Fluorocarbon and hydrocarbon benzodioxocycloalkane (C8-C 10) end groups: Effects on mesomorphism

Article abstract of DOI:10.1002/cjoc.201300286

A new class of benzodioxocycloalkane-based (C₈-C₁₀) liquid crystals were prepared. The impact of ring (C₈-C₁₀) as end group was investigated. The 8-9 membered ring derivatives, 3a-3b, exhibited the nematic phases (N). The mesomorphic behaviors were weakened with increasing the size of the ring. For the ?uorinated medium ring (C ₈-C₁₀) 3d-3f, it was found only the fluorinated ten membered ring 3f showed the LC phases behaviours. Modification of the ring size with different length alkyl groups and variation of the alkyl to polyfluoroalkyl markedly influenced the properties of these compounds. A new class of benzodioxocycloalkane-based (C₈-C₁₀) liquid crystals has been prepared. The impact of ring (C₈-C₁₀) as end group was investigated. The 8-9 membered ring derivatives, 3a-3b, exhibited the nematic phases (N). The mesomorphic behaviors were weakened with increasing the size of the ring. For the ?uorinated medium ring (C₈-C₁₀) 3d-3f, it was found only the fluorinated ten membered ring 3f showed the LC phases behaviours. Modification of the ring size with different length alkyl groups and variation of the alkyl to polyfluoroalkyl markedly influenced the properties of these compounds. Copyright

Full text of DOI:10.1002/cjoc.201300286

FULL PAPER
DOI: 10.1002/cjoc.201300286
Fluorocarbon and Hydrocarbon Benzodioxocycloalkane
(C8－C10) End Groups: Effects on Mesomorphism
Wanwan Cao,a Peilian Liu,a Hongren Chen,a Yaohang Zhu,a Rihao Chen,a Qifang Zhou,a and
Zhuo Zeng*,a,b
a College of Chemistry & Environment South China Normal University, Guangzhou, Guangdong 510006, China
b Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, Shanghai 200032, China
A new class of benzodioxocycloalkane-based (C8－C10) liquid crystals were prepared. The impact of ring (C8－
C10) as end group was investigated. The 8－9 membered ring derivatives, 3a－3b, exhibited the nematic phases (N).
The mesomorphic behaviors were weakened with increasing the size of the ring. For the fluorinated medium ring
(C8－C10) 3d－3f, it was found only the fluorinated ten membered ring 3f showed the LC phases behaviours. Modi-
fication of the ring size with different length alkyl groups and variation of the alkyl to polyfluoroalkyl markedly in-
fluenced the properties of these compounds.
Keywords fluorine, heterocycles, liquid crystals, mesophases, phase transitions
Introduction
Studies involving the use of bulky cyclic end
groups[18] have revealed that smectic A phases can be
suppressed while twist grain boundary phases are
formed due to the weakening of interlayer interactions
through steric effects. Other studies using fluorinated
end groups[19-23] have shown that mesophase stability
is increased with the terminal fluorine environment. It
shows that steric effects or polarity at layer interface are
more important in controlling mesophase sequence.
Modification of the ring size from benzodioxane (C8) to
(C10) as end groups markedly influences the properties
of the benzodioxane-based liquid crystals.
In this work, we report a series of benzodioxo-
cycloalkane-based (C8－C10) liquid crystals in an effort
to establish the impact of the ring steric effects or poly-
fluoroalkyl substituent on the liquid crystal physico-
chemistry properties.
The interest in the development of new liquid crystal
materials continues at a very high level,[1-8] particularly
for stable mesophases with broad mesomorphic
ranges[9,10] and low viscosities.[11-14] One of the special
interest is liquid crystal compound having alkyl or fluo-
rine-substituted benzodioxane ring, because it offers
significant advantages over currently used liquid crystal
materials.[15]
Low dense, chemically stable benzodioxane ring
with a variety of liquid crystal building blocks makes it
a promising candidate in the development of new liquid
crystal materials.[16] There are reports of many benzo-
dioxane derivatives as liquid crystal materials. Some of
these reported[15, 17] liquid crystal moleculars are shown
in Scheme 1.
