Synthesis, stereochemistry and adsorption studies of new spiranes and polyspiranes containing 1,2-dithiolane units

Article abstract of DOI:10.1002/jhet.5570440303

(Chemical Equation Presented) The synthesis and stereochemistry of a series of new cyclic disulfides containing (poly)spirane 1,2-dithiolane units are reported. Also included is a study of the self-assembled monolayers (SAMs) of these compounds on a gold

Full text of DOI:10.1002/jhet.5570440303

May-Jun 2007
521
Synthesis, Stereochemistry and Adsorption Studies of New Spiranes
and Polyspiranes Containing 1,2-Dithiolane Units
Radu A. Gropeanu1, Mihaela L. ꢀînꢁaꢂ1, Catherine Pilon2, Mario Morin2, Livain Breau2,3,
Raluca Turdean1 and Ion Grosu1,
1"Babes-Bolyai" University, Organic Chemistry Department and CCOCCAN, 11 Arany Janos str., RO-400028,
Cluj-Napoca, ROMANIA. Fax: 40 26459 0818; Tel: 40 26459 3833
2Département de Chimie, Université du Québec à Montréal, H3C 3P8, CP 8888, Succ. Centre Ville, Montréal,
Québec, CANADA ;
3Laboratoire de Synthèse Organique Apliquée, Université du Québec à Montréal, H3C 3P8, CP 8888, Succ.
Centre Ville, Montréal, Québec, CANADA.
* Corresponding Author: e-mail adress: igrosu@chem.ubbcluj.ro
Received February 5, 2006
R1
O
R2 R1
R2 R1
R2
O
O
S
O
O
O
R1
R2
O
O
R1
R2
O
O
Br
Br
Na2S2
Au(111)
S
S
S
S
S
S
S
Gold Substrate
where R1, R2 = H, methyl, phenyl, 1-naphthyl,
or R1- R2 = (un)substituted cyclohexyl
The synthesis and stereochemistry of a series of new cyclic disulfides containing (poly)spirane 1,2-
dithiolane units are reported. Also included is a study of the self-assembled monolayers (SAMs) of these
compounds on a gold surface. The characteristics of the resultant SAMs were determined by IR
spectroscopy using molecular mechanics calculations.
J. Heterocyclic Chem., 44, 521 (2007).
cleavage of a bisthiocyanate with TBAF [17], or c) the
steam distillation of an appropriate Bunte salt [18].
INTRODUCTION
The preparation and the characterization of SAMs from
oriented organic molecules are of great interest
particularly in those fields for which interface properties
are important [1]. Studies in electrochemistry [2],
vibrational spectroscopy [3], biological membranes [4],
electrical conduction [5], catalysis [6], photolithography
[7] and nanostructures [8] demonstrate just how important
these highly organized SAMs can be.
For those substrates having more than one anchor per
molecule, a stronger interaction is observed between the
organic species and the metal surface. This is particularly
the case when sulfur atoms are chelated within a ring [9].
1,2-Dithiane [10] and 1,2-dithiolane [11] rings were
effectively bound as the disulfide in deposition
experiments on gold. These SAMs were studied via IR
spectroscopy and cyclic voltammetry.
These cyclic disulfides can be synthesized by two
different pathways [12]. One involves the direct
conversion of a dihalide or a ditosylate using sodium
disulfide (prepared from sodium sulfide and sulfur [13])
or via tetrathiotungstates (as a sulfur transfer agent [14]).
The second path is based on the oxidation of a dithiol with
various oxidants [15].
We were interested in obtaining SAMs from complex
1,2-dithiolane derivatives having a spirane skeleton since
such structures combine common motifs of simple alkyl
chain with cyclic disulfide and have a high degree of
organization as well as being relatively flexible. Both of
these properties are important if one wishes to obtain
compact, uniform monolayers. When one considers the
retro-synthesis of the target SAMs, the first step is the
adsorption of a suitable disulfido-(poly)spirane onto the
gold surface. A (poly)spirane having a terminal disulfide
could potentially be prepared from the corresponding 5,5-
bis(bromomethyl)-1,3-dioxane (Scheme I).
