Synthesis and some features of phase behavior of chiral p-alkoxyphenyl glycerol ethers

Article abstract of DOI:10.1134/S1070428015020116

A series of (S)-3-(4-alkoxyphenoxy)propane-1,2-diols was prepared with the enantiomeric excess 86-92% by Sharpless asymmetric dihydroxylation of 1-alkoxy-4-allyloxybenzenes with an AD-mix-β mixture. R-Enantiomers with enantiomeric excess 97-99% and racemic samples were obtained by reaction of sodium p-substituted phenolates with (R)- and rac-3-chloropropane-1,2-diol. The phase behavior of racemates and scalemates in the produced homolog series of glycerol aryl ethers with hydrocarbon substituents of various length was examined by means of thermomicroscopy. The higher memberes of the homolog series of both racemic and scalemic diols undergo at heating an enantiotropic phase transition to a smectic liquid crystal phase.

Full text of DOI:10.1134/S1070428015020116

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2015, Vol. 51, No. 2, pp. 202–209. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © R.R. Fayzullin, O.A. Antonovich, D.V. Zakharychev, Z.A. Bredikhina, A.V. Kurenkov, A.A. Bredikhin, 2015, published in Zhurnal
Organicheskoi Khimii, 2015, Vol. 51, No. 2, pp. 214–221.
Synthesis and Some Features of Phase Behavior
of Chiral p-Alkoxyphenyl Glycerol Ethers
R. R. Fayzullin, O. A. Antonovich, D. V. Zakharychev, Z. A. Bredikhina,
A. V. Kurenkov, and A. A. Bredikhin
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences,
ul. Academika Arbuzova 8, Kazan, Tatarstan, 420088 Russia
e-mail: robert.fayzullin@gmail.com
Received September 24, 2014
Abstract―A series of (S)-3-(4-alkoxyphenoxy)propane-1,2-diols was prepared with the enantiomeric excess
86–92% by Sharpless asymmetric dihydroxylation of 1-alkoxy-4-allyloxybenzenes with an AD-mix-β mixture.
R-Enantiomers with enantiomeric excess 97–99% and racemic samples were obtained by reaction of sodium p-
substituted phenolates with (R)- and rac-3-chloropropane-1,2-diol. The phase behavior of racemates and
scalemates in the produced homolog series of glycerol aryl ethers with hydrocarbon substituents of various
length was examined by means of thermomicroscopy. The higher memberes of the homolog series of both
racemic and scalemic diols undergo at heating an enantiotropic phase transition to a smectic liquid crystal
phase.
DOI: 10.1134/S1070428015020116
Terminal ethers of glycerol are lipid-like compounds
of a special interest for physical and organic chemistry
owing to the molecular anisotropy and the capability to
form versatile supramolecular systems linked with
hydrogen bonds [1]. The presence of an asymmetric
center in the hydrophilic fragment of these molecules
may cause a chiral-dependent character of their phase
behavior, namely, of crystallization [1], formation of
mesophase [2–4] and supramolecular gels [5–7].
In this study a synthesis is described of a series of
scalemic (non-racemic, enantiomerically enriched) and
racemic p-alkoxysubstituted 3-phenoxypropane-1,2-
diols and preliminary data are obtained on the features
of their chiral-dependent phase behavior, in particular,
the dependence of the formation of thermotropic liquid
crystal phases on the enantiomeric composition of the
samples and the capability of these compounds to
supramolecular gel formation has been explored.
Asymmetric Sharpless dihydroxylation catalyzed
with coordination compounds of OsO4 with some
chiral amines is a synthetically powerful, useful, and
popular oxidation procedure for substituted olefins.
This method is widely utilized now in the organic
chemistry [13, 14]. In the most known version
derivatives of quinine and quinidine (DHQ)2-PHAL or
(DHQD)2-PHAL are used as ligands (Scheme 1) that
are contained in commercial reagents AD-mix-α and
AD-mix-β respectively.
The interest to the series of 3-(4-alkoxyphenoxy)-
propane-1,2-diols is due to several reasons. Some
racemic specimens of this series are lyotropic and
thermotropic liquid crystals [8]. Non-racemic analogs
have not been studied from this viewpoint. We
formerly investigated the related homolog series of
racemic and enantiomeric 3-(4-alkylphenoxy)propane-
1,2-diols where chiral-dependent low-molecular
gelation agents and thermally induced mesogens were
found [9–11]. It was established in [11] that 3-(4-
propylphenoxy)propane-1,2-diol crystallized in the
form of racemic conglomerate, i.e., it suffered a rare
phenomenon of the spontaneous resolution of the
racemate at crystallization. Some racemic 3-(4-
alkoxyphenoxy)propane-1,2-diols exhibit a moderate
antiviral action [12].
In this study we applied Sharpless reaction to the
preparation of non-racemic diols 1a–1g. In the first
stage from the corresponding phenols 3a–3g and allyl
bromide in the presence of a base K2CO3 the homolog
series of p-alkoxy-substituted phenylallyl ethers 2a–2g
was obtained in moderate yields (~65–70%). Compounds
202

SYNTHESIS AND SOME FEATURES OF PHASE BEHAVIOR OF CHIRAL
203
Scheme 1.
dihydroxylation afforded the corresponding scalemic
diols scal-1a–1g with a moderate enantiomer excess
(ee 86–92%). The length of the alkoxy substituent in
aryl allyl ethers 2a–2g located far from the prochiral
double bond virtually did not affect the
enantioselectivity of the reaction.
