Unusual mixed solvent supramolecular crystal framework formed of a new tecton-like tetracarboxylic building block

Article abstract of DOI:10.1080/10610278.2010.527979

A new tecton-like tetracarboxylic compound 1 featuring two isophthalic acid groups attached to both ends of a rigid 1,3- butadiyne spacer unit is synthesised using acetylene blocking/deblocking and coupling techniques. Crystallisation of 1 from DMSO-chloroform solution gives rise to the formation of an unusual mixed solvent crystalline framework structure 1a containing DMSO and chloroform as secondary and tertiary components in 1:2:1 stoichiometric ratio. The X-ray crystal structure of 1a shows interesting stacking mode and hydrogen-bonded, 3D network architecture with the two solvent species being involved in different behaviour pattern.

Full text of DOI:10.1080/10610278.2010.527979

Supramolecular Chemistry
Vol. 23, No. 5, May 2011, 398–406
Unusual mixed solvent supramolecular crystal framework formed of a new tecton-like
tetracarboxylic building block†
Ines M. Hauptvogel‡, Wilhelm Seichter and Edwin Weber*
¨ ¨
Institut fur Organische Chemie, Technische Universitat Bergakademie Freiberg, Leipziger Str. 29, D-09596 Freiberg,
Sachs, Germany
(Received 2 August 2010; final version received 19 September 2010)
A new tecton-like tetracarboxylic compound 1 featuring two isophthalic acid groups attached to both ends of a rigid 1,3-
butadiyne spacer unit is synthesised using acetylene blocking/deblocking and coupling techniques. Crystallisation of 1 from
DMSO-chloroform solution gives rise to the formation of an unusual mixed solvent crystalline framework structure 1a
containing DMSO and chloroform as secondary and tertiary components in 1:2:1 stoichiometric ratio. The X-ray crystal
structure of 1a shows interesting stacking mode and hydrogen-bonded, 3D network architecture with the two solvent species
being involved in different behaviour pattern.
Keywords: tetracarboxylic acid; dimethyl sulphoxide; chloroform; crystalline complex; X-ray crystal structure
0
0
´
1. Introduction
Kagome networks (11, 14). In the case of biphenyl-3,3 ,5,5 -
tetracarboxylic acid (two directly connected isophthalic acid
groups), open parallel network formation is observed in the
solid state structure, whereas the use of a very elongated 1,4-
phenylene-bis(ethynylene) spacer unit between the iso-
Carboxylic acids featuring a well-defined shape have
developed to a key position in the controlled assembly of
supramolecular systems with a variety of uses in different
branches of crystal engineering (1–3). This covers the
carboxylic acids as hosts for crystalline inclusion formation
(4) as well as their functional behaviour of a tecton (5),
allowingthetargetedformationof2Dand 3Dhydrogenbond
stabilised network structures (6, 7), although the carboxylic
building blocks are brought differently into action in these
particular fields. Although in the object of crystalline host–
guest complexation the carboxylic groups are primarily
intended for hydrogen bonding to the molecular guest
species (8), they are used in the network construction for
cyclic hydrogen-bonded pair formation (6, 7, 9–11).
Moreover, rigid oligocarboxylic acid molecules are also
very efficiently employed as coordinative linkers in the
formation of open organic–inorganic hybrid frameworks
(MOFs) (12, 13). This implies that for hydrogen-bonded
guest inclusion, the carboxylic groups are endo in the
attachment to the host molecule but at peripheral site in
the tectones and linkers. With reference to the tectons,
tetracarboxylic acids composed of two isophthalic acid
groups connected at both ends of a linear spacer moiety,
varying in the length, have been studied in their preference
towards the formation of close packed, open parallel or
´
phthalic acid moieties produces a Kagome assembly of the
respective molecules adsorbed on highly oriented pyrolytic
graphite, and the intermediate compound with a short
ethynylene spacer results in the formation of a mixed pattern
containing small areas of the two different motifs (14). Thus
the length of the spacer unit in the tetracarboxylic molecules
is shown to exert a distinct influence on the network structure
to be formed.
