Reaction of 1-alkylsilatranes with 2-methylphenoxyacetic acid

Full text of DOI:10.1134/S1070363209060334

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 6, pp. 1218–1219. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © S.N. Adamovich, A.I. Albanov, A.N. Mirskova, R.G. Mirskov, M.G. Voronkov, 2009, published in Zhurnal Obshchei Khimii, 2009,
Vol. 79, No. 6, pp. 1043–1044.
LETTERS
TO THE EDITOR
Reaction of 1-Alkylsilatranes with 2-Methylphenoxyacetic Acid
S. N. Adamovich, A. I. Albanov, A. N. Mirskova, R. G. Mirskov, and M. G. Voronkov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: mir@irioch.irk.ru
Received December 22, 2008
DOI: 10.1134/S1070363209060334
Tris(2-hydroxyethyl)ammonium 2-methylphenoxy-
acetate (“2-methylphenoxyacetoxyptotatrane”) N+Н·
(СН2СН2ОН)3·–OOСCH2OC6H4CH3 (I) under the
name of “crezacin” or “trecrezan” is used in
agriculture and medicine[1, 2]. Its Si-organyl analogs
“silatranes” RSi(ОСН2СН2)3N (II) are also widely
used in these fields [3].
of 1Н, 13С, 15N, 29Si NMR and IR spectroscopy
proved the formation of [R(OH)Si(OCH2CH2)2N+(H)
СН2СН2ОН] X– (VI), where R = CH3 (VIа), R = C2H5
(VIb), which, apparently, are formed after partial
hydrolysis of II or V with the air moisture.
The independent synthesis of VIа and VIb was
performed by the scheme:
RSi(OR1)3 + (НОСН2СН2)3N+Н·X–
I
→ [RSi(OCH2CH2)3N+H] X– + 3R1ОН
IV
→ [R(OH)Si(OCH2CH2)2N+(H)СН2СН2ОН] X–.
VIа, VIb
R = R1 = Me, Et; X = OOСCH2OC6H4–CH3.
With the aim to prepare compounds combining the
biological activity of I and II we have studied the
reaction of 1-alkylsilatranes with 2-methylphen-
oxyacetic acid, СН3С6Н4ОСН2СООН (III). So far, the
reactions of II with carboxylic acids practically were
not studied.
At the same time, the reaction of methyltri-
chlorosilane or tetramethoxysilane with I in THF or
benzene leads to insoluble, high-melting colorless
powders containing Si and showing in their IR spectra
the band at 1580 cm–1 (С=О).
Compound VIа was obtained was obtained by
refluxing 5 g (26 mmol) of methylsilatrane and 4.38 g
(26 mmol) of III in methanol for 6 h. The solvent was
removed, the residue was thoroughly washed with
The ability of II to form onium salts with
participation of N or O atoms was long discussed in
the literature [4, 5]. In [6, 7] it was shown that II and
boratrane form with trifluoromethanesulfonic acid the
corresponding ammonium complexes. One could
expect the reaction to follow two routes:
1
hexane and dried in vacuum. Н NMR (CD3OD):
7.13–6.80 m (С6Н4О), 4.50 s (СН2СОО), 3.90 t
(ОСН2), 3.39 t (NСН2), 2.29 s (СН3–Ph), 0.10 s
(СН3Si). 13С NMR: 173.65 (С=О), 156.53 (Сi–О),
130.14, 126.22, 120.28, 110.86 (Ar),126.49 (Сi–Ме),
66.12 (СН2СОО), 55.42 (ОСН2), 55.11 (NСН2), 14.97
(СН3–Ph), –10.37 (СН3Si). 15N NMR: –337.70. 29Si
NMR: –38.83. IR: 1590 (С=О), 3300 (ОН).
Si(OCH2CH2)3N + HX → [RSi(OCH2CH2)3N+H] X–, (1)
IV
RSi(OCH2CH2)3N + 2HX
→ [R(X)Si(OCH2CH2)2N+(H)СН2СН2ОН] X–,
(2)
V
R = Me, Et; X = OOСCH2OC6H4–CH3.
1
Compound VIb was prepared similarly. Н NMR
(CD3OD): 7.10–6.83 m (С6Н4О), 4.56 s (СН2СОО),
3.87 t (ОСН2), 3.40 t (NСН2), 2.25 s (СН3–Ph), 0.89 q
We have not detected the expected stable products
of reactions (1), (2) in our experiments. The methods
1218

1219
REACTION OF 1-ALKYLSILATRANES WITH 2-METHYLPHENOXYACETIC ACID
(СН2–Si), 0.27 t (СН3). 13С NMR: 174.35 (С=О),
157.80 (Сi–О), 131.67–112.24 (Ar), 125.39 (Сi–Ме),
66.99 (СН2СОО), 56.80 (ОСН2), 56.48 (NСН2), 16.45
(СН3–Ph), 9.35 (СН2). N NMR: –338.30, Si NMR:
–38.98. IR: 1600 (С=О), 3300 (ОН).
2. Voronkov, M.G., Kolesnikova, O.P., Rasulov, M.M.,
and Mirskova, A.N., Khim.-Farm. Zh., 2007, vol. 41,
no. 5, p. 13.
15
29
3. Voronkov, M.G. and Baryshok, V.P., Silatrany v me-
ditsine i sel’skom khozyaistve (Silatranes in Medicine
and Agriculture), Novosibirsk: Sib. Otd. Ross. Akad.
Nauk, 2005.
Compounds VIа and VIb was prepared by an
alternative procedure by refluxing equimolar amounts
of methyltriethoxy- or ethyltrimethoxysilane and I in
THF during 12 h. the residue was washed with hexane
and dried.
4. Voronkov, M.G., Dyakov, V.M., and Kirpichenko, S.V.,
J. Organomet. Chem., 1982, vol. 233, no. 1, p. 1.
5. Pestunovich, V.A., Kirpichenko, S.V., and Voron-
kov, M.G., Silatranes and Their Tricyclic Analogs, ch. 24,
Chemistry of Organosilicon Compounds, Rappoport, Z.
and Apeloig, Y., Eds., Chichester: Willy, 1998, part 2.
ACKNOWLEDGMENTS
This work was performed with financial support
from the Council of grants of the President of RF
(grant no. NSh-255-2008.3).
6. Roger, W. and Alder, Zhao Jin, J. Chem. Soc., Perkin
Trans. 2, 1996, p. 583.
REFERENCES
7. Attar-Bashi, M.T., Rickard, C.E.F., Roper, W.R.,
Wright, L.J., and Woodgate, S.D., Organometallics,
1998, vol. 17, no. 4, p. 504.
1. Khankhodzhaeva, D.A. and Voronkov, M.G., Dokl.
Ross. Akad. Nauk., 1993, vol. 333, no. 1, p. 124.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 6 2009