Multicomponent condensation of aliphatic amines with formaldehyde and hydrogen sulfide

Article abstract of DOI:10.1007/s11172-005-0268-6

Cyclothiomethylation of primary aliphatic amines with the reagent H ₂S - CH₂O (2:3) in aqueous medium mainly gave substituted dithiazines; oxathiazines and dioxazines were obtained from butylamine and ethanolamine. Under the chosen r

Full text of DOI:10.1007/s11172-005-0268-6

432
Russian Chemical Bulletin, International Edition, Vol. 54, No. 2, pp. 432—436, February, 2005
Multicomponent condensation of aliphatic amines
with formaldehyde and hydrogen sulfide
b
a
S. R. Khafizova,a V. R. Akhmetova,a L. F. Korzhova, T. V. Tyumkina,
ꢀ
G. R. Nadyrgulova,a R. V. Kunakova,a E. A. Kruglov,b and U. M. Dzhemileva
aInstitute of Petrochemistry and Catalysis, Russian Academy of Sciences,
141 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347 2) 31 2750. Eꢀmail: ink@anrb.ru
bBashkir Republic Research Center for Ecology,
147 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347 2) 31 3503. Eꢀmail: ecocnt@diaspro.com
Cyclothiomethylation of primary aliphatic amines with the reagent H2S—CH2O (2 : 3) in
aqueous medium mainly gave substituted dithiazines; oxathiazines and dioxazines were obꢀ
tained from butylamine and ethanolamine. Under the chosen reaction conditions, ethylenediꢀ
amine was converted into 5ꢀ[2ꢀ(perhydroꢀ1,3,5ꢀdithiazinꢀ5ꢀyl)ethyl]perhydroꢀ1,3,5ꢀdithiazine
or substituted thiazetidine and oxazetidine, depending on the order of mixing of the starting
reagents.
Key words: cyclothiomethylation, aliphatic amines, O,N,Sꢀcontaining heterocycles, formꢀ
aldehyde, hydrogen sulfide, 1,3,5ꢀdithiazines, 1,3,5ꢀoxathiazines.
The literature data on thiomethylation of amines with
and more accessible H2S makes this method preferred for
practical application.
hydrogen sulfide and formaldehyde to give the simplest
dithiazines are scarce.1—4 Recently,5 dithiazines were obꢀ
tained by thiomethylation of amino acids. Dithiazines
can also be synthesized by thiomethylation of imines6 or
by reactions of amines with sodium hydrosulfide and formꢀ
aldehyde.7,8 Such N,Sꢀcontaining heterocycles are bioꢀ
logically active9 and exhibit the properties of complexones
for precious metals.10
Scheme 1
To further investigate multicomponent condensation
of various amines with formaldehyde and hydrogen sulꢀ
fide and develop an efficient method for the synthesis of
N,Sꢀcontaining heterocycles (substituted dithiazines and
oxathiazines), we studied cyclothiomethylation of aliꢀ
phatic monoꢀ and diamines with formaldehyde and hydroꢀ
gen sulfide. nꢀButylꢀ (1a), nꢀhexylꢀ (1b), cyclohexylꢀ (1c),
nꢀnonylꢀ (1d), and ethanolamines (1e) were used as the
starting monoamines (Scheme 1). The reaction condiꢀ
tions were optimized with nꢀhexylamine as an example by
varying the temperature, the concentrations of the startꢀ
ing compounds, and the order of addition of the subꢀ
strates and the reagents to the reaction mixture. The yields
and ratios of the products are given in Table 1. It was
found that the heterocyclization of amine 1b with sodium
hydrosulfide and formaldehyde according to a known
method7 gave dithiazine 2b in a somewhat lower yield
than that attained in a hydrogen sulfide—formaldehyde
system (see Table 1). In addition, use of the less expensive
R = Bun (1a, 2a, 3a, 4), nꢀC6H13 (1b, 2b), cycloꢀC6H11 (1c, 2c),
nꢀC9H19 (1d, 2d), HO(CH2)2 (1e, 2e, 3b); R´ = OH (5a), SH (5b)
Cyclothiomethylation was carried out in two ways.