Scheme I
S
S
S
R2
O
R1
O
P
P
P
S
R2
O
R1
O
A
C
E
R
A
C
E
R
A
C
E
R
P
A
C
E
R
S
S
S
S
S
S
S
S
Br
Br
S
S
Gold substrate
where R1, R2 = H, methyl, phenyl, 1-naphthyl,
or R1- R2 = (un)substituted cyclohexyl
RESULTS AND DISCUSSION
Other methods for the synthesis of these cyclic disulfides
involve a) the reaction of a 1,3-dielectrophile with S4
2-
Synthesis of (poly)spiranes containing 1,2-dithiolane
(followed by the desulfurization with copper [16]), b) the
units. The starting 5,5-bis(bromomethyl)-1,3-dioxane

522
R. Gropeanu, M.Tintas, C. Pilon, M. Morin, L. Breau, R. Turdean and I. Grosu
Vol 44
derivatives (1-7) were obtained by ketalization reaction of
the appropriate carbonyl compound with 2,2-bis(bromo-
methyl)-1,3-propanediol [19].
(Scheme IV) and 14. These isomers are due to the
chirality of the spirane units with six-membered
rings [23,24] and to the fact that the peripheral rings
of the di or polyspirane skeleton may be in syn or
anti positions [25-28]. The flipping of the 1,3-
dioxane, cyclohexane and 1,2-dithiolane rings results
in the conformational equilibration of all the
possible isomers.
Spiranes 9 and 10 do not have the same substituents on
the 1,3-dioxane units thus these rings are anancomeric.
The flipping of the heterocycle shifts the conformational
equilibrium towards that conformation having the most
bulky substituent equatorial (Scheme V; Ph for 9 and Me
for 10; for similar cases see references [29-31]).
Dispiranes 12 and 13 have semi-flexible structures
(Scheme VI), the cyclohexane ring being rigid, its
We modified a procedure previously reported by
Chorbadijev et al [20] for the synthesis of the 1,2-
dithiolane (poly)spirane derivatives, 7-14, (Scheme II).
This group reported a synthesis for acyclic disulfides via
substitution of a halide atom with disodium disulfide
(previously generated from sulfur and sodium hydroxide).
In order to increase the yield of the cyclic disulfide via
suppression of polymer generation we greatly reduced the
reagent concentrations (from 0.5 M to 0.03 M).
The desired (poly)spiranes were obtained in fair to good
yields (35-74% for 8-13 and 27% for 14) after separation
with flash chromatography. Mass and NMR spectra of the
products confirmed the assigned structures.
Scheme II
EtOH, reflux
6 NaOH
+
6 S
2 Na2S2
+
Na2S2O3
+
3 H2O
1 hr.
9
O
10
1
R1
8
R2
2
3
R1
R2
O
O
Br
Br
EtOH, reflux
4 hrs.
S
S
4
+
Na2S2
5
6
O
7
1: R1 = CH3, R2 = CH3
2: R1 = H, R2 = C6H5
8: R1 = CH3, R2 = CH3
9: R1 = H, R2 = C6H5
3: R1 = CH3, R2 = C6H5
10: R1 = CH3, R2 = C6H5
12 13 14 15
1
2
3
O
EtOH, reflux
4 hrs.
O
O
Br
Br
S
S
R
8
5
+
Na2S2
R
11
O
10
9
7
6
4
4: R = H
5: R = C6H5
6: R = CH3
11: R = H
12: R = C6H5
13: R = CH3
20 21 22 23
18 19
14
24
5
1
4
EtOH, reflux
4 hrs.
17
16
O
11
O
O
Br
Br
O
O
O
O
Br
Br
2
3
S
S
S
S
8
9
+
Na2S2
O
7
15
13 12 10
6
7
14
Stereochemistry of (Poly)spiranes Containing
1,2-Dithiolane Units. In order to better understand
the structure of SAMs a stereochemistry study of
these spiranes was carried out. Monospirane 8,
dispirane 11 and tetraspirane 14 all have
symmetrically substituted six-membered rings and
exhibit flexible structures. The six-membered rings
prefer the chair conformation, while for the 1,2-
dithiolane ring we propose (based on data published
[21,22] for similar compounds) the envelope
conformer with the spirane moiety out of the plane.