N
N
N
N
O
O
H3CO
OCH3
The attempts to increase the enantiomeric purity of
diols scal-1a–1g by recrystallization failed, the ee
values remained virtually unchanged. This may be
attributed to the accidental coincidence of eutectic
composition of each diol 1a–1g with the enantiomeric
composition of the oxidation products, but this
assumption looks improbable. We believe that more
probably on the phase diagrams of diols 1a–1g exist
prolonged practically linear fragments corresponding
to solid solutions of enantiomers. This is indicated by
the close values of melting points of racemic and non-
racemic samples in the whole series of diols 1a–1g.
Testing of this hypothesis will be the subject of our
further studies.
N
N
(DHQ)2-PHAL
N
N
N
N
O
O
H3CO
OCH3
N
N
(DHQD)2-PHAL
2 were oxidized by a standard procedure using the
mixture AD-mix-β to obtain the target compounds.
Diols rac-1a–1g were obtained by the reaction of rac-
3-chloropropane-1,2-diol with the corresponding
phenols 3a–3g in the presence of NaOH (Scheme 2).
Since the enantiomeric purity of obtained diols
scal-1a–1g was not sufficient for physicochemical
investigations and also aiming at the reliable
establishing of the configuration of the Sharpless
oxidation products we synthesized a series of diols (R)-
1a–1g (ee ≥ 97%) from (R)-3-chloropropane-1,2-diol
(ee 98%) and the corresponding phenols 3a–3g
(Scheme 2). This reaction occurs without racemization
and inversion of the asymmetric center [1, 15].
The stereoselectivity of the Sharpless oxidation of
aryl allyl ethers 2a–2g was examined by HPLC using a
chiral stationary phase. According to HPLC data the
Scheme 2.
The dihydroxylation of olefins like allyl ethers 2a–
2g with AD-mix-β mixture leads commonly to the
formation of non-racemic diols of predominantly S-
configuration at the chiral atom С2. The oxidation of
studied aryl allyl ethers occurred along the common
rule [11, 16], but an exclusion was observed for 1-
allyloxy-2-nitrobenzene: the product of its reaction
with AD-mix-β turned out to be enriched with the R-
enantiomer [17].
K2CO3
RO
OH +
RO
O
Br
2a_2g
3a_3g
AD-mix-β
2a_2g
RO
O
OH
HO
(S)-1a_1g
H
In order to determine the absolute configuration of
glycerol ethers obtained by the stereoselective
dihydroxylation we compared the values of their
specific rotation with those of the reference samples
(R)-1a–1g. All diols (R)-1a–1g have a negative sign of
the specific rotation of the plane-polarized light in
anhydrous methanol, whereas the dihydroxylation
products in the same conditions possess a positive
sign. According to HPLC data, the predominant
enantiomer in the samples synthesized from (R)-3-
chloropropane-1,2-diol has a shorter retention time,
3a_3g
Cl
OH
RO
RO
O
OH
OH
NaOH
OH
OH
rac-1a_1g
Cl
OH 3a_3g
O
NaOH
H
OH
H
OH
(R)-1a_1g
R = Me (a), Et (b), Pr (c), Bu (d), Pentyl (e), Hexyl (f),
Heptyl (g).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 2 2015

FAYZULLIN et al.
204
whereas for the diols obtained from aryl allyl ethers,
the enantiomer with the longer retention time
prevailed. Therefore, undoubtedly the products of ethers
2 dihydroxylation with AD-mix-β are S-diols 1.
phase, and the melting points and the point of the
mesophase transition to the isotropic liquid
monotonically grow.
In the other words, in compounds rac- and scal-1e–
1g the transformation of a crystal into a common liquid
phase is preceded by the transition into a turbid, more
viscous anisotropic mesophase. The latter is easily
identified by characteristic colored textures observed
in microscope under a polarized light [18].
Some aspects of the phase behavior of racemic
glycerol ethers rac-1d–1g were studied in [8]. At
heating in ethers rac-1e–1g a smectic liquid crystal
phase SmA was observed. Yet, to our best knowledge,
no publications exist on the phase behavior of non-
racemic diols scal-1a–1g and racemic diols rac-1a–1c.
At the formation of a liquid crystal from a melt in
all cases an appearance and growth was observed of
seeds characteristic of smectic phase, the so-called
bâtonnets; growing in size and combining they
generated the confocal liquid-crystalline texture with
large isotropic zones. The behavior and textures of
racemic and scalemic samples were similar.
To the study of the phase behavior of compounds
1a–1g we applied the method of optical polarization
microscopy at a controlled heating of the sample. The
data on the temperatures of the phase transitions for
racemic and scalemic samples of diols rac- and (R)-
1a–1g are presented in the figure. It is clearly seen that
in all compounds series the temperatures of the phase
transitions of the racemic and enantiomeric samples
have close values. The plot of the dependence of these
values on the length of the alkoxy substituent (see the
figure) may be tentatively divided in two parts with the
node point corresponding to diol 1d whose melting
points of racemate and scalemate are virtually identic.
In contrast to analogs with alkyl substituents [10,
11] diols 1а–1g are not prone to the formation of
metastable (supercooled) liquid crystalline phases. A
fast crystallization starts at small decrease in the
temperature below the boarder of the phase transition.
A specific feature of 3-(4-alkylphenoxy)propane-
1,2-diols consists in their capability to act as low-
molecular gelation agents [9–11]. Such gelation agents
owing to noncovalent interactions form in the solvent
environment stable networks which immobilize the
amount of solvent of a many times larger mass [19].
