Design of postmetallocene catalytic systems of arylimine type for olefin polymerization: XIV.* synthesis of (N-allyloxyaryl)salicylaldimine ligands and their complexes with titanium(IV) dichloride

Article abstract of DOI:10.1134/S1070428012080076

By reaction of salicylaldehydes with bulky substituents in the positions 3 and 5 with o-, m-, and p-allyloxyaniline hydrochlorides in the presence of triethylamine a series of the corresponding (N-aryl)- salicylaldimines was obtained, which with TiCl₂(OPr-i)₂ afforded complexes of titanium(IV) dichloride L₂TiCl₂. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012080076

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 8, pp. 1071−1080. © Pleiades Publishing, Ltd., 2012.
Original English Text © I.I. Oleinik, I.V. Oleinik, S.S. Ivanchev, G.A. Tolstikov, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 8,
pp. 1075−1084.
Design of Postmetallocene Catalytic Systems
of Arylimine Type for Olefin Polymerization: XIV.*
Synthesis of (N-Allyloxyaryl)salicylaldimine
Ligands and Their Complexes
with Titanium(IV) Dichloride
I. I. Oleinika, I. V. Oleinika, S. S. Ivanchevb, and G. A. Tolstikova
aVorozhtsov Novosibirsk Institute of Organic Chemistry,
Siberian Division, Russian Academy of Sciences, Novosibirsk, 630090 Russia
e-mail:oleynik@nioch.nsc.ru
bSt. Petersburg Branch of Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Russia
Received March 14, 2012
Abstract—By reaction of salicylaldehydes with bulky substituents in the positions 3 and 5 with o-, m-, and
p-allyloxyaniline hydrochlorides in the presence of triethylamine a series of the corresponding (N-aryl)-
salicylaldimines was obtained, which with TiCl2(OPr-i)2 afforded complexes of titanium(IV) dichloride L2TiCl2.
DOI: 10.1134/S1070428012080076
In the course of a systematic research on the effect
of the structural modification of titanium(IV) dichloride
(N-aryl)salicylaldimine complexes on their activ-
ity in ethylene polymerization and on the properties
of polyethylene we have found [2] that in the catalytic
system the complexes with p-allyloxyphenylimino group
undergo a fast “self-immobilization” on the polyethylene
macromolecules. The activity of these catalytic systems
compared with the homogeneous analogs is more stable
in time, and they favor the formation of polyethylene of
a superhigh molecular weight with improve morphology
of the particles [2].
The synthesis of isomeric salicylaldimines with
allyloxy group in the arylimine fragment is underlain by
the reaction between the substituted salicylaldehydes and
the corresponding allyloxyanilines [3]. Since the latter are
prone to oxidation in air and thus require special measures
in handling and storage the condensation of the substitut-
ed salicylaldehydes was carried out with allyloxyanilines
hydrochlorides in the presence of triethylamine.
Substituted salicylaldehydes Iа–Ij react with
hydrochlorides II–IV in the presence of triethylamine at
boiling in methanol affording the corresponding imines
Va–Vj, VIa–VIj, VIIa–VIIj in 85–98% yields.
The limited amount of data available now impedes
the development of the concept of the optimization of the
ligands for the complexes capable of self-immobilization.
In order to study the catalytic ability of titanium(IV)
complexes in the ethylene polymerization we report
here on the synthesis of (N-aryl)salicylaldimine ligands
containing isomeric o-, m-, and p-allyloxyphenylimino
groups and versatile substituents in the salicylidene frag-
The structure of imines Va–Vj, VIa–VIj, VIIa–VIIj
was established based on the combination of analytic
and spectral data. The data of 1Н NMR spectra allow a
conclusion that the obtained Schiff bases are individual
1
Е-isomers. In the Н NMR spectra of compounds Va–
Vj, VIa–VIj, VIIa–VIIj alongside the signals of the
substituents of the salicylidene fragment singlets appear
of the group N=CH in the region of 8.44–8.75 ppm and
singlets of OH group in the region 13.17–14.39 ppm. The
allyloxy group of the arylimine fragment of Schiff bases
ment of the ligand.
__________________
*
For Communication XIII, see [1].
1071

OLEINIK et al.
1072
R2
O
R1
R2
R2
N
NH2 · HCl
O
TiCl2(OPr-i)2
Et3N, EtOH
R1
TiCl2
R1
OH
N
O
O
N
O
OH O
R1
Iа_Ij
O
II_IV
Va–Vj, VIa–VIj, VIIa–VIIj
Vа_Vj_VIIа_VIIj
R2
VIIIа_VIIIj_Xа_Xj
VIIIa–VIIIj, IXa–IXj, Xa–Xj
R1 = t-Bu, R2 = H (а); R1 = R2 = t-Bu (b); R1 = t-Bu, R2 = Me (c); R1 = t-Bu, R2 = OMe (d); R1 = t-Bu, R2 = CMe2(Ph) (e); R1 = CMe2Ph,
R2 = H (f); R1 = CMe2Ph, R2 = Me (g); R1 = CMe2Ph, R2 = t-Bu (h); R1 = R2 = CMe2Ph (i); R1 = CHMePh, R2 = H (j); 2-OAll (II, V,
VIII), 3-OAll (III, VI, IX), 4-OAll (IV, VII, X).
result and one among them is as a rule predominant. The
presence of isomeric forms is revealed by the appearance
in the 1Н NMR spectra of their solutions of several signals
corresponding to the protons of the imine moiety N=CH
[5, 7, 8, 11].
Va–Vj, VIa–VIj, VIIa–VIIj gives rise to a characteristic
set of signals.
In the IR spectra of compounds Va–Vj, VIa–VIj,
VIIa–VIIja strong absorption band appears in the re-
gion 1607–1620 cm–1 [ν(C=N)]. The mass spectra of
compounds synthesized contain an intensive peak of the
molecular ion.
The ratio of the isomers does not depend on the method
of complex synthesis [9], and the recrystallization does
not provide a possibility to get rid of the minor isomers for
the 1Н NMR spectra of the complexes after recrystalliza-
tion contain several signals of the imine group N=CH [7].
Complexes VIIIa–VIIIj, IXa–IXj, Xa–Xj were
prepared in a single-stage procedure by the reaction
of the ligand with diisopropoxytitanium dichloride
TiCl2(OPr-i)2 developed for the synthesis of complexes
with phenoxyimine ligands with bulky substituents [1,
4]. At treating imines Va–Vj, VIa–VIj, VIIa–VIIj with
equimolar amount of TiCl2(OPr-i)2 in toluene solution at
room temperature complexes of titanium(IV) dichloride
VIIIa–VIIIj, IXa–IXj, Xa–Xj formed in high yields.
The absence of interconversion of the isomeric forms
of the dichloride complexes was shown by special ex-
periments [8, 9, 12]. Yet complex cations formed at the
activation of the dichloride complexes are capable of
isomerization by themselves or at the coordination of an
alkene molecule [6, 13]. It is expectable that the behav-
ior of catalytic systems where one of them contains the
native mixture of isomeric forms of the dichloride com-
plexes and the other one, an individual isomer, should be
identical. This suggestion is confirmed by the data of [9,
14] where it has been shown that at the use of the com-
plex containing two isomers in a 2:1 ratio the obtained
polyethylene has a narrow molecular weight distribution
(MWD) [14], and the application of the complex con-
taining exclusively a single isomer has resulted in the
polymer with the MWD reaching the value of 13.8 [9].
These data show the lack of the direct influence of the
stereoisomerism of the complex on the polymerization
result and support the consideration that in the study of
the relation between the variation of the ligand structure
and the changes in the catalytic activity of the complex
The composition of complexes VIIIa–VIIIj, IXa–
IXj, Xa–Xj was confirmed by the combination of analytic
and spectral data. The IR spectra of the complexes contain
the absorption bands in the region 436–482 [ν(Ti–N)],
534–581[ν(Ti–O)], 1594–1611 cm–1 [ν(C=N)]. The
complexing results in the decrease in the frequency of
ν(N=CH) by 4–23 cm–1.
The coordination polyhedron of the salicylaldimine
complexes of titanium(IV) dichloride is a distorted octa-
hedron providing the possibility of the formation of five
stereoisomeric forms of complexes where in three com-
plexes the chlorine atoms are located in the cis-position,
and in two complexes, in the trans-position [5–10]. In
the course of complex formation several isomeric forms
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

DESIGN OF POSTMETALLOCENE CATALYTIC SYSTEMS
1073
the mixture of isomeric forms of the complex may be used
since in each form the structure of the ligand is the same.
tography on silica gel 2–25μ, eluent CHCl3–hexane, 1:2,
collecting the first bright-yellow fraction. The solvents
were distilled off, the residue was triturated with 5 ml of
methanol to obtain crystals, the precipitate was filtered
off, washed with 3 ml of methanol and maintained in a
vacuum-desiccator.
1
In the Н NMR spectra of complexes VIIIa–VIIIj,
IXa–IXj, Xa–Xj the closely located signals are present
belonging to the protons of the group НС=N in the re-
gion 7.67–8.22 ppm indicating the existence of several
stereoisomeric forms. Although these signals appear as
singlets, since [7] these groups of signals are commonly
described as multiplets.
