Octahydropentalene 2,5-Disulfonic Acid - A new linker molecule for coordination polymers

Article abstract of DOI:10.1055/s-0032-1317806

Octahydropentalene 2,5-disulfonic acid was prepared in five steps as a single stereoisomer from the corresponding bicyclic diketone. The latter was first reduced followed by activation of the secondary-alcohol functions and nucleophilic substitution with thioacetate. The thioester moieties were oxidatively degraded to the bischlorosulfonyl derivative. On this stage the configuration was established by a X-ray single-crystal analysis. Hydrolysis gave the target compound as the trihydrate. Georg Thieme Verlag Stuttgart . New York.

Full text of DOI:10.1055/s-0032-1317806

LETTER
▌959
letter
Octahydropentalene 2,5-Disulfonic Acid – A New Linker Molecule for Coordi-
nation Polymers
Synthesis of Octahydropentalene 2,5-Disulfonic Acid
Thomas W. T. Muesmann,1 Mathias S. Wickleder, Christina Zitzer, Jens Christoffers*
Institut für Chemie, Carl von Ossietzky-Universität Oldenburg, 26111 Oldenburg, Germany
Fax +49(441)7983873; E-mail: jens.christoffers@uni-oldenburg.de
Received: 27.02.2013; Accepted after revision: 20.03.2013
Dedicated to Professor Jürgen Martens on the occasion of his 65th birthday.
we recently presented the preparation of trans-cyclohex-
Abstract: Octahydropentalene 2,5-disulfonic acid was prepared in
ane-1,4-disulfonic acid,5 which turned out to be an excel-
five steps as a single stereoisomer from the corresponding bicyclic
lent linker perfectly suited for the formation of
coordination polymers with solvated zinc ions. The rigid-
diketone. The latter was first reduced followed by activation of the
secondary-alcohol functions and nucleophilic substitution with
thioacetate. The thioester moieties were oxidatively degraded to the ity of this almost linear linker evokes good crystallinity of
bischlorosulfonyl derivative. On this stage the configuration was es-
tablished by a X-ray single-crystal analysis. Hydrolysis gave the
target compound as the trihydrate.
derived materials, which is accompanied by thermal sta-
bility up to 400 °C, which is exceptionally high for a met-
al-organic coordination polymer.5 However, it has to be
Keywords: bicyclic compounds, carbocycles, diols, sulfur, thiols
mentioned that three-dimensional networks are difficult
to obtain when compared to the respective carboxylic ac-
ids, that is, the solvent molecules are competing ligands
Polycarboxylic acids are the most frequently used com- for the metal ions. This is also the reason that most of the
pounds for the construction of coordination polymers salts we have obtained so far are quite moisture sensitive
(CP) and metal-organic frameworks (MOF). This can be and soluble in polar solvents.
clearly attributed to the paramount inimitability in their
In order to achieve new coordination geometries we were
degree of tunability and structural diversity leading to a
looking for other rigid aliphatic scaffolds for binding two
large number of different CP and MOF displaying a large
sulfonic acid groups in a nonparallel fashion and envi-
range of chemical and physical properties.2 However, de-
sioned the octahydropentalene structure – the bicyc-
spite of all their structural diversity carboxylic acids show
lo[3.3.0]octane scaffold – to be a suitable candidate for
some significant drawbacks, which are inter alia moderate
this enterprise. We therefore developed the synthesis of
octahydropentalene 2,5-disulfonic acid (6). It is worth-
while to mention that for the carboxy analogue of disul-
acidity and limited thermal stability of their metal salts. In
order to overcome these drawbacks we have initiated a re-
search program for the preparation of new polysulfonic
acids. This class of organic compounds is – compared
fonic acid 6, which has already been reported in 1958, no
metal salts are known.6
with carboxylic acids – relatively rare, and reliable proto-
The synthesis of octahydropentalene 2,5-disulfonic acid
(6) started from commercially available glyoxal and ace-
tonedicarboxylate which were converted into diketone 1
in a two-step reaction initially reported by Weiss and
Cook.7 The reduction of 1 with an excess of NaBH4 fur-
nished the secondary dialcohol 2 (69%) as a mixture of
two diastereoisomers (dr = 5:1),8 which were not separat-
ed (Scheme 1). Whereas the relative configuration of the
ring fusion must be naturally cis, the alcohol groups can
be either in relative endo or exo configuration, thus three
diastereoisomers are expected. In accordance with the lit-
erature,9 the major of two isomers was assigned to be the
endo,endo compound, whereas the minor component was
the endo,exo isomer. The third exo,exo isomer was not ob-
served. Anyhow, the alcohol functions were activated by
tosylate formation. Bissulfonate 3 was also isolated (80%
yield) as a mixture of two diastereoisomers (dr = 6:1).10
This mixture was submitted to nucleophilic displacement
with potassium thioacetate which gave the bisthioester 4
as a single diastereoisomer.11 The relative exo,exo config-
uration (vide infra) of both acetylthio groups revealed a
SN2 process of the endo,endo isomer of compound 3.
