Synthesis and Characterization of Some Liquid Crystalline

Compounds based on a 2,7-dihydroxynaphtalene Core

GHEORGHE SIMION, IRINA CARLESCU, GABRIELA LISA, DAN SCUTARU*

“Gheorghe Asachi” Technical University of Iasi, Faculty of Chemical Engineering and Environmental Protection, Department of
Natural and Synthetic Polymers, 73 Dimitrie Mangeron Blv., 700050, Iasi, Romania

The paper presents the synthesis and structural characterization of some liquid crystalline compounds
derived from 2,7-dihydroxynaphthalene and containing azo-aromatic and esteric connecting groups. Two
classes of compounds were obtained by reacting 2,7-dihydroxynaphthalene with the corresponding 4-(4-
alkoxyphenylazo)-benzoic acid chlorides, in the presence of K2CO3 and THBAS as phase transfer catalyst, in
dichloromethane / water. Two classes of compounds have been isolated through mono- or di-esterification
of 2,7-dihydroxynaphthalene. Polarized optical microscopy and DSC investigations evidenced that only the
mono-esters of 2,7-dihydroxynaphthalene presented enantiotropic liquid crystalline properties, mainly of
nematic type.
Keywords: liquid crystals, 2,7-dihydroxynaphthalene, azo-aromatic compounds

In the recent years, a considerable interest focused on
the liquid cr ystalline properties of banana shaped
molecules [1]. The design and synthesis of novel achiral
banana shaped mesogens forming ferro- and/or antiferro-
electric smectic or columnar mesophases is one of the
most exciting research activities in the area of thermotropic
liquid cr ystals. Banana-shaped liquid cr ystalline
compounds broadly require two units: (i) a central unit,
which provides the bending angle, and (ii) two rodlike units
with a terminal aliphatic chain which could be attached to
the central unit [2-10]. Literature data reported several
central core aromatic molecules which are able to ensure
the necessary bending angle between 120-140 0 and
containing two reactive groups as substituent: 1,3-
disubstituted benzene, 2,7-disubstituted-naphtalene, 2,5-
disubstituted [1,3,4]-oxadiazole etc. Even 2,7-
dihydroxynaphthalene has been quite often as central core,
no date about compounds containing azo-aromatic groups
have been reported [11-13].
Most of the bent-core mesogens reported so far are
monomorphic and many of them exhibit an
antiferroelectric switching behaviour. In addition,
depending on the molecular structure of these compounds,
smectic A, smectic C, or nematic phases have been
obtained either individually or in combination with B-
phases. A direct transition from an antiferroelectric B2
phase to a nematic phase and a columnar B1 phase to a
nematic phase1 have also been observed[14-15]. Pelzl
have observed the spontaneous chiral ordering of
molecules in the nematic phase. On application of an
electric field to this texture, a fan-shaped texture with
equidistant stripes (chiral nature) can be induced, which
is very unusual. Although the nematic phase has been
observed in many bent-core compounds, its occurrence in
combination with B-phases is very limited. Hence, there is
a need to synthesize more compounds with varying
molecular structure in order to have a clear understanding
of the occurrence of this type of transition. In general, the
relationship between molecular structure and the
mesomorphic behavior involves different aspects; for
example, the position and magnitude of the bending angle,
the number of phenyl rings present in the bent-core, the
type and influence of lateral substituents, the nature and
orientation of linking groups, and length of the terminal
chains[1-4].
This paper presents the synthesis, structural
characterization and mesomorphic properties of two new
series of bent core compounds that have as central unit
2,7-dihydroxynaphthalene and as mesogenic groups 4-(4-
alcoxifenilazo)-benzoyl moieties. The liquid crystalline
properties were evaluated by means of polarized optical
microscopy and differential scanning calorimetry.
Experimental part
Materials and methods
4-(4-Alkoxyphenylazo)-benzoic acid chlorides have
been prepared according to literature data [16]. All other
materials used in the present work have been purchased
from Sigma Aldrich and were used as received. For column
chromatography Silica gel 60 (Merck) was used, while for
thin layer chromatography Silica gel plates (Merck Silica
gel F254) were used.
