Design of postmetallocene catalytic systems of arylimine type for olefi n polymerization: XV. Synthesis of (N-Aryl)salicylaldimine ligands containing a but-3-enyloxy group and their complexes with titanium(IV) dichloride

Article abstract of DOI:10.1134/S1070428013080095

A series of (N-aryl)salicylaldimines was synthesized by the reaction of salicylaldehydes substituted in the positions 3 and 5 by bulky tert-butyl or α-cumyl groups with hydrochlorides of o-, m-, and p-(but-3-enyloxy) aniline in the presence of triethylamine. The obtained compounds formed by the reaction with TiCl₂(OPr-i)₂ complexes of titanium(IV) dichloride L₂TiCl₂.

Full text of DOI:10.1134/S1070428013080095

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 8, pp. 1150−1156. © Pleiades Publishing, Ltd., 2013.
Original English Text © I.I. Oleinik, I V. Oleinik, S.S. Ivanchev, G.A. Tolstikov, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 8,
pp. 1168−1173.
Design of Postmetallocene Catalytic Systems of Arylimine Type
for Olefin Polymerization: XV.* Synthesis
of (N-Aryl)salicylaldimine Ligands Containing
a But-3-enyloxy Group 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 Branch of Russian Academy of Sciences,
Novosibirsk, 630090 Russia
е-mail: oleynik@nioch.nsc.ru
bSt. Petersburg Branch of Boreskov Institute of Catalysis,
Siberian Branch of Russian Academy of Sciences, Novosibirsk, Russia
Received February 4, 2013
Abstract—Aseries of (N-aryl)salicylaldimines was synthesized by the reaction of salicylaldehydes substituted in
the positions 3 and 5 by bulky tert-butyl or α-cumyl groups with hydrochlorides of o-, m-, and p-(but-3-enyloxy)
aniline in the presence of triethylamine. The obtained compounds formed by the reaction with TiCl2(OPr-i)2
complexes of titanium(IV) dichloride L2TiCl2.
DOI: 10.1134/S1070428013080095
The study of kinetic features of ethylene polymeriza-
tion on (N-aryl)salicylaldimine complexes of titanium(IV)
dichloride containing an allyloxyphenylimino group acti-
vated with methylalumoxane revealed the ability of the
catalytic system to produce polyethylenes of superhigh
molecular weight possessing an improved morphology of
particles [2]. The combination of results obtained allows
a conclusion that this feature of the studied catalytic sys-
tems is due to the ability of these complexes to immobilize
on the polyethylene macromolecules by copolymerization
with ethylene.
the synthesis and properties of such complexes are absent
the problem of the control of the complex self-immobi-
lization, of the activity of the obtained heterogeneous
catalyst, and of the properties of the formed polyolefin by
varying the number of the methylene units in the alkenyl
substituent and changing its position in the benzene ring
remains unsolved. In order to prove experimentally the
mentioned assumption we describe in this report the syn-
thesis of (N-aryl)salicylaldimine ligands and complexes
of titanium(IV) dichloride containing isomeric o-, m-,
and p-(but-3-enyloxy)phenylimino groups. The obtained
regularities of the variation in the catalytic activity at the
changes in the substituents ensemble in the salicylidene
fragment of the ligand show that at certain combination
of the substituents optimum values are reached of the
catalytic activity and the molecular weight distribution of
produced polymers [2, 4]. Evidently the revealed regulari-
ties are of a general character, and just these combina-
tions of substituents were used in the synthesis of new
salicylaldimine complexes of titanium(IV) dichloride.
The existing data on metallocene and bisaryl-
iminopyridine complexes containing an ω-alkenyl
group indicate that the activity of the catalytic system
is affected by the length of the alkenyl substituent [3].
Apparently in the case of (N-aryl)salicylaldimine com-
plexes of titanium(IV) dichloride it is possible to observe
a similar dependence. Inasmuch as the published data on
––––––––––––––––––
* For Communication XIV, see [1].
1150

DESIGN OF POSTMETALLOCENE CATALYTIC SYSTEM
1151
The isomeric salicylaldimines Vа–Vd–VIIа–VIId
containing in the arylimine moiety a but-3-enyloxy
group were obtained by the reaction of substituted
salicylaldehydes Iа–Id with but-3-enyloxyanilines gener-
ated in situ by treating their hydrochlorides II–IV with
triethylamine at boiling in methanol for 10–15 h. The
yields of the corresponding salicylaldimines Vа–Vd–
VIIа–VIId attained 85–96%.
R2
R1
R2
R2
O
N
N
NH2 · HCl
O
TiCl2(OPr-i)2
Et3N, MeOH
R1
TiCl2
+
R1
O
OH N
O
O
OH O
R1
O
Iа_Id
Vа_Vd_VIIа_VIId
II_IV
Vа–Vd, VIа–VId,
R2
VIIа–VIId
_
VIIIа–VIIId,
VIIIа VIIId,
_
IXа–IXd, Xа–Xd
Xа Xd
R1 = t-Bu, R2 = H (а); R1 = R2 = t-Bu (b); R1 = CMe2(Ph), R2 = H (c); R1 = R2 = CMe2(Ph) (d); 2-(but-3-enyloxy) (II, V, VIII); 3-(but-
3-enyloxy) (III, VI, IX); 4-(but-3-enyloxy) (IV,VII, X).