Since another diastereoisomer of compound 3 was not ob-
cols for their preparation are surprisingly limited.3 This is
particularly true if analogues of typical polycarboxylic ac-
ids are considered, for example, of terephthalic acid, tri-
mesic acid, and pyromellitic acid. Furthermore
polysulfonic acids bearing special carbon scaffolds are
hardly known. In the past few years we have provided a
large number of suitable routes to these acids allowing for
their preparation in scalable amounts.4 The investigation
of the coordination chemistry of the respective sulfonate
anions revealed that they are more weakly coordinating li-
gands compared to the carboxylate. They display, howev-
er, a large number of diverse coordination modes, and the
salts show a significantly enhanced thermal stability when
compared to their respective carboxylates. This is proba-
bly the most interesting feature that forced us to look for
the preparation of further sulfonic acids with more diverse
scaffolds. It turned out that especially compounds with al-
iphatic scaffolds are hardly to realize. As a first success
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DOI: 10.1055/s-0032-1317806; Art ID: ST-2013-B0182-L
© Georg Thieme Verlag Stuttgart · New York

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T. W. T. Muesmann et al.
LETTER
served, we presume the exo,endo isomer of bistosylate 3 close packed fashion, and the shortest distances between
to be not converted under reaction conditions, which the atoms of adjacent molecules suggest that there are
might actually be one of the reasons for the moderate yield only weak intermolecular interactions.
(36%) of this transformation. Another reason could be a
competing elimination reaction of a tosylate group. How-
ever, we were neither able to detect any unique byproduct
nor remaining starting material. The thioester moieties of
intermediate product 4 were oxidatively degraded with
chlorine formed in situ from NCS–HCl to furnish the
bischlorosulfonyl derivative 5 (79%).12 This crystalline
material 5 can be purified by column chromatography and
showed (in contrast to the final disulfonic acid 6) infinite
Figure 1 Structure and atom-labeling of the bischlorosulfonyl com-
stability under ambient conditions, that is, it is a very ap-
propriate storage form of the acid. Moreover, single crys-
tals of 5 were obtained which were suitable for an X-ray
structure determination (Figure 1). Hydrolysis with hot
water gave the title compound 6 (90%)13 as the trihydrate,
as was determined by means of DTA/TG measurements.
pound 5. The ellipsoids are drawn at a 70% probability level. Bond
lengths [pm]: C1–C2 154.4(3), C2–C3 153.5(3), C3–C3a 154.4(3),
C3a–C4 154.0(3), C4–C5 152.7(3), C5–C6 154.3(3), C6–C6a
154.9(3), C6a–C1 154.8(2), C3a–C6a 157.2(3), S1–O11 143.2(2),
S1–O12 142.9(2), S1–C2 179.1(2), S1–Cl1 205.5(1), S2–O21
142.7(1), S2–O22 142.8(2), S2–C5 178.7(2), S2–Cl2 204.6(1).