Nuclear magnetic resonance (NMR) spectra were
recorded on a BrukerÒ Avance DRX 400 MHz spectrometer.
Chemical shifts were reported in ppm relative to
tetramethylsilane (TMS) as internal standard. Mass spectra
were recorded on a quadrupole-time of flight mass
spectrometer equipped with an electrospray ion source
(Agilent® 6520 Accurate Mass Q-ToF LC/MS).The FTIR
spectra were recorded on a Nicolet Magna 550
spectrometer (NaCl cr ystal window). Transition
temperatures were determined using a Linkam heating
stage connected with a Linksys 32 temperature control
unit in conjunction with a Axioscop 40 Zeiss polarizing
optical microscope and Qimaging/Retiga-1000R camera
for image capture, the transitions being confirmed by DSC
analysis (Mettler Toledo DSC1). Heating and cooling cycles
were run at rates of 100C/min under nitrogen atmosphere,
with sample measured in closed lid aluminum pans. All
the thermal analysis were run in the same conditions, on
2.8 - 4.3 mg samples on a Mettler-Toledo® TGA SDTA851®

* email: dscutaru@ch.tuiasi.ro; Tel.: 0040 232 278683

REV. CHIM. (Bucharest) ♦ 63 ♦ No. 4 ♦ 2012 http://www.revistadechimie.ro 407

derivatograph in N2 atmosphere, with a flow rate of 20
mL/min and a heating rate of 10 0C/min from 25 to 900°C.
Synthesis
General method for the preparation of 7-hydroxy-
naphthalen-2-yl 4-((4-(alkyloxy)phenyl)azo) benzoates
(3a÷e) and naphthalene-2,7-diyl-bis(4-((4-(alkyloxy)
phenyl)azo)benzoates) (4a÷e)
Compounds were prepared by adapting literature data
[17]. A mixture of naphthalene-2,7-diol (1) (0.3 g, 1.875
mmol), 4-(4-alkyloxyphenylazo)-benzoyl chloride (2,06
mmol) (2a÷e), potassium carbonate (0.345g, 2.5 mmol),
tetrabutylammonium hydrogensulfate (0.016 g, 0.046
mmol) in dichloromethane (150 mL) and water (40 mL)
was vigorously stirred for 24 h. The organic layer was
separated, washed several times with distilled water, dried
on anhydrous magnesium sulphate and concentrated on
rotaevaporatory. Compounds of 3 and 4 type were
separated by column chromatography on Silica Gel using
a mixture of methylene chloride : ethyl acetate 20:1 as
eluent. Orange products. Yields: 10.75÷21,11 % for
compounds 3a÷3e and 8.81÷17.93 % for compounds
4a÷4e.
7-hydroxynaphthalen-2-yl 4-((4-(hexyloxy)phenyl) azo)
benzoate (3a)
Yield 11.50 % (0.1 g). 1H –NMR δH ppm (CDCl3 ): 1H –RMN
δH ppm (CDCl3 ): 8.41 (d, 2H, Ar, J=8.5 Hz), 8.03 (d, 2H, Ar,
J=8.55 Hz), 8.01 (d, 2H, Ar, J=8.7 Hz), 7.86 (d, 1H, Ar, J=8.8
Hz), 7.80 (d, 1H, Ar, J=8.8 Hz), 7.59 (d, 1H, Ar, J=1.9 Hz),
7.27 (dd, 1H, Ar, J1=2.2 Hz, J2=8.9 Hz), 7.16 (d, 1H, Ar,
J=2.0 Hz), 7.12 (dd, 1H, Ar, J1=2.4 Hz, J2=8.8 Hz), 7.08 (d,
2H, Ar, J=8.9 Hz), 5.06 (s, 1H,-OH), 4.06 (t, 2H, -O-CH2-),
1.89 (qv, 2H, -CH2-), 1.55 (qv, 2H, -CH2-), 1.42 (m, 4H, -
CH2-), 0.98 (t, 3H, -CH3). 13C-NMR δC ppm (CDCl3): 164.98,
162.64, 156.09, 154.25, 149.55, 147.14, 135.36, 131.30,
130.67, 129.81, 129.40, 127.19, 125.36, 122.61, 118.88,
117.79, 117.32, 115.02, 109.60 (1*>C=O esteric + 18 C,
aromatic), 68.64, 31.61, 29.23, 25.74, 22.61, 13.97 (1*-O-
CH2 + 5 C, aliphatic). FT-IR (KBr, cm-1): 3429.23 (νOH),
3068.74 ( νCH), 2929.86, 2858.5 (νCH, aliphatic), 1718.57
(νOCO); m/z (CHCl3): 469.31 [M+1].
