position of the latter indicates formation of
intramolecular hydrogen bond between the OH proton
1
and imino nitrogen atom. In the H NMR spectra of
R2
R2
VIa–VIl, protons in the tert-butyl groups resonated as
singlets at δ 1.40–1.47 ppm, while the spectra of di-
imines VIIa–VIIl contained two singlets from the tert-
butyl groups, at δ 1.24–1.34 and 1.35–1.49 ppm. Meth-
ylene protons in the cycloalkyl substituents in Schiff
bases Ve, Vf, VIe, VIf, VIIe, and VIIf gave multiplets
in the region δ 1.11–2.05 ppm, and the cycloalkyl CH
protons appeared as multiplets at δ 2.50–3.18 ppm.
Diimines Vd–Vf, VId–VIf, and VIId–VIIf showed
singlets from methyl protons at δ 2.12–2.20 ppm.
Aromatic protons resonated in the spectra of V–VII in
the region δ 6.44–8.51 ppm. Singlets from the bridging
N
N
O
O
O
O
R1
R1
R1
R1
TiCl2
Cl2Ti
N
N
R2
R2
B
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 4 2009

OLEINIK et al.
530
Scheme 1.
X
OH
OH
N
N
OH
R1
CHO
R1
R1
MeOH
H2N
NH2
+
R2
R2
R2
I–III
IVa–IVl
Va–Vl, VIa–VIl, VIIa–VIIl
I, V, R1 = R2 = H; II, VI, R1 = t-Bu, R2 = H; III, VII, R1 = R2 = t-Bu; X = (CH2)4 (a), (CH2)6 (b),
Me
Me
(c),
(d),
(e),
Me
Me
Me
Me
O
O
O
O
S
(f),
(g),
(h),
(i),
Me
Me
Me
Me
O
(j),
(k),
O
O
O
(l).
CH2 groups in diimines Vc–Vf, VIc–VIf, and VIIc–
VIIf derived from diaminodiphenylmethanes were
located at δ 3.77–4.01 ppm, while protons in the bridg-
ing methylene groups in compounds Va, Vb, VIa,
VIb, VIIa, and VIIb derived from diaminoalkanes IVa
and IVb resonated as multiplets at δ 1.39–1.92 ppm
and triplets (NCH2) at δ 3.61–3.70 ppm.
were measured on a Vector 22 spectrometer from
samples prepared as KBr pellets. The progress of re-
actions was monitored, and the purity of products was
checked, by TLC on Silufol UV-254 plates using
chloroform as eluent. The elemental compositions
were determined on a Carlo Erba 1106 CHN analyzer,
and their formulas were calculated from the high-reso-
lution mass spectra which were recorded on a Finnigan
MAT 8200 instrument. The melting points were deter-
mined by heating samples placed between glass plates
at a rate of 1 deg/min.
The IR spectra of Schiff bases Vc–Vl, VIc–VIl, and
VIIc–VIIl contained a strong absorption band in the
region 1614–1623 cm–1 due to stretching vibrations of
the C=N bonds. The corresponding absorption band in
the spectra of polymethylene-bridged derivatives Va,
Vb, VIa, VIb, VIIa, and VIIb was displaced to higher
frequencies (1632–1635 cm–1). The mass spectra of all
ligands V–VII were characterized by the presence of
strong molecular ion peaks.
Initial 2-cyclopentyl- and 2-cyclohexyl-6-methyl-
anilines were synthesized according to the procedure
described in [15].
4,4′-Methylenebis(2,6-dimethylaniline) (IVd).
A mixture of 3.8 g (31.35 mmol) of 2,6-dimethyl-
aniline and 6.2 ml of water was heated to 95°C, 2.6 ml
of concentrated hydrochloric acid was added, the mix-
ture was stirred for 10 min at 95°C, 0.45 g (15 mmol)
of paraformaldehyde was added, and the mixture was
stirred for 6 h at 100°C. The mixture was cooled,
diluted with 10 ml of water, neutralized with a 20%
EXPERIMENTAL
1
The H NMR spectra were recorded on a Bruker
WP-200 SY instrument at 200.13 MHz using hexa-
methyldisiloxane as internal reference. The IR spectra
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 4 2009

DESIGN OF POSTMETALLOCENE SCHIFF BASE-LIKE CATALYTIC SYSTEMS ... XII.
