Design of Schiff base-like postmetallocene catalytic systems for polymerization of olefins: V. Synthesis of salicylaldehyde imine ligands containing cycloalkyl substituents

Article abstract of DOI:10.1134/S1070428007110140

Reactions of substituted cycloalkylanilines with salicylaldehyde, 3-tert-butylsalicylaldehyde, and 3,5-di-tert-butylsalicylaldehyde in methanol in the presence of formic acid gave a series of the corresponding Schiff bases as ligands for titanium(IV) comp

Full text of DOI:10.1134/S1070428007110140

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 11, pp. 1671–1676. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © I.I. Oleinik, I.V. Oleinik, G.S. Zhilovskii, S.S. Ivanchev, G.A. Tolstikov, 2007, published in Zhurnal Organicheskoi Khimii, 2007,
Vol. 43, No. 11, pp. 1673–1677.
Design of Schiff Base-Like Postmetallocene Catalytic Systems
for Polymerization of Olefins: V.* Synthesis of Salicylaldehyde
Imine Ligands Containing Cycloalkyl Substituents
I. I. Oleinika, I. V. Oleinika, G. S. Zhilovskiia, S. S. Ivanchevb, and G. A. Tolstikovb
a Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: oleynik@nioch.nsc.ru
b St. Petersburg Branch, Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences,
St. Petersburg, Russia
Received September 15, 2006
Abstract—Reactions of substituted cycloalkylanilines with salicylaldehyde, 3-tert-butylsalicylaldehyde, and
3,5-di-tert-butylsalicylaldehyde in methanol in the presence of formic acid gave a series of the corresponding
Schiff bases as ligands for titanium(IV) complexes.
DOI: 10.1134/S1070428007110140
Matsui et al. [2] showed that titanium and zirco-
nium chelates derived from phenoxy imine ligands are
highly efficient as catalysts for olefin polymerization.
The catalytic properties of such complexes may be
controlled by variation of substituents in the ligand; as
a result, a broad spectrum of polyolefins with various
parameters can be obtained [3–5].
heating salicylaldehyde (I), 3-tert-butylsalicylaldehyde
(II), and 3,5-di-tert-butylsalicylaldehyde (III) with
o-cycloalkylanilines IVa–IVd, Va–Vd, and VIa–VIc
in boiling methanol containing a catalytic amount of
formic acid we obtained the corresponding Schiff
bases VII–XV in high yields (91–99%) (Scheme 1).
The structure of Schiff bases VII–XV was deter-
mined on the basis of their analytical and spectral data.
According to the H NMR spectra, the isolated com-
From the practical viewpoint, an important param-
eter of a catalytic system used in polymerization
processes is retention of its high activity at elevated
temperature. We showed in [6] that the temperature
range ensuring effective function of catalysts based on
2,6-bis(aryliminoalkyl)pyridine iron complexes and
1,2-bis(arylimino)acenaphthene nickel bromide com-
plexes can be extended considerably via introduction
of a cycloalkyl substituent into the ortho position of
the aryl ring [6]. In order to verify the general char-
acter of the cycloalkyl substitution effect it was neces-
sary to elucidate whether phenoxy imino chelates
modified by such substituents are active at elevated
temperature. For this purpose, in the present work we
synthesized the corresponding ligands having cyclo-
pentyl, cyclohexyl, and cyclooctyl groups.
1
pounds are individual E isomers. They showed multi-
plet signals from the cycloalkyl methylene protons at
δ 1.15–2.15, a signal at δ 2.53–3.44 ppm from the
CH proton in the cycloalkyl ring, a singlet at δ 8.18–
8.56 ppm from the azomethine CH=N proton, and
a singlet at δ 12.57–13.93 ppm from the hydroxy pro-
ton. The observed strongly downfield position of the
OH signals is typical of compounds with intramolec-
ular hydrogen bond. The IR spectra of VII–XV con-
tained a strong absorption band in the region 1613–
1624 cm–1 due to stretching vibrations of the C=N
bond. Compounds VII–XV gave intense molecular ion
peaks in the mass spectra.
EXPERIMENTAL
The ligands were obtained by reaction of substi-
tuted salicylaldehydes with primary amines, such as
aniline and its alkyl and fluoro derivatives [4, 5]. By
1
The H NMR spectra were measured on a Bruker
WP-200 SY spectrometer at 200 MHz from solutions
in carbon tetrachloride using HMDS as internal refer-
* For communication IV, see [1].