7-Hydroxynaphthalen-2-yl 4-((4-(heptyloxy)phenyl)
azo)benzoate (3b)
Yield 21.11 % (0.19 g). 1H –NMR δH ppm (CDCl3): 8.35 (d,
2H, Ar, J=8.5 Hz), 7.967 (d, 2H, Ar, J=8.55 Hz), 7.945 (d,
2H, Ar, J=8.77 Hz), 7.80 (d, 1H, Ar, J=8.8 Hz), 7.73 (d, 1H,
Ar, J=8.8 Hz), 7.53 (d, 1H, Ar, J=1.9 Hz), 7.21 (dd, 1H, Ar,
J1=2.2 Hz, J2=8.9 Hz), 7.09 (d, 1H, Ar, J=2.0 Hz), 7.06 (dd,
1H, Ar, J1=2.4 Hz, J2=8.8 Hz), 7.02 (d, 2H, Ar, J=8.9 Hz),
5.06 (s, 1H, -OH), 4.06 (t, 2H, -O-CH2-), 1.83 (qv, 2H, -
CH2-), 1.49 (qv, 2H, -CH2-), 1.37 (m, 6H, -CH2-), 0.91 (t, 3H,-
CH3). 13C-NMR δC ppm (CDCl3): 164.99, 162.67, 156.14,
154.31, 149.59, 147.20, 135.39, 131.30, 130.72, 129.80,
129.40, 127.22, 125.36, 122.62, 118.87, 117.82, 117.32,
115.06, 109.63 (1*>C=O esteric + 18 C, aromatic), 68.68,
31.30, 29.30, 29.07, 26.06, 22.62, 14.01 (1*-O-CH2 + 6 C,
aliphatic). FT-IR (KBr, cm-1): 3415.93 (νOH), 3068.74
(νCH), 2922.15, 2854.64 (νCH, aliphatic), 1722.43
(νOCO); m/z (CHCl3): 483.33 [M+1].
7-hydroxynaphthalen-2-yl 4-((4-(octyloxy)phenyl)azo)
benzoate (3c)
Yield 10.75 % (0.1 g). 1H –NMR δH ppm (CDCl3 ): 8.36 (d,
2H, Ar, J=8.5 Hz), 7.968 (d, 2H, Ar, J=8.55 Hz), 7.945 (d,
2H, Ar, J=8.77 Hz), 7.80 (d, 1H, Ar, J=8.8 Hz), 7.74 (d, 1H,
Ar, J=8.8 Hz), 7.53 (d, 1H, Ar, J=1.7 Hz), 7.22 (dd, 1H, Ar,
408 http://www.revistadechimie.ro
J1=2.2 Hz, J2=8.9 Hz), 7.09 (d, 1H, Ar, J=5.3 Hz), 7.06 (dd,
1H, Ar, J1=2.3 Hz, J2=8.8 Hz), 7.02 (d, 2H, Ar, J=8.9 Hz),
5.08 (s, 1H, -OH), 4.06 (t, 2H, -O-CH2-,), 1.83 (qv, 2H, -
CH2-), 1.48 (qv, 2H, -CH2-), 1.34 (m, 8H, -CH2-), 0.90 (t, 3H,
-CH3). 13C-NMR δC ppm (CDCl3): 165.00, 162.63, 156.08,
154.25, 149.53, 147.13, 135.34, 131.29, 130.65, 129.79,
129.39, 127.17, 125.36, 122.60, 118.85, 117.79, 117.31,
115.01, 109.59 (1*>C=O esteric + 18 C, aromatic), 68.64,
31.85, 29.37, 29.26, 29.25, 26.08, 22.67, 14.04 (1*-O-CH 2
+ 7 C, aliphatic). FT-IR (KBr, cm-1): 3421.71 (νOH), 3068.74
(νCH), 2922.15, 2852.71 (νCH, aliphatic), 1720.50
(νOCO); m/z (CHCl3): 497.35 [M+1].