The conformational equilibria are running between
homomeric structures in 8 (Scheme III) and between
syn and anti isomers in the cases of compound 11
Scheme III
S
2
S
B
1
S
B
O
S
B
9
A
3
H3C
10
O
O
5
H3C
A
O
4
8
7
6
CH3
CH3
A
A
CH3
CH3
B
O
A
O
A
H3C
H3C
O
O
B
S
B
S
S
S
8

May-Jun 2007 Synthesis, Stereochemistry and Adsorption Studies of New Spiranes and Polyspiranes
523
Scheme VI
substituents are efficient “holding groups” while the 1,3-
S2
S 3
C
dioxane and 1,2-dithiolane moieties flip, equilibrating any
possible stereoisomers (VII-X). The H NMR spectra of
12 and 13 do not differentiate between the axial or
equatorial protons of the heterocycles. Nonetheless,
different signals (singlets) were observed for the
1
R1
1
14
B
A
15
B
O
13
A
5
12
4
O
O
B
7
8
9
6
O
C
S
R1
11
S
syn (P)
IX
10
syn (M)
VII
diastereotopic positions at 6 and 15 (12: ꢀ6 = 3.81, ꢀ15
3.85, ꢀ1,4 = 3.04 ppm and 13: ꢀ6 = 3.71, ꢀ15 = 3.76, ꢀ1,4
2.98 ppm).
=
=
C
B
C
R1
S
C
S
A
Scheme IV
B
O
O
2
S
C
B
O
O
S
C
1
A
C
S
3
S
14
S
R1
15
C
anti (M)
anti (P)
13
O
S
O
5
B
6
VIII
X
4
O
B
12
11
O
7
8
A
12, 13
A
9
syn (M)
anti (P)
II
I
10
Adsorption studies. Individual gold (111) surfaces
were treated with one of each of the cyclic disulfides, 11-
14, in ethanol and the deposits were analyzed by IR
spectroscopy. The collected data are presented in Table 1
and some details of the IR spectra of 11-14 are shown in
Figure 1. The assignment of the vibrational bands and the
direction and magnitudes of the vibrational dipole
moments were obtained from Hartree-Fock calculations
done with Gaussian 98® software. The widths of the
bands at half-height in the IR spectra are in the range of
20-40 cm-1 which suggests that the molecules are
disordered on the gold surface. Also, the methylene
ꢁa(CH2) band at 2926-2930 cm-1 (that is present in all
samples) is indicative of a liquid like monolayer. This
disorder is probably due to the complex and relatively
rigid structure of the molecules which results in a large
distance between the adsorbed molecules and thus few
stabilizing inter-adsorbate interactions that usually results
in efficient self-assembly processes.
B
A
S
C
S
A
O
O
B
C
S
B
O
O
A
S
syn (P)
syn (P)
III
III
C
A
A
O
B
O
O
B
C
S
O
C
S
S
S
syn (P)
anti (P)
II
S
III
A
B
S
C
A
O
O
B
O
O
B
A
C
S
anti (M)
anti (M)
S
IV
IV
11
Although the monolayer is not very organized, some
information on the orientation of the adsorbed molecules
could be drawn from the IR investigations. Our analysis
of the IR spectra are based on the direction of the
vibrational dipole moments obtained from a compu-
tational chemistry calculation and the infrared surface
selection rule for adsorbates on metallic substrates [32]
which states that a vibrational mode is IR active if there is
a component of its dipole moment perpendicular to the
surface.
Scheme V
R2
S
B
S
A
O
R1
O
A
R2
A
O
O
B
S
R1
S
VI
V
2
S
B
S
B
1
S
S
3
9
O
B
10
O
O
R2
R2
A
5
A
6
4
O
8
R1
7
R1
VI''
VI'
The analysis of the wave numbers and intensity of the
vibrational bands of compounds 12 and 14 adsorbed on
gold suggest that they adopt the orientations shown in
Figures 2. Also, it is likely that both compounds bind to
the surface via at least two of their sulfur atoms, as
disulfides are known to dissociate upon adsorption on
gold [33].
9
: R1 = H, R2 = C6H5
10: R1 = C6H5, R2 = CH3
The diastereotopicity of positions 6 and 15 was also
observed in the 13C NMR (12: ꢀ 6 = 66.32, ꢀ 15 = 66.50
ppm and 13: ꢀ 6 = 66.34, ꢀ 15 = 66.61 ppm). Position 6 is
procis while position 15 is protrans with respect to a
substituent at 11.