1671

OLEINIK et al.
1672
Scheme 1.
R
N
OH
OH
CHO
( )n
R'
I
VIIa–VIId, VIIIa–VIIId, IXa–IXc
OH
R
R
Bu-t
t-Bu
CHO
NH2
( )n
N
OH
MeOH, HCOOH, 65°C
+
( )n
R'
R'
II
IVa–IVd, Va–Vd, VIa–VIc
Xa–Xd, XIa–XId, XIIa–XIIc
Bu-t
OH
R
Bu-t
t-Bu
CHO
N
OH
( )n
R'
Bu-t
III
XIIIa–XIIId, XIVa–XIVd, XVa–XVc
R = R′ = H (a), Me (c); R = Me, R′ = H (b); R = cyclo-C4H7(CH2)n, R′ = H (d); IV, VII, X, XIII, n = 1; V, VIII, XI, XIV, n = 2;
VI, IX, XI, XV, n = 4.
ence. The IR spectra were recorded on a Vector 22
spectrometer from samples prepared as KBr pellets or
neat substances. The progress of reactions and the
purity of products were monitored by TLC on Silufol
UV-254 plates using chloroform as eluent. Flash chro-
matography [7] was performed on silica gel (5–40 μm;
chloroform–hexane, 2:1). The elemental compositions
were determined from the high-resolution mass spectra
recorded on a Finnigan MAT-8200 spectrometer. The
melting points were determined by heating samples
placed between glass plates at a rate of 1 deg/min.
3,5-Di-tert-butylsalicylaldehyde and cycloalkyl-
anilines IV–VI were synthesized according to the
procedures reported in [8, 9]. 3-tert-Butylsalicylalde-
hyde was obtained by an improved procedure [10]; its
spectral parameters were consistent with those reported
in [4, 11].
cycloalkylaniline IVa–IVd, Va–Vd, or VIa–VIc,
10 ml of methanol, and 5 mg of anhydrous formic acid
was heated under reflux for 6–12 h until the initial
compounds disappeared according to the TLC data.
The solvent was distilled off on a rotary evaporator
under reduced pressure (water-jet pump) at a bath
temperature of 45°C, and the residue was subjected to
flash chromatography to isolate the first bright yellow
fraction. The solvent was distilled off, and the solid
residue was recrystallized from ethanol.
2-[(2-Cyclopentylphenylimino)methyl]phenol
(VIIa). Yield 96%, oily substance. IR spectrum:
ν 1618 cm–1 (N=CH). 1H NMR spectrum, δ, ppm: 1.41–
2.10 m (8H, CH2), 3.41 m (1H, CH), 6.80–7.35 m (8H,
Harom), 8.48 s (1H, CH=N), 13.04 s (1H, OH). Found:
[M]+ 265.1468. C18H19NO. Calculated: M 265.1467.
2-[(2-Cyclopentyl-2-methylphenylimino)methyl]-
Schiff Bases VII–XV (general procedure). A mix-
ture of 1 mmol of salicylaldehyde I–III, 1 mmol of
phenol (VIIb). Yield 91%, oily substance. IR spec-
1
trum: ν 1624 cm–1 (N=CH). H NMR spectrum, δ,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

DESIGN OF SCHIFF BASE-LIKE POSTMETALLOCENE CATALYTIC SYSTEMS ... V.
1673
ppm: 1.45–2.05 m (8H, CH2), 2.15 s (3H, CH3),
3.00 m (1H, CH), 6.81–7.39 m (7H, Harom), 8.25 s (1H,
CH=N), 12.80 s (1H, OH). Found: [M]+ 279.1623.
C19H21NO. Calculated: M 279.1623.
1.90 m (14H, CH2), 3.30 m (1H, CH), 6.82–7.36 m
(8H, Harom), 8.50 s (1H, CH=N), 12.97 s (1H, OH).
Found: [M]+ 307.1935. C21H25NO. Calculated:
M 307.1936.
2-[(2-Cyclooctyl-6-methylphenylimino)methyl]-
phenol (IXb). Yield 95%, oily substance. IR spectrum:
ν 1624 cm–1 (N=CH). 1H NMR spectrum, δ, ppm: 1.42–
1.80 m (14H, CH2), 2.14 s (3H, CH3), 2.95 m (1H,
CH), 6.82–7.39 m (7H, Harom), 8.27 s (1H, CH=N),
12.76 s (1H, OH). Found: [M]+ 321.2093. C22H27NO.
