Design of postmetallocene catalytic systems of arylimine type for olefin polymerization: XVI. Synthesis of (N-aryl)salicylaldimines containing pent-4-enyloxy group and their complexes with titanium(IV) dichloride

Article abstract of DOI:10.1134/S1070428014020092

Reactions of p-(pent-4-enyloxy)aniline with salicylaldehyde containing versatile substituents in the positions 3 and 5 in an open system without solvent at 130°C afforded a series of (N-aryl)salicylaldimines, which with TiCl₂(OPr-i)₂ formed complexes of titanium(IV) dichloride L₂TiCl₂.

Full text of DOI:10.1134/S1070428014020092

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No.2, pp. 191−199. © Pleiades Publishing, Ltd., 2014.
Original English Text © I.I. Oleinik, I.V. Oleinik, D.E. Zaitsev, S.S. Ivanchev, G.A. Tolstikov, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50,
No. 2, pp. 201−208.
Design of Postmetallocene Catalytic Systems
of Arylimine Type for Olefin Polymerization: XVI.*
Synthesis of (N-Aryl)salicylaldimines Containing
Pent-4-enyloxy Group and Their Complexes
with Titanium(IV) Dichloride
I. I. Oleinika, I. V. Oleinika, D. E. Zaitseva, S. S. Ivanchevb, and G. A. Tolstikova†
aVorozhtsov Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences,
Novosibirsk, 630090 Russia
b St. Petersburg Branch of Boreskov Institute of Catalysis,
Siberian Branch, Russian Academy of Sciences, St. Petersburg, Russia
е-mail: oleynik@nioch.nsc.ru
Received July 31, 2013
Abstract—Reactions of p-(pent-4-enyloxy)aniline with salicylaldehyde containing versatile substituents in the
positions 3 and 5 in an open system without solvent at 130°С afforded a series of (N-aryl)salicylaldimines, which
with TiCl2(OPr-i)2 formed complexes of titanium(IV) dichloride L2TiCl2.
DOI: 10.1134/S1070428014020092
In the context of systematic research on kinetic
features of ethylene polymerization on methylalumox-
ane-activated (N-aryl)salicylaldimine complexes of
titanium(IV) dichloride containing ω-alkenyloxy groups
the catalytic system was shown to be able to produce an
ultrahigh molecular weight polyethylene and improved
morphology of particles [2]. Depending on the number of
the methylene units in the ω-alkenyloxy group and on its
location in the aryl substituent of the ligand the activity of
the catalytic systems underlain by the studied complexes
and the molecular weight of the obtained polyethylene
notably varied. The dependence of the activity of catalytic
system and of the polyethylene molecular weight on the
temperature and the duration of polymetization has dif-
ferent characteristics at the variation of substituents in
the salicylidene fragment of the ligand. In certain events
the polyethylene molecular weight does not attain the
ultrahigh values indicating the distortion of the “liv-
ing” polymerization mechanism. The establishing of the
laws of appearance and disappearance in the complex
polyethylene of ultrahigh molecular weight requires
experimental data with wider variation of substituents
in the salicylidene fragment of ligand. In this article we
describe the synthesis of (N-aryl)salicylaldimine ligands
and complexes of titanium(IV) dichloride containing
p-(pent-4-enyloxy)phenylimino group with 17 kinds
of substituents combinations. The synthesis of (N-aryl)
salicylaldimines was performed by various procedures
depending on the reactivity of the substituted salicyl-
aldehyde and aniline: by heating initial aldehydes and
amines in alcohol (methanol or ethanol) in the presence
of catalytic quantity of acids (НСООН, p-toluenesulfonic
acid) and dehydrating agents (СаSO4, Na2SO4), by boiling
in an inert solvent (benzene, toluene) removing water by
azeotropic distillation, or at microwave heating without
solvent in a closed system [3].
Investigating the optimization of the synthesis con-
ditions of the (N-aryl)salicylaldimines containing an
ω-alkenyloxy group aiming at the simplest procedure and
the highest yields of Schiff bases we established that the
condensation of salicylaldehyde (Iа) and its substituted
derivatives Ib–Iq with equimolar amount of 4-(pent-
4-enyloxy)aniline at maintaining the melt of the initial
of the capability to produce at the polymerization the
_______________
* For Communication XV, see [1].
† Deceased.
191

OLEINIK et al.
192
R2
R2
R1
R2
NH2
O
O
N
N
TiCl2
O
i)
TiCl (OPr- )2
2
130°C
2
R1
O
R1
OH
O
N
OH O
R1
O
_
Iа–Iq
Ià Iq
R2
IIIа–IIIq
IIIà IIIq
IIа–_IIq
_
IIà IIq
R1 = R2 = H (a); R1 = t-Bu, R2 = H (b), Me (c), t-Bu (d), Cl (e), Br (f); R1 = CMe2(Ph), R2 = H (g), Me (h), t-Bu (i),
CMe2(Ph) (j), Cl (k), Br (l); R1 = CHMe(Ph), R2 = H (m), Me (n), t-Bu (o), Cl (p), Br (q).
compounds in an open system at 130°С occurred practi-
cally quantitatively furnishing imines IIа–IIq.
perature complexes of titanium(IV) dichloride IIIа–IIIq
formed in 90–97% yields.
The structure of imines IIа–IIq was established based
on combination of analytic and spectral data. Н NMR
The composition of the complexes of titanium(IV)
dichloride IIIа–IIIq was confirmed by the combina-
tion of analytic and spectral data. The IR spectra of the
complexes contain absorption bands at 442–476 (Ti–N),
557–584(Ti–O), 1595–1611 cm–1 (N=CH). The complex
formation results in decrease in the ν(N=CH) frequency.
1
spectra suggest that the obtained Schiff bases are indi-
vidual Е-isomers. In the 1Н NMR spectra of compounds
IIа–IIq along with the signals of the aromatic protons
and signals from the substituents in the aromatic frag-
ments singlets are observed of the protons of N=CH
groups in the region 8.46–8.61 ppm and singlet of OH
group protons in the region 13.08–14.09 ppm. Pent-4-
enyloxy group of imine IIа–IIq appears as a character-
istic set of signals: The protons of fragment ОСН2 give
rise to a triplet in the region 3.94–4.00 ppm, the protons
of ОСН2СН2СН2СН=СН2 are observed as a triplet
of triplets in the region 1.87–1.93 ppm, and protons
of ОСН2СН2СН2СН=СН2, as a triplet of doublets at
2.24–2.28 ppm; the terminal protons appear in the region
4.99–5.10 ppm as two closely located doublets of dou-
blets of triplets with the corresponding vicinal coupling
constants (Jcis 10.0–10.3, Jtrans17.0–17.3 Hz), the proton
ОСН2СН2СН2СН=СН2 gives rise toa doublet of doublets
of triplets at 5.83–5.89 ppm.
1
In the Н NMR spectra of complexes IIIа–IIIq along
with the signals of the aromatic protons, of protons of the
pent-4-enyloxy group, and signals from the substituents
in the aromatic fragments the proton signals are observed
from the НС=N groups of stereoisomeric forms [5] in the
region 7.69–8.04 ppm; the singlets of OH group observed
in the spectra of intial imines IIа–IIq are absent.
4-(Pent-4-enyloxy)aniline was synthesized along
a protocol involving the alkenylation of p-nitrophenol
followed by the reduction of the nitro group. Aldehydes
Ib–Id, Ig–Ij, Im–Io were prepared by formylation of
the corresponding phenols with paraformaldehyde in
acetonitrile in the presence of anhydrous magnesium
chloride and triethylamine analogously to the method
[6]. 5-Chloro- and 5-bromo-substituted salicylaldehyde
Ie, Ik, Ip and If, Il, Iq were obtained by halogenation of
aldehydes Ib, Ig, Im with sulfuryl chloride in the presence
ofAlCl3 and Ph2S in chloroform or with bromine in acetic
acid in the presence of sodium acetate [7, 8] respectively.