In the case of compound 12, the absence of C-H
deformation band for the aromatic ring in the range

524
R. Gropeanu, M.Tintas, C. Pilon, M. Morin, L. Breau, R. Turdean and I. Grosu
Vol 44
1400-1500 cm-1, suggests that the aromatic substituent in
12 is lying in either plane relatively parallel or
perpendicular to the gold surface. Weak C-H aromatic
stretches above 3000 cm-1 are observed for compound
12. This makes it more likely that the aromatic group is
in a plane perpendicular to the surface as is shown in
Figure 2a. Also in this orientation, the methylene
deformation bands (not observed in the range of 1200 to
1300 cm-1) should be weaker than the methylene C-H
stretching bands.
Table 1
IR wave numbers (ꢀ/cm-1) of the SAMs for each cyclic disulfide 11-14 on a gold (111) surface
Assignment
11
12
13
14
ꢀa(=C-H, Ar)
ꢀa(=C-H, Ar)
ꢀa(=C-H, Ar)
ꢀa(CH3)
-
3065 (weak)
3031 (weak)
3017 (weak)
2959a
-
-
-
-
-
-
2961a (weak)
2928
-
-
2958a (weak)
2926
2958
2926
2869
2857
1154
ꢀa(CH2)
2930
2874a
ꢀs(CH3)
-
-
ꢀs(CH2)
2857
2856
2857
ꢀa(C-O-C)
1096
1131
1130
a due to a small amount contaminant containing a methyl group
a
b
c
d
Figure 1. IR spectra (details) of compounds 11 (a), 12 (b), 13 (c) and 14 (d) adsorbed on Au (111).

May-Jun 2007 Synthesis, Stereochemistry and Adsorption Studies of New Spiranes and Polyspiranes
525
a
b
c
Figure 2. Possible orientations of compounds 12 (a) and 14 (b and c) adsorbed on Au (111) suggested by the analysis of theirs IR spectra
The absence of CH deformation bands between 1300 and
1400 cm-1 suggests that 14 is not oriented perpendicular to
the surface but is rather parallel to the surface. In this
orientation the C-H deformation modes of methylenes will
have a low intensity. It is thus possible that compound 14 is
anchored to the surface by both 1,2-dithiolane rings (Figure
2c). However, this would require an important reorganization
(the twisting of the middle cyclohexane ring) of the
optimized structure shown in Figure 2b. Hence, it is more
likely that compound 14 adopt the orientation shown in
Figure 2b and adsorb via two sulfurs.
semi-flexible conformational behaviour. The adsorption
of some of these derivatives on a gold surface and the
structural behavior of the resultant SAMs were
investigated using computational chemistry modeling as
well as IR spectroscopy. They all appear to adopt a tilted
orientation and a disorder of the molecules orientations in
the monolayer was observed
EXPERIMENTAL
The solvents were purified according to standard procedures
and were distilled prior to use. Column chromatography: silica
gel 60 (Merck, Darmstadt). Thin layer chromatography (TLC):
silica gel layered aluminium foil (60 F254 Merck, Darmstadt).
Melting points (uncorrected) were taken using a Kleinfeld
APOTEK apparatus. Starting materials 1-7 were synthesized
according to a procedure reported in the literature [16]. NaOH
and sulfur were purchased from Merck and used without further
The more narrow bands (Figure 1) observed in the IR
spectra of 13 (c) and 14 (d) as compared with those find in
the spectra of 11 (a) and 12 (b) suggest a better organization
of the monolayers for 13 and 14 than for 11 and 12.
