Nitrogen-containing organosilicon compounds

Metallocanes of group 14 elements. 1. Derivatives of silicon and germanium. (Review)

“…X-Ray Crystallographic Analysis. The initial view that there was no transannular Si←N interaction in the molecules of silacyclooctanes [15] was disproved in 1974, when the first structural data for these compounds were published [41][42][43]. It was found that in the solid phase the Si←N distances are comparable with those in silatranes, for which at that time the presence of transannular bonding was considered to have proved both by physicochemical methods and by reactivity data [15].…”

“…Silacyclooctane 1 (R 1 = Me, R 2 = R 3 = H, R 4 = R 5 = Ph) was obtained by a twostage synthesis according to Eq. (15). At the first stage the dimethoxysilane reacts with the ethylene chlorohydrin in the presence of the sodium alkoxide with the formation of the 2-(chloroethoxy) derivative.…”

“…The screening of the nitrogen increases with increase of temperature and with decrease of the solvent polarity [48]. The dipole moments (µ) for ten silocanes of the R 1 N(CH 2 CH 2 O) 2 SiR 4 R 5 type 1 were measured in benzene solutions [12,15] and in the liquid _______ * For the 29 Si-15 N spin-spin coupling constants in silocanes, see also: E. L. Kupce and E. Lukevics, Usp. Khim., 58, 1777 (1998) (Editor's note).…”

“…The review includes data on compounds in which the central group 14 atom forms four covalent bonds and is capable of forming one or two additional intramolecular hypervalent interactions. A major contribution to the development of the chemistry of these derivatives was made by several research groups led by E. Lukevics Historically this method became the first method for the production of such compounds [2][3][4] and was subsequently used widely in the synthesis of a large number of functionally substituted silocanes [5][6][7][8][9][10][11][12][13][14][15][16] Dimethoxysilanes react more quickly than the diethoxy derivatives [7]. The yields of compounds 1 vary within wide limits between 29 and 95%, depending on the nature of the substituents R 1 , R 4 , and R 5 .…”

“…Reaction of Dialkanolamines with Bis(dialkylamino)silanes. An alternative approach to the production of cyclic silyl ethers of dialkanolamines is the reaction of amino alcohols with bis(dialkylamino)silanes (heat, 10-15 h) [7,15,31]. (6) 1 R = Me, Et; R 1 = H, R 4 = R 5 = Me (37%); R 1 = H, R 4 = Me, R 5 = Ph (50%); R 1 = H, R 4 = R 5 = Ph (63%); R 1 = Me, R 4 = R 5 = Ph (75%)…”