Vinyl ethers and sulfides containing antioxidant functional groups

Article abstract of DOI:10.1007/s11172-009-0157-5

Methods for the synthesis of compounds combining in the molecule fragments of known antioxidants with reactive vinyloxy and vinylthio groups have been developed. Transesterification of methyl 3-[3,5-di(tert-butyl)-4-hydroxyphenyl] propionate with 2-(vinyl

Full text of DOI:10.1007/s11172-009-0157-5

Russian Chemical Bulletin, International Edition, Vol. 58, No. 6, pp. 1217—1223, June, 2009
1217
Vinyl ethers and sulfides containing antioxidant
functional groups*
L. N. Parshina, L. A. Oparina, M. Ya. Khil´ko, A. I. Albanov, and B. A. Trofimov
A. E. Favorsky Irkutsk Institute of Chemistry,
Siberian Branch of the Russian Academy of Sciences,
1
ul. Favorskogo, 664033 Irkutsk, Russian Federation.
Fax: +7 (395) 241 9346. Eꢀmail: boris_trofimov@irioch.irk.ru
Methods for the synthesis of compounds combining in the molecule fragments of known
antioxidants with reactive vinyloxy and vinylthio groups have been developed. Transesterification
of methyl 3ꢀ[3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxyphenyl]propionate with 2ꢀ(vinyloxy)ꢀ or 2ꢀ(vinylthio)ꢀ
ethanol furnished the high yields of 2ꢀ(vinyloxy)ꢀ and 2ꢀ(vinylthio)ethyl 3ꢀ[3,5ꢀdi(tertꢀbutyl)ꢀ
4
ꢀhydroxyphenyl]propionates. The reaction of 2ꢀ[(vinyloxy)ethoxymethyl]ꢀ and 2ꢀ[(vinylthio)ꢀ
ethoxymethyl]oxiranes with 2,2,6,6ꢀtetramethylpiperidinꢀ4ꢀol and 4ꢀaminodiphenylamine
proceeds with the oxirane ring opening and leads to the corresponding vinyloxy and vinylthio
derivatives of 2,2,6,6ꢀtetramethylpiperidinꢀ4ꢀol and monoꢀ and bisvinyloxy and ꢀvinylꢀ
thio derivatives of 4ꢀaminodiphenylamine at the primary amino group.
Key words: vinyl ethers and sulfides, antioxidants.
Most organic materials such as lubricants, rubbers,
polymers, biomaterials undergo oxidative destruction in
the presence of molecular oxygen, which is a complex
radical chain process.1 To inhibit autooxidation of
organic substrates antioxidants should be added. The most
well known antioxidants are sterically hindered phenols,
thiophenols, as well as aromatic and sterically hindered
heterocyclic amines, mainly derivatives of diphenylamine,
the best of our knowledge, this is the only class of antiꢀ
oxidants modified by introduction of a vinyloxy group. In
1
5
the work mentioned, the vinyl ethers of polyalkylꢀ
piperidinꢀ4ꢀol were obtained in 60—80% yield by the
vinylation of the corresponding alcohols with acetylene
under pressure in the presence of potassium or sodium
hydroxyde or by transvinylation with excess of vinyl ether
or ester in the presence of mercury salts. Later, it was
,2
1
,2
16
naphthylphenylamine, and piperidine. In the last years,
both a systematic search for new antioxidants3 and a
shown that the use of superbasic system KOH—DMSO
—5
allowed one to significantly reduce the temperature of
vinylation of polymethylꢀsubstituted piperidinꢀ4ꢀols (from
170—180 to 90 °C).
structural modification of existing antioxidants in order
to increase their efficiency are under way.6
—14
In this
case, an introduction of unsaturated groups into the strucꢀ
ture of antioxidants significantly increases a possibility of
Unlike piperidinols, other commonly used stabilizers
of polymers contain no functional groups capable of
vinylation with acetylene. In the present work, we
suggested a new approach to the synthesis of antioxidants
with vinyloxy and vinylthio groups based on the reaction
of stabilizers with functional fragments of available vinyl
ethers and sulfides, with reactive vinyloxy and vinylthio
groups in the molecule being unaffected.
The transesterification of methyl 3ꢀ[3,5ꢀdi(tertꢀbutyl)ꢀ
4ꢀhydroxyphenyl]propionate (1) with 2ꢀ(vinyloxy)ꢀ (2a)
or 2ꢀ(vinylthio)ethanol (2b) in the presence of base cataꢀ
lysts (10—40 mol.%) leads to the formation of 2ꢀ(vinylꢀ
oxy)ethyl or 2ꢀ(vinylthio)ethyl 3ꢀ[3,5ꢀdi(tertꢀbutyl)ꢀ
4ꢀhydroxyphenyl]propionates (3a,b, Scheme 1). The
alkoxides obtained by the reaction of alcohols 2a,b with
metallic sodium have proved the best catalysts of the
process.
their further transformations, providing preparation of new
monomeric or polymeric antioxidants.1
1—14
The latter
are considered as potential nonmigrating stabilizers of
plastics possessing important technical advantages, in
particular, they are nonvolatile, difficult to wash away,
1
1
and sometimes better compatible with the polymer.
The data published earlier1 have demonstrated that
antioxidants containing a vinyloxy group are very promisꢀ
ing. For example, it was shown that vinyl ethers of
polyalkylpiperidinꢀ4ꢀols, as well as their polymers, are
well compatible with polypropylene and exhibit excellent
lightꢀstabilizing properties over a long period of time. To
5
*
Dedicated to Academician O. N. Chupakhin on the occasion
of his 75th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1185—1191, June, 2009.
