Gallic esters of 4,5-dinitrocatechol as potential building blocks for thermotropic liquid crystals

Article abstract of DOI:10.1016/j.tet.2006.07.087

A series of unsubstituted and 1,4-disubstituted gallic catecholates 1, 6 and 7 as possible candidates for wedge-shaped mesogens were prepared starting from the respective benzene derivatives 2a-c and gallic esters 5a-h. The mesomorphic properties were inv

Full text of DOI:10.1016/j.tet.2006.07.087

Tetrahedron 62 (2006) 9681–9687
Gallic esters of 4,5-dinitrocatechol as potential building
blocks for thermotropic liquid crystals
a
Roxana Judele, Sabine Laschat, Angelika Baro and Manfred Nimtz
a,*
a
b
a
Institut f u€ r Organische Chemie, Universit a€ t Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
Gesellschaft f u€ r Biotechnologische Forschung, Mascheroder Weg 1, D-38124 Braunschweig, Germany
b
Received 11 May 2006; revised 24 July 2006; accepted 25 July 2006
Available online 21 August 2006
Abstract—A series of unsubstituted and 1,4-disubstituted gallic catecholates 1, 6 and 7 as possible candidates for wedge-shaped mesogens
were prepared starting from the respective benzene derivatives 2a–c and gallic esters 5a–h. The mesomorphic properties were investigated by
DSC. However, only the 4,5-dinitro derivatives 1d,f–h with C H and C H to C H alkyl side chains displayed mesophases, as evaluated
8
17
10 21
12 25
by fluidity and optical anisotropy.
Ó 2006 Elsevier Ltd. All rights reserved.
1. Introduction
2. Results and discussion
The effect of nitro groups on the mesomorphic and optical
properties of low molecular weight thermotropic liquid crys-
tals has been studied by several groups during the last couple
As shown in Scheme 2, target compound 1 was accessible via
three-step reaction. 1,2-Dimethoxybenzene 2a was treated
with nitric acid to give 1,2-dimethoxy-4,5-dinitrobenzene
1
5
of years. In most cases molecules exhibiting smectic,
nematic and banana phases have been investigated, whereas
3 in 90% yield following a procedure by Marquet. Com-
pound 3 was subsequently demethylated with BBr at
3
2
,3
ꢁ
6
wedge-shaped systems were not considered. Bushby and
Kumar observed that nitration of hexaalkyloxy-substituted
ꢀ78 C in CH Cl to afford 4,5-dinitrocatechol 4 in 68%
2
2
4
yield. The latter was esterified with tris(alkyloxy)gallic
acids 5a–h in the presence of DCC and DMAP to yield the
target gallic esters 1a–h in 56–82% (Scheme 2). Compound 5
7
triphenylenes leads to enhanced mesophase behaviour. This
prompted us to prepare gallic ester 1 of 4,5-dinitrocatechol as
potentialcandidatesforwedge-shapedmesogens(Scheme1).
Herein we report their synthesis and the study of mesomor-
phic properties.
OMe
OMe
O2N
O2N
OR
OR
HNO3, HOAc
°C→r.t., 0.5 h
0
O
n
2a
3 (R = Me), 90%
4 (R = H), 68%
BBr , CH Cl , –78°C, 3 h
3
2
2
O
n
O
OR1
O
n
OR1
OR1
O2N
O2N
O
O
DCC, DMAP
NO2
O
OH 5a–h
O
O
O
n
n
O2N
R1
=
1
Yield (%)
O
a
b
c
d
e
f
C H
66
67
69
74
57
72
82
56
5
11
13
15
17
19
H
H
H
n
C H
6
7
8
9
O
O
O
1
(n = 1–8)
C H
O
C H
Scheme 1. Gallic ester 1 derived from 4,5-dinitrocatechol.
C H
0
1
2
1
OR1
R O
C
1
C
1
C
1
21
23
25
g
1
OR1
1
OR1
R O
R O
h
1
a–h
Keywords: Catechol; Esterification; Gallic esters; Mesogens.
*
0
Corresponding author. Fax: +49 711 685 64285; e-mail: sabine.laschat@
oc.uni-stuttgart.de
Scheme 2. Synthesis of target gallic ester 1 starting from 1,2-dimethoxy-
benzene 2a.
040–4020/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2006.07.087

9682
R. Judele et al. / Tetrahedron 62 (2006) 9681–9687
was prepared from ethyl 3,4,5-trihydroxybenzoate via
O-alkylation and subsequent saponification. Slight modifi-
7
cation of this protocol by replacing DMF with acetonitrile
as the solvent and slow addition of the alkyl bromide mark-
edly improved the yields up to 99%.
8
The mesomorphic properties of ester 1 were investigated
by differential scanning calorimetry (DSC) and polarizing
optical microscopy (POM). The results are summarized in
1
Table 1. Whereas the derivatives 1a–c with R ¼C H to
5
11
C H side chain displayed only isotropic melting during
7
15
ꢁ
a clearing transition at 55 C were observed for octyloxy
the DSC heating scans, a melting transition at 37 C and
ꢁ
ester 1d. Surprisingly, only isotropic melting was found for
the homologous nonyloxy ester 1e. In contrast, derivatives
1
1
displayed a mesophase. The high clearing enthalpies of com-
f–h with longer alkyl chains (R ¼C H to C H ) again
1
0
21
12 25
pounds 1d,f–h deserve some additional comment. Although
they may be taken as evidence for plastic crystals, we have
9
previously reported high clearing enthalpies for both colum-
nar
1
0,11
11
and smectic mesophases.
Under the polarizing optical microscope small, poorly
defined textures were observed for compounds 1d,f–h
upon cooling from the isotropic liquid. Typical examples
are shown in Figure 1. Unfortunately, we were not able to
obtain suitable X-ray diffraction data. Thus, a crystal to crys-
tal transition instead of a crystal to mesophase (i.e., smectic)
transition cannot be completely excluded. However, the flu-
idity of the birefringent phase, which was obtained upon
cooling from the isotropic liquid, was proven by mechani-
cally shearing the sample between the cover slip and the
slide. The combination of fluidity and optical anisotropy
gives clear evidence of a liquid crystalline state.
In order to study the effect of the nitro groups on the meso-
morphic properties, the unsubstituted gallic esters 6a–h
(R¼H) were prepared as described above by esterification
of 1,2-dihydroxybenzene 2b with gallic acids 5a–h in the
ꢁ
ꢁ
Figure 1. Optical textures of compounds 1d at 50 C (a) and 1f at 64 C
(b) upon cooling from the isotropic liquid (cooling rate 1 K min , mag-
ꢀ
1
presence of DCC and DMAP in CH Cl at room tempera-
2
nification ꢂ200).
2
7
ture. In an analogous manner, the corresponding 4,5-di-
bromo gallic esters 7f–h were obtained in 77–87% yield
OR1
OR1
1
2
starting from 4,5-dibromo-1,2-dihydroxybenzene 2c and
gallic ester derivatives 5f–h (Scheme 3).