Referring to the present compound 1 (Scheme 1), we
describe the synthesis of a new member of this particular
substance class of bisisophthalic acids featuring with the
1,3-butadiyne-1,4-diyl spacer unit, a molecule of medium
length. Crystallisation of 1 from a solvent mixture of
DMSO and chloroform yielded an interesting stacking
mode and hydrogen-bonded, 3D mixed solvent containing
network architecture of 1a with the two solvent species
being involved in different behaviour pattern, the structure
of which is reported and discussed under the specific
circumstances.
*Corresponding author. Email: edwin.weber@chemie.tu-freiberg.de
†Dedicated to the late Professor Yurii A. Simonov, Institute of Applied Physics, Academy of Sciences of Moldova, Kishinev, Moldova.
‡Present address: Institut fu¨r Anorganische Chemie der TU Dresden, Helmholtzstr. 10, D-01069 Dresden, Germany.
ISSN 1061-0278 print/ISSN 1029-0478 online
q 2011 Taylor & Francis
DOI: 10.1080/10610278.2010.527979
http://www.informaworld.com

Supramolecular Chemistry
399
ternary complex 1a containing 1, DMSO and chloroform
in the stoichiometric ratio 1:2:1. Crystallographic data and
selected refinement parameters of the structure are
summarised in Table 1. Information regarding possible
non-covalent interactions in the crystal structure is
presented in Table 2. A perspective view of the molecular
structure, including atom numbering scheme, is shown in
Figure 1, whereas an illustration of the crystal packing is
given in Figure 2. Figure 3 demonstrates the potential
construction principle of the plain host lattice.
The crystal structure of 1a has the monoclinic space
group P21/c with one host molecule, two molecules of
DMSO and one molecule of CHCl3 in the asymmetric cell
unit (Figure 1). The bond lengths within the buta-1,3-diyne
part of 1 are 1.432(2)/1.433(2) for C(sp2)ZC(sp),
˚
1.199(2)/1.201(2) for CuC and 1.374(2)A for the single
C(sp)ZC(sp) bond, and are similar to those found in 1,4-
diphenylbutadiyne and its derivatives (23, 24). The high
degree of molecular association in the crystal structure
causes a slight bend of the host molecule along its
diacetylene element (25), so that the dihedral angle between
the planes of the aromatic rings is 11.58. The carboxy groups
are inclined at angles between 2.7(1) and 8.3(2)8 with respect
to the plane of the aromatic rings to which they are attached.
It is clear that assembly of the molecules via carboxylic
pairing (9, 26) would result in a highly expanded and, thus,
presumably too labile structure (27, 28). As a possible
consequence of this, we did not succeed in growing a crystal
of 1 in its solvent-free state. Instead, the distinctive
donor/acceptor character of the crystal components induces
a complicated network of non-covalent bonding between
molecules. As depicted in Figure 2, all strong donor atoms
of the tetracarboxylic acid are associated in the same
fashion with DMSO molecules via OZH· · ·O hydrogen
Scheme 1. Chemical formulas of the compounds studied.
2. Results and discussion
2.1 Synthesis
Synthesis of title compound 1 was performed as specified in
Scheme 2. This involves reaction of the starting compound
dimethyl 5-iodoisophthalate (2) (15) with MEBYNOL using
a Pd-catalysed Sonogashira coupling procedure (16, 17) to
give the blocked acetylenic diester 3. The 5-ethynyli-
sophthalic acid (4) was prepared from 3 via removal of the
blocking group with KOH in n-BuOH, yielding as an
intermediate the dipotassium salt of 4, which was converted
into 4 by the reaction with hydrochloric acid. Sulphuric acid
catalysed esterification of 4 with methanol gave the
corresponding diester 5. Alternatively, diester 5 could also
be obtained in a selective single-step deblocking reaction
from 3 using sodium hydride in toluene (18). Actually,
compound 5 has already been described in the literature
applying a similar synthetic route (19, 20), but being based
on the rather costly TMS-acetylene instead of the cheaper
MEBYNOL as the blocking reagent. Diester5 was subjected
to an Eglinton coupling reaction (21, 22) with copper(II)
acetate in pyridine–methanol to produce the tetraester 6.