Unlike the alkyl analogs neither of diols 1a–1g both in
racemic and enantiomerically pure state possessed
gelating properties with respect to hydrocarbon
solvents. For the formation of supramolecular gels the
solubility of the gelation agent is known to correspond
to strict demands. On the one hand, it should not be too
high in order to prevent a fast crystallization on
cooling the solution. On the other hand, it should not
be too low in order to ensure sufficient strength to the
supramolecular network penetrating the environment
to be gellated [19]. The studied p-alkoxy-substituted
phenyl ethers of glycerol 1a–1g are not sufficiently
soluble in hydrocarbons at room temparature. We
believe that it is just the reason of their incapability to
gel formation. Another reason may originate from the
crystal packing of diols 1a–1g unfavorable for the
formation of network or fibrillary structures.
In a series of ethers 1a–1c the crystalline phase at
melting transforms in an isotropic liquid (melt), and
the temperatures of this transition considerably grow
with the lengthening of the hydrocarbon substituent. In
the series of compounds 1e–1g the melting is
accompanied with the formation of the liquid crystal
100
95
4
3
90
2
85
1
80
75
1
2
3
4
5
6
7 п
Plot of temperatures of phase transitions in glycerol ethers
1a–1g as a function of the number of carbon atoms (n) in the
linear hydrocarbon substituent R. Melting points: (1) scalemic
samples (ee ≥ 97%); (2) racemates; temperature of transition
to isotropic state: (3) scalemic samples; (4) racemates.
Thus for the higher members of the series both of
racemic and scalemic diols rac- and scal-1е–1g we
found an existence of enantiotropic thermally induced
transition into a smectic liquid crystalline phase,
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SYNTHESIS AND SOME FEATURES OF PHASE BEHAVIOR OF CHIRAL
205
whereas in the total series of compounds 1а–1d the
formation of metastable mesophases was not observed
due to the inclination to spontaneous crystallization of
a slightly supercooled melt. The behavior of racemic
and scalemic samples at heating and the appearance of
the liquid crystal structures proved to be similar. No
one of the studied samples of ethers 1а–1d exhibited
an ability of supramolecular gelation of hydrocarbon
solvents.
(100 mmol) of 1,4-hydroquinone in 130 mL of DMSO
under an argon atmosphere was added at vigorous
stirring 6.17 g (110 mmol) of powdered KOH. The
reaction mixture turned yellow, and thereto was added
dropwise a solution of 15.1 g (100 mmol) of 1-
bromopentane in 30 mL of DMSO within 0.5 h. The
reaction mixture was stirred for 3 h at 40°C (TLC
monitoring; Rf of the reaction product ~0.58, eluent
hexane–EtOAc, 6 : 4). Then the reaction mixture was
poured in 400 mL of cold water, acidified to pH 1 with
dilute hydrochloric acid. The precipitate was filtered
off and washed with cold water, then it was subjected
to column chromatography on silica gel (eluent
hexane–CH2Cl2, 9 : 1–4 : 6). The obtained oily
substance was crystallized from hexane at cooling.
Yield 36%, white needle crystals, mp 46.5–47°C
(hexane). 1H NMR spectrum, δ, ppm: 0.93 t (3H, CH3,
J 7.2 Hz), 1.33–1.47 m [4H, CH2(CH2)2CH3], 1.76
quintet (2H, CH2CH2CH2, J 7.0 Hz), 3.90 t (2H, CH2, J
6.6 Hz), 4.20 br.s (1H, OH), 6.73–6.81 m (4Harom).
Mass spectrum, m/z (Irel, %): 180 (11) [M]+, 144 (4),
110 (100), 81 (8), 65 (5), 53 (5), 43 (18).
EXPERIMENTAL
NMR spectra were registered on a spectrometer
Bruker Avance-500 [500.13 (1H), 125.76 (13C) MHz]
in CDCl3. Chemical shifts in the NMR spectra were
measured with respect to the residual signals of
solvents. IR spectra were recorded on a spec-
trophotometer Bruker Tensor 27. Mass spectra (EI, 70
eV) were taken on an instrument DFS Thermo
Electron Corporation. Elemental analysis was carried
out on a CHN-analyzer EuroVector EA3000. HPLC
analysis was performed on a chromatograph Shimadzu
LC-20AD equipped with UV (λ 275 nm) detector,
column Chiralcel OD (0.46 × 25 cm), 20°С, flow rate
1 mL/min, eluent i-PrOH–hexane, 1 : 9 (1b–1g), 2 : 8
(1a). Optical rotation was measured on a polarimeter
Perkin Elmer 341 ([α], 10–1·deg·cm2·g–1; c, g/100 mL).
Melting points and temperature of transition to
isotropic state (transition point, tp) was determined on
Boëtius heating block and was reported without
corrections. The thermotropic phase behavior of diols
1а–1g was examined by thermomicroscopy using a
polarization optical microscope Polam P-312. The stage
was heated with a ceramic heating element, the heating
rate was determined by the voltage controlled with
laboratory autotransformer. The sample temperature was
controlled by electronic thermometer with a thermo-
couple K contacting the stage just near the sample. TLC
was carried out on Silufol UV-254 (254 nm) plates,
development under UV irradiation or in iodine vapor.
Aryl allyl ethers (2а–2g). General procedure
[11]. A slurry of 6 mmol of an appropriate phenol 3а–3g,
0.8 g (6.6 mmol) of allyl bromide, and 0.91 g (6.6 mmol)
of crushed calcined K2CO3 in 10 mL of anhydrous
acetone was boiled at stirring for 10–12 h. The reaction
was monitored by TLC (Rf of reaction products ~0.7,
eluent hexane–EtOAc, 9 : 1). Then the reaction mixture
was diluted with water (30 mL), the reaction products
were extracted with Et2O (3 × 40 mL). The combined
extracts were washed with 1 M water solution of
NaOH (15 mL) and dried with MgSO4. The solvent
was removed at a reduced pressure. The obtained low
melting crystals 2b, 2c, and 2g or oily substances 2а
and 2d–2f were purified by column chromatography
on silica gel, eluent hexane–EtOAc, 9 : 1–8 : 2.