2-[(2-Allyloxyphenylimino)methyl]-6-tert-
butylphenol (Vа). Yield 93%. Oily substance. IR
1
spectrum, cm–1: 1613 ν(С=N). Н NMR spectrum, δ,
ppm: 1.53 s [9Н, С(СН3)3], 4.66 d.t (2H, ОСН2СН=СН2,
J 4.7, 1.6 Hz), 5.34 d.q (1H, ОСН2СН=СН2, J 10.7,
1.6 Hz), 5.59 d.q (1H, ОСН2СН=СН2, J 17.3, 1.6 Hz),
The other protons are present as multiplets due to the
overlapping of the corresponding signals of the isomeric
forms of complexes. The signals of OH group observed
in the spectra of imines Va–Vj, VIa–VIj, VIIa–VIIj
are absent.
6.04–6.17 m (1H, ОСН2СН=СН2), 6.86 t (1Нarom
,
J 7.7 Hz), 6.96–7.28 m (5Harom), 7.39 d.d (1Нarom, J 7.7,
1.6 Hz), 8.75 s (1H, СH=N), 14.39 s (1H, OH). Found
[M]+ 309.1721. C20H23NO2. Calculated M 309.1723.
EXPERIMENTAL
2-[(2-Allyloxyphenylimino)methyl]-4,6-di-tert-
butylphenol (Vb). Yield 85%. Oily substance. IR
1Н NMR spectra were registered on a spectrometer
Bruker АV-400 at operating frequency 400.13 MHz
from solutions of compounds in CDCl3. IR spectra were
recorded on a spectrophotometer Vector 22 from crystal-
line samples as pellets with KBr, from oily samples in
pure state. The reaction progress was monitored and the
purity of compounds synthesized was checked by TLC
on Silufol UV-254 plates, eluent chloroform. Elemental
analyses were carried out on a CHNS-analyzer Euro EA
3000. The elemental formulas of compounds obtained
were calculated from the high resolution mass spec-
tra measured on an instrument DFS Thermo Electron
Corporation. The melting points were determined in
capillaries on an instrument Mettler Toledo FP90, heat-
ing rate 1 deg/min.
1
spectrum, cm–1: 1618 ν(С=N). Н NMR spectrum,
δ, ppm: 1.38 s [9Н, С(СН3)3], 1.54 s [9Н, С(СН3)3],
4.66 d.t (2H, ОСН2СН=СН2, J 4.7, 1.6 Hz), 5.32 d.q
(1H, ОСН2СН=СН2, J 10.5, 1.6 Hz), 5.58 d.q (1H,
ОСН2СН=СН2, J 17.2, 1.6 Hz), 6.04–6.15 m (1H,
ОСН2СН=СН2), 6.97–7.06 m (2Нarom), 7.18–7.27 m
(3Нarom), 7.46 d (1Нarom, J 2.5 Hz), 8.74 s (1H, СH=N),
14.17 s (1H, OH). Found [M]+ 365.2342. C24H31NO2.
Calculated M 365.2349.
2-[(2-Allyloxyphenylimino)methyl]-6-tert-butyl-4-
methylphenol (Vc). Yield 90%, mp 78°С. IR spectrum,
cm–1: 1616 ν(С=N). 1НNMR spectrum, δ, ppm: 1.52 s [9Н,
С(СН3)3], 2.36 s (3Н, СН3), 4.65 d.t (2H, ОСН2СН=СН2,
J 5.0, 1.5 Hz), 5.34 d.q (1H, ОСН2СН=СН2, J 10.0,
1.5 Hz), 5.59 d.q (1H, ОСН2СН=СН2, J 17.0, 1.5 Hz),
6.06–6.16 m (1H, ОСН2СН=СН2), 6.97–7.06 m (2Нarom),
7.19–7.25 m (4Нarom), 8.70 s (1H, СH=N), 14.18 s (1H,
OH). Found [M]+ 323.1879. C21H25NO2. Calculated
M 323.1880.
Substituted salicylaldehydes Iа–Ij and TiCl2(OPr-i)2
wereobtainedbyproceduresfrom[15, 16]. Hydrochlorides
II–IV were prepared by treating the solutions of appropri-
ate isomeric allyloxyanilines [3] in methanol by concn.
hydrochloric acid taken in 3–5% excess followed by
distilling off the solvents in the vacuum of the water-
aspirator pump till the constant weight.
2-[(2-Allyloxyphenylimino)methyl]-6-tert-butyl-
4-methoxyphenol (Vd). Yield 93%. Oily substance.
(N-Aryl)salicylaldimines Va–Vj, VIa–VIj, VIIa–
VIIj. A mixture of 3 mmol of aldehyde Iа–Ij, 0.612 g
(3.3 mmol) of an appropriate allyloxyaniline hydrochloride
II–IV, 0.333 g (3.3 mmol) of triethylamine, and 10 ml of
methanol was boiled for 10–20 h till the disappearance
of initial compounds (TLC monitoring). Methanol was
distilled off on a rotary evaporator, the residue was dis-
solved in 20 ml of CHCl3 and washed with 20 ml of water.
The organic layer was dried with MgSO4, chloroform was
distilled off, the residue was purified by flash-chroma-
1
IR spectrum, cm–1: 1617 ν(С=N). Н NMR spectrum,
δ, ppm: 1.50 s [9Н, С(СН3)3], 3.82 s (3Н, OСН3),
4.63 d.t (2H, ОСН2–СН=СН2, J 5.0, 1.4 Hz), 5.32 d.q
(1H, ОСН2СН=СН2, J 10.5, 1.4 Hz), 5.57 d.q (1H,
ОСН2СН=СН2, J 17.4, 1.4 Hz), 5.99–6.15 m (1H,
ОСН2СН=СН2), 6.73 d (1Нarom, J 2.6 Hz), 7.00 t (1Нarom
,
J 7.9 Hz), 7.06 d (1Нarom, J 2.6 Hz), 7.18–7.26 m (2Нarom),
8.71 s (1H, СH=N), 14.06 s (1H, OH). Found [M]+
339.1830. C21H25NO3. Calculated M 339.1829.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

OLEINIK et al.
1074
1
IR spectrum, cm–1: 1615 ν(С=N). Н NMR spectrum,
δ, ppm: 1.74 s [6Н, C(СН3)2], 1.76 s [6Н, C(СН3)2],
4.52 d.t (2H, ОСН2СН=СН2, J 5.0, 1.5 Hz), 5.19 d.q
(1H, ОСН2СН=СН2, J 10.7, 1.5 Hz), 5.38 d.q (1H,
ОСН2СН=СН2, J 17.3, 1.5 Hz), 5.90–6.01 m (1H,
ОСН2СН=СН2), 6.90 d.d (1Нarom, J 7.5, 1.3 Hz), 6.95 t.d
(1Нarom, J 7.5, 1.3 Hz), 7.00–7.33 m (12Нarom), 7.40 d
(1Нarom, J 2.1 Hz), 8.60 s (1H, СH=N), 13.80 s (1H,
OH). Found [M]+ 489.2667. C34H35NO2. Calculated M
489.2662.
2-[(2-Allyloxyphenylimino)methyl]-6-tert-butyl-
4-(2-phenylpropan-2-yl)phenol (Ve). Yield 87%,
1
mp 59°С. IR spectrum, cm–1: 1617 ν(С=N). Н NMR
spectrum, δ, ppm: 1.45 s [9Н, С(СН3)3], 1.72 s [6Н,
C(СН3)2], 4.61 d.t (2H, ОСН2СН=СН2, J 4.7, 1.6 Hz),
5.30 d.q (1H, ОСН2СН=СН2, J 10.6, 1.6 Hz), 5.56 d.q
(1H, ОСН2СН=СН2, J 17.1, 1.6 Hz), 6.02–6.12 m (1H,
ОСН2СН=СН2), 6.94–7.00 m (2Нarom), 7.07 d (1Нarom
,
J 2.3 Hz), 7.14–7.20 m (3Нarom), 7.26–7.29 m (5Нarom),
8.64 s (1H, СH=N), 14.23 s (1H, OH). Found [M]+
427.2507. C29H33NO2. Calculated M 427.2506.
2-[(2-Allyloxyphenylimino)methyl]-6-(1-phenyl-
ethyl)phenol (Vj). Yield 91%, mp 55°С. IR spectrum,
cm–1: 1616 ν(С=N). 1Н NMR spectrum, δ, ppm: 1.69 d
(3Н, СН3, J 7.3 Hz), 4.64 d.t (2H, ОСН2СН=СН2,
J 5.1, 1.5 Hz), 4.79 q (1Н, СН, J 7.3 Hz), 5.32 d.q
(1H, ОСН2СН=СН2, J 10.7, 1.5 Hz), 5.52 d.q (1H,
ОСН2СН=СН2, J 17.2, 1.5 Hz), 6.04–6.14 m (1H,
ОСН2СН=СН2), 6.87 t (1Нarom, J 7.5 Hz), 6.97–7.03 m
(2Нarom), 7.18–7.39 m (9Нarom), 8.73 s (1H, СH=N),
14.10 s (1H, OH). Found [M]+ 357.1724. C24H23NO2.