7-hydroxynaphthalen-2-yl 4-((4-(nonyloxy)phenyl)azo)
benzoate (3d)
Yield 15.78 % (0.14 g). 1H –NMR δH ppm (CDCl3): 8.35 (d,
2H, Ar, J=8.3 Hz), 7.965 (d, 2H, Ar, J=8.55 Hz), 7.945 (d,
2H, Ar, J=8.77 Hz), 7.79 (d, 1H, Ar, J=8.8 Hz), 7.72 (d, 1H,
Ar, J=.7 Hz), 7.51 (d, 1H, Ar, J=1.95 Hz), 7.21 (dd, 1H, Ar,
J1=1.5 Hz, J2=8.8 Hz), 7.07 (d, 1H, Ar, J=5.3 Hz), 7.03 (dd,
1H, Ar, J1=2.40 Hz, J2=8.71 Hz), 7.02 (d, 2H, Ar, J=8.9 Hz),
5.17 (s, 1H), 4.06 (t, 2H, -O-CH2-), 1.82 (qv, 2H, -CH2-), 1.49
(qv, 2H, -CH2-), 1.34 (m, 10H, -CH2-), 0.89 (t, 3H, -CH3 ). 13C-
NMR δ C ppm (CDCl 3): 165.04, 162.63, 156.08, 154.30,
149.51, 147.13, 135.34, 131.30, 130.65, 129.76, 129.39,
127.16, 125.36, 122.60, 118.82, 117.82, 117.31, 115.01,
109.59 (1*>C=O esteric + 18 C, aromatic), 68.64, 31.91,
29.56, 29.41, 29.27, 29.26, 26.07, 22.68, 14.05 (1*-O-CH 2
+ 8 C, aliphatic). FT-IR (KBr, cm-1): 3419.78 (νOH), 3068.74
(νCH,), 2918.29, 2858.78 (νCH, aliphatic), 1728.22
(νOCO); m/z (CHCl3): 511.36 [M+1].
7-hydroxynaphthalen-2-yl 4-((4-(decyloxy)phenyl)azo)
benzoate (3e)
Yield 12.44 % (0.122 g). 1H –RMN δH ppm (CDCl3): 8.35
(d, 2H, Ar, J=8.55 Hz), 7.965 (d, 2H, Ar, J=8.55 Hz), 7.945
(d, 2H, Ar, J=8.77 Hz), 7.79 (d, 1H, Ar, J=8.77 Hz), 7.72 (d,
1H, Ar, J=8.55 Hz), 7.52 (d, 1H, Ar, J=1.97 Hz), 7.205 (dd,
1H, Ar, J1=2.19 Hz, J2=8.77 Hz), 7.07 (d, 1H, Ar, J=2.0 Hz),
7.045 (dd, 1H, Ar, J1=2.41 Hz, J2=8.77 Hz), 7.01 (d, 2H, Ar,
J=8.98 Hz), 5.06 (s, 1H, -OH), 4.06 (t, 2H, -O-CH2-), 1.82
(qv, 2H, -CH2-), 1.49 (qv, 2H, -CH2-), 1.35 (m, 12H, -CH2-),
0.89 (t, 3H, -CH3).13C-NMR δC ppm (CDCl3): 165.05, 162.67,
156.14, 154.33, 149.55, 147.19, 135.38, 131.30, 130.70,
129.76, 129.39, 127.19, 125.36, 122.61, 118.82, 117.84,
117.32, 115.05, 109.63 (1*>C=O esteric + 18 C, aromatic),
68.68, 31.94, 29.59, 29.58, 29.41, 29.33, 29.28, 28.08, 22.69,
14.04 (1*-O-CH2 + 9 C, aliphatic). FT-IR (KBr, cm-1): 3421.71
(νOH), 3070.67 (νCH,), 2918.29, 2858.78 (νCH, aliphatic),
1728.22 (νCO); m/z (CHCl3): 525.38 [M+1].