In summary, in the course of our projects on sulfonate-
based metal-organic frameworks we have prepared anoth-
er new aliphatic disulfonic acid 6. The acid 6 shows the
[SO3H] moieties in exo configuration with respect to the
octahydropentalene scaffold, that is, the functional groups
show a linear arrangement. The straightforward five-step
synthesis was achieved with starting from cis-octahydro-
pentalenedione (1), which was readily available by chem-
istry introduced by Weiss and Cook. Although two
diastereoisomers (endo,endo and endo,exo) resulted in the
initial reduction to the diol 2, only one diastereoisomer of
the bisthioester 4 (exo,exo) was obtained after alcohol ac-
tivation and nucleophilic displacement with KSAc. The
relative configurations the sulfur compounds were deter-
mined by X-ray crystallography after oxidative transfor-
mation to the bis(chlorosulfonyl) derivative 5. The latter
compound 5 is stable, storable, and could be conveniently
converted into the disulfonic acid 6 by simply heating it in
hot water.
H
H
(a)
O
O
HO
OH
69%
H
H
1
2
(b) 80%
H
H
(c)
AcS
SAc
TsO
OTs
36%
H
H
4
3
(d) 79%
H
H
(e)
ClO2S
SO2Cl
HO3S
SO3H
90%
H
H
Acknowledgement
5
6
We are grateful to Birger Ruddigkeit for his assistance, to Wolfgang
Saak and Detlev Haase for X-ray crystallography, and the Deutsche
Forschungsgemeinschaft for generous financial support.
Scheme 1 Synthesis of disulfonic acid 6. Reagents and conditions:
(a) NaBH4 (2.5 equiv), MeOH, 23 °C, 2 h; (b) TosCl (5 equiv), Et3N
(5 equiv), CH2Cl2, 23 °C, 24 h; (c) excess KSAc, MeCN, reflux, 3.5
h; (d) NCS (8 equiv), HCl (2.2 equiv), MeCN, H2O, 10–23 °C, 3 h;
(e) H2O, 100 °C, 5.5 h.
References and Notes
(1) New address: Ferdinand Eimermacher GmbH & Co. KG,
Westring 24, 48356 Nordwalde, Germany.
The crystal structure14 of the bischlorosulfonyl derivative
5 reveals clearly the cis annulation of the two five-mem-
bered rings and the exo configuration of both functional
groups (Figure 1). Within the scaffold of carbon atoms the
C–C bond lengths range from 152.7(2) and 157.2(3) pm,
and the angles enclosed by the carbon atoms are close to
the ideal tetrahedral value (legend of Figure 1). An excep-
tion is the strained C3a–C6a bridge, which is elongated
(ca. 157 pm). The [SO2Cl] moieties of the molecule show
typical S–O distances of about 143 pm, and the bond
lengths S–Cl are 205.5(1) and 204.6(1) pm, respectively.
In the monoclinic unit cell the molecules are arranged in a
(2) Reviews: (a) Cook, T. R.; Zheng, Y.-R.; Stang, P. J. Chem.
Rev. 2013, 113, 734. (b) Kreno, L. E.; Leong, K.; Farha, O.
K.; Allendorf, M.; Van Duyne, R. P.; Hupp, J. T. Chem. Rev.
2012, 112, 1105. (c) Shah, M.; McCarthy, M. C.; Sachdeva,
S.; Lee, A. K.; Jeong, H.-K. Ind. Eng. Chem. Res. 2012, 51,
2179. (d) Xuan, W.; Zhu, C.; Liu, Y.; Cui, Y. Chem. Soc.
Rev. 2012, 41, 1677.
(3) Shimizu, G. K. H.; Vaidhyanathan, R.; Taylor, J. M. Chem.
Soc. Rev. 2009, 38, 1430.
(4) (a) Muesmann, T. W. T.; Wickleder, M. S.; Christoffers, J.