531
aqueous solution of potassium hydroxide, and ex-
tracted with diethyl ether (3×50 ml). The extract was
washed with water and dried over MgSO4, the solvent
was distilled off on a rotary evaporator, and the solid
residue was recrystallized from methanol. Yield 3.31 g
(87%), mp 114–115°C [16].
(CCl4), δ, ppm: 1.40 s (18H, t-Bu), 1.81–1.92 m (4H,
CH2), 3.65 t (4H, NCH2, J = 7.6 Hz), 6.68 t (2H, Harom
,
J = 7.5 Hz), 6.95 d.d (2H, Harom, J = 7.5, 1.5 Hz),
7.20 d.d (2H, Harom, J = 7.5, 1.5 Hz), 8.30 s (2H,
N=CH), 13.55 br.s (2H, OH). Found: [M]+ 408.27780.
C26H36N2O2. Calculated: M 408.27776.
4,4′-Methylenebis(2-cyclopentyl-6-methylani-
line) (IVe) was synthesized in a similar way from
2-cyclopentyl-6-methylaniline. Yield 80%, mp 94–
6,6′-[Hexamethylenebis(iminomethyl)]bis(2-tert-
butylphenol) (VIb). Yield 97%, mp 73–74°C. IR
1
spectrum: ν 1633 cm–1 (N=C). H NMR spectrum
1
95°C. H NMR spectrum, δ, ppm: 1.50–2.02 m (16H,
(CDCl3), δ, ppm: 1.40 s (18H, t-Bu), 1.42–1.53 m (4H,
CH2), 1.65–1.82 m (4H, CH2), 3.65 t (4H, NCH2, J =
7.5 Hz), 6.71 t (2H, Harom, J = 7.8 Hz), 6.99 d.d (2H,
Harom, J = 7.8, 1.8 Hz), 7.22 d.d (2H, Harom, J = 7.8,
1.8 Hz), 8.29 s (2H, N=CH), 13.84 br.s (2H, OH).
Found: [M]+ 436.30935. C28H40N2O2. Calculated:
M 436.30896.
CH2), 2.06 s (6H, Me), 2.39 m (2H, CH), 3.35 br.s
(4H, NH2), 3.59 s (2H, CH2), 6.54 s (2H, Harom), 6.66 s
(2H, Harom). Found: [M]+ 362.28544. C25H34N2. Calcu-
lated: M 362.28476.
4,4′-Methylenebis(2-cyclohexyl-6-methylaniline)
(IVf) was synthesized in a similar way from 6-cyclo-
hexyl-2-methylaniline. Yield 82%, mp 139–140°C.
1H NMR spectrum, δ, ppm: 1.20–1.49 m (12H, CH2),
1.60–1.95 m (8H, CH2), 2.09 s (6H, Me), 2.88 m
(2H, CH), 3.34 br.s (4H, NH2), 3.65 s (2H, CH2),
6.60 s (2H, Harom), 6.72 s (2H, Harom). Found:
[M]+ 390.30323. C27H38N2. Calculated: M 390.30348.
6,6′-[Tetramethylenebis(iminomethyl)]bis(2,4-di-
tert-butylphenol) (VIIa). Yield 94%, mp 143–144°C;
published data [18]: mp 144–145°C. IR spectrum:
ν 1635 cm–1 (N=C). 1H NMR spectrum (acetone-d6), δ,
ppm: 1.28 s (18H, t-Bu), 1.41 s (18H, t-Bu), 1.79–
1.88 m (4H, CH2), 3.70 t (4H, NCH2, J = 7.0 Hz),
7.23 d (2H, Harom, J = 2.0 Hz), 7.39 d (2H, Harom, J =
2.0 Hz), 8.54 s (2H, N=CH), 13.99 br.s (2H, OH).
Found: [M]+ 520.40348. C34H52N2O2. Calculated:
M 520.40286.
