Synthesis of organic thiosulfates tailored for the electrochemical deposition of 'self-assembled monolayers' at gold surfaces

Article abstract of DOI:10.1055/s-2005-916026

The synthesis of organic thiosulfates, up to 10 nm in length, which were tailored for generating artificial monomembranes on gold surfaces by electrochemically initiated deposition, was accomplished. (E)-3-(4- Hydroxyphenyl)acrylic acid (4-hydroxy cinnamic acid) was employed as aromatic head group and (C₁₀H₂₀-O)_n (n = 1, 3, 5, 7) building blocks were attached. The synthetic procedure comprises a series of nucleophilic substitutions under carefully defined conditions. Extended purification is crucial for eliminating non-reacted starting materials. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2005-916026

PAPER
3051
Synthesis of Organic Thiosulfates Tailored for the Electrochemical Deposition
of ‘Self-Assembled Monolayers’ at Gold Surfaces
L
ong-ChainOrg
l
a
nic
T
i
hiosulf
s
ates o Gogritchiani,*a Sandra Niebler,a Nicole Egner,a Michael Wörner,a André M. Braun,*a Tanya Young,b
Prachi Gupta,b Aibin Shi,b Stefan H. Bossmann*a,b
a
University of Karlsruhe, Department of Chemical & Process Engineering, 76128 Karlsruhe, Germany
E-mail: eliso.g@ciw.uni-karlsruhe.de; E-mail: andre.braun@ciw.uni-karlsruhe.de
Kansas State University, Department of Chemistry, 111 Willard Hall, Manhattan, Kansas 66506-3701, USA
b
Fax +1(785)5326666; E-mail: sbossman@ksu.edu
Received 28 April 2005
the most promising nanotechnological building elements
Abstract: The synthesis of organic thiosulfates, up to 10 nm in
length, which were tailored for generating artificial monomem-
branes on gold surfaces by electrochemically initiated deposition,
was accomplished. (E)-3-(4-Hydroxyphenyl)acrylic acid (4-hy-
available.26,27 In order to use mycobacterial porins as
nanotemplates or nanotransistors at electrodes’ surfaces
the synthesis of tailor-made surfactants, which can form
droxy cinnamic acid) was employed as aromatic head group and monomembranes that mimic the biophysical properties of
(C10H20-O-)n (n = 1, 3, 5, 7) building blocks were attached. The syn-
mycobacterial membranes, was planned and performed.
thetic procedure comprises a series of nucleophilic substitutions un-
The lengths of the hydrophobic surfactants should vary
der carefully defined conditions. Extended purification is crucial for
between 3 nm and 10 nm, because MspA as the prototype
eliminating non-reacted starting materials.
of mycobacterial porins possesses a hydrophobic docking
unit of approximately 4 nm in length.28 A phenyl group
Key words: self-assembled monolayer (SAM), organic thiosul-
fates (Bunte salts), oligoether, long-chain surfactants, nucleophilic
was introduced in close proximity to the polar head group
substitution
to enable the formation of densely packed self-assembled
monolayers (SAM).29 The deposition of the surfactant
onto the gold electrode should be precisely controlled.
Introduction
Electrochemical SAM deposition methods offer here a
distinct advantage. Especially the surface coverage of the
Inspired by the enormous progress in biotechnology and gold electrode during SAM formation can be a decisive
the growing demand for customized products consider- factor for protein reconstitution. Thermal methods such as
able efforts have been made to synthesize novel surfac- the addition of organic thiols to gold always lead to a max-
tants. Two major approaches can be discerned: a) imal surface coverage.30,31 Organic thiosulfates were de-
surfactants from regrowth/renewable materials1–5 and b) scribed as a method for a cautious deposition of thiols on
total syntheses of surfactants possessing very defined gold surfaces.32 This process is approximately 100 times
properties6–16 which can be tailored with regard to a mul- slower than the chemisorption of organic thiols on gold.
titude of surfactant applications.18,19 Whereas most of the However, it can be expedited by electrochemically initiat-
surfactants are of a molecular nature,1–11 oligomeric and ed deposition. Therefore, organic thiosulfates are very
polymeric surfactants have been designed as well.12–17 suitable precursors for the generation of defined nanolay-
The novel total syntheses of new surfactants were devel- ers on noble metal substrates (e.g. platinum, gold). Fur-
oped either with respect to utilizing new methods (for in- thermore, they possess the distinct advantage that a partial
stance: enzymatic synthesis3) or to create unique surface coverage can be attained. Such an experimental
properties, such as the inclusion of extremely hydropho- strategy is mandatory for the reconstitution of bio-nano-
bic groups into the surfactants’ structure.12–17 Another structures within an artificial monomembrane. There are
promising approach comprises the extraction of mem- several approaches for the synthesis of organic thiosul-
brane-lipids which can form mono and double mem- fates reported in the literature.33–35 However, we found
branes, which can host enzymes,20,21 channel-proteins22 only the ‘classic’ method, developed by Distler,33 suitable
and other bio-macromolecules of interest. One salient ex- for the synthesis of very long-chain organic thiosulfates.
ample is the extraction of archaeal tetraether lipids.23–25 The key reaction for the linking of the building units is the
Molecular modeling indicates that a monomembrane nucleophilic substitution of organic bromides by aliphatic
formed by tetraether lipids possesses a width of approxi- and aromatic alcoholates in dimethylformamide (DMF).
mately 5 nm.23 Although this may seem sufficient to host Although the chemistry of nucleophilic substitution36 is
a multitude of bio-macromolecules it is, however, not suf- certainly known, a real challenge can be found in the ex-
ficient for mycobacterial porins, which are emerging as treme demands of completeness for each stage of the lin-
ear synthesis and/or the development of reliable and
thorough purification methods.
SYNTHESIS 2005, No. 18, pp 3051–3058
x
x.
x
x
.
