Synthesis of dicycloheptano- and dicyclooctanothiacrown ethers their properties as extractants

Article abstract of DOI:10.1023/A:1016039507532

12- and 15-Membered thia- and oxathiacrown ethers and podands containing cycloheptane and cyclooctane fragments have been synthesized. The properties of the synthesized compounds as extractants for Ra²⁺ and Pd²⁺ ions have been studied.

Full text of DOI:10.1023/A:1016039507532

Chemistry of Heterocyclic Compounds, Vol. 38, No. 4, 2002
SYNTHESIS OF DICYCLOHEPTANO-
AND DICYCLOOCTANOTHIACROWN
ETHERS THEIR PROPERTIES
AS EXTRACTANTS
D. V. Nasyrov, A. A. Bobyleva, A. A. Abramov, S. N. Anfilogova, M. A. Vasil'kov
and A. V. Anisimov
1
2- and 15-Membered thia- and oxathiacrown ethers and podands containing cycloheptane and
cyclooctane fragments have been synthesized. The properties of the synthesized compounds as
2+
2+
extractants for Ra and Pd ions have been studied.
Keywords: oxathiacrown compounds, thiacrown compounds, thiacrown ethers, extraction.
The intensive development of the chemistry of crown ethers and their heteroanalogs has led to the
creation of a large number of macrocycles which possess powerful complexing properties, which are increased
by the such electron donating units as aliphatic or cycloaliphatic fragments [1]. For example, the previously
prepared thiacrowns containing cyclohexane units are excellent extracting agents for Pb(II) and Ag(I) ions,
which indicates a potential use for this type of macroligand [3].
In the present work thiacrown compounds containing cycloheptane and cyclooctane fragments have
been synthesized from the corresponding β,β'-dichlorodicycloalkyl sulfides, which in turn were prepared by the
addition of sulfur dichloride to cycloalkenes [4].
The dichloro sulfides 1 and 2 were obtained in 75 and 85% yields respectively by the reaction of
cycloheptene and cyclooctene with sulfur dichloride in a molar ratio of cycloalkene–SCl
chloride at -40°C.
2
of 2:1 in methylene
1
3
In the C NMR spectrum of compound 1 the signal of each carbon atom appears as a doublet, which
indicates that, as in the case of the reaction of cyclohexene with SCl , two diastereoisomeric
2
bis(2-chlorocycloheptyl) sulfides 1a and 1b were formed in the ratio of ~1:1.
1
3
The C NMR spectrum of the sulfide 2 also indicates that the two stereoisomers 2a and 2b were formed
in the reaction of cyclooctene with SCl
2
. The uniformity of the reaction of sulfur dichloride with cycloalkenes
1
and the values of the coupling constants in the H NMR spectrum for the protons of the –CHCl– and –CHS–
fragments (J = 9.22 and 8.13 Hz respectively) provides the basis for the conclusion that the substituents in the
dichlorosulfides 1 and 2 (Cl and S), as in the dichlorodicyclohexyl sulfides [2], are in trans-diequatorial
positions.
_
_________________________________________________________________________________________
M. V. Lomonsov Moscow State University, Moscow 119899, Russia; e-mail: pronina@petrol.chem.msu.ru.
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, 522-531, April 2002. Original submitted
November 11, 1999.
4
56
0009-3122/02/3804-0456$27.00©2002 Plenum Publishing Corporation

S
S
–
SCl2
X
(
CH )
(
CH2)n
2 n
(CH )
(CH )
(CH )
2 n
2 n
2 n
Cl Cl
X X
n = 3
n = 4
1
, 2
3, 4 X = OMe; 5, 6 X = SPh
S
S
(CH2)n
(CH )
(CH )
(CH )
2 n
2 n
2 n
X X
X X
n = 3, X = OMe
X = SPh
3a, meso
5a, meso
4a, meso
6a, meso
3b, DL
5b, DL
4b, DL
6b, DL
n = 4, X = OMe
X = SPh
S
S
S
S
S
Cl Cl
S
S
S
O
7
a, meso
S S S
1a, meso
S O S
9a, meso
+
+
+
S
S
S
S
S
S
Cl Cl
S
S
O
1
b, DL
7
b, DL
9b, DL
S
O
O
S
S
S
+
S
S
S
S
O O
O O
1
0a, meso
10b, DL
Considering that the stereochemical results of the reaction of dichlorodicycloalkyl sulfides with
binucleophiles (dithiols and glycols) and mononucleophiles could be the same, in the first stage we investigated
the reactions of the dichloro sulfides 1 and 2 with sodium methoxide and sodium thiophenoxide. Furthermore,
introduction into the molecules of the dichloro sulfides 1 and 2 of such nucleophilic centers as methoxy and
thiophenoxy with very different flexibility provided the possibility of forming the podands 3-6, which, like the
macrocycles, can form complexes with metals.