The structure of imines Vа–Vd, VIа–VId, VIIа–
VIId was established from the combination of analytic
and spectral data. The Н NMR spectra suggest that
The complexes of titanium(IV) dichloride were
synthesized in one stage [5] by the reaction of the ligand
with TiCl2(OPr-i)2. At treating imines Vа–Vd, VIа–VId,
VIIа–VIId with equimolar amount of the TiCl2(OPr-i)2
solution in toluene at room temperature complexes of
titanium(IV) dichloride VIIIа–VIIId, IXа–IXd, Xа–Xd
were obtained in high yields.
1
the Schiff bases we prepared are individual Е-isomers.
The 1Н NMR spectra of compounds Vа–Vd, VIа–VId,
VIIа–VIId contain the singlets of the N=CH group in
the region 8.45–8.66 ppm. The signals of ОH group of
the salicylaldimines appear as broadened singlets in the
region 13.23–14.41 ppm. The but-3-enyloxy group of
the Schiff bases Vа–Vd, VIа–VId, VIIа–VIId gives
rise to a characteristic set of signals: The protons of the
ОСН2 moiety appear as a triplet in the region 3.95–4.11
ppm, the terminal protons appear in the region 4.98–5.24
ppm as two separate doublets of doublets of triplets with
the appropriate vicinal spin-spin coupling constants
(Jcis 10.0–10.4 and Jtrans 17.0–17.4 Hz), the protons
of ОСН2CH2СН=СН2 group are observed as a multi-
plet in the region 2.44–2.63 ppm, and the protons of
ОСН2CH2СН=СН2 resonated as a doublet of doublets
of triplets at 5.80–5.99 ppm.
The composition of complexes VIIIа–VIIId, IXа–
IXd, Xа–Xd is confirmed by combined data of the
elemental analysis and the IR spectra from pellets with
KBr. In the IR spectra the absorption bands in the region
442–476 (Ti-N), and 541–581cm–1 (Ti–O) were observed.
At the complex formation the frequency of ν(N=CH)
decreased for the complexes with the ortho- (VIIIа–
VIIId) and para-location (Xа–Xd) of the oxybutenyl
substituents by 2–7 cm–1, for the meta-isomers IXа–IXd,
by 15–21 cm–1.
In the 1Н NMR spectra of complexes VIIIа–VIIId,
IXа–IXd, Xа–Xd alongside the protons of the oxybutenyl
fragments, tert-butyl and cumyl substituents, and the
aromatic protons the characteristic signals are pesent of
the protons of НС=N group of the stereoisomeric forms
of complexes VIIIа–VIIId, IXа–IXd, Xа–Xd in the
region 7.57–8.19 ppm; the singlets of OH group present
in the spectra of imines Vа–Vd, VIа–VId, VIIа–VIId
IR spectra of compounds Vа–Vd, VIа–VId, VIIа–
VIId contain a strong absorption band in the region
1610–1619 cm–1 corresponding to the stretching vibra-
tions of the C=N bond of the imine moiety. The mass
spectra of the synthesized ligands contain strong peaks
of the molecular ions.
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OLEINIK et al.
1152
o-(But-3-enyloxy)aniline. Yield 52%, bp 132–
are lacking.
134°С (10–12 mm Hg). Oily substance, fast darken-
ing in air. Н NMR spectrum, δ, ppm: 2.58 m (2H,
The isomeric (but-3-enyloxy)anilines were synthesized
1
along the protocol including the alkenylation of o-, m-,
and p-acetylaminophenols followed by the removal of
the acetyl protection analogous to the procedure [6], and
for convenient handling and storage the products were
converted into hydrochlorides II–IV.
ОСН2CH2СН=СН2), 3.80 br.s (2H, NH2), 4.05 t
(2H, ОСН2CH2СН=СН2, J 6.6 Hz), 5.13 d.d.t (1H,
ОСН2CH2СН=СН2, J 10.3, 1.8, 1.1 Hz), 5.20 d.d.t (1H,
ОСН2CH2СН=СН2, J 17.2, 1.8, 1.5 Hz), 5.92 d.d.t (1H,
ОСН2CH2СH=СН2, J 17.2, 10.3, 6.8 Hz), 6.71–6.81 m
(4Нarom). Found [M]+ 163.0996. C10H13NO. Calculated
M 163.0997 (сf. [6]).
EXPERIMENTAL
m-(But-3-enyloxy)aniline. Yield 75%, bp 133–135°С
(5 mm Hg). Oily substance, fast darkening in air. 1Н NMR
spectrum, δ, ppm: 2.52 m (2H, ОСН2CH2СН=СН2),
3.64 br.s (2H, NH2), 3.96 t (2H, ОСН2CH2СН=СН2,
J 6.7 Hz), 5.10 d.d.t (1H, ОСН2CH2СН=СН2, J 10.3, 1.9,
1.1 Hz), 5.16 d.d.t (1H, ОСН2CH2СН=СН2, J 17.4, 1.9,
1.5 Hz), 5.89 d.d.t (1H, ОСН2CH2СH=СН2, J 17.4, 10.3,
6.9 Hz), 6.23 t (1Нarom, J 2.2 Hz), 6.26–6.33 m (2Нarom),
7.04 t (1Нarom, J 8.02 Hz). Found [M]+ 163.0998.
C10H13NO. Calculated M 163.0997.
The analytic and spectral measurements were carried
out in the Chemical Service Center for collective use of
the Siberian Division, Russian Academy of Sciences.