This ester was hydrolysed with LiOH in THF–H2O
followed by acidification with hydrochloric acid to yield
tetracarboxylic acid 1.
˚
bonds (29) [d(O· · ·O) 2.598(3)–2.651(3)A], while a part of
the acidic hydrogens of the DMSO molecules are
coordinated to the carboxyl oxygens O(3), O(4) and O(7)
of 1 or fulfil DMSO· · ·DMSO interaction (30). Never-
theless, the donor–acceptor character of tetracarboxylic
acid 1 requires the presence of a second solvent species
having a complementary coordination behaviour compared
with DMSO. This is realised by the chloroform molecule,
more weakly interacting through CvO· · ·HZC (31) and
CvO· · ·ClZC contacts (32, 33) to different molecules of 1.
In more detail, the hydrogen atom of the chloroform
molecule is connected to O(5) of 1 by a relatively strong
˚
CZH· · ·OvC hydrogen bond [d(O· · ·H) 2.20 A]. The
observed angular parameters of the CvO· · ·ClZC contacts
contributing to the chloroform coordination (CvO· · ·Cl
85.6, 126.68; CZCl· · ·O 158.2, 167.98) agree well with the
concept of the so-called ‘electrophil–nucleophil pairing’
(34), which considers the oxygen of CvO as an
‘electrophil’ approaching the halogen of CZX (XvCl,
Br, I) at an angle of ,1008 (‘side on’), whereas the
nucleophil X approaches the oxygen of CvO at ,1658
2.2 X-ray structural study
Crystallisation of tetracarboxylic acid 1 from a solvent
mixture of dimethyl sulphoxide and chloroform yields a

400
I.M. Hauptvogel et al.
Scheme 2. Synthetic pathway for the preparation of compound 1.
(‘head on’). From this angle, the solvent molecules are
different in their effect for stabilisation of the lattice
framework. Although DMSO does mainly bonding like
assisting in stabilisation of the lattice construction, the
chloroform is less effective in this way but, on the contrary,
may be regarded as a volume stabilising component as it
fills lattice voids left by the 1· 2 DMSO network.
A view of the crystal structure in the direction of the b-
axis reveals that the molecules of1, one equivalent of DMSO
solvent and the molecules of CHCl3 are arranged to
corrugated layers, whereas the remaining solvent molecules
are located between the molecular layers. A more instructive
illustration of the lattice framework is shown in Figure 3,
which represents a view along the stacking of plain 1

Supramolecular Chemistry
401
Table 1. Crystallographic and structure refinement data of the compound studied (estimated standard deviations are in parentheses).
Compound
1a
Empirical formula
Formula weight
Crystal system
C20H10O8 · 2 C2H6SO· CHCl3
653.90
Monoclinic
P21/c
Space group
Unit cell dimensions
˚
a (A)
14.5144(6)
18.4714(7)
11.6806(5)
90.0
107.808(1)
90.0
2981.5(2)
4
420
1.457
0.500
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
V (A )
Z
3
˚
F(000)
Dc (mg m23
m (mm21
)
)
Data collection
Temperature (K)
No. of collected reflections
Within the u-limit/8
Index ranges ^h, ^k, ^l
No. of unique reflections
Rint
153(2)
56,412
1.5–29.1
219/19, 225/25, 215/10
7884
0.0373
Refinement calculations: full-matrix least-squares on all F 2 values
Weighting expression wa
No. of refined parameters
No. of F values used [I . 2s(I)]
Final R-indices
2
21
½s2ðF2oÞ þ ð0:0612PÞ þ 1:3816PÞꢀ
369
6322
P
P
Rð¼ jDFj= jFojÞ
0.0390
0.1203
1.079
0.65/20.61
wR on F 2
S (¼Goodness of fit on F 2)
23
˚
Final Drmax/Drmin/e A
a P ¼ ðF2o þ 2F2cÞ=3.