According to the NMR spectroscopic results a mixture of two diastereoisomeric dimethoxy- and
diphenylthio-substituted compounds 3-6 in a 1:1 ratio was formed by the interaction of the dichloro sulfides 1
and 2 with sodium methoxide and thiophenoxide, just as was observed with the corresponding cyclohexane
derivatives [2, 5].
The reaction of bis(2-chlorocycloheptyl) sulfide (1) with 2,2'-dimercaptodiethyl sulfide was carried out
in ethanol under high dilution conditions.
4
57

The mass spectrum of the compound isolated, show to be pure by TLC, showed a molecular ion* (376)
which corresponded to the molecular mass of 5,6,8,9-dicycloheptano-1,4,7,10-tetrathiacyclododecane (7). The
mass spectrum also contains peaks at 280, 269, 256, 248, 223, 189, 188, 154, 128, 120, and 95 which can be
interpreted by the following mass spectroscopic decomposition scheme:
S
+
–
C H S
– C H
2
4
5
10
S
1
88
+
+
+
S
–
SH
1
28
–
–
C H
95
7
11
S
–
SH
–
C H S
4
8
3
+
+
S
S
S
S
2
23
–
C H S
4
9
3
S
S
C H
256
7
12
– C H S
4 8 2
2
80
S
+
+
S
–
C H S
– C H S
14 24
1
4
24
2
S
S
S
S
S
S
1
S
54
1
20
+
3
76 [M ]
–
C H S
3 7 2
–
C H S
7 12
– C H S
9 15 2
+
+
S
+
S
S
S
S
SH
S
2
48
189
269
The presence of these ions in the mass spectrum of the macrocyclic compound obtained indicates that
the product of the reaction of dichlorosulfide 1 with 2,2'-dimercaptodiethyl sulfide is indeed compound 7.
1
3
All the signals of the carbon atoms in the C NMR spectrum of thiacrown 7 appear as doublets with an
intensity ratio (~1:1) corresponding to that of the initial sulfur dichloride 1. From this and the fact that
nucleophilic substitution in dichlorodicyclohexyl sulfide occurs with retention of configuration at the atom
attacked [4], it may be concluded that the thiacrown 7 is a mixture of two stereoisomers, 7a and 7b.
Bis(2-ethoxycycloheptyl) sulfide (8) is formed along with thiacrown 7 as a by-product when the reaction
1
3
is carried out in ethanol. Compound 8 is also a mixture of two stereoisomers to judge from its C NMR
1
13
spectrum in which the signal for each carbon atom appears as a doublet. The identity of the H and C NMR
signals for the diethoxy derivative 8 and bis(2-methoxycycloheptyl) sulfide 3 provides a basis for the conclusion
that mixture of the diastereoisomers 8a and 8b has been formed:
_
*
______
Here and below values of m/z are given for the ion peaks.
4
58

S
S
H C O
OC H
H C O
OC H
2 5
5
2
2
5
5
2
8
a
8b
The structure of compound was confirmed by the presence of the molecular ion peak (313) in its mass
spectrum.
We also used the template method for the synthesis of the thiacrown ether 7 using cesium carbonate in
DMF. This method permits the synthesis of macrocycles in sufficiently high yield (up to 90%) [8-10], but in this
case the yield of thiacrown 7 only reached 28%, which was lower than using the high dilution technique (40%).
Therefore we used the traditional method of macrocyclization in ethanol solution for the synthesis of the other
twelve-membered thiacrowns.
The reaction of the dichloro sulfide 1 with 2,2'-dimercaptodiethyl ether was carried under conditions
analogous to those for the synthesis of thiacrown 7. Mass spectroscopic data (molecular ion peak at 360 and a
1
3
fragmentation pattern consistent with the structure) and the C NMR spectrum indicated that the main product
of the reaction was 5,6,8,9-dicycloheptano-1-oxa-4,7,10-trithiacyclododecane (9). As was the case with
thiacrown 7, the signals of all of the carbon atoms appeared as doublets with intensity ratios (~1:1)
corresponding to those of the dichlorosulfide 1. This gave the basis for the conclusion that the oxathiacrown 9,
just like the thiacrown 7, can be formed as a mixture of the two diastereoisomers 9a and 9b with configurations
corresponding to those of the stereoisomers of thiacrown 7.