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 substances
in a pure state. The reaction progress and the purity of
compounds obtained were monitored by TLC on Silufol
UV-254 plates, eluent chloroform. Elemental analyses
were carried out on a CHNS-analyzer Euro EA3000. The
elemental formulas of compounds obtained were calcu-
lated from the high resolution mass spectra measured on
a spectrometer DFS Thermo Electron Corporation. The
melting points were determined in capillaries on an instru-
ment Mettler Toledo FP90 at the heating rate 1 deg/min.
p-(But-3-enyloxy)aniline. Yield 80%, bp 92–94°С (1
mm Hg). Oily substance, fast darkening in air. 1Н NMR
spectrum, δ, ppm: 2.49 m (2H, ОСН2CH2СН=СН2), 3.41
br.s (2H, NH2), 3.93 t (2H, ОСН2CH2СН=СН2, J 6.7 Hz),
5.07 d.d.t (1H, ОСН2CH2СН=СН2, J 10.4, 1.8, 1.0 Hz),
5.14 d.d.t (1H, ОСН2CH2СН=СН2, J 17.2, 1.8, 1.5 Hz),
5.89 d.d.t (1H, ОСН2CH2СН=СН2, J 17.2, 10.4, 6.9 Hz),
6.62 d (2Нarom, J 8.6 Hz), 6.74 d (2Нarom, J 8.6 Hz). Found
[M]+ 163.0995. C10H13NO. Calculated M 163.0997.
Substituted salicylaldehydes Iа–Id and TiCl2(OPr-i)2
were prepared by procedures [7, 8].
Hydrochlorides II–IV were obtained by treating the
methanol solutions of isomeric (but-3-enyloxy)anilines
with conc. hydrochloric acid taken in 3–5% excess with
the subsequent distilling off the solvents in a vacuum of
the water-aspirator pump till the constant weight.
o-, m-, and p-(But-3-enyloxy)anilines and their
hydrochlorides II–IV. A mixture of 15.1 g (0.1 mol) of
an appropriate isomer of acetylaminophenol, 100 ml of
acetone, and 13.8 g (0.1 mol) of anhydrous potassium
carbonate was stirred for 1 h. To the obtained slurry was
added 2 ml of dimethylformamide, ~10–20 mg of potas-
sium iodide, and 20.25 g (0.105 mol) of 4-bromobut-
1-ene. The reaction mixture was boiled for 20 h. The
precipitate was filtered off, washed with acetone (3 ×
20 ml). From the combined filtrates acetone was distilled
off, to the residue 75 ml of ethanol and 11 ml (0.11 mol)
of conc. hydrochloric acid was added, and the mixture
was boiled for 8 h. Ethanol (50 ml) was distilled off on
the rotary evaporator, the residue was diluted with 50 ml
of water, 20% solution of sodium hydroxide was added
to рН 8 , the (but-3-enyloxy)aniline was extracted into
methyl tert-butyl ether (4 × 30 ml), the extract was dried
with MgSO4. The solvent was distilled off, the residue
was distilled in a vacuum.
(N-Aryl)salicylaldimines Vа–Vd, VIa–VId, VIIа–
VIId. A mixture of 4 mmol of aldehyde Iа–Id, 0.798 g
(4.4 mmol) of an appropriate (but-3-enyloxy)aniline hy-
drochloride II–IV, 0.444 g (4.4 mmol) of triethylamine,
and 10 ml of methanol was boiled for 10–15 h till the
disappearance of the initial compounds (TLC monitor-
ing). Methanol was distilled off on a rotary evaporator, the
residue was dissolved 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 subjected
to flash-chromatography on silica gel 2–25 μm, 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 till crystals formed, the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 8 2013

DESIGN OF POSTMETALLOCENE CATALYTIC SYSTEM
1153
precipitate was filtered off, washed with 3 ml of methanol
and was kept in a vacuum-desiccator.
J 2.0 Hz), 8.63 s (1H, СH=N), 13.81 s (1H, OH). Found
[M]+ 503.2816. C35H37NO2. Calculated M 503.2819.
2-{[2-(But-3-enyl)oxyphenylimino]methyl}-6-
2-{[3-(But-3-enyl)oxyphenylimino]methyl}-6-
tert-butylphenol (Vа). Yield 87%. Oily substance.
tert-butylphenol (VIа). Yield 88%. Oily substance.
1
1
IR spectrum, ν, сm–1: 1613 (С=N). Н NMR spec-
IR spectrum, ν, cm–1: 1614 (С=N). Н NMR spec-
trum, δ, ppm: 1.51 s [9Н, С(СН3)3], 2.63 m (2H,
ОСН2CH2СН=СН2), 4.11 t (2H, ОСН2CH2СН=СН2,
J 6.4 Hz), 5.14 d.d.t (1H, ОСН2CH2СН=СН2, J 10.2,
1.8, 1.1 Hz), 5.24 d.d.t (1H, ОСН2CH2СН=СН2, J 17.1,
1.8, 1.5 Hz), 5.99 d.d.t (1H, ОСН2CH2СH=СН2, J 17.1,
10.2, 6.8 Hz), 6.85 t (1Нarom, J 7.6 Hz), 6.96–7.03 m
(2Нarom), 7.18–7.27 m (3Нarom), 7.38 d.d (1Нarom, J 7.6,
1.5 Hz), 8.76 s (1H, СH=N), 14.41 s (1H, OH). Found
[M]+ 323.1876. C21H25NO2. Calculated M 323.1880.