O
OR1
5a–h
R
R
OH
OH
R
R
O
O
In contrast to the dinitro ester 1 the corresponding unsubsti-
tuted derivative 6 did not display any mesophases. Only crys-
tal to crystal transitions and isotropic melting were observed
(Table 2). All melting points were much lower than those of
thedinitrocompound1,resultingfromthedecreasedpolarity.
DCC, DMAP
CH2Cl2, r.t., 20 h
OR1
OR1
2b (R = H)
c (R = Br)
O
2
OR1
ꢁ
ꢀ1
Table 1. Phase transition temperatures [ C] and enthalpies [kJ mol ] of
gallic esters 1a–h
6a–h (R = H)
7f–h (R = Br)
1
6, 7
a
b
c
d
e
f
g
h
Compd
R
Cr
1
T (DH)
I
T (DH)
1
R = C5H11 C6H13 C7H15 C8H17 C9H19 C10H21 C11H23 C12H25
1
1
1
1
1
1
1
1
a
b
c
d
e
f
C
C
C
C
C
C
C
C
5
6
7
8
9
H
H
H
H
H
H
H
H
11
13
15
17
19
Cr
Cr
Cr
Cr
Cr
Cr
Cr
Cr
69 (65.8)
75 (51.7)
63 (85.9)
37 (10.6)
62 (71.5)
44 (42.0)
46 (49.1)
61 (63.5)
I
I
I
M
I
M
M
M
6
Yield (%) 90
Yield (%)
84
90
92
77
94
77
94
84
89
87
7
x
55 (28.1)
I
Scheme 3. Preparationofgallicesters6a–hand4,5-dibromoderivatives7f–h.
10
11
12
21
23
25
x
x
x
61 (66.4)
63 (77.0)
65 (13.0)
I
I
I
g
h
As can be seen from Table 2, even the dibromo derivatives
7f–h with long alkyl chains (R ¼C H to C H ) did not
show any mesophases but crystal to crystal transitions.
1
1
0
21
12 25
Cr¼crystalline, M
x
¼mesophase, I¼isotropic.

R. Judele et al. / Tetrahedron 62 (2006) 9681–9687
9683
ꢁ
ꢀ1
Table 2. Phase transition temperatures [ C] and enthalpies [kJ mol ] of
gallic ester derivatives 6a–h and 7f–h
washed with water and dried under vacuum. In the case of
5g and 5h, the mixture was treated with cold MeOH
(20 mL), stirred for 30 min at 0 C, filtrated and dried. The
1
R
ꢁ
Compd
Cr
1
T (DH)
4 (12.4)
I
T (DH)
spectroscopic data of products 5 are in accordance with those
in the literature.
6
6
6
6
6
6
6
6
7
7
7
a
b
c
d
e
f
g
h
f
C
C
C
C
C
C
C
C
C
C
C
5
6
7
8
9
H
H
H
H
H
11
13
15
17
19
Cr
Cr
Cr
Cr
Cr
Cr
Cr
Cr
Cr
Cr
Cr
I
I
7
ꢀ5 (9.7)
1
1
3 (0.8)
8 (1.3)
Cr
Cr
I
Cr
Cr
Cr
I
2
9 (1.5)
11 (2.3)
I
I
2
3.1.2. General procedure for the preparation of 4,5-di-
nitro-2-{[3,4,5-tris(alkyloxy)benzoyl]oxy}phenyl 3,4,5-
tris(alkyloxy)benzoates 1a–h. DCC (3.1 equiv) was added
to a cooled solution of the appropriate acid 5 (2.2 equiv) in
18 (3.6)
ꢀ56 (8.2)
ꢀ22 (26.3)
5 (28.9)
33 (71.2)
ꢀ2 (49.0)
5 (28.9)
10
11
12
10
11
12
H
21
23
25
21
23
25
1
1
1
2
2
2
22 (12.0)
25 (12.7)
28 (8.7)
I
I
I
H
H
H
H
H
ꢁ
CH Cl (14 mL) at 0 C, and the reaction mixture was stirred
2
2
g
h
1
1
Cr
Cr
2
42 (47.1)
42 (64.2)
I
I
for 10 min. Then DMAP (1.0 equiv) and 3 (1.0 equiv)
were added and after stirring for five days, the reaction mix-
ture was treated with CH Cl (20 mL), washed with 1 M
2
Cr¼crystalline, I¼isotropic.
2
2
HCl (3ꢂ30 mL) and H O (30 mL), dried (MgSO ) and con-
2
4
centrated. The oily residue was treated with PE (30 mL) and
the white solid was filtered off. The filtrate was evaporated
and the residue purified by repeated flash chromatography
on SiO with PE/CH Cl [1:3, then 10:27 (1a), 2:2.3 (1b),
In conclusion, substituent effects on the phase behaviour of
gallic catecholates 1, 6 and 7 were evaluated. While some
of the dinitro derivative 1 displayed mesophases, both
the corresponding unsubstituted gallic ester 6 and the di-
bromo-substituted derivative 7 are certainly not mesomor-
phic. However, in the case of 1 it cannot be differentiated
undoubtedly between true mesophases or just soft crystal
phases. In general, phase transition temperatures decrease
in the order 1>7>6 with an approximate temperature differ-
ence of 20 C between the different series. Although com-
pounds 6 and 7 did not show any mesomorphic properties,
they are useful building blocks for the convergent prepara-
tion of larger mesogenic subunits via oxidative coupling
2
2
2
2:2.1 (1c), 2:2.2 (1d), 11:1 (1e), 20:23 (1f), 13:10 (1g,h)]
to give product 1 as bright yellow solid.
3.1.2.1. 4,5-Dinitro-2-{[3,4,5-tris(pentyloxy)benzoyl]-
oxy}phenyl 3,4,5-tris(pentyloxy)benzoate (1a). Mp
ꢁ
8H; 6CH ), 1.30–1.51 (m, 24H; 6(CH ) CH ), 1.70–1.80
1
6
1
9 C. H NMR (300 MHz, CDCl ): d¼0.92 (t, J¼6.8 Hz,
3
3
2 2
3
ꢁ
(
4
8
m, 12H; 6OCH CH ), 3.82 (t, J¼6.4 Hz, 8H; 4OCH ),
2
2
2
.02 (t, J¼6.4 Hz, 4H; 2OCH ), 7.23 (s, 4H; Ar-H),
2
13
.07 (s, 2H; Ar-H) ppm. C NMR (75 MHz, CDCl ):
3
d¼13.9 (4CH ), 14.0 (2CH ), 22.41 (2CH CH ), 22.47
Sch €o ll reaction)13 or Pd-catalyzed cross coupling.