TABLE 1. Distribution Coefficients of Radium(II) and Palladium (II) in the
Presence of Picrate (D
Chain*
1
) and Nitrate Ions (D
2
) with Macrocyclic and Open
D
1
D
2
Ion extracted Extractant, S
cS, mol/l
Solvent
(Counter ion
(Counter ion
-
2
- 3
Pic )*
NO )*
3
Ra2+
1.0 × 10-
3.4 × 10
7.1 × 10-
-2
CHCl
0.1000
0.1300
0.0065
0.0090
0.1400
—
18.6000
—
4.8000
0.0680
0.0170
0.0180
0.0080
0.0670
0.0700
0.0770
1.5100
16.6000
2.0000
2.4000
0.0900
0.2200
3
3
3
3
3
3
3
3
3
3
3
5
CHCl
CHCl
CHCl
CHCl
CHCl
7
9
-
4.2 × 10
DB-24-C-8
5.0 × 10-
5.0 × 10-
Pd2+
-3
7
7
3
3
3
2
5.0 × 10
2
CH ClCH
2
Cl
5.0 × 10-
CHCl
1
1
0
0
3
-
5.0 × 10
CH
CH
CH
2
2
2
ClCH
ClCH
ClCH
2
Cl
2
Cl
2
Cl
1
1
8-C-6
5-C-5
1.0 × 10-
1.0 × 10-2
_
*
______
The distribution coefficients for the extraction of palladium from aqueous
-
solution into chloroethane with thiacrowns 7 and 9 in the presence of ClO
4
(
*
*
1M LiClO
4
) as counterion were 5.00 and 5.85 respectively.
2
-2
c
c
LiPic = 10 mol/l.
HNO3 = 3 mol/l.
3
4
59

2
,2'-Dichlorodicycloheptyl sulfide (1) was also used to obtain the 15-membered oxathiacrown
8
,9,11,12-dicycloheptano-1,4-dioxa-7,10,13-trithiacyclopentadecane (10) by reaction with 1,8-dimercapto-3,6-
dioxaoctane. The reaction was carried out by the template method using a suspension of Cs
2
CO in DMF.
3
According to published results [8-10], the maximum yields with this method were achieved in the synthesis of
fifteen membered thiamacrocycles. The spectroscopic results for this compound (a molecular ion peak at 404 in
13
the mass spectrum) and the character of the C NMR spectrum (the signal for each carbon atom appeared as a
doublet) indicated the possibility of the formation of a mixture of two diastereoisomers 10a and 10b in
approximately equal amounts.
The reactions of bis(2-chlorocyclooctyl) sulfide (2) with 2,2'-dimercaptodiethyl sulfide and
2
,2'-dimercaptodiethyl ether were carried out under conditions analogous to those with the dichloro sulfide 1. As
in the case with the sulfide 1, the mass spectroscopic data (general agreement of the fractionation pattern with
13
those for compounds 7 and 9) and the C NMR spectra (signals of all carbon atoms were doublets) indicate that
the products of the reaction in each case are a pair of diastereoisomers (compounds 11a and 11b, and 12a and
1
2b respectively):
S
S
S
S
S
Cl Cl
–
–
2a, meso
1
1a, meso
S
S
S
–
–
S
O
S
+
S
+
S
S
S
Cl Cl
S
2
b, DL
1
1b, DL
S
S
S
O
1
2a, meso
+
S
S
S
O
1
2b, DL
So the interaction of dichlorodicycloalkyl sulfides 1 and 2 with dithiols gave mixtures of the
corresponding diastereoisomers of thia- and oxathiacrown compounds in yields of 35-40% (compounds 7, 9, 11,
2) and 61% (10) in ratios of ~1:1, which agrees well with results obtained previously for cyclohexane
derivatives [2, 5].
1
4
60

Radium and palladium ions and the use of a radiometric method of control were chosen to estimate the
extraction properties and to study the complex forming properties of some synthesized sulfur containing
macrocycles and open chain compounds. The radium ion was chosen for the following reasons. Firstly, radium
is a typical "hard" cation for which sulfur containing macrocycles appear to have negligible affinity, whereas
excellent extraction results may be expected with the dimethoxy derivative 1 because it contains a "hard"
oxygen atom. Secondly, the compounds synthesized in this work might be suitable for the separation of the
mixture of radium and actinium isotopes formed as the result of decay of the thorium radioactive series.