1-(Allyloxy)-4-methoxybenzene (2а). Yield 65%,
light yellow oily substance, bp 73–75°C (10 mmHg),
nD22 1.5271 {bp 76–76.5°C (1.5 mmHg), nD25 1.5265
[21]}. IR spectrum (film), cm–1: 1508, 1462, 1231, 1039,
928, 825, 522. 1H NMR spectrum, δ, ppm: 3.77 s (3H,
CH3), 4.49 d.d.d (2H, CH2O, J 1.5, 5.3 Hz), 5.27 d.d.t
(1Н, CH2, J 1.5, 1.5, 10.5 Hz), 5.41 d.d.t (1Н, CH2, J 1.5,
1.5, 17.2 Hz), 6.06 d.d.t (1H, CH, J 5.3, 10.5, 17.2 Hz),
6.81–6.89 m (4HAr). Mass spectrum, m/z (Irel, %): 164
(15) [M]+, 123 (100), 95 (28), 63 (7), 52 (8), 41 (24).
In the study commercial reagents were used: 4-
methoxyphenol (99%) from Acros Organics; 4-ethoxy-
phenol (99%), 4-propoxyphenol (98%), 4-butoxy-
phenol (98%), 4-hexyloxyphenol (98%), racemic 3-
chloropropane-1,2-diol (98%), (R)-3-chloropropane-
1,2-diol (97%, ee 98%), and allyl bromide (99%) from
Alfa Aesar; 4-heptyloxyphenol (97%) and AD-mix-β
from Aldrich.
4-Pentyloxyphenol (3е) was obtained by a slightly
1-(Allyloxy)-4-ethoxybenzene (2b). Yield 67%,
modified procedure [20]. To a solution of 11.01 g
colorless crystals, mp 44.5–45°C (mp 42.2–45°C [22]).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 2 2015

FAYZULLIN et al.
206
IR spectrum (mineral oil), cm–1: 1510, 1454, 1238, 1048,
922, 821, 533. H NMR spectrum, δ, ppm: 1.39 t (3H,
d.d.d (2H, CH2O, J 1.5, 5.3 Hz), 5.28 d.d.t (1Н, CH2, J
1.5, 1.5, 10.5 Hz), 5.41 d.d.t (1Н, CH2, J 1.5, 1.5,
17.3 Hz), 6.06 d.d.t (1H, CH, J 5.3, 10.5, 17.3 Hz),
6.81–6.89 m (4HAr). Mass spectrum, m/z (Irel, %): 234
(9) [M]+, 150 (7), 109 (100), 85 (12), 57 (10), 43 (96).
1
CH3, J 7.0 Hz), 3.98 q (2H, CH2, J 7.0 Hz), 4.49 d.d.d
(2H, CH2O, J 1.5, 5.3 Hz), 5.27 d.d.t (1Н, CH2, J 1.5,
1.5, 10.4 Hz), 5.40 d.d.t (1Н, CH2, J 1.5, 1.5, 17.3 Hz),
6.05 d.d.t (1H, CH, J 5.3, 10.4, 17.3 Hz), 6.80–6.88 m
(4HAr). Mass spectrum, m/z (Irel, %): 178 (11) [M]+,
137 (27), 109 (100), 81 (21), 63 (5), 53 (8), 41 (18).
1-(Allyloxy)-4-heptyloxybenzene (2g). Yield 68%,
colorless crystals, mp 32.5–33°C. IR spectrum (mine-
ral oil), cm–1: 1508, 1466, 1229, 1024, 931, 825, 533.
1H NMR spectrum, δ, ppm: 0.89 t (3H, CH3, J 6.9 Hz),
1.25–1.39 m [6H, CH2(CH2)3CH3], 1.44 quintet (2H,
CH2CH2CH2, J 7.1 Hz), 1.77 quintet (2H, CH2CH2·
CH2O, J 7.0 Hz), 3.90 t (2H, CH2O, J 6.6 Hz), 4.48 d.d.d
(2H, CH2O, J 1.5, 5.3 Hz), 5.26 d.d.t (1Н, CH2, J 1.5,
1.5, 10.5 Hz), 5.39 d.d.t (1Н, CH2, J 1.5, 1.5, 17.3 Hz),
6.05 d.d.t (1H, CH, J 5.3, 10.5, 17.3 Hz), 6.80–6.87 m
(4HAr). Mass spectrum, m/z (Irel, %): 248 (9) [M]+, 150
(9), 109 (100), 81 (5), 57 (95), 41 (53).
1-(Allyloxy)-4-propoxybenzene (2с). Yield 69%,
colorless crystals, mp 40–41°C. IR spectrum (mineral
1
oil), cm–1: 1508, 1463, 1229, 1027, 924, 825, 530. H
NMR spectrum, δ, ppm: 1.02 t (3H, CH3, J 7.4 Hz),
1.78 sextet (2H, CH2, J 7.1 Hz), 3.87 t (2H, CH2O, J
6.6 Hz), 4.48 d.d.d (2H, CH2O, J 1.5, 5.3 Hz), 5.26
d.d.t (1Н, CH2, J 1.5, 1.5, 10.5 Hz), 5.39 d.d.t (1Н,
CH2, J 1.5, 1.5, 17.2 Hz), 6.05 d.d.t (1H, CH, J 5.3,
10.5, 17.2 Hz), 6.81–6.88 m (4HAr). Mass spectrum, m/z
(Irel, %): 192 (10) [M]+, 151 (10), 109 (100), 81 (10),
64 (4), 53 (4), 43 (41).