14
3
3
3
2
(
(CH CH ), 28.1 (2CH CH CH ), 28.2 (CH CH CH ),
3 2 3 2 2 3 2 2
2
7
1
8.8 (2CH (CH ) ), 29.9 (CH (CH ) ), 69.1 (2OCH ),
3 2 3 3 2 3 2
3.5 (OCH ), 108.5 (4CH), 120.7 (2CH), 121.0, 140.0,
2
44.0, 145.8, 153.0, 162.5 (2CO) ppm. FTIR (ATR): 2954
3. Experimental
(
m), 2932 (vs), 2870 (vs), 1746 (vs), 1732 (vs), 1588 (m),
3
.1. General
1
(
540 (vs), 1430 (m), 1333 (vs), 1270 (vs), 1180 (vs), 1157
ꢀ
vs), 1084 (s), 934 (m), 743 (m) cm . UV–vis (CH Cl ):
2 2
1
Column chromatography was accomplished using SiO 60,
2
lmax (log 3)¼309 (3.29), 276 (3.42), 229 (0.74), 213
+
grain size 0.063–0.200 mm (Merck) with hexanes (PE, bp
3
(0.61). EIMS, m/z (%): 924.5 (40) [M ], 880.8 (100)
ꢁ
ents. Starting materials 2a,b are commercially available.
+
0–60 C), EtOAc, and dichloromethane (CH Cl ) as elu-
2
2
[M ꢀCO ], 809.8 (20), 742.6 (15), 696.4 (100), 626.5
2
(
(
15), 562.3 (25), 517.3 (40), 380.2 (45), 310.2 (28), 170.0
1
3
+
C NMR multiplicities were determined with DEPT experi-
ments. DSC was performed on a Mettler Toledo DSC822.
100), 43 (75). MS (ESI), m/z (%): 947.5 (100) [M +Na],
+
+
942.6 (25) [M +NH ], 925.6 (10) [M +H]. Anal. calcd for
C H N O (924.5): C, 64.91; H, 7.84; N, 3.03. Found:
C, 64.70; H, 7.81; N, 2.98.
4
Compounds 2c, 3 and 4 were prepared according to literature
procedures.
5
0 72 2 14
5
,6,12
3.1.1. General procedure for the preparation of gallic
esters 5a–h. A mixture of K CO (9 equiv) and ethyl 3,4,5-
3.1.2.2. 4,5-Dinitro-2-{[3,4,5-tris(hexyloxy)benzoyl]-
ꢁ
oxy}phenyl 3,4,5-tris(hexyloxy)benzoate (1b). Mp 75 C.
H NMR (300 MHz, CDCl ): d¼0.90 (t, J¼6.6 Hz, 18H;
2
3
1
trihydroxybenzoate (1 equiv) in MeCN (30–60 mL) was
refluxed for 30 min under N atmosphere. A solution of the
3
6CH ), 1.30–1.57 (m, 36H; 6(CH ) CH ), 1.69–1.80 (m,
3
2
2 3
3
respective alkyl bromide (4 equiv) in MeCN (6–12 mL) was
added dropwise to the slurry, maintaining reflux and stirring
for 20 h. The reaction was cooled to room temperature and
filtered. The inorganic residue was washed with CH Cl
12H; 6OCH CH ), 3.82 (t, J¼6.3 Hz, 8H; 6CH ), 4.02 (t,
2
2
3
J¼6.5 Hz, 4H; 2OCH ), 7.23 (s, 4H; Ar-H), 8.08 (s, 2H;
2
1
3
Ar-H) ppm. C NMR (75 MHz, CDCl ): d¼13.9 (4CH ),
3
3
14.0 (2CH ), 22.5, 22.6, 25.6, 25.7, 29.1, 30.2, 31.5, 31.6
3
2
2
(
the residue dissolved in CH Cl (75 mL) and washed with
2ꢂ50 mL). The filtrate was concentrated under vacuum,
(6CH (CH ) ), 69.1 (4OCH ), 73.6 (2OCH ), 108.5
3
2 4
2
2
(4CH), 120.7 (2CH), 121.0, 140.0, 144.0, 145.8, 153.0,
162.5 (2CO) ppm. FTIR (ATR): 2926 (vs), 2855 (vs), 1747
(vs), 1735 (vs), 1552 (s), 1540 (vs), 1430 (s), 1332 (vs),
1276 (vs), 1187 (vs), 1159 (vs), 1113 (vs), 930 (m), 744
2
2
a 0.5 M NaOH solution (50 mL) and water (2ꢂ50 mL),
dried (MgSO ) and concentrated, yielding an oil. A solution
4
of KOH (14 equiv) in EtOH (75 mL) was added to the gained
oil and the mixture was refluxed for 6 h. After evaporation of
ꢀ
1
(m), 631 (m) cm . UV–vis (CH Cl ): l
max
(log 3)¼282
2
2
ꢁ
the solvent, the oily solid was cooled at 0 C, then treated
with H O (50 mL) followed by 36.5% HCl (20 mL) after
(3.37), 229 (0.67), 208 (0.51). MS (ESI), m/z (%): 1031.6
(100) [M +Na], 1026.7 (15) [M +NH ], 1009.6 (8)
4
[M +H], 1008.6 (5) [M ]. Anal. calcd for C H N O
56 84 2 14
+
+
2
+
+
1
0 min. The white precipitate was isolated by filtration,

9684
R. Judele et al. / Tetrahedron 62 (2006) 9681–9687
(
8
1008.6): C, 66.64; H, 8.39; N, 2.78. Found: C 66.73; H,
.38; N, 2.75.
3.1.2.6. 4,5-Dinitro-2-{[3,4,5-tris(decyloxy)benzoyl]-
oxy}phenyl 3,4,5-tris(decyloxy)benzoate (1f). H NMR
1
(
300 MHz, CDCl ): d¼0.88 (t, J¼6.4 Hz, 18H; 6CH ),
3
3
3.1.2.3. 4,5-Dinitro-2-{[3,4,5-tris(heptyloxy)benzoyl]-
oxy}phenyl 3,4,5-tris(heptyloxy)benzoate (1c). Mp 63 C.
1.27–1.56 (m, 84H; 6(CH ) CH ), 1.68–1.79 (m, 12H;
2 7 3
ꢁ
6OCH CH ), 3.82 (t, J¼6.3 Hz, 8H; 4OCH ), 4.01 (t,
2
2
2
1
H NMR (300 MHz, CDCl ): d¼0.89 (t, J¼6.6 Hz, 18H;
J¼6.5 Hz, 4H; 2OCH ), 7.22 (s, 4H; Ar-H), 8.08 (s, 2H;
3 3
3
2
1
3
6
1
CH ), 1.30–1.57 (m, 48H; 6(CH ) CH ), 1.70–1.80 (m,
3
Ar-H) ppm. C NMR (75 MHz, CDCl ): d¼14.0 (6CH ),
2 4
3
2H; 6OCH CH ), 3.82 (t, J¼6.3 Hz, 8H; 4OCH ), 4.01 (t,
22.6, 26.0, 26.1, 29.3, 29.4, 29.5, 29.6, 29.66, 29.74, 30.3,
31.9 (6CH (CH ) ), 69.1 (4OCH ), 73.6 (2OCH ), 108.6
2
2
2
J¼6.5 Hz, 4H; 2OCH ), 7.22 (s, 4H; Ar-H), 8.08 (s, 2H;
2
3
2 8
2
2
1
3
Ar-H) ppm. C NMR (75 MHz, CDCl ): d¼14.0 (6CH ),
(4CH), 120.7 (2CH), 121.0, 140.0, 144.0, 145.9, 153.0,
162.5 (2CO) ppm. FTIR (ATR): 2917 (vs), 2849 (vs), 1743
(vs), 1590 (m), 1535 (vs), 1430 (vs), 1334 (vs), 1277 (vs),
1192 (s), 1167 (vs), 1117 (vs), 784 (s), 743 (m), 633
3
3
2
(
2.6, 22.7, 25.9, 26.0, 29.0, 29.1, 29.2, 30.3, 31.8, 31.9
6CH (CH ) ), 69.1 (4OCH ), 73.6 (2OCH ), 108.5 (4CH),
3
2 5
2
2
1
(
20.7 (2CH), 121.0, 140.0, 144.0, 145.8, 153.0, 162.5
2CO) ppm. FTIR (ATR): 2924 (vs), 2854 (vs), 1746 (vs),
ꢀ
1
(m) cm . UV–vis (CH Cl ): l
max
(log 3)¼276 (3.42), 229
2
2
1
1
735 (vs), 1589 (m), 1552 (vs), 1539 (vs), 1466 (m),
429 (vs), 1332 (vs), 1276 (vs), 1186 (vs), 1159 (vs), 1113
(0.70), 205 (0.53). MS (ESI), m/z (%): 1367.9 (100)
[M +Na], 1362.9 (20) [M +NH ], 1345.9 (10) [M +H].