2
0
0
5
The first step of the optimization of the surfactant before
synthesis consists in the determination of the surfactant
Advanced online publication: 16.09.2005
DOI: 10.1055/s-2005-916026; Art ID: M02905SS
© Georg Thieme Verlag Stuttgart · New York

3052
E. Gogritchiani et al.
PAPER
length. The length and three-dimensional structure of the accordance with these considerations, 3-(4-hydroxyphe-
surfactants were optimized employing PM3 as a semi-em- nyl)acrylic acid was chosen as the preferential head group
pirical method.37 Linking the C10-repeating units by of our tailor-made surfactants. Furthermore, the acrylic
means of ether connections was selected as a feasible syn- acid function of our tailored surfactants can be used to sta-
thetic pathway to long-chain surfactants. As it becomes bilize the artificial monomembrane by electrochemically
clear from Figure 1, the use of C10-repeating units togeth- initiated39 or radical-induced40 polymerization. In
er with an ether-linking of the building elements ensures Table 1, the calculated lengths (d, nm) are summarized.
the synthesis of straight hydrophobic units of variable
Table 1 Synthesis of Organic Thiosulfates (Bunte Salts) of Various
Lengths
length. A tilt-angle of 118° 2° is found between surfac-
tants’ chains and the cinnamic acid head groups which en-
sures an optimal packing pattern of monolayers of our
chemisorbed surfactants on metal electrodes’ surfaces.
O
O
Na
O
S
S
X
O
O
OH
n
d
Compound
Molecular formula
C19H27NaO6S2
C39H67NaO8S2
C39H69NaO8S2
C37H65NaO8S2
C59H107NaO10S2
C79H147NaO12S2
n
1
3
3
3
5
7
d (nm)
2.11
12
13
14
15
16
17
4.77
4.54
4.53
7.50
10.24
Synthesis of Oligo-Ether Chains
Figure 1 Structures of (very) long-chain organic thiosulfates as cal-
culated using PM3
The first step in the preparation of the targeted organic
thiosulfates was the optimization of the synthesis of 10-
bromodecan-1-ol (1). We have modified the procedure by
Kang et al.41 with respect to the obtained yield and envi-
ronmental considerations (Scheme 1).
Results and Discussion
Preoptimization of the Surfactants’ Lengths and
Structures: Molecular LEGO
48% HBr
Br
OH
HO
HO
toluene, reflux 72 h,
r.t., 24 h
To date, stable membrane systems which can be tailored
to host various channel forming proteins are still under de-
1
velopment. A stable monomembrane should be hydropho- Scheme 1 Proton-catalyzed SN reaction, synthesis of 10-bromo-de-
can-1-ol
bic in nature. Its packing should be sufficiently dense to
prevent any pathways other than the designed channels.
Furthermore, the synthesis and purification procedures
should be feasible. Based on these prerequisites, we have
selected a modified method for the formation of ethers
(Williamson’s ether synthesis38) as the linking reaction. A
variable number (n = 1, 3, 5, 7) of (-C10H22-O-) segments,
which possess a length of 1.37 nm, were connected by
means of an SN2 reaction between the corresponding
alkoxylates and aliphatic bromides in DMF. In order to
optimize the physical properties of the artificial
monomembranes formed by our surfactants on noble met-
al surfaces, a phenyl group was introduced in close prox-
imity to the polar head group. Due to the p-stacking of
phenyl units29 ordered islands of associating surfactants
can be formed, especially if the surface coverage is less
than 100%. These surface conditions are mandatory to
favor the reconstitution of a pore-forming protein. In
The right combination sequences of the commercially
available building blocks 1,10-decandiol and 1,10-dibro-
modecane with 10-bromodecan-1-ol enabled the synthe-
sis of long-chain a,w-bromoalkyl-oligoethers (2, 5)
possessing an odd number of (-C10H22-O-) segments
(Schemes 2 and 3). These SN2 reactions were performed
in anhydrous DMF using K2CO3 as a strong non-nucleo-
philic base. The choice of these reaction conditions was
encouraged by the successful synthesis of crownester-bi-
pyridines in one of the collaborating research teams.42–44
The conversion of the aliphatic a,w-alcohol (3), which
was also obtained from a sequence of SN2-reactions, into
the corresponding a,w-bromopentadecylether (4) was
achieved by reacting it with thinyl bromide in pyridine
(Scheme 2).45
Synthesis 2005, No. 18, 3051–3058 © Thieme Stuttgart · New York

PAPER
Long-Chain Organic Thiosulfates
3053
Br
especially cesium carboxylates are known to form esters
with aliphatic chlorides and bromides in DMF at slightly
elevated temperatures (T >50 °C).44 However, at lower
temperatures the competing pathway of the synthesis of
aryl-alkyl esters appears to be so fast in 2-ethoxyethanol,
DMF and acetonitrile that no formation of any ester was
observed in the crude reaction product using FT-IR spec-
trophotometry.
Br
O
K2CO3,
DMF, 70 °C 24 h
Br
2x
HO
HO
1
Br
Br
O
2
K2CO3,
DMF, 70 °C 24 h
OH
2x
The losses of material that we experienced during the
workup mostly occurred due to the physical properties of
these compounds. The formation of (pre)micelles in the
aqueous phases during the washing procedures could not
be completely suppressed as UV/Vis absorption spectros-
copy indicated.
O
O
OH
HO
O
3
3
PBr3,
pyridine, 0 °C 2 h,
r.t. 2 h
Br
Br
O
3
Attachment of the Thiosulfate Group
4
The last step in our (mostly) linear synthetic pathway was
the nuclear substitution of the aliphatic bromide against
the thiosulfate group (Scheme 5). Although phase transfer
reactions have been successfully employed to carry out
SN2 reactions,46 we decided to perform this reaction in the
aqueous phase in order to generate a reaction product of
maximal purity.