molecules. In this assembly, the longitudinal axes of
molecules of consecutive layers are rotated by nearly 908.
From this it follows that every fourth layer in the stacking
direction is congruent, thus producing an uncongested lattice
3. Conclusions
A new molecular building block 1 comprising two
isophthalic acid moieties attached in the 5-position to both
ends of a rigid rod-like diacetylene unit, which has been
synthesised, is shown to create a complex (1:2:1) mixed
solvent crystalline framework 1a with DMSO and
chloroform as secondary and tertiary components, the
structure of which has been solved.
˚
structure. Nevertheless, the relatively close distance of 3.3 A
between the aromatic residues of consecutive molecules 1
suggests that arene stacking (35) has a decisive effect on the
stabilisation of the lattice structure.
˚
Table 2. Distances (A) and angles (8) of possible hydrogen-bond type interactions of the compound studied.
Distance
Angle
DZH· · ·A
Atoms involved
Symmetry
D· · ·A
H· · ·A
1
O(2)ZH(2)· · ·O(1B)
O(4)ZH(4)· · ·O(1B)
C(2C)ZH(2C1)· · ·O(1B)
O(6)ZH(6)· · ·O(1C)
O(8)ZH(8)· · ·O(1C)
C(2C)ZH(2C2)· · ·O(3)
C(2B)ZH(2B2)· · ·O(4)
C(1A)ZH(1A)· · ·O(5)
C(1B)ZH(1B2)· · ·O(7)
21 þ x, 1.5 2 y, 21.5 þ z
1 2 x, 1 2 y, 1 2 z
x, y, z
2.637(2)
2.606(2)
3.313(3)
2.598(2)
2.651(2)
3.310(3)
3.535(3)
3.093(3)
3.143(3)
1.82
1.77
2.56
1.78
1.81
2.43
2.72
2.20
2.48
163
174
134
163
176
149
141
155
125
x, y, z
1 2 x, 0.5 þ y, 1.5 2 z
1 2 x, 0.5 þ y, 1.5 2 z
1 2 x, 0.5 þ y, 0.5 2 z
x, y, z
1 2 x, 2 2 y, 1 2 z

402
I.M. Hauptvogel et al.
C2B
O1B
S1B
H4
O4
C5
C1B
H2C1
C2C
O3
C7
C6
C1
O1C
C4
C3
S1C
C1C
H6
O6
O1
C8
C2
Cl1A
C9
C12
C10
C13
O5
H1A
O2
H2
C19
C11
C1A
C14
Cl3A
C16
C20
C15
Cl2A
O8
H8
O7
Figure 1. Perspective view of the asymmetric unit of 1a (1· 2 DMSO· CHCl3). Thermal ellipsoids are drawn at 50% probability level.
Broken lines represent hydrogen bonds.
While other tetracarboxylic acids with similar well-
defined shapes behave as tectons for the controlled
assembly of hydrogen-bonded open frameworks rather
than a close packed structure (11, 14), the present
compound 1, although corresponding to this molecular
design, behaves markedly different in structure formation
under the used condition. This can be attributed to
geometric parameters of the molecule leading to a highly
expanded labile crystal lattice on carboxylic pairing.