Racemic and enantiomeric 3-(4-alkoxyphenoxy)
propane-1,2-diols (1а–1g). General procedure [11].
To a solution of 15 mmol of an appropriate phenol
3а–3g in 9 mL of EtOH was added at stirring a
solution of 0.72 g (18 mmol) of NaOH in 3 mL of
water. The mixture was boiled at stirring for 2 h,
cooled to 50°C, and was added by portions a solution
of 1.95 g (17.6 mmol) of rac- or (R)-3-chloropropane-
1,2-diol in 3 mL of EtOH. The mixture was boiled at
stirring for ~15 h. The reaction completion was fixed
by TLC (Rf of reaction products ~0.2, eluent hexane–
EtOAc, 6 : 4). On cooling the reaction mixture was
diluted with water (70 mL), the reaction products were
extracted with Et2O (3 × 60 mL). The combined
extracts were washed with 1 M water solution of
NaOH (15 mL) to remove phenol residues and dried
with MgSO4. The solvent was removed in a vacuum.
The crystalline residue was purified by column
chromatography on silica gel (eluent hexane–EtOAc,
8 : 2–4 : 6). The recrystallization was done from a
mixture hexane–EtOAc, 5 : 1. NMR spectra of obtain-
ed diols (R)-1а–1g are identical to the spectra of race-
mic analogs.
1-(Allyloxy)-4-butoxybenzene (2d). Yield 65%,
colorless oily substance, nD22 1.5020. IR spectrum
(film), cm–1: 1508, 1474, 1230, 1030, 926, 824, 523.
1H NMR spectrum, δ, ppm: 0.97 t (3H, CH3, J 7.4 Hz),
1.48 sextet (2H, CH2CH3, J 7.4 Hz), 1.74 quintet (2H,
CH2CH2CH2O, J 7.0 Hz), 3.91 t (2H, CH2O, J 6.5 Hz),
4.48 d.d.d (2H, CH2O, J 1.5, 5.3 Hz), 5.26 d.d.t (1Н,
CH2, J 1.5, 1.5, 10.5 Hz), 5.39 d.d.t (1H, CH2, J 1.5, 1.5,
17.2 Hz), 6.05 d.d.t (1H, CH, J 5.3, 10.5, 17.2 Hz),
6.79–6.88 m (4HAr). Mass spectrum, m/z (Irel, %): 206
(9) [M]+, 165 (4), 109 (100), 81 (8), 57 (28), 41 (42).
1-(Allyloxy)-4-pentyloxybenzene (2е). Yield 70%,
colorless oily substance, nD22 1.5025. IR spectrum
(film), cm–1: 1508, 1470, 1229, 1032, 924, 824, 522.
1H NMR spectrum, δ, ppm: 0.93 t (3H, CH3, J 7.1 Hz),
1.37–1.47 m [4H, CH2(CH2)2CH3], 1.76 quintet (2H,
CH2CH2CH2O, J 6.9 Hz), 3.90 t (2H, CH2O, J 6.6 Hz),
4.49 d.d.d (2H, CH2O, J 1.5, 5.3 Hz), 5.27 d.d.t (1Н,
CH2, J 1.5, 1.5, 10.3 Hz), 5.40 d.d.t (1Н, CH2, J 1.5, 1.5,
17.2 Hz), 6.05 d.d.t (1H, CH, J 5.3, 10.3, 17.2 Hz),
6.80–6.88 m (4HAr). Mass spectrum, m/z (Irel, %): 220
(10) [M]+, 179 (4), 150 (6), 109 (100), 81 (5), 71 (13),
55 (6), 43 (66).
3-(4-Methoxyphenoxy)propane-1,2-diol (1а).
rac-(1а). Yield 75%, colorless plate crystals, mp
79.5°С. 1H NMR spectrum, δ, ppm: 2.01 t (1H,
CH2OH, J 6.1 Hz), 2.59 d (1H, CHOH, J 4.8 Hz), 3.75
d.d.d (1H, CH2OH, J 5.6, 11.4 Hz), 3.77 s (3H, CH3O),
3.83 d.d.d (1H, CH2OH, J 4.0, 6.5, 11.4 Hz), 4.00 d.d
(1H, CH2O, J 9.5, 14.3 Hz), 4.01 d.d (1H, CH2O, J 9.5,
12.2 Hz), 4.06–4.11 m (1H, CHOH), 6.82–6.87 m
(4HAr). 13C NMR spectrum, δ, ppm: 56.1, 64.1, 70.4,
1-(Allyloxy)-4-hexyloxybenzene (2f). Yield 66%,
colorless oily substance, nD22 1.5058. IR spectrum
1
(film), cm–1: 1508, 1469, 1229, 1033, 926, 824. H
NMR spectrum, δ, ppm: 0.93 t (3H, CH3, J 6.5 Hz),
1.32–1.41 m [4H, CH2(CH2)2CH3], 1.47 quintet (2H,
CH2CH2CH2, J 7.0 Hz), 1.77 quintet (2H, CH2CH2·
CH2O, J 7.1 Hz), 3.91 t (2H, CH2O, J 6.6 Hz), 4.49
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SYNTHESIS AND SOME FEATURES OF PHASE BEHAVIOR OF CHIRAL
207
70.8, 115.1, 116.0, 152.9, 154.7. Found, %: C 60.51; H
7.18. C10H14O4. Calculated, %: C 60.59; H 7.12.
ppm: 14.1, 19.5, 31.7, 64.1, 68.7, 70.3, 70.9, 115.8,
115.9, 152.8, 154.1. Found, %: C 65.04; H 8.33.