Scheme 2 Molecular LEGO using SN2 reactions (n = 3, 5)
O
Br
2x
Br
O
2
K2CO3,
DMF, 70 °C 24 h
OH
HO
O
Br
Br
O
5
Purification and Characterization of the Organic
Thiosulfates
5
Scheme 3 Molecular LEGO using SN2 reactions (n = 7)
The final step of the procedure reported here is the HPLC
purification of the final products employing a preparative
reverse phase (C18) column. All the separations have
been performed using H2O–acetonitrile as mobile phase
because this solvent mixture can be easily removed in
high vacuum and does not leave any traces, for example
any salt, in the final product. The average purity of the
samples, which has been checked by reinjection, was
98 2% before and greater than 99.95% after HPLC puri-
fication. The predicted MALDI-TOF spectra and correct
CH analyses for compounds 12–17 were obtained. These
Attachment of Polar Head Groups
The next step in our endeavor consists of the attachment
of either (E)-3-(4-hydroxyphenyl)acrylic acid, 4-hy-
droxybenzoic acid or 3-(4-hydroxyphenyl)propanoic acid
(Scheme 4). The reaction conditions were tailored to
avoid the formation of ester linkages between the carbox-
ylic acids and the phenol groups as well as aliphatic bro-
mines, respectively. The sodium, potassium, and
O
O
8
HO
OH
HO
O
CH2 O CH2
10
Br
Br CH2 O CH2
10
Br
10
n = 2
10
O
O
n = 0, 2, 4, 6
6, 7, 10, 11
HO
OH
OH
HO
O
O
CH2 O CH2
10
Br
10
n = 0,2,4,6
O
O
9
CH2 O CH2
10
Br
HO
HO
10
n = 2
Scheme 4 Attachment of polar head groups to (long-chain) ether-chains using SN2 reactions
O
O
8
HO
O
CH2 O CH2
10
Br
HO
O
CH2 O CH2
10
S2O3Na
n = 2
14
10
10
n = 2
O
O
Na2S2O4
– NaBr
6, 7, 10, 11
HO
O
O
CH2 O CH2
10
Br
HO
O
O
CH2 O CH2
10
S2O3Na 12, 13, 16, 17
10
10
n = 0, 2, 4, 6
n = 0, 2, 4, 6
O
O
9
CH2 O CH2
10
Br
CH2 O CH2
10
S2O3Na
n = 2
15
HO
HO
10
10
n = 2
Scheme 5 Attachment of the thiosulfate units, finalization of the (long chain) Bunte salts
Synthesis 2005, No. 18, 3051–3058 © Thieme Stuttgart · New York

3054
E. Gogritchiani et al.
PAPER
1-Bromo-10-({10-[(10-bromodecyl)oxy]decyl}oxy)decane (2)
results convincingly prove that the synthesis of our (very)
long-chain surfactants bearing organic thiosulfate func-
tions (Bunte salts) has been successful.
A continuously stirred mixture of 1,10-dibromodecane (22.50 g, 75
mmol) and K2CO3 (22.77 g, 165 mmol) in DMF (150 mL) was heat-
ed to 70 °C under nitrogen. A solution of 1,10-decandiol (5.22 g, 30
mmol) in DMF (100 mL) was added dropwise during 2 h and the
stirring was continued for additional 24 h at 70 °C. The reaction
mixture was cooled to 0 °C, then poured into 2% HCl (400 mL) un-
der ice cooling followed by extraction with CHCl3 (3 × 150 mL).
The combined organic layer was washed with 5% aq NaOH
(3 × 100 mL), with H2O (2 × 250 mL) and was dried (Na2SO4). The
solvent was removed under reduced pressure (100 hPa). The ob-
tained oil was taken up in n-hexane (50 mL) and stirred overnight.
The solvent was decanted and the residue was recrystallized twice
from acetone to obtain a colorless product.
Conclusion
The defined synthesis of (very) long organic thiosulfates
reported here can be regarded as a milestone with respect
to the generation of artificial monomembranes for hosting
various (channel forming) proteins and enzymes. We have
succeeded in the synthesis and thorough purification of
organic surfactants, which can be anchored to noble metal
electrodes by means of their organic thiosulfate groups.
The electrochemically assisted deposition of tailored
amounts of these (very) long-chain surfactants onto elec-
trodes will permit the design of novel components in bio-
electronics, bio/nano-catalysis and medicinal chemistry.
Furthermore, a polymerization of the chemisorbed surfac-
tants is possible due to the presence of alkene functions in
direct proximity to their carboxylic acid head groups
which will allow stabilization of the membrane/protein
assemblies.
Yield: 10.35 g (56%); mp 72 °C.
1-[(10-{[10-({10-[(10-Hydroxydecyl)oxy]decyl}oxy)de-
cyl]oxy}decyl)oxy]-10-hydroxydecane (3)
A continuously stirred mixture of 2 (15.0 g, 24.5 mmol) and K2CO3
(22.77 g, 165 mmol) in DMF (150 mL) was heated to 70 °C under
nitrogen. A solution of 1,10-decandiol (1.22 g, 7 mmol) in DMF (50
mL) was added dropwise during 2 h and the stirring was continued
for additional 24 h at 70 °C. The reaction mixture was cooled to
0 °C, then poured into 2% HCl (400 mL) under ice cooling followed
by extraction with CHCl3 (3 × 150 mL). The combined organic lay-
er was washed with 5% aq NaOH (3 × 100 mL), with H2O (2 × 250
mL) and was dried (Na2SO4). The solvent was removed under re-
duced pressure (100 hPa). The oil obtained was taken up in Et2O (10
mL) and stirred until crystallization occurred (usually overnight).
Solvents (ACS grade) and inorganic chemicals were purchased
from Roth and Acros Organics. DMF was further purified by azeo-
tropic distillation of DMF–toluene–H2O (85:10:5, v/v/v), anhy-
drous and amine-free DMF has been collected when reaching
152 °C at the top of a 20 cm Vigreux column. 1,10-decandiol, 1,10-
dibromodecane, 3-(4-hydroxyphenyl)propanoic acid, 4-hydroxy-
benzoic acid and (E)-3-(4-hydroxyphenyl)acrylic acid were pur-
chased from Aldrich.