DB-24-C-8 was used as the standard for the study of the extraction properties with respect to radium and
1
8-C-6 and 15-C-5 with respect to palladium. As the investigations showed, radium was extracted best by
DB-24-C-8, which is explained by its large cavity in comparison with DCHT-12-thiacrown-4 (7) and
DCHT-12O-1S3 (9) and the absence of "soft" sulfur atoms from its ring. It is interesting that the podands 3 and
5
show better extraction results in the presence of the picrate ion than the macroligands 7 and 9. An estimate of
2+
the complexing abilities of DCHT-12-thiacrown-4 (7) and the oxathiacrown 10 with respect to Pd ions was
carried out. The results of our studies of the extraction of radium and palladium ions from aqueous solutions are
shown in Table 1.
EXPERIMENTAL
1
H NMR spectra of 25% solutions in CDCl
3
with TMS as internal standard were recorded with a Varian
or DMSO-d were recorded
13
VXR-400 (400 MHz) spectrometer. C NMR spectra of 30-50% solutions in CDCl
3
6
1
3
with a WH-90 impulse spectrometer (90 MHz). C chemical shifts were measured relative to TMS.
Chromato-mass spectrometric analysis was carried out with a Finnigan MAT-112S machine (electron
impact, ionizing voltage 80 eV) with a glass capillary column (l = 30 m, d = 0.25 mm) with OV-101 as
stationary phase, and temperature programming from 100 to 250°C at a rate of 5-15°/min, and with helium as
the carrier gas.
Course of the reactions and purity of compounds were controlled by TLC on Silufol plates with various
systems of eluents. Starting materials and products were isolated by preparative TLC with loose sorbent layers
and by liquid column chromatography. Merck and L40/100 silica gels were used as absorbents. The eluents
were chosen separately for each mixture to be analyzed.
2
28
228
Extraction of radium was carried out with Ra (T1/2 = 6.3 y, E
β
-max = 0.053 meV). Ra is in
228
equilibrium with Ac (T1/2 = 6.13 h, E -max = 1 meV) and these isotopes were not separated during the
β
228 228
experiment. Recording of the radium samples was carried after equilibrium between Ra and Ac had been
228
232
10
established (2-3 d). Ra, which is obtained as the result of natural decay of Th (T1/2 =1.4·10 y), was
separated from the parent nucleus by precipitation of thorium as peroxide with subsequent washing out of the
2
28
radium from the precipitate with water [11]. Distribution coefficients of Ra were determined with a Canberra-
2
28
228
Packard 2700 liquid scintillation counter. Analysis of spectra of the Ra– Ac couple showed that the spectra
2
28
of the mother and daughter products did not overlap and that Ra can be detected in the tritium channel (up to
2
28
1
8.6 keV) on account of the shift of the radium spectrum to this channel. Ac and the other nuclides are
counted basically at much higher energies. To confirm the correctness of this approach to recording and the
choice of standard, we randomly checked the distribution coefficients from results obtained after equilibrium
had been established between the pair of isotopes.
The distribution coefficients for palladium were also determined radiometrically using the radionuclide
103
103
Pd. The basic type of decay of Pd is electron capture accompanied by characteristic X-rays which we also
recorded with the Canberra-Packard 2700 liquid scintillation counter.
Cycloheptene was obtained by a known method [12], starting from suberone (Merck). Cyclooctene was
obtained commercially (Merck). 2,2'-Dimercaptodiethyl sulfide was obtained commercially (Aldrich).
4
61

Bis(2-chlorocycloheptyl) Sulfide (1). A solution of dry cycloheptene (10 g, 0.104 mol) in dry
methylene chloride (50 ml) was cooled to -40°C and then a solution of freshly distilled (bp 56-58°C) sulfur
dichloride in methylene chloride (20 ml) was added over 1 h with intense stirring. The reaction mixture was
then stirred for a further hour at -40°C and for 4 h at room temperature. After removal of the solvent, the
product, a mixture of crystals and a yellow sticky oil, was recrystallized four times at -70°C from a 1:1 mixture
13
of diethyl ether and hexane to give a white crystalline substance, yield 12 g (75%); mp 67-67.5°C. C NMR
spectrum (CDCl , TMS), δ, ppm: 22.18, 22.28 (d, C(5)); 24.38, 24.48 (d, C(6)); 27.66, 27.80 (d, C(4)); 30.56,
0.60 (d, C(7)); 34.37, 34.44 (d, C(3)); 54.03, 54.41 (d, C(1)–CHS); 66.76, 67.08 (d, C(2)–CHCl). Mass spectrum,
3
3
+
m/z (Irel, %): 294 [M ] (2), 288 (60), 259 (2), 223 (12), 192 (50), 163 (3), 127 (20), 96 (15), 95 (100), 67 (30).