Scheme 1 Structure of some known benzodioxane-based liquid
crystals
Results and Discussion
Synthesis
O
O
C3H7
C3H7
Synthetic routes to target compounds benzodioxo-
cycloalkane-based liquid crystals, 3a－3f are depicted
in Scheme 2. In the previous report, macrocyclic benzo-
dioxocycloalkanes were prepared by using catechol with
α-ω-dibromoalkane to form o-(ω-bromoalkoxy)phenols
as intermediate, the intermediate further intramolecu-
larly cyclized to give the macrocyclic benzodioxocyclo-
alkane in low yield.
O
O
Merck Broad Nematic range liquid crystal
F
F
O
O
O
F
F
C5H11
O
Chisso large dielectric constant liquid crystal
*
E-mail: zhuoz@scnu.edu.cn
Received April 3, 2013; accepted June 27, 2013; published online July 19, 2013.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201300286 or from the author.
Chin. J. Chem. 2013, 31, 933—938
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Scheme 2 Synthesis of benzodioxocycloalkane-based liquid crystals
OHC
OH
OH
OHC
c
O
O
a
b
+
TfO
R
OTf
R
O
O
O
1a R = (CH2)4
1b R = (CH2)5
1c R = (CH2)6
2a R = (CH2)4
2b R = (CH2)5
2c R = (CH2)6
O
R
1d R = CH2(CF2)2CH2
1e R = CH2(CF2)3CH2
1f R = CH2(CF2)4CH2
2d R = CH2(CF2)2CH2
2e R = CH2(CF2)3CH2
2f R = CH2(CF2)4CH2
3a R = (CH2)4
3b R = (CH2)5
3c R = (CH2)6
3d R = CH2(CF2)2CH2
3e R = CH2(CF2)3CH2
3f R = CH2(CF2)4CH2
3CCA
=
COOH
c: 3CCA, DCC, DMAP, CHCl3, reflux
K2CO3, CH3CN, reflux
a:
b: MCPBA, CH2Cl2, reflux
TGA traces of 3a－3f are given in the Supporting In-
formation. In general, the new compounds with large
macrocyclic ring as end group are thermally less stable,
e.g., comparing the analogous 8, 9, 10 membered
fluorinated ring derivatives, 3d (C8), 3e (C9) and 3f (C10)
have Td values of 285, 271 and 272 ℃, respectively.
There exists strong strain in the larger 9, 10 membered
ring, which is the fundamental factor to influence ther-
mal stability.
The fluorinated derivatives also exhibited higher
melting point, e.g., 3d (C8F), m.p. 125.4 ℃ and 3a (C8),
m.p. 86.3 ℃. The introduction of a polyfluoroalkyl
group increases the van der Waals interactions which
contribute to the higher melting point of these com-
pounds.
The combination of trifluoromethanesulfonic fluoro-
alkylenediyl esters and benzylamine gave the fluori-
nated piperidine and azepine in high yield as our previ-
ous report.[24] The straightforward approach encouraged
us to employ trifluoromethanesulfonic acid long chain
alkyl or fluoroalkyldiyl esters and catechol to synthesize
macrocyclic benzodioxocycloalkane and its fluorinated
derivatives.
The trifluoromethanesulfonic alkylenediyl and fluoro-
alkyldily esters 1a－1f, were reacted with 3,4-dihy-
droxybenzaldehyde in the presence of K2CO3 in CH3CN
to give 2a－2f, respectively. The oxidation of benzal-
dehydes, 2a－2f, to phenols can be attained by Dakin or
Baeyer-Villiger reaction. When the fluorinated alde-
hydes, 2d－2f were reacted with H2O2 and H3BO3 un-
der the Dakin reaction condition, in an effort to obtain
the corresponding phenol, approximately six products
were observed by TLC. Treated the 2d － 2f with
m-chloroperoxybenzoic acid followed by base hydroly-
sis under the Baeyer-Villiger reaction condition gave
the corresponding phenol at the 80% yield, which was
used further without purification. Then trans-4'-propyl-
(1,1'-bicyclohexyl)-4-carboxylic acid (3CCA) was
esterified with the corresponding phenol using dicyclo-
hexylcarbodiimide (DCC) and N,N-dimethylamino-
pyridine (DMAP) in dichloromethane to give 3d－3f in
82% yield. This is the first example of the 3CCA de-
rivatives with macrocyclic benzodioxocycloalkane as
end group, some of which display good liquid crystal
properties.