Naphthalene-2,7-diyl-bis-(4-((4-(hexyloxy)phenyl)az)
benzoate) (4a)
Yield 17.93 % (0.26 g). 1H –NMR δH ppm (CDCl3): 8.36 (d,
4H, Ar, J=8.4 Hz), 7.95 (m, 10H), 7.73 (d, 2H, Ar, J=1.7 Hz),
7.40 (dd, 2H, Ar, J1=1.6 Hz, J2=8.9 Hz), 7.01 (d, 4H, Ar,
J=8.8 Hz), 4.06 (t, 4H, -O-CH2-), 1.83 (qv, 4H,-CH2-), 1.50
(qv, 4H, -CH2-), 1.37 (m, 8H, -CH2-), 0.92 (t, 6H,-CH3). 13C-
NMR δC (CDCl3): 164.78, 162.61, 156.06, 149.50, 147.08,
134.55, 131.31, 130.50, 129.72, 129.46, 125.35, 122.61,
121.25, 118.64, 114.97 (1*>C=O esteric + 14 C, aromatic),
68.59, 31.60, 29.21, 25.72, 22.60, 13.99 (1*-O-CH2 + 5 C,
aliphatic); m/z(CHCl3): 777.49 [M+1].
Naphthalene-2,7-diyl-bis-(4-((4-(heptyloxy)phenyl)
azo)benzoate) (4b)
Yield 11.46 %(0,17 g). 1H –NMR δH (CDCl3): 8.37 (d, 4H,
Ar, J=8.5 Hz), 7.96 (m, 10H), 7.73 (d, 2H, Ar, J=2.1 Hz),
REV. CHIM. (Bucharest) ♦ 63 ♦ No.4 ♦ 2012
7.40 (dd, 2H, Ar, J1=2.23 Hz, J2=8.91 Hz), 7.02 (d, 4H, Ar,
J=9.1 Hz), 4.06 (t, 4H, -O-CH2-), 1.83 (qv, 4H, -CH2-), 1.50
(qv, 4H, -CH2-), 1.37 (m, 12H), 0.91 (t, 6H, -CH3). 13C-NMR
δC (CDCl3): 164.77, 162.60, 156.05, 149.50, 147.07, 134.54,
131.31, 130.49, 129.71, 129.45, 125.35, 122.61, 121.24,
118.63, 114.96 (1*>C=O esteric + 14 C, aromatic), 68.58,
31.80, 29.24, 29.05, 26.02, 22.61, 14.04 (1*-O-CH2 + 6 C,
aliphatic); m/z (CHCl3): 805.53 [M+1].
Naphthalene-2,7-diyl-bis-(4-((4-(octyloxy)phenyl)azo)
benzoate) (4c)
Yield 10.06 %(0.15 g). 1H –NMR δH (CDCl3): 8.37 (d, 4H,
Ar, J=8.5 Hz), 7.96 (m, 10H), 7.73 (d, 2H, Ar, J=2.1 Hz),
7.40 (dd, 2H, Ar, J1=2.2 Hz, J2=8.9 Hz), 7.02 (d, 4H, Ar,
J=9.0 Hz), 4.06 (t, 4H, -OCH2-), 1.83 (qv, 4H, -CH2-), 1.48
(qv, 4H, -CH2-), 1.34 (m, 16H,), 0.90 (t, 6H,-CH3). 13C-NMR
δC (CDCl3): 164.76, 162.66, 156.16, 149.60, 147.19, 134.61,
131.32, 130.60, 129.76, 129.44, 125.37, 122.63, 121.25,
118.64, 115.04 (1*>C=O esteric + 14 C, aromatic), 68.66,
31.86, 29.38, 29.29, 29.25, 26.09, 22.67, 14.02 (1*-O-CH 2
+ 7 C, aliphatic); m/z (CHCl3): 833.56 [M+1].