Calculated: M 321.2093.
2-[(2,4-Dimethyl-6-cyclopentylphenylimino)-
methyl]phenol (VIIc). Yield 92%, mp 105–106°C. IR
spectrum: ν 1623 cm–1 (N=CH). 1H NMR spectrum, δ,
ppm: 1.45–1.98 m (8H, CH2), 2.12 s (3H, CH3), 2.28 s
(3H, CH3), 2.98 m (1H, CH), 6.79–7.38 m (6H, Harom),
8.24 s (1H, CH=N), 12.90 s (1H, OH). Found:
[M]+ 293.1773. C20H23NO. Calculated: M 293.1779.
2-[(2-Cyclooctyl-4,6-dimethylphenylimino)meth-
2-[(2,6-Dicyclopentylphenylimino)methyl]phenol
(VIId). Yield 91%, mp 78–79°C. IR spectrum:
ν 1624 cm–1 (N=CH). 1H NMR spectrum, δ, ppm: 1.54–
1.96 m (16H, CH2), 2.97 m (2H, CH), 6.78–7.37 m
(7H, Harom), 8.22 s (1H, CH=N), 12.60 s (1H, OH).
Found: [M]+ 333.2084. C23H27NO. Calculated:
M 333.2093.
yl]phenol (IXc). Yield 93%, oily substance. IR spec-
1
trum: ν 1622 cm–1 (N=CH). H NMR spectrum, δ,
ppm: 1.35–1.85 m (14H, CH2), 2.16 s (3H, CH3),
2.30 s (3H, CH3), 2.94 m (1H, CH), 6.82–7.41 m (6H,
Harom), 8.28 s (1H, CH=N), 12.86 s (1H, OH). Found:
[M]+ 335.2257. C23H29NO. Calculated: M 335.2249.
2-tert-Butyl-6-[(2-cyclopentylphenylimino)meth-
yl]phenol (Xa). Yield 92%, oily substance. IR spec-
2-[(2-Cyclohexylphenylimino)methyl]phenol
(VIIIa). Yield 91%, oily substance. IR spectrum:
ν 1617 cm–1 (N=CH). 1H NMR spectrum, δ, ppm: 1.20–
1.95 m (10H, CH2), 2.99 m (1H, CH), 6.80–7.35 m
(8H, Harom), 8.50 s (1H, CH=N), 13.01 s (1H, OH).
Found: [M]+ 279.1620. C19H21NO. Calculated:
M 279.1623.
1
trum: ν 1613 cm–1 (N=CH). H NMR spectrum, δ,
ppm: 1.44 s [9H, C(CH3)3], 1.53–1.88 m (6H, CH2),
1.96–2.15 m (2H, CH2), 3.44 m (1H, CH), 6.75 t (1H,
H
arom, J = 7.6 Hz), 6.89–6.99 m (1H, Harom), 7.01–
7.18 m (3H, Harom), 7.19–7.32 m (2H, Harom), 8.46 s
(1H, CH=N), 13.70 s (1H, OH). Found: [M]+ 321.2101.
C22H27NO. Calculated: M 321.2093.
2-[(2-Cyclohexyl-6-methylphenylimino)methyl]-
phenol (VIIIb). Yield 92%, oily substance. IR spec-
1
trum: ν 1624 cm–1 (N=CH). H NMR spectrum, δ,
2-tert-Butyl-6-[(2-cyclopentyl-2-methylphenyl-
imino)methyl]phenol (Xb). Yield 96%, oily sub-
ppm: 1.20–1.85 m (10H, CH2), 2.16 s (3H, CH3),
2.58 m (1H, CH), 6.82–7.39 m (7H, Harom), 8.26 s (1H,
CH=N), 12.75 s (1H, OH). Found: [M]+ 293.1778.
C20H23NO. Calculated: M 293.1779.
1
stance. IR spectrum: ν 1619 cm–1 (N=CH). H NMR
spectrum, δ, ppm: 1.46 s [9H, C(CH3)3], 1.55–1.84 m
(6H, CH2), 1.85–2.05 m (2H, CH2), 2.41 s (3H, CH3),
3.04 m (1H, CH), 6.77 t (1H, Harom, J = 7.6 Hz), 6.92–
7.05 m (2H, Harom), 7.07 d.d (2H, Harom, J = 7.4,
1.4 Hz), 7.31 d.d (1H, Harom, J = 7.7, 1.6 Hz), 8.27 s
(1H, CH=N), 13.44 s (1H, OH). Found: [M]+ 335.2244.
