Synthesis of 4-(ω-hydroxyalkyl)-2,6-di-tert-butylphenols and the properties of related sulfides

Article abstract of DOI:10.1134/S1070363210100208

Reaction of 2,6-di-tert-butylphenol with aliphatic linear and branched diols in an alkaline medium at a temperature of 180-220°C leads to the formation of 4-(ω-hydroxyalkyl)-2,6-di-tert-butylphenols. The increase in the product yield and reducing the reaction temperature was reached at the catalysis of this reaction with zinc oxide. The structure of the diphenylalkane derivatives generated in side reaction was proved and the structural influence of the length of the aliphatic residue on the antioxidant effectiveness of the sulfides derived from the corresponding hydroxyalkylphenols was examined.

Full text of DOI:10.1134/S1070363210100208

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 10, pp. 2001–2006. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.P. Krysin, I.I. Pustovskikh, V.A. Koptyug, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 10, pp. 1691–1696.
Synthesis of 4-(ω-Hydroxyalkyl)-2,6-di-tert-butylphenols
and the Properties of Related Sulfides
A. P. Krysin, I. I. Pustovskikh, and V. A. Koptyug
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: benzol@nioch.nsc.ru
Received October 29, 2009
Abstract―Reaction of 2,6-di-tert-butylphenol with aliphatic linear and branched diols in an alkaline medium
at a temperature of 180–220°C leads to the formation of 4-(ω-hydroxyalkyl)-2,6-di-tert-butylphenols. The
increase in the product yield and reducing the reaction temperature was reached at the catalysis of this reaction
with zinc oxide. The structure of the diphenylalkane derivatives generated in side reaction was proved and the
structural influence of the length of the aliphatic residue on the antioxidant effectiveness of the sulfides derived
from the corresponding hydroxyalkylphenols was examined.
DOI: 10.1134/S1070363210100208
A variety of spatially hindered phenols containing
in the aliphatic chain of the the para-substituent the
different functional groups can be obtained starting
with 4-(ω-hydroxyalkyl)-2,6-di-tert-butylphenol I.
Such compounds are required for systematic studies to
reveal effective antioxidants and biologically active
substances. Numerous phenol derivatives of the benzyl
type have been obtained previously on the basis of
industrially available 4-hydroxymethyl-2,6-di-tert-
butylphenol [1]. But to create a whole arsenal of
phenols I efficient one-step common methods for their
synthesis are required, desirably starting with the
available 2,6-di-tert-butylphenol II.
the yield of compounds I and the decrease in the
reaction temperature were achieved by adding zinc
oxide to the reaction mixture. This approach is an
exclusive general method for producing phenol-con-
taining functional groups in the aliphatic chain of a para-
substituent at any distance from the aromatic ring.
It was concluded in a later patent [3] that the key
stage of alkaline alkylation of compound II with linear
dihydric alcohols proceeding at a temperature of 235°C
was the oxidative activation of the alkylating agent.
This essentially radical process was initiated with an
oxidant. For this purpose as the initiator tert-
butylhydroperoxide was used, which was fed into the
reactor by portions in the course of the reaction. The
yield of compound Ib was 35%, and of compounds Ic
and Id, 60% . As a by-product at the manufacturing of
compound Id a derivative of 1,6-diphenylhexane IIId
was identified which was characterized by melting
Previously we have shown for the first time [2] that
compound II reacts on heating with diols in the
presence of strong bases affording compounds I, and
in the side reaction 1,ω-bis-(2,5-di-tert-butyl-4-
hydroxyphenyl)alkanes III are formed. The increase in
OH
OH
HO(CH2)nOH
(CH2)n
+
HO
OH
ZnO
200−250oC
(CH2)nOH
II
Iа−If
IIIа−IIIf
n = 2 (а), 3 (b), 4 (c), 6 (d), 7 (e), 10 (f).