In the analysis of the monolayers generated by the
deposit of our derivatives on gold surface we considered
the compounds anchored by two sulfur atoms as the
literature data [34,35,36,37] suggest for disulfides. The
anchorage of the compounds on the gold surface by
disulfides is more efficient than the fixation on gold in the
case of the compounds anchored by only one sulfur atom
(e.g. alkylmercaptanes [1b]) and cyclic disulfides showed
to be efficient in the anchorage on gold of our spiro
derivatives (other complex molecules as porphyrins [38]
or catenanes [39] were successfully deposited on gold via
cyclic disulfides). The degree of organization of the
monolayers for our compounds is lower than in the case
of the monolayers formed by the adsorbtion of more
simple compounds (alkylmercaptanes [1b] or linear
amides [40]). The relative flexible behavior of the
1
purification. The H and 13C NMR spectra were recorded with
1
Varian Gemini 300 and Bruker ARX 300 (300 MHz for H and
75 MHz for 13C) spectrometers with CDCl3 as solvent. The
assignments of quaternary C (Cquat), CH, CH2 and CH3 were
made on the basis of APT or DEPT spectra. Mass spectra (EI, 70
eV) were recorded using a Varian MAT 311 spectrometer.
The IR spectra were recorded on a Nicolet Nexus 670 FTIR
spectrometer using a grazing angle ATR accessory. The incident
angle of the IR beam was 85o. The number of scans per
spectrum was 1000 and a resolution of 2 cm-1 was used. The
background spectrum was that of an uncoated gold film. A 5
points baseline correction was done for all IR spectra.
The optimisation of the structures and calculation of the IR
spectra were done with the Gaussian 98 software. A restricted
Hartree-Fock calculation using a 6-31G basis set was done on
the electronic ground states. The optimisation of the structures
was done using the Berny algorithm. Once the structure was
optimized, the IR spectrum was calculated. A correction was
done on the calculated wavenumbers. This consisted in
multiplying the numbers by a factor of approx. 0.9 as suggested
in the Gaussian manual because the IR wavenumbers are usually
overestimated. These calculations were used for qualitative
purposes to help in the interpretation of the IR spectra of
absorbed monolayers on gold. A complete study of the stability
of numerous structures of spiro compounds is beyond the scope
of this study.
absorbed spiro compounds determines
a
higher
organization of the monolayers for our compounds than it
was observed for the monoloyers obtained by the
adsorbtion of the disulfides of rigid substrates (e.g.
disulfides with aromatic groups [41]).
CONCLUSION
The synthesis by an original procedure of a series of
new (poly)spiranes containing 1,2-dithiolane rings as
cyclic disulfides leads to compounds with flexible or

526
R. Gropeanu, M.Tintas, C. Pilon, M. Morin, L. Breau, R. Turdean and I. Grosu
Vol 44
The monolayers of all compounds were formed as follow: a
11-Methyl-7,14-dioxa-2,3-dithia-dispiro[4.2.5.2]penta-
decan (13). Yellow solid, m.p.=99-101°C, yield 61%. Rf=0.45.
1H nmr: ꢀ = 0.87 (3H, d, J=6.6 Hz, 11-CH3), 1.09-1.67 (7H,
overlapped peaks), 2.13-2.18 (2H, overlapped peaks), 2.98 (4H,
s, H-1, H-4), 3.71 (2H, s, H-6), 3.76 (2H, s, H-15). 13C nmr: ꢀ =
21.73 (CH3), 30.76 (CH2), 31.87 (CH2), 31.92 (CH), 45.21
(CH2), 50.52 (Cquat), 66.34 (CH2), 66.61 (CH2), 98.47 (Cquat). ms:
m/z 240 (M+). Anal. Calcd. for C12H20O2S2: C, 55.35; H, 7.74;
S, 24.62. Found: C, 55.57; H, 7.92; S, 24.45.
7,12,20,23-Tetraoxa-2,3,16,17-tetrathia-tetraspiro[4.2.2.2.
4.2.2.2]tetracosan (14). Yellow solid, m.p.=151-2°C, yield
27%. Rf=0.35. 1H nmr: ꢀ = 1.87 (8H, s, H-9, H-10, H-21, H-22),
3.00 (8H, s, H-1, H-4, H-15, H-18), 3.76 (8H, s, H-6, H-13, H-
19, H-24). 13C nmr: ꢀ = 28.22 (CH2), 45.21 (CH2), 50.52 (Cquat),
66.60 (CH2), 98.47 (Cquat). ms: m/z 408 (M+). Anal. Calcd. for
C16H24O4S4: C, 47.03; H, 5.92; S, 31.39. Found: C, 47.21; H,
6.19; S, 31.30.
solution of 10-3 M concentration of the compounds in ethanol
was done. A gold substrate from Arrandee was annealed in a
natural gas flame in order to remove organic impurities and to
remove surface imperfections. The gold substrate was then
immersed in the adsorbate solution overnight. The adsorption of
disulfide compounds on gold is known to cause their
dissociation. It is thus expected that the compounds adsorb via
its two sulfur atoms. The resulting monolayers were then rinsed
with ethanol and dried before recording their IR spectra.