+
+
+
4
ꢀ
1
(
(
(
[
(
vs), 930 (m), 744 (m) cm . UV–vis (CH Cl ): l
2
Anal. calcd for C H N O (1345.0): C, 71.39; H, 9.89;
80 132 2 14
N, 2.08. Found: C, 71.47; H, 9.95; N, 2.05.
2
max
log 3)¼277 (3.42), 229 (0.74). MS (ESI), m/z (%): 1115.7
+
+
100) [M +Na], 1110.7 (35) [M +NH ], 1093.7 (12)
4
+
+
M +H], 1092.7 (10) [M ]. Anal. calcd for C H N O
2 96 2 14
1092.7): C, 68.10; H, 8.85; N, 2.56. Found: C, 68.01; H,
.70; N, 2.48.
3.1.2.7. 4,5-Dinitro-2-{[3,4,5-tris(undecyloxy)benzoyl]-
oxy}phenyl 3,4,5-tris(undecyloxy)benzoate (1g). H NMR
6
1
8
(300 MHz, CDCl ): d¼0.88 (t, J¼6.2 Hz, 18H; 6CH ),
3
3
1.26–1.58 (m, 96H; 6(CH ) CH ), 1.68–1.79 (m, 12H;
2 8 3
3.1.2.4. 4,5-Dinitro-2-{[3,4,5-tris(octyloxy)benzoyl]-
oxy}phenyl 3,4,5-tris(octyloxy)benzoate (1d). H NMR
6OCH CH ), 3.81 (t, J¼6.3 Hz, 8H; 4OCH ), 4.01 (t,
2
2
2
1
J¼6.5 Hz, 4H; 2OCH ), 7.22 (s, 4H; Ar-H), 8.08 (s, 2H;
3 3
2
1
3
(
1
300 MHz, CDCl ): d¼0.88 (t, J¼6.3 Hz, 18H; 6CH ),
Ar-H) ppm. C NMR (75 MHz, CDCl ): d¼14.1 (6CH ),
3
3
.28–1.56 (m, 60H; 6(CH ) CH ), 1.68–1.79 (m, 12H;
3
22.6, 26.0, 26.1, 29.2, 29.3, 29.4, 29.5, 29.6, 29.7, 30.3,
31.9 (6CH (CH ) ), 69.1 (4OCH ), 73.6 (2OCH ), 108.6
2
5
6
OCH CH ), 3.82 (t, J¼6.3 Hz, 8H; 4OCH ), 4.01 (t,
2
2
2
3
2 9
2
2
J¼6.5 Hz, 4H; 2OCH ), 7.22 (s, 4H; Ar-H), 8.08 (s,
(4CH), 120.7 (2CH), 121.1, 140.0, 144.0, 145.9, 153.0,
162.5 (2CO) ppm. FTIR (ATR): 2917 (vs), 2849 (vs), 1743
(vs), 1590 (m), 1535 (vs), 1430 (vs), 1334 (vs), 1277 (vs),
1192 (vs), 1167 (vs), 1118 (vs), 930 (m), 742 (m), 721
2
13
2
H; Ar-H) ppm. C NMR (75 MHz, CDCl ): d¼14.0
3
(
(
(
6CH ), 22.6, 26.1, 29.2, 29.3, 29.5, 30.3, 31.8, 31.9
3
6CH (CH ) ), 69.1 (4OCH ), 73.6 (2OCH ), 108.5
3
4CH), 120.7 (2CH), 121.0, 140.0, 144.0, 145.8, 153.0,
62.5 (2CO) ppm. FTIR (ATR): 2918 (vs), 2851 (s), 1740
vs), 1735 (vs), 1591 (m), 1534 (vs), 1430 (m), 1333 (vs),
276 (vs), 1193 (vs), 1166 (vs), 1115 (vs), 743 (m), 633
2 6
2
2
ꢀ
1
(m) cm . UV–vis (CH Cl ): l
max
(log 3)¼285 (3.17), 229
2
2
1
(
1
(0.66), 207 (0.51). MS (MALDI-TOF), m/z (%): 1431.0
+
+
(92) [M +H], 1430.0 (100) [M ]. Anal. calcd for
C H N O (1429.1): C, 72.23; H, 10.15; N, 1.96. Found:
C, 71.59; H, 9.96; N, 1.89.
8
6 144 2 14
ꢀ1
(
m) cm . UV–vis (CH Cl ): l
max
(log 3)¼282 (3.37),
2
2
2
(
29 (0.67), 208 (0.51). MS (ESI), m/z (%): 1199.8
100) [M +Na], 1194.8 (35) [M +NH ], 1177.8 (37)
+
+
3.1.2.8. 4,5-Dinitro-2-{[3,4,5-tris(dodecyloxy)benzoyl]-
oxy}phenyl 3,4,5-tris(dodecyloxy)benzoate (1h). H NMR
4
+
1
[M +H]. HRMS (EI) calcd 1176.7801 (for C H N O ),
found 1176.7838 [M ]. Anal. calcd for C H N O
6
8 108 2 14
+
(300 MHz, CDCl ): d¼0.88 (t, J¼6.2 Hz, 18H; 6CH ),
6
8
108
2
14
3
3
(
9
1176.8): C, 69.36; H, 9.24; N, 2.38. Found: C, 69.19; H,
.11; N, 2.40.
1.26–1.56 (m, 108H; 6(CH ) CH ), 1.68–1.76 (m, 12H;
2 9 3
6OCH CH ), 3.81 (t, J¼6.3 Hz, 8H; 4OCH ), 4.01 (t,
2
2
2
J¼6.4 Hz, 4H; 2OCH ), 7.22 (s, 4H; Ar-H), 8.08 (s, 2H;
2
1
3
3.1.2.5. 4,5-Dinitro-2-{[3,4,5-tris(nonyloxy)benzoyl]-
oxy}phenyl 3,4,5-tris(nonyloxy)benzoate (1e). Mp 62 C.