Yield: 10.18 g (52%); mp 70 °C.
1-[(10-{[10-({10-[(10-Bromodecyl)oxy]decyl}oxy)decyl]oxy}de-
cyl)oxy]-10-bromodecane (4)
The following procedure was adapted from the literature.45 To a re-
fluxing solution of 3 (10.0 g, 12.74 mmol) in pyridine (100 mL)
thionyl bromide (SOBr2, 6.0 g, 28.84 mol), dissolved in toluene
(20mL) was added dropwise during 1 h. After heating the solution
at reflux for 24 h, the reaction mixture was cooled to 0 °C. 1 N HCl
(100 mL) at 0 °C was added slowly. The mixture was extracted with
toluene (3 × 100 mL). A brownish oil was obtained after the remov-
al of the solvent at reduced pressure (70 hPa). The oil obtained was
taken up in n-hexane (50 mL) and stirred overnight. The solvent was
decanted and the residue was recrystallized twice from acetone to
obtain a colorless product.
HPLC purification of the samples 12–17 has been performed using
a H2O–MeCN gradient. A Hewlett-Packard 1090 HPLC station,
equipped with a preparative reversed phase (C18) column (VyDAC
259VHP5415, particle diameter: 5 mm, pore size 300 Å, inner diam-
eter: 4.6 mm, length 150 mm) and an UV/Vis detector (l1 = 220 nm,
l2 = 260 nm) was employed (flow: 2.5 mL·min–1). The ratio of
H2O–MeCN was kept at 95:5 (v/v) for 5 min and then linearly in-
creased to 50:50 during 30 min. This solvent composition was fur-
ther used for 10 min. The following retention times have been
observed: (12: 6.2 min; 13: 14.5 min; 14: 14.7 min; 15: 14.1 min;
16: 22.7 min, 17: 32.5 min).
Yield: 9.08 g (77%); mp 63–64 °C.
1-{[10-({10-[(10-{[10-({10-[(10-Bromodecyl)oxy]decyl}oxy)de-
cyl]oxy}decyl)oxy]decyl}oxy)decyl]oxy}-10-bromodecane (5)
A mixture of 2 (8.88 g, 14.5 mmol) and K2CO3 (4.40 g, 31.9 mmol)
in DMF (150 mL) was heated to 70 °C under nitrogen. A solution
of 1,10-decandiol (1.15 g, 6.6 mmol) in DMF (30 mL) was added
dropwise during 2 h. The reaction mixture was stirred for an addi-
tional 48 h at 70 °C and then at r.t. for 24 h. After cooling to 0 °C
the reaction mixture was poured into 2% HCl (250 mL) and extract-
ed with CHCl3 (4 × 100 mL). The combined extract was washed
with 5% aq NaOH (3 × 100 mL), with H2O (2 × 100 mL) and dried
(Na2SO4). The organic phase was evaporated under reduced pres-
sure (100 hPa) and the golden oil obtained was taken up in Et2O–
hexane (1:4, 100 mL) and stirred for 3 h. The solvent was removed
by decantation and the liquid-crystalline residue was dissolved in a
minimal amount of acetone, precipitated with pentane and kept at
4 °C over 72 h. The obtained colorless solid was collected by filtra-
tion and dried under vacuum.
Further instrumentation: Ion Spec HiResRSI/MALDI, 400 MHz
NMR (Varian), FT-IR (Bruker Equinox), melting point apparatus
(Fisher), Carlo Erba Strumentatione (CHN analyses).
Compounds 6–11 underwent decomposition when heated above
T = 140 °C without melting.
Synthesis of 10-Bromodecan-1-ol (1)
An aqueous HBr solution (48%, 19 mL) was added dropwise to a
solution of 1,10-decandiol (15.0 g, 86 mmol) and toluene (300 mL).
The mixture was stirred under reflux for 72 h and then at r.t. for 24
h. The organic phase was separated, diluted with Et2O (150 mL) and
then washed consecutively with a) 1 M aq NaOH (200 mL), b) sat.
aq NaCl (3 × 200 mL) and finally dried over Na2SO4 (50 g). The
solvent was removed at normal pressure to yield the desired product
(1) as a pale yellow liquid, bp 129–130 °C (400 Pa), in agreement
with ref. 41.
Yield: 5.50 g (67%); mp 56–57 °C.
Synthesis 2005, No. 18, 3051–3058 © Thieme Stuttgart · New York

PAPER
Long-Chain Organic Thiosulfates
3055
Table 2 Characterization of Building Components for (Long-Chain) Surfactants 1–5
Producta MolecularFormula FT-IR (KBr) (cm–1)
1H NMR (400 MHz, CDCl3) d, 3J (Hz) 13C NMR (400 MHz, CDCl3) d (Hz)
1
2
C10H21BrO
3.64 (t, 2 H, J = 6.7), 3.41 (t, 2 H, 62.9, 33.5, 32.7, 32.5, 29.8, 29.7,
J = 6.9), 1.86 (q, 2 H), 1.57 (m, 2 H), 28.7, 28.0, 25.7
1.25–1.46 (m, 12 H)
C30H60Br2O2
3396, 3329, 2920, 2850,
1463, 1361, 1058, 1018,
615
3.67 (t, 8 H, J = 6.5), 3.44 (t, 4 H,
J = 6.6 H), 1.86 (q, 4 H), 1.60 (q, 8 H), 28.5, 28.6, 28.1, 26.0
1.25 (s, 36 H)
72.6, 33.6, 32.6, 30.1, 29.8, 29.7,
3
4
5
C50H102O6
3450, 2918, 1740, 1468,
1256, 1057
3.52 (t, 4 H, J = 6.7), 3.37 (t, 16 H,
J = 6.5), 1.27–1.48 (m, 80 H)
72.4, 63.0, 32.3, 30.1, 29.7, 26.0,
25.8, 29.5
C50H100 Br2O4
C70H140 Br2O6
3335, 2918, 1738, 1469,
1259, 1057, 612
3.37 (t, 16 H, J = 6.5), 3.32 (t, 4 H,
J = 6.4), 1.27–1.48 (m, 80 H)
72.4, 33.7, 32.8, 30.1, 29.7, 28.7,
28.1, 26.1
3332, 2918, 1738, 1469,
1259, 1057, 610
4.05 (t, 24 H, J = 6.4 Hz), 3.56 (t, 4 H, 72.4, 33.7, 32.8, 30.2, 29.7, 28.7,
J = 6.6), 1.62 (m, 28 H), 1.46–1.23 (m, 28.1, 26.0
84 H)
a Satisfactory microanalyses obtained: C 0.05, H 0.03 (all samples are essentially nitrogen-free).
