Abstract
One-pot synthesis of 2,2-dimethyl-4-R-1-oxa-4-aza-2-sila-5-benzocycloheptanones (R = Me, CH2SiMe2Cl) from the N-methylamide of salicylic acid and salicylamide, respectively, by treatment of these amides with a mixture of hexamethyldisilazane and dimethylchloromethylchlorosilane was developed. The hydrolysis and other nucleophilic substitution reactions of the resultant seven-membered silacyclanes were studied. In the case of the silacyclane with R = Me, hydrolysis leads to the corresponding disiloxane, while the silacyclane with R = CH2SiMe2Cl gives either 2,2,6,6-tetramethyl-4-(2-hydroxybenzoyl)-2,6-disilamorpholine or its hydrochloride, depending on the reaction conditions. The chlorine atom was replaced by fluorine in the silacyclane with R = CH2SiMe2Cl. The structures of 2,2,6,6-tetramethyl-4-(2-hydroxybenzoyl)-2,6-disilamorpholine and its hydrochloride as well as 2,2-dimethyl-4-R-1-oxa-4-az! a-2-sila-5-benzocycloheptanones (R = CH2SiMe2Cl, CH2SiMe2F) were confirmed by X-ray diffraction.
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Zamyshlyaeva, O.A., Shipov, A.G., Kramarova, E.P. et al. Synthesis and Some Chemical Properties of 2,2-Dimethyl-4-R-1-oxa-4-aza-2-sila-5-benzocycloheptanones. Chemistry of Heterocyclic Compounds 38, 116–127 (2002). https://doi.org/10.1023/A:1014871813405
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DOI: https://doi.org/10.1023/A:1014871813405