The IR spectra of compounds IIа–IIq contain a strong
absorption band in the region 1612–1622 cm–1 corre-
sponding to the stretching vibrations of the C=N bond of
the imine moiety. In the mass spectra of imines IIа–IIq
a strong peak of the molecular ion is present.
EXPERIMENTAL
Complexes were synthesized by a one-stage meth-
od consisting in the reaction of imines IIа–IIq with
TiCl2(OPr-i)2 [1, 4, 5].At the treatment with TiCl2(OPr-i)2
the toluene solution of imines IIа–IIq at room tem-
1Н NMR spectra were registered on a spectrometer
Bruker АV-400 at operating frequency 400.13 MHz
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DESIGN OF POSTMETALLOCENE CATALYTIC SYSTEMS..: XVI.
193
from solutions in CDCl3. IR spectra were recorded on
a spectrophotometer Vector 22 from pellets in KBr for
crystalline samples, from neat oily compounds. The reac-
tion progress was monitored and the purity of compounds
synthesized was checked by TLC on Silufol UV-254
plates, eluent chloroform. Elemental analysis was car-
ried out on a CHNS-analyzer Euro EA 3000. Empirical
formulas of compounds obtained were calculated from
high resolution mass spectra registered on a spectrometer
DFS Thermo Electron Corporation. Melting points were
measured in capillaries on an instrument Mettler Toledo
FP90 heating at a rate 1 deg/min.
NH2), 3.87 t (2H, ОСН2СН2СН2СН=СН2, J 6.8 Hz),
4.97 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 10.2, 1.4,
1.2 Hz), 5.09 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 17.0,
1.7, 1.4 Hz), 5.84 d.d.t (1H, ОСН2СН2СН2СН=СН2,
J 17.0, 10.2, 6.8 Hz), 6.59 d (2Harom, J 8.8 Hz), 6.70 d
(2Harom, J 8.8 Hz). Found [M]+ 177.1159. C11H15NO.
Calculated M 177.1154.
Aldehydes Ib–Id, Ig–Ij, Im–Io. A mixture of
0.05 mol of an appropriate 2- or 2,4-substituted phenol,
100 mL of anhydrous acetonitrile, 9.52 g (0.1 mol) of
anhydrous magnesium dichloride, 21 mL (0.15 mol) of
triethylamine, and 6.00 g (0.2 mol) of paraformaldehyde
was heated for 1–4 h at 90°С under argon while stirring
till the consumption of the initial phenol (TLC monitor-
ing). To the cooled mixture 120 mL of 5% HCl solution
was added, the product was extracted with chloroform
(3×30 mL), the extract was dried with MgSO4, the sol-
vents were distilled off, the residue was recrystallized
from methanol.
4-(Pent-4-enyloxy)aniline. A mixture of 9.20 g
(66 mmol) of p-nitrophenol, 40 mLof acetone, and 9.14 g
(66 mmol) of anhydrous potassium carbonate was stirred
for 1 h, to the slurry was added 2 mLof DMF, 10– 20 mg of
potassium iodide, and 10.85 g (73 mmol) of 5-bromopent-
1-ene. The mixture was boiled for 27 h. The precipitate
was filtered off, washed with acetone (3 × 10 mL). The
filtrates were combined, the solvent was distilled off, the
residue was dissolved in 30 mLof tert-butyl methyl ether,
the solution was washed with 10% NaOH solution (3 ×
25 mL) and water (2 × 20 mL), and dried with magnesium
sulfate. On distilling off the solvent we obtained 13.65 g
(99%) of 4-(pent-4-enyloxy)nitrobenzene. 1Н NMR spec-
trum, δ, ppm: 1.89 t.t (2H, ОСН2СН2СН2СН=СН2, J 7.1,
6.8 Hz), 2.23 t.d (2Н, ОСН2СН2СН2СН=СН2, J 7.1,
6.8 Hz), 4.04 t (2Н, ОСН2СН2СН2СН=СН2, J 6.8 Hz),
4.99 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 10.3, 1.4,
The spectral and analytic characteristics of aldehydes
Ib–Id, Ig–Ij, Im–Io were in agreement with the published
data [9].
Aldehydes Ie, Ik, Ip. To a solution of 20 mmol of
an appropriate 3-substituted salicylaldehyde Ib, Ig, Im
in 15 mL of chloroform was added at stirring 2.85 g
(21 mmol) of sulfuryl chloride, 0.1 mL of diphenyl
sulfide, and 10 mg of anhydrous aluminum chloride,
the mixture was heated for 3–4 h at 50°С till complete
consumption of the initial aldehyde (TLC monitoring).
The reaction mixture was washed with water (3 × 20 mL)
and dried with magnesium sulfate. On distilling off the
solvent the residue was recrystallized from methanol.
1.3 Hz), 5.07 d.d.t (1H, ОСН2СН2СН2СН=СН2,
J 17.1,
1.6, 1.4 Hz), 5.80 d.d.t (1Н, ОСН2СН2СН2СН=СН2,
J 17.1, 10.3, 6.8 Hz), 6.91 d (2Harom, J 9.1 Hz), 8.16 d
(2Harom, J 9.1 Hz). Found [M]+ 207.0889. C11H13NO3.
Calculated M 207.0895.
3-tert-Butyl-2-hydroxy-5-chlorobenzaldehyde (Ie).
Yield 94%, mp 62°С. IR spectrum, ν, cm–1: 1656 (С=О).
1Н NMR spectrum, δ, ppm: 1.36 s [9H, С(СН3)3], 7.35 d
(1Harom, J 2.6 Hz), 7.43 d (1Harom, J 2.6 Hz), 9.80 s
(1Н, CН=O), 11.71 s (1H, OH). Found [M]+ 212.0609.
C11H13ClO2. Calculated M 212.0604.
To a solution of 39.00 g (173 mmol) of SnCl2·2H2O in
45 mL of ethanol under an argon atmosphere was added
at stirring a solution of 7.16 g (35 mmol) of 4-(pent-4-
enyloxy)nitrobenzene in 30 mL of ethanol, the mixture
was boiled for 2 h and on cooling it was poured into
100 mL of water, 150 mL of saturated solution of so-
dium carbonate was added, the reaction products were
extracted with tert-butyl methyl ether (4 × 20 mL), the
extract was dried with sodium sulfate. On distilling off
the solvent the residue was distilled in a vacuum to obtain
4.24 g (69%) of 4-(pent-4-enyloxy)aniline, bp 88–93°С
(1 mm Hg). 1Н NMR spectrum, δ, ppm: 1.83 t.t (2H,
ОСН2СН2СН2СН=СН2, J 7.0, 6.8 Hz), 2.21 t.d (2H,
ОСН2СН2СН2СН=СН2, J 7.0, 6.8 Hz), 3.27 br.s (2H,
2-Hydroxy-3-(2-phenylpropan-2-yl)-5-chloroben-
zaldehyde (Ik). Yield 91%, mp 45°С. IR spectrum, ν,
1
cm–1: 1654 (С=О). Н NMR spectrum, δ, ppm: 1.73 s
[6H, С(СН3)2], 7.14–7.27 m (5Harom), 7.42 d (1Harom
,
J 2.6 Hz), 7.63 d (1Harom, J 2.6 Hz), 9.76 s (1H, CH=O),
11.26 s (1H, OH). Found [M]+ 274.0759. C16H15ClO2.
Calculated M 274.0761.
2-Hydroxy-3-(1-phenylethyl)-5-chlorobenzalde-
hyde (Ip). Yield 90%, mp 37°С. IR spectrum, ν, cm–1:
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OLEINIK et al.