066ꢀ5285/09/5806ꢀ1217 © 2009 Springer Science+Business Media, Inc.
1

1218
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 6, June, 2009
Parshina et al.
Scheme 1
X = O (a), S (b)
The reaction is reversible, which is typical of transꢀ
at the terminal carbon atom of the oxirane ring (the
Krasuskii rule).
esterification.17 In the case of 2ꢀ(vinyloxy)ethanol (2a),
the equilibrium is shifted to the right due to the low soluꢀ
bility of forming propionate 3a in this alcohol taken in
excess, the product precipitated from the reaction mixꢀ
ture as a colorless needleꢀlike crystals. When 30—40 mol.%
of the catalyst with respect to the starting compound 1
is used, the reaction is completed after 1 h at room temꢀ
perature, but can be carried out further by addition of a
fresh portion of propionate 1, which results in higher
conversion of vinyloxyethanol 2a, with the yield of ester
The reaction between 2ꢀ[(vinyloxy)ethoxymethyl]ꢀ
(4a) or 2ꢀ[(vinylthio)ethoxymethyl]oxirane (4b) and steriꢀ
cally hindered amine, viz., 2,2,6,6ꢀtetramethylpiperidinꢀ
4ꢀol (5), smoothly proceeds upon heating (90—150 °C)
and leads chemoꢀ and regioselectively to the formation
of 1ꢀ{2ꢀhydroxyꢀ3ꢀ[2ꢀ(vinyloxy)ethoxy]propyl}ꢀ2,2,6,6ꢀ
tetramethylpiperidinꢀ4ꢀol (6a) or 1ꢀ{2ꢀhydroxyꢀ3ꢀ
[2ꢀ(vinylthio)ethoxy]propyl}ꢀ2,2,6,6ꢀtetramethylpiperiꢀ
dinꢀ4ꢀol (6b) (Scheme 2). The process was carried out in a
sealed system with equimolar ratio of reagents in the
absence of a solvent and a catalyst. The reaction course
3
a being 78%.
Transesterification of propionate 1 with 2ꢀ(vinylthio)ꢀ
1
ethanol (2b) proceeds otherwise: the product 3b formed is
a viscous liquid, in which a part of unreacted starting
compound 1 dissolves. Since both esters have close propꢀ
erties, their separation failed. To drive the equilibrium
to the right, it is not enough to only use a large (up to
was monitored by IR and H NMR spectroscopy from
the disappearance of characteristic absorption band
–
1
(ν ~3000 cm ) and signals for the oxirane ring (δ 3.14,
–
1
2.77, 2.60) and retention of major frequencies (ν/cm :
1620 (H C=CHO), 1580 (H C=CHS)) and signals for
2
2
1
0ꢀfold) excess of vinylthioethanol 2b and the methanol
the vinyloxy (δ 6.49, 4.18, 4.01) or vinylthio groups
(δ 6.35, 5.12), respectively.
formed cannot be distilled off even at 145 °C, whereas
transesterification at temperatures above 100 °C is accomꢀ
panied by considerable resinification.
These difficulties can be avoided by running the
process in low vacuum (~20 Torr). In this case, methanol
is being distilled off at 80—100 °C during the entire
synthesis (in a mixture with (vinylthio)ethanol 2b
taken in excess), the equilibrium is driven to the right,
and pure vinyl sulfide 3b can be obtained in up to
Despite the hydroxy group in the molecule of pipeꢀ
ridinol 5 unlike the amine group is sterically unhindered,
there is no formation of alternative products of the oxirane
ring opening of compounds 4a,b with participation of the
hydroxy group of alcohol 5 even if potassium or sodium
hydroxyde is used as a catalyst. This is inferred from analyꢀ
1
13
sis of the H and C NMR spectra, in which there are
present the signals for the NCH group (in the region
2
9
1% yield.
δ 2.7, 2.5, and 44.4—44.8) and absent additional signals
The reaction of 2ꢀ[(vinyloxy)ethoxymethyl]ꢀ and
ꢀ[(vinylthio)ethoxymethyl]oxiranes (4a,b) with 2,2,6,6ꢀ
for the OCH group (δ ~3.3—3.8 and ~60—75). The fact
2
2
that oxiranes 4a,b do not react with cyclohexanol under
indicated conditions serves as an indirect evidence that
the hydroxy group is inert in this process.
Adducts 6a,b are viscous undistillable liquids. They
need no purification, since, according to the IR and NMR
spectra, the process occurs with 100% conversion of
reagents. Heating in vacuo does not lead to isolation
of the starting or other volatile compounds.
tetramethylpiperidinꢀ4ꢀol or 4ꢀaminodiphenylamine,
common antioxidants belonging to the classes of heteroꢀ
cyclic and aromatic amines, became a basis for the method
of introduction of vinyloxy or vinylthio groups into
1
8,19
the structure of these amine antioxidants. Earlier,
it has been shown that oxirane 4a easily reacts with
aliphatic amines to exclusively form addition products

Vinyl ethers and sulfides with antioxidant moieties
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 6, June, 2009
1219
Scheme 2
X = O (a), S (b)
The reaction of oxiranes 4a,b with 4ꢀaminodiphenylꢀ
amine (7), containing amino groups different in characꢀ
ter, leads to the formation of addition products excluꢀ
sively involving the primary amino group (Scheme 3).