The elemental analyses were performed at IRCOF, University
of Rouen, France, and are in good agreement with the assigned
structures.
General method for the synthesis of the cyclic disulfides. A
mixture of 0.6 g of sodium hydroxide (15 mmol) and 0.48 g
sulfur (15 mmol) in 10 cm3 of 96% ethanol was refluxed for 1 h,
and was added over a solution of 5 mmol of starting material in
150 ml of 96% ethanol. After 4 h of reflux the reaction mixture
was cooled to rt and was added to a mixture of 200 cm3 of water
and 50 cm3 of methylene chloride. The aqueous layer was
separated, extracted with 2x50 cm3 of methylene chloride, the
organic layers were combined, washed with 100 cm3 of water
followed by 100 cm3 of brine and finally dried over sodium
sulfate. The residue was adsorbed on silica gel and was
separated (petroleum ether-methylene chloride = 1:1) to afford
the products.
Acknowledgements. We are grateful to PNCDI for financial
support (CERES program, grant 4-37). Special thanks to K.
Walsh for providing assistance with the editing of the
manuscript.
REFERENCES
[1a] Murray, R. W. Acc. Chem. Res. 1980, 13, 135-14; [b] Love,
J. C.; Estroff, L. A.; Kriebel, J. K.; Nuzzo, R. G.; Whitesides, G. M.
Chem. Rev. 2005, 105, 1103-1170.
[2a] Finklea, H. O. Electroanal. Chem. 1996, 19, 109-115; [b]
Chidsey, C. E. D.; Murray, R. W. Science 1986, 231, 25-31.
[3a] Rabolt, J. F.; Santo, R.; Swalen, J. D. Appl. Spectrosc. 1980,
34, 517-521; [b] Knoll, W.; Philpott, M. R.; Golden, W. G. J. Chem.
Phys. 1982, 77, 219-225.
8,8-Dimethyl-7,9-dioxa-2,3-dithiaspiro[4.5]decan (8).
1
Yellow solid, m.p.=51-2°C, yield 74%. Rf=0.55. H nmr: ꢀ =
1.37 (6H, s, 8-CH3ae), 2.94 (4H, s, H-1, H-4), 3.71 (4H, s, H-6,
H-10). 13C nmr: ꢀ = 23.65 (CH3), 45.08 (CH2), 50.30 (Cquat),
66.98 (CH2), 97.39 (Cquat). ms: m/z 206 (M+). Anal. Calcd. for
C8H14O2S2: C, 46.57; H, 6.84; S, 31.08. Found: C, 46.79; H,
7.03; S, 30.95.
[4a] Kornberg, R.D.; McConnell, H. M. Biochemistry 1971, 10,
1111-1120; [b] Chaki, N. K.; Vijayamohanan, K. Biosens. Bioelectron.
2002, 17, 1-12.
8-Phenyl-7,9-dioxa-2,3-dithia-spiro[4.5]decan (9). Yellow
1
solid, m.p.=67-69°C yield 52%. H nmr and 13C nmr spectra
[5a] Polymeropulos, E. E.; Sagiv, J. J. Chem. Phys. 1978, 69,
1836-1847; [b] Kevtyukhova, N. I.; Mallouk, T. E. Chem. Eur. J. 2002,
8, 4354-4363.
[6] Richard, M. A.; Deutsch, J.; Whitesides, G. M. J. Am. Chem.
Soc. 1979, 100, 6613-6625.
were found to be identical with the one described in Ref. [15].
8-Methyl-8-phenyl-7,9-dioxa-2,3-dithia-spiro[4.5]decan (10).