2001

2002
KRYSIN et al.
point (mp 147–149°C; according to our data, mp
152.5–153°C, see below).
propane-1,3-diol with compound II at a temperature of
180°C in the presence of ZnO results in the formation
of γ-propanol Ib. Along with this compound, methyl-
enebisphenol IIIa and a derivative of 1,1-diphenyl-
propane IV were isolated, but the derivative of 1,3-di-
phenylpropane IIIb, whose formation could be ex-
pected according to the general scheme, was not detected
in a significant amount. An authentic sample of com-
pound IV we obtained by the reaction of compound II
with allylamine in the presence of alkali [5]. In our
case, compound IV is formed presumably by condensa-
tion of compounds II with propionic aldehyde, the pro-
duct of dehydration of propane-1,3-diol followed by the
rearrangement of the intermediately forming cyclic ether.
We have previously shown that the reaction of
compound I with ethylene glycol occurs at a tem-
perature above 200°C and is complicated by its typical
fragmentation under the influence of bases leading to
the formation of aldehydes. The latter were “trapped”
by compound II to form byproducts. Yield of 4-(2-
hydroxyethyl)-2,6-di-tert-butylphenol Ia did not exceed
25%. When ethylene glycol was replaced by di- or
triethyleneglycol, then the predominant formation of 4-
ethyl-2,6-di-tert-butylphenol [4] was observed.
In the present work we found that the reaction of
C2H5
CH
HO(CH2)3OH
Ib + IIIа +
II
NaOH, ZnO
170oC
HO
OH
IV
The reaction of 1,4-butanediol with compound II in
the presence of ZnO at a temperature of 190°C resulted
in the formation of 4-(4-hydroxybutyl)-2,6-di-tert-
butylphenol Ic in 76% yield and a derivative of 1,4-
diphenylbutane IIIc in 8% yield. This process, which
takes place at the atmospheric pressure, at 50-fold
scaling was successfully reproduced in a steel
equipment of the pilot plant facility of the Novosibirsk
Institute of Organic Chemistry, Siberian Branch of the
Russian Academy of Sciences. At carrying out this
reaction under the same conditions but without zinc
oxide the yield the compound Ic decreased to 25%.
The reaction of compound II with 1,3-butanediol in
the presence of ZnO at a temperature of 200°C over 5 h
led to the formation of 4-(3,5-di-tert-butyl-4-hydroxy-
phenyl)butan-2-ol V, that indicates a preference for the
reaction of compound II at the primary hydroxy group
of the initial dihydric alcohol.
OH
OH
HO
OH
HO
OH
+ IIIа
II
NaOH
NaOH
CH2C(CH3)2CH2OH
VI
(CH2)2CH(CH)3OH
V
Compound II reacts with 2-methylpentane-2,5-diol
in alkaline medium under the above conditions with
the formation of a mixture of three isomeric difficultly
separable 4-(ω-hydroxypentyl)-2,6-di-tert-butylphenols.
This reaction, which has a relation to the mechanism of
alkaline alkylation of phenols, will be discussed in
detail in the subsequent publication.
The reaction of 2,6-di-tert-butylphenol with neo-
pentylglycol in alkaline medium led to hydroxy-
alkylphenol VI in a moderate yield (15%). Along with
VI a large quantity of methylenebisphenol IIIa was
detected. The formation of IIIa indicates the ability of
neopentylglycol to be split in alkaline medium with the
formation of formaldehyde and isobutanol; the latter
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 10 2010

SYNTHESIS OF 4-(ω-HYDROXYALKYL)-2,6-DI-tert-BUTYLPHENOLS
2003
was isolated from the reaction products by distillation.
The formaldehyde reacts with 2,6-di-tert-butylphenol
to form compound IIIa.
regularity was revealed: the higher the temperature of
the polymer processing, the more significant is the
effectiveness of sulfides containing in their structure a
longer aliphatic chain. Thus, for the stabilization of
polypropylene in the process of its processing at a
temperature of 240°C the most effective are compounds
VII, n = 3,4 [9], and for the ABS (acrylonitrile–
butadiene–styrene) plastics (the processing tem-
perature 200°C) was more effective compound VII,
n = 3) [10].
A series of 4-(ω-hydroxyalkyl)-2,6-di-tert-butyphenols
Id–If was obtained along the general procedure in
about 50% yield; in addition the derivatives of 1,ω-
diphenylalkane IIId–IIIf were isolated in up to 5%
yield. In particular, condensation of 1,10-decanediol
with 2,6-di-tert-butylphenol resulted in 4-(10-hyd-
roxydecyl)-2,6-tert-butylphenol If in 40% yield and in
compound IIIf in 5% yield.