The evidence comes from the IR spectra of dilute soluꢀ
oxiranes 4a,b both the monoꢀ and the diadducts or their
mixtures. The synthesis of monoadducts of oxiranes 4a,b
with amine 7, in which the content of the starting antiꢀ
oxidant fragments is higher than in diadducts, corresponds
better to the goal of the present work.
tions of the reaction mixtures in CCl . As the reaction
Monitoring of the reaction course can be performed
by IR spectroscopy from the disappearance of the absorpꢀ
tion bands for the primary amino group, however more
precisely the reaction course can be controlled using
4
progresses, the absorption bands for the primary amino
group at 3390 and 3470 cm–1 gradually decrease, whereas
the absorption band for the secondary amino group at
–1
20
1
3
425 cm remains. In addition, earlier it has been shown
H NMR spectra, in which the signals for the oxirane ring
that diphenylamine, the structural analog of amine 7,
does not react with oxirane 4a.
(δ 2.77 and 2.60), having no overlap with the signals for
the forming products, gradually disappear.
2
1
It is known that alkyloxiranes react with aromatic
According to the literature data, the reaction of
oxiranes 4a,b with aminodiphenylamine 7 (Scheme 3) is
slower than the earlier studied reactions of oxirane 4a
2
1
amines significantly slower than with aliphatic. In addiꢀ
tion, the reactions of monoalkyloxiranes with aliphatic
amines lead only to the addition products of the amines to
the terminal carbon atom,1 whereas their reactions with
aromatic amines can give both regioisomers, though the
1
8,19
with aliphatic amines.
For instance, at room temperaꢀ
8,21
ture and equimolar ratio of reagents (7 and 4a or 4b), the
signals for the oxirane ring completely disappear after
4—5 days, whereas at the ratio 4a,b : 7 = 2 : 1, after
12—14 days. At 50 °C, the reaction time decrease to
13—14 h (equimolar ratio of reagents) and 18—20 h
addition product to the less substituted carbon atom of
the oxirane ring is still predominant.2
2,23
In addition, deꢀ
pending on the ratio of reagents amine 7 can give with
Scheme 3
4
—5 days
X = O (a), S (b)

1220
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 6, June, 2009
Parshina et al.
Scheme 4
X = O (a), S (b)
(
4a,b : 7 = 2 : 1), at 100 °C, to 3 and 5 h, respectively,
respectively) at ~20 °C in CDCl3 with HMDS as an internal
1
13
standard. Assignment of signals in the H and C NMR spectra
was performed using twoꢀdimensional homonuclear (COSY) and
heteronuclear (HMBS, HSQC) correlation techniques. Comꢀ
mercial methyl 3ꢀ[3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxyphenyl]propionate
however, at temperatures 100 °C and above, there is
observed an increase in viscosity of the products, that can
be due to the partial polymerization at the epoxide group.
1
13
Analysis of the H and C NMR spectra of the prodꢀ
ucts of this transformation shows that along with monoꢀ
adducts 8a,b, a significant amount of the corresponding
diadducts 9a,b is formed not only at the equimolar ratio
of reagents, but also if a 2ꢀfold excess of amine 7 is used,
whereas no formation of regioisomeric addition products
of the amine at the internal carbon atom is observed. This
is also confirmed by analysis of the IR spectra of dilute
(
2
(
1), 4ꢀaminodiphenylamine (7) (Uniroyal Chemical Co.),
,2,6,6ꢀtetramethylpiperidinꢀ4ꢀol (5), 2ꢀ(vinyloxy)ethanol (2a)
Aldrich Chemical Co.) were used in this work. 2ꢀ(Vinylthio)ꢀ
ethanol (2b) was obtained by vinylation of 2ꢀhydroxyethanethiol
2
4
with acetylene according to procedure described earlier.
2ꢀ[(Vinyloxy)ethoxymethyl]oxirane (4a) was synthesized from
2
ꢀ(vinyloxy)ethanol (2a) and epichlorohydrin as described in
1
8
monograph.
2
ꢀ(Vinyloxy)ethyl 3ꢀ[3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxyphenyl]ꢀ
propionate (3a). A catalyst prepared from metallic sodium (0.3 g,
3 mmol) and 2ꢀ(vinyloxy)ethanol (2a) (5.6 g, 63 mmol) was
solutions of products obtained in CCl . They contain only
4
the absorption band for the secondary hydroxy group at
1
–
1
3
580 cm , whereas the absorption band for the primary
added to a solution of methyl 3ꢀ[3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxyꢀ
phenyl]propionate (1) (10.0 g, 34 mmol) in 2ꢀ(vinyloxy)ethanol
(2a) (22.0 g, 250 mmol). After 1 h, a white precipitate formed
was filtered off, propionate 1 (5.0 g, 17 mmol) was added to the
mother liquor, and the homogeneous reaction mixture formed
was stirred for another 3 h at ~20 °C, a precipitate formed was
again filtered off, the last portion of propionate 1 (5.0 g, 17 mmol)
was added, and the mixture was left for 24 h. A precipitate
obtained was combined with two previous, dissolved in diethyl
ether, the ethereal solution was repeatedly washed with cold
water, dried with K CO . After the solvent was evaporated,
–
1
OH group (ν ~3630 cm ) is absent.