C23H29NO. Calculated: M 335.2249.
2-[(2-Cyclohexyl-4,6-dimethylphenylimino)-
methyl]phenol (VIIIc). Yield 91%, mp 71–72°C. IR
spectrum: ν 1621 cm–1 (N=CH). 1H NMR spectrum, δ,
ppm: 1.20–1.85 m (10H, CH2), 2.13 s (3H, CH3),
2.27 s (3H, CH3), 2.55 m (1H, CH), 6.75–7.37 m (6H,
Harom), 8.22 s (1H, CH=N), 12.68 s (1H, OH). Found:
[M]+ 307.1911. C21H25NO. Calculated: M 307.1936.
2-tert-Butyl-6-[(2-cyclopentyl-4,6-dimethylphen-
ylimino)methyl]phenol (Xc). Yield 98%, mp 111.5–
1
113.5°C. IR spectrum: ν 1620 cm–1 (N=CH). H NMR
2-[(2,6-Dicyclohexylphenylimino)methyl]phenol
(VIIId). Yield 90%, mp 119–120°C. IR spectrum:
ν 1621 cm–1 (N=CH). 1H NMR spectrum, δ, ppm: 1.15–
1.85 m (20H, CH2), 2.53 m (2H, CH), 6.83–7.42 m
(7H, Harom), 8.21 s (1H, CH=N), 12.57 s (1H, OH).
Found: [M]+ 361.2402. C25H31NO. Calculated:
M 361.2406.
spectrum, δ, ppm: 1.45 s [9H, C(CH3)3], 1.51–1.68 m
(4H, CH2), 1.71–1.79 m (2H, CH2), 1.85–1.98 m (2H,
CH2), 2.15 s (3H, CH3), 2.28 s (3H, CH3), 3.00 m (1H,
CH), 6.76 t (1H, Harom, J = 7.6 Hz), 6.77 s (1H, Harom),
6.86 s (1H, Harom), 7.05 d.d (1H, Harom, J = 7.6,
1.6 Hz), 7.30 d.d (1H, Harom, J = 7.6, 1.6 Hz), 8.24 s
(1H, CH=N), 13.53 s (1H, OH). Found: [M]+ 349.2407.
C24H31NO. Calculated: M 349.2406.
2-[(2-Cyclooctylphenylimino)methyl]phenol
(IXa). Yield 94%, oily substance. IR spectrum:
ν 1617 cm–1 (N=CH). 1H NMR spectrum, δ, ppm: 1.45–
2-tert-Butyl-6-[(2,6-dicyclopentylphenylimino)-
methyl]phenol (Xd). Yield 98%, oily substance. IR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

OLEINIK et al.
1674
spectrum: ν 1619 cm–1 (N=CH). 1H NMR spectrum, δ,
ppm: 1.47 s [9H, C(CH3)3], 1.51–1.84 m (12H, CH2),
1.85–2.05 m (4H, CH2), 3.00 m (2H, CH), 6.78 t (1H,
Harom, J = 7.6 Hz), 6.99–7.11 m (4H, Harom), 7.32 d.d
(1H, Harom, J = 7.8, 1.6 Hz), 8.23 s (1H, CH=N),
13.45 s (1H, OH). Found: [M]+ 389.2717. C27H35NO.
Calculated: M 389.2719.
ppm: 1.44 s [9H, C(CH3)3], 1.50–1.95 m (14H, CH2),
3.35 m (1H, CH), 6.75 t (1H, Harom, J = 7.8 Hz), 6.93–
7.20 m (5H, Harom), 7.31 d.d (1H, Harom, J = 7.8, 1.6 Hz),
8.52 s (1H, CH=N), 13.93 s (1H, OH). Found:
[M]+ 363.2559. C25H33NO. Calculated: M 363.2562.
