Synthesis of silicon-containing monomers with aldehyde groups

Full text of DOI:10.1134/S1070428014060268

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 6, pp. 904–905. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © A.E. Petrov, I.N. Bardasov, V.O. Lapin, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 6, pp. 916–917.
SHORT
COMMUNICATIONS
Synthesis of Silicon-Containing Monomers
with Aldehyde Groups
A. E. Petrov, I. N. Bardasov, and V. O. Lapin
I.N. Ul’yanov Chuvash State University, Moskovskii pr. 15, Cheboksary, 428015 Russia
e-mail: ae.petrov@mail.ru
Received December 26, 2013
DOI: 10.1134/S1070428014060268
Silicon-containing monomers with different func-
tional groups are used in the synthesis of heat and cor-
rosion resistant polymers, as well as modifiers for vari-
ous polymers to improve their operational character-
istics [1–3]. The goal of the present work was to
synthesize silicon-containing monomers functionalized
with aldehyde groups, which may be used for the pre-
paration of polymers with enhanced heat and frost
resistance and tensile strength as compared to carboxy-
containing polymers [3].
The procedure developed by us for the synthesis of
such monomers is based on the reaction of trichloro-
(phenyl)silane with hydroxy aldehydes. The reaction
of trichloro(phenyl)silane with β-hydroxybutyralde-
hyde gave tris-butanal I (Scheme 1).
alcohols, ketones, and ethers and insoluble in aliphatic
hydrocarbons and water.
3,3′,3″-[Phenylsilanetriyltris(oxy)]tributanal (I).
A solution of 17.0 mL (0.1 mol) of trichloro(phenyl)-
silane in 10 mL of toluene was added in small portions
in a nitrogen atmosphere to a solution of 36.6 g
(0.32 mol) of β-hydroxybutyraldehyde and 37 mL
(0.3 mol) of triethylamine in 20 mL of toluene. The
progress of the reaction was monitored by IR spectros-
copy, following disappearance of the OH absorption
band. When the reaction was complete (after 2–3 h),
the precipitate was filtered off, the filtrate was evapo-
rated under reduced pressure to a volume of 5 mL, and
10 mL of hexane was added. The jelly-like material
was dried under reduced pressure at 50°C. Yield 46.6 g
(87%), mp 112°C. IR spectrum, ν, cm–1: 3080–3030
(C–H), 1090–1020 (Si–O–C), 1715–1696 (C=O).
1H NMR spectrum, δ, ppm: 1.32 m (9H, CH3), 2.67 m
(6H, CH2), 3.62 m (3H, CH), 7.23 m (5H, Harom),
9.70 s (3H, CHO). Mass spectrum: m/z 366 (Irel 25%).
Found, %: C 58.99; H 7.15; O 26.19; Si 7.66.
C18H26O6Si. Calculated, %: C 58.75; H 7.07; O 26.36;
Si 7.72. M 366.49.
2,2′,2″-[Phenylsilanetriyltris(oxy)]tribenzalde-
hyde (II) was synthesized in a similar way. Yield 81%,
mp 129°C. IR spectrum, ν, cm–1: 3080–3030 (C–H),
1090–1020 (Si–O–C), 1715–1696 (C=O). 1H NMR spec-
trum, δ, ppm: 6.88 m (6H, Harom), 7.23 m (5H, Harom),
7.37 m (3H, CH), 7.64 m (3H, CH), 10.24 s (3H, CHO).
Mass spectrum: m/z 468 (Irel 20%). Found, %: C 69.21;
H 4.30; O 20.49; Si 5.99. C27H20O6Si. Calculated, %:
C 69.05; H 4.25; O 20.75; Si 5.85. M 468.54.
Scheme 1.
Me
Me
PhSiCl3
–3HCl
CHO
CHO
OH
PhSi
O
3
I
Under analogous conditions, from aromatic hy-
droxy aldehydes (salicylaldehyde and vanillin) we ob-
tained trialdehydes II and III, respectively (Scheme 2).
Scheme 2.
CHO
CHO
O
PhSiCl3
–3HCl
HO
PhSi
R
R
3
II, III
4,4′,4″-[Phenylsilanetriyltris(oxy)]tris(3-me-
thoxybenzaldehyde) (III). Yield 78%, mp 137°C. IR
spectrum, ν, cm–1: 3080–3030 (C–H), 1090–1020
II, 2-PhSiO, R = H; III, 4-PhSiO, R = MeO.
The products were isolated as light yellow powders
which are readily soluble in aromatic hydrocarbons,
1
(Si–O–C), 1715–1696 (C=O). H NMR spectrum, δ,
904

SYNTHESIS OF SILICON-CONTAINING MONOMERS WITH ALDEHYDE GROUPS
ppm: 3.73 m (3H, CH3), 6.81 m (3H, CH), 7.20 m (1H,
905
REFERENCES
Ph), 7.20 m (6H, Harom), 9.87 s (3H, CHO). Mass
spectrum: m/z 558 (Irel 25%). Found, %: C 64.50;
H 4.69; O 25.78; Si 5.03. C30H26O6Si. Calculated, %:
C 64.30; H 4.55; O 25.95; Si 5.19. M 558.61.
1. Tekhnologiya plasticheskikh mass (Technology of
Plastics), Korshak, V.V., Ed., Moscow: Khimiya, 1985,
3rd ed.
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2008, p. 46; Maiorov, D.N., Kolyamshin, O.A., Verkhu-
nov, S.M., and Kol’tsov, N.I., Vestn. Chuvash. Gos. Univ.,
2001, p. 66; Verkhunov, S.M., Petrov, A.E., and Kol’-
tsov, N.I., Vestn. Chuvash. Gos. Univ., 2009, p. 37.
The purity of the isolated compounds was checked
by TLC on Silufol UV-254 plates; spots were visual-
ized under UV light, by treatment with iodine vapor, or
by thermal treatment. The IR spectra were recorded on
an FSM 1201 spectrometer from samples dispersed in
3. Pudovik, A.N., Gur’yanova, I.V., and Ishmaeva, E.A.,
Reaktsii i metody issledovaniya organicheskikh soedine-
nii (Reactions and Methods of Investigation of Organic
Compounds), Kazanskii, B.A., Knunyants, I.L., Shemya-
kin, M.M., and Mel’nikov, N.N., Eds., Moscow:
Khimiya, 1968, vol. 19, p. 22.
1
mineral oil. The H NMR spectra were measured on
a Bruker AM-500 spectrometer at 500.13 MHz from
solutions in DMSO-d6. The mass spectra (electron
impact, 70 eV) were obtained on a Finnigan MAT
INCOS 50 instrument.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014