Liquid crystalline properties
The new compounds were investigated for their po-
tential liquid crystalline properties by a combination of
hot stage polarizing optical microscopy and differential
scanning calorimetry (DSC). The transition tempera-
tures are presented in Table 1. The assignment of the
mesophases was made based on their optical texture.
Table 1 Transition temperatures (℃) of new compounds
Compd
3a
Phase behavior T a/℃
Cr→N
86.3
N→Iso
N→Iso
106.0
108.1
3b
Cr→N
78.1
3c
Cr→Iso
Cr→Iso
Cr→Iso
Cr→SmA
78.8
3d
125.4
121.7
Thermal stability
3e
3f
104.6 SmA→Iso
119.9
Thermal stabilities, which range from 250 to 300 ℃
and depend on the size of macrocyclic ring, were deter-
mined by thermal gravimetric analysis (TGA). The
a
Cr＝Crystalline state; N＝Nematic phase; SmA＝Smectic A
phase; Iso＝Isotropic liquid state.
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Fluorocarbon and Hydrocarbon Benzodioxocycloalkane (C8－C10) End Groups
As shown in Table 1, the three new compounds 3a,
3b and 3f with macrocyclic ring as end group display
good liquid crystal properties. Two factors which affect
the mesomorphic behaviour include: (1) the size of the
macrocyclic ring; (2) the polyfluoroalkyl substituent
group.
behaviour. Closer examination of 3d－3e by polarized
optical microscopy (POM) revealed that they are not
liquid crystals. No typical texture of the LC could be
observed when 3d－3e were heated to the melting point,
there was no texture change upon further heating, and
these compounds did not show mesophase behavior. These
are in agreement with the observation by DSC, they
only have one endothermic peak in the heating cycle
(see Supporting Information).
Interestingly, focal-conic fan of SmA phase can be
seen in 3f (C10). In order to ascertain the structures of
the smectic observed, variable-temperature X-ray dif-
fraction (VTXRD) experiments were carried out on 3f.
The diffraction patterns were recorded by heating the
sample into the isotropic phase from the crystal. A rep-
resentative and typical diffraction pattern obtained for
compound 3f at 115 ℃ is shown in Figure 3. A sharp
scattering at 5.22° corresponding to the d spacing of
16.89 Å given in the small angle region. One diffuse
scattering at 15.26° corresponding to the d spacing of
5.80 Å was also obtained. These results indicate the
formation of a smectic phase at 115 ℃. The optical
polarizing micrograph (Figure 4) reveals focal-conic fan
for 3f at this temperature range. Both results are consis-
tent with a smectic A structure. This arises from the fact
that the benzodioxocycloalkane has weakly associated
layers, whereby the steric nature of the end group pre-
vents strong interactions between the layers in stark
The nematic phase was evidenced based on its mar-
bled or threaded texture. An example of such a texture
can be seen in Figures 1 and 2. Compounds 3a and 3b,
which use 8 and 9 membered hydrocarbon ring as ter-
minal group, showed a nematic phase. This transition
also could be evaluated from the DSC trace (see Sup-
porting Information), two endothermic peaks at 86.3
and 106.0, 78.1 and 108.1 ℃ were observed for 3a and
3b, respectively. Investigations of DSC and POM
showed that 3c melted into isotropic liquid at 78.8 ℃
directly and no texture of liquid crystal was observed. It
shows that the mesomorphic behaviour is dominated by
the size of the macrocyclic benzodioxocycloalkane ring
from 3a－3c. As the terminal benzodioxocycloalkane
size increases from eight to ten membered ring, the
range of mesomorphic phases narrows rapidly.
Figure 1 POM texture for compound 3a at 88 ℃.
Figure 3 POM texture for compound 3f at 110 ℃.
Figure 2 POM texture for compound 3b at 90 ℃.