Hence, as a way out, the molecule uses its secondary mode
of synthon formation (26) which is aromatic stacking (35),
allowing a partly overlap of the molecules and, thus,
considerable shrinking of the lattice volume. The
carboxylic groups being now extremely unsatisfied in
terms of their hydrogen donor–acceptor property take the
opportunity to interact with the coordinating solvent
molecules, giving rise to a close packed structure.
4. Experimental
4.1 Methods and materials
The melting points (uncorrected) were measured on a hot-
stage microscope PHMK (Rapido, Dresden). NMR
spectra were recorded on a Bruker DPX 400 spectrometer
(1H 400 MHz, 13C 100 MHz) in solutions using TMS as
internal standard. IR spectra were recorded on a Nicolet
510 FT-IR spectrometer. MS were obtained using
Hewlett-Packard MS 5989A (GC-MS) and Finnigan Mat
8200 (EI-MS) instruments. Elemental analyses were
performed on a Heraeus CHN-Rapid analyser. Thin layer
chromatography was carried out using Merck Silica gel 60
F254 on aluminium backed plates. Solvents were purified
and dried using standard laboratory procedures (42).
The following reagents were purchased from commercial
sources: MEBINOL (Acros Organics) palladiumtriphenyl-
phosphane dichloride (ABCR), copper(II) acetate, copper(I)
iodide, lithium hydroxide and sodium hydride (60% in
mineral oil) (Sigma-Aldrich). Dimethyl 5-iodoisophthalate
was prepared as described in the literature (15).
Another line of reasoning is using metal ions strongly
coordinating to the carboxylate groups of 1 in order to
stabilise a porous framework structure (36). Actually, this
has become possible as recently demonstrated by the
generation and structural solution of a corresponding
coordination polymer based on 1 and copper(II) (37),
opening promising aspects of 1 in the actual field of metal-
organic-frameworks (MOFs) (12, 13). Moreover, due to
the molecular shape and functionality, compound 1 may
also excite interest as tecton in the topical research area of
surface-assisted 2D crystal engineering (6, 38–41).
4.2 Synthesis
4.2.1 Dimethyl 5-(3-hydroxy-3-methyl-1-
butynyl)isophthalate (3)
A mixture of dimethyl 5-iodoisophthalate (2) (10.0 g,
31.2mmol), 2-methylbut-3-yne-2-ol (MEBINOL, 3.20g,
37.5mmol), Pd(PPh3)2Cl2 (180mg, 0.26mmol) and CuI

Supramolecular Chemistry
403
b
c
a
Figure 2. Packing excerpt of 1a showing the mode of intermolecular interactions. Chlorine atoms are displayed as cross-hatched circles,
oxygen atoms as dotted and sulphur atoms as shaded circles. Broken lines represent hydrogen-bond type interactions.
(40 mg, 0.21mmol) in pyridine (25 ml) and triethylamine
(60 ml) under Ar was heated to refluxfor 1 h. After cooling to
room temperature, the triethylammonium chloride, which
has formed, was filtered off using celite and washed with
diethyl ether. The filtrate was added dropwise under cooling
to 6N hydrochloric acid. The aqueous phase was separated
and extracted three times with diethyl ether. The combined
organic layers were washed with 2N hydrochloric acid,
aqueous sodium hydrogen carbonate and water, in this
sequence, and dried with sodium sulphate. The solvent was
evaporated and the crude product crystallised from toluene–
n-hexane(1:1, v/v)toyield76%ofawhitepowder:Mp104–
1068C. IR (KBr, cm21): 3452 (OH), 3084 (CZH, Ar), 2981,
2955 (CZH), 2231 (CuC), 1734 (CvO), 1636, 1605 (Ar),
1440 (CZH), 1347, 1259, 1202, 1176 (CZO), 1005, 917,
866 (Ar); 1H NMR (CDCl3): d 1.63 (s, 6 H, CCH3), 2.05 (s, 1
H, OH), 3.95 (s, 6 H, OCH3), 8.25 (d, 4J ¼ 1.5 Hz, 2 H, Ar-
H), 8.60 (t, 4J ¼ 1.5 Hz, 1 H, Ar-H); 13C NMR (CDCl3): d
31.4 (CCH3), 52.5 (OCH3), 65.6 [C(CH3)2OH], 80.3 (Ar-
CuC), 95.7 (Ar-CuC), 123.9, 130.1, 130.9, 136.6 (Ar-C),
165.6 (COOCH3). MS (GC): m/z calcd for C15H16O5:
276.28. Found 276 [Mþ]. Anal. calcd for C15H16O5: C,
65.21,; H, 5.84. Found: C, 64.86; H, 5.97%.