Schiff bases Va, Vb, VIa, VIb, VIIa, and VIIb
(general procedure). Diamine IVa or IVb, 1 mmol,
was added to a solution of 2 mmol of aldehyde I–III
in 20 ml of methanol, and the mixture was stirred for
10 min at room temperature (until the initial com-
pounds disappeared according to the TLC data). The
light yellow precipitate was filtered off and washed
with 2 ml of cold methanol.
6,6′-[Hexamethylenebis(iminomethyl)]bis(2,4-di-
tert-butylphenol) (VIIb). Yield 95%, mp 125–126°C;
published data [18]: mp 120–122°C. IR spectrum:
ν 1634 cm–1 (N=C). 1H NMR spectrum (acetone-d6), δ,
ppm: 1.26 s (18H, t-Bu), 1.39 s (18H, t-Bu), 1.45–
1.53 m (4H, CH2), 1.60–1.79 m (4H, CH2), 3.61 t (4H,
NCH2, J = 7.0 Hz), 7.21 d (2H, Harom, J = 2.0 Hz),
7.37 d (2H, Harom, J = 2.0 Hz), 8.49 s (2H, N=CH),
14.02 br.s (2H, OH). Found: [M]+ 548.434615.
C36H56N2O2. Calculated: M 548.43415.
2,2′-[Tetramethylenebis(iminomethyl)]diphenol
(Va). Yield 98%, mp 87–89°C; published data [17]:
1
mp 90°C. IR spectrum: ν 1632 cm–1 (N=C). H NMR
spectrum (acetone-d6), δ, ppm: 1.72–1.83 m (4H,
CH2), 3.66 t (4H, NCH2, J = 7.5 Hz), 6.80–6.89 m (4H,
H
arom), 7.22–7.38 m (4H, Harom), 8.50 s (2H, N=CH),
13.39 br.s (2H, OH). Found: [M]+ 296.16264.
C18H20N2O2. Calculated: M 296.16370.
Schiff bases Vc–Vh, VIc–Vh, and VIIc–VIIh
(general procedure). A mixture of 2 mmol of aldehyde
I–III, 1 mmol of diamine IVc–IVh, 20 ml of metha-
nol, and 10 mg of 99% formic acid was heated under
reflux with stirring for 1–4 h (until the initial com-
pounds disappeared according to the TLC data). The
mixture was cooled, and the light yellow precipitate
was filtered off and washed with 2 ml of cold
methanol.
2,2′-[Hexamethylenebis(iminomethyl)]diphenol
(Vb). Yield 97%, mp 74–75°C; published data [17]:
1
mp 73°C. IR spectrum: ν 1633 cm–1 (N=C). H NMR
spectrum (acetone-d6), δ, ppm: 1.39–1.53 m (4H,
CH2), 1.62–1.79 m (4H, CH2), 3.61 t (4H, NCH2, J =
7.6 Hz), 6.79–6.90 m (4H, Harom), 7.23–7.37 m (4H,
Harom), 8.48 s (2H, N=C), 13.42 br.s (2H, OH). Found:
[M]+ 324. 18342. C20H24N2O2. Calculated:
M 324.18377.
2,2′-{Methylenebis[(p-phenylene)iminomethyl]}-
diphenol (Vc). Yield 93%, mp 216–217°C. IR spec-
6,6′-[Tetramethylenebis(iminomethyl)]bis(2-tert-
butylphenol) (VIa). Yield 95%, mp 146–147°C. IR
1
trum: ν 1619 (N=C). H NMR spectrum (DMSO-d6),
1
spectrum: ν 1632 cm–1 (N=C). H NMR spectrum
δ, ppm: 4.01 s (2H, CH2), 6.85–7.62 m (16H, Harom),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 4 2009

OLEINIK et al.
532
8.90 s (2H, N=CH), 13.02 br.s (2H, OH). Found:
Found: [M]+ 518.29359. C35H38N2O2. Calculated:
M 518.29331.
[M]+ 406.16812. C27H22N2O2. Calculated: M 406.16812.
