Zur Kenntnis der Chemie der Silazane. Über Reaktionen von Hexamethyl‐disilazan und Trimethyl‐N‐methyl‐aminosilan

Abstract

Soc. 68,241 (1946).

Reactions of phosphorus acid halides withN-silylated organic compounds

“…As in the case of P(III) derivatives, the reaction of P(V) acid chlorides with disilazanes can be used for the preparation of N-silylated amides. 72,73 Successful synthesis of these amides requires that appropriate reaction conditions are selected depending on the structure of the phosphorylating agent used. Reactions at room temperature mainly involve more electrophilic MePOCl 2 and 1-chloro-1oxophosphol-3-ene, 72 whereas diphenyl phosphorochloridate reacts at 60 8C, 73 and phosphinothioic chlorides react only at 130 ± 150 8C.…”

“…72,73 Successful synthesis of these amides requires that appropriate reaction conditions are selected depending on the structure of the phosphorylating agent used. Reactions at room temperature mainly involve more electrophilic MePOCl 2 and 1-chloro-1oxophosphol-3-ene, 72 whereas diphenyl phosphorochloridate reacts at 60 8C, 73 and phosphinothioic chlorides react only at 130 ± 150 8C. 74 N,N-Bis(trimethylsilyl)-P-phenylphosphonothioic diamide is obtained under even more drastic conditions (in the presence of aluminium chloride).…”

Organosilicon Derivatives of Sulfur

“…The rate of the reaction depends on the structure of the radicals Hand H' and increases with a change in H in the following series: n-C 4 Hg < Compounds containing the grouping 8i -N-8 are formed when hexamethyldisilazan reacts with sulfuryl chloride, the ethyl ester of chlorosulfonic acid, or benzenesulfamide [180]: In the case of benzenesulfamide it is possible to introduce two trimethylsilyl radicals into the amide group, but p-acetamidobenzenesulfamide does not react at all with trimethylchlorosilane under these conditions [45]. 5,5-Dimethylsulfodiimine reacts with trialkylchlorosilanes by a scheme analogous to (2.217) [833].…”

“…However, sodium methylsulfate may be used successfully to prepare trialkylsilyl esters of methylsulfuric acid[619]:(2.178)4.1.6. Other Synthesis MethodsOf the other reactions for the formation of the grouping Si -O-S we should mention the reaction of the ethyl ester of chlorosulfonic acid with hexamethyldisilazan, which proceeds according to the scheme[180] [(CHa)aSihNH + CzH50S0zCl ---+ (CHalaSiNHS020Si(CHa)a+CzH6Cl(2.179) and the reaction of triethylgermyl ethanesulfonate with triphenyl-sHyl isocyanate[159]:(CZH6)3GeOSOzCzH6+ (CaH5)aSiNCO -~ (CaH6)3SiOSOzCzH6+ (C2HIi)3GeNCO(2.180) Siloxysulfanes R 3 SiOSnOSiR 3 are formed by the reaction of sodium triorganosilanolates with sulfur chloride SnCl2[869].…”

Stereoelectronic structure and self-association of N-trimethylsilylsulfonamides RSO2NHSiMe3 (R = Me, CF3, Ph)

“…The introduction of a silicon atom in the molecule results in substantial changes in its stereoelectronic structure and, consequently, in the physicochemical properties of the compounds. First representatives of triorganylsilyl sulfonamides were synthesized in the middle of the last century [26,27]. N-Trimethylsilylcarboxamides are known to exist in solution as amido-imidate tautomers due to the migration of the trimethylsilyl group between the nitrogen and oxygen atoms, the amide form being 10-20 kcal/mol more stable than the imidate form [28][29][30][31][32][33][34] (Scheme 1).…”