trum, δ, ppm: 1.50 s [9Н, С(СН3)3], 2.59 m (2H,
ОСН2CH2СН=СН2), 4.08 t (2H, ОСН2CH2СН=СН2,
J 6.6 Hz), 5.15 d.d.t (1H, ОСН2CH2СН=СН2, J 10.3, 1.8,
1.1 Hz), 5.21 d.d.t (1H, ОСН2CH2СН=СН2, J 17.1, 1.8,
1.5 Hz), 5.94 d.d.t (1H, ОСН2CH2СН=СН2, J 17.1, 10.3,
6.9 Hz), 6.84–6.91 m (4Нarom), 7.25 d.d (1Harom, J 7.8,
1.0 Hz), 7.32 t (1Нarom, J 7.8 Hz), 7.41 d.d (1Нarom, J 7.8,
1.0 Hz), 8.63 s (1H, СH=N), 13.86 s (1H, OH). Found
[M]+ 323.1882. C21H25NO2. Calculated M 323.1880.
2-{[2-(But-3-enyl)oxyphenylimino]methyl}-4,6-di-
tert-butylphenol (Vb). Yield 85%. Oily substance. IR
spectrum, ν, cm–1:1617(С=N). 1НNMRspectrum, δ, ppm:
1.33 s [9Н, С(СН3)3], 1.48 s [9Н, С(СН3)3], 2.59 m (2H,
ОСН2CH2СН=СН2), 4.08 t (2H, ОСН2CH2СН=СН2,
J 6.5 Hz), 5.10 d.d.t (1H, ОСН2CH2СН=СН2, J 10.0, 1.8,
1.1 Hz), 5.22 d.d.t (1H, ОСН2CH2СН=СН2, J 17.0, 1.8,
1.5 Hz), 5.95 d.d.t (1H, ОСН2CH2СН=СН2, J 17.0, 10.0,
6.8 Hz), 6.94–7.01 m (2Нarom), 7.14–7.22 m (3Нarom),
7.42 d (1Нarom, J 2.4 Hz), 8.72 s (1H, СH=N), 14.11 s
(1H, OH). Found [M]+ 379.2500. C25H33NO2. Calculated
M 379.2506.
2-{[3-(But-3-enyl)oxyphenylimino]methyl}-4,6-
di-tert-butylphenol (VIb). Yield 86%, mp 60°С. IR
1
spectrum, ν, cm–1: 1619 (С=N). Н NMR spectrum, δ,
ppm: 1.35 s [9Н, С(СН3)3], 1.49 s [9Н, С(СН3)3], 2.58 m
(2H, ОСН2CH2СН=СН2), 4.07t(2H, ОСН2CH2СН=СН2,
J 6.6 Hz), 5.13 d.d.t (1H, ОСН2CH2СН=СН2, J 10.2, 1.9,
1.1 Hz), 5.20 d.d.t (1H, ОСН2CH2СН=СН2, J 17.2, 1.9,
1.5 Hz), 5.93 d.d.t (1H, ОСН2CH2СH=СН2, J 17.2, 10.2,
6.9 Hz), 6.76–6.87 m (3Нarom), 7.18 d (1Нarom, J 2.4 Hz),
7.27 t (1Нarom, J 8.0 Hz), 7.42 d (1Нarom, J 2.4 Hz), 8.64 s
(1H, СH=N), 13.60 s (1H, OH). Found [M]+ 379.2503.
C25H33NO2. Calculated M 379.2506.
2-{[2-(But-3-enyl)oxyphenylimino]methyl}-6-
2-{[3-(But-3-enyl)oxyphenylimino]methyl}-6-(2-
phenylpropan-2-yl)phenol (VIc). Yield 87%. Oily
substance. IR spectrum, ν, cm–1: 1614 (С=N). 1Н NMR
spectrum, δ, ppm: 1.81 s [6Н, С(СН3)2], 2.56 m (2H,
ОСН2CH2СН=СН2), 4.03 t (2H, ОСН2CH2СН=СН2,
J 6.6 Hz), 5.13 d.d.t (1H, ОСН2CH2СН=СН2, J 10.4,
1.9, 1.0 Hz), 5.20 d.d.t (1H, ОСН2CH2СН=СН2, J 17.0,
1.9, 1.5 Hz), 5.92 d.d.t (1H, ОСН2CH2СH=СН2, J 17.0,
(2-phenylpropan-2-yl)phenol (Vc). Yield 91%, mp
1
66°С. IR spectrum, ν, cm–1: 1610 (С=N). Н NMR
spectrum, δ, ppm: 1.80 s [6Н, С(СН3)2], 2.48 m (2H,
ОСН2CH2СН=СН2), 4.00 t (2H, ОСН2CH2СН=СН2,
J 6.4 Hz), 5.04 d.d.t (1H, ОСН2CH2СН=СН2, J 10.2, 1.8,
0.9 Hz), 5.10 d.d.t (1H, ОСН2CH2СН=СН2, J 17.1, 1.8,
1.5 Hz), 5.85 d.d.t (1H, ОСН2CH2СН=СН2, J 17.1, 10.2,
6.8 Hz), 6.87–6.96 m (3Нarom), 7.10–7.29 m (8Нarom), 7.52
d.d (1Нarom, J 7.8, 1.4 Hz), 8.69 s (1H, СH=N), 13.96 s
(1H, OH). Found [M]+ 385.2030. C26H27NO2. Calculated
M 385.2036.