2-tert-Butyl-6-[(2-cyclooctyl-6-methylphenyl-
imino)methyl]phenol (XIIb). Yield 92%, oily sub-
1
stance. IR spectrum: ν 1620 cm–1 (N=CH). H NMR
2-tert-Butyl-6-[(2-cyclohexylphenylimino)meth-
yl]phenol (XIa). Yield 93%, oily substance. IR spec-
spectrum, δ, ppm: 1.46 s [9H, C(CH3)3], 1.48–1.80 m
(14H, CH2), 2.20 s (3H, CH3), 3.00 m (1H, CH), 6.79 t
(1H, Harom, J = 7.6 Hz), 6.93–7.16 m (3H, Harom),
7.19 d.d (1H, Harom, J = 7.6, 1.6 Hz), 7.34 d.d (1H,
1
trum: ν 1613 cm–1 (N=CH). H NMR spectrum, δ,
ppm: 1.33–1.51 m (4H, CH2), 1.45 s [9H, C(CH3)3],
1.74–1.93 m (6H, CH2), 3.01 m (1H, CH), 6.77 t (1H,
H
arom, J = 7.6 Hz), 6.99–7.03 m (1H, Harom), 7.11–
H
arom, J = 7.6, 1.6 Hz), 8.28 s (1H, CH=N), 13.60 s
(1H, OH). Found: [M]+ 377.2716. C26H35NO. Calculat-
ed: M 377.2719.
7.18 m (3H, Harom), 7.19–7.24 m (1H, Harom), 7.29 d
(1H, Harom, J = 7.6 Hz), 8.53 s (1H, CH=N), 12.83 s
(1H, OH). Found: [M]+ 335.2241. C23H29NO. Calculat-
ed: M 335.2249.
2-tret-Butyl-6-[(6-cyclooctyl-4,6-dimethylphenyl-
imino)methyl]phenol (XIIc). Yield 98%, oily sub-
stance. IR spectrum: ν 1617 cm–1 (N=CH). H NMR
1
2-tert-Butyl-6-[(2-cyclohexyl-6-methylphenyl-
imino)methyl]phenol (XIb). Yield 97%. IR spectrum:
ν 1619 cm–1 (N=CH). 1H NMR spectrum, δ, ppm: 1.21–
1.41 m (4H, CH2), 1.46 s [9H, C(CH3)3], 1.63–1.90 m
(6H, CH2), 2.20 s (3H, CH3), 2.58 m (1H, CH), 6.81 t
(1H, Harom, J = 7.6 Hz), 6.89–7.09 m (4H, Harom),
7.32 d.d (1H, Harom, J = 7.6, 1.8 Hz), 8.26 s (1H,
CH=N), 13.37 s (1H, OH). Found: [M]+ 349.2410.
C24H31NO. Calculated: M 349.2406.
spectrum, δ, ppm: 1.51 s [9H, C(CH3)3], 1.53–1.82 m
(14H, CH2), 2.22 s (3H, CH3), 2.33 s (3H, CH3),
3.02 m (1H, CH), 6.82 t (1H, Harom, J = 7.6 Hz), 6.84 s
(1H, Harom), 6.87 s (1H, Harom), 7.13 d.d (1H, Harom, J =
7.6, 1.6 Hz), 7.38 d.d (1H, Harom, J = 7.6, 1.6 Hz), 8.31 s
(1H, CH=N), 13.70 s (1H, OH). Found: [M]+ 391.2872.
C27H37NO. Calculated: M 391.2875.
4,6-Di-tert-butyl-2-[(2-cyclopentylphenylimino)-
methyl]phenol (XIIIa). Yield 92%, mp 95–96°C. IR
spectrum: ν 1617 cm–1 (N=CH). 1H NMR spectrum, δ,
ppm: 1.30 s [9H, C(CH3)3], 1.44 s [9H, C(CH3)3],
1.55–2.12 m (8H, CH2), 3.43 m (1H, CH), 6.91–
7.27 m (5H, Harom), 7.34 d (1H, 3-H, J = 2.5 Hz), 8.48 s
(1H, CH=N), 13.42 s (1H, OH). Found: [M]+ 377.2712.
C26H35NO. Calculated: M 377.2718.
2-tert-Butyl-6-[(2-cyclohexyl-4,6-dimethylphen-
ylimino)methyl]phenol (XIc). Yield 99%, oily sub-
stance. IR spectrum: ν 1619 cm–1 (N=CH). H NMR
1
spectrum, δ, ppm: 1.19–1.41 m (6H, CH2), 1.46 s [9H,
C(CH3)3], 1.62–1.88 m (4H, CH2), 2.17 s (3H, CH3),
2.27 s (3H, CH3), 2.57 m (1H, CH), 6.76 t (1H, Harom
J = 7.6 Hz), 6.78 s (1H, Harom), 6.82 s (1H, Harom),
7.06 d.d (1H, Harom, J = 7.6, 1.6 Hz), 7.31 d.d (1H,
,
4,6-Di-tert-butyl-2-[(6-cyclopentyl-6-methyl-
phenylimino)methyl]phenol (XIIIb). Yield 96%,
mp 107–108°C. IR spectrum: ν 1622 cm–1 (N=CH).