Since diadducts 9a,b are formed, a part of the starting
4
ꢀaminodiphenylamine remains unconsumed. According
to the NMR spectroscopic data, the reaction of oxiranes
a,b with amine 7 with an equimolar ratio of reagents
4
leads to a mixture of monoadduct 8, diadduct 9, and
unreacted compound 7 in the ratio ~3 : 1 : 1.
When a 2ꢀfold amount of oxirane 4a,b is used in
the reaction with amine 7, diadducts 9a,b are formed
2
3
(
1
Scheme 4) as a mixture of two diastereomers in the ratio
: 1, that can be clearly seen from the double set of
the product was obtained (18.6 g, 78%), m.p. 86 °C (light
petroleum—ethanol, 3 : 1), colorless crystals, well soluble in
diethyl ether, acetone, chloroform, moderately in alcohols and
1
13
signals in the H and especially C NMR spectra.
Products 8a,b and 9a,b are very viscous liquids black
in color, liquefying on heating. From the practical point
of view, there is no need to isolate individual monoadducts
hydrocarbons. Found (%): C, 72.54; H, 9.38. C21H32O .
4
Calculated (%): C, 72.38; H, 9.26. IR (KBr), ν/cm–1: 3431
(
OH); 3080, 3005 (=CH, =CH ); 1713 (C=O); 1622 (C=C).
2
1
H NMR, δ: 1.47 (s, 18 H, Me); 2.67 (t, 2 H, ArCH , J = 7.8 Hz);
2
8
a,b from the forming reaction mixtures. Most likely, the
2
.92 (t, 2 H, ArCH CH , J = 7.8 Hz); 3.92 (t, 2 H, CH O,
2
2
2
whole mixtures, as well as polymers on their basis, will
behave as antioxidants.
J = 4.7 Hz); 4.07 (dd, 1 H, =CHcis, J = 6.8 Hz, J = 2.1 Hz); 4.22
dd, 1 H, =CHtrans, J = 14.4 Hz, J = 2.1 Hz); 4.35 (t, 2 H,
(
In conclusion, compounds combining fragments of
known antioxidants and reactive vinyloxy and vinylthio
groups have been synthesized. The products obtained are
promising for the use both as independent antioxidants
and for the synthesis of new compounds with antioxidant
properties on their basis, including highꢀmolecularꢀmass
nonmigrating stabilizers for industrial polymers.
OCOCH , J = 4.7 Hz); 5.08 (s, 1 H, ArOH); 6.51 (dd, 1 H,
2
OCH=, J = 14.4 Hz, J = 6.8 Hz); 7.01 (s, 2 H, H(2), H(6)
arom.). 1 C NMR, δ: 30.2 (Me); 31.0 (CMe ); 34.2 (ArCH CH );
3
3
2
2
3
1
6.3 (ArCH ); 62.5 (OCOCH ); 65.7 (CH O); 87.0 (=CH );
24.7 (C(2), C(6) arom.); 130.9 (C(1) arom.); 135.9 (C(3),
2 2 2 2
C(5) arom.); 151.3 (OCH=); 152.1 (C(4) arom.); 173.0 (C=O).
ꢀ(Vinylthio)ethyl 3ꢀ[3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxyphenyl]ꢀ
propionate (3b). A mixture of methyl 3ꢀ[3,5ꢀdi(tertꢀbutyl)ꢀ
ꢀhydroxyphenyl]propionate (1) (1.75 g, 6 mmol), 2ꢀ(vinylthio)ꢀ
2
4
Experimental
ethanol (2b) (3.06 g, 29 mmol), and hydroquinone (0.3 g) was
placed into a threeꢀneck flask equipped with thermometer,
dropping funnel, and an adapter with condenser for distillation
of volatile compounds. The system was connected to a vacuum
pump (20 Torr), heated with stirring to 91 °C, followed by a slow
IR spectra were recorded on a Bruker JFSꢀ25 spectrometer
1
13
neat and in KBr pellets. H and C NMR spectra were recorded
on a Bruker DPXꢀ400 spectrometer (400.13 and 100.62 MHz,

Vinyl ethers and sulfides with antioxidant moieties
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 6, June, 2009
1221
(
over entire synthesis) dropwise addition of a catalyst (prepared
(ddd, 2 H, CH ring, J = 3.7 Hz, J = 11.6 Hz, J = 11.6 Hz); 2.54
2
from metallic sodium (0.014 g, 0.6 mmol) and 2ꢀ(vinylthio)ꢀ
ethanol (2b) (1.73 g, 17 mmol)) to the solution formed with
simultaneous evaporation of liberated methanol (in a mixture
with 2ꢀ(vinyloxy)ethanol). The process was stopped after 5 h,
a residual (2.88 g) viscous dark liquid was dissolved in diethyl
ether and the solution was passed through a short column with
Al O to remove the resinꢀlike products. The ethereal solution
(dd, 1 H, NCH , J = 9.1 Hz, J = 15.0 Hz); 2.66 (dd, 1 H,
2
NCH , J = 6.1 Hz, J = 15.0 Hz); 3.49 (d, 2 H, CH(OH)CH O,
2
2
J = 4.5 Hz); 3.62 (m, 1 H, CHOH); 3.74, 3.84 (both m, 4 H,
OCH CH O); 3.99 (dd, 2 H, =CHcis, CHOH ring, J = 6.8 Hz,
2
2
J = 1.8 Hz); 4.17 (dd, 1 H, =CHtrans, J = 14.4 Hz, J = 1.8 Hz);
4.22 (br.s, 1 H, OH); 6.47 (dd, 1 H, =CHO, J = 14.4 Hz,
J = 6.8 Hz). 1 C NMR, δ: 22.33, 23.50, 33.40, 34.46 (Me); 44.81
(NCH ); 49.97 (CH ring); 56.42, 56.77 (NCMe ); 63.31
3
2
3
was washed 4 times with small amounts of water and dried with
2
2
2
K CO . Diethyl ether and the residue of unreacted 2ꢀ(vinylꢀ
(CHOH ring); 66.90 (CHOH); 67.41 (OCH CH O); 70.02
2
3
2
2
thio)ethanol (2b) were evaporated (the latter, in vacuo (5 Torr)).