For the thermal stabilization of polyethylene at a
temperature 160°C the first place by performance
occupies compound VII with a short chain (n = 2).
Even greater performance showed compound VII,
n = 3, containing in the α-position of the aliphatic
chain an additional methyl group [9]. In practice, the
choice of antioxidants is limited to the sulfides with
the aliphatic chain –(CH2)n with the distance between
the aromatic ring and the sulfur atom not exceeding
n = 4, but not only the antioxidant effectiveness should
be taken into account, but also an important ability of
the phenols di- and polysulfides to the thermal
cleavage with the formation of large blocks [6].
Finally, we obtained from the compound II a sys-
tematic series of 4-(ω-hydroxyalkyl)-2,6-di-tert-butyl-
phenols I. Further studies on the synthesis of deriva-
tives obtained from these compounds led to the
creation of non-toxic and highly effective antioxidants
and the modifiers of performance properties of a wide
range of polymeric materials (a review of patents, see
[6]). This provided a basis for the long term
prohibition of the publication [2]. Among the most
accessible and interesting by the properties were
sulfur-containing derivatives VII, whose properties, as
we disclose below, are dependent on the length of the
aliphatic fragment of the para-substituent in the
starting compound I.
In fats, the antioxidant activities of sulfides VII and
their structurally relative disulfides are close, but for
the latter was noted a higher reactivity in the reactions
with peroxides [11]. These compounds significantly
increase the antioxidant properties of the products used
in medical practice (vitamin E, mexidol, and others)
that determines the prospects of their use in medicine
[12].
The most technologically promising among the
known methods for producing sulfides VII was
implemented on an experimental facility of the
Institute of Organic Chemistry NIOCh SB RAS: a one-
pot reaction in the presence of DMF consisting in the
consecutive action of PCl3 on a compound I, and then
of anhydrous Na2S, leading to pure sulfides in 80–85%
yield [7].
EXPERIMENTAL
Elemental composition and molecular weight of
compounds were obtained at the analysis of their high
resolution mass spectra taken on a Finnigan MAT
8200 mass-spectrometer at a temperature of 200°C.
(1) PCl3
(2) Na2S
(CH2)n
I
S
HO
90−100oC
1
The H NMR spectra were taken on a Varian A-56/60
instrument at operating frequency 60 MHz from 10%
solutions in CDCl3. Complete IR, UV, and H NMR
1
2
spectra of the synthesized compounds are listed in the
atlas of spectra [14]. Their melting temperatures were
determined on a Köffler heating block. The GLC
analysis of reaction mixtures was performed on a gas
chromatograph “Tsvet.”
VII
I, VII, n = 2–10.
The results of the study of the effectiveness of
sulfides VII as the antioxidants for polymers were
obtained in Plastpolymer enterprise (St. Petersburg)
[8]. They showed a high efficiency of these sulfur-
Reaction of 2,6-di-tert-butylphenol with propane-
1,3-diol. A mixture of 13.8 (0.067 mol) of 2,6-di-tert-
butylphenol, 7.5 g of NaOH, and 1.5 g of ZnO in
21 ml of propanediol-1,3 (molar ratio 1:2.8:0.26:3.8)
containing compounds. Therewith
a
remarkable
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 10 2010

2004
KRYSIN et al.
was placed in a steel rotating autoclave of capacity 0.1 l
and maintained at 180°C for 15 h. After cooling, the
reaction mixture was neutralized with hydrochloric
acid, extracted with ether, the organic layer was
evaporated and the residue, 18.7 g, was distilled in a
vacuum. 7.9 g of a fraction with the bp in the range
160–170°C at 1 mm Hg was isolated, which was
crystallized from n-heptane and gave 5.3 g (yield 30%)
of compound Ib, mp 66.5–67.5°C. At standing in air of
toluene solution of this compound the solvent slowly
evaporated with the formation of transparent cubic
crystals with mp 69–70°C. According to [3], mp of
compound Ib 66.5–67.5°C.
off and butane-1,4-diol excess was separated by
distillation. Organic extract was evaporated, and 16.4 g
of oil was separated. According to GLC it contains
73% of 4-(4-hydroxybutyl)-2,6-di-tert-butylphenol Ib,
9% of di-tert-butylphenol, 8% of 1,4-bis-(3,5-di-tert-
butyl-4-oxyphenyl)butane IIIc, and 6% of other
products. The mixture was distilled in a vacuum. First
fraction, 2,6-di-tert-butylphenol, 2.5 g, bp 75–100°C at
1–2 mm Hg. Second fraction, 10 g, bp 165–175°C at
1–2 mm Hg, according to the GLC consisted of 4-(4-
hydroxybutyl)-2,6-di-tert-butylphenol Ic. On keeping,
the product solidified, mp 27–28°C (from n-heptane).