10.4, 6.9 Hz), 6.73–6.82 m (3Нarom), 6.97 t (1Нarom
,
J 7.8 Hz), 7.15–7.32 m (7Нarom), 7.57 d.d (1Нarom, J 7.8,
1.6 Hz), 8.57 s (1H, СH=N), 13.39 s (1H, OH). Found
[M]+ 385.2035. C26H27NO2. Calculated M 385.2036.
2-{[2-(But-3-enyl)oxyphenylimino]methyl}-4,6-
2-{[3-(But-3-enyl)oxyphenylimino]methyl}-4,6-
di(2-phenylpropan-2-yl)phenol (VId). Yield 93%. Oily
substance. IR spectrum, ν, cm–1: 1619 (С=N). 1Н NMR
spectrum, δ, ppm: 1.71 s [6Н, С(СН3)2], 1.75 s [6Н,
С(СН3)2], 2.55 m (2H, ОСН2CH2СН=СН2), 4.01 t
(2H, ОСН2CH2СН=СН2, J 6.6 Hz), 5.11 d.d.t (1H,
ОСН2CH2СН=СН2, J 10.0, 1.9, 1.1 Hz), 5.17 d.d.t (1H,
ОСН2CH2СН=СН2, J 17.0, 1.9, 1.5 Hz), 5.90 d.d.t (1H,
ОСН2CH2СH=СН2, J 17.0, 10.0, 6.9 Hz), 6.70–6.78 m
di(2-phenylpropan-2-yl)phenol (Vd). Yield 96%, mp
1
89°С. IR spectrum, ν, cm–1: 1613 (С=N). Н NMR
spectrum, δ, ppm: 1.73 s [6Н, С(СН3)2], 1.75 s [6Н,
С(СН3)2], 2.44 m (2H, ОСН2CH2СН=СН2), 3.95 t
(2H, ОСН2CH2СН=СН2, J 6.4 Hz), 4.98 d.d.t (1H,
ОСН2CH2СН=СН2, J 10.2, 1.9, 1.1 Hz), 5.05 d.d.t (1H,
ОСН2CH2СН=СН2, J 17.1, 1.9, 1.5 Hz), 5.80 d.d.t (1H,
ОСН2CH2СH=СН2, J 17.1, 10.2, 6.9 Hz), 6.87–6.95 m
(2Нarom), 7.11–7.31 m (13Нarom), 7.39 d (1Нarom
,
(2Нarom), 7.13-7.32 m (13Нarom), 7.42 d (1Нarom,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 8 2013

OLEINIK et al.
1154
J 2.2 Hz), 8.51 s (1H, СH=N), 13.23 s (1H, OH). Found
[M]+ 503.2818. C35H37NO2. Calculated M 503.2819.
(1H, ОСН2CH2СH=СН2, J 17.0, 10.0, 6.9 Hz), 6.87 d
(2Нarom, J 8.9 Hz), 7.12-7.32 m (13Нarom), 7.41 d (1Нarom
,
J 2.3 Hz), 8.50 s (1H, СH=N), 13.40 s (1H, OH). Found
[M]+ 503.2810. C35H37NO2. Calculated M 503.2819.
2-{[4-(But-3-enyl)oxyphenylimino]methyl}-6-tert-
butylphenol (VIIа). Yield 89%, mp 59°С. IR spectrum,
ν, cm–1: 1613 (С=N). 1Н NMR spectrum, δ, ppm: 1.49 s
[9Н, С(СН3)3], 2.59 m (2H, ОСН2CH2СН=СН2), 4.06 t
(2H, ОСН2CH2СН=СН2, J 6.6 Hz), 5.15 d.d.t (1H,
ОСН2CH2СН=СН2, J 10.2, 1.8, 1.1 Hz), 5.21 d.d.t
(1H, ОСН2CH2СН=СН2, J 17.2, 1.8, 1.5 Hz), 5.93 d.d.t
(1H, ОСН2CH2СH=СН2, J 17.2, 10.2, 6.9 Hz), 6.87 t
(1Нarom, J 7.7 Hz), 6.95 d (2Нarom, J 8.7 Hz), 7.23 d.d
(1Нarom, J 7.7, 1.6 Hz), 7.29 d (2Нarom, J 8.7 Hz), 7.37 d.d
(1Нarom, J 7.7, 1.6 Hz), 8.62 s (1H, СH=N), 14.04 s (1H,
OH). Found [M]+ 323.1879. C21H25NO2. Calculated
M 323.1880.
Complexes VIIIа–VIIId, IXa–IXd, Xа–Xd.
A mixture of 2 mmol of (N-aryl)salicylaldimine Vа–Vd,
VIa–VId, VIIа–VIId, 10 ml of anhydrous dichlorometh-
ane, and 2.39 g of toluene solution containing 0.237 g
(1 mmol) of TiCl2(OPr-i)2 was stirred at room temperature
under an argon atmosphere for 24 h. The solvent was dis-
tilled off from the formed dark-red solution in a vacuum
of the water-aspirator pump. The residue was washed with
hexane (2 × 2 ml) on the filter and was dried in a vacuum
of an oil pump at 100°С for 1 h. The corresponding com-
plexes were obtained as red-brown powders.
2-{[4-(But-3-enyl)oxyphenylimino]methyl}-4,6-
Bis(2-{[2-(but-3-enyl)oxyphenylimino]methyl}-6-
tert-butylphenoxy)titanium(IV) dichloride (VIIIa).