According to the first method (method A), hydrogen sulꢀ
fide was bubbled through a mixture of an amine and formꢀ
aldehyde. According to the second one (method B), the
starting amine was added to a thiomethylating mixture
prepared by bubbling gaseous H2S through an aqueous
solution of formaldehyde (see Scheme 1).
The first method (at 80 °C) proved to be more effiꢀ
cient for the preparation of dithiazines 2 (see Table 1).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 423—427, February, 2005.
1066ꢀ5285/05/5402ꢀ0432 © 2005 Springer Science+Business Media, Inc.

Cyclothiomethylation of amines with H2S—CH2O
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 2, February, 2005
433
Table 1. Effects of the structure of the aliphatic amine, the reaction temperature T, and the order of mixing of the
starting reagents (methods A and B) on the total yield (Y ) and ratio of the reaction products
Starting
reagent
R
Kb*
T/°C Method Y (wt.%)
Ratio of the reaction products (%)
2
3
4
5a,b
1a
1b
Bun
4.0•10–4
4.0•10–4
4.4•10–4
4.4•10–4
4.4•10–4
4.4•10–4
4.4•10–4
4.4•10–4
4.4•10–4
4.4•10–4
4.4•10–4
4.4•10–4
3.1•10–5
3.1•10–5
20
40
20
40
80
20
40
80
20
20
80
20
20
80
A
A
A
A
A
B
B
B
—**
A
45
50
10
24
60
51
26
56
11
27
43
24
48
60
73
60
35
42
60
27
39
55
100
100
100
40
86
94
15
40
—
—
—
—
—
—
—
—
—
—
14
6
12
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
65
58
40
73
61
21
—
—
—
60
—
—
Bun
nꢀС6Н13
nꢀС6Н13
nꢀС6Н13
nꢀС6Н13
nꢀС6Н13
nꢀС6Н13
nꢀС6Н13
cycloꢀС6Н11
cycloꢀС6Н11
nꢀС9Н19
НО(СН2)2
НО(СН2)2
1с
A
A
A
A
1d
1e
* The basicity constant Kb was taken from Ref. 11.
** Heterocyclization in the formaldehyde—sodium hydrosulfide system according to a known method.7
Along with dithiazine 2b, the reaction mixture contained
a mixture of mercaptomethanol 5a and methanedithiol 5b
(GCꢀMS data), which seem to be intermediate products
involved in amine thiomethylation. Analogous compounds
5a,b were obtained by thiomethylation of nꢀnonylamine
(1d) according to method A.
The reactions of amines 1a—e with formaldehyde and
H2S afford dithiazines 2a—e (GCꢀMS data); in the case
of butylamine (1a) and ethanolamine (1e), individual
oxathiazines 3a,b and dioxazine 4 were isolated and idenꢀ
tified by 13C and 1H NMR spectroscopy.
C(6) atoms, respectively. The 1H NMR spectrum of prodꢀ
uct 3a shows signals for the methylene protons at δ 4.22,
4.71, and 4.00 with an integrate intensity ratio of 1 : 1 : 1.
The mass spectrum of compound 3a contains the peak of
the molecular ion [M]+ with m/z 161 and peaks of charꢀ
acteristic fragmentation ions produced by successive deꢀ
tachment from [M]+ of fragments containing the methylꢀ
ene groups and the S and O atoms. Based on these data,
we formulated compound 3a as 5ꢀnꢀbutylperhydroꢀ1,3,5ꢀ
oxathiazine.
In the 13C NMR spectrum of product 4, signals are
shifted downfield. The signal at δ 94.6 was assigned to the
C(2) atom between two O atoms, while the signal at δ 78.8
belongs to the C atoms between the N and O atoms in the
The formation of three products in the thiomethylation
1
of nꢀbutylamine (1a) was also confirmed by H and
13C NMR spectra. The major product was nꢀbutyldiꢀ
thiazine 2a; this is evident from the 13C NMR spectrum
containing a signal at δ 53.6 for two magnetically equivaꢀ
lent C atoms of the methylene groups of the NCH2S
fragment in the dithiazine ring and a signal at δ 34.6 for
the C atom of the methylene group between two S atoms.