Calculated M 357.1723.
2-[(2-Allyloxyphenylimino)methyl]-6-(2-phenyl-
propan-2-yl)phenol (Vf). Yield 90%, mp 84°С. IR
1
spectrum, cm–1: 1619 ν(С=N). Н NMR spectrum, δ,
ppm: 1.81 s [6Н, C(СН3)2], 4.52 d.t (2H, ОСН2СН=СН2,
J 4.6, 1.5 Hz), 5.20 d.q (1H, ОСН2СН=СН2, J 10.6,
1.5 Hz), 5.38 d.q (1H, ОСН2СН=СН2, J 17.2, 1.5 Hz),
5.90–6.00 m (1H, ОСН2СН=СН2), 6.88–6.98 m (3Нarom),
7.11–7.18 m (3Нarom), 7.25–7.31 m (5Нarom), 7.53 d
(1Нarom, J 8.0 Hz), 8.67 s (1H, СH=N), 13.95 s (1H,
OH). Found [M]+ 371.1881. C25H25NO2. Calculated
M 371.1880.
2-[(3-Allyloxyphenylimino)methyl]-6-tert-
butylphenol (VIа). Yield 99%. Oily substance. IR
spectrum, cm–1: 1615 ν(С=N). Н NMR spectrum, δ,
2-[(2-Allyloxyphenylimino)methyl]-4-methyl-6-
1
(2-phenylpropan-2-yl)phenol (Vg). Yield 92%, mp
1
121°С. IR spectrum, cm–1: 1618 ν(С=N). Н NMR
ppm: 1.48 s [9Н, С(СН3)3], 4.57 d.t (2H, ОСН2СН=СН2,
J 5.3, 1.5 Hz), 5.31 d.q (1H, ОСН2СН=СН2, J 10.3,
1.5 Hz), 5.44 d.q (1H, ОСН2СН=СН2, J 17.9, 1.5 Hz),
6.02–6.12 m (1H, ОСН2СН=СН2), 6.80–6.89 m (4Нarom),
7.22 d.d (1Нarom, J 7.8, 1.6 Hz), 7.29 t.d (1Нarom, J 7.8,
0.9 Hz), 7.38 d.d (1Нarom, J 7.8, 1.6 Hz), 8.60 s (1H,
СH=N), 13.80 s (1H, OH). Found [M]+ 309.1720.
C20H23NO2. Calculated M 309.1723.
spectrum, δ, ppm: 1.80 s [6Н, C(СН3)2], 2.40 s (3Н,
СН3), 4.51 d.t (2H, ОСН2СН=СН2, J 4.6, 1.5 Hz),
5.19 d.q (1H, ОСН2СН=СН2, J 10.7, 1.5 Hz), 5.38 d.q
(1H, ОСН2СН=СН2, J 17.3, 1.5 Hz), 5.90–6.00 m (1H,
ОСН2СН=СН2), 6.91 d.d (1Нarom, J 8.1, 1.2 Hz), 6.95 t.d
(1Нarom, J 8.1, 1.2 Hz), 7.07 d (1Нarom, J 2.0 Hz), 7.10–
7.17 m (3Нarom), 7.22–7.30 m (4Нarom), 7.35 d (1Нarom
,
J 2.0 Hz), 8.62 s (1H, СH=N), 13.67 s (1H, OH). Found
[M]+ 385.2037. C26H27NO2. Calculated M 385.2036.
2-[(3-Allyloxyphenylimino)methyl]-4,6-di-tert-
butylphenol (VIb). Yield 92%. Oily substance. IR
1
spectrum, cm–1: 1618 ν(С=N). Н NMR spectrum,
2-[(2-Allyloxyphenylimino)methyl]-4-tert-butyl-
6-(2-phenylpropan-2-yl)phenol (Vh). Yield 97%,
δ, ppm: 1.36 s [9Н, С(СН3)3], 1.51 s [9Н, С(СН3)3],
4.59 d.t (2H, ОСН2СН=СН2, J 5.3, 1.4 Hz), 5.32 d.q
(1H, ОСН2СН=СН2, J 10.4, 1.4 Hz), 5.46 d.q (1H,
ОСН2СН=СН2, J 17.4, 1.4 Hz), 6.05–6.14 m (1H,
1
mp 87°С. IR spectrum, cm–1: 1613 ν(С=N). Н NMR
spectrum, δ, ppm: 1.38 s [9Н, С(СН3)3], 1.81 s [6Н,
C(СН3)2], 4.51 d.t (2H, ОСН2СН=СН2, J 4.5, 1.4 Hz),
5.18 d.t (1H, ОСН2СН=СН2, J 10.7, 1.4 Hz), 5.37 d.q
(1H, ОСН2СН=СН2, J 17.4, 1.4 Hz), 5.89–6.00 m
(1H, ОСН2СН=СН2), 6.90 d.d (1Нarom, J 8.0, 1.1 Hz),
6.95 t.d (1Нarom, J 8.0, 1.1 Hz), 7.10–7.16 m (3Нarom),
7.22–7.29 m (5Нarom), 7.56 d (1Нarom, J 2.2 Hz), 8.66 s
(1H, СH=N), 13.70 s (1H, OH). Found [M]+ 427.2500.
C29H33NO2. Calculated M 427.2506.
ОСН2СН=СН2), 6.82–6.91 m (3Нarom), 7.23 d (1Нarom
J 2.4 Hz), 7.31 t (1Нarom, J 7.9 Hz), 7.48 d (1Нarom
,
,
J 2.4 Hz), 8.65 s (1H, СH=N), 13.65 s (1H, OH). Found
[M]+ 365.2352. C24H31NO2. Calculated M 365.2349.
2-[(3-Allyloxyphenylimino)methyl]-6-tert-butyl-
4-methylphenol (VIc). Yield 89%. Oily substance.
1
IR spectrum, cm–1: 1620 ν(С=N). Н NMR spectrum,
δ, ppm: 1.46 s [9Н, С(СН3)3], 2.31 s (3Н, СН3),
4.57 d.t (2H, ОСН2СН=СН2, J 5.2, 1.5 Hz), 5.30 d.q
2-[(2-Allyloxyphenylimino)methyl]-4,6-di-(2-
phenylpropan-2-yl)phenol (Vi). Yield 86%, mp 109°С.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

DESIGN OF POSTMETALLOCENE CATALYTIC SYSTEMS
1075
(1H, ОСН2СН=СН2, J 10.5, 1.5 Hz), 5.43 d.q (1H,
ОСН2СН=СН2, J 17.3, 1.5 Hz), 6.01–6.11 m (1H,
[M]+ 385.2039. C26H27NO2. Calculated M 385.2036.
2-[(3-Allyloxyphenylimino)methyl]-4-tert-butyl-6-
(2-phenylpropan-2-yl)phenol (VIh). Yield 91%. Oily
ОСН2СН=СН2), 6.79–6.87 m (3Нarom), 7.00 d (1Нarom
J 2.0 Hz), 7.17 d (1Нarom, J 2.0 Hz), 7.28 t (1Нarom
,
,
1
substance. IR spectrum, cm–1: 1619 ν(С=N). Н NMR
J 7.8 Hz), 8.55 s (1H, СH=N), 13.55 s (1H, OH). Found
[M]+ 323.1881. C21H25NO2. Calculated M 323.1880.
spectrum, δ, ppm: 1.41 s [9Н, С(СН3)3], 1.81 s [6Н,
C(СН3)2], 4.55 d.t (2H, ОСН2СН=СН2, J 5.1, 1.4 Hz),
5.31 d.t (1H, ОСН2СН=СН2, J 10.3, 1.4 Hz), 5.43 d.q
(1H, ОСН2СН=СН2, J 17.2, 1.4 Hz), 6.02–6.11 m (1H,
ОСН2СН=СН2), 6.76–6.83 m (3Нarom), 7.16–7.30 m
(7Нarom), 7.62 d (1Нarom, J 2.5 Hz), 8.59 s (1H, СH=N),
13.17 s (1H, OH). Found [M]+ 427.2505. C29H33NO2.
Calculated M 427.2506.
2-[(3-Allyloxyphenylimino)methyl]-6-tert-butyl-
4-methoxyphenol (VId). Yield 87%. Oily substance.
1
IR spectrum, cm–1: 1617 ν(С=N). Н NMR spectrum,
δ, ppm: 1.48 s [9Н, С(СН3)3], 3.80 s (3Н, OСН3),
4.57 d.t (2H, ОСН2СН=СН2, J 5.3, 1.4 Hz), 5.31 d.q
(1H, ОСН2СН=СН2, J 10.6, 1.4 Hz), 5.44 d.q (1H,
ОСН2СН=СН2, J 17.3, 1.4 Hz), 6.02–6.12 m (1H,
ОСН2СН=СН2), 6.70 d (1Нarom, J 2.9 Hz), 6.82–6.89 m
(3Нarom), 7.05 d (1Нarom, J 2.9 Hz), 7.30 t.d (1Нarom, J 7.8,
0.9 Hz), 8.57 s (1H, СH=N), 13.47 s (1H, OH). Found
[M]+ 339.1833. C21H25NO3. Calculated M 339.1829.