(E)-3-{4-[(10-Bromodecyl)oxy]phenyl}acrylic Acid (6)
tallized from MeCN–H2O (1:1.5) and kept at 4 °C overnight to ob-
tain 8 as a colorless powder.
To a mixture of 1,10-dibromodecane (3.60 g, 12 mmol) and K2CO3
(4.14 g, 30 mmol) in 2-ethoxyethanol (40 mL) a solution of (E)-3-
(4-hydroxyphenyl)acrylic acid (1.64 g, 10 mmol) in 2-ethoxyetha-
nol (80 mL) was added. The reaction mixture was stirred continu-
ously at 45 °C for 48 h under nitrogen. A white precipitate formed.
The mixture was cooled to 0 °C and diluted with ice water (200 mL)
and extracted with CHCl3 (3 × 100 mL). The organic phase was
treated with 2% aq HCl (100 mL), washed with H2O (3 × 100 mL)
and then dried (Na2SO4). The solvent was removed under reduced
pressure (100 hPa) and the residue was recrystallized from acetone–
hexane (5:1) to give 6 as colorless solid.
Yield: 1.4 g (65%).
4-{[10-({10-[(10-Bromodecyl)oxy]decyl}oxy)decyl]oxy}benzoic
Acid (9)
A mixture of 2 (1.35 g, 2.20 mmol), K2CO3 (0.69 g, 5.00 mmol) and
4-hydroxybenzoic acid (0.28 g, 2.00 mmol) in MeCN (100 mL) was
heated to reflux for 24 h under nitrogen. A white precipitate formed.
The mixture was cooled to 0 °C, diluted with ice water (200 mL)
and extracted with CHCl3 (3 × 150 mL). The organic phase was
washed with 2% aq HCl (100 mL), with H2O (3 × 100 mL) and was
dried (Na2SO4). The solvent was evaporated to dryness under re-
duced pressure (100 hPa) and the residue was recrystallized from
MeCN–H2O (1:1) to obtain 9 as colorless soft crystals.
Yield: 1.60 g (42%).
(E)-3-(4-{[10-({10-[(10-Bromodecyl)oxy]decyl}oxy)de-
cyl]oxy}phenyl)acrylic Acid (7)
Yield: 1.11 g (83%).
A mixture of 2 (1.90 g, 3.1 mmol), K2CO3 (0.91 g, 6.6 mmol) and
(E)-3-(4-hydroxyphenyl)acrylic acid (0.50 g, 3.0 mmol) in DMF
(130 mL) was kept at 40 °C for 24 h, stirring continuously. The re-
action mixture was cooled to 0 °C, then poured into 2% HCl (250
mL, 0 °C) followed by extraction with CHCl3 (3 × 100 mL). The
combined organic fractions were washed with 5% aq NaOH
(3 × 100 mL), with H2O (3 × 100 mL) and was dried (Na2SO4). The
solvent was evaporated and the residual golden oil was taken up in
H2O (80 mL) and stirred for 3 h at r.t. The pale yellow precipitate
obtained was collected by filtration. The crude product was recrys-
tallized from MeCN–H2O (1:1) and kept at 4 °C overnight to obtain
7 as a colorless powder.
(E)-3-[4-({10-[(10-{[10-({10-[(10-Bromodecyl)oxy]de-
cyl}oxy)decyl]oxy}decyl)oxy]decyl}oxy)phenyl]acrylic Acid
(10)
A mixture of 4 (2.7 g, 3.1 mmol), K2CO3 (0.91 g, 6.6 mmol) and
(E)-3-(4-hydroxyphenyl)acrylic acid (0.50 g, 3.0 mmol) in DMF
(130 mL) was heated at 45 °C for 24 h, stirring continuously. The
reaction mixture was cooled to 0 °C, then poured into 2% HCl (250
mL, 0 °C) and extracted with CHCl3 (3 × 100 mL). The combined
organic fractions were washed with 5% aq NaOH (3 × 100 mL),
with H2O (3 × 100 mL) and were dried (Na2SO4). The solvent was
evaporated and the residual golden oil was taken up in H2O (50 mL)
and stirred for 48 h at r.t. The pale yellow precipitate obtained was
collected by filtration. The crude product was recrystallized from
acetone–H2O (2:1) and kept at 4 °C for 24 h to obtain 10 as a color-
less powder.
Yield: 1.0 g (48%).
3-(4-{[10-({10-[(10-Bromodecyl)oxy]decyl}oxy)decyl]oxy}phe-
nyl)propanoic Acid (8)
A mixture of 2 (1.90 g, 3.1 mmol), K2CO3 (0.91 g, 6.6 mmol) and
3-(4-hydroxyphenyl)propanoic acid (0.51 g, 3.0 mmol) in DMF
(130 mL) was kept at 40 °C for 24 h, stirring continuously. The re-
action mixture was cooled to 0 °C, then poured into 2% HCl (250
mL, 0 °C) followed by extraction with CHCl3 (3 × 100 mL). The
combined organic fractions were washed with 5% aq NaOH
(2 × 100 mL), with H2O (3 × 100 mL) and was dried (Na2SO4). The
solvent was evaporated and the residual dark-yellow oil was taken
up in H2O (50 mL) and stirred for 3 h at r.t. The yellow precipitate
obtained was collected by filtration. The crude product was recrys-
Yield: 1.0 g (48%).
