Thiomethylation of aromatic amines: Efficient method for the synthesis of heterocyclic compounds

Article abstract of DOI:10.1023/A:1026021124424

Primary aromatic amines were thiomethylated by formaldehyde and hydrogen sulfide. N-Substituted 1,3-thiazetidines, 4,5-dihydro-1,3,5-dithiazines, 3,4,5,6-tetrahydro-2H-1,3,5-thiadiazines, and 4,5-dihydro-1,3,5-oxathiazines were prepared for the first time

Full text of DOI:10.1023/A:1026021124424

Russian Chemical Bulletin, International Edition, Vol. 52, No. 8, pp. 1817—1821, August, 2003
1817
Thiomethylation of aromatic amines: efficient method for the synthesis
of heterocyclic compounds
ꢀ
S. R. Khafizova, V. R. Akhmetova, R. V. Kunakova, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis,
Bashkortostan Republic Academy of Sciences and Ufa Research Center of the Russian Academy of Sciences,
141 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347 2) 31 2750. Eꢀmail: ink@anrb.ru
Primary aromatic amines were thiomethylated by formaldehyde and hydrogen sulfide.
NꢀSubstituted 1,3ꢀthiazetidines, 4,5ꢀdihydroꢀ1,3,5ꢀdithiazines, 3,4,5,6ꢀtetrahydroꢀ2Hꢀ1,3,5ꢀ
thiadiazines, and 4,5ꢀdihydroꢀ1,3,5ꢀoxathiazines were prepared for the first time starting from
metaꢀ and paraꢀtoluidines, metaꢀ, paraꢀ, and orthoꢀanisidines, and paraꢀxylidine. Amines
characterized by higher mobility of hydrogen atoms produced previously unknown fourꢀmemꢀ
bered thiazetidines, whereas amines characterized by lower mobility of hydrogen atoms gave
sixꢀmembered thiadiazines. The sorption properties with respect to silver were studied for the
compounds, which were prepared from pꢀtoluidine and pꢀanisidine.
Key words: thiomethylation, primary aromatic amines, O,N,Sꢀcontaining heterocyclic
compounds, formaldehyde, hydrogen sulfide, 1,3ꢀthiazetidines, 4,5ꢀdihydroꢀ1,3,5ꢀdithiazines,
3,4,5,6ꢀtetrahydroꢀ2Hꢀ1,3,5ꢀthiadiazines, 4,5ꢀdihydroꢀ1,3,5ꢀoxathiazines, sorption of precious
metals.
The reactions of formaldehyde and hydrogen sulfide
with amines open up new possibilities for the synthesis of
heterocycles containing simultaneously the oxygen, niꢀ
trogen, and sulfur atoms. This synthesis was first carried
out using the reaction of methylamine with formaldehyde
and hydrogen sulfide as an example.1,2 Later on, acyclic
bis(4ꢀmorpholinomethyl)ꢀ and bis(1ꢀpiperidinomethyl)
sulfides and selenides have been prepared by these reacꢀ
tions starting from piperidine and morpholine, respecꢀ
tively.3—5
Recently, we have demonstrated that thiomethylation
of amino acids can be used for preparing difficultly accesꢀ
sible carboxyꢀcontaining 1,3,5ꢀdithiazine derivatives.6 The
resulting heterocyclic compounds exhibit high complexꢀ
forming ability with respect to silver. Such heterocyclic
compounds hold considerable promise as sorbents7,8 and
biologically active compounds.9
out in a twoꢀphase water—diethyl ether medium, which
provided solubility of formaldehyde and hydrogen sulfide
in water and solubility of aromatic amines in ether. We
examined metaꢀ (1a) and paraꢀtoluidines (1b), metaꢀ (1c),
paraꢀ (1d), and orthoꢀanisidines (1e), and paraꢀxyliꢀ
dine (1f). Crystalline products 2—5 were prepared by bubꢀ
bling hydrogen sulfide through a solution of formaldeꢀ
hyde in water in a molar ratio of 2 : 3 followed by the
addition of a solution of amine 1 in diethyl ether at the
temperature from 0 to 40 °C. The conversions of the startꢀ
ing amines were ≥90% (Scheme 1), except for orthoꢀsubꢀ
stituted aromatic amine, viz., oꢀanisidine (1е), whose conꢀ
version was 20%.