1
dioxazine ring. The H NMR spectrum of compound 4
shows singlet signals for the methylene protons at δ 4.74
and 5.07 in the 1 : 2 ratio. The mass spectrum of product 4
contains the peak of the molecular ion [M]+ with m/z 145
and peaks of fragmentation ions produced by successive
detachment from [M]+ of fragments containing the meꢀ
thylene groups and the O atoms. Based on these data, the
structure of 5ꢀnꢀbutylperhydroꢀ1,3,5ꢀdioxazine was asꢀ
signed to compound 4.
1
The H NMR spectrum shows, along with the signals for
the protons of the Bun group, broadened singlets at δ 4.14
and 4.50 in the 1 : 2 ratio corresponding to the methylene
protons of the dithiazine ring at the C(2), C(4), and C(6)
atoms, respectively. The mass spectrum of product 2a
contains the peak of the molecular ion [M]+ with m/z 177
and peaks of fragmentation ions produced by successive
detachment from [M]+ of fragments containing the meꢀ
thylene groups and the S atoms.
The structures of dithiazines 2b—e were determined
analogously.
The fairly selective thiomethylation of ethylenediꢀ
amine (6) by method A predominantly gave 5ꢀ[2ꢀ(perꢀ
hydroꢀ1,3,5ꢀdithiazinꢀ5ꢀyl)ethyl]perhydroꢀ1,3,5ꢀdiꢀ
thiazine (7) (Scheme 2, Table 2). Its content in the reacꢀ
tion mixture at 80 °C was ~90%, the overall conversion of
the starting reagents being ~50%. In each experiment,
1,3ꢀthiazetidine 8 was detected in the reaction mixture
along with dithiazine 7. The thiomethylation of ethyleneꢀ
In nꢀbutyloxathiazine 3a, all the C atoms of the ring
are magnetically nonequivalent and manifest themselves
in the 13C NMR spectrum as three signals at δ 72.1, 81.7,
and 55.2. They were assigned, with consideration of the
increments of the heteroatoms, to the C(2), C(4), and

434
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 2, February, 2005
Khafizova et al.
Table 2. Effects of the reaction temperature T and the order of
mixing of the starting reagents (methods A and B) on the total
with m/z 268 and peaks of fragmentation ions with
m/z 235, 222, 190, 176, and 130 ([M – HS]+,
[M – SCH2]+, [M – SCH2S]+, [M – SCH2SCH2]+, and
[M – SCH2SCH2SCH2]+, respectively).
yield (Y ) and ratio of the cyclothiomethylation products from
11
ethylenediamine (6) (Kb = 1.15•10–4
)
The mass spectrum of compound 8 contains the peak
of the molecular ion [M]+ with m/z 130 and peaks of
fragmentation ions with m/z 98, 84, and 56 ([M – SCH2]+
and [M – SCH2NCH2]+). In the 13C NMR spectrum,
three signals at δ 54.9, 55.2, and 128.1 correspond to the
thiazetidine, ethylene, and imino fragments, respectively.
According to these data, we assigned the 3ꢀ(2ꢀmethylꢀ
ideneaminoethyl)ꢀ1,3ꢀthiazetidine structure to comꢀ
pound 8.
T
/°C
Method
Y
Ratio of the reaction products (%)
(wt.%)
7
8
9
10
11
60
80
20
60
A
A
B
B
46
49
24
27
53
90
12
18
25
10
62
66
22
—
5
—
—
6
—
—
15
8
4
4
diamine by method B reduced the selectivity of the reacꢀ
tion. The reaction products were 1,3ꢀthiazetidine 8,
1,3ꢀoxazetidine 9, 1,3,5ꢀdioxazine 10, and 1,3,5ꢀoxaꢀ
thiazine 11 (see Scheme 2, Table 2).
As can be seen from Table 1, the yields of cyclothioꢀ
methylation products increase with a decrease in the baꢀ
sicity of the starting amine. The highest yields of diꢀ
thiazines were attained with ethanolamine (1e) (56%) and
ethylenediamine (6) (44%). The yields of dithiazines from
nꢀbutylꢀ (1a), nꢀhexylꢀ (1b), and cyclohexylamines (1c)
were somewhat lower (33, 36, and 43%, respectively).
nꢀNonylamine (1d) proved to be least reactive in cycloꢀ
thiomethylation (10%).