2-[(3-Allyloxyphenylimino)methyl]-4,6-(2-
phenylpropan-2-yl)phenol (VIi). Yield 87%. Oily
1
substance. IR spectrum, cm–1: 1619 ν(С=N). Н NMR
spectrum, δ, ppm: 1.71 s [6Н, C(СН3)2], 1.74 s [6Н,
C(СН3)2], 4.52 d.t (2H, ОСН2СН=СН2, J 5.2, 1.5 Hz),
5.28 d.q (1H, ОСН2СН=СН2, J 10.5, 1.5 Hz), 5.40 d.q
(1H, ОСН2СН=СН2, J 17.2, 1.5 Hz), 5.99–6.08 m (1H,
ОСН2СН=СН2), 6.71 d (1Нarom, J 2.2 Hz), 6.73–6.78 m
2-[(3-Allyloxyphenylimino)methyl]-6-tert-butyl-4-
(2-phenylpropan-2-yl)phenol (VIe). Yield 90%. Oily
1
substance. IR spectrum, cm–1: 1618 ν(С=N). Н NMR
spectrum, δ, ppm: 1.44 s [9Н, C(СН3)3], 1.72 s [6Н,
C(СН3)2], 4.58 d.t (2H, ОСН2СН=СН2, J 5.2, 1.5 Hz),
5.32 d.q (1H, ОСН2СН=СН2, J 10.5, 1.5 Hz), 5.44 d.q
(1H, ОСН2СН=СН2, J 17.3, 1.5 Hz), 6.03–6.13 m (1H,
(2Нarom), 7.13–7.30 m (12Нarom), 7.41 d (1Нarom,
J 2.2 Hz), 8.49 s (1H, СH=N), 13.20 s (1H, OH). Found
[M]+ 489.2663. C34H35NO2. Calculated M 489.2662.
2-[(3-Allyloxyphenylimino)methyl]-6-(1-
ОСН2СН=СН2), 6.81–6.89 m (3Нarom), 7.08 d (1Нarom
,
phenylethyl)phenol (VIj). Yield 90%. Oily substance.
1
IR spectrum, cm–1: 1616 ν(С=N). Н NMR spectrum,
J 2.3 Hz), 7.17–7.31 m (8Нarom), 8.55 s (1H, СH=N),
13.65 s (1H, OH). Found [M]+ 427.2504. C29H33NO2.
Calculated M 427.2506.
δ, ppm: 1.67 d (3Н, СН3, J 7.2 Hz), 4.58 d.t (2H,
ОСН2СН=СН2, J 5.3, 1.5 Hz), 4.71 q (1Н, СН, J 7.2 Hz),
5.32 d.q (1H, ОСН2СН=СН2, J 10.6, 1.5 Hz), 5.47 d.q
(1H, ОСН2СН=СН2, J 17.5, 1.5 Hz), 6.03–6.13 m (1H,
2-[(3-Allyloxyphenylimino)methyl]-6-(2-
phenylpropan-2-yl)phenol (VIf). Yield 87%, mp 65°С.
IR spectrum, cm–1: 1615 ν(С=N). 1Н NMR spectrum, δ,
ppm: 1.80 s [6Н, C(СН3)2], 4.55 d.t (2H, ОСН2СН=СН2,
J 5.3, 1.5 Hz), 5.31 d.q (1H, ОСН2СН=СН2, J 10.5,
1.5 Hz), 5.43 d.q (1H, ОСН2СН=СН2, J 17.2, 1.5 Hz),
6.01–6.12 m (1H, ОСН2СН=СН2), 6.75–6.82 m (3Нarom),
6.97 t.d (1Нarom, J 7.4, 1.5 Hz), 7.14–7.32 m (7Нarom),
7.58 d (1Нarom, J 7.4 Hz), 8.57 s (1H, СH=N), 13.37 s
(1H, OH). Found [M]+ 371.1882. C25H25NO2. Calculated
M 371.1880.
ОСН2СН=СН2), 6.80–6.88 m (3Нarom), 6.90 t (1Harom
,
J 7.6 Hz), 7.14–7.34 m (8Нarom), 8.60 s (1H, СH=N),
13.53 s (1H, OH). Found [M]+ 357.1721. C24H23NO2.
Calculated M 357.1723.
2-[(4-Allyloxyphenylimino)methyl]-6-tert-
butylphenol (VIIа). Yield 97%, mp 45°С. IR spectrum,
cm–1: 1613 ν(С=N). 1Н NMR spectrum, δ, ppm: 1.46 s
(9Н, С(СН3)3), 4.55 d.t (2H, ОСН2СН=СН2, J 5.0,
1.5 Hz), 5.30 d.q (1H, ОСН2СН=СН2, J 10.5, 1.5 Hz),
5.42 d.q (1H, ОСН2СН=СН2, J 17.5, 1.5 Hz), 5.96–
6.17 m (1H, ОСН2СН=СН2), 6.80–7.38 m (7Нarom),
8.60 s (1H, СH=N), 14.03 s (1H, OH). Found [M]+
309.1722. C20H23NO2. Calculated M 309.1723.
2-[(3-Allyloxyphenylimino)methyl]-4-methyl-6-
(2-phenylpropan-2-yl)phenol (VIg). Yield 97%. Oily
1
substance. IR spectrum, cm–1: 1620 ν(С=N). Н NMR
spectrum, δ, ppm: 1.86 s [6Н, C(СН3)2], 2.46 s (3Н,
СН3), 4.58 d.t (2H, ОСН2СН=СН2, J 5.3, 1.5 Hz),
5.36 d.q (1H, ОСН2СН=СН2, J 10.5, 1.5 Hz), 5.48 d.q
(1H, ОСН2СН=СН2, J 17.2, 1.5 Hz), 6.06–6.16 m (1H,
ОСН2СН=СН2), 6.78–6.88 m (3Нarom), 7.15–7.47 m
(8Нarom), 8.59 s (1H, СH=N), 13.22 s (1H, OH). Found
2-[(4-Allyloxyphenylimino)methyl]-4,6-di-
tert-butylphenol (VIIb). Yield 96%, mp 77°С. IR
1
spectrum, cm–1: 1615 ν(С=N). Н NMR spectrum,
δ, ppm: 1.16 s [9Н, С(СН3)3], 1.31 s [9Н, С(СН3)3],
4.39 d.t (2H, ОСН2СН=СН2, J 5.0, 1.4 Hz), 5.13 d.q
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

OLEINIK et al.
1076
8.54 s (1H, СH=N), 14.00 s (1H, OH). Found [M]+
371.1878. C25H25NO2. Calculated M 371.1880.
(1H, ОСН2СН=СН2, J 10.3, 1.5 Hz), 5.26 d.q (1H,
ОСН2СН=СН2, J 17.5, 1.5 Hz), 5.82–5.95 m (1H,
ОСН2СН=СН2), 7.85 d (1Нarom, J 8.0 Hz), 7.10 d (1Нarom
J 2.5 Hz), 7.17 d (1Harom, J 8.0 Hz), 7.33 d (1Нarom
J 2.5 Hz), 8.44 s (1H, СH=N), 13.60 s (1H, OH). Found
[M]+ 365.2352. C24H31NO2. Calculated M 365.2355.
,
,
2-[(4-Allyloxyphenylimino)methyl]-4-methyl-6-
(2-phenylpropan-2-yl)-phenol (VIIg). Yield 92%,
1
mp 134°С. IR spectrum, cm–1: 1619 ν(С=N). Н NMR
spectrum, δ, ppm: 1.78 s [6Н, C(СН3)2], 2.40 s (3Н,
СН3), 4.54 d.t (2H, ОСН2СН=СН2, J 5.0, 1.4 Hz),
5.31 d.q (1H, ОСН2СН=СН2, J 10.0, 1.4 Hz), 5.43 d.q
(1H, ОСН2СН=СН2, J 17.0, 1.4 Hz), 6.02–6.11 m
(1H, ОСН2СН=СН2), 6.91 d (2Нarom, J 8.5 Hz), 7.09 s
(2Нarom), 7.16 d (2Нarom, J 8.5 Hz), 7.38 s (2Нarom), 8.51 s
(1H, СH=N), 13.30 s (1H, OH). Found [M]+ 385.2046.
C26H27NO2. Calculated M 385.2036.
2-[(4-Allyloxyphenylimino)methyl]-6-tert-butyl-4-
methylphenol (VIIc). Yield 97%, mp 86°С. IR spectrum,
cm–1: 1617 ν(С=N). 1НNMR spectrum, δ, ppm: 1.48 s [9Н,
С(СН3)3], 2.34 s (3Н, СН3), 4.58 d.t (2H, ОСН2СН=СН2,
J 5.5, 1.5 Hz), 5.33 d.q (1H, ОСН2СН=СН2, J 10.0,
1.5 Hz), 5.46 d.q (1H, ОСН2СН=СН2, J 17.0, 1.5 Hz),
6.03–6.14 m (1H, ОСН2СН=СН2), 6.96 d (1Нarom
J 9.0 Hz), 7.03 d (1Нarom, J 2.0 Hz), 7.18 d (1Нarom
,
,
2-[(4-Allyloxyphenylimino)methyl]-4-tert-butyl-
6-(2-phenylpropan-2-yl)phenol (VIIh). Yield 98%,
J 2.0 Hz), 7.28 d (1Нarom, J 9.0 Hz), 8.57 s (1H, СH=N),
13.77 s (1H, OH). Found [M]+ 323.1881. C21H25NO2.