Naphthalene-2,7-diyl-bis-(4-((4-(hexyloxy)phenyl)azo)
benzoate) (4d)
Yield 8.81% (0.14 g). 1H –NMR δH (CDCl3): 8.36 (d, 4H,
Ar, J=8.55 Hz), 7.95 (m, 10H), 7.73 (d, 2H, Ar, J=1.75 Hz),
7.40 (dd, 2H, Ar, J1=1.97 Hz, J=8.99 Hz), 7.01 (d, 4H, Ar,
J=8.99 Hz), 4.06 (t, 4H, -OCH2-), 1.83 (qv, 4H, -CH2-), 1.49
(qv, 4H, -CH2-), 1.35 (m, 20H, CH2-), 0.89 (t, 6H, -CH3). 13C-
NMR δC (CDCl3): 164.76, 162.68, 156.17, 149.61, 147.21,
134.62, 131.31, 130.62, 129.77, 129.45, 125.36, 122.64,
121.26, 118.65, 115.05 (1*>C=O esteric + 14 C, aromatic),
68.67, 31.92, 29.57, 29.43, 29.30, 29.28, 26.09, 22.69, 14.03
(1*-O-CH2 + 8 C, aliphatic); m/z (CHCl3): 861.59 [M+1].
Naphthalene-2,7-diyl-bis-(4-((4-(decyloxy)phenyl)azo)
benzoate) (4e)
Yield 10,2%(0.17 g). 1H –NMR δH (CDCl3): 8.36 (d, 4H, Ar,
J=8.4 Hz), 7.95 (m, 10H), 7.73 (d, 2H, Ar, J=1.7 Hz), 7.40
(dd, 2H, Ar, J1=1.6 Hz, J2=8.9 Hz), 7.01 (d, 4H, Ar, J=8.8
Hz), 4.06 (t, 4H, -OCH2-), 1.82 (qv, 4H, -CH2-), 1.49 (qv, 4H,
-CH 2-), 1.35 (m, 24H), 0.89 (t, 6H, -CH 3). 13C-NMR δ C
(CDCl3): 164.73, 162.68, 156.20, 149.65, 147.24, 134.64,
131.29, 130.65, 129.77, 129.42, 125.34, 122.62, 121.23,
118.62, 115.07 (1*>C=O esteric + 14 C, aromatic), 68.69,
31.93, 29.58, 29.54, 29.40, 29.31, 29.28, 26.08, 22.67, 13.99
(1*-O-CH2 + 8 C, aliphatic); m/z(CHCl3): 889.63 [M+1].
Results and discussions
Synthesis
Initially, the general idea was to obtain some mono esters
of 2,7-dihydroxinaphtalene by its reaction with a series of
4-(4-alkoxyphenylazo)-benzoic acid chlorides which may
be used for the synthesis of asymmetric bent core
compounds with potential liquid crystalline properties.
REV. CHIM. (Bucharest) ♦ 63 ♦ No. 4 ♦ 2012 http://www.revistadechimie.ro
The reactions were performed in the presence of
aqueous potassium carbonate / dichloromethane, using
TBHAS as phase transfer catalyst. Several other attempts
to obtain the esters of 2,7-dihydroxinaphtalene failed (DCCI
/ DMAP method, working in homogeneous media with
pyridine or TEA as bases etc).
Not unexpectedly, thin layer chromatography evidenced
a quite complex composition of the reaction mixture.
Column chromatography separation afforded the mono-
and di-esters of 2,7-dihydroxinaphtalene in an approximate
1:1 molar ratio (scheme 1). The obtained yields were
between 10.75÷21.11 % for compounds 3a÷3e and
8.81÷17.93 % for compounds 4a÷4e.
Liquid crystalline properties
The investigations through polarized optical microscopy
(POM) and differential scanning calorimetry (DSC)
indicated the existence of the mesomorphic properties only
for the mono-esters 3a÷3e. Compounds 4a÷4e do not
present liquid crystalline properties, which is quite
unexpected taking into consideration that literature data
present several classes of symmetric bent core liquid
crystalline compounds, with similar structures and with a
rich polymorphism.