1H NMR spectrum, δ, ppm: 1.35 s [9H, C(CH3)3],
1.46 s [9H, C(CH3)3], 1.50–2.05 m (8H, CH2), 2.18 s
(3H, CH3), 3.00 m (1H, CH), 6.92–7.15 m (4H, Harom),
7.36 d (1H, 3-H, J = 2.5 Hz), 8.26 s (1H, CH=N),
13.23 s (1H, OH). Found: [M]+ 391.2880. C27H37NO.
Calculated: M 391.2875.
H
arom, J = 7.6, 1.6 Hz), 8.24 s (1H, CH=N), 13.55 s
(1H, OH). Found: [M]+ 363.2558. C25H33NO. Calculat-
ed: M 363.2562.
2-tert-Butyl-6-[(2,6-dicyclohexylphenylimino)-
methyl]phenol (XId). Yield 96%, oily substance. IR
spectrum: ν 1618 cm–1 (N=CH). 1H NMR spectrum, δ,
ppm: 1.23–1.48 m (8H, CH2), 1.48 s [9H, C(CH3)3],
1.55–1.90 m (12H, CH2), 2.55 m (2H, CH), 6.78 t (1H,
Harom, J = 7.6 Hz), 6.88–7.11 m (4H, Harom), 7.33 d.d
(1H, Harom, J = 7.6, 1.6 Hz), 8.20 s (1H, CH=N),
13.50 s (1H, OH). Found: [M]+ 417.3017. C29H39NO.
Calculated: M 417.3031.
4,6-Di-tert-butyl-2-[(2-cyclopentyl-4,6-dimethyl-
phenylimino)methyl]phenol (XIIIc). Yield 94%,
mp 124–125°C. IR spectrum: ν 1620 cm–1 (N=CH).
1H NMR spectrum, δ, ppm: 1.30 s [9H, C(CH3)3],
1.45 s [9H, C(CH3)3], 1.53–2.01 m (8H, CH2), 2.15 s
(3H, CH3), 2.28 s (3H, CH3), 3.01 m (1H, CH), 6.77 s
(1H, Harom), 6.85 s (1H, Harom), 7.00 d (1H, 5-H, J =
2-tert-Butyl-6-[(2-cyclooctylphenylimino)methyl]-
phenol (XIIa). Yield 98%, oily substance. IR spec-
trum: ν 1614 cm–1 (N=CH). H NMR spectrum, δ,
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

DESIGN OF SCHIFF BASE-LIKE POSTMETALLOCENE CATALYTIC SYSTEMS ... V.
1675
ppm: 1.35 s [9H, C(CH3)3], 1.47 s [9H, C(CH3)3], 1.55–
1.98 m (14H, CH2), 3.42 m (1H, CH), 6.99–7.22 m
(5H, Harom), 7.39 d (1H, 3-H, J = 2.5 Hz), 8.56 s (1H,
CH=N), 13.73 s (1H, OH). Found: [M]+ 419.3168.
C29H41NO. Calculated: M 419.3188.
2.5 Hz), 7.34 d (1H, 3-H, J = 2.5 Hz), 8.23 s (1H,
CH=N), 13.32 s (1H, OH). Found: [M]+ 405.3033.
C28H39NO. Calculated: M 405.3032.
4,6-Di-tert-butyl-2-[(2,6-dicyclopentylphenyl-
imino)methyl]phenol (XIIId). Yield 94%, mp 147–
1
148°C. IR spectrum: ν 1622 cm–1 (N=CH). H NMR
4,6-Di-tert-butyl-2-[(2-cyclooctyl-6-methylphen-
ylimino)methyl]phenol (XVb). Yield 92%, mp 89–
spectrum, δ, ppm: 1.31 s [9H, C(CH3)3], 1.47 s [9H,
C(CH3)3], 1.50–2.05 m (16H, CH2), 3.00 m (2H, CH),
6.92–7.11 m (4H, Harom), 7.38 d (1H, 3-H, J = 2.5 Hz),
8.21 s (1H, CH=N), 13.29 s (1H, OH). Found:
[M]+ 445.3348. C31H43NO. Calculated: M 445.3345.