6,6′-{Methylenebis[(3,5-dimethyl-1,4-phenylene)-
iminomethyl]}bis(2-tert-butylphenol) (VId). Yield
93%, mp 170–171°C. IR spectrum: ν 1617 cm–1
2,2′-{Methylenebis[(3,5-dimethyl-1,4-phenylene)-
iminomethyl]}diphenol (Vd). Yield 91%, mp 132–
1
133°C. IR spectrum: ν 1622 cm–1 (N=C). H NMR
1
(N=C). H NMR spectrum (CDCl3), δ, ppm: 1.45 s
spectrum (acetone-d6), δ, ppm: 2.15 s (12H, Me),
3.79 s (2H, CH2), 6.84–6.95 m (8H, Harom), 7.29–7.47 m
(4H, Harom), 8.44 s (2H, N=CH), 12.89 br.s (2H, OH).
Found: [M]+ 462.23093. C31H30N2O2. Calculated:
M 462.23071.
(18H, t-Bu), 2.22 s (12H, Me), 3.79 s (2H, CH2), 6.72–
6.93 m (6H, Harom), 7.09 d.d (2H, Harom, J = 7.8,
1.8 Hz), 7.34 d.d (2H, Harom, J = 7.8, 1.8 Hz), 8.31 s
(2H, N=CH), 13.55 br.s (2H, OH). Found: [M]+
574.35694. C39H46N2O2. Calculated: M 574.35591.
2,2′-{Methylenebis[(3-cyclopentyl-5-methyl-1,4-
phenylene)iminomethyl]}diphenol (Ve). Yield 92%,
mp 77–78°C. IR spectrum: ν 1623 cm–1 (N=C).
1H NMR spectrum (acetone-d6), δ, ppm: 1.49–1.99 m
(16H, CH2), 2.13 s (6H, Me), 2.95–3.12 m (2H, CH),
3.84 s (2H, CH2), 6.83–7.09 m (8H, Harom), 7.28–
7.45 m (4H, Harom), 8.38 s (2H, N=CH), 12.85 br.s (2H,
OH). Found: [M]+ 570.32464. C39H42N2O2. Calculated:
M 570.32461.
6,6′-{Methylenebis[(3-cyclopentyl-5-methyl-1,4-
phenylene)iminomethyl]}bis(2-tert-butylphenol)
(VIe). Yield 91%, mp 212–213°C. IR spectrum:
1
ν 1616 cm–1 (N=C). H NMR spectrum (CDCl3), δ,
ppm: 1.46 s (18H, t-Bu), 1.51–2.05 m (16H, CH2),
2.17 s (6H, Me), 2.95–3.13 m (2H, CH), 3.84 s (2H,
CH2), 6.70–7.02 m (6H, Harom), 7.10 d (2H, Harom, J =
7.8 Hz), 7.34 d (2H, Harom, J = 7.8 Hz), 8.29 s (2H,
N=CH), 13.55 br.s (2H, OH). Found: [M]+ 682.44931.
C47H58N2O2. Calculated: M 682.44980.
2,2′-{Methylenebis[(3-cyclohexyl-5-methyl-1,4-
phenylene)iminomethyl]}diphenol (Vf). Yield 98%,
mp 154–155°C. IR spectrum: ν 1621 cm–1 (N=C).
1H NMR spectrum (acetone-d6), δ, ppm: 1.15–1.85 m
(20H, CH2), 2.12 s (6H, Me), 2.57–2.75 m (2H, CH),
3.89 s (2H, CH2), 6.90–7.18 m (8H, Harom), 7.36–
7.57 m (4H, Harom), 8.49 s (2H, N=CH), 12.98 s (2H,
OH). Found: [M]+ 598.35551. C41H46N2O2. Calculated:
M 598.35591.