4.2.2 5-Ethynylisophthalic acid (4)
Toasolutionofpotassiumhydroxide(11.6 g,207.3 mmol)in
n-butanol (250 ml) was added compound 3 (6.0 g,
21.7mmol) and the mixture heated under reflux for 30min.
After cooling to room temperature, the precipitate which has
formed was separated and washed with ethanol to yield 88%
of an off-white powder of the dipotassium salt of 4

404
I.M. Hauptvogel et al.
b
c
Figure 3. Illustration of the plain lattice of 1 (excluding solvent molecules) viewed along the crystallographic a-axis. Oxygen atoms are
displayed as shaded circles. Only the hydrogens of the carboxy groups are displayed for clarity.
(Mp.3508C). This was dissolved in water (20 ml) and
acidified to pH 1 with 5N hydrochloric acid. The precipitate
which has formed was separated, washed with water and
dried for 4 h at 508C under vacuum to yield 98% of a white
powder: Mp 247–2508C. IR (KBr, cm21): 3297 (CZH,
ethynyl), 3076 (CZH, Ar), 2983, 2933, 2876 (CZH), 2116
(CuC), 1706 (CvO), 1599 (Ar), 1278, 1246 (CZO), 917,
860 (Ar); 1H NMR ([d6]DMSO): d 4.43 (s, 1 H, CuCZH),
8.18 (s, 2 H, Ar-H), 8.47 (s, 1 H, Ar-H), 13.49 (s, 2 H,
COOH); 13C NMR ([d6]DMSO): d 81.7 (CuCZH), 82.7
(CuCZH), 122.8, 130.1, 132.1, 136.0 (Ar-C), 165.8
(COOH). MS (EI): m/z calcd for C10H6O4: 190.15. Found:
189.9 [Mþ]. Anal. calcd for C10H6O4: C, 63.16; H, 3.18.
Found: C, 62.88; H, 3.42%.
were washed with conc. aqueous solution of sodium
carbonate and water, in this sequence, and dried with sodium
sulphate. Evaporation of the solvent and crystallisation from
ethanol yielded 55% of colourless needles; mp 134–1368C
(lit. (19) 130–1318C). Spectroscopic data correspond with
the literature (19).
Via deblocking of 3. To a solution of 3 (6.0g, 21.7mmol) in
dry toluene (300ml), sodium hydride (60% in mineral oil,
1.56g, 39.0mmol) was added and the mixture heated for 1 h
to 758C. After cooling to room temperature, the mixture was
carefully quenched with water. The organic layer was
separated, washed with water and dried with sodium
sulphate. Evaporation of the solvent and crystallisation from
ethanol yielded 60% of the compound.