Found, %: C 57.37; H 8.45; Cl 23.84; S 11.00. C14 S. Calculated, %: C 56.95; H 8.10; Cl 24.10; S 10.85.
Bis(2-chlorocyclooctyl) Sulfide (2) was obtained by a method analogous to sulfide 1 from cyclooctene
H24Cl
2
1
3
(
6 g, 0.054 mol) and sulfur dichloride (2.8 g, 0.027 mol) as a light yellow oil. Yield 7.4 g (85%). C NMR
spectrum (CDCl , TMS), δ, ppm: 23.94, 24.48 (d, C(6)); 25.55, 25.86 (d, C(5)); 26.04, 26.73 (d, C(7)); 29.10, 29.60
d, C(4)); 30.54, 31.12 (d, C(8)); 32.40, 33.17 (d, C(3)); 53.15, 54.60 (d, C(1)–CHS); 67.48, 68.93 (d, C(2)–CHCl).
3
(
+
Mass spectrum, m/z (Irel, %): 322 [M ], 287 (1), 250 (1), 210 (1), 177 (12), 142 (10), 109 (53), 67 (100), 41 (75).
Found, %: C 59.80; H 8.87; Cl 22.10; S 9.23. C16
H
28Cl S. Calculated, %: C 59.44; H 8.67; Cl 21.98; S 9.91.
2
Bis(2-methoxycycloheptyl) Sulfide (3). Sodium (0.16 g, 6.8 mmol) was dissolved in methanol (50 ml)
and then a solution of 1 (1 g, 3.4 mmol) in hexane (20 ml) was added with stirring, after which the mixture was
boiled for 5 h. The solvent was evaporated and a mixture of ether (50 ml) and water (50 ml) was added to the
residue. The water layer was extracted twice with ether. The combined ether extracts were dried over MgSO .
4
After removal of the ether the chromatographically pure product was obtained as light yellow oil. Yield 0.6 g
1
3
(
70%). C NMR spectrum (CDCl
3
, TMS), δ, ppm: 21.92, 21.99 (d, C(5)); 25.61, 25.64 (d, C(6)); 29.03, 29.09 (d,
(4)); 29.46, 29.47 (d, C(7)); 31.07 (s, C(3)); 49.96, 50.20 (d, C(1)–CHS); 56.66, 56.78 (d, CH O); 85.77, 85.94 (d,
(2)–CHO). Mass spectrum, m/z (Irel, %): 286 [M ] (1), 255 (1), 254 (6), 159 (2), 128 (8), 126 (100), 95 (80),
C
C
3
+
4
5 (81). Found, %: C 67.62; H 11.00; O 11.00; S 10.38. C16
H
30
O S. Calculated, %: C 67.13; H 10.49; O 11.19;
2
S 11.19.
Bis(2-methoxycyclooctyl) Sulfide (4) was made analogously to sulfide 3. A solution of sulfide 2
(
0.64g, 2 mmol) in hexane (20 ml) was added to a solution of sodium (1 g, 4 mmol) in methanol (50 ml). As a
13
result an oily substance was isolated (yield 0.5 g, 80%). C NMR spectrum (CDCl
3
, TMS), δ, ppm: 19.08,
1
2
9.12 (d, C(6)); 22.04, 22.07 (d, C(5)); 23.05, 23.11 (d, C(7)); 25.87, 26.04 (d, C(4)); 28.11, 28.16 (d, C(8)); 29.30,
9.42 (d, C(3)); 53.98, 54.23 (d, C(1)–CHS); 56.47, 56.84 (d, CH
3
O); 77.65, 78.02 (d, C(2)–CHO). Mass spectrum,
+
m/z (Irel, %): 314 [M ] (2), 283 (4), 234 (1), 217 (1), 171 (1), 169 (3), 149 (4), 142 (1), 141 (2), 138 (18),
1
09 (62), 67 (100), 43 (57), 41 (50). Found, %: C 69.32; H 11.11; O 9.57; S 10.00. C18
H
34
O S. Calculated, %:
2
C 68.79; H 10.83; O 10.19; S 10.19.
Bis(2-phenylthiocycloheptyl) Sulfide (5). Sodium (0.14 g, 6 mmol) was dissolved in ethanol (50 ml)
and thiophenol (0.63 g, 6 mmol) was added. The reaction mixture was stirred with gentle heating for 3 h.