1
90°C. IR spectrum: ν 1621 cm–1 (N=CH). H NMR
spectrum, δ, ppm: 1.31 s [9H, C(CH3)3], 1.46 s [9H,
C(CH3)3], 1.49–1.82 m (14H, CH2), 2.21 s (3H, CH3),
3.01 m (1H, CH), 6.92–7.01 m (3H, Harom), 7.04 d (1H,
5-H, J = 2.5 Hz), 7.39 d (1H, 3-H, J = 2.5 Hz), 8.28 s
(1H, CH=N), 13.35 s (1H, OH). Found: [M]+ 433.3345.
C30H43NO. Calculated: M 433.3345.
4,6-Di-tert-butyl-2-[(2-cyclohexylphenylimino)-
methyl]phenol (XIVa). Yield 92%, mp 83–84°C. IR
spectrum: ν 1616 cm–1 (N=CH). 1H NMR spectrum, δ,
ppm: 1.30 s [9H, C(CH3)3], 1.46 s [9H, C(CH3)3], 1.58–
1.95 m (10H, CH2), 3.01 m (1H, CH), 6.98–7.20 m
(5H, Harom), 7.33 d (1H, 3-H, J = 2.5 Hz), 8.53 s (1H,
CH=N), 13.59 s (1H, OH). Found: [M]+ 391.2880.
C27H37NO. Calculated: M 391.2875.
4,6-Di-tert-butyl-2-[(2-cyclooctyl-4,6-dimethyl-
phenylimino)methyl]phenol (XVc). Yield 92%,
mp 85–86°C. IR spectrum: ν 1621 cm–1 (N=CH).
1H NMR spectrum, δ, ppm: 1.31 s [9H, C(CH3)3],
1.48 s [9H, C(CH3)3], 1.40–1.80 m (14H, CH2), 2.17 s
(3H, CH3), 2.27 s (3H, CH3), 2.99 m (1H, CH), 6.79 s
(1H, Harom), 6.82 s (1H, Harom), 7.03 d (1H, 5-H, J =
2.5 Hz), 7.37 d (1H, 3-H, J = 2.5 Hz), 8.25 s (1H,
CH=N), 13.40 s (1H, OH). Found: [M]+ 447.3503.
C31H45NO. Calculated: M 447.3501.
4,6-Di-tert-butyl-2-[(2-cyclohexyl-6-methylphen-
ylimino)methyl]phenol (XIVb). Yield 92%, mp 95–
1
96°C. IR spectrum: ν 1624 cm–1 (N=CH). H NMR
spectrum, δ, ppm: 1.31 s [9H, C(CH3)3], 1.45 s [9H,
C(CH3)3], 1.55–1.95 m (10H, CH2), 2.20 s (3H, CH3),
2.61 m (1H, CH), 6.91–7.11 m (4H, Harom), 7.38 d (1H,
3-H, J = 2.5 Hz), 8.26 s (1H, CH=N), 13.25 s (1H,
OH). Found: [M]+ 405.3036. C28H39NO. Calculated:
M 405.3032.
REFERENCES
1. Kochnev, A.I., Oleinik, I.I., Oleinik, I.V., Ivanchev, S.S.,
and Tolstikov, G.A., Russ. J. Org. Chem., 2007, vol. 43,
no. 4, p. 571.
4,6-Di-tert-butyl-2-[(2-cyclohexyl-4,6-dimethyl-
phenylimino)methyl]phenol (XIVc). Yield 99%,
mp 137–138°C. IR spectrum: ν 1620 cm–1 (N=CH).
1H NMR spectrum, δ, ppm: 1.31 s [9H, C(CH3)3],
1.40 s [9H, C(CH3)3], 1.48–1.87 m (10H, CH2), 2.17 s
(3H, CH3), 2.27 s (3H, CH3), 2.58 m (1H, CH), 6.78 s
(1H, Harom), 6.81 s (1H, Harom), 7.00 d (1H, 5-H, J =
2.5 Hz), 7.35 d (1H, 3-H, J = 2.5 Hz), 8.23 s (1H,
CH=N), 13.38 s (1H, OH). Found: [M]+ 419.3187.
C29H41NO. Calculated: M 419.3188.
2. Matsui, S., Tohi, Y., Mitani, M., Saito, J., Makio, H.,
Tanaka, H., Nitabaru, M., Nakano, T., and Fujita, T.,
Chem. Lett., 1999, vol. 28, p. 1065; Matsui, S., Mita-
ni, M., Saito, J., Tohi, Y., Makio, H., Tanaka, H., and
Fujita, T., Chem. Lett., 1999, vol. 28, p. 1263.
