142
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 1, January, 2004
Getmanova et al.
135 H, SiMe); 0.53 (m, 372 H, SiCH2); 1.28—1.37 (m, 186 H,
CH2CH2CH2); 1.52—1.56 (d, 192 H, SiCH2CH=CH2, J =
8.0 Hz); 4.85 (m, 192 H, CH2=CH); 5.82 (m, 96 H, CH2=CH);
7.26—7.44 (m, 5 H, Ph).
Polyallylcarbosilane dendrimer of the fifth generation with the
tetrafunctional branching center (9, Gꢀ5(128All)) was syntheꢀ
sized by a known procedure.8
pound 14 similarly to the synthesis of compound 13. IR, ν/cm–1
:
3400 (OH). 1H NMR (CD3OD), δ: 0.01—0.12 (m, 1908 H,
SiMe); 0.63 (m, 1264 H, SiCH2); 1.44 (m, 504 H,
SiCH2CH2CH2Si); 1.61 (m, 256 H, CH2CH2O); 3.45 (m, 512 H,
CH2OCH2); 3.63 (m, 768 H, CH2OSi).
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 02ꢀ03ꢀ32359)
and the Program of the Division of Chemistry and Mateꢀ
rials Sciences of the Russian Academy of Sciences "Chemꢀ
istry and Physicochemistry of Supramolecular Systems
and Atomic Clusters."
Dendrimer with the tetrafunctional branching center and one
terminal protected OH group at each branch (12). A mixture of
dendrimer 9 (0.3868 g, 0.024 mmol), compound 4 (0.7606 g,
3.2 mmol), anhydrous hexane (2.5 mL), and a solution of the
catalyst (3.5 µL) was kept in a tightly closed flask (which was
preliminarily flushed with argon) for 15 days at 30—35 °С until
signals of protons at the double bond almost completely disapꢀ
peared from the 1H NMR spectra of samples of the reaction
mixture. 1H NMR (CDCl3), δ: –0.06 (s, 1140 H, SiMe); 0.11 (s,
1152 H, OSiMe); 0.52 (m, 1256 H, SiCH2); 1.28 (m, 504 H,
SiCH2CH2CH2Si); 1.55 (m, 256 H, CH2CH2O); 3.38 (t, 256 H,
CH2CH2CH2O, J = 18.0 Hz); 3.47 (t, 256 H, OCH2CH2OSi,
J = 11.0 Hz); 3.71 (t, 256 H, CH2OSiMe, J = 18.0 Hz).
Dendrimer with the tetrafunctional branching center and one
terminal OH group at each branch (13) was synthesized from
compound 12 purified from the catalyst by chromatography on
silica gel (Kieselgel (Merck), hexane as the eluent). A mixture of
compound 12 (0.126 g, 0.0027 mmol), toluene (3 mL), MeOH
(2 mL), and glacial AcOH (1 mL) was heated with stirring for
48 h at 70 °С. The solvents were evaporated to dryness, and the
dendrimer was dried in vacuo at 1 Torr. IR, ν/cm–1: 3420 (OH).
1Н NMR (CD3OD), δ: 0.02 (s, 1140 H, SiMe); 0.64 (m, 1256 H,
SiCH2); 1.42 (m, 504 H, SiCH2CH2CH2Si); 1.60 (m, 256 H,
CH2CH2O); 3.44 (t, 256 H, CH2CH2CH2O, J = 9.2 Hz); 3.51
(t, 256 H, OCH2CH2OH, J = 10.0 Hz); 3.66 (t, 256 H, CH2OH,
J = 10.3 Hz).
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