The residue contained propionate 3b (2.0 g, 91%) as a moderately
viscous yellowish liquid, nD20 1.4771. Found (%): C, 69.11;
H, 8.70; S, 8.65. C H O S. Calculated (%): C, 69.19; H, 8.85;
(OCH CH O); 74.83 (CH(OH)CH O); 86.78 (=CH ); 151.83
(=CHO).
2
2
2
2
1ꢀ{2ꢀHydroxyꢀ3ꢀ[2ꢀ(vinylthio)ethoxy]propyl}ꢀ2,2,6,6ꢀtetraꢀ
methylpiperidinꢀ4ꢀol (6b) was obtained similarly to compound
6a by heating a mixture of alcohol 5 (1.57 g, 10 mmol) and
oxirane 4b (1.60 g, 10 mmol) for 4.5 h at 135 °C in a sealed
tube. The yield of product 6b was quantitative, viscous yellowish
liquid, nD2 1.5280. Found (%): C, 59.86; H, 9.94; N, 4.43;
21
32
3
–
1
S, 8.79. IR (neat), ν/cm : 3637 (OH); 3089, 3005 (=CH,
1
=
CH ); 1736 (C=O); 1586 (C=C). H NMR, δ: 1.48 (s, 18 H,
2
Me); 2.67 (t, 2 H, ArCH , J = 7.8 Hz); 2.93 (t, 2 H, ArCH CH ,
2
2
2
0
J = 7.8 Hz); 2.96 (t, 2 H, CH S, J = 6.8 Hz); 4.31 (t, 2 H,
2
CH CH S, J = 6.8 Hz); 5.13 (s, 1 H, ArOH); 5.26 (d, 1 H,
S, 9.63. C16H31NO S. Calculated (%): C, 60.53; H, 9.84;
2
2
3
–
1
=
CHtrans, J = 16.6 Hz); 5.29 (d, 1 H, =CHcis, J = 10.0 Hz); 6.37
N, 4.41; S, 10.10. IR (neat), ν/cm : 3406 (OH); 3093 (=CH);
1
(
dd, 1 H, SCH=, J = 16.6 Hz, J = 10.0 Hz); 7.04 (s, 2 H, H(2),
1584 (C=C). H NMR, δ: 1.06, 1.11 (both s, 12 H, Me); 1.38
1
3
H(6) arom.). C NMR, δ: 29.9 (CH S); 30.2 (Me); 30.8
(t, 2 H, CH2 ring, J = 11.4 Hz); 1.87 (ddd, 2 H, CH2 ring,
J = 3.7 Hz, J = 11.4 Hz, J = 11.4 Hz); 2.55 (dd, 1 H, NCH2,
2
(
CMe ); 34.2 (ArCH ); 36.2 (ArCH CH ); 62.6 (OCOCH );
3 2 2 2 2
1
1
1
11.9 (CH =); 124.7 (C(2), C(6) arom.); 130.9 (C(1) arom.);
31.2 (SCH=); 135.9 (C(3), C(5) arom.); 152.1 (C(4) arom.);
72.8 (C=O).
J = 9.2 Hz, J = 15.0 Hz); 2.66 (dd, 1 H, NCH , J = 6.1 Hz,
2
2
J = 15.0 Hz); 2.90 (t, 2 H, CH S, J = 6.8 Hz); 3.45 (d, 2 H,
2
CH(OH)CH O, J = 4.8 Hz); 3.61 (m, 1 H, CHOH); 3.69 (t,
2
2
ꢀ[(Vinylthio)ethoxymethyl]oxirane (4b). Epichlorohydrin
2 H, OCH CH S, J = 6.8 Hz); 3.99 (m, 1 H, CHOH ring);
2
2
(
37.0 g, 400 mmol) was added to a mixture of 2ꢀ(vinylthio)ꢀ
4.12 (br.s, 1 H, OH); 5.15 (d, 1 H, =CHcis, J = 10.2 Hz);
5.18 (d, 1 H, =CHtrans, J = 16.6 Hz); 6.35 (dd, 1 H, =CHS,
J = 16.6 Hz, J = 10.2 Hz). 1 C NMR, δ: 21.95, 23.13 (Me);
30.68 (CH S); 33.04, 34.15 (Me); 44.45 (NCH ); 49.53 (CH
ethanol (2b) (10.4 g, 100 mmol) and NaOH (6.0 g, 150 mmol)
over 20 min, followed by stirring for 6 h at 45—50 °C.
A precipitate formed was filtered off, washed with diethyl ether,
the ethereal solution obtained was combined with the filtrate.