Found, %: C 77.72; H 10.80; M 280 (by isothermal
distillation). C18H30O2. Calculated, %: C 77.69; H
The bottom residue, 5.0 g, was separated by column
chromatography on silica gel. Eluents: a mixture of
petroleum ether with benzene, benzene, a mixture of
benzene with ethyl acetate. Isolated: 2.0 g of 4,4'-
methylene-bis-(2,6-di-tert-butylphenol) IIIa, mp 151–
153°C (by the data of [15] mp 154°C) and 0.9 g of 1,1-
1
10.78; M 278.42. H NMR spectrum (100 MHz), δ,
ppm (CCl4): 1.40 s (18H, C4H9-tert), 1.55 m (4H,
CH2CH2), 2.48 t (J = 7 Hz, 2H, ArCH2), 3.53 t (J = 8 Hz,
CH2OH), 3.80–4.40 br (2H, OH), 6.85 s (2H, ArH).
Third fraction, 2.5 g, bp 175–220°C (1 mm Hg). It was
applied to a column containing 50 ml of silica gel and
eluted with a mixture of benzene–petpoleum ether 1:3.
After evaporation of solvent was obtained 1.0 g (8%)
of 1,4-bis(3,5-di-tert-butyl-4-oxyphenyl)butane IIIc,
mp 126–128°C (according to [14], mp 126–128°C).
Found: m/z 466.380 (mass spectrometry). C32H50O2.
Calculated: M 446.742. 1H NMR spectrum (100 MHz),
δ, ppm (CCl4): 1.40 s (36H, C4H9-tert), 1.55 m (4H,
CH2CH2), 2.47 t (J = 7 Hz, 4H, ArCH2), 6.80 s (4H,
ArH).
bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane
IV,
mp 156–157°C, whose structure is established by
comparison with known sample obtained by the reac-
tion of 2,6-di-tert-butylenol with allylamine [5].
Reaction of 2,6-di-tert-butylphenol with 3-methyl-
butane-1,3-diol. A mixture of 6.6 g of 2,6-di-tert-butyl-
phenol, 3.5 g of NaOH, and 18 g of 3-methylbutane-
1,3-diol (molar ratio 1:2.7:5.3) was maintained at
rotation in a steel autoclave of 0.1 l capacity for 5 h at
a temperature of 200°C. The product was cooled,
acidified, and extracted with ether. The extract was
washed with water and evaporated to obtain 14.7 g of
oil which was separated on a column with silica gel,
eluent benzene–ethyl acetate 5:1 mixture. The fraction
of 5.3 g of 4-hydroxyalkyl-2,6-di-tert-butylphenol was
distilled in a vacuum and 4.0 g of oil with bp 160–162°C
at 2–3 mm Hg was isolated. Found, m/z: 292.446.
C19H32O2 (by mass spectrometry). Calculated: M
4-(3,5-Di-tert-butyl-4-hydroxyphenyl)butan-2-ol
(V). In a flask was placed 12.3 g of crude 2,6-di-tert-
butylphenol, 6 g of NaOH, and 27 g of butane-1,3-diol
(molar ratio 1:2.7:5.3), and at a temperature of 150°C
(bath temperature) under a flow of an inert gas from
the reactor water was distilled off and then the reaction
mixture was kept at 200°C for 5 h. After cooling, the
product was diluted with water, neutralized with 10%
hydrochloric acid, and extracted with ether. The solvent
was evaporated and residual oil (19.3 g) was distilled
in a vacuum collecting the fraction with boiling point
170°C at 2 mm Hg. 9.5 g (61%) of 4-(3,5-di-tert-butyl-
4-oxyphenyl)butan-2-ol with mp 66–68°C (from hexane)
was isolated. Found (mass spectrometry): m/z
278.2250. C18H30O2. Calculated: M 278.2246. 1H
NMR spectrum (100 MHz), δ, ppm (CCl4): 1.17 d (J =
9 Hz, CH3CH), 1.43 s [8H, C(CH3)3], 1.70 m
(CH2CH), 2.58 t (J = 7 Hz, ArCH2), 4.84 s (OH), 6.88
s (2H, ArH).