According to the data from HLPC, the reactions of
metaꢀ (1a,c) and paraꢀsubstituted anilines (1b,d) at 20
and 40 °C afforded mixtures of compounds 2—4 with the
predominant formation of one of them. The composiꢀ
tions of heterocycles 2—4 depend on the nature of amine,
the ratio between the starting reagents, and the reaction
temperature (Table 1).
For toluidines 1a,b, a decrease in the temperature to
0 °C led to a decrease in the selectivity of the reaction.
Under these conditions, thiazetidines 2a,b and thiaꢀ
diazines 4a,b were produced in equal amounts, whereas
dithiazines 3a,b were prepared in lower yields. The inꢀ
verse dependence was observed for pꢀxylidine (1f), i.e.,
only dithiazine 3f was generated upon a decrease in the
temperature to 0 °C.
Taking into account the practical value of O,N,Sꢀconꢀ
taining compounds and also with the aim of extending the
field of application of thiomethylation, we studied liquidꢀ
phase condensation of formaldehyde and hydrogen sulꢀ
fide with primary aromatic amines, which have not been
earlier involved in such transformations.
Results and Discussion
Liquidꢀphase thiomethylation of primary aromatic
amines by formaldehyde and hydrogen sulfide was carried
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1722—1726, August, 2003.
1066ꢀ5285/03/5208ꢀ1817 $25.00 © 2003 Plenum Publishing Corporation

1818
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 8, August, 2003
Khafizova et al.
Scheme 1
the following series: mꢀtoluidine > oꢀtoluidine > pꢀtoꢀ
luidine.
Oxathiazine 5 was generated only from pꢀtoluidine
(1b) and pꢀxylidine (1f) in a yield of no higher than 6%
(see Table 1).
Heterocyclic compounds 2—5 were isolated in indiꢀ
vidual form by column chromatography. The mass specꢀ
trum of product 2a has the molecuar ion peak
[M]+ at m/z 165 and the fragmentation ion peaks
[M – S]+, [M – CH2S]+, [M – CH2SCH2]+, and
[M – NCH2SCH2]+ at m/z 133, 119, 105, and 91, respecꢀ
tively, corresponding to the characteristic fragments
formed from [M]+ by the abstraction of the sulfur atom
and thiomethylene groups, among them those involving
the nitrogen atom. The 1H NMR spectrum shows a signal
at δH 4.87 assigned to the protons of the CH2 groups of
the thiazetidine ring and signals for the protons of the aroꢀ
matic moiety containing the methyl group at δH 6.58—7.22
and 2.3511 (Table 2). The 13C NMR spectrum has a signal
for the carbon atom of the thiazetidine ring of 2a at
δC 56.75 (Table 3). In the IR spectrum of product 2a, the
stretching vibration band of the amino group at 3150 cm–1
disappears. The stretching vibration band of the methyl
group is observed at 2850 cm–1 and absorption characterꢀ
istic of the aromatic ring is observed at 1600 cm–1. The
absorption band at 1050 cm–1 is assigned to stretching
vibrations of the C—N bond. Weak absorption of the
C—S bond is observed at 580—650 cm–1 (see Table 2).
The structure of thiadiazine 4b as N,Nꢀdisubstituted
tetrahydroꢀ2Hꢀ1,3,5ꢀthiadiazine was established based on
spectroscopic data (see Tables 2 and 3). The mass specꢀ
trum of product 4b shows the molecular ion [M]+
at m/z 284 and the fragmentation ions [M – H2S]+,
R = mꢀCH3 (a); pꢀCH3 (b); mꢀOCH3 (c); pꢀOCH3 (d);
oꢀOCH3 (e); 2,5ꢀ(CH3)2 (f); n = 1—6
[M
– –
CH2NPhCH3]+, [M SCH2NPhCH3]+,
The composition of the products of thiomethylation
of toluidines 1a,b depends ambiguously on the excess of
formaldehyde with respect to amine (6 : 1, see Table 1).
The reaction of mꢀtoluidine (1a) afforded thiazetidine 2a
as the major product (in 66% yield) and 1,3,5ꢀdithiazine
3a as a byꢀproduct (8%), whereas the reaction of pꢀtoluꢀ
idine (1b) gave rise to 1,3,5ꢀdithiazine 3b as the major
product (28%), 1,3,5ꢀoxathiazine 5b (6%) being formed
along with heterocycles 2b—4b (52%).