6,6′-{Methylenebis[(3-cyclohexyl-3-methyl-1,4-
phenylene)iminomethyl]}bis(2-tert-butylphenol)
(VIf). Yield 91%, mp 239–240°C. IR spectrum:
1
ν 1616 cm–1 (N=H). H NMR spectrum (CDCl3), δ,
ppm: 1.11–1.39 m (8H, CH2), 1.46 s (18H, t-Bu),
1.55–1.85 m (12H, CH2), 2.15 s (6H, Me), 2.50–
2.71 m (2H, CH), 3.87 s (2H, CH2), 6.75–7.03 m (6H,
Harom), 7.14 d.d (2H, Harom, J = 7.6, 1.8 Hz), 7.38 d.d
(2H, Harom, J = 7.6, 1.8 Hz), 8.29 s (2H, N=CH),
13.70 br.s (2H, OH). Found: [M]+ 710.48320.
C49H62N2O2. Calculated: M 710.48110.
2,2′-{Sulfonylbis[(p-phenylene)iminomethyl]}di-
phenol (Vg). Yield 96%, mp 268–269°C. IR spectrum:
ν 1618 cm–1 (N=C). 1H NMR spectrum (DMSO-d6), δ,
ppm: 6.97 m (4H, Harom), 7.43 t.d (2H, Harom, J = 7.8,
2.0 Hz), 7.56 d (4H, Harom, J = 7.8 Hz), 7.67 d.d (2H,
Harom, J = 7.8, 2.0 Hz), 8.02 d (4H, Harom, J = 7.8 Hz),
8.92 s (2H, N=CH), 12.33 br.s (2H, OH). Found: [M]+
456.11544. C26H20N2O4S. Calculated: M 456.11437.
6,6′-{Sulfonylbis[(p-phenylene)iminomethyl]}bis-
(2-tert-butylphenol) (VIg). Yield 91%, mp 178–
1
179°C. IR spectrum: ν 1614 cm–1 (N=C). H NMR
spectrum (CDCl3), δ, ppm: 1.43 s (18H, t-Bu), 6.83 t
(2H, Harom, J = 7.8 Hz), 7.19 d.d (2H, Harom, J = 7.8,
2.0 Hz), 7.29–7.42 m (6H, Harom), 7.97 d (4H, Harom
,
2,2′-{Oxybis[(o-phenylene)iminomethyl]}di-
phenol (Vh). Yield 99%, mp 181–182°C. IR spectrum:
ν 1619 cm–1 (N=C). 1H NMR spectrum (acetone-d6), δ,
ppm: 6.79–6.98 m (6H, Harom), 7.19–7.51 m (10H,
Harom), 8.90 s (2H, N=CH), 13.09 br.s (2H, OH).
Found: [M]+ 408.14845. C26H20N2O3. Calculated:
M 408.14738.
J = 8.0 Hz), 8.55 s (2H, N=CH), 13.16 br.s (2H, OH).
Found: [M]+ 568.23930. C34H36N2O4S. Calculated:
M 568.23956.
6,6′-{Oxybis[(o-phenylene)iminomethyl]}bis-
(2-tert-butylphenol) (VIh). Yield 93%, mp 127–
1
128°C. IR spectrum: ν 1614 cm–1 (N=CH). H NMR
spectrum (CDCl3), δ, ppm: 1.40 s (18H, t-Bu), 6.69 t
(2H, Harom, J = 8.0 Hz), 6.92–7.28 m (12H, Harom),
8.61 s (2H, N=CH), 13.50 br.s (2H, OH). Found:
[M]+ 520.27307. C34H36N2O3. Calculated: M 520.27258.
6,6′-{Methylenebis[(p-phenylene)iminomethyl]}-
bis(2-tert-butylphenol) (VIc). Yield 94%, mp 96–
97°C. IR spectrum: ν 1616 cm–1 (N=C). 1H NMR spec-
trum (CDCl3), δ, ppm: 1.44 s (18H, t-Bu), 4.00 s (2H,
CH2), 6.79 t (2H, Harom, J = 7.7 Hz), 7.08–7.37 m
(12H, Harom), 8.57 s (2H, N=CH), 13.73 br.s (2H, OH).
6,6′-{Methylenebis[(p-phenylene)iminomethyl]}-
bis(2,4-di-tert-butylphenol) (VIIc). Yield 98%,
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DESIGN OF POSTMETALLOCENE SCHIFF BASE-LIKE CATALYTIC SYSTEMS ... XII.