1
292.240. According to H NMR spectrum, it is a
mixture of three isomeric 4-hydroxypentyl-2,6-di-tert-
butylphenols with close content of each.
Reaction of 2,6-di-tert-butylphenol with butane-
1,4-diol. In a flask was placed 12 g of 2,6-di-tert-
butylphenol, 2.96 g of NaOH, 27 g of freshly distilled
butane-1,4-diol, and 0.2 g of ZnO (molar ratio
1:1.3:5.5:0.03). The reaction mixture was stirred for
5 h at 190°C under an inert atmosphere with simul-
taneous distilling off of the formed water. After cool-
ing, the product was neutralized with 10% hydro-
chloric acid and extracted with petroleum ether. Water
solution was evaporated, NaCl precipitate was filtered
3-(3,5-Di-tert-butyl-4-hydroxyphenyl)-2,2-dime-
thylpropan-1-ol (VI). 2,6-Di-tert-butylphenol, 75 g,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 10 2010

SYNTHESIS OF 4-(ω-HYDROXYALKYL)-2,6-DI-tert-BUTYLPHENOLS
2005
NaOH, 19 g, and neopentyl glycol, 200 g, (molar ratio
1:1.3:5.3) was placed in a steel rotating 0.5 l autoclave
and maintained for 5 h at 220°C. The reaction mixture
was then cooled, neutralized with 10% hydrochloric
acid, and extracted with petroleum ether. 95 g of oil
was obtained that contained by the GLC data 40% of
3-(3,5-di-tert-butyl-4-oxyphenyl)-2,2-dimethylpropan-
1-ol, 35% of bis-(3,5-di-tert-butyl-4-hydroxyphenyl)
methane IIIa and 4.5% of the initial 2,6-di-tert-
butylphenol, as well as some other com-ponents. Com-
pound IIIa precipitated, 19.9 g, mp 152.5–153°C
(according to [15] mp 154°C). The filtrate after
separation of compound IIIa was distilled in a vacuum.
First fraction, 14.8 g of isobutanol, bp 60–95°C at
760 mm Hg. Second fraction, 11.2 g of neopentyl
glycol, bp 112–113°C at 2–3 mm Hg, mp 127°C. Third
fraction, 16.2 g (yield 15%), bp 160–173°C at 2–
3 mm Hg, oil, solidified on keeping. After crys-
tallization from n-heptane was isolated 13.2 g of 3-
(3,5-di-tert-butyl-4-hydroxyphenyl)-2,2-dimethyl-
propan-1-ol VI, mp 68–69°C. Found, %: C 79.07; H
10.67. M 292.5 (isothermal distillation). C19H22O2.
11.33. M 308.5. 1H NMR spectrum (100 MHz), δ, ppm
(CCl4): 1.40 s (18H, C4H9-tert), 1.3–1.8 m [8H, (CH2)4],
2.45 t (J = 7 Hz, ArCH2), 2.68 s (1H, OH), 3.5 t (J =
8 Hz, 2H, CH2OH), 4.89 s (1H, ArOH), 6.89 s (2H,
ArH).
1,6-Bis-(3,5-di-tert-butyl-4-hydroxyphenyl)hextane
(IIId), mp 152.5–153°C (from n-heptane), yield 7%.
Found, %: C 81.93, H 10.84. M 492 (by isothermal
distillation). Calculated, %: C 82.53, H 11.00. M
494.77. 1H NMR spectrum (100 MHz), δ, ppm (CCl4):
1.42 s (36 H, C4H9-tert), 1.1–1.9 m [8H, (CH2)4], 2.47
t (J = 7 Hz, 4H, ArCH2), 4.80 s (2H,OH), 6.85 s (4H,
Ar–H).
4-(7-Hydroxyheptyl)-2,6-di-tert-butylphenol (If),
mp 39–40°C (from n-heptane). Yield 40%. Found, %:
C 78.83 H 11.38. M 320 (by isothermal distillation).