Synthesis 2011, 2775. (b) Muesmann, T. W. T.; Zitzer, C.;
Mietrach, A.; Klüner, T.; Christoffers, J.; Wickleder, M. S.
Synlett 2013, 24, 959–962
© Georg Thieme Verlag Stuttgart · New York

LETTER
Dalton Trans. 2011, 40, 3128. (c) Mietrach, A.; Muesmann,
Synthesis of Octahydropentalene 2,5-Disulfonic Acid
961
(s), 1096 (m), 1018 (m), 969 (m), 926 (m), 880 (s), 855 (s),
813 (s) 768 (m), 752 (s), 666 (s) cm–1. MS (ESI, +):
m/z = 473 [M + Na+]; C22H26O6S2 (450.57).
T. W. T.; Zilinski, C.; Christoffers, J.; Wickleder, M. S. Z.
Anorg. Allg. Chem. 2011, 637, 195. (d) Muesmann, T. W.
T.; Mietrach, A.; Christoffers, J.; Wickleder, M. S. Z. Anorg.
Allg. Chem. 2010, 636, 1307. (e) Mietrach, A.; Muesmann,
T. W. T.; Christoffers, J.; Wickleder, M. S. Eur. J. Inorg.
Chem. 2009, 5328.
(11) exo,exo-2,5-Di(acetylthio)octahydropentalene (4)
KSAc (4.81 g, 42.2 mmol) was added to a solution of
bistosylate 3 (3.79 g, 8.43 mmol) in MeCN (34 mL), and the
resulting mixture was heated to reflux for 3.5 h.
(5) Muesmann, T. W. T.; Zitzer, C.; Wickleder, M. S.;
Christoffers, J. Inorg. Chim. Acta 2011, 369, 45.
(6) Cope, A. C.; Keller, W. J. J. Am. Chem. Soc. 1958, 80, 5502.
(7) Bertz, S. H.; Cook, J. M.; Gawish, A.; Weiss, U. Org. Synth.
1986, 64, 27; Org. Synth., Coll. Vol. VII 1990, 50.
Subsequently, it was diluted with MTBE (80 mL) and H2O
(80 mL), and the layers were separated. The aqueous layer
was extracted twice with MTBE (2 × 50 mL). The combined
organic layers were dried (MgSO4) and evaporated after
filtration. The residue was chromatographed [SiO2, hexane
→ hexane–CH2Cl2 = 1:1 → CH2Cl2 → MTBE; Rf = 0.40
(hexane–CH2Cl2 = 1:1)] to furnish the title compound 3 (787
mg, 3.04 mmol, 36%) as a single isomer and as a brown
solid, mp 74–76 °C. 1H NMR (500 MHz, CDCl3): δ = 1.78
(t, J = 6.5 Hz, 8 H), 2.27 (s, 6 H), 2.66–2.67 (m, 2 H), 3.80
(pent, J = 6.5 Hz, 2 H) ppm. 13C{1H} NMR (125 MHz,
CDCl3): δ = 30.67 (CH), 39.89 (CH2), 41.09 (CH3), 43.03
(CH), 196.08 (C) ppm. IR (ATR): 3363 (w), 2976 (w), 2943
(m), 2930 (m), 2855 (m), 1675 (s), 1442 (m), 1421 (m), 1353
(m), 1276 (m), 1261 (m), 1148 (m), 1122 (s), 1104 (s), 1005
(m), 956 (s), 931 (m), 907 (m), 83 5 (m), 646 (m), 624 (s)
cm–1. MS (ESI, +): m/z = 281 [M + Na+]. Anal. Calcd for
C12H18O2S2 (258.40): C, 55.78; H, 7.02. Found C, 55.56; H,
7.01.