194
1
2-{[4-(Pent-4-enyloxy)phenylimino]methyl}phe-
1660 (С=О). Н NMR spectrum, δ, ppm: 1.63 d (3H,
СНCH3, J 7.3 Hz), 4.61 q (1H, СНСН3, J 7.3 Hz), 7.19–
nol (IIа). Yield 90%, mp 50°С. IR spectrum, ν, cm–1:
1
1622 (С=N). Н NMR spectrum, δ, ppm: 1.92 t.t (2H,
7.34 m (5Harom), 7.36 d (1Harom, J 2.7 Hz), 7.38 d (1Harom
,
ОСН2СН2СН2СН=СН2, J 7.1, 6.7 Hz), 2.28 t.d (2Н,
ОСН2СН2СН2СН=СН2, J 7.1, 6.8 Hz), 4.00 t (2H,
ОСН2СН2СН2СН=СН2, J 6.7 Hz), 5.04 d.d.t (1H,
ОСН2СН2СН2СН=СН2, J 10.3, 1.4, 1.3 Hz), 5.10 d.d.t
(1H, ОСН2СН2СН2СН=СН2, J 17.1, 1.7, 1.4 Hz),
5.89 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 17.1, 10.3,
6.8 Hz), 6.91–7.05 m (4Нarom), 7.26 d (2Harom, J 8.7 Hz),
7.32–7.39 m (2Harom), 8.59 s (1H, СH=N), 13.47 br.s
(1H, OH). Found [M]+ 281.1409. C18H19NO2. Calculated
M 281.1416.
J 2.7 Hz), 9.81 s (1Н, CH=O), 11.32 s (1H, OH). Found
[M]+ 260.0598. C15H13ClO2. Calculated M 260.0604.
Aldehydes If, Il, Iq. To a mixture of 32 mmol of an ap-
propriate 3-substituted salicylaldehyde Ib, Ig, Im, 45 mL
of glacial acetic acid, and 2.90 g (35 mmol) of molten
sodium acetate was added dropwise 5.65 g (35 mmol) of
bromine in 45 mLof acetic acid, and the reaction mixture
was stirred for 3–5 h till the consumption of the intial
aldehyde (TLC monitoring). The reaction mixture was
poured into 150 mL of water, the reaction product was
extracted with chloroform (3 × 15 mL). The combined
extracts were washed with water (3 × 20 mL), and dried
with MgSO4, the solvent was distilled off, the residue
was recrystallized from methanol.
2-tert-Butyl-6-{[4-(pent-4-enyloxy)phenylimino]-
methyl}phenol (IIb). Yield 98%, mp 52°С. IR spectrum,
ν, cm–1: 1612 (С=N). 1Н NMR spectrum, δ, ppm: 1.49 s
[9H, С(СН3)3], 1.90 t.t (2H, ОСН2СН2СН2СН=СН2, J 7.1,
6.8 Hz), 2.25 t.d (2Н, ОСН2СН2СН2СН=СН2, J 7.1,
6.8 Hz), 3.98 t (2H, ОСН2СН2СН2СН=СН2, J 6.8 Hz),
5.01 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 10.3, 1.4,
5-Bromo-3-tert-butyl-2-hydroxybenzaldehyde (If).
Yield 83%, mp 66°С. IR spectrum, ν, cm–1: 1660 (С=О).
1Н NMR spectrum, δ, ppm: 1.39 s [9H, С(СН3)3], 7.49 d
(1Harom, J 2.5 Hz), 7.55 d (1Harom, J 2.5 Hz), 9.80 s (1Н,
CH=O), 11.72 s (1H, OH). Found [M]+ 256.0093.
C11H13BrO2. Calculated M 256.0099.
1.3 Hz), 5.07 d.d.t (1H, ОСН2СН2СН2СН=СН2,
J 17.1,
1.6, 1.4 Hz), 5.84 d.d.t (1H, ОСН2СН2СН2СН=СН2,
J 17.1, 10.3, 6.8 Hz), 6.85 t (1Harom, J 7.7 Hz),
6.90–7.28 m (4Нarom), 7.22 d.d (1Harom, J 7.7, 1.5 Hz),
7.36 d.d(1Harom, J 7.7, 1.5 Hz), 8.61 s (1H, СH=N),
14.02 br.s (1H, OH). Found [M]+ 337.2041. C22H27NO2.
Calculated M 337.2036.
5-Bromo-2-hydroxy-3-(2-phenylpropan-2-yl)
benzaldehyde (Il). Yield 74%, mp 82°С. IR spectrum,
ν, cm–1: 1649 (С=О). 1Н NMR spectrum, δ, ppm: 1.71 s
[6H, С(СН3)2], 7.10–7.27 m (5Harom), 7.55 d (1Harom
,
2-tert-Butyl-4-methyl-6-{[4-(pent-4-enyloxy)phe-
nylimino]methyl}phenol (IIc). Yield 95%, mp 83°С.
J 2.4 Hz), 7.77 d (1Harom, J 2.4 Hz), 9.75 s (1Н, CH=O),
11.26 s (1H, OH). Found [M]+ 318.0254. C16H15BrO2.
Calculated M 318.0255.
1
IR spectrum, ν, cm–1: 1616 (С=N). Н NMR spec-
trum, δ, ppm: 1.46 s [9H, С(СН3)3], 1.88 t.t (2H,
ОСН2СН2СН2СН=СН2, J 7.1, 6.7 Hz), 2.25 t.d (2Н,
ОСН2СН2СН2СН=СН2, J 7.1, 6.7 Hz), 2.30 s (3H, СН3),
3.98 t (2H, ОСН2СН2СН2СН=СН2, J 6.7 Hz), 5.01 d.d.t
(1H, ОСН2СН2СН2СН=СН2, J 10.3, 1.4, 1.3Hz),
5.07 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 17.0, 1.7,
1.4 Hz), 5.85 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 17.0,
5-Bromo-2-hydroxy-3-(1-phenylethyl)benzalde-
hyde (Iq). Yield 70%, mp 41°С. IR spectrum, ν, cm–1:
1
1659 (С=О). Н NMR spectrum, δ, ppm: 1.61 d (3H,
СНCH3, J 7.1 Hz), 4.59 q (1H, СНСН3, J 7.1 Hz), 7.14–
7.34 m (5Harom), 7.46 d (1Harom, J 2.3 Hz), 7.50 d (1Harom
,
J 2.3 Hz), 9.79 s (1Н, CH=O), 11.31 s (1H, OH). Found
[M]+ 304.0090. C15H13BrO2. Calculated M 304.0099.
10.3, 6.7 Hz), 6.91 d (2Нarom, J 8.0 Hz), 6.99 d (1Harom
J 1.5 Hz), 7.14 d (1Harom, J 1.5 Hz), 7.23 d (2Нarom
,
,
(N-Aryl)salicylaldimines IIа–IIq. To a melt of
3 mmol of aldehyde Iа–Iq heated to 130°С was added at
stirring 532 mg (3 mmol) of 4-(pent-4-enyloxy)aniline,
and the mixture was stirred for 1 h. On cooling to room
temperature the product was purified by flash chromatog-
raphy on silica gel, eluent CHCl3–hexane, 1 : 2, collecting
the first bright-yellow fraction The solvents were distilled
off, the product crystallized by triturating with 5 mL of
methanol, the crystals were filtered off, washed with 3 mL
of methanol, and dried in a vacuum-desiccator.
J 8.0 Hz), 8.54 s (1H, СH=N), 13.77 s (1H, OH). Found
[M]+ 351.2188. C23H29NO2. Calculated M 351.2193.
2,4-Di-tert-butyl-6-{[4-(pent-4-enyloxy)pheny-
limino]methyl}phenol (IId). Yield 97%, mp 66°С. IR
1
spectrum, ν, cm–1: 1618 (С=N). Н NMR spectrum,
δ, ppm: 1.33 с [9Н, С(СН3)3], 1.47 s [9Н, С(СН3)3],
1.90 t.t (2H, ОСН2СН2СН2СН=СН2, J 7.0, 6.7 Hz),
2.25 t.d (2Н, ОСН2СН2СН2СН=СН2, J 7.0, 6.7 Hz),
3.98 t (2H, ОСН2СН2СН2СН=СН2, J 6.7 Hz), 5.02 d.d.t
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DESIGN OF POSTMETALLOCENE CATALYTIC SYSTEMS..: XVI.