1
C21H36O2. Calculated: C 78.70 H 11.26. M 320.5. H
NMR spectrum (100 MHz), δ, ppm (CCl4): 1.4 s (18H,
C4H9-tert), 2.45 t (J = 7 Hz, ArCH2), 4.89 s (ArOH),
6.85 s (2H, ArH), 1.2–1.8 m [10H, (CH2)5], 3.50 t (J =
8 Hz, CH2OH), 2.7 s( OH).
1
Calculated, %: C 79.02; H 11.02. M 292.44. H NMR
1,6-Bis-(3,5-di-tert-butyl-4-hydroxyphenyl)heptane
(IIIe), mp 97–98°C (from n-heptane), yield 5%.
Found: m/z 508.426 (mass spectrometry). C35H56O2.
Calculated: M 508.798. 1H NMR spectrum (100 MHz),
δ, ppm (CCl4): 1.40 s (36H, C4H9-tert), 1.1–1.9 m
(10H, (CH2)5), 2.40 t (J = 7 Hz, 4H, ArCH2), 4.80 s
(2H, OH), 6.80 s (4H, Ar–H).
spectrum (100 MHz), δ, ppm (CCl4): 0.85 s 6H, CH3),
1.43 s [8H, C(CH3)3] 2.44 s (ArCH2), 3.23 s (OH),
3.50 s (CH2OH), 4.92 s (OH), 6.87 s (2H, ArH).
General procedure for joint synthesis of 4-(ω-
hydroxyalkyl)-2,6-di-tert-butylphenol (Id–If) and
1,ω-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)alkanes
(IIId–IIIf). In a glass reactor were placed 2,6-di-tert-
butylphenol, granulated NaOH, and 1,ω-alkandiol at
the reagent ratio 1:1.3:4 (mol), and the mixture was
stirred for 5 h in a flow of inert gas with heating at
220°C, with distilling off the reaction water. On
cooling, the product was neutralized with hydrochloric
acid and extracted with petroleum ether. The solvent
was evaporated, and the residue containing up to 60%
of alcohol I and 5% of a bis-alkane IIId–IIIf was
applied to a column with silica gel and eluted suc-
cessively with a mixture of petroleum ether–benzene
3:1, benzene and ethyl acetate. The evaporation of the
first fraction gave 1,ω-bis-(3,5-di-tert-butyl-4-hyd-
roxyphenyl)alkane IIId–IIIf (yield about 5%). The
evaporation of the third fraction resulted in 4-(ω-
hydroxyalkyl)-2,6-di-tert-butylphenol I, which was
purified by distillation in a vacuum, yield 45–60%.
4-(10-Hydroxydecyl)-2,6-di-tert-butylphenol (If).
Oil, bp176–180°C at 2–3mm Hg. Yield 39.3%. Found,
%: C 79.76. H 11.88. M 362 (by isothermal
distillation). C24H42O2. Calculated, %: C 79.49, H
1
11.67. M 362.57. H NMR spectrum (100 MHz), δ,
ppm (CCl4): 1.2–1.8 m (CH2)8, 1,4 s (18H, C4H9-tert),
2.45 t (J = 7 Hz, ArCH2), 2.67 s (OH), 3.50 t (J = 8
Hz, 2H,CH2OH), 4.9 s (1H, ArOH), 6.85 s (2H, ArH).
1,10-Bis-(3,5-di-tert-butyl-4-hydroxyphenyl)decane
(IIIf), mp 93–95°C (from n-heptane). Yield 5%.
Found: m/z 550.47510 (mass spectrometry). C38H62O2.
Calculated: M 550.47498. 1H NMR spectrum (100 MHz),
δ, ppm (CCl4): 1.1–1.9 m [10H, (CH2)5], 1.43 s (36H,
C4H9-tert), 2.47 t (J = 7 Hz, 4H, ArCH2), 4.82 s (2H,
OH), 6.85 s (4H, ArH).
REFERENCES
4-(6-Hydroxyhexyl)-2,6-di-tert-butylphenol (Id),
oil, bp 174–181°C at 2–3 mm Hg. Yield 46,5%.