533
mp 196–197°C. IR spectrum: ν 1620 cm–1 (N=C).
6,6′-{Oxybis[(o-phenylene)iminomethyl]}bis-
(2,4-di-tert-butylphenol) (VIIh). Yield 98%, mp 155–
1H NMR spectrum (CDCl3), δ, ppm: 1.30 s (18H,
t-Bu), 1.44 s (18H, t-Bu), 4.01 s (2H, CH2), 7.13 d
(2H, Harom, J = 2.0 Hz), 7.16–7.23 m (8H, Harom),
7.37 d (2H, Harom, J = 2.0 Hz), 8.59 s (2H, N=CH),
13.54 br.s (2H, OH). Found: [M]+ 630.41786.
C43H54N2O2. Calculated: M 630.41850.
1
156°C. IR spectrum: ν 1618 cm–1 (N=C). H NMR
spectrum (acetone-d6), δ, ppm: 1.24 s (18H, t-Bu),
1.35 s (18H, t-Bu), 6.96–7.54 m (12H, Harom), 8.93 s
(2H, N=CH), 13.72 br.s (2H, OH). Found: [M]+
632.39695. C42H52N2O3. Calculated: M 632.39777.
6,6′-{Methylenebis[(3,5-dimethyl-1,4-phenylene)-
iminomethyl]}bis(2,4-di-tert-butylphenol) (VIId).
Yield 93%, mp 147–148°C. IR spectrum: ν 1622 cm–1
Schiff bases Vi–Vl, VIi–VIl, and VIIi–VIIl (gen-
eral procedure). A mixture of 2 mmol of aldehyde
I–III, 1 mmol of diamine IVi–IVl, 10 ml of methanol,
10 ml of methylene chloride, and 10 mg of 99% formic
acid was heated for 8–12 h under reflux with stirring
(until the initial compounds disappeared according to
the TLC data). The solvent was distilled off on a rotary
evaporator, the residue was ground with 5 ml of meth-
anol, and the light yellow precipitate was filtered off
and washed with 2 ml of cold methanol.
1
(N=C). H NMR spectrum (CDCl3), δ, ppm: 1.30 s
(18H, t-Bu), 1.45 s (18H, t-Bu), 2.27 s (12H, Me),
3.77 s (2H, CH2), 6.61–6.92 m (4H, Harom), 7.01 d (2H,
Harom, J = 1.5 Hz), 7.35 d (2H, Harom, J = 1.5 Hz),
8.31 s (2H, N=CH), 13.29 br.s (2H, OH). Found, %:
C 82.32; H 8.97; N 4.10. [M]+ 686.5. C47H62N2O2. Cal-
culated, %: C 82.23; H 9.04; N 4.08. M 686.5.
2,2′-{Oxybis[(p-phenylene)iminomethyl]}diphe-
nol (Vi). Yield 84%, mp 213–214°C; published data
[19]: mp 210–211°C. IR spectrum: ν 1621 cm–1 (N=C).
1H NMR spectrum (CDCl3–DMSO-d6), δ, ppm: 6.44–
6.68 m (8H, Harom), 6.85–7.04 m (8H, Harom), 8.27 s
(2H, N=CH), 12.74 br.s (2H, OH). Found: [M]+
408.14740. C26H20N2O3. Calculated: M 408.14738.
6,6′-{Methylenebis[(3-cyclopentyl-3-methyl-1,4-
phenylene)iminomethyl]}bis(2,4-di-tert-butylphe-
nol) (VIIe). Yield 94%, mp 176–177°C. IR spectrum:
1
ν 1621 cm–1 (N=C). H NMR spectrum (CDCl3), δ,
ppm: 1.30 s (18H, t-Bu), 1.45 s (18H, t-Bu), 1.51–
2.05 m (16H, CH2), 2.17 s (6H, Me), 2.95–3.18 m (2H,
CH), 3.83 s (2H, CH2), 6.79 s (2H, Harom), 6.95 s (2H,
Harom), 7.03 s (2H, Harom), 7.38 s (2H, Harom), 8.29 s
(2H, N=CH), 13.35 br.s (2H, OH). Found, %: C 83.09;
H 9.26; N 3.59. [M]+ 794. C55H74N2O2. Calculated, %:
C 83.12; H 9.32; N 3.53. M 794.