(E)-3-{4-[(10-{[10-({10-[(10-{[10-({10-[(10-Bromodecyl)oxy]
decyl}oxy)decyl]oxy}decyl)oxy]decyl}oxy)decyl]oxy}de-
cyl)oxy]phenyl}acrylic Acid (11)
A mixture of 5 (5.50 g, 4.44 mmol), (E)-3-(4-hydroxyphenyl)acryl-
ic acid (0.73 g, 4.45 mmol) and K2CO3 (1.23 g, 8.91 mmol) in
MeCN (160 mL) was stirred continuously at 40 °C for 24 h under
nitrogen. The reaction mixture was cooled to 0 °C, then poured into
2% HCl (250 mL, 0 °C) and extracted with CHCl3 (3 × 100 mL).
Synthesis 2005, No. 18, 3051–3058 © Thieme Stuttgart · New York

3056
E. Gogritchiani et al.
PAPER
Table 3 Characterization of w-Bromo (Long-Chain) Surfactants 6–11
Producta Molecular formula, MALDI-TOF
FT-IR (KBr)
(cm–1)
1H NMR (400 MHz, CDCl3) d, 3J 13C NMR (400 MHz,
(Hz) CDCl3) d (Hz)
(calcd, g·mol–1)
m/z (%)
6
C19H27BrO3
(383.32)
384 (100), 382
(60), 152 (75)
3248, 2917, 2850, 1667,
1602, 1573, 1512, 1477,
1426, 1311, 1244, 1175,
1044, 978, 830, 507
7.60 (d, 1 H, J = 15.9), 7.19 (d, 2 170.4, 156.4, 148.0,
H, J = 8.5), 6.72 (d, 2 H, J = 8.5), 127.2, 126.7, 115.5,
6.42 (d, 1 H, J = 15.9), 3.94 (t, 2 114.5, 68.9, 33.8,
H, J = 6.4), 3.31 (m, 2 H), 1.80
32.7, 29.7, 28.7, 28.0,
26.0
(m, 2 H), 1.22–1.42 (m, 14 H)
7
C39H67BrO5
(695.85)
700 (0.5), 699
(10), 697 (2),
696 (100), 152
(80)
3306, 2916, 2852, 1704,
1637, 1603, 1514, 1474,
1312, 1262, 1172, 1016,
817
7.61 (d, 1 H, J = 16.0), 7.19 (d, 2 170.5, 156.5, 148.0,
H, J = 8.5), 6.70 (d, 2 H, J = 8.5), 127.1, 126.8, 115.7,
6.41 (d, 1 H, J = 16.0), 3.94 (t, 2 114.4, 72.4, 69.3,
H, J = 6.4), 3.37 (t, 8 H, J = 6.5), 33.7, 32.8, 30.1, 29.6,
(3.30 (m, 2 H), 1.79 (m, 2 H), 1.71 28.6, 26.1
(d, 2 H, J = 6.3), 1.46 (m, 8 H),
1.22–1.30 (m, 36 H)
8
C39H69BrO5
(697.87)
702 (0.2), 701
(10), 699 (45),
697 (100), 152
(58)
3410, 3345, 2985, 2920,
2855, 1463, 1362, 1057,
1017, 970, 612
7.02 (d, 2 H, J = 8.3), 6.73 (d, 2
178.1, 154.3, 128.6,
H, J = 8.3), 3.94 (t, 2 H, J = 6.4), 131.0, 114.5, 72.4,
3.37 (t, 8 H, J = 6.5), (3.30 (m, 2 68.9, 33.7, 32.7, 30.1,
H), 2.82 (m, 2 H), 2.59 (m, 2 H), 29.7, 28.6, 26.0
1.79 (m, 2 H), 1.71 (d, 2 H,
J = 6.3), 1.44 (m, 8 H), 1.23–1.28
(m, 36 H)
9
C37H65BrO5
(669.81)
674 (1.7), 673
(11.4), 672
(7.5), 671 (28),
670 (100), 668
(95), 152 (43)
3400, 3345, 2920, 2849,
1461, 1360, 1057, 1017,
970, 613
8.02 (d, 2 H, J = 8.7), 7.01 (d, 2
H, J = 8.7), 3.94 (t, 2 H, J = 6.4), 122.0, 114.6, 72.4,
3.37 (t, 8 H, J = 6.5), (3.30 (m, 2 68.9, 33.6, 32.7, 30.1,
H), 1.78 (m, 2 H), 1.71 (d, 2 H,
J = 6.3), 1.46 (m, 8 H), 1.21–1.28
(m, 36 H)
169.1, 162.5, 131.4,
29.7, 28.6, 26.1
10
C59H107BrO7
(1008.38)
1012 (6), 1011
(26), 1010 (68), 1639, 1603, 1514, 1474,
1009 (26), 1008 1312, 1260, 1172, 1018,
3308, 2916, 2853, 1704,
7.61 (d, 1 H, J = 15.9), 7.19 (d, 2 170.5, 156.6, 148.0,
H, J = 8.5), 6.71 (d, 2 H, J = 8.5), 127.0, 126.8, 115.7,
6.41 (d, 1 H, J = 15.9), 3.94 (t, 2 114.4, 72.4, 69.8,
(100), 1007
819
H, J = 6.4), 3.37 (t, 16 H,
33.7, 32.7, 30.1, 29.6,
(90), 152 (68)
J = 6.5), (3.30 (m, 2 H), 1.79 (m, 28.6, 26.1
2 H), 1.71 (d, 2 H, J = 6.3), 1.46
(m, 16 H), 1.21–1.29 (m, 60 H)
11
C79H147BrO9
(1320.91)
1326 (3), 1324
(11), 1323 (41), 1637, 1601, 1514, 1474,
1321 (100),
1320 (92), 152
(74)
3310, 2920, 2852, 1707,
7.62 (d, 1 H, J = 16.0), 7.19 (d, 2 170.6, 156.6, 148.0,
H, J = 8.5), 6.70 (d, 2 H, J = 8.5), 127.0, 126.8, 115.7,
6.41 (d, 1 H, J = 16.0), 3.94 (t, 2 114.4, 72.4, 69.8,
1315, 1262, 1176, 1016,
819
H, J = 6.4), 3.37 (t, 24 H,
33.7, 32.7, 30.1, 29.6,
J = 6.5), (3.30 (m, 2 H), 1.79 (m, 28.7, 26.1
2 H), 1.71 (d, 2 H, J = 6.3), 1.46
(m, 24 H), 1.20–1.30 (m, 84 H)
a Satisfactory microanalyses obtained: C 0.06, H 0.03 (all samples are essentially nitrogen-free).
