Abstract
The influence of the number of 3, 3, 3-trifluoropropyl(methyl)siloxane links (Φ/Φ) in the cyclotetrasiloxanes ΦmD4-m, where D represents the dimethylsiloxane link and m=0–4, on the rearrangement of these compounds in acetone solution under the action of sodium siloxanolate has been studied. The rearrangement takes place with the formation of a linear polysiloxane the degradation of which yields, in addition to the initial ring, cyclosiloxanes with a different structure. The rate of rearrangement of ΦmD4-m and of the formation of a linear polysiloxane rises with an increase in m from 0 to 3. The equilibrium concentration of the linear polysiloxane formed from ΦmD4-m is inversely proportional to m. Results have been obtained on the kinetics of the formation of the cyclosiloxanes ΦmDn, where m=0–5, n=0–5, and m+n=3–6, in the rearrangement of the rings ΦD3, Φ2D2, Φ3D, and Φ4. The reactivity of the siloxane links rises in the sequence ∼ (CH3)2Si-O-Si(CH3)2 ∼<∼ (CF3CH2CH2)-(CH3) Si-O-Si(CH3)2 ∼<(CF3CH2CH2) (CH3)Si-O-Si(CH3) (CH2CH2CF3) ∼. Because of the negative inductive effect transferred through the siloxane links, the 3, 3, 3-trifluoropropyl groups strongly activate the siloxane ring with respect to nucleophiiic reagents.
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For part I, see [3].
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Yuzhelevskii, Y.A., Kagan, E.G., Frolov, V.N. et al. 3, 3, 3-Trifluoropropyl(methyl)cyclosiloxanes. Chem Heterocycl Compd 4, 24–28 (1970). https://doi.org/10.1007/BF00478069
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DOI: https://doi.org/10.1007/BF00478069