(8) Octahydropentalene-2,5-diol (2)
NaBH4 (1.86 g, 49.3 mmol) was added to a solution of
diketone 1 (2.73 g, 19.7 mmol) in MeOH (33 mL), while
cooling the reaction mixture with an ice-water bath. After
stirring the mixture for further 2 h at ambient temperature, it
was first diluted (upon cooling with an ice-water bath) with
hydrochloric acid (62 mL, 2 mol/L), then with aq NaOH
solution (155 mL, 4 mol/L) and finally extracted with MTBE
(3 × 140 mL). The combined organic layers were dried
(MgSO4) and evaporated after filtration. The residue was
recrystallized from MTBE (ca. 70 mL) to give the title
compound (1.92 g, 13.5 mmol, 69%) as a colorless solid (mp
72–73 °C), which consisted of two diastereoisomers
(endo,endo/endo,exo = 5:1 by GLC). Alternatively, the
crude product could be purified by chromatography [SiO2,
MTBE → acetone; Rf = 0.26 (MTBE)], then yielding a
mixture with a dr of 3.5:1 (by GLC). 1H NMR (500 MHz,
CDCl3): δ (major isomer) = 1.69–1.78 (m, 4 H), 2.06–2.12
(m, 4 H), 2.51–2.53 (m, 2 H), 3.92 (br s, 2 H), 4.23–4.26 (m,
2 H) ppm; δ (minor isomer) = 1.27–1.29 (m, 4 H), 1.78–1.79
(m, 4 H), 2.53–2.56 (m, 2 H), 4.16–4.17 (m, 1 H), 4.43–4.44
(m, 1 H) ppm. 13C{1H} NMR (125 MHz, CDCl3): δ (major
isomer) = 41.15 (CH), 43.41 (CH2), 76.19 (CH) ppm; δ
(minor isomer) = 38.84 (CH), 42.35 (CH2) 42.58 (CH2),
74.68 (CH), 75.14 (CH) ppm. IR (ATR): 3263 (br, s), 2943
(s), 2903 (m), 2870 (br, m), 1465 (m), 1439 (m), 1344 (s),
1303 (m), 1256 (m), 1192 (m), 1105 (s), 1072 (s), 1032 (s),
983 (s), 777 (m), 694 (br, m) cm–1. HRMS (ESI, +): m/z
calcd for C8H14LiO2: 149.1154; found: 149.1154 [M + Li+];
C8H14O2 (142.20).
(12) exo,exo-Octahydropentalene-2,5-disulfonic Acid
Dichloride (5)
While cooling with an ice-water bath, NCS (2.71 g, 20.3
mmol) and hydrochloric acid (2.8 mL, 5.6 mmol, 2 mol/L)
were added to a suspension of dithioacetate 4 (656 mg, 2.54
mmol) in MeCN (7.3 mL). The resulting mixture was stirred
at 10–15 °C, until a clear solution was formed (ca. 1–1.5 h).
It was then stirred at ambient temperature for further 2 h and
subsequently diluted with H2O (40 mL) and CH2Cl2 (40
mL). After phase separation, the aqueous layer was extracted
twice with CH2Cl2 (2 × 40 mL). The combined organic
layers were dried (MgSO4) and evaporated after filtration.
The residue was chromatographed [SiO2, hexane–CH2Cl2 =
1:1, Rf = 0.70 (CH2Cl2)] to yield a crude material, which was
further purified by recrystallization from hexane–CHCl3
(1:1, 25 mL) to furnish a title compound 5 (615 mg, 2.00
mmol, 79%) as colorless needles, mp 100–101 °C. 1H NMR
(500 MHz, CDCl3): δ = 2.02 (ddd, J = 15.0, 4.5, 7.5 Hz, 4
H), 2.62 (ddd, J = 15.0, 7.0, 8.5 Hz, 4 H), 3.13–3.18 (m, 2
H), 4.18 (dt, J = 7.0, 7.5 Hz, 2 H) ppm. 13C{1H} NMR (125
MHz, CDCl3): δ = 35.27 (CH2), 42.09 (CH), 75.49 (CH)
ppm. IR (ATR): 2974 (w), 2942 (w), 2871 (w), 1359 (s),
1331 (m), 1283 (m), 1261 (m), 1149 (s), 1098 (m), 934 (m),
664 (s) cm–1. MS (CI, NH3): m/z (%) = 324 (0.5) [M +
(9) Camps, P.; Lukach, A. E.; Vazquez, S. Tetrahedron 2001,
57, 2419.