Scheme 2
Thus, the optimum conditions for the synthesis of
dithiazines from aliphatic amines were found to arise at
80 °C in the presence of a triple molar excess of the
thiomethylating mixture CH2O—H2S. We found that with
a decrease in the basicity of the primary aliphatic amine,
it becomes more reactive in cyclothiomethylation.
Experimental
1
H and 13C NMR spectra were recorded on a Jeol FX 90 Q
spectrometer (89.55 and 22.50 MHz, respectively) in CDCl3
with Me4Si as the internal standard. IR spectra were recorded
on a Specord 75IR spectrophotometer (Nujol). GCꢀMS analyꢀ
sis was carried out with a Finnigan 4021 instrument (glass capilꢀ
lary column 50 000×0.25 mm, HPꢀ5 stationary phase, helium as
a carrier gas, temperature rise from 50 to 300 °C at a rate of
5 deg min–1, evaporator temperature 280 °C, ion source temꢀ
perature 250 °C, 70 eV). Compounds 2a—e, 3a,b, 4, 7, and 8
were isolated by fractional recrystallization from chloroform.
Cyclothiomethylation of aliphatic amines (general proceꢀ
dure A). A threeꢀneck flask fitted with a stirrer, a reflux conꢀ
denser, and a bubbler and controlled at a given temperature was
charged with formalin (5.5 mL, 0.075 mol) and an amine
(0.025 mol). After two hours, gaseous hydrogen sulfide (1.12 L,
0.05 mol) was added for 1 h. The products were extracted from
the resulting mixture with chloroform.
General procedure B. Gaseous hydrogen sulfide (1.12 L,
0.05 mol) was bubbled through formalin (5.5 mL, 0.075 mol)
for 2 h. Then, an amine (0.025 mol) was added dropwise for 1 h.
The products were extracted from the resulting mixture with
chloroform.
5ꢀnꢀButylperhydroꢀ1,3,5ꢀdithiazine (2a) was obtained acꢀ
cording to procedure A (20 °C). The yield of compound 2a was
1.46 g (33%), m.p. 95—96 °C, I = 1443. Found (%): C, 47.71;
H, 8.24; N, 8.12; S, 35.93. C7H15NS2. Calculated (%): C, 47.46;
The thiomethylation of ethylenediamine (6) by
method B with formaldehyde and hydrogen sulfide in the
1 : 6 : 4 ratio mainly gave thiazetidine 8 (GCꢀMS data).
Minor products were heterocycles 7 and 9—11 (see
Table 2). The mass spectra of compounds 9—11 contain
the molecular ion peaks and peaks of fragmentation ions
produced by successive detachment from [M]+ of fragꢀ
ments containing the methylene groups and the S, O, and
N atoms.
For some of the heterocycles obtained, Kováts12 reꢀ
tention indices (I) were determined by GCꢀMS analysis.
Heterocycles 7 (method A) and 8 (method B) were
isolated by fractional recrystallization from chloroform.
The 13C NMR spectrum of compound 7 shows, apart
from the characteristic signals for the dithiazine ring
(δ 33.9 and 58.4), a signal at δ 46.1 belonging to the C(7)
and C(8) atoms of the ethylene fragment. In the 1H NMR
spectrum of compound 7, the chemical shifts and intenꢀ
sity ratio of the signals observed (δ 3.20, 4.09, and 4.45)
confirmed the structure proposed. The mass spectrum of
product 7 contains the peak of the molecular ion [M]+

Cyclothiomethylation of amines with H2S—CH2O
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 2, February, 2005
435
H, 8.47; N, 7.91; S, 36.16. IR, ν/cm–1: 720 (C—S), 1120—1190
(C—N), 1460 (CH3), 1470 (CH2), 2830 (CH2). H NMR, δ:
C(4), C(6)); 59.2 (t, C(8)). MS, m/z (Irel (%)): 165 [M]+
(84); 133 [M – S]+ (12); 119 [M – SCH2]+ (48); 87 [M –
SCH2S]+ (100).