Calculated M 323.1880.
1
mp 90°С. IR spectrum, cm–1: 1616 ν(С=N). Н NMR
spectrum, δ, ppm: 1.39 s [9Н, C(СН3)3], 1.79 s [6Н,
C(СН3)2], 4.54 d.t (2H, ОСН2СН=СН2, J 5.5, 1.5 Hz),
5.30 d.q (1H, ОСН2СН=СН2, J 10.0, 1.5 Hz), 5.42 d.q
(1H, ОСН2СН=СН2, J 17.0, 1.5 Hz), 6.01–6.11 m (1H,
ОСН2СН=СН2), 6.90 d (2Нarom, J 8.9 Hz), 7.14–7.28 m
(9Нarom), 7.60 d (1Нarom, J 2.5 Hz), 8.57 s (1H, СH=N),
13.33 s (1H, OH). Found [M]+ 427.2509. C29H33NO2.
Calculated M 427.2506.
2-[(4-Allyloxyphenylimino)methyl]-6-tert-butyl-
4-methoxyphenol (VIId). Yield 98%, mp 60°С. IR
1
spectrum, cm–1: 1607 ν(С=N). Н NMR spectrum,
δ, ppm: 1.46 s [9Н, С(СН3)3], 3.78 s (3Н, OСН3),
4.54 d.t (2H, ОСН2СН=СН2, J 5.3, 1.4 Hz), 5.29 d.q
(1H, ОСН2СН=СН2, J 10.5, 1.4 Hz), 5.41 d.q (1H,
ОСН2СН=СН2, J 17.5, 1.4 Hz), 5.99–6.09 m (1H,
ОСН2СН=СН2), 6.67 d (1Нarom, J 2.9 Hz), 6.92 d (1Нarom
J 8.8 Hz), 6.99 d (1Нarom, J 2.9 Hz), 7.23 d (1Нarom
J 8.8 Hz), 8.54 s (1H, СH=N), 13.57 s (1H, OH). Found
[M]+ 339.1824. C21H25NO3. Calculated M 339.1829.
,
,
2-[(4-Allyloxyphenylimino)methyl]-4,6-(2-
phenylpropan-2-yl)phenol (VIIi). Yield 95%, mp
1
124°С. IR spectrum, cm–1: 1617 ν(С=N). Н NMR
spectrum, δ, ppm: 1.72 s [6Н, C(СН3)2], 1.75 s [6Н,
C(СН3)2], 4.54 d.t (2H, ОСН2СН=СН2, J 5.5, 1.5 Hz),
5.29 d.q (1H, ОСН2СН=СН2, J 10.5, 1.5 Hz), 5.42 d.q
(1H, ОСН2СН=СН2, J 17.5, 1.5 Hz), 6.00–6.10 m
(1H, ОСН2СН=СН2), 6.88–7.43 m (16Нarom), 8.49 s
(1H, СH=N), 13.39 s (1H, OH). Found [M]+ 489.2669.
C34H35NO2. Calculated M 489.2662.
2-[(4-Allyloxyphenylimino)methyl]-6-tert-butyl-4-
(2-phenylpropan-2-yl)phenol (VIIe). Yield 91%. Oily
1
substance. IR spectrum, cm–1: 1617 ν(С=N). Н NMR
spectrum, δ, ppm: 1.44 s [9Н, C(СН3)3], 1.72 s [6Н,
C(СН3)2], 4.57 d.t (2H, ОСН2–СН=СН2, J 5.2, 1.5 Hz),
5.32 d.q (1H, ОСН2СН=СН2, J 10.0, 1.5 Hz), 5.44 d.q
(1H, ОСН2СН=СН2, J 17.1, 1.5 Hz), 6.03–6.13 m (1H,
2-[(4-Allyloxyphenylimino)methyl]-6-(1-
ОСН2СН=СН2), 6.94 d (1Нarom, J 8.9 Hz), 7.06 d (1Нarom
,
phenylethyl)phenol (VIIj). Yield 90%. Oily substance.
J 2.3 Hz), 7.16–7.31 m (9Нarom), 8.56 s (1H, СH=N),
13.84 s (1H, OH). Found [M]+ 427.2502. C29H33NO2.
Calculated M 427.2506.
1
IR spectrum, cm–1: 1615 ν(С=N). Н NMR spectrum,
δ, ppm: 1.70 d (3Н, СН3, J 7.3 Hz), 4.57 d.t (2H,
ОСН2СН=СН2, J 5.5, 1.5 Hz), 4.76 q (1Н, СН, J 7.3 Hz),
5.35 d.q (1H, ОСН2СН=СН2, J 10.5, 1.5 Hz), 5.47 d.q
(1H, ОСН2СН=СН2, J 17.5, 1.5 Hz), 6.05–6.15 m (1H,
2-[(4-Allyloxyphenylimino)methyl]-6-(2-
phenylpropan-2-yl)phenol (VIIf). Yield 96%, mp 48°С.
IR spectrum, cm–1: 1615 ν(С=N). 1Н NMR spectrum, δ,
ppm: 1.76 s [6Н, C(СН3)2], 4.52 d.t (2H, ОСН2СН=СН2,
J 5.0, 1.4 Hz), 5.28 d.q (1H, ОСН2СН=СН2, J 10.0,
1.4 Hz), 5.40 d.q (1H, ОСН2СН=СН2, J 17.0, 1.4 Hz),
ОСН2СН=СН2), 6.93 t (1Нarom, J 7.5 Hz), 6.98 d (2Нarom
,
J 9.0 Hz), 7.21–7.39 m (9Нarom), 8.61 s (1H, СH=N),
13.86 s (1H, OH). Found [M]+ 357.1719. C24H23NO2.
Calculated M 357.1723.
5.94–6.15 m (1H, ОСН2СН=СН2), 6.96 d (2Нarom
J 9.0 Hz), 7.03 t (1Нarom, J 8.0 Hz), 7.21 d (2Нarom
,
,
Complexes VIIIa–VIIIj, IXa–IXj, Xa–Xj. Amixture
of 2.3 mmol of compound Va–Vj, VIa–VIj, VIIa–VIIj,
10 ml of anhydrous dichloromethane, 4.25 g of toluene
J 9.0 Hz), 7.25–7.41 m (6Harom), 7.64 d (1Нarom, J 8.0 Hz),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 8 2012

DESIGN OF POSTMETALLOCENE CATALYTIC SYSTEMS
1077
dichloride (VIIIe). Yield 88%. IR spectrum, ν, cm–1:
1606 (C=N), 571 (Ti–O), 473 (Ti–N). 1Н NMR spectrum,
δ, ppm: 1.27–1.54 m [18Н, С(СН3)3], 1.62–1.74 m [12Н,
С(СН3)2], 4.60–5.01 m (4H, ОСН2СН=СН2), 5.20–
6.13 m (6H, ОСН2СН=СН2), 6.48–7.50 m (22Нarom),
7.72–7.74 m (2H, СH=N). Found, %: С 71.37; H 6.79;
Cl 7.30; N 2.92. C58H64Cl2N2O4Ti. Calculated, %:
С 71.68; H 6.64; Cl 7.30; N 2.88.
solution containing 0.273 g (1.15 mmol) of TiCl2(OPr-i)2
was stirred at room temperature in an argon atmosphere
over 24 h. A dark-red solution formed. The solvent was
distilled off in a vacuum of the water-aspirator pump, the
residue was washed on the filter with hexane (2 × 2 ml)
and was maintained for 1 h in a vacuum of an oil pump
at 95°С. The corresponding complexes were obtained as
dark red-brown powders.
Bis{2-[(2-allyloxyphenylimino)methyl]-6-tert-
butylphenoxy}titanium(IV) dichloride (VIIIа). Yield
93%. IR spectrum, ν, cm–1: 1607 (C=N), 568 (Ti–O),
Bis{2-[(2-allyloxyphenylimino)methyl]-6-(2-
phenylpropan-2-yl)phenoxy}titanium(IV) dichloride
(VIIIf). Yield 84%. IR spectrum, ν, cm–1: 1605 (C=N),
1
1
455 (Ti–N). Н NMR spectrum, δ, ppm: 1.12–1.62 m
566 (Ti–O), 478 (Ti–N). Н NMR spectrum, δ, ppm:
[18Н, С(СН3)3], 3.72–4.21 m (4H, ОСН2СН=СН2),
4.93–6.15 m (6H, ОСН2СН=СН2), 6.34–7.40 m
(14Нarom), 7.76–7.80 m (2H, СH=N). Found, %: С 65.60;
H 6.17; Cl 9.31; N 4.09. C40H44Cl2N2O4Ti. Calculated,
%: С 65.31; H 6.03; Cl 9.64; N 3.81.