The following dependence was found: fourꢀmembered
thiazetidine 2a was predominantly prepared from
mꢀtoluidine (1a), dithiazines 3 were generated from all
anilines (see Table 1), whereas thiadiazines 4 were preꢀ
dominantly produced from pꢀtoluidine (1b). Apparently,
these results can be attributed to the difference in the
mobility of the hydrogen atoms in the starting anilines.
For example, less basic mꢀtoluidine (1a) gave thiazetidine
2a, whereas more basic pꢀtoluidine (1b) produced thiaꢀ
diazine 4b. These facts are in agreement with the data
published in the literature10 according to which the rate of
the reaction of toluidines with formaldehyde decreases in
[CH3PhNCH2]+, [CH3PhN]+, and [CH3Ph]+ at m/z 250,
1
165, 133, 119, 105, and 91, respectively. The H NMR
spectrum has signals at δH 4.90 and 5.09 with the integral
intensity ratio of 2 : 1, which are assigned to the methylꢀ
ene protons located between the S and N atoms and beꢀ
tween two nitrogen atoms, respectively. In addition, the
spectrum has signals of the methyl group and aromatic
protons at δH 2.30 and 6.91—7.01, respectively (see
Table 2). The 13C NMR spectrum shows a signal for two
carbon atoms located between the S and N atoms at
δC 54.29 and a signal for one carbon atom located beꢀ
tween two nitrogen atoms at δC 70.10.
We studied the sorption properties of a mixture of the
products of thiomethylation of pꢀtoluidine (1b) and
pꢀanisidine (1d) with respect to silver. Solutions of wastes
from photographic industry were used as a source of silꢀ
ver. The sorption was carried out in a static mode in a
solution of the metal extracted and determined photoꢀ
metrically on a KFKꢀ2 instrument according to standard
procedures.12 Based on the kinetic curves, it was found
that the equilibrium was attained after 100 min of expoꢀ

Thiomethylation of aromatic amines
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 8, August, 2003
1819
Table 1. Effects of the structure of aromatic amines, reaction temperature, and ratio between the starting
reagents on the yields and compositions of the reaction products
Starting
Ra
T/°C
Amine : CH2O : H2Sb
Y c
Reaction products (%)
compound
(wt.%)
1
2
3
4
5
1a
mꢀCH3
20
0
20
40
0
20
0
20
40
0
20
20
20
20
0
1 : 1 : 1
1 : 3 : 2
1 : 3 : 2
1 : 3 : 2
1 : 6 : 4
1 : 2 : 2
1 : 3 : 2
1 : 3 : 2
1 : 3 : 2
1 : 6 : 4
1 : 3 : 2
1 : 2 : 2
1 : 3 : 2
1 : 3 : 2
1 : 3 : 2
1 : 3 : 2
15
32
20
36
77
28
30
64
62
61
24
14
21
10
18
16
80
6
5
2
5
6
6
1
3
5
5
8
—
80
68
53
—
20
—
—
43
60
98
85
—
38
5
—
20
—
92
60
—
—
—
12
25
—
39
10
—
—
32
36
2
45
20
30
—
30
—
—
—
—
—
—
—
—
5
—
—
10
—
—
—
—
—
6
10
62
15
92
52
45
65
—
10
20
32
41
1b
pꢀCH3
1c
1d
mꢀОСН3
pꢀОСН3
1e
1f
oꢀОСН3
pꢀ(СН3)2
20
a The position in the starting amine.
b The molar ratio between the starting reagents.
c The total yield of the products.
150×4), λ = 254 nm. Bubbling of hydrogen sulfide was conꢀ
trolled using an ANPꢀ10 peristaltic pump.
sure of the sorbent (solid phase) to a solution of the metal
extracted at room temperature. The maximum capacity of
the mixture of the products derived from pꢀtoluidine and
pꢀanisidine was 1.1 and 0.76 g g–1, respectively. An inꢀ
crease in the temperature to 80 °C led to a decrease in
the time required for the attainment of equilibrium to
5—10 min, the sorbent capacity remaining virtually unꢀ
changed. The degree of extraction of silver is close
to 100%.