Yellow solid, m.p.=63°C, yield 60%. Rf=0.40. 1H nmr: ꢀ = 1.53
(3H, s, 8-CH3), 2.45 (2H, s, H-1), 3.71 (2H, s, H-4), 3.68 (2H, d,
J=11.1 Hz, H-6ax, H-10ax), 3.75 (2H, d, J=11.1 Hz, H-6eq, H-
10eq), 7.35-7.46 (5H, overlapped peaks, phenyl protons). 13C
nmr: ꢀ = 31.89 (CH3), 47.21 (CH2), 50.19 (Cquat), 67.99 (CH2),
101.04 (Cquat), 126.69 (CH) 128.07 (CH) 128.90 (CH) 139.90
(Cquat). ms: m/z 322 (M+). Anal. Calcd. for C13H16O2S2: C,
58.18; H, 6.01; S, 23.89. Found: C, 58.31; H, 6.17; S, 23.72.
7,14-dioxa-2,3-dithia-dispiro[4.2.5.2]pentadecan (11).
[7] Ronse,
K.; De Bisschop, P.; Goethals, A. M.; Hermans,
J.; Jonckheere, R.; Light, S.; Okoroanyanwu, U.; Watso, B.; MacAfferty,
D.; Ivaldi, J.; Oneil T.; Sewell, H. Microelectron. Eng. 2004, 73-74, 5-
10.
[8] Keating, C. D.; Natan, M. J. J. Adv. Mater. 2003, 15, 451-
454.
[9] Shon, Y.-S.; Lee, T. R. Langmuir 1999, 15, 1136-1140.
[10] Nuzzo, R. G.; Allara, D.L. J. Am. Chem. Soc. 1983, 105,
4481-4483.
[11] Herranz, M. A.; Yu, L.; Martin, N.; Echegoyen, L. J. Org.
Chem. 2001, 68, 8379-8385.
[12] Smith, M. B.; March, J. March’s Advanced Organic
Chemistry: Reactions, Mechanisms, and Structure, 5th; John Wiley &
Sons, Inc.: New York, 2001, pp. 498.
[13] Dodson, R. M.; Nelson, V. C. J. Org. Chem. 1968, 33, 3966-
3968.
1
Yellow solid, m.p.=84-6°C, yield 46%. Rf=0.45. H nmr: ꢀ =
1.38-1.73 ppm (10H, overlapped peaks), 2.96 (4H, s, H-1, H-4),
3.74 (4H, s, H-6, H-15). 13C nmr: ꢀ = 22.52 (CH2), 25.65 (CH2),
32.45 (CH2), 45.21 (CH2), 50.52 (Cquat), 66.14 (CH2), 98.90
(Cquat). ms: m/z 246 (M+). Anal. Calcd. for C11H18O2S2: C,
53.62; H, 7.36; S, 26.03 Found: C, 53.88; H, 7.54; S, 25.88.
11-Phenyl-7,14-dioxa-2,3-dithia-dispiro[4.2.5.2]pentadecan
1
(12). Yellow solid, m.p.=118-9°C, yield 56%. Rf=0.40. H nmr:
[14] Dhar, P.; Chidambaram, N.; Chandrasekaran, S. J. Org.
Chem. 1992, 57, 1699-1702.
[15] Harpp, D. N.; Gleason, J. G. J. Org. Chem. 1970, 35, 3259-
3263 and references cited therein.
[16] Backer, H. J.; Evenhuis, N. Recl. Trav. Chim. Pays-Bas 1937,
56, 129-136.
[17a] Burns, C. J.; Field, L. D.; Morgan, J.; Ridley, D. D.;
Vignevich, V. Tetrahedron Lett. 1999, 40(35), 6489-6492; [b] Folkins,
P. L.; Harpp, D. N. J. Org. Chem 1992, 57, 2013-2017.
ꢀ = 1.48-2.36 (8H, overlapped peaks), 2.53-2.63 (1H, m), 3.04
(4H, s, H-1, H-4), 3.81 (2H, s, H-6), 3.85 (2H, s, H-15), 7.18-
7.33 (5H, m, phenyl protons). 13C nmr: ꢀ = 30.04 (CH2), 32.46
(CH2), 43.83 (CH), 45.23 (CH2), 50.58 (Cquat), 66.32 (CH2),
66.50 (CH2), 98.90 (Cquat), 126.20 (CH) 126.90 (CH) 128.43
(CH), 146.38 (Cquat). ms: m/z 322 (M+). Anal. Calcd. for
C17H22O2S2: C, 63.32; H, 6.88; S, 19.89. Found: C, 63.50; H,
7.01; S, 19.75.