1
1.07 (s, 3 H, C(10)H3); 1.17—1.29 (m, 4 H, C(8)H2, C(9)H2);
3.68—3.91 (m, 2 H, C(7)H2); 4.14 (s, 2 H, C(2)H2); 4.50 (s,
4 H, C(4)H2, C(6)H2). 13C NMR, δ: 27.5 (q, C(10)); 29.5 (t,
C(9)); 29.7 (t, C(8)); 34.6 (t, C(2)); 50.9 (t, C(7)); 53.6 (t, C(4),
C(6)). MS, m/z (Irel (%)): 177 [M]+ (60); 162 [M – Me]+ (24);
131 [M – CH2S]+ (23); 99 [M – SCH2S]+ (56); 57
[M – SCH2S(CH2)3]+ (100).
5ꢀnꢀButylperhydroꢀ1,3,5ꢀoxathiazine (3a) was obtained acꢀ
cording to procedure A (40 °C). The yield of compound 3a was
0.8 g (20%), m.p. 88—89 °C, I = 1217. Found (%): C, 51.84;
H, 9.50; N, 8.51; S, 20.02. C7H15NOS. Calculated (%): C, 52.17;
H, 9.32; N, 8.69; S, 19.87. IR, ν/cm–1: 580—650 (C—S), 1170
1
(C—N), 1460 (CH3), 1470 (CH2), 2850 (CH2). H NMR, δ:
5ꢀnꢀHexylperhydroꢀ1,3,5ꢀdithiazine (2b) was obtained acꢀ
cording to procedure A (80 °C). The yield of compound 2b was
1.84 g (36%), m.p. 84—85 °C, I = 1720. Found (%): C, 52.49;
H, 9.39; N, 6.68; S, 31.44. C9H19NS2. Calculated (%): C, 52.68;
H, 9.27; N, 6.83; S, 31.22. IR, ν/cm–1: 690—720 (C—S), 1090
1.07 (s, 3 H, C(10)H3); 1.17—1.29 (m, 4 H, C(8)H2, C(9)H2);
3.68—3.91 (m, 2 H, C(7)H2); 4.00 (s, 2 H, C(6)H2); 4.22 (m,
2 H, C(2)H2); 4.71 (s, 2 H, C(4)H2). 13C NMR, δ: 28.0 (q,
C(10)); 29.4 (t, C(9)); 29.6 (t, C(8)); 50.7 (t, C(7)); 55.2 (t,
C(6)); 72.1 (t, C(2)); 81.7 (t, C(4)). MS, m/z (Irel (%)):
161 [M]+ (15); 146 [M – CH3]+ (13); 114 [M – CH3 – S]+ (9);
100 [M – CH3SCH2]+ (9); 70 [M – CH3S(CH2)2O]+ (100).
2ꢀ(Perhydroꢀ1,3,5ꢀoxathiazinꢀ5ꢀyl)ethanꢀ1ꢀol (3b) was obꢀ
tained according to procedure A (20 °C). The yield of compound
3b was 0.26 g (7%), m.p. 41—42 °C. Found (%): C, 40.26;
H, 7.43; N, 9.31; S, 21.59. C5H11NO2S. Calculated (%):
C, 40.27; H, 7.38; N, 9.40; S, 21.48. IR, ν/cm–1: 650—730
(C—S), 1170 (C—N), 1420 (S—CH2), 2850 (CH2), 3610 (OH).
13C NMR, δ: 48.8 (t, C(7)); 48.9 (t, C(8)); 57.5 (t, C(6)); 65.0
(t, C(2)); 89.0 (t, C(4)). MS, m/z (Irel (%)): 149 [M]+ (100); 103
[M – CH2S]+ (36); 70 [M – CH2SOOH]+ (72).
5ꢀnꢀButylperhydroꢀ1,3,5ꢀdioxazine (4) was obtained accordꢀ
ing to procedure A (20 °C). The yield of compound 4 was 0.18 g
(5%), m.p. 45—46 °C, I = 996. Found (%): C, 58.08; H, 10.12;
N, 9.47. C7H15O2N. Calculated (%): C, 57.93; H, 10.34; N, 9.66.