C13H20O4. Calculated, %: C 64.98; H 8.39.
(R)-(1а). Yield 77%, colorless plate crystals, mp
77.3°С, [α]D20 –7.6 (c 1, MeOH), [α]20 –26.7 (c 1,
(R)-(1d). Yield 69%, colorless plate crystals, mp
365
MeOH), ee 98.8% [HPLC, chiral column, tR, min: 7.1
93.8°C, [α]D20 –6.1 (c 1.0, MeOH), [α]20 –20.9 (c 1,
365
(major), 10.7 (minor)].
MeOH), ee 98.9% [HPLC, chiral column, tR, min: 15.9
(major), 21.5 (minor)].
3-(4-Ethoxyphenoxy)propane-1,2-diol (1b).
3-(4-Pentyloxyphenoxy)propane-1,2-diol (1е).
rac-(1е). Yield 63%, colorless needle crystals, mp
rac-(1b). Yield 69%, colorless plate crystals, mp
86°C. H NMR spectrum, δ, ppm: 1.39 t (3H, CH3, J
1
1
7.0 Hz), 2.15 br.s (2H, OH), 3.74 d.d (1H, CH2OH, J
5.3, 11.4 Hz), 3.83 d.d (1H, CH2OH, J 3.6, 11.4 Hz),
3.94–4.02 m (4H, CH2O, CH3CH2O), 4.05–4.12 m
(1H, CHOH), 6.79–6.89 m (4HAr). 13C NMR spectrum,
δ, ppm: 15.2, 64.1, 64.4, 70.4, 70.8, 115.87, 115.93,
152.9, 154.0. Found, %: C 62.19; H 7.52. C11H16O4.
Calculated, %: C 62.25; H 7.60.
89.8°C, tp 92.3°C (mp 92°C, tp 92°C [8]). H NMR
spectrum, δ, ppm: 0.93 t (3H, CH3, J 7.1 Hz), 1.33–
1.47 m [4H, CH2(CH2)2CH3], 1.76 quintet (2H,
CH2CH2CH2O, J 7.0 Hz), 3.08 br.s (2H, OH), 3.76 d.d
(1H, CH2OH, J 5.6, 11.5 Hz), 3.81 d.d (1H, CH2OH, J
3.6, 11.5 Hz), 3.89 t (2H, CH2O, J 6.6 Hz), 3.99 d.d
(1H, CH2O, J 9.5, 12.2 Hz), 4.00 d.d (1H, CH2O, J 9.5,
10.2 Hz), 4.04–4.11 m (1H, CHOH), 6.77–6.85 m
(4HAr). 13C NMR spectrum, δ, ppm: 14.3, 22.8, 28.5,
29.4, 64.1, 69.0, 70.3, 70.9, 115.8, 115.9, 152.8, 154.2.
Found, %: C 66.05; H 8.76. C14H22O4. Calculated, %:
C 66.12; H 8.72.
(R)-(1b). Yield 70%, colorless plate crystals, mp
84.3°C, [α]D20 –7.1 (c 1.0, MeOH), [α]20 –25.1 (c 1,
365
MeOH), ee 97.2% [HPLC, chiral column, tR, min: 19.2
(major), 27.0 (minor)].
3-(4-Propoxyphenoxy)propane-1,2-diol (1с).
(R)-(1е). Yield 70%, colorless plate crystals, mp
88.5°C, tp 91°C, [α]D20 –6.2 (c 1.0, MeOH), [α]20
rac-(1с). Yield 62%, colorless plate crystals, mp
95.5°C. 1H NMR spectrum, δ, ppm: 1.02 t (3H, CH3, J
7.5 Hz), 1.78 sextet (2H, CH2, J 7.1 Hz), 2.38 br.s (2H,
OH), 3.74 d.d (1H, CH2OH, J 5.3, 11.4 Hz), 3.83 d.d (1H,
CH2OH, J 3.7, 11.4 Hz), 2.87 t (2H, CH2O, J 6.6 Hz),
3.99 d.d (1H, CH2O, J 9.5, 12.6 Hz), 4.00 d.d (1H,
CH2O, J 9.5, 10.0 Hz), 4.04–4.11 m (1H, CHOH),
6.80–6.87 m (4HAr). 13C NMR spectrum, δ, ppm: 10.8,
23.0, 64.1, 70.4, 70.6, 70.8, 115.88, 115.93, 152.8,
154.2. Found, %: C 63.76; H 8.05. C12H18O4. Cal-
culated, %: C 63.70; H 8.02.
365
–20.6 (c 1, MeOH), ee 97.7% [HPLC, chiral column,
tR, min: 17.4 (major), 21.8 (minor)].
3-(4-Hexyloxyphenoxy)propane-1,2-diol (1f).
rac-(1f). Yield 65%, colorless plate crystals, mp
90°C, tp 93.5°C (mp 91°C, tp 97°C [8]). 1H NMR spec-
trum, δ, ppm: 0.90 t (3H, CH3, J 7.0 Hz), 1.30–1.39 m
[4H, CH2(CH2)2CH3], 1.41–1.48 m (2H, CH2CH2CH2),
1.75 quintet (2H, CH2CH2CH2O, J 7.0 Hz), 2.44 br.s
(2H, OH), 3.73 d.d (1H, CH2OH, J 5.4, 11.5 Hz), 3.82
d.d (1H, CH2OH, J 3.7, 11.5 Hz), 3.90 t (2H, OCH2, J
6.6 Hz), 3.98 d.d (1H, CH2O, J 9.6, 12.3 Hz), 4.00 d.d
(1H, CH2O, J 9.6, 10.2 Hz), 4.05–4.10 m (1H,
CHOH), 6.78–6.87 m (4HAr). 13C NMR spectrum, δ,
ppm: 14.4, 22.9, 26.1, 29.7, 31.9, 64.1, 69.0, 70.4,
70.8, 115.87, 115.93, 152.8, 154.2. Found, %: C 67.09;
H 9.07. C15H24O4. Calculated, %: C 67.14; H 9.01.