Yield 91%. IR spectrum, ν, cm–1: 1609 (C=N), 570 (Ti–
O), 462 (Ti–N). 1Н NMR spectrum, δ, ppm: 1.43–1.62 m
[18Н, С(СН3)3], 2.59–2.68 m (4H, ОСН2CH2СН=СН2),
4.09–4.12 m (4H, ОСН2CH2СН=СН2), 4.96–
5.25 m (4H, ОСН2CH2СН=СН2), 5.89–6.03 m (2H,
ОСН2CH2СН=СН2), 6.55–7.42 m (14Harom), 7.70–
7.82 m (2H, СH=N). Found, %: С 65.98; H 6.55; Cl 9.05;
N 3.67. C42H48Cl2N2O4Ti. Calculated, %: С 66.06;
H 6.34; Cl 9.29; N 3.67.
di-tert-butylphenol (VIIb). Yield 91%, mp 63°С. IR
1
spectrum, ν, cm–1: 1616 (С=N). Н NMR spectrum, δ,
ppm: 1.33 s [9Н, С(СН3)3], 1.47 s [9Н, С(СН3)3], 2.56 m
(2H, ОСН2CH2СН=СН2), 4.03t(2H, ОСН2CH2СН=СН2,
J 6.5 Hz), 5.12 d.d.t (1H, ОСН2CH2СН=СН2, J 10.0,
1.8, 1.1 Hz), 5.20 d.d.t (1H, ОСН2CH2СН=СН2, J 17.0,
1.8, 1.5 Hz), 5.94 d.d.t (1H, ОСН2CH2СH=СН2, J 17.0,
10.0, 6.9 Hz), 6.91 d (2Нarom, J 9.0 Hz), 7.18 d (1Нarom
J 2.5 Hz), 7.25 d (2Нarom, J 9.0 Hz), 7.40 d (1Нarom
,
,
J 2.5 Hz), 8.61 s (1H, СH=N), 13.76 s (1H, OH). Found
[M]+ 379.2508. C25H33NO2. Calculated M 379.2506.
Bis(2-{[2-(but-3-enyl)oxyphenylimino]methyl}-4,6-
di-tert-butylphenoxy)titanium(IV) dichloride (VIIIb).
Yield 89%. IR spectrum, ν, cm–1: 1612 (C=N), 581 (Ti–
O), 473 (Ti–N). 1Н NMR spectrum, δ, ppm: 1.34–1.63 m
[36Н, С(СН3)3], 2.58–2.69 m (4H, ОСН2CH2СН=СН2),
4.07–4.13 m (4H, ОСН2CH2СН=СН2), 4.94–5.31 m
(4H, ОСН2CH2СН=СН2), 5.86–6.04 m (2H,
ОСН2CH2СН=СН2), 6.62-7.52 m (12Harom), 7.60–7.78 m
(2H, СH=N). Found, %: С 68.29; H 7.44; Cl 8.03; N 3.22.
C50H64Cl2N2O4Ti. Calculated, %: С 68.57; H 7.37;
Cl 8.10; N 3.20.
2-{[4-(But-3-enyl)oxyphenylimino]methyl}-6-(2-
phenylpropan-2-yl)phenol (VIIc). Yield 89%, mp
1
75°С. IR spectrum, ν, cm–1: 1613 (С=N). Н NMR
spectrum, δ, ppm: 1.79 s [6Н, С(СН3)2], 2.56 m (2H,
ОСН2CH2СН=СН2), 4.02 t (2H, ОСН2CH2СН=СН2,
J 6.6 Hz), 5.13 d.d.t (1H, ОСН2CH2СН=СН2, J 10.2,
1.8, 1.0 Hz), 5.19 d.d.t (1H, ОСН2CH2СH=СН2, J 17.2,
1.8, 1.5 Hz). 5.91 d.d.t (1H, ОСН2CH2СH=СН2, J 17.2,
10.2, 6.9 Hz), 6.87 d (2Нarom, J 8.9 Hz), 6.94 t (1Нarom
,
J 7.8 Hz), 7.15–7.19 m (3Нarom), 7.26–7.30 m (5Нarom),
7.54 d.d (1Нarom, J 7.8, 1.5 Hz), 8.55 s (1H, СH=N),
13.54 s (1H, OH). Found [M]+ 385.2032. C26H27NO2.
Calculated M 385.2036.
Bis[2-{[2-(but-3-enyl)oxyphenylimino]methyl}-6-
(2-phenylpropan-2-yl)phenoxy]titanium(IV) dichloride
(VIIIc). Yield 86%. IR spectrum, ν, cm–1: 1608
1
2-{[4-(But-3-enyl)oxyphenylimino]methyl}-4,6-
di-(2-phenylpropan-2-yl)phenol (VIId). Yield 89%,
mp 110°С. IR spectrum, ν, cm–1: 1617 (С=N). 1Н NMR
spectrum, δ, ppm: 1.72 s [6Н, С(СН3)2], 1.76 s [6Н,
С(СН3)2], 2.56 m (2H, ОСН2CH2СН=СН2), 4.02 t
(2H, ОСН2CH2СН=СН2, J 6.7 Hz), 5.13 d.d.t (1H,
ОСН2CH2СН=СН2, J 10.0, 1.8, 1.1 Hz), 5.20 d.d.t
(1H, ОСН2CH2СН=СН2, J 17.0, 1.8, 1.5 Hz), 5.91 d.d.t
(C=N), 566 (Ti-O), 444 (Ti-N). Н NMR spectrum, δ,
ppm: 1.53–1.89 m [12Н, С(СН3)2], 2.48–2.66 m (4H,
ОСН2CH2СН=СН2),3.89–4.13m(4H,ОСН2CH2СН=СН2),
4.89–5.16 m (4H, ОСН2CH2СН=СН2), 5.62–6.01 m
(2H, ОСН2CH2СН=СН2), 6.39–7.53 m (24Harom),
7.68–7.81 m (2H, СH=N). Found, %: С 70.42; H 5.99;
Cl 7.76; N 3.11. C52H52Cl2N2O4Ti. Calculated, %:
С 70.35; H 5.90; Cl 7.99; N 3.16.