To summarize, we studied for the first time thioꢀ
methylation of aromatic amines giving rise to practically
valuable heterocyclic O,N,Sꢀcontaining compounds. We
synthesized previously unknown derivatives of 1,3ꢀthiazeꢀ
tidine, 1,3,5ꢀdithiazine, 1,3,5ꢀthiadiazine, and 1,3,5ꢀoxaꢀ
thiazine.
Thiomethylation of aromatic amines 1a—f. Calculated
amounts of a formaldehyde solution were placed in a temperaꢀ
tureꢀcontrolled threeꢀneck flask equipped with a magnetic stirꢀ
rer, a reflux condenser, and a bubbler. Hydrogen sulfide (preꢀ
pared from calculated amounts of Na2S and HCl) was bubbled
at a rate of 2.8 L h–1 to form a CH2O : H2S mixture in a ratio of
3 : 2. Then the corresponding amine dissolved in diethyl ether
was added dropwise to the reaction mixture. In the experiments,
the temperature was varied from 0 to 40 °C. The molar ratio
between the reagents was also varied (amine : CH2O = 1—6).
The crystals that precipitated were filtered off and dried. The
products were separated by column chromatography. The physiꢀ
cochemical and spectroscopic characteristics are given in
Tables 2 and 3.
3ꢀ(3ꢀMethylphenyl)ꢀ1,3ꢀthiazetidine (2a). The yield was 66%,
m.p. 184—185 °C, Rf 0.34. MS, m/z (Irel (%)): 165 [M]+ (26), 133
[M – S]+ (69), 119 [M – CH2S]+ (75), 105 [M – CH2SCH2]+
(82), 91 [M – NCH2SCH2]+ (29). Found (%): C, 65.54; H, 6.83;
N, 8.15; S, 19.48. C9H11NS. Calculated (%): C, 65.46; H, 6.67;
N, 8.48; S, 19.39.
Experimental
The 1H and 13C NMR spectra of compounds 2a, 3b, and
4a,b,d were recorded on a Bruker AMꢀ300 spectrometer operatꢀ
ing at 300 MHz. The 1H and 13C NMR spectra of all other
compounds were measured on a Jeol FX 90 Q spectrometer
operating at 89.55 and 22.50 MHz, respectively using CDCl3 as
the solvent. The IR spectra were recorded on a Specord 75 IR
spectrophotometer in Nujol mulls with KBr. The mass spectra
were obtained on an MX 1320 instrument with direct inlet of
samples at 100—150 °C and 70 eV. Thinꢀlayer chromatography
was carried out on Silufol UVꢀ254 silica gel using a 9 : 1 benꢀ
zene—ethanol mixture as the eluent. The HPLC analysis was
performed on an Altex chromatograph (Separon C18 column,
3ꢀ(4ꢀMethylphenyl)ꢀ1,3ꢀthiazetidine (2b). The yield was 12%,
m.p. 171—172 °C, Rf 0.34. MS, m/z (Irel (%)): 165 [M]+ (25), 133
[M – S]+ (10), 119 [M – CH2S]+ (29), 105 [M – CH2SCH2]+
(14), 91 [M – NCH2SCH2]+ (19). Found (%): C, 65.87; H, 6.74;
N, 8.23; S, 19.16. C9H11NS. Calculated (%): C, 65.46; H, 6.67;
N, 8.48; S, 19.39.
3ꢀ(4ꢀMethoxyphenyl)ꢀ1,3ꢀthiazetidine (2d). The yield was
13%, m.p. 119—120 °C, Rf 0.33. MS, m/z (Irel (%)): 181 [M]+
(4), 149 [M
– –
S]+ (4), 135 [M CH2S]+ (88), 121
[M – CH2SCH2]+ (14), 107 [M – NCH2SCH2]+ (4), 92
[M – CH3NCH2SCH2]+ (37). Found (%): C, 59.89; H, 6.27;

1820
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 8, August, 2003
Khafizova et al.