4.2.3 Dimethyl 5-ethynylisophthalate (5)
Via esterification of 4. A mixture of diacid 4 (5.70 g,
30.0mmol) in dry methanol (25 ml) and conc. sulphuric acid
(1.20 g, 12.2mmol) was heated to reflux for 5 h under dry
conditions. The most part of the alcohol was evaporated and
the residue added to five times the amount of iced water. The
organic layer was separated and the aqueous phase extracted
three times with diethyl ether. The combined organic layers
4.2.4 Tetramethyl 5,50-(1,3-butadiyne-1,4-
diyl)diisophthalate (6)
A solution of diester 5 (0.50 g, 2.30 mmol) in pyridine–
methanol (10 ml, 1:1, v/v) was heated for 30 min under an
atmosphere of argon, in order to remove oxygen. After
cooling to room temperature, copper(II) acetate (0.60 g,

Supramolecular Chemistry
405
3.22 mmol) was added and the mixture heated to reflux for
4 h under argon. The mixture was then cooled to room
temperature and dropped slowly into 18N sulphuric acid
under cooling with ice. The solid which has formed was
dissolved in diethyl ether. The ethereal solution was
washed with water and dried with sodium sulphate. The
solvent was evaporated and the crude product crystallised
from acetone–chloroform (1:1, v/v) to yield 88% of a
colourless solid; mp 221–2228C. IR (KBr, cm21): 3079,
3037, 3008 (CZH, Ar), 2951 (CZH), 1729 (CvO), 1634,
1595 (Ar), 1438 (CZH), 1331, 1271, 1131, 1110 (CZO),
Analysis of hydrogen bonds was carried out by using the
HTAB instruction of the SHELXTL program. Crystal-
lographic data for the structure in this paper have
been deposited with the Cambridge Crystallographic Centre
as supplementary publication number CCDC-780477.
Copies of data can be obtained, free of charge, on application
to the Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK (Fax: þ44-1223-336033, E-mail: deposit@
ccdc.cam.ac.uk).
1
999, 914, 875 (Ar); H NMR (CDCl3) d 3.97 (s, 12 H,
Acknowledgement
CH3), 8.37 (s, 4 H, Ar-H), 8.67 (s, 2 H, Ar-H); 13C NMR
(CDCl3) d 52.6 (C H3), 75.1 (CZCuC), 80.2 (CZCuC),
122.6, 131.2, 131.3, 137.4 (Ar-C), 165.3 (COOCH3); MS
(GC): m/z calcd for C24H18O8: 434.39. Found: 434 [Mþ].
Anal. calcd for C24H18O8: C, 66.36; H, 4.18. Found: C,
66.18; H, 4.15%.
This work was financially supported by the Deutsche
Forschungsgemeinschaft (SPP 1362/1).
References
(1) Tiekink, E.R.T., Vittal, J., Eds. Frontiers in Crystal
Engineering; Wiley: Hoboken, NJ, 2006.
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4.2.5 5,50-(1,3-Butadiyne-1,4-diyl)diisophthalic acid (1)
Tetraester 6 (0.20 g, 0.46 mmol) was dissolved in THF
(15 ml). Lithium hydroxide (0.80 g, 19.0 mmol) was added
and the suspension mixed with water (4.5 ml). The mixture
was stirred for 15 h at room temperature and then diluted
with water (20 ml). The solution was acidified with 3N
hydrochloric acid and the precipitate, which has formed,
was dissolved with a mixture of diethylether and THF. The
ethereal solution was dried with sodium sulphate and
evaporated to yield after drying at 1008C under vacuum
83% of a colourless solid: Mp .3508C. IR (KBr, cm21):
3415 (br, H2O), 3038 (CZH, Ar), 2637, 2551 (COOH),
1703 (CvO), 1595, 1542, 1510 (Ar), 1142 (CZO), 914
(Ar). 1H NMR ([d6]DMSO): d 8.30 (s, 4 H, Ar-H), 8.50 (s,
2 H, Ar-H), 13.62 (s, 4 H, COOH); 13C NMR ([d6]DMSO):
d 74.5 (CZCuC), 80.6 (CZCuC), 121.4, 131.0, 132.3,
136.6 (Ar-C), 165.6 (COOH). MS (EI): m/z calcd for
C20H10O8: 378.29. Found: 378.1 [Mþ]. Anal. calcd for
C20H10O8 · H2O: C, 60.61; H, 3.05. Found: C, 60.28; H,
2.93%.
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