2,2′-{p-Phenylenedioxybis[(p-phenylene)imino-
methyl]}diphenol (Vj). Yield 83%, mp 231–232°C.
1
IR spectrum: ν 1620 cm–1 (N=C). H NMR spectrum
(DMSO-d6), δ, ppm: 6.58–7.15 m (12H, Harom), 7.36–
7.68 m (8H, Harom), 8.94 s (2H, N=CH), 14.04 br.s (2H,
OH). Found: [M]+ 500.17299. C32H24N2O4. Calculated:
M 500.17359.
6,6′-{Methylenebis[(3-cyclohexyl-5-methyl-1,4-
phenylene)iminomethyl]}bis(2,4-di-tert-butylphe-
nol) (VIIf). Yield 92%, mp 110–112°C. IR spectrum:
1
ν 1621 cm–1 (N=C). H NMR spectrum (CDCl3), δ,
2,2′-{Propane-2,2-diylbis[(p-phenylene)oxy-
(p-phenylene)iminomethyl]}diphenol (Vk). Yield
81%, mp 122–123°C. IR spectrum: ν 1618 cm–1
ppm: 1.31 s (18H, t-Bu), 1.32–1.43 m (8H, CH2),
1.46 s (18H, t-Bu), 1.58–1.96 m (12H, CH2), 2.20 s
(6H, Me), 2.50–2.73 m (2H, CH), 3.82 s (2H, CH2),
6.76 s (2H, Harom), 6.88 s (2H, Harom), 7.00 d (2H,
Harom, J = 1.5 Hz), 7.35 d (2H, Harom, J = 1.5 Hz),
8.29 s (2H, N=CH), 13.35 br.s (2H, OH). Found, %:
C 83.10; H 9.49; N 3.46. C57H78N2O2. Calculated, %:
C 83.21; H 9.49; N 3.41.
1
(N=C). H NMR spectrum (CDCl3), δ, ppm: 1.69 s
(6H, Me), 6.91–7.06 (12H, Harom), 7.20–7.38 m (12H,
Harom), 8.60 s (2H, N=CH), 13.21 br.s (2H, OH).
Found: [M]+ 618.25140. C41H34N2O4. Calculated:
M 618.25184.
2,2′-[(4,4″-p-Terphenylene)bis(iminomethyl)]-
diphenol (Vl). Yield 84%, mp 309–310°C. IR spec-
6,6′-{Sulfonylbis[(p-phenylene)iminomethyl]}bis-
(2,4-di-tert-butylphenol) (VIIg). Yield 91%, mp 172–
1
trum: ν 1622 cm–1 (N=C). H NMR spectrum
1
173°C. IR spectrum: ν 1618 cm–1 (N=C). H NMR
(DMSO-d6), δ, ppm: 6.66 t (2H, Harom, J = 7.7 Hz),
6.93–7.02 m (4H, Harom), 7.34–7.81 m (14H, Harom),
9.03 s (2H, N=CH), 13.10 br.s (2H, OH). Found: [M]+
468.18320. C32H24N2O2. Calculated: M 468.18377.
spectrum (acetone-d6), δ, ppm: 1.31 s (18H, t-Bu),
1.45 s (18H, t-Bu), 7.47–7.64 m (8H, Harom), 8.08–
8.12 m (4H, Harom), 8.95 s (2H, N=CH), 13.36 br.s (2H,
OH). Found, %: C 83.10; H 9.35; N 3.47. [M]+ 680.
C34H36N2O4S. Calculated, %: C 83.21; H 9.49; N 3.41.
M 680.
6,6′-{Oxybis[(p-phenylene)iminomethyl]}bis-
(2-tert-butylphenol) (VIi). Yield 90%, mp 146–
1
147°C. IR spectrum: ν 1613 cm–1 (N=C). H NMR
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OLEINIK et al.