Table 2. 1H NMR and IR spectra of compounds 2—5
Table 3. 13C NMR spectra of compounds 2—5
Comꢀ
pound
δ (J/Hz)
IR,
ν/cm–1
Comꢀ
pound
δ (J/Hz)*
2а
2.35 (s, 3 H, Ме); 4.87 (m, 4 H,
NCH2S); 6.62 (s, 1 H, C6H4);
6.64 and 6.70 (d, 2 H, Ph, J = 7.8);
7.17 (t, 1 H, C6H4, J = 7.8)
2.08 (s, 3 H, Ме); 5.04 (m, 4 H,
NCH2S); 6.47—7.07 (m, 4 H, C6H4)
3.84 (s, 3 H, OМе); 4.63 (m, 4 H,
NCH2S); 6.70—7.28 (m, 4 H, C6H4)
2.10 (s, 3 H, Ме); 3.80 (s, 2 H,
SCH2S); 4.03 (s, 4 H, СH2N);
6.82—7.32 (m, 4 H, C6H4)
1050
2а
2b
2d
3а
3b
3c
3d
3e
3f
22.02 (q, Me); 56.75 (t, С(2), C(4)); 112.02 (d,
С(10)); 115.53 (d, С(6)); 120.35 (d, С(8)); 129.19
(d, С(7)); 139.07 (s, С(9)); 144.21 (s, С(5))
19.93 (q, Me); 56.54 (t, С(2), C(4)); 114.42
(d, С(6), C(10)); 118.71 (d, С(7), C(9));
(C—N),
580—650
(C—S)
1600,
2b
2d
3а
2850
129.44 (s, С(8)); 141.21 (s, С(5))
55.57 (q, OMe); 57.32 (t, С(2), C(4)); 114.88 (d,
С(6), C(10)); 115.85 (d, С(7), C(9)); 137.90
(s, С(5)); 152.46 (s, С(8))
21.88 (q, Me); 33.26 (t, С(2)); 56.67 (t, С(4), C(6));
115.14 (d, С(12)); 117.93 (d, С(8)); 119.17 (d, С(10));
129.12 (d, С(9)); 138.35 (s, С(11)); 143.68 (s, С(7))
20.19 (q, Me); 33.65 (t, С(2)); 53.81 (t, С(4), C(6));
117.02 (d, С(8), C(12)); 126.64 (s, С(10));
1050 (C—N),
580—650
(C—S)
1600,
2850
3b
2.23 (s, 3 H, Ме); 4.00 (s, 2 H,
SCH2S); 4.97 (s, 4 H, СH2N);
6.98 and 7.15 (both d, 4 H,
C6H4, J = 8.5)
128.44 (d, С(9), C(11)); 144.46 (s, С(7))
3c
3d
3e
3f
3.82 (s, 3 H, ОМе); 3.88 (s, 2 H,
SCH2S); 4.38 (s, 4 H, СH2N);
7.04—7.36 (m, 4 H, C6H4)
3.62 (s, 3 H, ОМе); 3.74 (s, 2 H,
SCH2S); 4.30 (s, 4 H, СH2N);
6.83—7.21 (m, 4 H, C6H4)
3.67 (s, 3 H, ОМе); 3.88 (s, 2 H,
SCH2S); 4.30 (s, 4 H, СH2N);
6.54—6.77 (m, 4 H, C6H4)
2.07 and 2.20 (both s, 3 H each, Ме);
3.50 (s, 2 H, SCH2S); 4.36 (s, 4 H,
СH2N); 6.74—7.07 (m, 3 H, C6H3)
2.30 (s, 6 H, Ме); 4.82 (s, 4 H,
SCH2N); 5.33 (s, 4 H, NCH2N);
6.60—7.15 (m, 8 H, 2 C6H4)
2.25 (s, 6 H, Ме); 4.90 (s, 4 H,
SCH2N); 5.09 (s, 2 H, NCH2N);
6.91 (d, 4 H, C6H4, 3J = 8.5);
7.01 (d, 4 H, C6H4, 3J = 8.5)
3.82 (s, 6 H, ОМе); 4.80 (s, 4 H,
SCH2N); 4.91 (s, 4 H, NCH2N);
7.21—7.36 (m, 8 H, 2 C6H4)
3.42 (s, 6 H, ОМе); 4.63 (s, 4 H,
SCH2N); 4.80 (s, 2 H, NCH2N);
6.72—6.95 (m, 8 H, 2 C6H4)
2.36 (s, 3 H, Ме); 4.34 (s, 2 H,
NCH2S); 4.71 (s, 2 H, SCH2O);
5.25 (s, 2 H, NCH2O); 6.52—7.11
(m, 4 H, C6H4)
34.70 (t, С(2)); 55.12 (q, OMe); 58.18 (t, С(4), C(6));
