Verwendung von Organo-Silicium-Verbindungen als Standardsubstanz für die Kernresonanzspektroskopie

1,206,069. Deuterated organic silicon compounds. E. MERCK A.G. 19 June, 1969 [27 July, 1968; 1 Aug., 1968; 21 March, 1969], No. 31171/69. Heading C3S. [Also in Division G1] Deuterium derivatives of organic silicon compounds, used as standards in NMR determination, comprise (a) 1,1,3,3,5,5 - hexakis - (trideuteromethyl) - 1,3,5 - trisilacyclo - hexane, (b) α,α,#,# - tetradeutero - # - (trimethylsilyl)- propionic acid [(CH 3 ) 3 SiCD 2 CD 2 COOH] and its alkali metal salts and (c) α,α,#,#,O - pentadeutero- # - (trimethylsilyl) propionic acid [(CH 3 ) 3 Si- CD 2 CD 2 COOD] and its alkali metal salts # - (trimethylsilyl)propionic acid and its alkali metal salts may also be used. Compound (a) may be prepared by reaction of methylene chloride on a Si-Cu(I)-chloride catalyst and reaction of the resulting 1,1,3,3,5,5 - hexachloro - 1,3,5 - trisilacyclohexane with trideuteromethyl magnesium chloride, bromide or iodide. Compounds (b) and (c) can be prepared by boiling deuterated # (trimethylsilyl)propionic acid nitrile with aqueous alcoholic sodium deuteroxide. The deuterated silyl propionic acid nitrile is obtained by reacting HSiCl 3 with trideuteroacrylonitrile and reacting the product with MeMgI. Acidification of the final deuterated product gives the tetra- and penta-deuteropropionic acids. Alternatively, sodium acetylide is reacted with Me 3 SiCl to form Me 3 SiC#CH which is reacted with EtMgBr to form Me 3 SiC#CMgBr. This is reacted with CO 2 and the product hydrolysed to form Me 3 SiC#C.COOH or Me 3 SiC#C.COOD which is catalytically hydrogenated or deuterated on palladium.