For all the compounds 3a÷3e, polarized optical
microscopy indicated that the liquid crystalline properties
are of enantiotropic type, the ordering into mesophases
being evidenced both on heating and cooling cycles.
Table 1 synthetically presents the mesomorphic
properties and transition enthalpies of compounds 3a÷3e
and 4a÷4e. Taking into consideration the importance of
thermal stability in the existing range of mesophases, table
1 also presents, based on thermal stability studies, the Tonset
temperatures, the initial temperature at which the
degradation processes begin.
Graphic representation of temperature variation of
isotropisation and crystallization depending on the number
of carbon atoms of the terminal alkyl chain highlights the
appearance of the even/odd effect, meaning that
derivatives with an odd number of carbon atoms present
isotropisation and crystallization temperatures inferior to
their superior and inferior homologues.
Compounds 3a÷3e present mesomorphic properties
with ordering in nematic mesophases, with ribbon and
Schlieren like textures. For compounds 3d and 3e
differential calorimetric data evidenced also the existence
of crystalline-crystalline transitions both on cooling and
heating cycles. In the case of compounds 3a-3c, no
crystalline-crystalline transitions, both on cooling and
heating cycles could be observed (fig.2).
When heated, compound 3a presents Schlieren
characteristic textures, the mesophase starting at 1900C
and lasting up to isotropic temperature at 2140C (fig. 3a).
On cooling, nematic droplets come into view at 2180C
(fig. 3b), which maintain down to 2100C, when a Schliren
Scheme 1. The synthesis
2,7-dihydroxynaphthalene
mono- and di-esters
409

Abbreviation: Cr-crystalline, N-nematic, I-isotropic, Tonset – the initial temperature of the
beginning of thermal degradation
• Data obtained from POM investigations
Fig. 1. Variation of isotropisation and
crystalisation temperatures for 3a÷3e
compounds as a function of the odd/even number
of carbon atoms of the alkyl chain (1. Cr/Liq.
Cryst.; 2. Liq. Cryst/Cr)
a b
nematic texture appears (fig. 3c). In the case of compound
3b, on heating, the same Schliren texture appears, the
mesophase begins at 1780C and isotropisation at 1900C
(fig. 4a). On cooling, compound 3b evidenced nematic
drops (fig. 4b) which maintained down to 1800C, when a
nematic Schliren texture appeared (fig. 4c) and which
transforms to a ribbon type texture at 1750C (fig. 4d).
410 http://www.revistadechimie.ro
Table 1
TRANSITION TEMPERATURES [°C],
TRANSITION ENTHALPIES [J·g-1] AND
of Tonset[OC] TEMPERATURES FOR
COMPOUNDS 3a÷3e AND 4a÷4e
Fig. 2. DSC curves of compound 3a: 1: first
heating; 2: first cooling.
c
Fig. 3. Optical micographs of
compund 3a: (a) first heating, 2120C;
(b) first cooling, 2150C and (c) first
cooling, 2080C
Differential calorimetric analysis of derivatives 3d and
3e highlights the appearance of crystallin-crystallin
transitions. Durring the first heating of compound 3e it was
noted the appearance of a crystallin-crystallin transition at
1350C, while the crystalline - liquid crystalline switch takes
place at 1750C (fig. 5). Isotropisation takes place at 1960C.
The same polymorphism was observed on the cooling
phase.
REV. CHIM. (Bucharest) ♦ 63 ♦ No.4 ♦ 2012
 Fig. 4. Optical micographs of
compound 3b: (a) first
heating, 1850C; first cooling
(b) 1830C (c) 1790C and
(d)1730C

Fig. 6. The texture of sample 3e:

first heating at 1810C

Fig. 5. DSC curbes (heating and cooling) of compund 3e. 2. LINK, D. R., NATALE, G., SHAO, R., MACLENNAN, J. E., CLARK, N.
A., KÖRBLOVA, E., WALBA, D. M., Science, 278, 1997, p.1924.
