Dibenzyl(methyl)[γ-(1-piperidyl)propyl]silane hydrooxalate

Full text of DOI:10.1134/S1070363208090284

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 9, pp. 1819–1820. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © N.P. Erchak, V.V. Kovalenko, S.M. Lenivko, K. Pypovski, E. Liepin’sh, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78,
No. 9, pp. 1580–1581.
LETTERS
TO THE EDITOR
Dibenzyl(methyl)[γ-(1-piperidyl)propyl]silane Hydrooxalate
N. P. Erchaka,b, V. V. Kovalenkoa, S. M. Lenivkoa, K. Pypovskib, and E. Liepin’shc
a Pushkin Brest State University,
blv. Kosmonavtov 32, Brest, 224665 Belarus
e-mail: erchak@ap.siedlce.pl
b Chemistry Department, University of Podlasie, Siedlce, Poland
c Latvian Institute of Organic Synthesis, Riga, Latvia
Received April 8, 2008
DOI: 10.1134/S1070363208090284
Alkyl(benzyl)(γ-aminopropyl)silane hydrooxalates
present interest as ecologically friendly plant growth
regulators of a new type, which favor higher
germinating energy and germinating ability of seeds,
as well as longer seed roots [1]. For biological research
on dibenzyl silicon derivatives we considered it of
interest to synthesize the corresponding dibenzyl-
(methyl)[γ-(1-piperidyl)propyl]silane hydrooxalates.
We undertook an attempt to prepare dibenzyl(methyl)
[γ-(1-piperidyl)propyl]silane hydrooxalate (I). The
synthesis of organic salts of aminoalkylsilyl
derivatives involves a risk of replacement of the
substituents on the silicon atom by more nucleophilic
ones with simultaneous extension of the coordination
sphere of the heteroatom [2–5]. For minimization of
negative processes, the synthesis of compound I was
performed by reacting an ether solution of dibenzyl-
(methyl)[γ-(1-piperidyl)propyl]silane (II) with an-
hydrous oxalic acid in THF. The yield of hydrooxalate
I was 96%.
Starting silane II was obtained by hydrosilylation
of N-allylpiperidine with dibenzyl(methyl)hydrosilane
in the presence of catalytic amounts of a 0.1 М
solution of H2PtCl6·6H2O in THF.
CH2=CHCH
2N
(COOH)2
(COOH)
II
MeBz2SiH
MeBz2Si(CH2)3N
2
II
I
Dibenzyl(methyl)hydrosilane was described as
described in [6].
by laboratory germination. It was found that low-
concentrated solutions of compound I (0.01 and
0.001 mM) stimulate seed germination. Thus, after 2-h
treatment of fine bent grass seeds with a 0.001 mM
solution of compound I, the laboratory germination
reliably increased (against control) by 19 % within
7 days and by 22% within 8 days (at Р < 0.01). The
respective values for red fescue were 16.5 and 22.5%.
For laboratory tests on the growth-regulating
activity of compound I, aqueous solutions of four
concentrations (1 mM, 0.1 mM, 0.01 mM, and 0.001 mM)
and seeds of two kinds of lawn grasses, red fescue
(Festuca rubra) and fine bent grass (Agrostis viridis),
were used. In all experiments, 200 seeds of each lawn
grass were used. The norm for consumption of each
test solution was 5 ml per 200 seeds. The seeds were
germinated in distilled water on a filter paper at 20 2°C.
The control was distilled water. The response of the
plants on treatment of their seeds with solutions of
compound I of various concentrations was measured
Dibenzyl(methyl)[γ-(1-piperidyl)propyl]silane hyd-
rooxalate (I). A solution of 3.31 g of dibenzyl(methyl)-
[γ-(1-piperidyl)propyl]silane in 10 ml of diethyl ether
was added dropwise to a solution of 0.85 g of oxalic
acid in 10 ml of THF. The reaction is exothermic. The
reaction mixture was left to stand for 2 h at room
1819