104.28 (d, С(8)); 109.94 (d, С(10)); 112.8 (d, С(12));
129.91 (d, С(11)); 145.97 (s, С(7)); 160.47 (s, С(9))
30.92 (t, С(2)); 55.37 (q, OMe); 57.19 (t, С(4), C(6));
114.81 (d, С(9), C(11)); 115.72 (d, С(8), C(12));
137.83 (s, С(7)); 152.33 (s, С(10))
33.52 (t, С(2)); 47.30 (t, С(4), C(6)); 55.89 (q, OMe);
111.69 (d, С(9)); 120.99 (d, С(12)); 122.55 (d, С(11));
123.92 (d, С(10)); 138.55 (s, С(7)); 147.00 (s, С(8))
17.59 and 21.57 (both q, Me); 33.07 (t, С(2)); 56.74 (t,
С(4), C(6)); 112.01 (d, С(12)); 119.56 (d, С(10));
130.03 (d, С(9)); 131.00 (s, С(8)); 135.56
4а
4b
1150 (C—N),
1600, 2850
(s, С(11)); 143.94 (s, С(7))
4а
4b
4c
4d
21.81 (q, Me); 54.04 (t, С(2), C(6)); 69.51 (t, С(4));
111.82 (d, С(8), C(18)); 114.16 (d, С(12), C(14));
120.14 (d, С(10), C(16)); 128.66 (d, С(11), C(15));
138.30 (s, С(9), C(17)); 144.18 (s, С(7), C(13))
20.40 (q, Me); 54.29 (t, С(2), C(6)); 70.10 (t, С(4));
117.92 (d, С(8), C(12), C(14), C(18)); 129.32 (d,
С(9), C(11), C(15), C(17)); 129.82 (s, С(10),
C(16)); 145.51 (s, С(7), C(13))
46.08 (t, С(2), C(6)); 55.12 (q, OMe); 65.72 (t, С(4));
103.76 (d, С(8), C(14)); 104.83 (d, С(10), C(16));
107.40 (d, С(12), C(18)); 128.93 (d, С(11), C(17));
150.32 (s, С(7), C(13)); 157.93 (s, С(9), C(15))
55.20 (t, С(2), C(6)); 55.94 (q, OMe); 71.17 (t, С(4));
114.92 (d, С(9), C(11), C(15), C(17)); 120.28 (d, С(8),
C(12), C(14), C(18)); 142.34 (s, С(7), C(13));
154.62 (s, С(10), C(16))
4c
4d
5b
1050
(C—N),
580—650
(C—S)
5f
2.12 and 2.28 (both s, 3 H each, Ме); 1600,
5b
5f
20.19 (q, Me); 53.62 (t, С(6)); 71.70 (t, С(2)); 82.43
(t, С(4)); 118.97 (d, С(8), C(12)); 126.84 (s, С(10));
129.64 (d, С(9), C(11)); 141.41 (s, С(7))
19.09 and 21.55 (both q, Me); 53.34 (t, С(6)); 72.15
(t, С(2)); 81.45 (t, С(4)); 110.45 (d, С(12)); 118.91
(d, С(10)); 124.50 (d, С(9)); 124.89 (s, С(8));
134.32 (s, С(11)); 147.20 (s, С(7))
4.09 (s, 2 H, NCH2S); 4.53 (s, 2 H,
SCH2O); 4.78 (s, 2 H, NCH2O);
6.34—6.99 (m, 3 H, C6H3)
2850
N, 7.53; O, 8.53; S, 17.78. C9H11NOS. Calculated (%): C, 59.67;
H, 6.08; N, 7.73; O, 8.84; S, 17.68.
5ꢀ(3ꢀMethylphenyl)perhydroꢀ1,3,5ꢀdithiazine (3a). The yield
was 8%, m.p. 154—155 °C, Rf 0.83. MS, m/z (Irel (%)): 211
[M]+ (27), 165 [M – CH2S]+ (7), 133 [M – SCH2S]+ (17), 119
[M – SCH2SCH2]+ (40). Found (%): C, 56.78; H, 6.36; N, 6.28;
* In CDCl3.