Diethyl ether and excess epichlorohydrin were evaporated, the
residue was distilled in vacuo to obtain compound 4b (10.2 g,
3
2
2
2
ring); 56.01, 56.37 (NCMe ); 62.63 (CHOH ring); 66.40
2
(CHOH); 69.87 (OCH CH S); 74.07 (CH(OH)CH O); 110.81
2
2
2
(=CH ); 131.83 (SCH=).
2
2
0
6
4%), b.p. 80—82 °C (4 Torr), n
1.5025, which corresponds
Reaction of 2ꢀ[(vinyloxy)ethoxymethyl]ꢀ and 2ꢀ[(vinylthio)ꢀ
ethoxymethyl]oxiranes (4a,b) with 4ꢀaminodiphenylamine (7).
A. Monoadducts. An equimolar mixture of oxirane 4a,b and
4ꢀaminodiphenylamine (7) was thoroughly stirred until complete
dissolution of amine 7 in oxirane 4a,b and kept for 5 days at
~20 °C until complete disappearance of signals at δ 2.60 (dd)
D
2
5
to the literature data. Found (%): C, 52.88; H, 7.79; S, 19.65.
C H O S. Calculated (%): C, 52.47; H, 7.55; S, 20.01.
IR (neat), ν/cm : 3054 (=CH); 2999 (CH oxirane); 1585
(
7
12
2
–
1
1
C=C); 1254, 907 (oxirane ring). H NMR, δ: 2.61 (dd, 1 H,
CHCH , J = 2.7 Hz, J = 5.0 Hz); 2.79 (dd, 1 H, CHCH ,
2
2
J = 4.2 Hz, J = 5.0 Hz); 2.90 (t, 2 H, SCH , J = 6.7 Hz); 3.14
and 2.78 (t) (corresponding to the CH group of the oxirane
ring) in the H NMR spectrum of the reaction mixture to obtain
2
2
1
(
m, 1 H, CH); 3.40 (dd, 1 H, OCH CH, J = 5.8 Hz, J = 11.6 Hz);
2
3
.70 (m, 2 H, CH O); 3.78 (dd, 1 H, OCH CH, J = 2.8 Hz,
dark very viscous products, which liquefied upon heating, soluble
in acetone, chloroform, benzene, and insoluble in water and
2
2
J = 11.6 Hz); 5.15 (d, 1 H, =CHtrans, J = 16.7 Hz); 5.19 (d, 1 H,
CHcis, J = 10.1 Hz); 6.35 (dd, 1 H, =CHS, J = 16.7 Hz,
1
13
=
hexane. According to the H and C NMR spectra, the products
obtained are mixtures of the starting amine 7 (~20%), monoꢀ
adduct 8a,b (~60%), and diadduct 9a,b (~20%), the latter, as
two diastereomers. Column chromatography of the reaction
mixture (alumina, eluent, CH Cl —hexane, 1 : 1) resulted in
13
J = 10.1 Hz). C NMR, δ: 30.99 (SCH ); 44.05 (CHCH );
2
2
5
1
0.65 (CH); 70.0 (CH O); 71.56 (CH O); 111.26 (CH =);
2 2 2
31.93 (=CHS).
ꢀ{2ꢀHydroxyꢀ3ꢀ[2ꢀ(vinyloxy)ethoxy]propyl}ꢀ2,2,6,6ꢀtetraꢀ
methylpiperidinꢀ4ꢀol (6a). A mixture of alcohol 5 (1.57 g,
0 mmol) and oxirane 4a (1.44 g, 10 mmol) in a tightly capped
1
2
2
the separation of the mixture of monoadduct 8a and the starting
amine 7 from diadduct 9a, which remained on the column.
1ꢀ(4ꢀAnilinoanilino)ꢀ3ꢀ[2ꢀ(vinyloxy)ethoxy]propanꢀ2ꢀol (8a).
IR (neat), ν/cm–1: 3386 (NH); 3540 sh (OH); 3114, 3015 (=CH,
1
vessel or tube was heated for 4.5 h at 135 °C with magnetic
stirring. The reaction reached completion if the reaction mixture
became homogeneous after cooling; otherwise, the reaction
mixture grew turbid due to the precipitation of the starting
compound 5. The product 6a was obtained as a viscous yellowish
liquid in quantitative yield, nD20 1.4930. Found (%): C, 64.00;
1
=CH ); 1636, 1618 (C=C). H NMR, δ: 2.63 (br.s, 1 H, OH);
2
3.14 (dd, 1 H, NCH , J = 6.8 Hz, J = 12.7 Hz); 3.28 (dd, 1 H,
2
NCH , J = 4.3 Hz, J = 12.7 Hz); 3.57 (dd, 1 H, CH(OH)CH O,
2
2
J = 6.6 Hz, J = 9.8 Hz); 3.64 (dd, 1 H, CH(OH)CH O,
2
H, 10.71; N, 4.60. C16H31NO . Calculated (%): C, 63.75;
J = 3.6 Hz, J = 9.8 Hz); 3.75, 3.85 (both m, 4 H, OCH CH O);
4
2
2
–
1
H, 10.37; N, 4.65. IR (neat), ν/cm : 3402 (OH); 3117, 3072,
4.04 (dd, 2 H, =CHcis, CHOH, J = 6.8 Hz, J = 2.0 Hz); 4.22
(dd, 1 H, =CHtrans, J = 14.3 Hz, J = 2.0 Hz); 5.38 (br.s, 2 H,
NH); 6.49 (dd, 1 H, =CHO, J = 14.3 Hz, J = 6.8 Hz); 6.62 (d,
1
3
031 (=CH , =CH); 1636, 1619 (C=C). H NMR, δ: 1.05, 1.10
2
(
both s, 12 H, Me); 1.38 (t, 2 H, CH ring, J = 11.6 Hz); 1.88
2

1222
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 6, June, 2009
Parshina et al.