534
spectrum (CDCl3), δ, ppm: 1.47 s (18H, t-Bu), 6.87 t
(2H, Harom, J = 7.6 Hz), 7.07 d (4H, Harom, J = 7.6 Hz),
7.25 d (2H, Harom, J = 7.6 Hz), 7.30 d (4H, Harom, J =
7.6 Hz), 7.39 d (2H, Harom, J = 7.6 Hz), 8.62 s (2H,
N=CH), 13.83 s (2H, OH). Found: [M]+ 520.27260.
C34H36N2O3. Calculated: M 520.27258.
6,6′-{Propane-2,2-diylbis[(p-phenylene)oxy-
(p-phenylene)iminomethyl]}bis(2,4-di-tert-butyl-
phenol) (VIIk). Yield 88%, mp 91–92°C. IR spec-
trum: ν 1618 cm–1 (N=C). 1H NMR spectrum (CDCl3),
δ, ppm: 1.31 s (18H, t-Bu), 1.46 s (18H, t-Bu), 1.68 s
(6H, Me), 6.93 d (4H, Harom, J = 7.8 Hz), 7.04 d (4H,
H
H
arom, J = 7.8), 7.18–7.28 m (10H, Harom), 7.43 d (2H,
arom, J = 1.8 Hz), 8.61 s (2H, N=CH), 13.63 br.s (2H,
6,6′-{p-Phenylenedioxybis[(p-phenylene)imino-
methyl]}bis(2-tert-butylphenol) (VIj). Yield 94%,
mp 198–199°C. IR spectrum: ν 1614 cm–1 (N=C).
1H NMR spectrum (CDCl3), δ, ppm: 1.47 s (18H, t-Bu),
6.87 t (2H, Harom, J = 7.7 Hz), 7.01–7.33 m (14H,
OH). Found, %: C 81.15; H 7.93; N 3.27. C57H66N2O4.
Calculated, %: C 81.20; H 7.89; N 3.32.
6,6′-{(4,4″-p-Terphenylene)bis(iminomethyl)}bis-
(2,4-di-tert-butylphenol) (VIIl). Yield 93%, mp 290–
H
arom), 7.38 d (2H, Harom, J = 7.7 Hz), 8.62 s (2H,
N=CH), 13.89 br.s (2H, OH). Found: [M]+ 612.29940.
C40H40N2O4. Calculated: M 612.29879.
291°C. IR spectrum: ν 1618 cm–1 (N=C). H NMR
1
spectrum (CDCl3), δ, ppm: 1.34 s (18H, t-Bu), 1.49 s
(18H, t-Bu), 7.25–7.29 m (6H, Harom), 7.38 d (4H,
H
7.69–7.73 m (4H, Harom), 8.70 s (2H, N=CH), 13.68 br.s
(2H, OH). Found: [M]+ 692.43390. C48H56N2O2. Cal-
culated: M 692.43415.
6,6′-{Propane-2,2-diylbis[(p-phenylene)oxy-
(p-phenylene)iminomethyl]}bis(2-tert-butylphenol)
(VIk). Yield 85%, mp 83–84°C. IR spectrum:
arom, J = 8.0 Hz), 7.47 d (2H, Harom, J = 2.0 Hz),
1
ν 1612 cm–1 (N=C). H NMR spectrum (CDCl3), δ,
ppm: 1.46 s (18H, t-Bu), 1.69 s (6H, Me), 6.86 t (2H,
H
arom, J = 7.8 Hz), 6.93 d (4H, Harom, J = 8.0), 7.04 d
REFERENCES
(4H, Harom, J = 8.0), 7.19–7.29 m (10H, Harom),
7.37 d.d (2H, Harom, J = 8.0, 2.0 Hz), 8.61 s (2H,
N=CH), 13.89 br.s (2H, OH). Found: [M]+ 730.37740.
C49H50N2O4. Calculated: M 730.37703.
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(N=C). H NMR spectrum (CDCl3), δ, ppm: 1.32 s
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H
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DESIGN OF POSTMETALLOCENE SCHIFF BASE-LIKE CATALYTIC SYSTEMS ... XII.
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