(R)-(1c). Yield 62%, colorless plate crystals, mp
94.5°C, [α]D20 –7.6 (c 1.0, MeOH), [α]20 –24.0 (c 1,
365
MeOH), ee 98.6% [HPLC, chiral column, tR, min: 18.0
(major), 23.8 (minor)].
3-(4-Butoxyphenoxy)propane-1,2-diol (1d).
rac-(1d). Yield 65%, colorless plate crystals, mp
1
93.5°C (mp 96.5°C [8]). H NMR spectrum, δ, ppm:
(R)-(1f). Yield 69%, colorless plate crystals, mp
89°C, tp 93.5°C, [α]D20 –5.4 (c 1.0, MeOH), [α]20
0.97 t (3H, CH3, J 7.4 Hz), 1.48 sextet (2H, CH2CH3, J
7.4 Hz), 1.74 quintet (2H, CH2CH2CH2O, J 7.0 Hz), 2.49
br.s (2H, OH), 3.73 d.d (1H, CH2OH, J 5.4, 11.4 Hz),
3.83 d.d (1H, CH2OH, J 3.7, 11.4 Hz), 3.91 t (2H,
CH2O, J 6.6 Hz), 3.98 d.d (1H, CH2O, J 9.5, 12.2 Hz),
3.99 d.d (1H, CH2O, J 9.5, 10.1 Hz), 4.04–4.11 m (1H,
CHOH), 6.79–6.88 m (4HAr). 13C NMR spectrum, δ,
365
–18.9 (c 1, MeOH), ee 97.1% [HPLC, chiral column,
tR, min: 16.5 (major), 21.1 (minor)].
3-(4-Heptyloxyphenoxy)propane-1,2-diol (1g).
rac-(1g). Yield 64%, colorless plate crystals, mp
1
91.8°C, tp 97.3°C (mp 96°C, tp 103°C [8]). H NMR
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FAYZULLIN et al.
208
spectrum, δ, ppm: 0.89 t (3H, CH3, J 6.9 Hz), 1.25–
1.39 m [6H, CH2(CH2)3CH3], 1.40–1.78 m (2H, CH2·
CH2CH2), 1.75 quintet (2H, CH2CH2CH2O, J 7 Hz),
2.32 br.s (2H, OH), 3.74 d.d (1H, CH2OH, J 5.5,
11.4 Hz), 3.82 d.d (1H, CH2OH, J 3.8, 11.4 Hz), 3.90 t
(2H, OCH2, J 6.6 Hz), 3.99 d.d (1H, CH2O, J 9.5,
12.8 Hz), 4.00 d.d (1H, CH2O, J 9.5, 10.7 Hz), 4.06–
4.10 m (1H, CHOH), 6.81–6.85 m (4HAr). 13C NMR
spectrum, δ, ppm: 14.4, 22.9, 26.4, 29.4, 29.7, 32.1,
64.1, 69.0, 70.4, 70.8, 115.87, 115.93, 152.8, 154.2.
Found, %: C 68.11; H 9.29. C16H26O4. Calculated, %:
C 68.06; H 9.28.
(S)-3-(4-Butoxyphenoxy)propane-1,2-diol (S)-(1d).
Yield 69%, colorless plate crystals, mp 94°C, [α]D20
+5.7 (c 1.0, MeOH), ee 92.3% [HPLC, chiral column,
tR, min: 16.6 (minor), 21.9 (major)].
(S)-3-(4-Pentyloxyphenoxy)propane-1,2-diol (S)-
(1е). Yield 76%, colorless plate crystals, mp 88.5°C, tp
91°C, [α]D20 +5.7 (c 1.0, MeOH), ee 89.6% [HPLC,
chiral column, tR, min: 17.3 (minor), 21.7 (major)].
(S)-3-(4-Hexyloxyphenoxy)propane-1,2-diol (S)-
(1f). Yield 70%, colorless plate crystals, mp 89°C, tp
93.5°C, [α]D20 +5.0 (c 1.0, MeOH), ee 90.5% [HPLC,
chiral column, tR, min: 16.3 (minor), 20.6 (major)].
(R)-(1g). Yield 68%, colorless plate crystals, mp
20
91.5°C, tp 97.3°C, [α]D20 –5.3 (c 1.0, MeOH), [α]365
–
(S)-3-(4-Heptyloxyphenoxy)propane-1,2-diol (S)-
(1g). Yield 74%, colorless plate crystals, mp 91.5°C, tp
97.3°C, [α]D20 +5.0 (c 1.0, MeOH), ee 90.4% [HPLC,
chiral column, tR, min: 15.5 (minor), 19.2 (major)].
18.2° (c 1, MeOH), ee 97.1% [HPLC, chiral column,
tR, min: 15.2 (major), 19.2 (minor)].