1.50–1.74 m [12Н, С(СН3)2], 4.50–4.89 m (4H,
ОСН2СН=СН2), 5.35–6.21 m (6H, ОСН2СН=СН2),
6.42–7.60 m (24Нarom), 7.77–7.80 m (2H, СH=N). Found,
%: С 70.32; H 5.80; Cl 7.93; N 3.40. C50H48Cl2N2O4Ti.
Calculated, %: С 69.85; H 5.63; Cl 8.25; N 3.26.
Bis{2-[(2-allyloxyphenylimino)methyl]-4,6-di-tert-
butylphenoxy}titanium(IV) dichloride (VIIIb). Yield
88%. IR spectrum, ν, cm–1: 1610 (C=N), 577 (Ti–O),
Bis{2-[(2-allyloxyphenylimino)methyl]-4-methyl-
6-(2-phenylpropan-2-yl)phenoxy}titanium(IV)
dichloride (VIIIg). Yield 87%. IR spectrum, ν, cm–1:
1610 (C=N), 572 (Ti–O), 479 (Ti–N). 1Н NMR spectrum,
δ, ppm: 1.21–1.85 m [12Н, С(СН3)2], 2.16–2.29 m (6Н,
СН3), 4.50–5.09 m (4H, ОСН2СН=СН2), 5.35–6.08 m
(6H, ОСН2СН=СН2), 6.63–7.46 m (22Нarom), 7.67–
7.73 m (2H, СH=N). Found, %: С 70.29; H 6.10; Cl 7.75;
N 3.31. C52H52Cl2N2O4Ti. Calculated, %: С 70.35;
H 5.90; Cl 7.99; N 3.17.
1
472 (Ti–N). Н NMR spectrum, δ, ppm: 1.29–1.61 m
[36Н, С(СН3)3], 3.73–4.62 m (4H, ОСН2СН=СН2),
5.05–6.29 m (6H, ОСН2СН=СН2), 6.48–7.48 m
(12Нarom), 7.79–7.84 m (2H, СH=N). Found, %: С 68.19;
H 7.08; Cl 8.06; N 3.17. C48H60Cl2N2O4Ti. Calculated,
%: С 68.00; H 7.13; Cl 8.36; N 3.30.
Bis{2-[(2-allyloxyphenylimino)methyl]-6-tert-
butyl-4-methylphenoxy}titanium(IV) dichloride
(VIIIc). Yield 87%. IR spectrum, ν, cm–1: 1611 (C=N),
Bis{2-[(2-allyloxyphenylimino)methyl]-4-tert-
butyl-6-(2-phenylpropan-2-yl)phenoxy}titanium(IV)
dichloride (VIIIh). Yield 87%. IR spectrum, ν, cm–1:
1
571 (Ti–O), 438 (Ti–N). Н NMR spectrum, δ, ppm:
1
1.36–1.60 m [18Н, С(СН3)3], 2.23–2.38 m (6Н, СН3),
3.66–4.63 m (4H, ОСН2СН=СН2), 5.10–6.56 m (6H,
ОСН2СН=СН2), 6.56–7.45 m (12Нarom), 7.73–7.75 m
(2H, СH=N). Found, %: С 66.18; H 6.52; Cl 8.97; N 3.88.
C42H48Cl2N2O4Ti. Calculated, %: С 66.06; H 6.34;
Cl 9.29; N 3.67.
1608 (C=N), 573 (Ti–O), 473 (Ti–N). Н NMR spec-
trum, δ, ppm: 1.32–1.50 m [18Н, С(СН3)3], 1.92–2.18 m
[12Н, С(СН3)2], 4.69–4.77 m (4H, ОСН2СН=СН2),
5.06–5.56 m (4H, ОСН2СН=СН2), 6.02–6.16 m (2H,
ОСН2СН=СН2), 6.38–7.58 m (22Нarom), 7.87–7.92 m
(2H, СH=N). Found, %: С 71.51; H 6.59; Cl 6.89; N 3.10.
C58H64Cl2N2O4Ti. Calculated, %: С 71.68; H 6.64;
Cl 7.30; N 2.88.
Bis{2-[(2-allyloxyphenylimino)methyl]-6-tert-
butyl-4-methoxyphenoxy}titanium(IV) dichloride
(VIIId). Yield 94%. IR spectrum, ν, cm–1: 1599 (C=N),
Bis{2-[(2-allyloxyphenylimino)methyl]-4,6-(2-
phenylpropan-2-yl)phenoxy}titanium(IV) dichloride
(VIIIi). Yield 89%. IR spectrum, ν, cm–1: 1607 (C=N),
558 (Ti–O), 475 (Ti–N). 1Н NMR spectrum, δ, ppm: 1.68–
1.81m[24Н,С(СН3)2],4.45–5.02m(4H,ОСН2СН=СН2),
5.52–6.06 m (6H, ОСН2СН=СН2), 6.47–7.53 m (32Н,
Нarom), 7.69–7.73 m (2H, СH=N). Found, %: С 74.23;
H 6.33; Cl 6.39; N 2.72. C68H68Cl2N2O4Ti. Calculated,
%: С 74.52; H 6.25; Cl 6.47; N 2.88.
1
575 (Ti–O), 474 (Ti–N). Н NMR spectrum, δ, ppm:
1.40–1.58 m [18Н, С(СН3)3], 3.74–3.82 m (6Н, OСН3),
4.38–4.70 m (4H, ОСН2СН=СН2), 5.04–5.65 m (4H,
ОСН2СН=СН2), 5.72–5.94 m (2H, ОСН2СН=СН2),
6.40–7.38 m (12Нarom), 7.80–7.83 m (2H, СH=N). Found,
%: С 63.59; H 6.11; Cl 8.50; N 3.52. C42H48Cl2N2O6Ti.
Calculated, %: С 63.40; H 6.04; Cl 8.93; N 3.52.
Bis{2-[(2-allyloxyphenylimino)methyl]-6-tert-
butyl-4-(2-phenylpropan-2-yl)phenoxy}-titanium(IV)
Bis{2-[(2-allyloxyphenylimino)methyl]-6-(1-
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OLEINIK et al.
1078
phenylethyl)phenoxy}titanium(IV) dichloride (VIIIj).
Calculated, %: С 63.40; H 6.08; Cl 8.91; N 3.52.
Yield 88%. IR spectrum, ν, cm–1: 1604 (C=N), 543
Bis{2-[(3-allyloxyphenylimino)methyl]-6-tert-
butyl-4-(2-phenylpropan-2-yl)phenoxy}titanium(IV)
dichloride (IXe). Yield 90%. IR spectrum, ν, cm–1:
1
(Ti–O), 461 (Ti–N). Н NMR spectrum, δ, ppm: 1.63–
1.97 m (6Н, СНСН3), 4.33–4.38 m (4H, ОСН2СН=СН2),
4.62–4.91 m (2H, СНСН3), 5.22–5.54 m (4H, ОСН2–
СН=СН2), 5.70–6.15 m (2H, ОСН2СН=СН2), 6.55–
7.56 m (24Нarom), 7.85–7.96 m (2H, СH=N). Found,
%: C 69.70; H 5.34; Cl 8.31; N 3.49. C48H44Cl2N2O4Ti.
Calculated, %: C 69.32; H 5.33; Cl 8.53; N 3.37.
1
1597 (C=N), 571 (Ti–O), 479 (Ti–N). Н NMR spec-
trum, δ, ppm: 1.27–1.38 m [18Н, С(СН3)3], 1.57–1.71 m
[12Н, C(СН3)2], 4.20–4.59 m (4H, ОСН2СН=СН2),
5.22–5.46 m (4H, ОСН2СН=СН2), 5.88–6.11 m (2H,
ОСН2СН=СН2), 6.54–7.41 m (22Нarom), 7.90–8.02 m
(2H, СH=N). Found, %: С 71.69; H 6.56; Cl 7.23; N 2.69.
C58H64Cl2N2O4Ti. Calculated, %: С 71.68; H 6.64;
Cl 7.30; N 2.88.
Bis{2-[(3-allyloxyphenylimino)methyl]-6-tert-
butylphenoxy}titanium(IV) dichloride (IXа). Yield
93%. IR spectrum, ν, cm–1: 1597 (C=N), 574 (Ti–O),
1
458 (Ti–N). Н NMR spectrum, δ, ppm: 1.29–1.52 m
Bis{2-[(3-allyloxyphenylimino)methyl]-6-(2-
phenylpropan-2-yl)phenoxy}titanium(IV) dichloride
(IXf). Yield 89%. IR spectrum, ν, cm–1: 1597 (C=N),
[18Н, С(СН3)3], 4.30–4.60 m (4H, ОСН2СН=СН2),
5.22–5.47 m (4H, ОСН2СН=СН2), 5.85–6.13 m (2H,
ОСН2СН=СН2), 6.85–7.52 m (14Нarom), 8.12–8.22 m
(2H, СH=N). Found, %: С 65.21; H 6.19; Cl 9.52; N 3.65.
C40H44Cl2N2O4Ti. Calculated, %: С 65.31; H 6.03;
Cl 9.64; N 3.81.