195
13.55 s (1H, OH). Found [M]+ 399.2195. C27H29NO2.
Calculated M 399.2193.
(1H, ОСН2СН2СН2СН=СН2, J 10.2, 1.4, 1.3 Hz),
5.07 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 17.0, 1.6,
1.4 Hz), 5.86 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 17.0,
4-Methyl-2-{[4-(pent-4-enyloxy)phenylimino]-
methyl}-6-(2-phenylpropan-2-yl)phenol (IIh). Yield
96%, mp 75°С. IR spectrum, ν, cm–1: 1618 (С=N).
1Н NMR spectrum, δ, ppm: 1.79 s [6H, С(СН3)2], 1.91 t.t
(2H, ОСН2СН2СН2СН=СН2, J 7.1, 6.8 Hz), 2.27 t.d
(2H, ОСН2СН2СН2СН=СН2, J 7.1, 6.7 Hz), 2.40 с (3H,
СН3), 3.97 t (2H, ОСН2СН2СН2СН=СН2, J 6.8 Hz),
5.03 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 10.2, 1.4,
1.3 Hz), 5.09 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 17.2,
1.6, 1.4 Hz), 5.86 d.d.t (1Н, ОСН2СН2СН2СН=СН2,
J 17.2, 10.2, 6.7 Hz), 6.85–6.89 m (2Harom), 7.08 d
(1Harom, J 1.9 Hz), 7.13–7.18 m (3Harom), 7.26–7.29 m
(4Harom), 7.35 d (1Harom, J 2.1 Hz), 8.50 s (1H, СH=N),
13.29 s (1H, OH). Found [M]+ 413.2347. C28H31NO2.
Calculated M 413.2349.
10.2, 6.7 Hz), 6.90 d (2Harom, J 8.0 Hz), 7.17 d (1Harom
J 2.0 Hz), 7.27 d (2Harom, J 8.0 Hz), 7.40 d (1Harom
,
,
J 2.0 Hz), 8.60 s (1Н, СH=N), 13.77 s (1Н, OH). Found
[M]+ 393.2657. C26H35NO2. Calculated M 393.2662.
2-tert-Butyl-6-{[4-(pent-4-enyloxy)phenylimino]
methyl}-4-chlorophenol (IIe). Yield 98%, mp 76°С.
1
IR spectrum, ν, cm–1: 1617 (С=N). Н NMR spec-
trum, δ, ppm: 1.46 s [9H, С(СН3)3], 1.93 t.t (2H,
ОСН2СН2СН2СН=СН2, J 7.0, 6.6 Hz), 2.28 t.d (2H,
ОСН2СН2СН2СН=СН2, J 7.0, 6.7 Hz), 4.00 t (2H,
ОСН2СН2СН2СН=СН2, J 6.6 Hz), 5.02 d.d.t (1H,
ОСН2СН2СН2СН=СН2, J 10.2, 1.4, 1.2 Hz), 5.08 d.d.t
(1H, ОСН2СН2СН2СН=СН2, J 17.0, 1.6, 1.4 Hz),
5.83 d.d.t (1Н, ОСН2СН2СН2СН=СН2, J 17.0, 10.2,
4-tert-Butyl-2-{[4-(pent-4-enyloxy)phenylimino]-
methyl}-6-(2-phenylpropan-2-yl)phenol (IIi). Yield
92%, mp 119°С. IR spectrum, ν, cm–1: 1614 (С=N).
1Н NMR spectrum, δ, ppm: 1.38 s [9H, С(СН3)3], 1.78 s
[6H, С(СН3)2], 1.88 t.t (2H, ОСН2СН2СН2СН=СН2,
J 7.1, 6.8 Hz), 2.24 t.d (2H, ОСН2СН2СН2СН=СН2, J 7.1,
6.8 Hz), 3.96 t (2H, ОСН2СН2СН2СН=СН2, J 6.8 Hz),
4.99 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 10.3, 1.4,
1.3 Hz), 5.06 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 17.3,
1.7, 1.4 Hz), 5.84 d.d.t (1Н, ОСН2СН2СН2СН=СН2,
J 17.3, 10.3, 6.8 Hz), 6.81–6.88 m (2Harom), 7.11–7.18 m
(3Harom), 7.22–7.27 m (5Harom), 7.56 d (1Harom, J 2.3 Hz),
8.55 s (1H, СH=N), 13.30 s (1H, OH). Found [M]+
455.2818. C31H37NO2. Calculated M 455.2819.
6.7 Hz), 6.93 d (2Harom, J 8.0 Hz), 7.19 d (1Harom
J 2.4 Hz), 7.26 d (2Harom, J 8.0 Hz), 7.28 d (1Harom
J 2.4 Hz), 8.53 s (1H, СH=N), 14.05 s (1H, OH). Found
[M]+ 371.1643. C22H26ClNO2. Calculated M 371.1647.
,
,
4-Bromo-2-tert-butyl-6-{[4-(pent-4-enyloxy)phe-
nylimino]methyl}phenol (IIf). Yield 95%, mp 84°С.
1
IR spectrum, ν, cm–1: 1617 (С=N). Н NMR spec-
trum, δ, ppm: 1.45 s [9H, С(СН3)3], 1.90 t.t (2H,
ОСН2СН2СН2СН=СН2, J 7.0, 6.8 Hz), 2.27 t.d (2H,
ОСН2СН2СН2СН=СН2, J 7.0, 6.7 Hz), 4.00 t (2H,
ОСН2СН2СН2СН=СН2, J 6.8 Hz), 5.02 d.d.t (1H,
ОСН2СН2СН2СН=СН2, J 10.2, 1.4, 1.3 Hz), 5.08 d.d.t
(1H, ОСН2СН2СН2СН=СН2, J 17.0, 1.7, 1.4 Hz),
5.85 d.d.t (1Н, ОСН2СН2СН2СН=СН2, J 17.0, 10.2,
6.7 Hz), 6.93 d (2Harom, J 8.0 Hz), 7.26 d (2Harom
J 8.0 Hz), 7.34 d (1Harom, J 2.4 Hz), 7.40 d (1Harom
J 2.4 Hz), 8.53 s (1H, СH=N), 14.09 s (1H, OH). Found
[M]+ 415.1138. C22H26BrNO2. Calculated M 415.1141.
4,6-Di(2-phenylpropan-2-yl)-2-{[4-(pent-4-eny-
loxy)phenylimino]methyl}phenol (IIj). Yield 98%,
mp 93°С. IR spectrum, ν, cm–1: 1616 (С=N). 1Н NMR
spectrum, δ, ppm: 1.70 s [6Н, С(СН3)2], 1.73 s [6Н,
С(СН3)2], 1.87 t.t (2H, ОСН2СН2СН2СН=СН2, J 7.1,
6.8 Hz), 2.24 t.d (2H, ОСН2СН2СН2СН=СН2, J 7.1,
6.8 Hz), 3.95 t (2H, ОСН2СН2СН2СН=СН2, J 6.8 Hz),
5.00 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 10.3, 1.4,
,
,
2-{[4-(Pent-4-enyloxy)phenylimino]methyl}-6-
(2-phenylpropan-2-yl)phenol (IIg). Yield 98%, mp
1
80°С. IR spectrum, ν, cm–1: 1614 (С=N). Н NMR
spectrum, δ, ppm: 1.79 s [6H, С(СН3)2], 1.90 t.t (2H,
ОСН2СН2СН2СН=СН2, J 7.1, 6.8 Hz), 2.26 t.d (2H,
ОСН2СН2СН2СН=СН2, J 7.1, 6.7 Hz), 3.97 t (2H,
ОСН2СН2СН2СН=СН2, J 6.8 Hz), 5.02 d.d.t (1H,
ОСН2СН2СН2СН=СН2, J 10.2, 1.4, 1.3 Hz), 5.08 d.d.t
(1H, ОСН2СН2СН2СН=СН2, J 17.2, 1.6, 1.4 Hz),
5.85 d.d.t (1Н, ОСН2СН2СН2СН=СН2, J 17.2, 10.2,
6.7 Hz), 6.85–6.96 m (3Harom), 7.15–7.29 m (8Harom),
7.54 d.d(1Harom, J 7.7, 1.2 Hz), 8.55 s (1H, СH=N),
1.3 Hz), 5.06 d.d.t (1H, ОСН2СН2СН2СН=СН2,
J 17.0,
1.7, 1.4 Hz), 5.84 d.d.t (1Н, ОСН2СН2СН2СН=СН2,
J 17.0, 10.3, 6.8 Hz), 6.81–6.85 m (2Harom), 7.09–7.29 m
(13Harom), 7.38 d (1Harom, J 2.2 Hz), 8.48 s (1Н, СH=N),
13.37 s (1H, OH). Found [M]+ 517.2971. C36H39NO2.