Found, %: C 78.68, H 11.27. M 306 (by isothermal
distillation). C20H34O2. Calculated, %: C 78.74, H
1. Ershov, V.V., Volod’kin, A.A., Kudrina, L.I., and
Vol’eva, V.B., USSR Inventor’s Certificate no. 727614,
1978, Byul. Izobret., 1980, no. 14.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 10 2010

2006
KRYSIN et al.
2. Krysin, A.P., Pustovskikh, I.I., Borisenko, L.A., Kop-
tyug, V.A., and Gorodetskaya, N.N., USSR Inventor’s
Certificate no. 877918, 1979, Byul. Izobret., 2009, no. 26.
Tsvetkova, A.I., Lazareva, N.P., Sokolova, T.G., Ki-
rillova, E.I., Emel’yanova, A.T., Lenin, E.S.,
Kuznetsova, S.V., and Malakhova, G.P., USSR
Inventor’s Certificate no. 988840, 1983, Byul. Izobret.,
1983, no. 2.
3. Parker, D.K. and Kline, R.H., US Patent no. 4260832,
1979, Chem. Abstr., 1981, vol. 95, no. 9, P80467g.
11. Storozhok, N.M., Gureeva, N.V., and Krysin, A.P.,
Nauchnyi Vestnik Tomskoi Med. Akad., 2003, vol. 23,
no. 1, pp. 18–22.
12. Perevozkina, M.G., Storozhok, N.M., Krysin, A.P., and
Borisenko, V.E., Izv. Akad. Nauk, Ser. Khim., 2006,
no. 8, pp. 1330–1337.
4. Krysin, A.P. and Pokrovskii, L.M., Zh. Obshch. Khim.,
2008, vol 78, no. 9, pp. 1496–1501.
5. Krysin, A.P. and Khalikova, N.U., Izv. Sib. Otd. Akad.
Nauk SSSR, Ser. Khim., 1984, no. 2, pp. 131–132;
6. Nikulicheva, O.N., Krysin, A.P., and Fadeeva, V.P., Zh.
Prikl. Khim., 2008, vol. 81, no. 9, pp. 1517–1522.
13. Anisimova, I.L., Krysin, A.P., and Storozhenko, V.G.,
Atlas spektrov aromaticheskikh i geterotsiklicheskikh
soedinenii. IK-, UF- i PMR-spektry 2-tret-butyl- i 2,6-
di-tret-butylfenolov (Atlas of the Spectra of Aromatic
7. Prosenko, A.E., Markov, A.F., Pinko, P.I., Krysin, A.P.,
and Koptyug, V.A., USSR Inventor’s Certificate
no. 1658601, 1989, Byul. Izobret., 1995, no. 26.
8. Lugova, L.I., Makarova, G.P., Tsvetkova, A.I., Sotni-
kova, L.K., Dudinova, L.N., and Lazareva, N.P., Coll.
of Publications: Organic Compounds, New Stabilizers.
Synthesis, Properties, and Processing of Polyphenols,
Leningrad: Plastpolymer, 1984, pp. 152–158.
9. Demidov,a V.M., Lugova, L.I., Prosenko, A.E.,
Kim, A.M., Koptyug, V.A., Krysin, A.P., Shiryaeva, L.V.,
and Dudinova, L.N., USSR Inventor’s Certificate
no. 979428, 1981, Byul. Izobret., 1982, no. 45.
10. Makarova, G.P., Lugova, L.I., Prosenko, A.E.,
Kim, A.M., Koptyug, V.A., Krysin, A.P., Sotnikova, L.K.,
1
and Heterocyclic Compounds. IR, UV, and H NMR
Spectra of 2-tert-Butyl- and 2,6-Di-tert-butylphenols),
Koptyug, V.A., Ed., Novosibirsk, 1983, no. 25.
14. Plekhanova, L.G., Nikifopov, G.A., Ershov, V.V., and
Zakharov, E.P., Izv. Akad. Nauk SSSR, Ser. Khim.,
1973, no. 4, p. 843.
15. Gorbunov, B.N., Gurvich, Ya.A., and Maslova, I.P.,
Khimiya i tekhnologiya stabilizatorov polimernykh
materialov (Chemistry and Technology of the
Stabilizers of Chemical Materials), Moscow: Khimiya,
1981, p. 255.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 10 2010