Ar-H) ppm. C NMR (75 MHz, CDCl ): d¼14.1 (6CH ),
3
3
ꢁ
22.6, 26.0, 26.1, 29.2, 29.3, 29.4, 29.5, 29.6, 29.7, 30.3,
31.9 (6CH (CH ) ), 69.1 (4OCH ), 73.6 (2OCH ), 108.5
1
H NMR (300 MHz, CDCl ): d¼0.88 (t, J¼6.3 Hz, 18H;
3
3
2 10
2
2
6
1
(
2
(
CH ), 1.27–1.56 (m, 72H; 6(CH ) CH ), 1.68–1.79 (m,
3
(4CH), 120.7 (2CH), 121.0, 140.0, 144.0, 145.9, 153.0,
162.5 (2CO) ppm. FTIR (ATR): 2917 (vs), 2849 (vs), 1742
(vs), 1591 (m), 1534 (vs), 1430 (vs), 1334 (s), 1277 (vs),
1192 (vs), 1167 (s), 1116 (vs), 933 (m), 825 (m), 742 (m),
2 6
3
2H; 6OCH CH ), 3.82 (t, J¼6.3 Hz, 8H; 4OCH ), 4.01
2
2
2
t, J¼6.5 Hz, 4H; 2OCH ), 7.22 (s, 4H; Ar-H), 8.08 (s,
2
13
H; Ar-H) ppm. C NMR (75 MHz, CDCl ): d¼14.0
3
3
ꢀ
1
6CH ), 22.6, 29.2, 29.32, 29.37, 29.4, 29.61, 29.68, 30.3,
721 (m), 606 (m) cm
.
UV–vis (CH Cl ): lmax
2 2
3
1
1
1.91, 31.94 (6CH (CH ) ), 69.1 (4OCH ), 73.6 (2OCH ),
3
08.6 (4CH), 120.7 (2CH), 121.1, 140.0, 144.0, 145.9,
53.0, 162.5 (2CO) ppm. FTIR (ATR): 2918 (vs), 2849
(log 3)¼229 (0.74), 216 (0.64), 208 (0.59), 202 (0.54). MS
2 7
2
2
+
(MALDI-TOF), m/z (%): 1515.1 (100) [M +2H], 1514.1
+
+
(100) [M +H], 1513.0 (10) [M ]. Anal. calcd for
C H N O (1513.2): C, 72.97; H, 10.38; N, 1.85. Found:
C, 72.95; H, 10.14; N, 1.87.
(
1
vs), 1743 (vs), 1735 (vs), 1590 (m), 1535 (vs), 1430 (vs),
332 (vs), 1277 (vs), 1193 (vs), 1166 (vs), 1115 (vs), 742
9
2 156 2 14
ꢀ
1
(
(
m), 722 (m) cm . UV–vis (CH Cl ): l
max
1.16), 230 (0.45), 221 (0.42), 208 (0.35). MS (ESI),
(log 3)¼286
2
2
3.1.3. General procedure for the preparation of 2-{[3,4,5-
tris(alkyloxy)benzoyl]oxy}phenyl 3,4,5-tris(alkyloxy)-
benzoates 6a–h. DCC (3.1 equiv) was added to a cooled
solution of the appropriate 5 (2.2 equiv) in CH Cl (7–
+
+
m/z (%): 1284.0 (100) [M +Na], 1278.9 (18) [M +NH ],
4
+
+
1262.0 (35) [M +2H], 1260.8 (8) [M ]. Anal. calcd for
C H N O (1260.9): C, 70.44; H, 9.59; N, 2.22. Found:
C, 70.22; H, 9.48; N, 2.10.
7
4
120
2
14
2
2
ꢁ
10 mL) at 0 C. After stirring for 10 min, DMAP and 2b

R. Judele et al. / Tetrahedron 62 (2006) 9681–9687
9685
(
1.0 equiv each) were added and the reaction mixture was
(s), 2924 (vs), 2855 (vs), 1738 (vs), 1585 (vs), 1495 (s),
1428 (s), 1334 (vs), 1241 (m), 1196 (vs), 1103 (vs), 937
stirred at room temperature for 20 h. The reaction mixture
was treated with CH Cl (10 mL), washed with 1 M HCl
ꢀ
1
(m), 861 (m), 748 (m) cm . UV–vis (CH Cl ): l
max
2
2
2
2
(
2ꢂ20 mL) and H O (20 mL), dried (MgSO ) and con-
(log 3)¼255 (3.39), 210 (0.60). MS (ESI), m/z (%): 1022.7
2
4
+
centrated. The oily solid was treated with PE (30 mL) and
the white solid was filtered off. The filtrate was evaporated
and the residue purified by flash chromatography on
SiO with PE/CH Cl [20:29 (6a), 20:27 (6b), 20:24 (6c),
(10), 1021.7 (25), 1020.7 (30) [M +NH ], 1005.7 (22),
4
+
+
1004.7 (65), 1003.7 (100) [M +H], 1002.6 (5) [M ]. Anal.
calcd for C H O (1002.7): C, 74.21; H, 9.84. Found:
C, 74.20; H, 9.81.
6
2 98 10
2
2
2
2
products 6a–h as yellowish to white oils, which were dried
0:22 (6d), 1:1 (6e,f), 22:20 (6g), 26:20 (6h)] to give the
3.1.3.4. 2-{[3,4,5-Tris(octyloxy)benzoyl]oxy}phenyl
3,4,5-tris(octyloxy)benzoate (6d). H NMR (500 MHz,
CDCl ): d¼0.88 (t, J¼6.7 Hz, 18H; 6CH ), 1.25–1.50 (m,
1
for 1 h under freezing conditions (liquid N ) and vacuum
2
ꢀ
3
(
10 mbar).
3
3
6
0H; 6(CH ) CH ), 1.70–1.77 (m, 12H; 6OCH CH ), 3.82
2 5 3 2 2
3
,4,5-tris(pentyloxy)benzoate (6a). Mp 4 C. H NMR
.1.3.1. 2-{[3,4,5-Tris(pentyloxy)benzoyl]oxy}phenyl
ꢁ
(t, J¼6.4 Hz, 8H; 4OCH ), 3.98 (t, J¼6.5 Hz, 4H; 2OCH ),
2
2
13
1
3
7.26 (s, 4H; Ar-H), 7.32–7.40 (2m, 4H; Ar-H) ppm.