2
H, H(2), H(6) arom., J = 8.7 Hz); 6.77 (t, 1 H, H(4´) arom.,
69.97, 70.03 (OCH CH O); 73.24, 73.33 (CH(OH)CH O);
2
2
2
J = 7.2 Hz); 6.83 (d, 2 H, H(2´), H(6´) arom., J = 7.8 Hz); 6.99
d, 2 H, H(3), H(5) arom., J = 8.7 Hz); 7.17 (m, 2 H, H(3´),
86.98 (CH =); 113.95, 115.10 (C(2), C(6) arom.); 115.29, 115.42
2
(
(C(2´), C(6´) arom.); 119.01, 119.14 (C(4´) arom.); 122.71,
123.22 (C(3), C(5) arom.); 129.28 (C(3´), C(5´) arom.); 132.75,
133.37 (HN—C(1) arom.); 144.21, 144.88 (HN—C(4) arom.);
145.65, 145.88 (HN—C(1´) arom.); 151.67 (=CHO).
13
H(5´) arom.). C NMR, δ: 47.13 (NCH ); 67.20 (OCH CH O);
2
2
2
6
8
8.91 (CHOH); 69.81 (OCH CH O); 73.65 (CH(OH)CH O);
2 2 2
6.98 (CH =); 114.12 (C(2), C(6) arom.); 114.84 (C(2´),
2
C(6´) arom.); 118.72 (C(4´) arom.); 123.46 (C(3), C(5) arom.);
29.13 (C(3´), C(5´) arom.); 133.20 (HN—C(1) arom.); 144.32
HN—C(4) arom.); 146.00 (HN—C(1´) arom.); 151.56 (=CHO).
ꢀ(4ꢀAnilinoanilino)ꢀ3ꢀ[2ꢀ(vinylthio)ethoxy]propanꢀ2ꢀol (8b).
10ꢀ(Anilinophenyl)ꢀ6,14ꢀdioxaꢀ3,17ꢀdithiaꢀ10ꢀazaꢀ
1,18ꢀnonadecadieneꢀ8,12ꢀdiol (9b). Found (%): C, 61.54;
H, 7.05; N, 5.41; S, 12.68. C H N O S . Calculated (%):
1
(
2
6
36
2
4 2
–
1
1
C, 61.87; H, 7.19; N, 5.55; S, 12.71. IR (neat), ν/cm : 3378
–
1
IR (neat), ν/cm : 3385 (NH); 3540 sh (OH); 3086, 3020
(NH); 3530 sh (OH); 3091, 3030 (=CH, =CH ); 1585 (C=C).
2
1
1
(
=CH, =CH ); 1585 (C=C). H NMR, δ: 2.91 (t, 2 H, SCH ,
H NMR, δ: 2.90, 2.91 (both t, 4 H, SCH , J = 6.4 Hz); 3.17
2
2
2
J = 6.3 Hz); 3.14 (dd, 1 H, NCH , J = 6.9 Hz, J = 12.7 Hz);
(dd, 1 H, NCH , J = 9.0 Hz, J = 15.0 Hz); 3.36 (dd, 1 H, NCH ,
2
2
2
3
1
.27 (dd, 1 H, NCH , J = 4.3 Hz, J = 12.7 Hz); 3.52 (dd,
J = 7.9 Hz, J = 15.0 Hz); 3.44 (dd, 1 H, NCH , J = 4.3 Hz,
2
2
H, CH(OH)CH O, J = 6.6 Hz, J = 9.6 Hz); 3.59 (dd, 1 H,
J = 15.0 Hz); 3.47 (dd, 2 H, CH(OH)CH O, J = 5.9 Hz,
2
2
CH(OH)CH O, J = 3.7 Hz, J = 9.6 Hz); 3.70 (m, 2 H,
J = 9.5 Hz); 3.54, 5.56 (both dd, 2 H, CH(OH)CH O, J = 4.4 Hz,
2
2
OCH CH S); 4.00 (m, 1 H, CHOH); 5.17 (d, 1 H, =CHtrans,
J = 9.5 Hz); 3.70 (m, 7 H, OCH CH S, CHOH, NCH ); 4.06,
2
2
2
2
2
J = 16.8 Hz); 5.20 (d, 1 H, =CHcis, J = 10.1 Hz); 5.38 (br.s, 2 H,
NH); 6.35 (dd, 1 H, =CHS, J = 16.8 Hz, J = 10.1 Hz); 6.62
4.15 (both br.s, 2 H, OH); 5.16 (d, 2 H, =CHtrans, J = 16.5 Hz);
5.19 (d, 2 H, =CHcis, J = 10.1 Hz); 5.42 (br.s, 1 H, NH); 6.35
(dd, 2 H, =CHS, J = 16.5 Hz, J = 10.1 Hz); 6.68 (d, 1 H, H(2),
H(6) arom., J = 8.8 Hz); 6.80 (m, 2 H, H(2), H(6), H(4´) arom.);
6.85, 6.86 (both d, 2 H, H(2´), H(6´) arom., J = 7.0 Hz); 7.02,
7.04 (both d, 2 H, H(3), H(5) arom., J = 8.4 Hz); 7.18 (t, 2 H,
(
d, 2 H, H(2), H(6) arom., J = 8.7 Hz); 6.76 (t, 1 H, H(4´) arom.,
J = 7.2 Hz); 6.82 (d, 2 H, H(2´), H(6´) arom., J = 8.0 Hz);
.99 (d, 2 H, H(3), H(5) arom., J = 8.7 Hz); 7.16 (t, 2 H, H(3´),
6
1
3
H(5´) arom., J = 7.2 Hz). C NMR, δ: 31.37 (CH S);
2
H(3´), H(5´) arom., J = 7.0 Hz). 1 C NMR, δ: 31.27 (CH S);
3
4
7.26 (NCH ); 69.02 (CHOH); 70.13 (OCH CH S); 73.33
2
2
2
2
(
CH(OH)CH O); 111.57 (CH =); 114.23 (C(2), C(6) arom.);
55.78, 57.65 (NCH ); 68.33, 68.80 (CHOH); 70.19, 70.26
2
2
2
1
