Selective synthesis of isomeric dithioglycerols

Article abstract of DOI:10.1134/S1070428008100059

Reactions of 2,3-dibromopropan-1-ol and 1,3-dichloropropan-2-ol with elemental sulfur activated in the system hydrazine hydrate-2-aminoethanol at 30-35°C gave oligomeric polysulfides which were subjected to reductive cleavage with formation of individual dithioglycerol isomers. Activation of sulfur with the use of alkali gives rise to mixtures of isomeric products.

Full text of DOI:10.1134/S1070428008100059

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 10, pp. 1428–1433. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © E.P. Levanova, V.A. Grabel’nykh, E.N. Sukhomazova, I.A. Zemirova, N.V. Russavskaya, A.I. Albanov, L.V. Klyba, E.R. Zhanchi-
pova, N.A. Korchevin, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 10, pp. 1452–1457.
Dedicated to Full Member of the Russian Academy of Sciences
B.A. Trofimov on his 70th anniversary
Selective Synthesis of Isomeric Dithioglycerols
E. P. Levanova, V. A. Grabel’nykh, E. N. Sukhomazova, I. A. Zemirova, N. V. Russavskaya,
A. I. Albanov, L. V. Klyba, E. R. Zhanchipova, and N. A. Korchevin
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: venk@irioch.irk.ru
Received May 27, 2008
Abstract—Reactions of 2,3-dibromopropan-1-ol and 1,3-dichloropropan-2-ol with elemental sulfur activated
in the system hydrazine hydrate–2-aminoethanol at 30–35°C gave oligomeric polysulfides which were
subjected to reductive cleavage with formation of individual dithioglycerol isomers. Activation of sulfur with
the use of alkali gives rise to mixtures of isomeric products.
DOI: 10.1134/S1070428008100059
The role of glycerol in organic synthesis and bio-
chemical processes is difficult to overestimate [1]. The
use of superbasic systems proposed by B.A. Trofimov
made it possible to obtain glycerol trivinyl ether from
glycerol and acetylene [2], while vinylation of glycerol
with acetylene in cesium superbasic system was ac-
companied by elimination with formation of 1,2- and
2,3-divinyloxypropenes [3]. Sulfur-containing analogs
of glycerol are effective antidotes for heavy metals [4],
analytical reagents [5], and ligands stabilizing nano-
particles of chalcogenide materials [6]. 2,3-Disulfanyl-
propan-1-ol (Ia) and some its derivatives exhibit tuber-
culostatic activity [7], and 1,3-disulfanylpropan-2-ol
(Ib) is used as starting material in the synthesis of
effective growth regulator Brugierol [8]. Nevertheless,
wide application of dithioglycerols Ia and Ib in
organic synthesis is restricted due to difficulties in
their preparation, especially as individual isomers.
2-ol (III) with a solution of sulfur in the system aque-
ous hydrazine−alkali at 60°C, followed by reduction of
polysulfide oligomers thus formed [12]. The yield of
dithiols Ia and Ib was 37–42%, and it was improved to
62–64% using lead acetate at the isolation stage. How-
ever, although initial compounds II and III were pure
isomers, in both cases dithiols Ia and Ib were isolated
as mixtures containing 10% and more of isomerization
product, which were difficult to separate. It was pre-
sumed [12] that the isomerization occurs at the stage of
formation of polysulfide oligomers, where strongly
basic hydrazine hydrate–alkali system promotes dehy-
drohalogenation to give oxirane fragments; subsequent
opening of the oxirane ring by the action of disulfide
ion (S22–) gives rise to isomeric products.
We found that the synthesis of polysulfide oligo-
mers from dihalopropanols II and III and a solution of
sulfur in the system hydrazine hydrate−2-aminoetha-
nol, which was successfully used previously for the
preparation of di- and polythiols [13], gives (after
reduction) dithioglycerols Ia and Ib as almost pure
isomers. The process may be described as follows.
Dissolution of sulfur in a mixture of hydrazine hydrate
Dithioglycerols are commonly prepared by reaction
of the corresponding dihalohydrins with an alcoholic
solution of sodium hydrogen sulfide [7]. However, the
scope of application of this procedure is limited be-
cause of difficult preparation of sodium hydrogen sul-
fide [9] and high probability for dehydrohalogenation
by the action of its alcoholic solution [10].
Scheme 1.