The combined organic fractions were washed with 5% aq NaOH
(3 × 100 mL), with H2O (3 × 100 mL) and were dried (Na2SO4).
The removal of solvent gave a yellow liquid-crystalline crude prod-
uct (3.05 g) that was taken up in H2O (50 mL). Stirring for 72 h pro-
duced a yellow precipitate which was dried in high vacuum (yield
2.1 g, 47%). Further recrystallization attempts failed, however CH
analysis was within acceptable limits for 11.
pale yellow liquid-crystalline product obtained was collected by fil-
tration and dried in high vacuum.
Yield: 0.81 g (46%); mp 147 °C (dec.)
(2E)-3-[4-({10-[(10-{[10-(Sodiumsulfothio)decyl]oxy}de-
cyl)oxy]decyl}oxy)phenyl]acrylic Acid (13)
A mixture of 7 (0.90 g, 1.30 mmol) and Na2S2O3 (0.62 g, 3.90mmol)
in H2O (100 mL) was continuously stirred at 40 °C for 24 h under
nitrogen. The reaction mixture was cooled to 0 °C, diluted with ice
water (120 mL) and stirred under ice cooling for 3 h. The precipitate
was then filtered off. The solid residue was taken up in Et2O (20
mL) and stirred under reflux for 1 h and then at r.t. for 5 h. The col-
orless solid obtained was collected by filtration and dried in vacu-
um.
(2E)-3-(4-{[10-(Sodiumsulfothio)decyl]oxy}phenyl)acrylic Acid
(12)
A mixture of 6 (1.53 g, 4.00 mmol) and Na2S2O3 (1.90 g, 12.00
mmol) in H2O (100 mL) was continuously stirred at 40 °C for 24 h
under nitrogen. The precipitate was extracted with CHCl3 (3 × 50
mL) and dried (Na2SO4). After the solvent was evaporated under re-
duced pressure (100 hPa), the oily residue was taken up in n-pentane
(50 mL), heated to reflux for 2 h and kept at 4 °C overnight. The
Yield: 0.72 g (74%); mp 73–74 °C.
Synthesis 2005, No. 18, 3051–3058 © Thieme Stuttgart · New York

PAPER
Long-Chain Organic Thiosulfates
3057
Table 4 Characterization of w-Thiosulfato (Long-Chain) Surfactants (Bunte Salts) 12–17
Producta Molecular formula MALDI-TOF
FT-IR (KBr)
(cm–1)
1H NMR (400 MHz, DMSO-d6) d, 3J (Hz) 13C NMR (400 MHz,
DMSO-d6) d (Hz)
(calcd, g·mol–1)
m/z (%)
12
13
14
15
16
17
C19H27NaO6S2
(438.53)
441 (1.8), 440
3392, 3327, 2921, 7.57 (d, 2 H, J = 8.5), 7.51 (d, 1 H,
171.5, 157.0, 148.1,
(11), 439 (23), 2850, 1461, 1360, J = 15.9), 6.97 (d, 2 H, J = 8.5), 6.39 (d, 1 128.1, 126.5, 116.5,
438 (100), 152 1065, 1017, 970, H, J = 8.5), 3.99 (t, 2 H, J = 6.4), 3.43 (m, 114.8, 72.5, 68.4,
(39)
620
2 H), 1.68 (m, 2 H), 1.22–1.42 (m, 14 H)
29.8, 29.2, 28.7, 28.0,
25.9
C39H67NaO8S2
(751.06)
754 (0.4), 753
3396, 3329, 2921, 7.63 (m, 3 H), 6.93 (d, 2 H, J = 8.5), 6.49 (d, 172.5, 158.0, 149.1,
(15), 752 (23), 2850, 1461, 1360, 1 H, J = 15.8), 4.11 (t, 2 H, J = 6.6), 3.99 (t, 128.1, 126.5, 116.5,
751 (49), 750 1058, 1017, 970, 2 H, J = 6.4), 3.39 (m, 8 H), 1.59–1.72 (m, 114.8, 72.5, 68.4,
(100), 152 (24) 613
12 H), 1.25 (m, 36 H)
30.7, 30.1, 29.5, 28.7,
28.0, 25.9
C39H69NaO8S2
(753.08)
757 (1.6), 755
(6), 754 (22),
753 (52), 752
3396, 2995, 2921, 7.04 (d, 2 H, J = 8.3), 6.76 (d, 2 H, J = 8.3), 177.2, 155.0, 131.2,
2850, 1461, 1360, 3.94 (t, 2 H, J = 6.4), 3.39 (t, 8 H, J = 6.4), 128.2, 116.3, 72.5,
1060, 1017, 972, (3.30 (m, 2 H), 2.82 (m, 2 H), 2.56 (m, 2 H), 69.7, 36.4, 33.9, 30.1,
(100), 152 (56) 615
1.79 (m, 2 H), 1.70 (d, 2 H, J = 6.3), 1.44
(m, 8 H), 1.23–1.28 (m, 36 H)
29.9, 29.3, 28.7, 27.7,
25.8
C37H65NaO8S2
(725.03)
727 (13), 726
3397, 3331, 2921, 7.90 (d, 2 H, J = 8.8), 6.86 (d, 2 H, J = 8.8), 165.7, 162.9, 132.1,
(10), 725 (0.7), 2850, 1461, 1360, 3.58 (m, 10 H), 3.35 (t, 2 H, J = 6.7), 1.80 122.0, 114.8, 72.5,
724 (100), 152 1057, 1017, 613
(23)
(m, 2 H), 1.45–1.53 (m, 10 H), 1.24 (m, 36 69.1, 36.4, 33.9, 30.1,
H)
29.9, 29.3, 28.7, 27.9,
25.8
C59H107NaO10S2
(1063.59)