Calculated M 517.2975.
2-{[4-(Pent-4-enyloxy)phenylimino]methyl}-6-
(2-phenylpropan-2-yl)-4-chlorophenol (IIk). Yield
98%. Oily substance. IR spectrum, ν, cm–1: 1617 (С=N).
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OLEINIK et al.
196
1Н NMR spectrum, δ, ppm: 1.77 s [6H, С(СН3)2], 1.90 t.t
(2H, ОСН2СН2СН2СН=СН2, J 7.1, 6.7 Hz), 2.26 t.d
(2H, ОСН2СН2СН2СН=СН2, J 7.1, 6.8 Hz), 3.97 t
(2H, ОСН2СН2СН2СН=СН2, J 6.7 Hz), 5.02 d.d.t (1H,
ОСН2СН2СН2СН=СН2, J 10.2, 1.4, 1.3 Hz), 5.07 d.d.t
(1H, ОСН2СН2СН2СН=СН2, J 17.2, 1.7, 1.4 Hz),
5.84 d.d.t (1Н, ОСН2СН2СН2СН=СН2, J 17.2, 10.2,
6.9 Hz), 6.82–6.91 m (2Harom), 6.99 d (1Harom, J 2.3 Hz),
7.01 d (1Harom, J 2.3 Hz), 7.12–7.29 m (7Harom), 8.52 s
(1H, СH=N), 13.47 s (1H, OH). Found [M]+ 399.2190.
C27H29NO2. Calculated M 399.2193.
(1H, ОСН2СН2СН2СН=СН2,
(1Н, ОСН2СН2СН2СН=СН2, J 17.2, 10.2, 6.8 Hz), 6.87 d
(2Harom, J 7.9 Hz), 7.15–7.29 m (8Harom), 7.48 d (1Harom
J 17.2, 1.7, 1.4 Hz), 5.85 d.d.t
4-tert-Butyl-2-{[4-(pent-4-enyloxy)phenylimino]-
methyl}-6-(1-phenylethyl)phenol (IIo). Yield 98%. Oily
substance. IR spectrum, ν, cm–1: 1617 (С=N). 1Н NMR
spectrum, δ, ppm: 1.29 s [9H, С(СН3)3], 1.65 d (3H,
СНCH3, J 7.3 Hz), 1.89 t.t (2H, ОСН2СН2СН2СН=СН2,
J 7.0, 6.7 Hz), 2.24 t.d (2H, ОСН2СН2СН2СН=СН2,
J 7.0, 6.8 Hz), 3.97 t (2H, ОСН2СН2СН2СН=СН2,
J 6.7 Hz), 4.66 q (1H, СНСН3, J 7.3 Hz), 5.00 d.d.t (1H,
ОСН2СН2СН2СН=СН2, J 10.2, 1.4, 1.3 Hz), 5.07 d.d.t
,
J 2.4 Hz), 8.47 s (1H, СH=N), 13.57 s (1H, OH). Found
[M]+ 433.1798. C27H28ClNO2. Calculated M 433.1803.
4-Bromo-2-{[4-(pent-4-enyloxy)phenylimino]-
methyl}-6-(2-phenylpropan-2-yl)phenol (IIl). Yield
96%. Oily substance. IR spectrum, ν, cm–1: 1615 (С=N).
1Н NMR spectrum, δ, ppm: 1.77 s [6H, С(СН3)2],
1.89 t.t (2H, ОСН2СН2СН2СН=СН2, J 7.0, 6.8 Hz),
2.27 t.d (2H, ОСН2СН2СН2СН=СН2, J 7.0, 6.8 Hz),
3.97 t (2H, ОСН2СН2СН2СН=СН2, J 6.8 Hz), 5.02 d.d.t
(1H, ОСН2СН2СН2СН=СН2, J 10.1, 1.4, 1.2 Hz),
5.08 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 17.2, 1.6,
1.4 Hz), 5.86 d.d.t (1Н, ОСН2СН2СН2СН=СН2, J 17.2,
(1H, ОСН2СН2СН2СН=СН2,
J 17.2, 1.7, 1.4 Hz),
5.84 d.d.t (1Н, ОСН2СН2СН2СН=СН2, J 17.2, 10.2,
6.8 Hz), 6.86–6.93 m (2Harom), 7.09–7.33 m (9Harom),
8.58 s (1H, СH=N), 13.48 s (1H, OH). Found [M]+
441.2660. C30H35NO2. Calculated M 441.2662.
10.1, 6.8 Hz), 6.87 d (2Harom, J 7.9 Hz), 7.15 d (2Harom
,
2-{[4-(Pent-4-enyloxy)phenylimino]methyl}-6-
(1-phenylethyl)-4-chlorophenol (IIp). Yield 98%. Oily
substance. IR spectrum, ν, cm–1: 1616 (С=N). 1Н NMR
spectrum, δ, ppm: 1.62 d (3H, СНCH3, J 7.3 Hz), 1.89 t.t
(2H, ОСН2СН2СН2СН=СН2, J 7.0, 6.7 Hz), 2.24 t.d
(2H, ОСН2СН2СН2СН=СН2, J 7.0, 6.8 Hz), 3.97 t (2H,
ОСН2СН2СН2СН=СН2, J 6.7 Hz), 4.63 q (1H, СНСН3,
J 7.3 Hz), 4.96–5.11 m (2H, ОСН2СН2СН2СН=СН2),
5.83 d.d.t (1Н, ОСН2СН2СН2СН=СН2, J 17.1, 10.3,
6.8 Hz), 6.84–6.93 m (2Harom), 7.10–7.30 m (9Harom),
8.48 s (1H, СH=N), 13.69 s (1H, OH). Found [M]+
419.1646. C26H26ClNO2. Calculated M 419.1647.
J 7.9 Hz), 7.17–7.27 m (5Harom), 7.40 d (1Harom, J 2.4 Hz),
7.62 d (1Harom, J 2.4 Hz), 8.46 s (1H, СH=N), 13.61 s (1H,
OH). Found [M]+ 477.1296. C27H28BrNO2. Calculated
M 477.1298.
2-{[4-(Pent-4-enyloxy)phenylimino]methyl}-6-(1-
phenylethyl)phenol (IIm). Yield 96%. Oily substance.
IR spectrum, ν, cm–1: 1616 (С=N). 1Н NMR spectrum,
δ, ppm: 1.66 d (3H, СНCH3, J 7.1 Hz), 1.92 t.t (2H,
ОСН2СН2СН2СН=СН2, J 7.1, 6.7 Hz), 2.28 t.d (2H,
ОСН2СН2СН2СН=СН2, J 7.1, 6.9 Hz), 4.00 t (2H,
ОСН2СН2СН2СН=СН2, J 6.7 Hz), 4.71 q (1H, СНСН3,
J 7.1 Hz), 5.03 d.d.t (1H, ОСН2СН2СН2СН=СН2, J 10.3,
1.4, 1.2 Hz), 5.09 d.d.t (1H, ОСН2СН2СН2СН=СН2,
J17.1,1.7,1.4Hz),5.87d.d.t(1Н,ОСН2СН2СН2СН=СН2,
J 17.1, 10.3, 6.9 Hz), 6.88 t (1Harom, J 7.6 Hz), 6.90–6.95 m
(2Harom), 7.18 t.t (1Harom, J 6.9, 1.9 Hz), 7.21–7.34 m
(8Harom), 8.59 s (1H, СH=N), 13.74 s (1H, OH). Found
[M]+ 385.2038. C26H27NO2. Calculated M 385.2036.
