Reaction of bis(trifluoromethyl)amino-oxyl with alkylchlorosilanes and allyldichloro(methyl)silane and of perfluoro-2,5-diazahexane 2,5-dioxyl with vinylsilanes and hydrolysis of the products

Article abstract of DOI:10.1016/0022-1139(93)02976-L

Treatment of the silanes MeSiHCl2, Me2SiHCl and EtSiMeCl2 with the oxyl (CF3)2NO(.) (1) gives the substitution products (CF3)2NOSiMeCl2 (4) and (CF3)2NOSiMe2Cl (5), and a mixture of (CF3)2NOCHMeSiMeCl2 (8) and (CF3)2NOCH2CH2SiMeCl2 (9) (ratio 20:37), respectively, while the silane EtSiMe2Cl affords mainly the ester (CF3)2NO2CMe (7).Attack of oxyl 1 on the silane CH2=CHCH2SiMeCl2 results in both allylic substitution and addition to give the compounds CH2=CHCH(SiMeCl2)ON(CF3)2 (14) and (CF3)2NOCH2CH(CH2SiMeCl2)ON(CF3)2 (15) (ratio 56:40).Reaction of the dioxyl (.)ON(CF3)CF2CF2N(CF3)O(.) (2) with the vinylsilanes CH2=CHSiX3 (X3 = Me3, Cl3, MeCl2) gives mainly 1:1 copolymers n (17), although the cyclic 1:1 adduct (18) is also formed in low yield.Hydrolysis of the silanes 15, (CF3)2NOCH2CH(SiMeCl2)ON(CF3)2 (19a) and (CF3)2NOCH2CH(SiCl3)ON(CF3)2 (19b) affords the corresponding polysiloxanes 24 and 25, and the polysilsesquioxane 26, respectively; the polymers 25 and 26 undergo rearrangement of the type -CH(Si<*>)ON(CF3)2 --> -CH(OSi<*>)N(CF3)2 on storage.The 1:1 copolymers 17b (X3 = MeCl2) and 17c (X3 = Cl3) are also hydrolysed to the corresponding siloxane and silsesquioxane polymers.In contrast, hydrolysis of the compounds 4,5 and (CF3)2NOCH2CH(OSiX3)N(CF3)2 (20a; X3 = MeCl2) and (20b; X3 = Cl3) results in Si-O bond cleavage.