Trofimov and co-workers previously synthesized
trithioglycerol [11] and proposed a procedure for the
preparation of dithioglycerols Ia and Ib by reactions of
2,3-dibromopropan-1-ol (II) and 1,3-dichloropropan-
1/2 S8
+ N2H4 · H2O + 4 H2NCH2CH2OH
(HOCH2CH2NH3)2 S22– + (H2NNH3)2 S22– + N2 + H2O
IVa IVb
1428

SELECTIVE SYNTHESIS OF ISOMERIC DITHIOGLYCEROLS
1429
1
with 2-aminoethanol results in preferential formation
of 2-hydroxyethylammonium and hydrazinium disul-
fides IVa and IVb [14] (Scheme 1).
the GLC, GC–MS, and H and 13C NMR data, com-
pounds Ia and Ib were pure isomers.
Thus, with account taken of the data given in [12],
dehydrohalogenation of dihalopropanols II and III to
the corresponding oxiranes is unlikely to occur in the
system hydrazine hydrate–2-aminoethanol at a tem-
perature below 35°C (cf. [16]). A probable reason is
lower basicity of the system hydrazine hydrate–
2-aminoethanol as compared to hydrazine hydrate–
alkali. The reaction of elemental sulfur with 2-(chloro-
methyl)oxirane (VIII) in hydrazine hydrate–2-amino-
ethanol at 20–25°C, i.e., even under milder conditions,
also gives oligomeric product whose reductive cleav-
age leads to formation of 70% of dithiol Ib containing
3–5% of isomer Ia (according to the GLC and
1H NMR data). Raising the temperature favors forma-
tion of dithiol Ia. Therefore, had the dehydrohalogena-
tion process occurred at the stage of formation of
oligomers from dihalides II and III, the formation of
isomeric dithiols could not be avoided.
Addition of dihalopropanol II or III to the resulting
solution of disulfides IV at 30–35°C leads to fast
formation of oligomeric products V and VI, respec-
tively (Scheme 2).
Scheme 2.
nS22–
S
Br
Cl
OH
S
n
–2n Br–
Br
OH
S
n
II
V
nS22–
–2nCl–
Cl
S
n
OH
OH
n
III
VI
Oligomers V and VI are formed in almost quan-
titative yield; judging by the concentration of residual
bromine and chlorine, their molecular weight is about
2000 a.m.u., which corresponds to an average n value
of 15 to 17. It should be noted that the molecular
weight of analogous oligomers obtained in the system
hydrazine hydrate–alkali was approximately twice as
large [12].
An additional proof for the proposed reaction path
(i.e., that involving no dehydrohalogenation) in the
system hydrazine hydrate–2-aminoethanol is provided
by the synthesis in the same system of 1,3-diseleno-
glycerol IX from dichloride III and elemental sele-
nium [17] (Scheme 4).
Scheme 4.
Reductive cleavage of oligomers V and VI at S–S
bonds by the action of hydrazine hydrate−KOH [15]
afforded the corresponding dipotassium dithiolates
VIIa and VIIb which were converted (without isola-
tion) into dithiols Ia and Ib (Scheme 3). According to
N2H4 ·H2O–H2NCH2CH2OH
Se
Se22–
nSe22–
Se
Se
nIII
–2nCl–
OH
n
Scheme 3.
IX
S K+
K+S
N2H4 · H2O–KOH
We previously showed [18] that neither compounds
II and III nor 2-(chloromethyl)oxirane (VIII) gave
rise to oligomeric products in the reactions with sele-
nium in hydrazine hydrate–alkali. Here, the major
product was allyl alcohol, and elemental selenium was
regenerated. It was presumed that 1,3-dichloropropan-
2-ol (III) is preliminarily converted into 2-(chloro-
methyl)oxirane (VIII) and that reaction of the latter
with diselenide ion (Se22–) is responsible for the forma-
tion of allyl alcohol. On the other hand, dichloride III
reacted with selenium in the system hydrazine hy-
drate–2-aminoethanol to give oligomer IX (Scheme 4).
The yield of IX is 95%; its average molecular weight
(determined on the basis of the concentration of resi-
dual chlorine) was 3500 (n = 16). Reductive cleavage
of compound IX gave 78% of diselenol X (Scheme 5).
V
OH
VIIa
SH
H+, 0°C, argon
HS
OH
Ia, 58%
K+S
S K+
N2H4 ·H2O–KOH
VI
OH
VIIb
H+, 0°C, argon
HS
SH
OH
Ib, 47%
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 10 2008

LEVANOVA et al.