4-Bromo-2-{[4-(pent-4-enyloxy)phenylimino]-
methyl}-6-(1-phenylethyl)phenol (IIq). Yield 98%. Oily
substance. IR spectrum, ν, cm–1: 1615 (С=N). 1Н NMR
spectrum, δ, ppm: 1.64 d (3H, СНCH3, J 7.3 Hz), 1.92 t.t
(2H, ОСН2СН2СН2СН=СН2, J 7.1, 6.8 Hz), 2.26 t.d
(2H, ОСН2СН2СН2СН=СН2, J 7.1, 6.8 Hz), 3.99 t (2H,
ОСН2СН2СН2СН=СН2, J 6.8 Hz), 4.65 q (1H, СНСН3,
J 7.3 Hz), 4.96–5.12 m (2H, ОСН2СН2СН2СН=СН2),
5.87 d.d.t (1Н, ОСН2СН2СН2СН=СН2, J 17.1, 10.3,
6.8 Hz), 6.90–6.94 m (2Harom), 7.17–7.32 m (8Harom),
7.34 d (1Harom, J 2.5 Hz), 8.50 s (1H, СH=N), 13.78 s
(1H, OH). Found [M]+ 463.1143. C26H26BrNO2. Calcu-
lated M 463.1141.
4-Methyl-2-{[4-(pent-4-enyloxy)phenylimino]-
methyl}-6-(1-phenylethyl)phenol (IIn). Yield 96%,
mp 91°С. IR spectrum, ν, cm–1: 1618 (С=N). 1Н NMR
spectrum, δ, ppm: 1.63 d (3H, СНCH3, J 7.3 Hz),
1.87 t.t (2H, ОСН2СН2СН2СН=СН2, J 7.1, 6.8 Hz),
2.23 t.d (2H, ОСН2СН2СН2СН=СН2, J 7.1, 6.9 Hz),
2.28 s (3H, CH3), 3.97 t (2H, ОСН2СН2СН2СН=СН2,
J 6.8 Hz), 4.66 q (1H, СНСН3, J 7.3 Hz), 5.00 d.d.t (1H,
ОСН2СН2СН2СН=СН2, J 10.2, 1.4, 1.3 Hz), 5.07 d.d.t
Titanium(IV) dichloride complexes IIIa–IIIq.
A mixture of 2 mmol of imine IIa–IIq, 10 mL of an-
hydrous dichloromethane, and 6.20 g of a toluene solu-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 2 2014

DESIGN OF POSTMETALLOCENE CATALYTIC SYSTEMS..: XVI.
197
tion containing 0.237 g (1 mmol) of TiCl2(OPr-i)2 was
stirred at room temperature in an argon atmosphere for
24 h. From the formed dark red solution the solvent was
distilled off in a vacuum of a water aspirator pump, the
residue was washed with hexane (2 × 2 mL) on the filter
and dried in a vacuum of an oil pump at 100°С for 1 h.
The corresponding complexes were obtained in the form
of red-brown powders.
8.04 m (2Н, СH=N). Found, %: С 69.04; H 7.64; Cl 7.70;
N 3.15. C52H68Cl2N2O4Ti. Calculated, %: С 69.10;
H 7.58; Cl 7.84; N 3.10.
Bis(2-tert-butyl-6-{[4-(pent-4-enyloxy)phenyl-
imino]methyl}-4-chlorophenoxy)titanium(IV) di-
chloride (IIIe). Yield 96%. IR spectrum, ν, cm–1:
1
1608 (C=N), 571 (Ti–O), 450 (Ti–N). Н NMR
spectrum, δ, ppm: 1.21–1.58 m [18Н, С(СН3)3],
1.79–1.95 m (4Н, ОСН2СН2–СН2СН=СН2),
2.18–2.29 m (4Н, ОСН2СН2СН2СН=СН2), 3.81–
4.02 m (4Н, ОСН2СН2СН2СН=СН2), 4.99–5.12 m
(4Н, ОСН2СН2СН2СН=СН2), 5.79–5.92 m (2Н,
ОСН2СН2СН2СН=СН2), 6.58–7.47 m (12Harom),
7.87–7.98 m (2Н, СH=N). Found, %: С 61.35; H 5.78;
Cl 16.47; N 3.23. C44H50Cl4N2O4Ti. Calculated, %:
С 61.41; H 5.86; Cl 16.48; N 3.26.
Bis(2-{[4-(pent-4-enyloxy)phenylimino]methyl}-
phenoxy)titanium(IV) dichloride (IIIа). Yield 92%.
IR spectrum, ν, cm–1: 1607 (C=N), 571 (Ti–O), 451
(Ti–N). Found, %: С 62.49; H 5.66; Cl 10.36; N 3.22.
C36H36Cl2N2O4Ti. Calculated, %: С 63.64; H 5.34;
Cl 10.44; N 4.12.
Bis(2-tert-butyl-6-{[4-(pent-4-enyloxy)phenylimi-
no]methyl}phenoxy)titanium(IV) dichloride (IIIb).
Yield 95%. IR spectrum, ν, cm–1: 1607 (C=N), 563 (Ti–O),
449 (Ti–N). 1НNMR spectrum, δ, ppm: 1.31–1.61 m [18H,
С(СН3)3], 1.73–1.93 m (4H, ОСН2СН2СН2СН=СН2),
2.13–2.27 m (4Н, ОСН2СН2СН2СН=СН2), 3.76–
3.98 m (4H, ОСН2СН2СН2СН=СН2), 4.99–5.06 m
(4H, ОСН2СН2–СН2СН=СН2), 5.75–5.86 m (2H,
ОСН2СН2СН2СН=СН2), 6.51–7.42 m (14Harom), 7.91–
8.01 m (2H, СH=N). Found, %: С 66.39; H 6.61; Cl 9.00;
N 3.48. C44H52Cl2N2O4Ti. Calculated, %: С 66.75; H 6.62;
Cl 8.96; N 3.54.
Bis(4-bromo-2-tert-butyl-6-{[4-(pent-4-enyloxy)-
phenylimino]methyl}phenoxy)titanium(IV) di-
chloride (IIIf). Yield 93%. IR spectrum, ν, cm–1:
1
1608 (C=N), 570 (T–O), 450 (Ti–N). Н NMR
spectrum, δ, ppm: 1.25–1.66 m [18Н, С(СН3)3],
1.79–1.96 m (4Н, ОСН2СН2СН2СН=СН2),
2.19–2.30 m (4Н, ОСН2СН2–СН2СН=СН2), 3.81–
4.02 m (4Н, ОСН2СН2СН2СН=СН2), 5.00–5.13 m
(4Н, ОСН2СН2СН2СН=СН2), 5.80–5.92 m (2Н,
ОСН2СН2СН2СН=СН2), 6.58–7.52 m (12Harom),
7.69–7.97 m (2Н, СH=N). Found, %: С 55.90; H 5.26;
Br 16.80; Cl 7.25; N 2.95. C44H50Br2Cl2N2O4Ti. Cal-
culated, %: С 55.66; H 5.31; Br 16.83; Cl 7.47; N 2.95.