The introduction of a polyfluoroalkyl group affects
the steric conformation of the macrocycle which attracts
us to investigate the relationship between the fluorinated
macrocyclic ring and liquid crystal properties. Com-
pared with 3a－3c, the fluorinated macrocyclic deriva-
tives 3d－3f (C8－C10) display a different mesomorphic
Figure 4 XRD diffraction pattern for 3f recorded at 115 ℃.
Chin. J. Chem. 2013, 31, 933—938
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Cao et al.
FULL PAPER
contrast to the strongly associated layers of the
fluorinated benzodioxocycloalkane, hence the formation
of a SmA phase in the phase diagram as the polar inter-
actions begins to dominate at the interface.
was removed under a vacuum to give trifluorome-
thanesulfonic acid 1,4-butanedily ester 1a, which was
used without further purification.
General procedure for the preparation of 2a－2f
All the above mentioned compounds were synthe-
sized by the same method. The synthetic method will be
described taking the example of compound 2a.
A mixture of 3,4-dihydroxy-benzaldehyde (0.345 g,
2.5 mmol), potassium carbonate (3.453 g, 25 mmol) was
refluxed in acetonitrile (20 mL) at 373 K for 45 min,
then a solution of trifluoromethanesulfonic acid 1,4-
butanedily ester 1a, in acetonitrile (5 mL) was added.
The mixture was heated under reflux for 12 h. After
cooling to room temperature, the inorganic salts were
removed by filtration. The filtrate was concentrated un-
der reduced pressure. The residue was purified by flash
chromatography on silica gel to afford a white solid
2,3,4,5-tetrahydro-1,6-benzodioxocine-8-carbaldehyde
(2a).
2,3,4,5-Tetrahydro-1,6-benzodioxocine-8-carbal-
dehyde (2a)[25] 72% yield; white solid. 1H NMR (400
MHz, CDCl3) δ: 9.78 (s, 1H), 7.46－7.47 (m, 2H), 6.99
(s, 1H), 4.37 (d, J＝12.0 Hz, 4H), 1.88 (d, J＝4.0 Hz,
4H).
3,4,5,6-Tetrahydro-2H-1,7-benzodioxonin-9-carb-
aldehyde (2b) 72.5% yield; colorless liquid. 1H NMR
(400 MHz, CDCl3) δ: 9.82 (s, 1H), 7.57－7.37 (m, 2H),
7.01 (dd, J＝26.8, 8.3 Hz, 1H), 4.49 (t, J＝4.9 Hz, 2H),
4.19 (t, J＝4.5 Hz, 2H), 2.01－1.65 (m, 6H). MS (ESI)
m/z: 207.3 [M＋H]＋. Anal. calcd for C12H14O3: C 69.21,
H 7.74, found: C 69.17, H 7.76.
Conclusions
We have synthesized and characterized novel liquid
crystals containing benzodioxocycloalkane as the termi-
nal heterocycle. The C8－C9 membered 3a－3b, dis-
played good liquid crystals properties. The properties of
these liquid crystals can be adjusted by varying the size
of ring. It is shown that the nature of a bulky end group
can have a strong effect on the behaviour of a classical
mesogen. The compound, which bear the ten membered
benzodioxocycloalkane as terminal heterocycle, does not
show liquid crystal properties. Its fluorinated derivative
3f shows the SmA phases behaviours. It was also found
that terminal fluorinated heterocycle configurations
have a great impact on liquid crystal properties. Further
research should provide broad insight into the develop-
ment of the novel liquid crystals.
Experimental
All the reagents were of analytical grade, purchased
from commercial sources and used as received. H and
1
19F and spectra were recorded on a 400 MHz nuclear
magnetic resonance spectrometer operating at 400, 376
MHz respectively. Chemical shifts were reported rela-
tive to Me4Si for 1H, and CCl3F for 19F. The solvent was
CDCl3 unless otherwise specified. Thermogravimetric
analysis (TGA) measurements were performed at a
heating rate of 10 ℃•min−1 with a Netzsch STA409PC
(Germany) instrument. The DSC curves were recorded
on a differential scanning calorimeter at a scan rate of
10 ℃/min. Optical micrographs were observed with a
polarizing optical microscope (POM) (Nikon LINKAM-
THMSE600); Variable-temperature X-ray diffraction
(XRD) experiments were performed on a Bruker D8
Advance X-ray diffractometer (using Cu Kα1 radiation
of a wavelength of 1.54 Å) with temperature controller.