Oligomer XI has a molecular weight of ~4000
1430
Scheme 5.
(n ≈ 33) (cf. [12]), and its reduction leads to a mixture
of dithiols Ia and Ib at a ratio of 9 : 1 (GLC and
1H data). Thus dilution of the system with water does
not reduce the contribution of dehydrochlorination of
compound III, and oligomeric product XI contains
structural fragments intrinsic to oligomers V and VI.
+ Se
Se K+
N2H4 · H2O–KOH
K
IX
OH
H+, 0°C, argon
HSe
SeH
OH
X
Heterocyclic compounds XII–XIV were identified
by GLC and GC–MS analysis of the reaction mixture.
At a KOH-to-sulfur ratio of 1:1 (preferential genera-
tion of K2S2 [15]) compounds XII–XIV were formed
at a ratio of 1:10:1.5. We failed to isolate heterocyclic
products XII–XIV by vacuum distillation, though
Dittmer and Christy [20] previously reported that
3-hydroxythietane (XII) can be distilled under reduced
pressure. Obviously, the presence in the product mix-
ture of thermally unstable trisulfide derivative, 5-hy-
droxy-1,2,3-trithiane (XIV), promotes fast polymeriza-
tion of all compounds. The reductive cleavage of
oligomers XI may be represented by Scheme 7.
According to the GLC, GC–MS, and 1H NMR data,
no isomeric 1,2-diselenoglycerol was present in the
product.
Using as an example the reaction of dichloride III
with sulfur we examined the effect of the basicity of
the hydrazine hydrate–KOH system (the basicity was
varied by dilution with water) on the selectivity of
formation of dithiol Ib and its isomer Ia. Oligomeric
polysulfides were obtained in [12] using 300 ml of
water per mole of sulfur. We carried out the reaction of
1,3-dichloropropan-2-ol (III) with sulfur in the system
containing 1800 ml of water per mole of sulfur (sixfold
dilution). As a result, the yield of oligomer XI de-
creased to 29%, and its composition and properties
resembled those of oligomer VI. The reaction was ac-
companied by formation of cyclic products XII–XIV
in an overall yield of 28% (Scheme 6).
Scheme 7.
H+
N2H4 ·H2O–KOH
XI
VIIa
+
VIIb
Ia + Ib
Thus the use of the hydrazine hydrate–2-amino-
ethanol system ensures preparation of individual iso-
meric dithioglycerols from the corresponding dihalo-
propanols and elemental sulfur.
Scheme 6.
S–N2H4 ·H2O
KOH–H2O
S
S
S
S
III
OH
EXPERIMENTAL
OH
n
m
XI
The progress of reactions was monitored, and liquid
products were analyzed, by GLC on LKhM 80-MD-2
(2000×3-mm column packed with 5% of DC-550 on
Chromaton N-AW-HMDS; linear oven temperature
programming at a rate of 12 deg/min; carrier gas
helium) and Tsvet-500 chromatographs (2000×5-mm
steel column packed with 5% of XE-60 on Chromaton
N-AW-HMDS; linear oven temperature programming
from 30 to 230°C at a rate of 12 deg/min; carrier gas
helium). The IR spectra were recorded on Specord
75IR and Bruker IFS-25 spectrometers from thin films.
S
S
+
+
OH
S
OH
S
OH
+
S
S
XII
XIII
XIV
In the reaction of dichloride III with sulfur in hy-
drazine hydrate–2-aminoethanol only traces of com-
pounds XII–XIV were detected; however, by treat-
ment of oligomer VI with chloroform-d we succeeded
in isolating fairly pure compound XIII (yield ~1%)
and recording its NMR spectra (see Experimental).
When the polycondensation was carried out under the
conditions given in [12], the overall yield of hetero-
cyclic compounds XII–XIV did not exceed 5%. In-
crease in the yield of cyclic products with reduction of
the monomer concentration (in our case Sx2–) is con-
sistent with the general relations holding in polycon-
densation processes [19].