Bis(2-tert-butyl-4-methyl-6-{[4-(pent-4-enyloxy)-
phenylimino]methyl}phenoxy)titanium(IV) di-
chloride (IIIc). Yield 96%. IR spectrum, ν, cm–1:
1
1608 (C=N), 571 (Ti–O), 450 (Ti–N). Н NMR
Bis[2-{[4-(pent-4-enyloxy)phenylimino]methyl}-
6-(2-phenylpropan-2-yl)phenoxy]titanium(IV)
dichloride (IIIg). Yield 95%. IR spectrum, ν, cm–1:
spectrum, δ, ppm: 1.25–1.61 m [18Н, С(СН3)3],
1.61–1.98 m (4Н, ОСН2СН2СН2СН=СН2), 2.16–
2.42 m (10Н, СН3, ОСН2СН2СН2СН=СН2), 3.76–
4.06 m (4Н, ОСН2СН2СН2СН=СН2), 4.96–5.16 m
(4Н, ОСН2СН2СН2СН=СН2), 5.76–5.95 m (2Н,
ОСН2СН2СН2СН=СН2), 6.56–7.42 m (12Harom), 7.90–
7.97 m (2Н, СH=N). Found, %: С 67.39; H 6.88; Cl 8.73;
N 3.39. C46H56Cl2N2O4Ti. Calculated, %: С 67.40;
H 6.89; Cl 8.65; N 3.42.
1
1609 (C=N), 563 (Ti–O), 443 (Ti–N). Н NMR
spectrum, δ, ppm: 1.42–1.52 m [12Н, С(СН3)2],
1. 81–1. 93 m (4Н, ОСН2СН2СН2СН=СН2),
2.19–2.28 m (4Н, ОСН2СН2СН2СН=СН2), 3.79–
3.99 m (4Н, ОСН2СН2СН2СН=СН2), 4.98–5.11 m
(4Н, ОСН2СН2СН2СН=СН2), 5.80–5.93 m (2Н,
ОСН2СН2СН2СН=СН2), 6.42–7.62 m (24Нarom), 7.82–
7.95 m (2Н, СH=N). Found, %: С 70.93; H 6.12; Cl 7.52;
N 3.11. C54H56Cl2N2O4Ti. Calculated, %: С 70.82;
H 6.16; Cl 7.74; N 3.06.
Bis(2,4-di-tert-butyl-6-{[4-(pent-4-enyloxy)-
phenylimino]methyl}phenoxy)titanium(IV) dichloride
(IIId). Yield 96%. IR spectrum, ν, cm–1: 1609 (C=N), 573
1
(Ti–O), 471 (Ti–N). Н NMR spectrum, δ, ppm: 1.25–
Bis[4-methyl-2-{[4-(pent-4-enyloxy)phenylimi-
no]methyl}-6-(2-phenylpropan-2-yl)phenoxy]-
titanium(IV) dichloride (IIIh). Yield 93%. IR spec-
trum, ν, cm–1: 1610 (C=N), 584 (Ti–O), 445 (Ti–N).
1Н NMR spectrum, δ, ppm: 1.50–1.74 m [12Н, С(СН3)2],
1.78–1.93 m (4H, ОСН2СН2СН2СН=СН2), 2.16–2.27 m
1.64 m [36Н, С(СН3)3], 1.64–1.94 m (4Н, ОСН2СН2–
СН2СН=СН2),2.15–2.27m(4Н,ОСН2СН2СН2СН=СН2),
3.75–4.02 m (4Н, ОСН2СН2СН2СН=СН2), 4.98–5.11 m
(4Н, ОСН2СН2СН2СН=СН2), 5.76–5.93 m (2Н,
ОСН2СН2СН2СН=СН2), 6.51–7.55 m (12Harom), 7.93–
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OLEINIK et al.
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titanium(IV) dichloride (IIIl). Yield 92%. IR spec-
trum, ν, cm–1: 1609 (C=N), 564 (Ti–O), 476 (Ti–N).
1Н NMR spectrum, δ, ppm: 1.48–1.72 m [12Н,
С(СН3)2], 1.79–1.99 m (4Н, ОСН2СН2СН2СН=СН2),
2.13–2.29 m (4Н, ОСН2СН2СН2СН=СН2), 3.81–
4.00 m (4Н, ОСН2СН2СН2СН=СН2), 4.98–5.12 m
(4Н, ОСН2СН2СН2СН=СН2), 5.78–6.03 m (2Н,
ОСН2СН2СН2СН=СН2), 6.44–7.60 m (22Harom),
7.75–7.92 m (2Н, СH=N). Found, %: С 60.21; H 5.03;
Br 14.79; Cl 6.70; N 2.59. C54H54Br2Cl2N2O4Ti. Cal-
culated, %: С 60.41; H 5.07; Br 14.89; Cl 6.60; N 2.61.
(4H, ОСН2СН2СН2СН=СН2), 2.41–2.49 m (6Н, СН3),
3.79–4.00 m (4Н, ОСН2СН2СН2СН=СН2), 4.97–
5.12 m (4Н, ОСН2СН2СН2СН=СН2), 5.79–5.93 m
(2Н, ОСН2СН2СН2СН=СН2), 6.43–7.62 m (22Нarom),
7.77–7.85 m (2Н, СH=N). Found, %: С 71.36; H 6.51;
Cl 7.50; N 2.94. C56H60Cl2N2O4Ti. Calculated, %:
С 71.26; H 6.41; Cl 7.51; N 2.97.
Bis[4-tert-butyl-2-{[4-(pent-4-enyloxy)pheny-
limino]methyl}-6-(2-phenylpropan-2-yl)phenoxy]-
titanium(IV) dichloride (IIIi). Yield 91%. IR spec-
trum, ν, cm–1: 1610 (C=N), 570 (Ti–O), 467 (Ti–N).
1Н NMR spectrum, δ, ppm: 1.32–1.42 m [18Н, С(СН3)3],
1.72–1.93 m [16Н, С(СН3)2, ОСН2СН2СН2СН=СН2],
2.17–2.28 m (4H, ОСН2СН2СН2СН=СН2), 3.79–
4.07 m (4Н, ОСН2СН2СН2СН=СН2), 4.98–5.11 m
(4Н, ОСН2СН2СН2СН=СН2), 5.79–5.92 m (2Н,
ОСН2СН2СН2СН=СН2), 6.48–7.59 m (22Нarom), 7.80–
7.92 m (2Н, СH=N). Found, %: С 72.39; H 7.03; Cl 7.00;
N 2.71. C62H72Cl2N2O4Ti. Calculated, %: С 72.44;
H 7.06; Cl 6.90; N 2.72.
Bis[2-{[4-(pent-4-enyloxy)phenylimino]methyl}-
6-(1-phenylethyl)phenoxy]titanium(IV) dichlo-
ride (IIIm). Yield 91%. IR spectrum, ν, cm–1: 1609
1
(C=N), 557 (Ti–O), 442 (Ti–N). Н NMR spec-
trum, δ, ppm: 1.45–1.63 m (6Н, СНCH3), 1.75–
1.92 m (4Н, ОСН2СН2СН2СН=СН2), 2.11–2.27 m
(4Н, ОСН2СН2СН2СН=СН2), 3.65–4.05 m (4Н,
ОСН2СН2СН2СН=СН2), 4.46–4.71 m (2H, СНСН3),
4.97–5.10 m (4Н, ОСН2СН2СН2СН=СН2), 5.74–5.91 m
(2Н, ОСН2СН2СН2СН=СН2), 6.38–7.60 m (24Harom),
7.91–8.01 m (2Н, СH=N). Found, %: С 70.51; H 5.91;
Cl 6.76; N 3.15. C52H52Cl2N2O4Ti. Calculated, %:
С 70.35; H 5.90; Cl 7.99; N 3.16.
Bis[2-{[4-(pent-4-enyloxy)phenylimino]-
methyl}-4,6-di(2-phenylpropan-2-yl)phenoxy]-
titanium(IV) dichloride (IIIj). Yield 96%. IR spec-
trum, ν, cm–1: 1609 (C=N), 565 (Ti–O), 469 (Ti–N).