(10) Octahydropentalene-2,5-diylbis(4-toluenesulfonate) (3)
4-MeC6H4SO2Cl (15.4 g, 80.7 mmol) was added to an ice-
cooled suspension of Et3N (11.3 mL, 80.7 mmol) and diol 2
(2.30 g, 16.1 mmol, dr = 5:1) in CH2Cl2 (40 mL). After
stirring for 24 h at ambient temperature, the mixture was
diluted with H2O (60 mL) and MTBE (60 mL). The layers
were separated, and the aqueous phase was diluted with
brine (50 mL) and extracted twice with MTBE (each 50 mL).
The combined organic layers were washed with brine (50
mL), dried (MgSO4), and evaporated after filtration.
Chromatography of the residue [SiO2, hexane–MTBE = 5:1
→ 1:1 → MTBE, Rf = 0.72 (MTBE)] gave the title
compound (5.77 g, 12.8 mmol, 80%) as a light yellow oil,
which consisted of two diastereoisomers
+
NH4 ], 143 (22), 107 (100). Anal Calcd for C8H12Cl2O4S2
(307.21): C, 31.28; H, 3.94; S, 20.87. Found: C, 31.23; H,
3.75; S, 21.21.
(13) exo,exo-Octahydropentalene-2,5-disulfonic Acid
Trihydrate (6)
A suspension of dichloride 5 (220 mg, 0.72 mmol) in H2O
(15 mL) was heated for 5.5 h to reflux. After filtration
through Celite, all volatile materials were removed under
high vacuum to yield the title compound 6 (209 mg, 0.64
mmol, 90%) as a grey solid, which was determined by
DTA/TG to be the trihydrate (mp 185 °C). 1H NMR (300
MHz, D2O): δ = 1.58–1.65 (m, 4 H), 1.89–1.99 (m, 4 H),
2.69 (br m, 2 H), 3.30 (tt, J = 7.8, 8.1 Hz, 2 H) ppm. 13C{1H}
NMR (125 MHz, D2O): δ = 35.38 (CH2), 42.57 (CH), 60.27
(CH) ppm. IR (ATR): 2967 (w), 2873 (w), 1684 (br, m),
1185 (s), 1028 (br, s), 989 (s), 710 (m), 627 (m) cm–1. HRMS
(endo,endo/endo,exo = 6:1 by NMR). 1H NMR (500 MHz,
CDCl3): δ = 1.68–1.71 (m, 4 H), 1.98–2.00 (m, 4 H), 2.28–
2.33 (m, 2 H), 2.44 (s, 6 H), 4.78–4.80 (m, 2 H), 7.32 (d,
J = 8.0 Hz, 4 H), 7.75 (d, J = 8.0 Hz, 4 H) ppm; signals of the
minor isomer were not listed. 13C{1H} NMR (125 MHz,
CDCl3): δ = 14.06 (CH3), 37.62 (CH), 38.75 (CH2), 83.97
(CH), 127.60 (2 CH), 129.82 (2 CH), 134.14 (C), 144.55 (C)
ppm; signals of the minor isomer were not listed. IR (ATR):
2964 (br, w), 1598 (m), 1352 (s), 1306 (w), 1188 (m), 1171
© Georg Thieme Verlag Stuttgart · New York
Synlett 2013, 24, 959–962

962
T. W. T. Muesmann et al.
LETTER
(ESI, –): m/z calcd for C8H13O6S2: 269.0154; found
via www.ccdc.cam.ac.uk, or by emailing
269.0160 [M – H+]; C8H14O6S2·3H2O (270.32 + 54.05).
data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12, Union Road,
Cambridge CB2 1EZ, UK; fax: +44(1223)336033.
(14) CCDC 914780 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
Synlett 2013, 24, 959–962
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