1
The H and 13C NMR spectra were measured on
a Bruker DPX-400 instrument (400.1 and 100.6 MHz,
respectively) using CDCl3 as solvent and hexamethyl-
disiloxane as internal reference. The mass spectra
(electron impact, 70 eV) were obtained on a Shimadzu
GCMS-QP5050A instrument (SPB-5 capillary column,
60 000 ×0.25 mm, film thickness 0.25 μm; injector
temperature 200°C; carrier gas helium, flow rate
0.7 ml/min; oven temperature programming from 60 to
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 10 2008

SELECTIVE SYNTHESIS OF ISOMERIC DITHIOGLYCEROLS
1431
240°C at a rate of 10 deg/min; detector temperature
200°C; quadrupole mass analyzer, ion source tempera-
ture 200°C, a.m.u. range 34–650 D).
was added, and the mixture was stirred for 2 h at that
temperature. The mixture was then cooled to 25°C,
poured under argon into a mixture of ice with 55 ml of
concentrated hydrochloric acid, and extracted with
methylene chloride. The extract was dried over
MgSO4, and the solvent was distilled off to leave
1.44 g of almost pure dithiol Ia. Yield 58%, bp 106°C
(5 mm). IR spectrum, ν, cm–1: 3386 (OH); 2927, 2873
Poly[sulfanediyl(3-hydroxypropane-1,2-diyl)sul-
fanediyl] (V). Elemental sulfur, 1.6 g (50 mmol), was
dissolved in a mixture of 8.3 ml (166 mmol) of
hydrazine hydrate and 1.0 ml (16.6 mmol) of 2-amino-
ethanol, heated to 65°C. The mixture was heated under
stirring for 2.5 h at 70–73°C and cooled, 2.5 ml
(25 mmol) of 2,3-dibromopropan-1-ol (II) was added
dropwise, the mixture was stirred for 2 h at 45–50°C
and cooled, and oligomer V separated as a green vis-
cous ductile material. The product was washed with
water, ethanol, and diethyl ether, and dried under
reduced pressure. Yield 3.4 g (98%). IR spectrum, ν,
cm–1: 3408, 2924, 2865, 1619, 1457, 1402, 1262, 1227,
1181, 1143, 1038, 964, 894, 840, 812, 580, 497, 426.
Found, %: C 27.20; H 4.90; Br 8.74; S 48.16.
(C3H6OS2)n. Calculated, %: C 29.51; H 4.92; S 52.46
(the carbon and sulfur percentages were considerably
underestimated due to high concentration of residual
bromine). M ~1830.
1
(CH); 2547 (SH). H NMR spectrum (50°C), δ, ppm:
3
1.68 t (1H, CH2SH, J = 8.4 Hz), 1.74 d (1H, CHSH,
3J = 8.5 Hz), 2.59 s (1H, OH), 2.83 d.d (2H, CH2SH,
3J = 6.24 Hz), 3.02 m (1H, CH), 3.74 d (2H, CH2OH,
3J = 5.8 Hz); in the spectrum recorded at 25°C, the SH
proton signals were displaced downfield to δ 1.71 and
1.76 ppm, respectively. 13C NMR spectrum, δC, ppm:
29.4 (CH2S), 44.8 (CHS), 65.2 (CH2O). Mass spec-
trum, m/z (Irel, %): 124 [M]+· (1), 106 [M – H2O]+· (16),
93 (10), 90 [M – H2S]+· (11), 77 [M – HSCH2]+ (12),
73 (12), 72 (8), 64 (20), 61 (16), 60 [C2H4S]+· (34), 59
(100), 58 (20), 57 (41), 48 (1), 47 [CH3S]+ (21), 45
[HCS]+ (27) (cf. [12]). Found, %: C 29.15; H 6.48;
S 51.81. C3H8OS2. Calculated, %: C 29.03; H 6.45;
S 51.61.
Poly[sulfanediyl(2-hydroxypropane-1,3-diyl)sul-
fanediyl] (VI). Elemental sulfur, 9.6 g (300 mmol),
was dissolved in a mixture of 45 ml (900 mmol) of
hydrazine hydrate and 5.5 g (90 mmol) of 2-amino-
ethanol, heated to 65°C. 1,3-Dichloropropan-2-ol (III),
19.35 g (150 mmol), was slowly added to the resulting
solution at 27–35°C, the mixture was stirred for 2.5 h
at room temperature, and oligomer VI separated as
a light yellow viscous ductile material. The product
was washed with water, ethanol, and diethyl ether, and
dried under reduced pressure. Yield 17.9 g (98%). IR
spectrum, ν, cm–1: 3332, 2970, 2813, 2745, 2650,
1608, 1402, 1339, 1250, 1183, 1128, 1070, 1010, 982,
930, 850, 822, 739, 475, 423. Found, %: C 28.40;
H 5.22; Cl 3.28; S 50.3. (C3H6OS2)n. Calculated, %:
C 29.51; H 4.92; S 52.46. M ~2160.