Sulfide 1 (0.85 g, 3 mmol) in ether (15 ml) was added with stirring over 15 min. The reaction mixture was
stirred with heating for a further 3 h and then for 5 h at room temperature. The reaction was carried out under an
inert atmosphere. When the reaction had ended, most of the ethanol was evaporated, then ether (50 ml) and
water (50 ml) were added to the residue, and the water layer was extracted twice with ether. The ether extracts
were washed with alkali and then water. The ether extracts were then combined and dried over magnesium
sulfate. After evaporation of the ether a yellow oil was obtained which was purified by passage of an ether
1
3
solution through a layer of silica gel. Yield 1.16 g (87%). C NMR spectrum, (CDCl
3
, TMS), δ, ppm: 24.57,
2
5
4.99 (d, C(4)); 25.43, 25.87 (d, C(5)); 26.08, 26.19 (d, C(6)); 34.65, 34.92 (d, C(7)); 36.24, 37.32 (d, C(3)); 52.97,
3.56 (d, C(1)); 54.30, 55.12 (d, C(2)); 125.12, 126.03 (d, C(4-Ar)); 127.97, 128.79 (d, C(3-Ar)); 129.42, 129.46 (d,
+
C
2
(2-Ar)); 136.59, 137.05 (d, C(1-Ar)). Mass spectrum, m/z (Irel, %): 442 [M ] (1), 332 (1), 269 (1), 254 (1), 237 (2),
23 (3), 205 (50), 145 (2), 123 (20), 95 (100) 45 (10). Found, %: C 71.20; H 8.58; S 20.22. C26
H S .
34 3
Calculated, %: C 70.59; H 7.69; S 21.72.
4
62

Bis(2-phenylthiocyclooctyl) Sulfide (6) was prepared as for compound 5. Sodium (0.14 g, 6 mmol)
was dissolved in ethanol (50 ml), thiophenol (0.63 g, 6 mmol) was added to this solution, followed a solution of
1
3
sulfide 2 (0.92 g, 3 mmol) in ether (10 ml). Yield 1.2 g (85%). C NMR spectrum (CDCl
3
, TMS), δ, ppm:
2
3
3.20, 23.50 (d, C(5)); 24.42, 24.80 (d, C(6)); 26.20, 26.62 (d, C(4)); 26.80, 27.12 (d, C(7)); 34.88, 35.20 (d, C(8));
6.99, 37.60 (d, C(3)); 55.22, 55.60 (d, C(1)); 56.30, 56.98 (d, C(2)); 125.12, 126.01 (d, C(4-Ar)); 127.93, 128.79 (d,
+
C
(3-Ar)); 129.42, 129.46 (d, C(2-Ar)); 136.20, 136.85 (d, C(1-Ar)). Mass spectrum, m/z (Irel, %): 470 [M ] (1), 436 (1),
4
34 (2), 393 (1), 359 (2), 326 (2), 252 (3), 249 (14), 219 (30), 141 (36), 109 (100), 67 (98), 45 (37). Found, %:
C 72.24; H 8.22; S 19.54. C28 . Calculated, %: C 71.49; H 8.08; S 20.43.
H S
38 3
2
,2'-Dimercaptodiethyl Ether was prepared by a known method [6,7] from diethylene glycol via
2
2
,2'-dibromodiethyl ether. 2,2'-Dibromodiethyl ether; bp 87-90°C (7 mm Hg). Yield 55.3 g (56%).
+
,2'-Dimercaptodiethyl ether; bp 80-81°C (8 mm Hg). Yield 23 g (70%). Mass spectrum: M 138.
1
,8-Dimercapto-3,6-dioxaoctane was prepared analogously to 2,2'-dimercaptodiethyl ether, starting
from triethyleneglycol.
1
,8-Dibromo-3,6-dioxooctane. Pyridine (80 g) and commercial triethyleneglycol (90 g, 0.6 mol) were
added to phosphorus tribromide (115.2 g, 0.4 mol). Yield 97.2 g (63%); bp 120-122°C (5 mm Hg). Thiourea
(
53.2 g, 0.7 mol) was added to solution of the dibromide (97.2 g, 0.35 mol) in ethanol (200 ml), followed by
+
4
0% aqueous KOH (120 ml). Yield 40.95 g (64.3 %); bp 117-119°C (2 mm Hg). Mass spectrum: M 182.