C
(
1
6
500 MHz, CDCl ): d¼0.92 (t, J¼7.0 Hz, 18H; 6CH ),
NMR (125 MHz, CDCl ): d¼14.0 (6CH ), 22.67, 22.69,
3
3
3
3
.32–1.50 (m, 24H; 6(CH ) CH ), 1.71–1.78 (m, 12H;
2
26.0, 26.1, 29.3, 29.38, 29.41, 29.5, 30.3, 31.8, 31.9
(6CH (CH ) ), 69.0 (4OCH ), 73.4 (2OCH ), 108.3 (4CH),
2
3
OCH CH ), 3.83 (t, J¼6.4 Hz, 8H; 4OCH ), 3.99 (t,
2
2
2
3
2 6
2
2
J¼6.4 Hz, 4H; 2OCH ), 7.26 (s, 4H; Ar-H), 7.32–7.40
123.1 (2CH), 123.5 (2CH), 126.4, 142.5, 142.9, 152.8,
164.0 (2CO) ppm. FTIR (ATR): 2953 (s), 2922 (vs), 2853
(vs), 1738 (vs), 1585 (vs), 1495 (s), 1429 (s), 1335 (vs),
1241 (m), 1196 (vs), 1104 (vs), 947 (w), 861 (m), 748
2
1
3
(
2m, 4H; Ar-H) ppm.
C NMR (125 MHz, CDCl ):
3
d¼13.9 (4CH ), 14.0 (2CH ), 22.4 (2CH CH ), 22.5
3
3
3
2
(
2
(
(
CH CH ), 28.1 (2CH CH CH ), 28.2 (CH CH CH ),
3 2 3 2 2 3 2 2
ꢀ
1
8.94 (2CH CH CH CH ), 29.98 (CH CH CH CH ), 69.0
2
(m) cm . UV–vis (CH Cl ): l
max
(log 3)¼256 (3.37), 212
3
2
2
2
3
2
2
2
2
+
2OCH ), 73.4 (OCH ), 108.3 (4CH), 123.1 (2CH), 123.5
2
(0.57). MS (ESI), m/z (%): 1104.8 (20) [M +NH ], 1089.8
4
2
+
+
2CH), 126.5, 142.5, 142.9, 152.8, 164.0 (2CO) ppm.
(25), 1088.8 (60), 1087.7 (100) [M +H], 1086.7 (10) [M ].
Anal. calcd for C H110O10 (1086.8): C, 75.09; H, 10.19.
Found: C, 75.48; H, 10.27.
FTIR (ATR): 2954 (s), 2930 (vs), 2870 (vs), 1738 (vs),
585 (vs), 1495 (s), 1428 (s), 1334 (vs), 1241 (m), 1192
6
8
1
(
ꢀ
vs), 1102 (vs), 948 (m), 748 (w) cm . UV–vis (CH Cl ):
2 2
1
lmax (log 3)¼257 (3.39), 210 (0.63). MS (ESI), m/z (%):
3.1.3.5. 2-{[3,4,5-Tris(nonyloxy)benzoyl]oxy}phenyl
ꢁ
+
+
1
8
53.5 (50) [M +NH +H], 852.5 (100) [M +NH ], 836.5
4
3,4,5-tris(nonyloxy)benzoate (6e). Mp 18 C. H NMR
(500 MHz, CDCl ): d¼0.88 (t, J¼6.8 Hz, 18H; 6CH ),
4
+
(
(
20), 835.5 (32) [M +H]. Anal. calcd for C H O
50 74 10
3
3
834.6): C, 71.91; H, 8.93. Found: C, 72.07; H, 8.94.
1.28–1.50 (m, 72H; 6(CH ) CH ), 1.70–1.77 (m, 12H;
2 6 3
6
OCH CH ), 3.82 (t, J¼6.4 Hz, 8H; 4OCH ), 3.98 (t,
2
2
2
3
.1.3.2. 2-{[3,4,5-Tris(hexyloxy)benzoyl]oxy}phenyl
ꢁ
J¼6.5 Hz, 4H; 2OCH ), 7.26 (s, 4H; Ar-H), 7.32–7.40
2
1
13
3
(
1
6
,4,5-tris(hexyloxy)benzoate (6b). Mp ꢀ5 C. H NMR
(2m, 4H; Ar-H) ppm.
C NMR (125 MHz, CDCl ):
3
500 MHz, CDCl ): d¼0.90 (t, J¼6.3 Hz, 18H; 6CH ),
d¼14.1 (6CH ), 22.6, 26.0, 26.1, 29.3, 29.4, 29.5, 29.6,
3
3
3
.28–1.50 (m, 36H; 6(CH ) CH ), 1.70–1.77 (m, 12H;
3
29.7, 30.3, 31.9, 32.0 (6CH (CH ) ), 69.0 (4OCH ), 73.4
2
2
3
3
2 7
OCH CH ), 3.83 (t, J¼6.4 Hz, 8H; 4OCH ), 3.98 (t,
(2OCH ), 108.3 (4CH), 123.1 (2CH), 123.5 (2CH), 126.5,
2
2
2
2
J¼6.5 Hz, 4H; 2OCH ), 7.26 (s, 4H; Ar-H), 7.32–7.40
142.5, 142.9, 152.8, 164.0 (2CO) ppm. FTIR (ATR): 2953
(s), 2921 (vs), 2852 (vs), 1738 (vs), 1585 (vs), 1495 (s),
1429 (s), 1335 (vs), 1241 (m), 1196 (vs), 1104 (vs), 748
2
1
3
(
2m, 4H; Ar-H) ppm.
C NMR (125 MHz, CDCl ):
3
d¼14.0 (4CH ), 14.1 (2CH ), 22.6, 22.7, 25.6, 25.7, 29.2,
3
3
ꢀ1
3
0.2, 31.5, 31.7 (6CH (CH ) ), 69.0 (4OCH ), 73.4
2
(m) cm . UV–vis (CH Cl ): l
max
(0.57). MS (ESI), m/z (%): 1188.8 (18) [M +NH ], 1173.8
4
(log 3)¼256 (3.37), 212
3
2 4
2
2
+
(
2OCH ), 108.3 (4CH), 123.1 (2CH), 123.5 (2CH), 126.5,
2
+
+
1
(
1
42.5, 142.9, 152.8, 164.0 (2CO) ppm. FTIR (ATR): 2953
s), 2927 (vs), 2858 (vs), 1738 (vs), 1585 (vs), 1495 (s),
428 (s), 1334 (vs), 1241 (m), 1192 (vs), 1102 (vs), 957
(30), 1172.8 (75), 1171.8 (100) [M +H], 1170.8 (20) [M ].
Anal. calcd for C H122O10 (1170.9): C, 75.85; H, 10.49.
Found: C, 76.19; H, 10.59.
7
4
ꢀ1
(
(
(
[
(
m), 748 (w) cm . UV–vis (CH Cl ): l
2
3.33), 236 (2.54), 209 (0.63). MS (ESI), m/z (%): 937.6
50) [M +NH +H], 936.6 (90) [M +NH ], 919.6 (100)
M +H], 918.6 (5) [M ]. Anal. calcd for C H O
6
918.6): C, 73.17; H, 9.43. Found: C, 73.40; H, 9.44.