14.97 (C(2´), C(6´) arom.); 118.89 (C(4´) arom.); 123.58 (C(3),
(OCH CH S); 72.84, 72.93 (CH(OH)CH O); 111.45 (CH =);
2
2
2
2
C(5) arom.); 129.24 (C(3´), C(5´) arom.); 132.15 (SCH=);
33.18 (HN—C(1) arom.); 144.40 (HN—C(4) arom.); 146.07
113.91, 114.96 (C(2), C(6) arom.); 115.11, 115.33 (C(2´), C(6´)
arom.); 119.02, 119.16 (C(4´) arom.); 122.59, 123.14 (C(3),
C(5) arom.); 129.26 (C(3´), C(5´) arom.); 132.16 (SCH=);
132.77, 133.47 (HN—C(1) arom.); 144.12, 144.77 (HN—C(4)
arom.); 145.56, 145.80 (HN—C(1´) arom.).
1
(
HN—C(1´) arom.).
B. Diadducts were obtained from oxiranes 4a,b and
4
ꢀaminodiphenylamine (7) at molar ratio 4a,b : 7 = 2 : 1 under
conditions described above for the reaction at equimolar ratio of
reagents. In this case, the entire disappearance of the signals for
the oxirane rings in compounds 4a,b (δ 2.60 (dd) and 2.78 (t))
in the H NMR spectrum of the reaction mixture, indicating
the completion of the reaction, at ~20 °C was observed after
This work was partially financially supported by
Council on Grants of the President of the Russian
Federation (Program for the State Support of Leading
Scientific Schools, Grant NSh 263ꢀ2008.3).
1
1
1—13 days, at 47—50 °C, after 18—20 h, at 100 °C, after 5 h.
The diadducts 9a,b were obtained as dark, very viscous liquids,
liquefying on heating. The double character of the most of signals
in the 1H and C NMR spectra of diadducts 9a,b indicates
formation of two diastereomers.
References
13
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1
0ꢀ(4ꢀAnilinophenyl)ꢀ3,6,14,17ꢀtetraoxaꢀ10ꢀazaꢀ1,18ꢀnonaꢀ
decadieneꢀ8,12ꢀdiol (9a). Found (%): C, 66.19; H, 8.09;
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2
6
–
1
N, 5.93. IR (neat), ν/cm : 3385 (NH); 3520 sh (OH); 3115,
3
015 (=CH, =CH ); 1636, 1619 (C=C). 1H NMR, δ: 3.16
2
(
dd, 1 H, NCH , J = 8.8 Hz, J = 14.9 Hz); 3.36 (dd, 1 H,
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2
NCH , J = 7.8 Hz, J = 14.9 Hz); 3.44 (dd, 1 H, NCH ,
J = 3.9 Hz, J = 14.9 Hz); 3.50 (dd, 2 H, CH(OH)CH O,
2
2
2
J = 6.1 Hz, J = 9.8 Hz); 3.57, 3.60 (both dd, 2 H, CH(OH)CH O,
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2
J = 4.3 Hz, J = 9.8 Hz); 3.75, 3.85 (both m, 11 H, OCH CH O,
2
2
CH(OH), NCH ); 4.02 (dd, 2 H, =CHcis, J = 6.7 Hz,
2
J = 1.8 Hz); 4.07 (br.s, 1 H, OH); 4.19 (dd, 3 H, =CHtrans, OH,
J = 14.3 Hz, J = 1.8 Hz); 5.41 (br.s, 1 H, NH); 6.48 (dd, 2 H,
=
CHO, J = 14.3 Hz, J = 6.7 Hz); 6.68 (d, 1 H, H(2), H(6)
arom., J = 8.7 Hz); 6.81 (m, 2 H, H(2), H(6), H(4´) arom.);
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8. R. Amorati, M. G. Fumo, S. Menichetti, V. Mugnaini,
G. F. Pedulli, J. Org. Chem., 2006, 71, 6325.
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J. Am. Chem. Soc., 2006, 128, 16432.
6
7
.85, 6.87 (both d, 2 H, H(2´), H(6´) arom., J = 6.11 Hz); 7.02,
.03 (both d, 2 H, H(3), H(5) arom., J = 8.5 Hz); 7.17 (t, 2 H,
13
H(3´), H(5´) arom., J = 7.1 Hz). C NMR, δ: 55.78, 57.65
NCH ); 67.35, 67.38 (OCH CH O); 68.40, 68.85 (CHOH);
(
2
2
2

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Received June 3, 2008