S, 30.58. C10H13NS2. Calculated (%): C, 56.87; H, 6.16; N, 6.64;
S, 30.33.

Thiomethylation of aromatic amines
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 8, August, 2003
1821
5ꢀ(4ꢀMethylphenyl)perhydroꢀ1,3,5ꢀdithiazine (3b). The yield
was 59%, m.p. 147—148 °C, Rf 0.83. MS, m/z (Irel (%)): 211
[M]+ (29), 165 [M – CH2S]+ (8), 133 [M – SCH2S]+ (29), 119
[M – SCH2SCH2]+ (100). Found (%): C, 56.63; H, 6.24;
N, 6.31; S, 30.82. C10H13NS2. Calculated (%): C, 56.87; H, 6.16;
N, 6.64; S, 30.33.
5ꢀ(3ꢀMethoxyphenyl)perhydroꢀ1,3,5ꢀdithiazine (3c). The
yield was 16%, m.p. 119—120 °C, Rf 0.84. MS, m/z (Irel (%)):
227 [M]+ (69), 181 [M – CH2S]+ (4), 149 [M – SCH2S]+ (4),
135 [M – SCH2SCH2]+ (88). Found (%): C, 52.97; H, 5.45;
N, 6.27; O, 7.27; S, 28.04. C10H13NOS2. Calculated (%):
C, 52.86; H, 5.72; N, 6.17; O, 7.05; S, 28.19.
5ꢀ(4ꢀMethoxyphenyl)perhydroꢀ1,3,5ꢀdithiazine (3d). The
yield was 2%, m.p. 109—110 °C, Rf 0.84. MS, m/z (Irel (%)): 227
[M]+ (14), 181 [M – CH2S]+ (4), 149 [M – SCH2S]+ (4), 135
[M – SCH2SCH2]+ (86). Found (%): C, 52.64; H, 5.52; N, 6.02;
O, 7.23; S, 28.59. C10H13NOS2. Calculated (%): C, 52.86;
H, 5.72; N, 6.17; O, 7.05; S, 28.19.
5ꢀ(2ꢀMethoxyphenyl)perhydroꢀ1,3,5ꢀdithiazine (3e). The
yield was 2%, m.p. 104—105 °C, Rf 0.84. MS, m/z (Irel (%)): 227
[M]+ (14), 181 [M – CH2S]+ (6), 149 [M – SCH2S]+ (6), 135
[M – SCH2SCH2]+ (82). Found (%): C, 52.71; H, 5.46; N, 6.15;
O, 7.18; S, 28.50. C10H13NOS2. Calculated (%): C, 52.86;
H, 5.72; N, 6.17; O, 7.05; S, 28.19.
5ꢀ(2,5ꢀDimethylphenyl)perhydroꢀ1,3,5ꢀdithiazine (3f). The
yield was 7%, m.p. 127—128 °C, Rf 0.81. Found (%): C, 59.14;
H, 6.45; N, 6.37; S, 28.04. C11H15NS2. Calculated (%): C, 58.67;
H, 6.67; N, 6.22; S, 28.44.
3,5ꢀBis(3ꢀmethylphenyl)ꢀ3,4,5,6ꢀtetrahydroꢀ2Hꢀ1,3,5ꢀthiaꢀ
diazine (4a). The yield was 13%, m.p. 196—197 °C, Rf 0.21. MS,
m/z (Irel (%)): 284 [M]+ (23), 250 [M – H2S]+ (6), 165
[M – CH2NPhCH3]+ (37), 133 [M – SCH2NPhCH3]+ (27),
119 [CH3PhNCH2]+ (100), 105 [CH3PhN]+ (8), 91 [CH3Ph]+
(62). Found (%): C, 71.67; H, 7.15; N, 9.74; S, 11.44.
3,5ꢀBis(4ꢀmethoxyphenyl)ꢀ3,4,5,6ꢀtetrahydroꢀ2Hꢀ1,3,5ꢀ
thiadiazine (4d). The yield was 6%, m.p. 145—146 °C, Rf 0.23.
Found (%): C, 64.47; H, 6.24; N, 8.75; O, 10.40; S, 10.14.