(log 3)¼260
2
max
3.1.3.6. 2-{[3,4,5-Tris(decyloxy)benzoyl]oxy}phenyl
3,4,5-tris(decyloxy)benzoate (6f). H NMR (500 MHz,
+
+
1
4
4
+
+
CDCl ): d¼0.88 (t, J¼6.5 Hz, 18H; 6CH ), 1.27–1.50 (m,
5
86 10
3
3
84H; 6(CH ) CH ), 1.68–1.78 (m, 12H; 6OCH CH ), 3.82
2 7 3 2 2
(
t, J¼6.4 Hz, 8H; 4OCH ), 3.98 (t, J¼6.5 Hz, 4H;
2
3
.1.3.3. 2-{[3,4,5-Tris(heptyloxy)benzoyl]oxy}phenyl
,4,5-tris(heptyloxy)benzoate (6c). H NMR (500 MHz,
2OCH ), 7.26 (s, 4H; Ar-H), 7.31–7.40 (m, 4H; Ar-H) ppm.
2
1
13
3
C NMR (125 MHz, CDCl ): d¼14.0 (6CH ), 22.6, 26.0,
3
3
CDCl ): d¼0.89 (t, J¼6.5 Hz, 18H; 6CH ), 1.27–1.50
26.1, 29.3, 29.38, 29.40, 29.5, 29.6, 29.7, 29.8, 30.3,
31.92, 31.93 (6CH (CH ) ), 69.0 (4OCH ), 73.4 (2OCH ),
3
3
(
m, 48H; 6(CH ) CH ), 1.70–1.77 (m, 12H; 6OCH CH ),
2
2
4
3
2
3
2 8
2
2
3
.82 (t, J¼6.4 Hz, 8H; 4OCH ), 3.98 (t, J¼6.5 Hz,
108.3 (4CH), 123.1 (2CH), 123.5 (2CH), 126.5, 142.5,
142.9, 152.8, 164.0 (2CO) ppm. FTIR (ATR): 2953 (s),
2920 (vs), 2852 (vs), 1738 (vs), 1585 (vs), 1495 (s), 1429
(s), 1335 (vs), 1241 (m), 1196 (vs), 1105 (vs), 749
2
4
Ar-H) ppm.
H; 2OCH ), 7.26 (s, 4H; Ar-H), 7.31–7.40 (2m, 4H;
C NMR (125 MHz, CDCl ): d¼14.08
2
1
3
3
(
4CH ), 14.09 (2CH ), 22.6, 22.7, 25.9, 26.0, 29.1, 29.2,
3
3
ꢀ1
2
9.3, 30.3, 31.8, 31.9 (6CH (CH ) ), 69.0 (4OCH ), 73.4
3
(m) cm . UV–vis (CH Cl ): l
max
(1.58). MS (ESI), m/z (%): 1272.9 (15) [M +NH ], 1257.9
4
(log 3)¼277 (2.74), 232
2 5
2
2
2
+
(
2OCH ), 108.3 (4CH), 123.1 (2CH), 123.5 (2CH), 126.5,
2
+
1
42.5, 142.9, 152.8, 164.0 (2CO) ppm. FTIR (ATR): 2953
(35), 1256.9 (80), 1255.9 (100) [M +H]. Anal. calcd for

9686
R. Judele et al. / Tetrahedron 62 (2006) 9681–9687
C H134O10 (1255.0): C, 76.51; H, 10.75. Found: C, 76.79;
8
(6CH ), 22.6, 26.0, 26.1, 29.2, 29.3, 29.4, 29.6, 29.7, 30.3,
3
0
H, 10.86.
31.9 (6CH (CH ) ), 69.0 (4OCH ), 73.5 (2OCH ), 108.3
3
2 8
2
2
(4CH), 121.3 (2CBr), 122.3, 128.1 (2CH), 142.1, 143.1,
3.1.3.7. 2-{[3,4,5-Tris(undecyloxy)benzoyl]oxy}phenyl
,4,5-tris(undecyloxy)benzoate (6g). H NMR (500 MHz,
152.9, 163.6 (2CO) ppm. FTIR (ATR): 2953 (s), 2917 (vs),
2849 (vs), 1743 (vs), 1589 (s), 1468 (s), 1430 (s), 1335
(vs), 1256 (m), 1196 (vs), 1112 (vs), 944 (m), 740 (w), 720
1
3
CDCl ): d¼0.88 (t, J¼6.8 Hz, 18H; 6CH ), 1.27–1.50 (m,
3
3
ꢀ1
9
(
6H; 6(CH ) CH ), 1.70–1.77 (m, 12H; 6OCH CH ), 3.82
2
(w), 637 (w), 609 (w) cm . UV–vis (CH Cl ): l (log 3)¼
2
8
3
2
2
2
max
t, J¼6.3 Hz, 8H; 4OCH ), 3.98 (t, J¼6.5 Hz, 4H; 2OCH ),
283 (2.94), 229 (0.52). MS (ESI), m/z (%): 1436.1 (45)
[M +Na+H], 573.7 (100), 433.6 (35). Anal. calcd for
2
2
1
3
+
7
.26 (s, 4H; Ar-H), 7.33–7.40 (m, 4H; Ar-H) ppm.
C
NMR (125 MHz, CDCl ): d¼14.1 (6CH ), 22.6, 26.0, 26.1,
C H Br O (1410.8): C, 67.97; H, 9.41. Found: C,
80 132 2 10
67.97; H, 9.37.
3
3
2
3
1
1
2
9.3, 29.39, 29.40, 29.5, 29.6, 29.69, 29.72, 29.8, 30.3,
1.93, 31.95 (6CH (CH ) ), 69.0 (4OCH ), 73.4 (2OCH ),
3
2 9
2
2
08.3 (4CH), 123.1 (2CH), 123.5 (2CH), 126.4, 142.5,
42.9, 152.8, 164.0 (2CO) ppm. FTIR (ATR): 2953 (s),
920 (vs), 2852 (vs), 1738 (vs), 1585 (vs), 1496 (s), 1466
3.1.4.2. 4,5-Dibromo-2-{[3,4,5-tris(undecyloxy)benzoyl]-
oxy}phenyl 3,4,5-tris(undecyloxy)benzoate (7g). H NMR
1
(300 MHz, CDCl ): d¼0.88 (t, J¼6.4 Hz, 18H; 6CH ),
3
3
(
m), 1429 (s), 1336 (vs), 1241 (m), 1198 (vs), 1115 (vs),
1.21–1.50 (m, 96H; 6(CH ) CH ), 1.67–1.78 (m, 12H;
2 8 3
ꢀ
1
1
2
1
104 (vs), 750 (w) cm . UV–vis (CH Cl ): l
2
77 (2.74), 232 (1.58). MS (ESI), m/z (%): 1341.0 (80),
340.0 (100) [M +H], 1338.9 (20) [M ], 1338.0 (10). Anal.
(log 3)¼
6OCH CH ), 3.81 (t, J¼6.3 Hz, 8H; 4OCH ), 3.98 (t,
2
max
2
2
2
J¼6.5 Hz, 4H; 2OCH ), 7.21 (s, 4H; Ar-H), 7.69 (s, 2H;
2
+
+
13
Ar-H) ppm. C NMR (75 MHz, CDCl ): d¼14.1 (6CH ),
3
3
calcd for C H146O10 (1339.1): C, 77.08; H, 10.98. Found:
8
22.6, 26.0, 26.1, 29.2, 29.3, 29.4, 29.5, 29.6, 29.7, 30.3, 31.9
(6CH (CH ) ), 69.0 (2OCH ), 73.5 (2OCH ), 108.3 (4CH),
6
C, 77.35; H, 11.03.