1820
ERCHAK et al.
temperature, the precipitate that formed was filtered
off, washed with THF and diethyl ether, as dried first
in a water-jet and then an oil-pump vacuum to obtain
(PhCH2)2Si], 7.06–7.11 m [2H, (PhCH2)2Si], 7.19–
7.26 m [4H, (PhCH2)2Si]. 13C NMR spectrum (CDCl3),
δC, ppm: –5.4 (CH3), 10.4 (SiCH2), 20.5 (PhCH2), 22.3
[N(CH2CH2)2CH2], 23.1 (SiCH2CH2CH2), 23.5 [N
(CH2CH2)2CH2], 53.2 [N(CH2CH2)2CH2], 62.1
(NCH2); 124.2, 128.2, 128.3, 139.8 (CPh). 29Si NMR
spectrum (CDCl3), δSi, ppm: 2.5.
1
3.99 g of compound I, mp 139°C. H NMR spectrum
(DMSO-d6 ), δ, ppm: 0.14 s (3H, SiCH3), 0.31–0.35 m
(2H, SiCH2), 1.43–1.55 m (2H, SiCH2CH2CH2), 1.43–
1.55 m [2H, N(CH2CH2)2CH2], 1.62–1.75 m [4H, N
(CH2CH2)2CH2], 2.11 s [4H, (PhCH2)2Si], 2.76–2.92 m
(2H, SiCH2CH2CH2N), 2.70–3.15 m [4H, N(CH2CH2)
2CH2], 6.98–7.06 m [6H, (PhCH2)2Si], 7.18–7.21 m
[4H, (PhCH2)2Si]. 13C NMR spectrum (DMSO-d6 ), δC,
ppm: –5.3 (CH3 ), 9.6 (SiCH2), 18.0 (PhCH2), 21.9
[N(CH2CH2)2CH2], 22.9 (SiCH2CH2CH2), 23.2
[N(CH2CH2)2CH2], 52.3 [N(CH2CH2)2CH2], 59.0
(NCH2); 124.5, 128.5, 128.7, 139.8 (CPh), 165.0
(CОО). 29Si NMR spectrum (DMSO-d6), δSi, ppm: 2.4.
Found, %: C 68.14; H 7.90; N 3.30. C25H35NO4Si.
Calculated, %: C 67.99; H 7.99; N 3.17.
The NMR spectra of ~5 mM solutions were
measured at 25°C on a Varian MERCURY-Plus
spectrometer at 400, 100.5, and 79.5 MHz (for 1H, 13C,
and 29Si, respectively) for compound I in DMSO-d6
and for compound II in CDCl3. Internal reference
TMS.
REFERENCES
1. Lamakova, V.A., Kavalenka, V.V., Luk’’yanchyk I.D.,
Yuўka A., Sal’shchaў V.G., and Yarchak, M.P., Vesn.
Brest. Univ., Ser. Pryrod. Navuk, 2007, no. 1, issue 28,
p. 100.
Dibenzyl(methyl)[γ-(1-piperidyl)propyl]silane (II).
N-Allylpiperidine, 3.13 g, and 2 drops of a 0.1 m
solution of H2PtCl6·6H2O in THF were added to 5.65 g
of dibenzyl(methyl)hydrosilane. The reaction mixture
was heated at 170°C for 3 h. Distillation gave 6.94 g of
compound II (79%), bp 222°C (1.5 mm Hg), nD20
2. Erchak, N.P. and Liepin’sh, E.E., USSR Inventor’s
Certificate 1680713, 1991; Byull. Izobret., 1991, no. 36.
3. Erchak, N.P., Doctoral (Chem.) Dissertation, Irkutsk,
1991.
4. Tacke, R., Ulmer, B., Wagner, B., and Arlt, M.,
Organometallics, 2000, vol. 19, no. 25, p. 5297.
5. Tacke, R., Heermann, J., Pulm, M., and Richter, I.,
Organometallics, 1998, vol. 17, no. 9, p. 1663.
1
1.5461. H NMR spectrum (CDCl3), δ, ppm: 0.06 s
(3H, SiCH3), 0.43–0.47 m (2H, SiCH2), 1.41–1.47 m
(2H, SiCH2CH2CH2), 1.43–1.46 m [2H, N(CH2CH2)2·
CH2], 1.57–1.63 m [4H, N(CH2CH2)2CH2], 2.12 s [4H,
(PhCH2)2Si], 2.21–2.25 m (SiCH2CH2CH2N), 2.30–
2.39 m [4H, N(CH2CH2)2CH2], 6.99–7.02 m [4H,
6. Boudin, A., Cerveau, G., Chust, C., Corriu, R.J.P., and
Reye, C., Angew. Chem., 1996, vol. 98, no. 5, p. 472.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008