Asymmetric Sharpless dihydroxylation. General
procedure [11, 16]. A slurry of 1.4 g of AD-mix-β in
5 mL of t-BuOH and 5 mL of water was cooled at
stirring to 0°C. To the slurry 1 mmol of an appropriate
aryl allyl ether 2а–2g was added, the reacton mixture
was vigorously stirred at 0°C for 20 h. Then 1.5 g of
Na2SO3 was added to the mixture, and the reaction
mixture was stirred at room temperature for 30 min. The
organic layer was separated, the reaction products were
extracted from water layer with EtOAc (3 × 30 mL).
The combined organic solutions were washed with
brine (20 mL) and dried with MgSO4. The solvent was
removed at a reduced pressure. The crude product
when necessary was purified by column chromatogra-
phy on silica gel (eluent hexane–EtOAc, 8 : 2–4 : 6).
At the application of AD-mix-β the S-enantiomer
prevailed in the product. The spectra of diols (S)-1а–
1g obtained by this procedure are identic to the spectra
of racemic analogs.
REFERENCES
1. Bredikhin, A.A., Bredikhina, Z.A., and Zakha-
rychev, D.V., Mendeleev Commun., 2012, vol. 22,
p. 171.
2. Tschierske, C., Chirality at the Nanoscale:
Nanoparticles, Surfaces, Materials and More,
Amabilino, D.B., Ed., Weinheim: Wiley-VCH, 2009.
3. Reddy, R.A. and Tschierske, C., J. Mater. Chem., 2006,
vol. 16, p. 907.
4. Goodby, J.W., J. Mater. Chem., 1991, vol. 1, p. 307.
5. Malik, S., Fujita, N., and Shinkai, S., Chirality at the
Nanoscale: Nanoparticles, Surfaces, Materials and
More, Amabilino, D.B., Ed., Weinheim: Wiley-VCH,
2009.
6. Smith, D.K., Chem. Soc. Rev., 2009, vol. 38, p. 684.
7. Brizard, A., Oda, R., and Huc, I., Top. Curr. Chem.,
2005, vol. 256, p. 167.
8. Tschierske, C., Hentrich, F., Joachimi, D., Agert, O.,
(S)-3-(4-Methoxyphenoxy)propane-1,2-diol (S)-
(1а). Yield 78%, colorless plate crystals, mp 77.3°С,
[α]D20 +6.6 (c 1, MeOH), ee 86.1% [HPLC, chiral
column, tR, min: 7.0 (minor), 10.3 (major)].
and Zaschke, H., Liq. Cryst., 1991, vol. 9, p. 571.
9. Bredikhin, A.A., Bredikhina, Z.A., Akhatova, F.S., and
Gubaidullin, A.T., Chem. Commun., 2010, vol. 46,
p. 3523.
(S)-3-(4-Ethoxyphenoxy)propane-1,2-diol (S)-
(1b). Yield 59%, colorless plate crystals, mp 84.3°C,
[α]D20 +6.4 (c 1.0, MeOH), ee 86.4% [HPLC, chiral
column, tR, min: 19.7 (minor), 27.1 (major)].
10. Bredikhin, A.A., Zakharychev, D.V., Bredikhina, Z.A.,
Gubaidullin, A.T., and Fayzullin, R.R.,
CrystEngComm., 2012, vol. 14, p. 211.
11. Bredikhin, A.A., Zakharychev, D.V., Fayzullin, R.R.,
Antonovich, O.A., Pashagin, A.V., and Bredikhina, Z.A.,
Tetrahedron: Asymmetry, 2013, vol. 24, p. 807.
12. Ueda, T., Toyoshima, S., Takahashi, K., Muraoka, M.,
Koibuchi, H., and Seto, Y., Chem. Pharm. Bull., 1960,
vol. 8, p. 921.
(S)-3-(4-Propoxyphenoxy)propane-1,2-diol (S)-
(1с). Yield 62%, colorless plate crystals, mp 94.5°C,
[α]D20 +6.0 (c 1.0, MeOH), ee 89.7% [HPLC, chiral
column, tR, min: 18.0 (minor), 23.8 (major)].
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SYNTHESIS AND SOME FEATURES OF PHASE BEHAVIOR OF CHIRAL
209
13. Kolb, H.C., VanNieuwenhze, M.S., and Sharpless, K.B.,
18. Dierking, I., Textures of Liquid Crystals, Weinheim:
Chem. Rev., 1994, vol. 94, p. 2483.
Wiley-VCH, 2009.
14. Zaitsev, A.B. and Adolfsson, H., Synthesis., 2006, vol. 11,
19. Molecular Gels: Materials with Self-assembled
Fibrillar Networks, Weiss, R.G. and Terech, P., Eds.,
Dordrecht: Springer, Nether-lands, 2006.
20. Liu, L.-M., Liu, K.-P., Dong, Y.-P., Chen, E.-Q.,
and Tang, B.Z., Macromolecules, 2010, vol. 43,
p. 6014.
p. 1725.
15. Bredikhin, A.A., Gubaidullin, A.T., Bredikhina, Z.A.,
Fayzullin, R.R., Samigullina, A.I., and Zakharychev, D.V.,
J. Mol. Struct., 2013, vol. 1045, p. 104.
16. Wang, Z.-M., Zhang, X.-L., and Sharpless, K.B.,
21. White, W.N. and Norcross, B.E., J. Am. Chem. Soc.,
Tetrahedron Lett., 1993, vol. 34, p. 2267.
1961, vol. 83, p. 3265.
22. Goering, H.L. and Jacobson, R.R., J. Am. Chem. Soc.,
17. Bredikhina, Z.A., Kurenkov, A.V., Antonovich, O.A.,
Pashagin, A.V., and Bredikhin, A.A., Tetrahedron:
Asymmetry, 2014, vol. 25, p. 1015.
1958, vol. 80, p. 3277.
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