S-(TRIMETHOXYSILYLMETHYL)- AND S-(SILATRANYLMETHYL)ISOTHIURONIUM HALIDES
557
the solvent was distilled off in a vacuum (1.0 1.5 mm
Hg). The residue was diluted with 50 ml of ether and
thoroughly stirred. The resulting solid reaction prod-
uct was recrystallized from C H OH. Yield of VIII
S-(Silatranylmethyl)-N-phenylisothiuronium
iodide XIV. a. By Scheme 2. A solution of 3.5 g of
S-(trimethoxysilylmethyl)-N-isothiuronium iodide in
5 ml of CHCl was mixed with a solution of 1.3 g of
2
5
3
13 g (87%), mp 266 268 C.
tris(2-hydroxyethyl)amine in 1 ml of CHCl . The exo-
3
thermic reaction was complete in 1 2 min. After cool-
ing to 20 C, a mixture of solids was obtained, from
which 3.2 g (83%) of XIV (mp 245 247 C, from
MeOH) and 0.5 g of tris(2-hydroxyethyl)ammonium
iodide (mp 181 C) were isolated.
S-(Silatranylmethyl)isothiuronium iodide IX.
a. By Scheme 2. Compound IX was prepared similarly
to VIII from 1.3 g of S-(trimethoxysilylmethyl)isothiu-
ronium iodide and 0.6 g of tris(2-hydroxyethyl)amine
in 1 ml of MeOH. Yield of IX 1.3 g (86%), mp 246
2
48 C (from MeOH).
b. By Scheme 3. A mixture of 2.4 g of N-phenyl-
thiourea, 4.8 g of 1-(iodomethyl)silatrane, and 15 ml
of butanol was refluxed for 12 h in the device de-
scribed above. The resulting solution was cooled to
b. By Scheme 3. To 2.0 g of thiourea and 8.3 g of
1-(iodomethyl)silatrane, 10 ml of butanol was added,
and the mixture was refluxed for 10 h in the device
described above (see synthesis of I). The solution was
cooled to 20 C, and the precipitate of IX was filtered
off on a glass frit, washed with ether, and vacuum-
dried. Yield 9.3 g (90%), mp 240 242 C.
2
0 C. The precipitate was filtered off on a glass frit
and washed with ether. Yield of XIV 6.3 g (87%),
mp 240 242 C (from MeOH).
1
2
S-(Silatranylmethyl)-N ,N -ethyleneisothiuro-
nium chloride [2-(silatranylmethylthio)imidazo-
linium chloride] XV was prepared similarly to VIII
from 2.6 g of trimethoxysilyl derivative VI and 1.4 g
1
2
S-(Silatranylmethyl)-N ,N -dimethylisothiuro-
nium chloride X was prepared by Scheme 3, by
refluxing 2.5 g of N ,N -dimethylthiourea and 5.4 g
of 1-(chloromethyl)silatrane in 15 ml of butanol for
1
1
2
of tris(2-hydroxyethyl)amine in CHCl solution. Yield
3
3
.4 g (86%), mp 270 272 C (from MeOH).
0 h. Yield 6.1 g (78%), mp 292 294 C (dec.).
1
2
1
2
S-(Silatranylmethyl)-N ,N -ethyleneisothiuro-
S-(Silatranylmethyl)-N ,N -dimethylisothiuro-
nium iodide [2-(silatranylmethylthio)imidazo-
linium iodide] XVI. a. By Scheme 2. Compound
XVI was preepared similarly to IX in MeOH from
nium iodide XI. a. By Scheme 2. Compound XI was
prepared similarly to IX from 3.3 g of trimethoxy de-
rivative III and 1.4 g of tris(2-hydroxyethyl)amine in
1
.3 g of the corresponding trimethoxysilyl derivative
5
ml of MeOH. Yield 3.2 g (84%), mp 240 242 C.
and 0.5 g of tris-(2-hydroxyethyl)amine. Yield of XVI
1
2
b. By Scheme 3. A mixture of 5.2 g of N ,N -di-
1
.3 g (88%), mp 308 310 C (dec.).
methylthiourea and 15.6 g of 1-(iodomethyl)silatrane
in 40 ml of butanol was refluxed for 10 h. The result-
ing solution was cooled to 0 C, and the precipitate
was filtered off on a glass frit, washed with ether, and
vacuum-dried. Yield of XI 18.8 g (91%), mp 235
b. By Scheme 3. Compound XVI was prepared by
1
2
refluxing a mixture of 2.1 g of N ,N -ethylenethiourea
imidazoline-2-thione) and 6.6 g of 1-(iodomethyl)-
silatrane in 15 ml of butanol for 12 h. Yield of XVI
(
6
.9 g (79%), mp 312 315 C (dec.).
2
37 C.
S-(Silatranylmethyl)-N-phenylisothiuronium
chloride XII was prepared by Scheme 3 similarly
to VIII. A mixture of 4.8 g of N-phenylthiourea and
.0 g of 1-(chloromethyl)silatrane in 20 ml of DMF
was kept at 120 125 C for 12 h. Yield of XII 9.8 g
REFERENCES
1. Bakhareva, E.V., Pestunovich, A.E., Vlasova, N.N.,
Vasil’eva, N.N., and Voronkov, M.G., Abstracts of
Papers, 4-ya Vsesoyuznaya konferentsiya Biologi-
cheski aktivnye soedineniya kremniya, germaniya i
olova (4th All-Union Conf. Biologically Active
Compounds of Silicon, Germanium, and Tin ), Ir-
kutsk, 1990, p. 20.
7
(
83%), mp 245 247 C (from MeOH).
S-(Silatranylmethyl)-N-phenylisothiuronium
bromide XIII and S-(silatranylmethyl)-N-phenyl-
isothiourea XVII. A solution of 3.2 g of S-(trime-
thoxysilylmethyl)-N-phenylisothiuronium bromide in
2
. Safaev, R.D., Voronkov, M.G., Fuks, S.Yu., Lyche-
va, T.A., Khitrova, I.L., Belitskii, G.A., Pakho-
mov, V.Yu., Vlasova, N.N., and Pestunovich, A.E.,
Dokl. Ross. Akad. Nauk, 1992, vol. 322, no. 5, p. 994.
5
ml of MeOH was mixed with a solution of 1.6 g of
tris(2-hydroxyethyl)amine in 2 ml of MeOH. After
completion of the exothermic reaction, a mixture of
solids was obtained, from which 1.5 g (70%) of XIII
mp 244 246 C), 0.6 g (7%) of XVII (mp 194 C),
and 0.7 g of tris(2-hydroxyethyl)ammonium bromide
mp 190 C) were isolated.
3. Kazimirovskaya, V.B., Pestunovich, A.E., Usov, V.A.,
Dorofeev, I.A., Vlasova, N.N., and Voronkov, M.G.,
Abstracts of Papers, 4-ya Vsesoyuznaya konferentsiya
Biologicheski aktivnye soedineniya kremniya, ger-
(
(
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 4 2004