1Н NMR spectrum, δ, ppm: 1.40–1.69 m [24Н,
С(СН3)2], 1.78–1.92 m (4Н, ОСН2СН2СН2СН=СН2),
2.15–2.29 m (4Н, ОСН2СН2СН2СН=СН2), 3.80–
3.99 m (4Н, ОСН2СН2СН2СН=СН2), 4.99–5.12 m
(4Н, ОСН2СН2СН2СН=СН2), 5.79–5.92 m (2Н,
ОСН2СН2СН2СН=СН2), 6.38–7.56 m (32Нarom), 7.72–
7.85 m (2Н, СH=N). Found, %: С 75.15; H 6.59; Cl 5.82;
N 2.48. C72H76Cl2N2O4Ti. Calculated, %: С 75.06;
H 6.65; Cl 6.15; N 2.43.
Bis[4-methyl-2-{[4-(pent-4-enyloxy)phenylimino]-
methyl}-6-(1-phenylethyl)phenoxy]titanium(IV)
dichloride (IIIn). Yield 92%. IR spectrum, ν, cm–1:
1
1610 (C=N), 575 (Ti–O), 442 (Ti–N). Н NMR spec-
trum, δ, ppm: 1.47–1.73 m (6Н, СНCH3), 1.78–1.94 m
(4Н, ОСН2СН2СН2СН=СН2), 2.14–2.43 m (10Н,
CH3, ОСН2СН2СН2СН=СН2), 3.70–3.99 m (4Н,
ОСН2СН2СН2СН=СН2), 4.50–4.76 m (2H, СНСН3),
5.00–5.16 m (4Н, ОСН2СН2СН2СН=СН2), 5.77–6.00 m
(2Н, ОСН2СН2СН2СН=СН2), 6.42–7.62 m (22Harom),
7.84–7.98 m (2Н, СH=N). Found, %: С 70.87; H 6.18;
Cl 7.76; N 3.06. C54H56Cl2N2O4Ti. Calculated, %:
С 70.82; H 6.16; Cl 7.74; N 3.06.
Bis[2-{[4-(pent-4-enyloxy)phenylimino]methyl}-
6-(2-phenylpropan-2-yl)-4-chlorophenoxy]-
titanium(IV) dichloride (IIIk). Yield 90%. IR spec-
trum, ν, cm–1: 1610 (C=N), 557 (Ti–O), 452 (Ti–N).
1Н NMR spectrum, δ, ppm: 1.38–1.75 m [12Н,
С(СН3)2], 1.81–1.95 m (4Н, ОСН2СН2СН2СН=СН2),
2.15–2.31 m (4Н, ОСН2СН2СН2СН=СН2), 3.82–
4.02 m (4Н, ОСН2СН2СН2СН=СН2), 4.99–5.15 m
(4Н, ОСН2СН2СН2СН=СН2), 5.78–6.15 m (2Н,
ОСН2СН2СН2СН=СН2), 6.49–7.55 m (22Harom),
7.79–7.84 m (2Н, СH=N). Found, %: С 65.73; H 5.53;
Cl 14.70; N 2.81. C54H54Cl4N2O4Ti. Calculated, %:
С 65.87; H 5.53; Cl 14.40; N 2.84.
Bis[4-tert-butyl-2-{[4-(pent-4-enyloxy)phenylimi-
no]methyl}-6-(1-phenylethyl)phenoxy]titanium(IV)
dichloride (IIIo). Yield 93%. IR spectrum, ν, cm–1:
1
1611 (C=N), 565 (Ti–O), 453 (Ti–N). Н, δ, ppm:
1.12–1.37 m [18Н, С(СН3)3], 1.46–1.65 m (6Н,
СНCH3), 1.68–1.92 m (4Н, ОСН2СН2СН2СН=СН2),
2.09–2.26 m (4Н, ОСН2СН2СН2СН=СН2), 3.57–3.99 m
(4Н, ОСН2СН2СН2СН=СН2), 4.41–4.69 m (2H,
СНСН3), 4.96–5.09 m (4Н, ОСН2СН2–СН2СН=СН2),
5.74–5.90 m (2Н, ОСН2СН2СН2СН=СН2), 6.30–6.55,
6.88–7.63 m (22Harom), 7.91–7.99 m (2Н, СH=N). Found,
Bis[4-bromo-2-{[4-(pent-4-enyloxy)phenylimi-
no]methyl}-6-(2-phenylpropan-2-yl)phenoxy]-
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DESIGN OF POSTMETALLOCENE CATALYTIC SYSTEMS..: XVI.
199
Ya., Ivanchev, S.S., and Tolstikov, G.A., Dokl. Phys. Chem,
2007, vol. 417, p. 301; Ivanchev, S.S., Vasil’eva, M.Yu.,
Ivancheva, N.I., Badaev, V.K., Oleinik, I.I., Sviridova, E.V.,
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p. 276; Ivancheva, N.I., Badaev, V.K., Sviridova, E.V.,
Nikolaev, D.A., Oleinik, I.V., and Ivanchev, S.S., Russ.
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Sanieva, D.V., Fedorov, S.P., Oleinik, I.V., Oleinik, I.I.,
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Bull., 2012, p. 836; Ivancheva, N.I., Khaikin, S.Ya.,
Sviridova, E.V., Fedorov, S.P., Sanieva, D.V., Molev, O.V.,
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%: С 72.11; H 6.82; Cl 6.95; N 2.76. C60H68Cl2N2O4Ti.
Calculated, %: С 72.07; H 6.85; Cl 7.09; N 2.80.
Bis[2-{[4-(pent-4-enyloxy)phenylimino]methyl}-
6-(1-phenylethyl)-4-chlorophenoxy]titanium(IV)
dichloride (IIIp). Yield 95%. IR spectrum, ν, cm–1:
1
1609 (C=N), 562 (Ti–O), 463 (Ti–N). Н NMR
spectrum, δ, ppm: 1.46–1.71 m (6Н, СНCH3), 1.77–
1.93 m (4Н, ОСН2СН2СН2СН=СН2), 2.13–2.28 m
(4Н, ОСН2СН2СН2СН=СН2), 3.67–4.02 m (4Н,
ОСН2СН2СН2СН=СН2), 4.34–4.68 m (2H, СНСН3),
4.98–5.13 m (4Н, ОСНСН2СН2СН=СН2), 5.76–5.94 m
(2Н, ОСН2СН2СН2–СН=СН2), 6.40–6.65, 6.86–7.58 m
(22Harom), 7.87–7.94 m (2Н, СH=N). Found, %: С 65.56;
H 5.51; Cl 14.76; N 2.91. C52H50Cl4N2O4Ti. Calculated,
%: С 65.29; H 5.27; Cl 14.82; N 2.93.
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Bis[4-bromo-2-{[4-(pent-4-enyloxy)phenylimino]
methyl}-6-(1-phenylethyl)phenoxy]titanium(IV)
dichloride (IIIq). Yield 92%. IR spectrum, ν, cm–1:
1
1609 (C=N), 560 (Ti–O), 461 (Ti–N). Н NMR
spectrum, δ, ppm: 1.46–1.71 m (6Н, СНCH3), 1.77–
1.91 m (4Н, ОСН2СН2СН2СН=СН2), 2.14–2.29 m
(4Н, ОСН2СН2–СН2СН=СН2), 3.66–4.00 m (4Н,
ОСН2СН2СН2СН=СН2), 4.40–4.66 m (2H, СНСН3),
4.98–5.13 m (4Н, ОСН2СН2–СН2СН=СН2), 5.76–5.95 m
(2Н, ОСН2СН2СН2СН=СН2), 6.39–6.61, 6.90–7.57 m
(22Harom), 7.83–7.93 m (2Н, СH=N). Found, %: С 59.73;
H 4.82; Br 15.23; Cl 6.49; N 2.68. C52H50Br2Cl2N2O4Ti.
Calculated, %: С 59.73; H 4.82; Br 15.28; Cl 6.78; N 2.68.
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