3. Matsui, S., Mitani, M., Saito, J., Matsukawa, N., Tana-
ka, H., Nakano, T., and Fujita, T., Chem. Lett., 2000,
vol. 29, p. 1263; Saito, J., Mitani, M., Mohri, J., Yoshi-
da, Y., Matsui, S., Ishii, S., Kojoh, S., Kashiwa, N., and
Fujita, T., Angew. Chem., Int. Ed., 2001, vol. 40, p. 2918.
4. Matsui, S., Mitani, M., Saito, J., Tohi, Y., Makio, H.,
Matsukawa, 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.
4,6-Di-tert-butyl-2-[(2,6-dicyclohexylphenyl-
imino)methyl]phenol (XIVd). Yield 91%, mp 185–
1
186°C. IR spectrum: ν 1617 cm–1 (N=CH). H NMR
spectrum, δ, ppm: 1.33 s [9H, C(CH3)3], 1.48 s [9H,
C(CH3)3], 1.55–1.95 m (20H, CH2), 2.55 m (2H, CH),
6.97–7.04 m (4H, Harom), 7.39 d (1H, 3-H, J = 2.5 Hz),
8.18 s (1H, CH=N), 13.27 s (1H, OH). Found:
[M]+ 473.3649. C33H47NO. Calculated: M 473.3657.
5. Mitani, M., Mohri, J., Yoshida, Y., Saito, J., Ishii, S.,
Tsuru, K., Matsui, S., Furuyama, R., Nakano, T., Tana-
ka, H., Koyoh, S., Matsugi, T., Kashiwa, N., and Fuji-
ta, T., J. Am. Chem. Soc., 2002, vol. 124, p. 3327.
6. Ivancheva, N.I., Badaev, V.K., Oleinik, I.I., Ivanchev, S.S.,
and Tolstikov, G.A., Dokl. Ross. Akad. Nauk, 2000,
vol. 374, p. 648; Ivanchev, S.S., Tolstikov, G.A., Bada-
ev, V.K., Ivancheva, N.I., Oleinik, I.I., Serushkin, M.I.,
4,6-Di-tert-butyl-2-[(2-cyclooctylphenylimino)-
methyl]phenol (XVa). Yield 98%, mp 74–75°C. IR
spectrum: ν 1617 cm–1 (N=CH). 1H NMR spectrum, δ,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

OLEINIK et al.
1676
and Oleinik, I.V., Vysokomol. Soedin., 2000, vol. 43,
7. Still, W.C., Kahn, M., and Mitra, A., J. Org. Chem.,
p. 2053; Ivanchev, S.S., Tolstikov, G.A., Gabutdinov, M.S.,
Kudryashov, V.N., Oleinik, I.I., Ivancheva, N.I., Bada-
ev, V.K., and Oleinik, I.V., Russian Patent no. 2194056,
2002; Byull. Izobret., 2002, no. 34; Ivanchev, S.S., Tolsti-
kov, G.A., Badaev, V.K., Ivancheva, N.I., Oleinik, I.I.,
Khaikin, S.Ya., and Oleinik, I.V., Vysokomol. Soedin. A,
2002, vol. 44, p. 1478; Ivanchev, S.S., Tolstikov, G.A.,
Kudryashov, V.N., Ivancheva, N.I., Oleinik, I.I., Gabutdi-
nov, M.S., Badaev, V.K., Oleinik, I.V., Rogozin, D.G.,
Tikhonov, M.V., Vakhbreit, A.Z., Khasanshin, R.A., and
Balabueva, G.Ch., Russian Patent no. 2202559, 2003;
Byull. Izobret., 2003, no. 11.
1978, vol. 43, p. 2923.
8. Org. Synth., 1998, vol. 75, p. 1.
9. Oleinik, I.I., Oleinik, I.V., Abdrakhmanov, I.B., Ivan-
chev, S.S., and Tolstikov, G.A., Russ. J. Gen. Chem.,
2004, vol. 74, p. 1423.
10. Casiraghi, G., Casnati, G., Puglia, G., Sartori, G., and
Terenghi, G., J. Chem. Soc., Perkin Trans. 1, 1980,
p. 1862.
11. Saito, J., Mitani, M., Matsui, S., Tohi, Y., Makio, H.,
Nakano, T., Tanaka, H., Kasiwa, N., and Fujita, T.,
Macromol. Chem. Phys., 2002, vol. 203, p. 59.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007