Elemental analyses were performed on an EXETER
CE-440 Elemental Analyzer.
2,3,4,5,6,7-Hexahydro-1,8-benzodioxecin-10-carb-
1
aldehyde (2c) 72% yield; White solid. H NMR (400
MHz, CDCl3) δ: 9.82 (s, 1H), 7.57－7.37 (m, 2H), 7.01
(dd, J＝26.8, 8.3 Hz, 1H), 4.49 (t, J＝4.9 Hz, 2H), 4.19
(t, J＝4.5 Hz, 2H), 2.01－1.65 (m, 6H). MS (ESI) m/z:
220.3 (M＋). Anal. calcd for C13H16O3: C 70.89, H 7.32;
found C 70.35, H 7.36.
3,3,4,4-Tetrafluoro-2,3,4,5-tetrahydro-1,6-benzo-
dioxocine-8-carbaldehyde (2d)[26] 75% yield; white
1
solid. H NMR (400 MHz, CDCl3) δ: 9.87 (s, 1H), 7.61
－7.58 (m, 2H), 7.20－7.15 (m, 1H), 4.67－4.61 (m,
2H), 4.48－4.42 (m, 2H); 19F NMR (CDCl3) δ: −123.03
－−123.27 (m, 2F), −123.49－−123.68 (m, 2F).
General procedure for the preparation of trifluoro-
methanesulfonic acid alkyldily and fluoroalkyldily
esters 1a－1f
3,3,4,4,5,5-Tetrafluoro-3,4,5,6-tetrahydro-2H-1,7-
benzodioxonin-9-carbaldehyde (2e)
73% yield;
white solid. 1H NMR (400 MHz, CDCl3) δ: 9.91－9.88
(m, 1H), 7.71－7.56 (m, 2H), 7.24－7.21 (m, 1H), 4.83
－4.65 (m, 2H), 4.59－4.52 (m, 2H); 19F NMR (CDCl3)
δ: −116.70－−117.08 (m, 2F), −117.18－−117.63 (m,
2F), −125.58 (s, 2F); MS (ESI) m/z: 354.6 (M＋). Anal.
calcd for C12H8F6O3•2H2O: C 41.39, H 2.89; found C
41.18, H 2.56.
All the above mentioned compounds were synthe-
sized by the same method. The synthetic method will be
described taking the example of compound 1a.
1,4-Butanediol (1 mmol), pyridine (2.3 mmol), and
dichloromethylene (20 mL) were stirred at room tem-
perature under a nitrogen atmosphere. After 20 min,
trifluoromethanesulfonic anhydride (2.5 mmol) was
slowly added (over 1 h) by using an addition funnel.
The mixture was stirred for 24 h, washed with water (10
mL×3) and then 10% sodium bicarbonate (10 mL×2),
and dried over anhydrous sodium sulfate. The solvent
3,3,4,4,5,5,6,6-Octafluoro-2,3,4,5,6,7-hexahydro-
1,8-benzodioxecin-10-carbaldehyde (2f) 70% yield;
white solid. 1H NMR (400 MHz, CDCl3) δ: 9.88 (s, 1H),
7.61 (dd, J＝8.2, 1.9 Hz, 1H), 7.55 (d, J＝1.8 Hz, 1H),
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Fluorocarbon and Hydrocarbon Benzodioxocycloalkane (C8－C10) End Groups
7.16 (d, J＝8.2 Hz, 1H), 4.60 (d, J＝12.0 Hz, 4H); 19F
NMR (CDCl3) δ: −114.68 (s, 4F), −119.85 (d, J＝86.1
Hz, 4F); MS (ESI) m/z: 420.6 (M＋). Anal. calcd for
C13H8F8O3•H2O: C 40.85, H,2.64; found C 41.10, H
2.21.