5
,6,8,9-Dicycloheptano-1,4,7,10-tetrathiacyclododecane (7). A. Sodium (0.46 g, 0.02 mol) was
dissolved in ethanol (300 ml). 2,2'-Dimercaptodiethyl sulfide (1.54 g, 0.01 mol) was added under an atmosphere
of argon. Then a solution of sulfide 1 (2.95 g, 0.01 mol) in ethanol (50 ml) was added to the reaction mixture
over 10 h. The reaction mixture was stirred at 60°C for 5 h and then at 20°C for 3 h. The reaction mixture was
cooled, filtered, the ethanol was evaporated, and ether and 20% NaOH were added to the residue. The ether
layer was extracted with water and the water layer extracted with ether. The ether extract was dried and the
ether evaporated. The residue was dissolved in a 1:8 mixture of ether and hexane and purified by preparative
thin layer chromatography on silica gel. Yield 1.53 g (40%).
B. Finely divided cesium carbonate (3.9 g, 0.012 mol) was dispersed in DMF (200 ml) and
dimercaptodiethyl sulfide (1.54 g, 0.01 mol) was added to the solution. The dichloro sulfide 1 (2.95 g, 0.01 mol)
dissolved in DMF (50 ml) was then added over 15 h with gentle heating. At the end of the addition the mixture
was stirred for a further 12 h. It was then filtered, most of the solvent was removed in vacuum, and water and
ether added to the residue. The water layer was separated and washed twice with ether. The ether extracts were
shaken with 20% sodium hydroxide solution (100 ml), then water, and dried over magnesium sulfate. The
solvent was evaporated and the reaction product purified chromatographically (1:8 ether:hexane). Yield 1 g
1
3
(
28%). C NMR spectrum (DMSO-d , TMS), δ, ppm: 21.57, 21.65, 24.60, 24.68, 24.77, 24.90, 30.58, 30.73,
6
3
3.80, 33.89 (d, d, d, d, d - carbon atoms of the cycloheptane ring); 39.27, 38.99 (d, C(3) and C(11)); 39.54, 39.82
(
3
6
d, C(2) and C(12)); 49.57, 49.68 (d, C(6) and C(8)); 52.46, 52.58 (d, C(5) and C(9)). Mass spectrum, m/z (Irel, %):
+
76 [M ] (6), 269 (2), 280 (1), 256 (5), 248 (8), 223 (1), 189 (7), 188 (7), 154 (12), 128 (21), 120 (10), 95 (100),
7 (45), 41 (43). Found, %: C 58.04; H 8.09; S 33.87. C18
H S
32 4
. Calculated, %: C 57.45; H 8.51; S 34.04.
Bis(2-ethoxycycloheptyl) Sulfide (8). C NMR spectrum (CDCl , TMS), δ, ppm: 15.68, 15.71
); 22.23, 22.25 (d, CH O); 25.33, 25.40, 29.01, 29.12, 30.25, 30.36, 31.19, 31.30 (d, d, d, d - carbon
atoms of the cycloheptane ring); 50.40, 50.77 (d, C(1)–CHS); 64.35, 64.45 (d, C(8)–CH O); 84.03, 84.21 (d,
(2)–CHO). Mass spectrum, m/z (Irel, %): 313 [M ] (1), 269 (1), 253 (1), 207 (1), 190 (3), 161 (1), 159 (1),
28 (3), 113 (24), 95 (100), 59 (51), 43 (22). Found, %: C 69.00; H 10.45; O 10.53; S 10.02. C18 S.
Calculated, %: C 68.79; H 10.83; O 10.19; S 10.19.
,6,8,9-Dicycloheptano-1-oxa-4,7,10-trithiacyclododecane (9) was synthesized as for 7 by method A.
Sodium (0.46 g, 0.02 mol) was dissolved with stirring in ethanol (300 ml), 2,2'-dimercaptodiethyl ether (1.38 g,
.01 mol) was added to the solution, and then the dichloro sulfide 1 (2.95 g, 0.01 mol) in ethanol (50 ml) was
added over 10 h. After removal of the ethanol and ether, the residue was purified on silica gel (1:8 ether–hexane).
1
3
3
(d, CH
3
2
2
+
C
1
H
34
O
2
5
0
4
63

1
3
Yield 1.33 g (38%). C NMR spectrum (DMSO-d , TMS), δ, ppm: 22.02, 22.13, 26.32, 26.73, 27.01, 27.07,
6
3
6
3
4
9.21, 39.49, 40.32, 40.66 (d, d, d, d, d - carbon atoms of the cycloheptane ring); 29.61, 29.68 (d, C(3), C(11));
1.42, 61.49 (d, C(6), C(8)); 63.45, 63.47 (d, C(5), C(9)); 73.48, 73.66 (d, C(2), C(12)). Mass spectrum, m/z (Irel, %):
+
60 [M ] (1), 330 (1), 313 (3), 269 (1), 223 (2), 204 (1), 189 (3), 172 (1), 138 (2), 128 (1), 95 (100), 67 (30),
3 (67). Found, %: C 60.92; H 8.54; O 5.08; S 25.46. C18
H
32OS . Calculated, %: C 60.00; H 8.88; O 4.45;
3
S 26.67.