IR, ν/cm–1: 1170 (C—N), 1460 (CH3), 1470 (CH2), 2850 (CH2).
1H NMR, δ: 1.07 (s, 3 H, C(10)H3); 1.17—1.29 (m, 4 H, C(8)H2,
C(9)H2); 3.68—3.91 (m, 2 H, C(7)H2); 4.74 (s, 2 H, C(2)H2);
5.07 (s, 4 H, C(4)H2, C(6)H2). 13C NMR, δ: 28.5 (q, C(10));
29.5 (t, C(9)); 29.7 (t, C(8)); 54.6 (t, C(7)); 78.8 (t, C(4), C(6));
94.6 (t, C(2)). MS, m/z (Irel (%)): 145 [M]+ (10); 130
[M – CH3]+ (19); 84 [M – CH3OCH2O]+ (8); 70 [M –
CH3O(CH2)2O]+ (100).
1
(C—N), 1380 (CH3), 1470 (CH2), 2900 (CH2). H NMR, δ:
0.85 (s, 3 H, C(12)H3); 1.20—1.35 (m, 6 H, C(9)H2, C(10)H2,
C(11)H2); 1.35—1.50 (t, 2 H, C(8)H2, 3J = 7.1 Hz); 2.97 (t,
2 H, C(7)H2, 3J = 7.1 Hz); 4.19 (s, 2 H, C(2)H2); 4.52 (s, 4 H,
C(4)H2, C(6)H2). 13C NMR, δ: 14.2 (q, C(12)); 23.0 (t, C(11));
27.3 (t, C(9)); 27.3 (t, C(8)); 32.1 (t, C(10)); 33.6 (t, C(2)); 49.0
(t, C(7)); 58.2 (t, C(4), C(6)). MS, m/z (Irel (%)): 205 [M]+
(88); 173 [M – S]+ (8); 159 [M – CH2S]+ (16); 127
[M – SCH2S]+ (100); 112 [M – SCH2SCH3]+ (24); 98 [M –
SCH2SCH3CH2]+ (24); 84 [M – SCH2SCH3(CH2)2]+ (56).
5ꢀCyclohexylperhydroꢀ1,3,5ꢀdithiazine (2c) was obtained acꢀ
cording to procedure A (80 °C). The yield of compound 2c was
2.2 g (43%), m.p. 58 °C, I = 1814. Found (%): C, 53.25; H, 8.24;
N, 6.73; S, 31.78. C9H17NS2. Calculated (%): C, 53.20; H, 8.37;
N, 6.90; S, 31.53. IR, ν/cm–1: 670—720 (C—S), 1120—1180
(C—N), 1370 (S—CH2), 1450 (CH2), 2850 (CH2). 1H NMR, δ:
0.40—1.50 (m, 10 H, C(8)H2, C(9)H2, C(10)H2, C(11)H2,
C(12)H2); 3.15 (m, 2 H, C(7)H2); 3.45 (s, 4 H, C(4)H2,
C(6)H2); 3.77 (s, 2 H, C(2)H2). 13C NMR, δ: 24.5 (t, C(9),
C(11)); 25.1 (t, C(10)); 28.9 (t, C(8), C(12)); 30.1 (t, C(2));
53.0 (t, C(7)); 57.2 (t, C(4), C(6)). MS, m/z (Irel (%)): 203 [M]+
(98); 171 [M – S]+ (6); 157 [M – CH2S]+ (30); 125
[M – SCH2S]+ (100); 111 [M – SCH2SCH2]+ (12); 97 [M –
SCH2SCH2CH2]+ (12); 83 [M – SCH2SCH2CH2N]+ (51).