(400 MHz, CDCl3) δ: 7.02 (d, J＝8.6 Hz, 1H), 6.76 (s,
1H), 6.70 (d, J＝8.6 Hz, 1H), 4.19－4.06 (m, 4H), 2.46
－2.38 (m, 1H), 2.13 (d, J＝12.4 Hz, 2H), 1.90－1.44
(m, 15H), 1.44－1.20 (m, 3H), 1.20－0.91 (m, 9H),
0.86 (dd, J＝14.7, 7.8 Hz, 5H). MS (ESI) m/z: 884
(2M＋). Anal. calcd for C28H42O4: C 75.98, H 9.56;
found C 75.66, H 9.60.
General procedure for the preparation of 3a－3f
All the above mentioned compounds were synthe-
sized by the same method. The synthetic method will be
described taking the example of compound 3a.
(trans,trans)-4-Propyl-[1,1'-bicyclohexyl]-4-carb-
oxylic acid 3,3,4,4-tetrafluoro-2,3,4,5-tetrahydro-
1,6-benzodioxocine-8-yl ester (3d)
83.5% yield;
white solid. 1H NMR (400 MHz, CDCl3) δ: 7.05 (d, J＝
8.8 Hz, 1H), 6.80 (d, J＝2.6 Hz, 1H), 6.74 (dd, J＝8.8,
2.6 Hz, 1H), 4.59－4.40 (m, 4H), 2.45－2.39 (m, 1H),
2.12 (d, J＝12.4 Hz, 2H), 1.89－1.67 (m, 6H), 1.56－
1.44 (m, 2H), 1.33－1.25 (m, 2H), 1.19－0.91 (m, 9H),
0.91－0.78 (m, 5H); 19F NMR (CDCl3) δ: −123.49－
−123.73 (m, 2F), −123.75－−123.91 (m, 2F). MS (ESI)
m/z: 525.7 [M＋K]＋. Anal. calcd for C26H34F4O4: C
64.18, H 7.04; found C 63.90, H 6.95.
2,3,4,5-Tetrahydro-1,6-benzodioxocine-8-carbalde-
hyde 2a (1 mmol) and m-CPBA (1.8 mmol) were re-
fluxed in CHCl3 for 20 h. Most of the CHCl3 was re-
moved by distillation under reduced pressure and the
residue was dissolved in ethyl acetate (75 mL). The so-
lution was washed with aq. NaHCO3 until effervescence
ceased, then with brine, and dried over anhydrous so-
dium sulfate. Removal of the solvent left crude formate.
The crude formate was dissolved in a little MeOH and
hydrolyzed with a slight excess of 10% KOH at room
temperature. After completion of the reaction, the reac-
tion mixture was acidified with dilute HCl and extracted
with ethyl acetate (100 mL×2). The combined organic
layers were washed with water, brine. Removal of the
solvent gave curde phenol, which was used further with-
out purification. 3CCA, DCC, DMAP were taken in
CHCl3 at room temperature. After 10 min the crude
phenol was added. The reation mixture was stirred and
heated at reflux for 12 h. After cooling, the organic sol-
vent was removed under reduced pressure. After the
solvent was removed, the crude product was purified by
silica gel column chromatography (DCM∶Hexane＝
1∶2) to give 3a.
(trans,trans)-4-Propyl-[1,1'-bicyclohexyl]-4-carb-
oxylic acid 3,3,4,4,5,5-tetrafluoro-3,4,5,6-tetrahydro-
2H-1,7-benzodioxonin-9-yl ester (3e) 85% yield;
white solid. 1H NMR (400 MHz, CDCl3) δ: 7.10 (d, J＝
8.7 Hz, 1H), 6.86 (d, J＝2.2 Hz, 1H), 6.79 (dd, J＝8.7,
2.4 Hz, 1H), 4.63－4.50 (m, 4H), 2.52－2.36 (m, 1H),
2.12 (d, J＝12.3 Hz, 2H), 1.91－1.65 (m, 6H), 1.50 (dd,
J＝22.7, 10.2 Hz, 2H), 1.33－1.26 (m, 2H), 1.19－0.91
(m, 9H), 0.91－0.78 (m, 5H); 19F NMR (CDCl3) δ:
−117.20 (d, J＝83.8 Hz, 4F), −125.73 (s, 2F). MS (ESI)
m/z: 536.5 (M＋). Anal. calcd for C27H34F6O4: C 60.44,
H 6.39; found C 60.12, H 6.41.