1,3-Disulfanylpropan-2-ol (Ib, 1,3-dithioglycer-
ol). Oligomer VI, 10 g (82 mmol), was dissolved in
a mixture of 102 ml (2.05 mol) of hydrazine hydrate
and 23 g (0.41 mol) of KOH on heating to 75–80°C
(2.5 h). The solution was cooled to room temperature,
poured under argon into a mixture of ice with 240 ml
of concentrated hydrochloric acid, and extracted with
methylene chloride and diethyl ether. The extract was
purged with argon and dried over MgSO4. Removal of
the solvent left 4.25 g of 1,3-dithioglycerol Ib which
was purified by vacuum distillation. Yield 47%, light
yellow liquid, bp 88–90°C (2 mm). IR spectrum, ν,
cm–1: 3386 (OH); 2927, 2873 (CH); 2553 (SH).
1H NMR spectrum, δ, ppm: 1.48 t (2H, SH), 2.63–
2.69 m (4H, CH2), 3.1 s (1H, OH), 3.70 m (1H, CH).
13C NMR spectrum, δC, ppm: 29.55 (CH2), 72.70 (CH).
Mass spectrum, m/z (Irel, %): 124 [M]+· (3), 122 (1),
106 [M – H2O]+· (39), 77 (48), 76 (11), 73 (23),
72 (20), 64 (1), 61 (13), 59 (100), 58 (14), 57 (7), 49
(12), 48 (26), 47 (62), 46 (20), 45 [CH2SH]+ (50), 44
(11), 43 (24), 42 (6) (cf. [12]). Found, %: C 28.84;
H 6.52; S 52.00. C3H8OS2. Calculated, %: C 29.03;
H 6.45; S 51.61.
A 1-g sample of oligomer VI was treated with
1
CDCl3 over a period of 18 h. According to the H and
13C NMR data, the transparent extract contained
1
1,3-dithiolan-4-ol (XIII). H NMR spectrum, δ, ppm:
3.17 d.d (2H, CH2S), 3.95 br.s (1H, OH), 4.94 m (1H,
2
3
3
CHO, ABX spin system, JAB = 11.5, JAX = 3.4, JBX
=
1.5 Hz). 13C NMR spectrum, δC, ppm: 46.6 (CH2S),
75.2 (CHO).
Reaction of 2-(chloromethyl)oxirane (VIII) with
a solution of sulfur. Powdered sulfur, 9.6 g
(300 mmol), was dissolved in a mixture of 45 ml
(900 mmol) of hydrazine hydrate and 5.52 g
(90 mmol) of 2-aminoethanol on heating to 60–65°C.
2,3-Disulfanylpropan-1-ol (Ia, 1,2-dithioglycer-
ol). A solution of 5.6 g (100 mmol) of potassium
hydroxide in 25 ml (500 mmol) of hydrazine hydrate
was heated to 80°C, 2.5 g (20 mmol) of oligomer V
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 10 2008

LEVANOVA et al.
1432
The solution was heated for 2 h at that temperature and
cooled to 18–25°C, 13.87 g (150 mmol) of 2-(chloro-
methyl)oxirane (VIII) was slowly added dropwise, the
mixture was stirred for 3 h at 22°C, and the precipitate
was separated, washed with water, ethanol, and diethyl
ether, and dried under reduced pressure. Yield 17.93 g
(98%); the product was a goldish viscous material.
IR spectrum, ν, cm–1: 3393, 3331, 3195, 2964, 2907,
1606, 1398, 1338, 1250, 1183, 1127, 1068, 1029, 980,
821, 740, 565, 471, 457. Found, %: C 26.94; H 6.00;
Cl 1.50; S 45.62. (C3H6OS2)n. Calculated, %: C 29.51;
H 4.92; S 52.46.
was almost pure diselenol X. Yield 78%, bp 95–97°C
(2 mm). The elemental analysis of X and its spectral
parameters were given in [17].