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DESIGN OF POSTMETALLOCENE CATALYTIC SYSTEM
1155
Bis[2-{[2-(but-3-enyl)oxyphenylimino]methyl}-
4,6-di-(2-phenylpropan-2-yl)phenoxy]titanium(IV)
dichloride (VIIId). Yield 85%. IR spectrum, ν, cm–1:
1608 (C=N), 558 (Ti–O), 471 (Ti–N). 1Н NMR spectrum,
δ, ppm: 1.55–1.82 m [24Н, С(СН3)2], 2.42–2.67 m (4H,
ОСН2CH2СН=СН2),3.95–4.15m(4H,ОСН2CH2СН=СН2),
4.94–5.15 m (4H, ОСН2CH2СН=СН2), 5.77–6.11 m (2H,
ОСН2CH2СН=СН2), 6.69–7.48 m (32Harom), 7.63–
7.78 m (2H, СH=N). Found, %: С 75.33; H 6.43; Cl 6.21
N 2.57. C70H72Cl2N2O4Ti. Calculated, %: С 74.79;
H 6.46; Cl 6.31; N 2.49.
ppm: 1.66-1.76 m [24Н, С(СН3)2], 2.50–2.57 m (4H,
ОСН2CH2СН=СН2),3.95–4.04m(4H,ОСН2CH2СН=СН2),
5.09–5.20 m (4H, ОСН2CH2СН=СН2), 5.79–5.93 m
(2H, ОСН2CH2СН=СН2), 6.72–7.44 m (32Harom),
7.57–7.75 m (2H, СH=N). Found, %: С 75.01; H 6.61;
Cl 6.21; N 2.46. C70H72Cl2N2O4Ti. Calculated, %:
С 74.79; H 6.46; Cl 6.31; N 2.49.
Bis(2-{[4-(but-3-enyl)oxyphenylimino]methyl}-6-
tert-butylphenoxy)titanium(IV) dichloride (Xa). Yield
90%. IR spectrum, ν, cm–1: 1608 (C=N), 560 (Ti–O),
1
450 (Ti–N). Н NMR spectrum, δ, ppm: 1.40–1.61 m
Bis(2-{[3-(but-3-enyl)oxyphenylimino]methyl}-6-
tert-butylphenoxy)titanium(IV) dichloride (IXa). Yield
93%. IR spectrum, ν, cm–1: 1599 (C=N), 573 (Ti–O),
[18Н, С(СН3)3], 2.41–2.60 m (4H, ОСН2CH2СН=СН2),
3.84–4.07 m (4H, ОСН2CH2СН=СН2), 5.01–
5.22 m (4H, ОСН2CH2СН=СН2), 5.79–5.98 m (2H,
ОСН2CH2СН=СН2), 6.54–7.45 m (14Harom), 7.94–
8.18 m (2H, СH=N). Found, %: С 66.37; H 6.48; Cl 9.34;
N 3.77. C42H48Cl2N2O4Ti. Calculated, %: С 66.06;
H 6.34; Cl 9.29; N 3.67.
1
459 (Ti–N). Н NMR spectrum, δ, ppm: 1.33–1.62 m
[18Н, С(СН3)3], 2.42–2.54 m (4H, ОСН2CH2СН=СН2),
3.62–4.00 m (4H, ОСН2CH2СН=СН2), 5.08–
5.21 m (4H, ОСН2CH2СН=СН2), 5.76–5.97 m (2H,
ОСН2CH2СН=СН2), 6.57–7.64 m (14Harom), 7.97–
8.12 m (2H, СH=N). Found, %: С 65.81; H 6.38; Cl 9.36;
N 3.49. C42H48Cl2N2O4Ti. Calculated, %: С 66.06;
H 6.34; Cl 9.29; N 3.67.
Bis(2-{[4-(but-3-enyl)oxyphenylimino]methyl}-4,6-
di-tert-butylphenoxy)titanium(IV) dichloride (Xb).
Yield 95%. IR spectrum, ν, cm–1: 1609 (C=N), 572 (Ti–
O), 473 (Ti–N). 1Н NMR spectrum, δ, ppm: 1.27–1.63 m
[36Н, С(СН3)3], 2.41–2.60 m (4H, ОСН2CH2СН=СН2),
3.81–4.07 m (4H, ОСН2CH2СН=СН2), 5.09–5.23 m
(4H, ОСН2CH2СН=СН2), 5.78–5.98 m (2H,
ОСН2CH2СН=СН2), 6.52–7.80 m (12Harom), 7.94–
8.19 m (2H, СH=N). Found, %: С 68.45; H 7.54; Cl 7.91;
N 3.11. C50H64Cl2N2O4Ti. Calculated, %: С 68.57;
H 7.37; Cl 8.10; N 3.20.