(trans,trans)-4-Propyl-[1,1'-bicyclohexyl]-4-carb-
oxylic acid 3,3,4,4,5,5,6,6-octafluoro-2,3,4,5,6,7-hexa-
hydro-1,8-benzodioxecin-10-yl ester (3f) 82.5%
(trans,trans)-4-Propyl-[1,1'-bicyclohexyl]-4-carb-
oxylic acid 2,3,4,5-tetrahydro-1,6-benzodioxocine-8-
1
yield; white solid. H NMR (400 MHz, CDCl3) δ: 7.15
1
(d, J＝8.7 Hz, 1H), 6.91 (d, J＝1.9 Hz, 1H), 6.85 (dd,
J＝8.7, 2.0 Hz, 1H), 4.68－4.55 (m, 4H), 2.49 (dd, J＝
16.8, 7.7 Hz, 1H), 2.17 (d, J＝12.1 Hz, 2H), 1.98－1.71
(m, 6H), 1.61－1.48 (m, 2H), 1.38－1.31 (m, 2H), 1.24
－0.97 (m, 9H), 0.97－0.83 (m, 5H); 19F NMR (CDCl3)
δ: −115.68 (d, J＝74.7 Hz, 4F), −118.85 (d, J＝139.6
Hz, 4F). MS (ESI) m/z: 586.6 (M＋). Anal. calcd for
C28H34F8O4•H2O: C 55.33, H 6.00; found C 55.55, H
6.00.
yl ester (3a) 85% yield; white solid. H NMR (400
MHz, CDCl3) δ: 6.94 (d, J＝8.6 Hz, 1H), 6.67 (d, J＝
2.6 Hz, 1H), 6.62 (dd, J＝8.7, 2.6 Hz, 1H), 4.38－4.36
(m, 2H), 4.27－4.24 (m, 2H), 2.44－2.38 (m, 1H), 2.12
(d, J＝12.1 Hz, 2H), 1.95－1.80 (m, 6H), 1.79－1.66
(m, 4H), 1.53－1.44 (m, 2H), 1.33－1.25 (m, 2H), 1.19
－0.91 (m, 9H), 0.90－0.78 (m, 5H). MS (ESI) m/z:
414.66 (M＋). Anal. calcd for C26H38O4: C 75.32, H 9.24;
found C 75.11, H 9.33.
(trans,trans)-4-Propyl-[1,1'-bicyclohexyl]-4-carb-
oxylic acid 3,4,5,6-tetrahydro-2H-1,7-benzodioxonin-
9-yl ester (3b) 86% yield; white solid. H NMR (400
Acknowledgement
1
The authors gratefully acknowledge the support of
the National Natural Science Foundation of China (No.
21272080), Department of Science and Technology,
Guangdong Province (Nos. 2010A020507001-76,
5300410, FIPL-05-003), and the Scientific Research
Foundation for the Returned Overseas Chinese Scholars,
State Education Ministry.
MHz, CDCl3) δ: 6.97 (d, J＝8.6 Hz, 1H), 6.71 (d, J＝
2.8 Hz, 1H), 6.65 (dd, J＝8.7, 2.8 Hz, 1H), 4.24 (dd,
J＝37.3, 5.1 Hz, 4H), 2.42 (tt, J＝12.1, 3.5 Hz, 1H),
2.12 (d, J＝10.9 Hz, 2H), 1.83 (s, 7H), 1.79－1.68 (m,
4H), 1.51 (dd, J＝25.2, 12.6 Hz, 2H), 1.37－1.23 (m,
3H), 1.18－0.92 (m, 9H), 0.91－0.75 (m, 5H). MS (ESI)
m/z: 467.5 [M＋K]＋. Anal. calcd for C27H40O4: C 75.66,
H 9.41; found C 75.21, H 9.33.
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Chin. J. Chem. 2013, 31, 933—938