3
2 9
2
2
121.3 (2CBr), 122.3, 128.1 (2CH), 142.1, 143.1, 152.9,
3.1.3.8. 2-{[3,4,5-Tris(dodecyloxy)benzoyl]oxy}phenyl
,4,5-tris(dodecyloxy)benzoate (6h). H NMR (500 MHz,
163.6 (2CO) ppm. FTIR (ATR): 2953 (s), 2916 (vs), 2849
(vs), 1744 (vs), 1589 (s), 1471 (s), 1463 (s), 1429 (s), 1336
(vs), 1259 (m), 1196 (vs), 1113 (vs), 944 (m), 739 (w),
1
3
CDCl ): d¼0.88 (t, J¼6.8 Hz, 18H; 6CH ), 1.26–1.50 (m,
3
3
ꢀ
1
1
3
2
08H; 6(CH ) CH ), 1.70–1.77 (m, 12H; 6OCH CH ),
2
720 (w) cm . UV–vis (CH Cl ): l
max
(log 3)¼276 (3.36),
2
9
3
2
2
2
.82 (t, J¼6.4 Hz, 8H; 4OCH ), 3.98 (t, J¼6.5 Hz, 4H;
229 (0.54), 211 (0.47), 208 (0.47). MS (ESI), m/z (%):
1520.1 (100) [M +Na], 615.5 (90), 461.4 (35). Anal. calcd
2
+
OCH ), 7.26 (s, 4H; Ar-H), 7.32–7.40 (m, 4H; Ar-H) ppm.
2
1
3
C NMR (125 MHz, CDCl ): d¼14.1 (6CH ), 22.7, 26.0,
for C H Br O (1497.9): C, 68.96; H, 9.69. Found: C,
86 144 2 10
68.95; H, 9.69.
3
3
2
2
7
1
2
6.1, 29.3, 29.39, 29.41, 29.5, 29.6, 29.69, 29.71, 29.75,
9.76, 29.78, 30.3, 31.9 (6CH (CH ) ), 69.0 (4OCH ),
3.4 (2OCH ), 108.3 (4CH), 123.1 (2CH), 123.5 (2CH),
2
26.4, 142.5, 142.9, 152.8, 164.0 (2CO) ppm. FTIR (ATR):
953 (s), 2920 (vs), 2852 (vs), 1739 (vs), 1586 (vs), 1496
3
2 10
2
3.1.4.3. 4,5-Dibromo-2-{[3,4,5-tris(dodecyloxy)benzoyl]-
oxy}phenyl 3,4,5-tris(dodecyloxy)benzoate (7h). H NMR
1
(250 MHz, CDCl ): d¼0.88 (t, J¼6.1 Hz, 18H; 6CH ),
3
3
(
(
(
(
(
s), 1430 (s), 1337 (vs), 1242 (m), 1199 (vs), 1105 (vs), 751
m) cm . UV–vis (CH Cl ): l
1.20–1.52 (m, 108H; 6(CH ) CH ), 1.61–1.80 (m, 12H;
2 9 3
ꢀ
1
(log 3)¼276 (2.90), 232
6OCH CH ), 3.81 (t, J¼6.2 Hz, 8H; 4OCH ), 3.98 (t,
2
2
max
2
2
2
1.66). MS (ESI), m/z (%): 1426.1 (50), 1425.1 (90), 1424.1
100) [M +H], 1423.1 (15) [M ]. Anal. calcd for C H158O10
1423.2): C, 77.58; H, 11.18. Found: C, 77.96; H, 11.14.
J¼6.4 Hz, 4H; 2OCH ), 7.21 (s, 4H; Ar-H), 7.69 (s, 2H;
2
+
+
13
Ar-H) ppm. C NMR (62.9 MHz, CDCl ): d¼14.1 (6CH ),
92
3
3
22.7, 26.0, 26.1, 29.2, 29.3, 29.4, 29.6, 29.7, 29.8, 30.3, 31.9
(6CH (CH ) ), 69.0 (4OCH ), 73.5 (2OCH ), 108.3 (4CH),
3 2 10 2 2
3
.1.4. General procedure for the preparation of 4,5-di-
121.3 (2CBr), 122.3, 128.1 (2CH), 142.1, 143.1, 152.9,
163.6 (2CO) ppm. FTIR (ATR): 2953 (s), 2916 (vs), 2849
(vs), 1744 (vs), 1589 (s), 1464 (s), 1430 (s), 1336 (vs), 1258
bromo-2-{[3,4,5-tris(alkyloxy)benzoyl]oxy}phenyl 3,4,5-
tris(alkyloxy)benzoates 7f–h. DCC (3.1 equiv) was added
to a cooled solution of the appropriate 5 (2.2 equiv) in
(m), 1197 (vs), 1113 (vs), 945 (m), 739 (w), 720 (w), 607
(w) cm . UV–vis (CH Cl ): l
ꢁ
ꢀ1
CH Cl (10 mL) at 0 C and after stirring for 10 min,
2
(log 3)¼277 (3.37), 229
2
2
2
max
DMAP and 2c (1 equiv each) were added and the reaction
mixture was stirred at room temperature for a further 20 h.
The reaction mixture was treated with CH Cl (30 mL),
(0.60), 219 (0.56). MS (Micro Tof), m/z (%): 1604.0 (75)
[M +NaꢀH], 711.5 (12). Anal. calcd for C H Br O
+
92
156
2 10
(1579.0): C, 69.85; H, 9.94. Found: C, 70.21; H, 10.02.
2
2
washed with 1 M HCl (2ꢂ30 mL) and H O (30 mL), dried
2
(
MgSO ) and concentrated. The oily solid was treated with
4
Acknowledgements
PE (30 mL) and the white solid was filtered off. The filtrate
was evaporated and the residue purified by flash chromato-
graphy on SiO with PE/CH Cl (15:10) to give product 7
Generous financial support by the Deutsche Forschungs-
gemeinschaft and the Fonds der Chemischen Industrie
(fellowship for R.J.) is gratefully acknowledged. We would
like to thank the referees for valuable suggestions.
2
2
2
as white solid, which was dried for 1 h under freezing con-
ditions (liquid N ) and high vacuum (10 mbar).
ꢀ3
2
3
oxy}phenyl 3,4,5-tris(decyloxy)benzoate (7f). Mp 33 C.
.1.4.1. 4,5-Dibromo-2-{[3,4,5-tris(decyloxy)benzoyl]-
ꢁ
References and notes
1
H NMR (500 MHz, CDCl ): d¼0.88 (t, J¼6.4 Hz, 18H;
3
6
1
CH ), 1.27–1.50 (m, 84H; 6(CH ) CH ), 1.69–1.76 (m,
3
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