C
17H20N2O2S. Calculated (%): C, 64.56; H, 6.33; N, 8.86;
O, 10.13; S, 10.13.
5ꢀ(4ꢀMethylphenyl)perhydroꢀ1,3,5ꢀoxathiazine (5b). The
yield was 6%, m.p. 124—125 °C, Rf 0.67. Found (%): C, 61.44;
H, 6.37; N, 7.23; O, 8.32; S, 16.64. C10H13NOS. Calculated (%):
C, 61.53; H, 6.67; N, 7.18; O, 8.21; S, 16.41.
5ꢀ(2,5ꢀDimethylphenyl)perhydroꢀ1,3,5ꢀoxathiazine (5f). The
yield was 1%, m.p. 122—123 °C, Rf 0.69. Found (%): C, 62.97;
H, 7.53; N, 6.54; O, 7.32; S, 15.64. C11H15NOS. Calculated (%):
C, 63.16; H, 7.18; N, 6.70; O, 7.66; S, 15.30.
References
1. A. Wohl, Ber., 1886, 19, 2344.
2. R. S. Aleev, Yu. S. Dal´nova, Yu. N. Popov, and R. M.
Masagutov, Dokl. Akad. Nauk SSSR, 1988, 303, 873 [Dokl.
Chem., 1988 (Engl. Transl.)].
3. C. G. Le Fevre and R. J. Le Fevre, J. Chem. Soc., 1932, 1142.
4. A. H. Binz and L. H. Pence, J. Am. Chem. Soc., 1939,
61, 3134.
5. A. H. Binz, F. E. Reinhart, and H. C. Winter, J. Am. Chem.
Soc., 1940, 62, 7.
6. 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.)].
7. Yu. I. Murinov, V. N. Maistrenko, and N. G. Afzaletdinova,
Ekstraktsiya metallov S,Nꢀorganicheskimi soedineniyami
[Extraction of Metals by S,NꢀOrganic Compounds], Nauka,
Moscow, 1993, 192 (in Russian).
8. USSR Inventor's Certificate No. 2116362; Byul. Izobr., 1998,
21 (in Russian).
9. USSR Inventor's Certificate No. 2160233; Byul. Izobr., 2000,
34 (in Russian).
10. Y. Ogata, M. Okano, and M. Sugawara, J. Chem. Soc., 1951,
73, 1715.
C
18H20N2S. Calculated (%): C, 71.83; H, 7.04; N, 9.86; S, 11.27.
3,5ꢀBis(4ꢀmethylphenyl)ꢀ3,4,5,6ꢀtetrahydroꢀ2Hꢀ1,3,5ꢀthiaꢀ
diazine (4b). The yield was 28%, m.p. 161—162 °C, Rf 0.22. MS,
m/z (Irel (%)): 284 [M]+ (23), 250 [M – H2S]+ (6), 165
[M – CH2NPhCH3]+ (37), 133 [M – SCH2NPhCH3]+ (27),
119 [CH3PhNCH2]+ (100), 105 [CH3PhN]+ (8), 91 [CH3Ph]+
(62). Found (%): C, 71.58; H, 7.21; N, 9.80; S, 11.41.
C18H20N2S. Calculated (%): C, 71.83; H, 7.04; N, 9.86; S, 11.27.
3,5ꢀBis(3ꢀmethoxyphenyl)ꢀ3,4,5,6ꢀtetrahydroꢀ2Hꢀ1,3,5ꢀ
thiadiazine (4c). The yield was 7%, m.p. 153—154 °C, Rf 0.23.
Found (%): C, 64.68; H, 6.39; N, 8.71; O, 10.21; S, 10.01.
C17H20N2O2S. Calculated (%): C, 64.56; H, 6.33; N, 8.86;
O, 10.13; S, 10.13.
11. A. J. Gordon and R. A. Ford, The Chemist´s Companion, The
Handbook of Practical Data, Techniques and References,
J. Wiley, New York—London—Sydney—Toronto, 1972.
12. I. A. Nikiforov and A. Yu. Nikiforov, Zh. Prikl. Khim. 1996,
69, 705 [Russ. J. Appl. Chem., 1996, 69 (Engl. Transl.)].
Received March 28, 2003;
in revised form June 3, 2003