5ꢀnꢀNonylperhydroꢀ1,3,5ꢀdithiazine (2d) was obtained acꢀ
cording to procedure A (20 °C). The yield of compound 2d was
0.5 g (10%), m.p. 60—61 °C, I = 2055. Found (%): C, 58.14;
H, 10.23; N, 5.49; S, 26.14. C12H25NS2. Calculated (%):
C, 58.30; H, 10.12; N, 5.67; S, 25.91. IR, ν/cm–1: 700 (C—S),
1180 (C—N), 1380 (CH3), 1420 (S—CH2), 1450 (CH2),
2840 (CH2). 1H NMR, δ: 0.20—0.80 (m, 17 H, C(15)H3,
C(8)H2—C(14)H2); 3.25 (m, 2 H, C(7)H2); 3.65 (s, 4 H,
C(4)H2, C(6)H2); 4.01 (s, 2 H, C(2)H2). 13C NMR, δ: 14.1
(q, C(15)); 22.6 (t, C(14)); 27.0 (t, C(13)); 27.2 (t, C(12)); 29.2
(t, C(11)); 29.5 (t, C(10)); 29.5 (t, C(9)); 31.8 (t, C(8)); 34.0
(t, C(2)); 48.8 (t, C(7)); 58.2 (t, C(4), C(6)). MS, m/z (Irel (%)):
247 [M]+ (42); 215 [M – S]+ (12); 169 [M – SCH2S]+ (100);
154 [M – SCH2SCH3]+ (36); 140 [M – SCH2SCH3CH2]+ (36).
2ꢀ(Perhydroꢀ1,3,5ꢀdithiazinꢀ5ꢀyl)ethanꢀ1ꢀol (2e) was obꢀ
tained according to procedure A (80 °C). The yield of compound
2e was 2.36 g (56%), m.p. 44—45 °C. Found (%): C, 36.42;
H, 6.55; N, 8.59; S, 38.83. C5H11NOS2. Calculated (%):
C, 36.36; H, 6.67; N, 8.48; S, 38.79. IR, ν/cm–1: 580—650
(C—S), 1170 (C—N), 1420 (S—CH2), 2850 (CH2), 3610 (OH).
1H NMR, δ: 1.95 (t, 2 H, C(7)H2, 3J = 7.1 Hz); 2.75 (s, 2 H,
C(2)H2); 3.41 (s, 4 H, C(4)H2, C(6)H2); 3.60 (t, 2 H, C(8)H2,
3J = 7.1 Hz). 13C NMR, δ: 33.5 (t, C(2)); 51.5 (t, C(7)); 58.7 (t,
Mercaptomethanol (5a). MS, m/z (Irel (%)): 62 [M – H2]+
(51); 46 [M – H2O]+ (100).
Methanedithiol (5b). MS, m/z (Irel (%)): 80 [M]+ (100); 78
[M – H2]+ (38); 46 [M – H2S]+ (90); 34 [H2S]+ (78).
5ꢀ[2ꢀ(Perhydroꢀ1,3,5ꢀdithiazinꢀ5ꢀyl)ethyl]perhydroꢀ1,3,5ꢀ
dithiazine (7) was obtained according to procedure A (80 °C).
The yield of compound 7 was 2.9 g (44%), m.p. 179—180 °C,
I = 2600. Found (%): C, 36.07; H, 5.73; N, 10.26; S, 47.94.
C6H12N4S2. Calculated (%): C, 35.82; H, 5.97; N, 10.45;
S, 47.76. IR, ν/cm–1: 670—690 (C—S), 1090 (C—N), 1450
(S—CH2), 2840—2900 (CH2). 1H NMR, δ: 3.20 (s, 4 H, C(2)H2,
C(12)H2); 4.09 (s, 4 H, C(7)H2, C(8)H2); 4.45 (s, 8 H, C(4)H2,
C(6)H2, C(10)H2, C(14)H2). 13C NMR, δ: 33.9 (t, C(2), C(12));
46.1 (t, C(7), C(8)); 58.4 (t, C(4), C(6), C(10), C(14)). MS,
m/z (Irel (%)): 268 [M]+ (12); 222 [M – SCH2]+ (30); 190
[M – SCH2S]+ (54); 176 [M – SCH2SCH2]+ (54); 130 [M –
SCH2SCH2SCH2]+ (100).