Reaction of 1,3-dichloropropan-2-ol (III) with
a dilute solution of sulfur in hydrazine hy-
drate−KOH. A solution of 2.8 g (50 mmol) of
potassium hydroxide in a mixture of 3.5 ml (70 mmol)
of hydrazine hydrate and 15 ml of water was heated to
70–80°C, 1.6 g (50 mmol) of sulfur and 10 ml of water
were added, and the mixture was heated for 1 h at 80–
85°C. The mixture was then diluted with 105 ml of
water, 3.22 g (25 mmol) of dichloride III was added
dropwise at 55–60°C, the mixture was stirred for 1 h at
that temperature and cooled, and viscous sticky oligo-
mer XI was separated, washed with water and ethanol,
and dried under reduced pressure. Yield 0.89 g (29%).
IR spectrum, ν, cm–1: 3429, 2921, 2858, 1658, 1625,
1584, 1452, 1404, 1270, 1224, 1176, 1070, 1009, 743,
589, 466, 442, 412. Found, %: C 30.70; H 4.42;
Cl 1.81; S 52.08. (C3H6OS2)n. Calculated, %: C 29.51;
H 4.92; S 52.46.
Reductive cleavage of a 8-g portion of the resulting
oligomer under the conditions described above for the
synthesis of dithiol Ia gave 6.44 g of a mixture of
isomers Ia and Ib containing ~96% of the former
(yield 75%).
When the synthesis of oligomer was performed at
65–70°C, a goldish yellow product was obtained
(99%). Reductive cleavage of 7.1 g of the product gave
3.5 g of a mixture of dithiols Ia and Ib at a ratio of
2:3; yield of Ib 27%. Apart from dithiols Ia and Ib,
the mixture contained 1,2-dithiolan-4-ol (XIII, 3%).
After separation of oligomer XI, the aqueous
hydrazine solution was extracted with methylene
chloride, and the extract was dried over MgSO4 and
analyzed by GLC and GC–MS, It contained com-
pounds XII–XIV.
Poly[selanediyl(2-hydroxypropane-1,3-diyl)sel-
anediyl] (IX). Elemental selenium, 7.9 g (100 mmol),
was dissolved in a mixture of 15 ml (300 mmol) of
hydrazine hydrate and 1.84 g (30 mmol) of 2-amino-
ethanol, heated to 70–75°C. The solution was heated
for 2.5 h at that temperature and allowed to cool down
to 40–45°C, 6.45 g (50 mmol) of dichloride III was
slowly added dropwise, the mixture was stirred for 1 h
at about 50°C and cooled to 25°C, and the precipitate
was separated, washed with water, ethanol, and diethyl
ether, and dried under reduced pressure. Yield 10.2 g
(95%). IR spectrum, ν, cm–1: 3420, 3259, 3148, 3052,
2962, 2927, 2705, 2581, 1627, 1494, 1399, 1258,
1190, 1102, 1064, 1005, 947, 792, 518, 478, 447, 413.
Found, %: C 16.56; H 3.08; Cl 2.01; Se 71.54.
(C3H6OSe2)n. Calculated, %: C 16.67; H 2.78;
Se 73.15.
Thietan-3-ol (XII). Mass spectrum, m/z (Irel, %):
90 [M]+· (92), 61 [C2H5S]+ (46), 47 (8), 46 (100), 45
(62), 44 (96), 43 (66).
1,2-Dithiolan-4-ol (XIII). Mass spectrum, m/z (Irel,
%): 122 [M]+· (100), 80 (11), 79 (35), 78 (57), 76 (13),
64 (11), 61 [C2H5S]+ (9), 59 (11), 58 (75), 57 (33), 48
(21), 47 (61), 46 (58), 45 (67), 44 (13), 43 (85), 42 (9).
1,2,3-Trithian-5-ol (XIV). Mass spectrum, m/z
(Irel, %): 154 [M]+· (100), 110 (44), 108 (27), 90 (14),
89 (38), 79 (14), 78 (11), 71 (7), 64 (30), 61 [C2H5S]+
(13), 58 (11), 57 (20), 47 (39), 46 (42), 45 (82), 44
(37), 43 (56), 42 (7).
REFERENCES
1,3-Diselanylpropan-2-ol (X). A solution of 8.4 g
(150 mmol) of potassium hydroxide in 37 ml
(750 mmol) of hydrazine hydrate was heated to 55–
60°C, 6.4 g (30 mmol) of oligomer IX was added, and
the mixture was stirred for 2 h at that temperature,
cooled to 25°C, and treated as described above in the
synthesis of dithiols Ia and Ib. The oily product was
extracted into methylene chloride, the extract was
dried over magnesium sulfate, and the solvent was
distilled off. According to the GLC data, the residue
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