1
541 (Ti–O), 457 (Ti–N). Н NMR spectrum, δ, ppm:
1.49–1.91 m [12Н, C(СН3)2], 4.17–4.68 m (4H,
ОСН2СН=СН2), 5.22–5.44 m (4H, ОСН2СН=СН2),
5.85–6.11 m (2H, ОСН2СН=СН2), 6.47–7.62 m
(24Нarom), 7.89–7.96 m (2H, СH=N). Found, %: С 70.15;
H 5.82; Cl 8.00; N 3.14. C50H48Cl2N2O4Ti. Calculated,
%: С 69.85; H 5.63; Cl 8.25; N 3.26.
Bis{2-[(3-allyloxyphenylimino)methyl]-4,6-di-tert-
butylphenoxy}titanium(IV) dichloride (IXb). Yield
93%. IR spectrum, ν, cm–1: 1599 (C=N), 567 (Ti–O),
1
469 (Ti–N). Н NMR spectrum, δ, ppm: 1.22–1.64 m
Bis{2-[(3-allyloxyphenylimino)methyl]-4-methyl-
6-(2-phenylpropan-2-yl)phenoxy}titanium(IV)
dichloride (IXg). Yield 91%. IR spectrum, ν, cm–1: 1597
[36Н, С(СН3)3], 4.12–4.25 m (4H, ОСН2СН=СН2),
5.21–5.47 m (4H, ОСН2СН=СН2), 5.83–6.11 m (2H,
ОСН2СН=СН2), 6.54–7.49 m (12Harom), 8.08–8.12 m
(2H, СH=N). Found, %: С 67.52; H 7.15; Cl 8.50; N
3.14. C48H60Cl2N2O4Ti. Calculated, %: С 68.00; H 7.13;
Cl 8.36; N 3.30.
1
(C=N), 580 (Ti–O), 471 (Ti–N). Н NMR spectrum, δ,
ppm: 1.50–1.86 m [12Н, C(СН3)2], 2.35–2.50 m (6Н,
СН3), 4.05–4.69 (4H, ОСН2СН=СН2), 5.26–5.41 m (4H,
ОСН2СН=СН2), 5.91–6.08 m (2H, ОСН2СН=СН2),
6.45–7.66 m (22Нarom), 8.00–8.03 m (2H, СH=N). Found,
%: С 69.86; H 5.99; Cl 8.20; N 3.09. C52H52Cl2N2O4Ti.
Calculated, %: С 70.35; H 5.90, Cl 7.99; N 3.17.
Bis{2-[(3-allyloxyphenylimino)methyl]-6-tert-
butyl-4-methylphenoxy}titanium(IV) dichloride
(IXc). Yield 92%. IR spectrum, ν, cm–1: 1597 (C=N),
1
580 (Ti–O), 436 (Ti–N). Н NMR spectrum, δ, ppm:
Bis{2-[(3-allyloxyphenylimino)methyl]-4-tert-
butyl-6-(2-phenylpropan-2-yl)phenoxy}titanium(IV)
dichloride (IXh). Yield 93%. IR spectrum, ν, cm–1:
1.30–1.62 m [18Н, С(СН3)3], 2.28–2.40 m (6Н, СН3),
4.13–4.60 m (4H, ОСН2СН=СН2), 5.23–5.47 m (4H,
ОСН2СН=СН2), 5.85–6.13 m (2H, ОСН2СН=СН2),
6.55–7.54 m (12Нarom), 7.91–8.08 m (2H, СH=N). Found,
%: С 65.93; H 6.36; Cl 8.96; N 3.57. C42H48Cl2N2O4Ti.
Calculated, %: С 66.06; H 6.34; Cl 9.29; N 3.67.
1
1597 (C=N), 573 (Ti–O), 472 (Ti–N). Н NMR spec-
trum, δ, ppm: 1.35–1.49 m [18Н, С(СН3)3], 1.78–1.95 m
[12Н, C(СН3)2], 4.09–4.54 m (4H, ОСН2СН=СН2),
5.23–5.44 m (4H, ОСН2СН=СН2), 5.83–6.09 m (2H,
ОСН2СН=СН2), 6.38–7.63 m (22Нarom), 7.79–7.92 m
(2H, СH=N). Found, %: С 71.59; H 6.80; Cl 7.22; N 2.85.
C58H64Cl2N2O4Ti. Calculated, %: С 71.68; H 6.64;
Cl 7.30; N 2.88.
Bis{2-[(3-allyloxyphenylimino)methyl]-6-tert-
butyl-4-methoxyphenoxy}titanium(IV) dichloride
(IXd). Yield 93%. IR spectrum, ν, cm–1: 1597 (C=N),
1
573 (Ti–O), 482 (Ti–N). Н NMR spectrum, δ, ppm:
1.30–1.61 m [18Н, С(СН3)3], 3.75–3.83 m (6Н, OСН3),
4.17–4.52 m (4H, ОСН2СН=СН2), 5.26–5.45 m (4H,
ОСН2СН=СН2), 5.87–6.10 m (2H, ОСН2СН=СН2),
6.57–7.28 m (12Нarom), 7.93–8.10 m (2H, СH=N). Found,
%: С 63.30; H 6.30; Cl 8.50; N 3.49. C42H48Cl2N2O6Ti.
Bis{2-[(3-allyloxyphenylimino)methyl]-4,6-(2-
phenylpropan-2-yl)phenoxy}titanium(IV) dichloride
(IXi). Yield 92%. IR spectrum, ν, cm–1: 1596 (C=N),
555 (Ti–O), 470 (Ti–N). Н NMR spectrum, δ, ppm:
1.65–1.83 m [24Н, C(СН3)2], 4.37–4.54 m (4H,
1
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DESIGN OF POSTMETALLOCENE CATALYTIC SYSTEMS
1079
1
ОСН2СН=СН2), 5.25–5.44 m (4H, ОСН2СН=СН2),
5.89–6.10 m (2H, ОСН2СН=СН2), 6.39–7.55 m
(32Нarom), 7.77–7.85 m (2H, СH=N). Found, %: С 74.29;
H 6.36; Cl 6.23; N 2.93. C68H68Cl2N2O4Ti. Calculated,
%: С 74.52; H 6.25; Cl 6.47; N 2.88.
580 (Ti–O), 476 (Ti–N). Н NMR spectrum, δ, ppm:
1.31–1.56 m [18Н, С(СН3)3], 3.75–3.82 m (6Н, OСН3),
4.34–4.57 m (4H, ОСН2СН=СН2), 5.25–5.47 m (4H,
ОСН2СН=СН2), 5.90–6.12 m (2H, ОСН2СН=СН2),
6.51–7.29 m (12Harom), 7.90–8.09 m (2H, СH=N). Found,
%: С 63.30; H 6.30; Cl 8.50; N 3.49. C42H48Cl2N2O6Ti.
Calculated, %: С 63.40; H 6.14; Cl 8.93; N 3.52.
Bis{2-[(3-allyloxyphenylimino)methyl]-6-(1-
phenylethyl)phenoxy}titanium(IV) dichloride (IXj).
Yield 92%. IR spectrum, ν, cm–1: 1594 (C=N), 540 (Ti–
O), 469 (Ti–N). 1Н NMR spectrum, δ, ppm: 1.61–1.67 m
(6Н, СНСН3), 4.50–4.59 m (4H, ОСН2СН=СН2), 4.61–
4.74 m (2Н, СНСН3), 5.27–5.47 m (4H, ОСН2СН=СН2),
5.96–6.13 m (2H, ОСН2СН=СН2), 6.83–7.42 m
(24Нarom), 8.02–8.08 m (2H, СH=N). Found, %: C 69.58;
H 5.46; Cl 8.42; N 3.41. C48H44Cl2N2O4Ti. Calculated,
%: C 69.32; H 5.33; Cl 8.53; N 3.37.
Bis{2-[(4-allyloxyphenylimino)methyl]-6-tert-
butyl-4-(2-phenylpropan-2-yl)phenoxy}titanium(IV)
dichloride (Xe). Yield 89%. IR spectrum, ν, cm–1: 1609
1
(C=N), 564 (Ti–O), 476 (Ti–N). Н NMR spectrum,
δ, ppm: 1.35–1.42 m [18Н, С(СН3)3], 1.65–1.69 m
[12Н, C(СН3)2], 4.38–4.58 m (4H, ОСН2СН=СН2),
5.25–5.47 m (4H, ОСН2СН=СН2), 5.91–6.12 m (2H,
ОСН2СН=СН2), 6.54–7.48 m (22Нarom), 7.92–7.94 m
(2H, СH=N). Found, %: С 71.41; H 6.63; Cl 7.10; N 2.82.
C58H64Cl2N2O4Ti. Calculated, %: С 71.68; H 6.64;
Cl 7.30; N 2.88.