The polarized optical microscopy analysis indicates the
3. PELZL, G., DIELE, S., WEISSFLOG, W., Adv. Mater. 11,1999, p. 707.
existence of Schliren textures that are specific for nematic
4. WALBA, D. M., KÖRBLOVA, E., SHAO, R., MACLENNAN, J. E., LINK,
mesophases, starting with 1750C and up to isotropisation
D. R., GLASER, M. A., CLARK, N. A., Science, 288, 2000, p. 2181.
at 1960C (fgi. 6).
5. PRATIBHA, R., MADHUSUDANA, N.V., SADASHIVA, B. K., Science,
The presence of a reactive hydroxy group and the
288, 2000, p. 2184.
existence of liquid crystalline properties of compounds 3a-
6. SADASHIVA, B. K., RAGHUNATHAN, PRATIBHA, V.A., Ferroelectrics,
3e make them very suitable for the synthesis of new classes
R., 243, 2000, p. 29.
of asymmetric bent core type compounds, by reacting the
7. SHEN, D., PEGENAU, A., DIELE, S., WIRTH, I., TSCHIERSKE, C. J.,
hydroxyl group with different mesogenic molecules.
Am. Chem. Soc. 122, 2000, p. 1593.
8. BEDEL, J. P., ROUILLON, J. C., MARCEROU, J. P., LAGUERRE, M.,
Conclusions
NGUYEN, H. T., ACHARD, M. F. J., Mater. Chem. 12, 2002, p. 2214.
Ten new compounds were synthesized through
9. (a) PELZL, G., EREMIN, A., DIELE, S., KRESSE, H., WEISSFLOG,
esterification of 2,7-dihydroxynaphthalene with the
W.J., Mater. Chem. 12, 2002, p. 1316. (b) NADASI, H., WEISSFLOG, W.,
corresponding 4-(4-alkoxyphenylazo)-benzoic acid
EREMIN, A., PELZL, G., DIELE, S., DAS, B., GRANDE, S.J., Mater. Chem.
chlorides.
12, 2002, p. 1316
The synthesized compounds have been completely
10. NIORI, T., SEKINE, T., WATANABE, J., FURUKAWA, T., TAKEZOE, H.
characterized by means of 1H-NMR, 13 C-NMR, IR, MS
J., Mater. Chem. 6, 1996, p. 1231.
spectra.
11. AMARANATHA REDDY, R., SADASHIVA, B. K., Liq. Cryst. 27, 2000,
After DSC and POM analysis it was found that only the
p. 1613.
mono-esters of 2,7-dihydroxynaphthalene present liquid
12. AMARANATHA REDDY, R., SADASHIVA, B. K., DHARA, S. Chem.
cr ystalline properties of enantiotropic type, with
Commun. 19, 2001, 1972.
mesophasic ordering both on heating and cooling cycles.
13. THISAYUKTA, J., NAKAYAMA, Y., KAWAUCHI, S., TAKEZOE, H.,
These compounds may be further used for the synthesis of
WATANABE, J. J., Am. Chem. Soc. 122, 2000, p. 7441.
asymmetric bent core type molecules.
14. WEISSFLOG, W., NADASI, H., DUNEMANN, U., PELZL, G., DIELE, S.,
EREMIN, A., KRESSE, H. J., Mater. Chem. 11, 2001, p. 2748.
Acknowledgements: This work was supported by CNCS –UEFISCDI
15. SCHRODER, M. W., DIELE, S., PELZL, G., DUNEMANN, U., KRESSE,
(Romania), project number PNII – IDEI 356/2008.. This paper was
H., WEISSFLOG, W.J., Mater. Chem. 13, 2003, p. 1877.
also realized with the support of BRAIN “Doctoral scholarships as an
16. SIMION, G., IUGANU, D.F., CARLESCU, I., SCUTARU, D., Bulletin of
investment in intelligence” project, financed by the European Social
the Polytechnic Institute of Iaºi, Section Chemistry and Chemical
Found and Romanian Government.
Engineering, 57 (3), 2011, p. 213.
17. SVABODA, J., NOVOTNA, V., KOZMIK, V., GLAGOROVA, M.,
References
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Manuscript received: 23.03.2011

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