3ꢀ(2ꢀMethylideneaminoethyl)ꢀ1,3ꢀthiazetidine (8) was obꢀ
tained according to procedure B (60 °C). The yield of comꢀ
pound 8 was 0.6 g (18%), m.p. 153—154 °C. IR, ν/cm–1
:
670—680 (C—S), 1110 (C—N), 1450 (S—CH2), 2840—2900
(CH2). 1H NMR, δ: 3.10 (s, 4 H, C(5)H2, C(6)H2); 4.93 (s, 4 H,
C(2)H2, C(4)H2); 7.28 (s, 2 H, C(8)H2). 13C NMR, δ: 54.9
(t, C(2), C(4)); 55.2 (t, C(5), C(6)); 128.1 (t, C(8)). MS,

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Russ.Chem.Bull., Int.Ed., Vol. 54, No. 2, February, 2005
Khafizova et al.
m/z (Irel (%)): 130 [M]+ (100); 98 [M – S]+ (16); 84
[M – SCH2]+ (16); 56 [M – SCH2CH2N]+ (90).
3ꢀ(2ꢀMethylideneaminoethyl)ꢀ1,3ꢀoxazetidine (9) was obꢀ
tained according to procedure A (60 °C). The yield of comꢀ
pound 9 was 0.28 g (10%). MS, m/z (Irel (%)): 114 [M]+ (82); 84
[M – OCH2]+ (96); 56 [M – OCH2CH2N]+ (100).
5ꢀ(2ꢀMethylideneaminoethyl)perhydroꢀ1,3,5ꢀdioxazine (10)
was obtained according to procedure B (20 °C). The yield of
compound 10 was 0.04 g (1%). MS, m/z (Irel (%)): 144 [M]+
(57); 114 [M – OCH2]+ (100); 100 [M – CH2OCH2]+ (62); 84
[M – CH2OCH2O]+ (12); 70 [M – CH2OCH2OCH2]+ (33).
5ꢀ(2ꢀMethylideneaminoethyl)perhydroꢀ1,3,5ꢀoxathiazine
(11) was obtained according to procedure B (20 °C). The yield
of compound 11 was 0.16 g (4%). MS, m/z (Irel (%)): 160 [M]+
(40); 128 [M – S]+ (5); 114 [M – SCH2]+ (28); 100
[M – CH2SCH2]+ (10); 84 [M – CH2SCH2O]+ (28); 70
[M – CH2SCH2OCH2]+ (100).
5. R. V. Kunakova, S. R. Khafizova, Yu. S. Dal´nova, R. S.
Aleev, L. M. Khalilov, and U. M. Dzhemilev, Neftekhimiya,
2002, 42, 382 [Petroleum Chemistry, 2002, 42, 347 (Engl.
Transl.)].
6. D. Collins and J. Graymore, J. Chem. Soc., 1953, 143.
7. E. Juaristi, E. Gonzalez, B. Pinto, B. Johnston, and
R. Nagelkerke, J. Am. Chem. Soc., 1989, 111, 6745.
8. A. N. Kurchan and A. G. Kutateladze, Org. Lett., 2002,
4(23), 4129.
9. RF Pat. 2 160 233; Byull. Izobret., 2000, 34.
10. Yu. I. Murinov, V. N. Maistrenko, and N. G. Afzaletdinova,
Ekstraktsiya metallov S,Nꢀorganicheskimi soedineniyami [Exꢀ
traction of Metals with S,NꢀContaining Organic Compounds],
Nauka, Moscow, 1993, 192 (in Russian).
11. Spravochnik khimika [The Chemist´s Reference Book],
Ed. B. P. Nikol´skii, Khimiya, Moscow—Leningrad, 1964,
3, 98 pp. (in Russian).
12. M. S. Vigdergauz, L. V. Semenchenko, V. A. Ezrets, and
Yu. N. Bogoslovskii, Kachestvennyi gazokhromatograficheskii
analiz [Qualitative Analysis by Gas Chromatography], Nauka,
Moscow, 1978, 244 (in Russian).
References
1. A. Wohl, Ber., 1886, 19, 2344.
2. D. Collins and J. Graymore, J. Chem. Soc., 1953, 4089.
3. D. Collins and J. Graymore, J. Chem. Soc., 1957, 9.
4. R. S. Aleev, Yu. S. Dal´nova, Yu. N. Popov, R. M.
Masagutov, and S. R. Rafikov, Dokl. Akad. Nauk SSSR,
1988, 303, 873 [Dokl. Chem., 1988 (Engl. Transl.)].
Received November 19, 2003;
in revised form April 6, 2004