Bis (2-{[3-(but-3-enyl)oxyphenylimino]methyl}-4,6-
di-tert-butylphenoxy)titanium(IV) dichloride (IXb).
Yield 88%. IR spectrum, ν, cm–1: 1599 (C=N), 573 (Ti–
O), 476 (Ti–N). 1Н NMR spectrum, δ, ppm: 1.33–1.48 m
[36Н, С(СН3)3], 2.47–2.60 m (4H, ОСН2CH2СН=СН2),
3.96–4.09 m (4H, ОСН2CH2СН=СН2), 5.07–5.22 m
(4H, ОСН2CH2СН=СН2), 5.81–5.98 m (2H,
ОСН2CH2СН=СН2), 6.83–7.46 m (12Harom), 7.60–
7.71 m (2H, СH=N). Found, %: С 68.76; H 7.47; Cl 7.96;
N 3.08. C50H64Cl2N2O4Ti. Calculated, %: С 68.57;
H 7.37; Cl 8.10; N 3.20.
Bis[2-{[4-(but-3-enyl)oxyphenylimino]methyl}-
6-(2-phenylpropan-2-yl)phenoxy]titanium(IV)
dichloride (Xc). Yield 94%. IR spectrum, ν, cm–1: 1609
1
(C=N), 558 (Ti–O), 442 (Ti–N). Н NMR spectrum, δ,
Bis[2-{[3-(but-3-enyl)oxyphenylimino]methyl}-
6-(2-phenylpropan-2-yl)phenoxy]titanium(IV) di-
chloride (IXc). Yield 93%. IR spectrum, ν, cm–1: 1598
ppm: 1.75–1.79 m [12Н, С(СН3)2], 2.51–2.59 m (4H,
ОСН2CH2СН=СН2),3.94–4.03m(4H,ОСН2CH2СН=СН2),
5.11–5.22 m (4H, ОСН2CH2СН=СН2), 5.83–5.97 m
(2H, ОСН2CH2СН=СН2), 6.79–7.56 m (24Harom),
7.70–7.75 m (2H, СH=N). Found, %: С 70.36; H 5.86;
Cl 7.89; N 3.11. C52H52Cl2N2O4Ti. Calculated, %:
С 70.35; H 5.90; Cl 7.99; N 3.16.
1
(C=N), 541 (Ti–O), 468 (Ti–N). Н NMR spectrum, δ,
ppm: 1.66–1.81 m [12Н, С(СН3)2], 2.47–2.59 m (4H,
ОСН2CH2СН=СН2),3.88–4.07m(4H,ОСН2CH2СН=СН2),
5.09–5.21 m (4H, ОСН2CH2СН=СН2), 5.83–5.95 m
(2H, ОСН2CH2СН=СН2), 6.64–7.58 m (24Harom),
7.70–7.73 m (2H, СH=N). Found, %: С 70.53; H 6.02;
Cl 7.73; N 3.06. C52H52Cl2N2O4Ti. Calculated, %:
С 70.35; H 5.90; Cl 7.99; N 3.16.
Bis[2-{[4-(but-3-enyl)oxyphenylimino]methyl}-
4,6-di-(2-phenylpropan-2-yl)phenoxy]titanium(IV)
dichloride (Xd). Yield 87%. IR spectrum, ν, cm–1: 1609
1
(C=N), 558 (Ti–O), 466 (Ti–N). Н NMR spectrum, δ,
Bis[2-{[3-(but-3-enyl)oxyphenylimino]methyl}-
4,6-di-(2-phenylpropan-2-yl)phenoxy]titanium(IV)
dichloride (IXd). Yield 91%. IR spectrum, ν, cm–1: 1598
ppm: 1.68–1.78 m [24Н, С(СН3)2], 2.48–2.59 m (4H,
ОСН2CH2СН=СН2),3.97–4.05m(4H,ОСН2CH2СН=СН2),
5.13–5.22 m (4H, ОСН2CH2СН=СН2), 5.87–5.98 m
(2H, ОСН2CH2СН=СН2), 6.90–7.45 m (32Harom),
1
(C=N), 554 (Ti–O), 470 (Ti–N). Н NMR spectrum, δ,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 8 2013

OLEINIK et al.
1156
4. Ivancheva, N.I., Malinskaya, M.Yu., Ivanchev, S.S., Ole-
inik, I.I., Kochnev, A.I., and Tolstikov, G.A., Kinetika i
kataliz, 2007, vol. 48, p. 887; Malinskaya, M.Yu., Ivanche-
va, N.I., Oleinik, I.I., Tolstikov, G.A., and Ivanchev, S.S., Zh.
Prikl. Khim., 2007, vol. 80, p. 1479;Vasil’eva, M.Yu., Fedo-
rov, S.P., Nikolaev, D.A., Oleinik, I.I., and Ivanchev, S.S.,
Vysokomol. Soedin., 2010, vol. 52, p. 1483.
5. Gagieva, S.Ch., Sukhova, T.A., Savinov, D.V., Optov, V.A.,
Bravaya, N.M., Belokon’, Yu.N., and Bulychev, B.M., Izv.
Akad. Nauk, Ser. Khim., 2003, p. 1605; Clarkson, G.J.,
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.
7.60–7.72 m (2H, СH=N). Found, %: С 74.73; H 6.57;
Cl 6.21; N 2.49. C70H72Cl2N2O4Ti. Calculated, %:
С 74.79; H 6.46; Cl 6.31; N 2.49.
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