Bis{2-[(4-allyloxyphenylimino)methyl]-6-tert-
butylphenoxy}titanium(IV) dichloride (Xа). Yield
94%. IR spectrum, ν, cm–1: 1606 (C=N), 554 (Ti–O),
1
455 (Ti–N). Н NMR spectrum, δ, ppm: 1.22–1.61 m
Bis{2-[(4-allyloxyphenylimino)methyl]-6-(2-
phenylpropan-2-yl)phenoxy}titanium(IV) dichloride
(Xf). Yield 98%. IR spectrum, ν, cm–1: 1610 (C=N),
[18Н, С(СН3)3], 4.36–4.54 m (4H, ОСН2СН=СН2),
5.23–5.46 m (4H, ОСН2СН=СН2), 5.86–6.08 m (2H,
ОСН2СН=СН2), 6.52–7.44 m (14Нarom), 7.92–8.01 m
(2H, СH=N). Found, %: С 65.08; H 6.00; Cl 9.70; N 3.77.
C40H44Cl2N2O4Ti. Calculated, %: С 65.31; H 6.03;
Cl 9.64; N 3.81.
1
534 (Ti–O), 437 (Ti–N). Н NMR spectrum, δ, ppm:
1.69–1.89 m [12Н, C(СН3)2], 4.33–4.54 m (4H,
ОСН2СН=СН2), 5.20–5.42 m (4H, ОСН2СН=СН2),
5.95–6.08 m (2H, ОСН2СН=СН2), 6.43–7.63 m
(24Нarom), 7.76–7.82 m (2H, СH=N). Found, %: С 69.55;
H 5.80; Cl 8.09; N 3.12. C50H48Cl2N2O4Ti. Calculated,
%: С 69.85; H 5.63; Cl 8.25; N 3.26.
Bis{2-[(4-allyloxyphenylimino)methyl]-4,6-di-tert-
butylphenoxy}titanium(IV) dichloride (Xb). Yield
97%. IR spectrum, ν, cm–1: 1608 (C=N), 569 (Ti–O),
1
471 (Ti–N). Н NMR spectrum, δ, ppm: 1.26–1.38 m
Bis{2-[(4-allyloxyphenylimino)methyl]-4-methyl-
6-(2-phenylpropan-2-yl)phenoxy}titanium(IV)
dichloride (Xg). Yield 92%. IR spectrum, ν, cm–1: 1611
[36Н, С(СН3)3], 4.34–4.57 m (4H, ОСН2СН=СН2),
5.23–5.47 m (4H, ОСН2СН=СН2), 5.92–6.05 m (2H,
ОСН2СН=СН2), 6.51–7.46 m (12Harom), 7.99–8.03 m
(2H, СH=N). Found, %: С 67.87; H 7.07; Cl 8.40; N 3.38.
C48H60Cl2N2O4Ti. Calculated, %: С 68.00; H 7.13;
Cl 8.36; N 3.30.
1
(C=N), 579 (Ti–O), 442 (Ti–N). Н NMR spectrum, δ,
ppm: 1.47–1.84 m [12Н, C(СН3)2], 2.15–2.47 m (6Н,
СН3), 4.37–4.65 m (4H, ОСН2СН=СН2), 5.22–5.43 m
(4H, ОСН2СН=СН2), 5.94–6.15 m (2H, ОСН2СН=СН2),
6.44–7.58 m (22Нarom), 7.73–7.85 m (2H, СH=N). Found,
%: С 70.25; H 5.94; Cl 8.24; N 3.15. C52H52Cl2N2O4Ti.
Calculated, %: С 70.35; H 5.90; Cl 7.99; N 3.17.
Bis{2-[(4-allyloxyphenylimino)methyl]-6-tert-
butyl-4-methylphenoxy}titanium(IV) dichloride
(Xc). Yield 96%. IR spectrum, ν, cm–1: 1609 (C=N),
1
581 (Ti–O), 437 (Ti–N). Н NMR spectrum, δ, ppm:
Bis{2-[(4-allyloxyphenylimino)methyl]-4-tert-
butyl-6-(2-phenylpropan-2-yl)phenoxy}titanium(IV)
dichloride (Xh). Yield 96%. IR spectrum, ν, cm–1: 1609
1.28–1.61 m [18Н, С(СН3)3], 2.27–2.39 m (6Н, СН3),
4.37–4.59 m (4H, ОСН2СН=СН2), 5.25–5.49 m (4H,
ОСН2СН=СН2), 5.91–6.11 m (2H, ОСН2СН=СН2),
6.56–7.45 m (12Harom), 7.87–7.96 m (2H, СH=N). Found,
%: С 66.38; H 6.33; Cl 8.95; N 3.71. C42H48Cl2N2O4Ti.
Calculated, %: С 66.06; H 6.34; Cl 9.29; N 3.67.
1
(C=N), 567 (Ti–O), 451 (Ti–N). Н NMR spectrum,
δ, ppm: 1.33–1.52 m [18Н, С(СН3)3], 1.75–1.87 m
[12Н, C(СН3)2], 4.37–4.55 m (4H, ОСН2СН=СН2),
5.25–5.45 m (4H, ОСН2СН=СН2), 5.98–6.10 m (2H,
ОСН2СН=СН2), 6.39–7.63 m (22Нarom), 7.78–7.82 m
(2H, СH=N). Found, %: С 71.98; H 6.71; Cl 7.21; N 2.86.
C58H64Cl2N2O4Ti. Calculated, %: С 71.68; H 6.64;
Bis{2-[(4-allyloxyphenylimino)methyl]-6-tert-
butyl-4-methoxyphenoxy}titanium(IV) dichloride
(Xd). Yield 93%. IR spectrum, ν, cm–1: 1611 (C=N),
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OLEINIK et al.
Akad. Nauk, Ser. Khim., 2003, p. 1605; Clarkson, G.J.,
1080
Cl 7.30; N 2.88.
Gibson, V.C., Goh, P.K.Y., Hammond, M.L., Knight, P.D.,
Scott, P., Smit, T.M., White, A.J.P., and Williams, D.J.,
Dalton Trans., 2006, vol. 46, p. 5484.
Bis{2-[(4-allyloxyphenylimino)methyl]-4,6-(2-
phenylpropan-2-yl)phenoxy}titanium(IV) dichloride
(Xi). Yield 95%. IR spectrum, ν, cm–1: 1609 (C=N),
5. Mitani, M., Saito, J., Ishii, S., Nakayama, Y., Makio, H.,
Matsukawa, N., Matsui, S., Mohri, J., Furuyama, R.,
Terao, H., Bando, H., Tanaka, H., and Fujita, T., Chem.
Rec., 2004, vol. 4, p. 137.
6. Makio, H.and Fujita, T., Acc. Chem. Res., 2009, vol. 42,
p. 1532.
7. Matsui, S., Mitani, M., Saito, J., Tohi, Y., Makio, H., Mat-
sukawa, N., Takagi, Y., Tsuru, K., Nitabaru, M., Nakano, T.,
Tanaka, H., Kashiwa, N., and Fujita, T., J. Am. Chem. Soc.,
2001, vol. 123, p. 6847.
8. Tohi, Y., Makio, H., Matsui, S., Onda, M., and Fujita, T.
Macromolecules, 2003, vol. 36, p. 523.
9. Cherian, A.E., Lobkovsky, E.B., and Coates, G.W., Mac-
romolecules, 2005, vol. 38, p. 6259.
10. Makio, H., Kashiwa, N., and Fujita, T., Adv. Synth. Catal.,
2002, vol. 344, p. 477.
11. Tohi, Y., Nakano, T., Makio, H., Matsui, S., Fujita, T., and
Yamaguchi, T., Macromol. Chem. Phys., 2004, vol. 205,
p. 1179.
12. Axenov, K.V., Klinga, M., Lehtonen, O., Koskela, H. T.,
Leskelä, M., and Repo, T., Organometallics, 2007, vol. 26,
p. 1444.
1
553 (Ti–O), 466 (Ti–N). Н NMR spectrum, δ, ppm:
1.62–1.81 m [24Н, C(СН3)2], 4.36–4.53 m (4H,
ОСН2CН=СН2), 5.19–5.42 m (4H, ОСН2СН=СН2),
5.89–6.06 m (2H, ОСН2СН=СН2), 6.38–7.54 m
(32Нarom), 7.72–7.78 m (2H, СH=N). Found, %: С 74.41;
H 6.21; Cl 6.26; N 2.68. C68H68Cl2N2O4Ti. Calculated,
%: С 74.52; H 6.25; Cl 6.47; N 2.88.
Bis{2-[(4-allyloxyphenylimino)methyl]-6-(1-
phenylethyl)phenoxy}titanium(IV) dichloride (Xj).
Yield 96%. IR spectrum, ν, cm –1: 1610 (C=N), 575 (Ti–
O), 457 (Ti–N). 1Н NMR spectrum, δ, ppm: 1.48–1.74 m
(6Н, СНСН3), 4.26–4.40 m (4H, ОСН2СН=СН2), 4.48–
4.73 m (2Н, СНСН3), 5.23–5.47 m (4H, ОСН2СН=СН2),
5.89–6.12 m (2H, ОСН2СН=СН2), 6.58–7.62 m
(24Нarom), 7.94–8.04 m (2H, СH=N). Found, %: C 69.35;
H 5.43; Cl 8.41; N 3.33. C48H44Cl2N2O4Ti. Calculated,
%: C 69.32; H 5.33; Cl 8.53; N 3.37.
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