1067 (8), 1066 3399, 2921, 2850, 7.56 (d, 1 H, J = 16.0), 7.44 (d, 2 H,
(16), 1065 (85), 1740, 1461, 1361, J = 8.5), 6.68 (d, 2 H, J = 8.5), 6.41 (d, 1 H, 128.4, 126.0, 117.0,
1064 (3), 1063 1260, 1058, 1019, J = 16.0), 3.88 (m, 2 H), 3.56–3.60 (m, 18 114.9, 72.5, 68.4,
172.7, 158.5, 149.3,
(100), 152 (43) 615
H), 1.45–1.72 (m, 26 H), 1.24 (m, 54 H)
30.7, 30.1, 29.5, 28.7,
28.0, 25.9
C79H147NaO12S2
(1376.13)
1380 (0.2),
3400, 2921, 2850, 7.54 (d, 1 H, J = 15.9), 7.30 (d, 2 H,
173.5, 158.7, 148.8,
1379 (13), 1378 1740, 1462, 1361, J = 8.5), 6.38 (d, 2 H, J = 8.5), 6.27 (d, 1 H, 127.6, 126.3, 116.0,
(15), 1377
(100), 1375
(82), 152 (38)
1262, 1058, 1018, J = 15.9), 4.06 (m, 2 H), 3.58 (m, 26 H),
615 1.45–1.72 (m, 28 H), 1.24 (m, 84 H)
115.2, 72.5, 68.4,
31.0, 30.3, 29.5, 28.9,
28.6, 26.2
a Satisfactory microanalyses obtained: C 0.05, H 0.03 (all samples are essentially nitrogen-free).
3-[4-({10-[(10-{[10-(Sodiumsulfothio)decyl]oxy}decyl)oxy]de-
cyl}oxy)phenyl]propanoic Acid (14)
(2E)-3-{4-[(10-{[10-({10-[(10-{[10-(Sodiumsulfothio)de-
cyl]oxy}decyl)oxy]decyl}oxy)decyl]oxy}decyl)oxy]phe-
nyl}acrylic Acid (16)
A mixture of 8 (0.91 g, 1.30 mmol) and Na2S2O3 (0.62 g, 3.90
mmol) in H2O (100 mL) was stirred continuously at 40 °C for 24 h
under nitrogen. The reaction mixture was cooled to 0 °C, diluted
with ice water (120 mL) and stirred under ice cooling for 3 h. The
precipitate was then filtered off. The solid residue was taken up in
Et2O (30 mL) and stirred under reflux for 2 h and then at r.t. for 24
h. The colorless solid obtained was collected by filtration and dried
in vacuum.
A mixture of 10 (1.51 g, 1.50 mmol) and Na2S2O3 (0.71 g, 4.50
mmol) in H2O (100 mL) was heated at 45 °C for 24 h under nitro-
gen. The mixture was cooled to 0 °C, diluted with ice water (120
mL) and stirred under ice cooling for additional 5 h. The water was
decanted off and the oily product was taken up in benzene, heated
to reflux for 15 min and precipitated with n-hexane. The mixture
was kept at 4 °C for 24 h. The pale yellow precipitate obtained was
collected by filtration and dried in high vacuum.
Yield: 0.70 g (72%); mp 75–76 °C.
Yield: 1.05 g (66%); mp 68 °C.
4-({10-[(10-{[10-(Sodiumsulfothio)decyl]oxy}decyl)oxy]de-
cyl}oxy)benzoic Acid (15)
(2E)-3-(4-{[10-({10-[(10-{[10-({10-[(10-{[10-(Sodiumsulfo-
thio)decyl]oxy}decyl)oxy]decyl}oxy)decyl]oxy}decyl)oxy]decyl}
oxy)decyl]oxy}phenyl)acrylic Acid (17)
A mixture of 9 (1.00 g, 1.50 mmol) and Na2S2O3 (0.71 g, 4.50
mmol) in H2O (100 mL) was heated at 45 °C for 24 h under nitro-
gen. The mixture was cooled to 0 °C, diluted with ice water (120
mL) and stirred under ice cooling for additional 2 h. The precipitate
was filtered off, washed with Et2O and dried to obtain a colorless
solid.
An aqueous solution (150 mL) of Na2S2O3 (3.63 g, 23 mmol) was
added to 11 (3.04 g, 2.30 mmol). The reaction mixture was heated
to 40 °C for 24 h under nitrogen. After the mixture was cooled to
0 °C, diluted with ice water (200 mL) and stirred an additional 2 h
at r.t., the water was decanted off. The oily product was taken up in
benzene, heated to reflux for 15 min and precipitated with n-hexane.
The mixture was kept at 4 °C for 24 h. The pale yellow precipitate
obtained was collected by filtration and dried in high vacuum.
Yield: 0.70 g (64%); mp 73 °C.
Yield: 2.52 g (82%); mp 61–62 °C.
Synthesis 2005, No. 18, 3051–3058 © Thieme Stuttgart · New York

3058
E. Gogritchiani et al.
PAPER
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Financial support from the Volkswagen-Foundation (77728) and
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Synthesis 2005, No. 18, 3051–3058 © Thieme Stuttgart · New York