May-Jun 2007 Synthesis, Stereochemistry and Adsorption Studies of New Spiranes and Polyspiranes
527
[18] Affleck, J. G.; Dougherty, G. J. J. Org. Chem. 1950, 15,
865-868.
[19] Gropeanu, R. A.; Woiczechowski-Pop, A.; Tintas, M.;
Turdean, R.; Grosu, I. Studia Univ. Babes-Bolyai, Chem. 2005, 50, 247-
252.
1976, 4, 293-371.
[30] Mager, S.; Grosu, I. Stud. Univ. Babes-Bolyai, Chemia 1988,
33, 47-53.
[31] Grosu, I.; Plé, G.; Mager, S.; Mesaros, E.; Dulau, A.; Gego,
C. Tetrahedron 1998, 54, 2905-2916.
[20] Chorbadjiev, S.; Roumian C.; Markov, P. J. Prakt. Chem.
1977, 319, 1036-1038.
[21] Morera, E.; Lucente, G.; Ortar, G.; Nalli, M.; Mazza, F.;
Gavuzzo, E.; Spisani, S. Bioorganic & Medicinal Chemistry 2002 10,
147-157.
[32] Greenler, R. G. J. Chem. Phys. 1949, 44, 310-315.
[33] Fenter, P.; Eberhardt, A.; Eisenberg, P. Science 1994, 266,
1216-1218.
[34] Nuzzo, R. G.; Zegarski, B. R.; Dubois, L. H. J. Am. Chem.
Soc. 1987, 109, 733-740.
[22] Wilhelm, M.; Koch, R.; Strasdeit, H. New. J. Chem. 2002,
26, 560-566.
[35] Grönbeck, H.; Curioni, A.; Andreoni, W. J. Am. Chem. Soc.
2000, 122, 3839-3842.
[23] Grosu, I.; Mager, S.; Ple, G.; Horn, M. J. Chem. Soc., Chem.
Commun. 1995, 167-168.
[24] Grosu, I.; Mager, S.; Ple, G. J. Chem. Soc., Perkin Trans. 2
1995, 1351-1357.
[25] Grosu, I.; Mager, S.; Ple, G.; Mesaros, E. Tetrahedron 1996,
52, 12783-12798.
[26] Opris, D.; Grosu, I.; Toupet, L.; Ple, G.; Terec, A.; Mager S.;
Muntean, L. J. Chem. Soc., Perkin Trans. 1 2001, 2413-2420.
[27] Terec, A.; Grosu, I., Condamine, E.; Breau, L.; Ple, G.;
Ramondenc, Y.; Rochon, F. D.; Peulon-Agasse, V.; Opris, D.
Tetrahedron 2004, 60, 3173-3189.
[28] Cismaꢀ, C.; Terec, A.; Mager S.; Grosu, I. Curr. Org. Chem.
2005, 9, 1287-1314.
[29] Anteunis, M. J. O.; Tavernier D.; Borremans, F. Heterocycles
[36] Schönherr, H.; Kremer, F. J. B.; Kumar, S.; Rego, J. A.;
Wolf, H.; Ringsdorf, H.; Jaschke, M.; Butt, H.-J.; Bamberg, E. J. Am.
Chem. Soc. 1996, 118, 13051-13057.
[37] Yonezawa, T.; Yasui, K. Kimizuka, N. Langmuir 2001, 17,
271-273.
[38] Redman, J. E.; Sanders, J. K. M. Org. Lett. 2000, 2, 4141-
4144.
[39] Raehm, L.; Hamann, C.; Kern J.-M.; Sauvage, J.-P. Org. Lett.
2000, 2, 1991-1994.
[40] Vance, A. L.; Willey, T. M.; Nelson, A. J.; van Buuren, T.;
Bostedt, C.; Terminello, L. J.; Fox, G. A.; Engelhard M.; Baer, D.
Langmuir 2002, 18, 8123-8128.
[41] Garg, N.; Friedman J. M.; Lee, T. R. Langmuir 2000, 16,
4266-4271.