8
,9,11,12-Dicycloheptano-1,4-dioxa-7,10,13-trithiacyclopentadecane (10) was prepared analogously
to compound 7 by method B. Finely divided cesium carbonate (3.9 g, 0.012 mol) was dispersed in DMF
200 ml) and 1,8-dimercapto-3,6-dioxooctane (1.82 g, 0.01 mol) was added to the reaction mixture. Then a
solution of the dichlorosulfide 1 (2.95 g, 0.01 mol) in DMF (50 ml) was added. The reaction product was
(
1
3
purified chromatographically (1:9 ethanol–hexane). Yield 2.46 g (61%). C NMR spectrum (CDCl , TMS),
3
δ, ppm: 24.47, 25.16, 25.88, 25.90, 26.05, 26.15, 35.06, 35.14, 35.77, 36.18 (d, d, d, d, d - C atoms of the
cycloheptane ring); 28.30, 28.73 (d, C(6), C(14)), 50.34, 51.07 (d, C(9), C(11)), 52.30, 52.89 (d, C(8), C(12)), 68.90,
+
6
3
9.27 (d, C(2), C(3)), 70.92, 71.45 (d, C(5), C(15)). Mass spectrum, m/z (Irel, %): 404 [M ] (5), 371 (1), 340 (1),
09 (1), 277 (11), 256 (3), 216 (8), 181 (5), 128 (32), 95 (100), 67 (50).
5
,6,8,9-Dicyclooctano-1,4,7,10-tetrathiacyclododecane (11) was synthesized analogously to the
thiacrown 7 (method A). Sodium (0.23 g, 0.01 mol) was dissolved in ethanol (200 ml) and
2
0
,2-dimercaptodiethyl sulfide (0.77 g, 0.005 mol) was added. Then a solution of the sulfide 2 (1.62 g,
.005 mol) in ethanol (50 ml) was added. An oil was obtained which was purified chromatographically (1:8
13
ether–hexane). Yield 0.8 g (39%). C NMR spectrum (DMSO-d
6
, TMS), δ, ppm: 22.27, 23.45, 24.57, 24.82,
2
3
5.03, 25.32, 29.05, 29.82, 30.69, 30.94, 32.92, 33.12 (d, d, d, d, d, d - C atoms of the cyclooctane ring); 39.01,
9.28 (d, C(3), C(11)); 39.54, 39.84 (d, C(2), C(12)); 40.40, 41.02 (d, C(6), C(8)), 55.5 (s, C(5), C(9)). Mass spectrum,
m/z (Irel, %): 299 (1), 285 (1), 251 (1), 203 (2), 167 (5), 154 (2), 141 (25), 109 (60), 67 (100), 41 (87). Found, %:
C 60.37; H 9.41; S 30.22. C20
,6,8,9-Dicyclooctano-1-oxa-4,7,10-trithiacyclododecane (12) was obtained using the method in
ethanolic solution. 2,2'-Dimercaptodiethyl ether (0.69 g, 0.005 mol) was added to a solution of sodium ethoxide
0.23 g, 0.01 mol) in ethanol (200 ml). Then a solution of sulfide 2 (1.62 g, 0.005 mol) in ethanol (50 ml) was
added over 10 h. An oil was obtained which was purified chromatographically (1:8 ether:hexane). Yield 0.68 g
H
36
S
4
. Calculated, %: C 59.41; H 8.91; S 31.68.
5
(
1
3
(
35%). C NMR spectrum (DMSO-d , TMS), δ, ppm: 22.29, 22.50, 23,32, 23.99, 28.46, 28.79, 29.11, 29.62,
6
3
6
2
9.93, 39.60, 40.77, 41.06 (d, d, d, d, d, d - C atoms of the cyclooctane ring); 29.88, 30.06 (d, C(3), C(11)); 60.09,
0.74 (d, C(6), C(8)); 62.60, 63.94 (d, C(5), C(9)); 71.81, 75.03 (d, C(2), C(12)). Mass spectrum, m/z (Irel, %): 328 (1),
79 (42), 204 (2), 186 (1), 167 (60), 149 (100), 142 (12), 138 (5), 109 (58), 67 (43), 43 (70).
This work was carried out with the support of MNTP "General and Technical Chemistry" and the
"
Fundamental Research in Chemical Technology" program of the Ministry of Higher Education of the Russian
Federation.
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4
65