Trimethylsilyldiethylamine

Aoyama, T. Terasawa, S. Sudo, K. Shioiri, T., Chem. Pharm. Bull. 1984, 32, 3759. 

A list of General Abbreviations appears on the front Endpapers 

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Me3SiNEt2- Trimethylsilyldiethylamine selectively silylates equatorial hydroxyl groups in quantitative yield (4-10 h, 25°). The report indicated no reaction at axial hydroxyl groups. In the prostaglandin series the order of reactivity of trimethylsilyldiethylamine is Cii > Ci5 C9 (no reaction). These trimethylsilyl ethers are readily hydrolyzed in aqueous methanol containing a trace of acetic acid. The reagent is also useful for the silylation of amino-acids. ... 

Treatment of the allylic sulfoxide 1227 a with diisopropylethylamine (DIPEA) or of 1227 b with N-trimethylsilyldiethylamine 146 and TMSOTf 20 leads in ca. 90% yield to the quaternary amino derivatives 1228 and 1229 and HMDSO 7 [36] (Scheme 8.15). Tetramethylene sulfoxide 1230 reacts with silylated thymine 1231 in the presence of three equivalents of TMSOTf 20 to give the 4 -thio-nucleoside analogue 1232 and HMDSO 7 [37]. Other silylated pyrimidine, pyridine, and purine bases react analogously with cyclic sulfoxides to give 4 -thio-nucleoside analogues [37, 37a, 38]. 

There are rarely more than eight alkaloids present in a species, and the possibility of the same GC retention time is not normally a problem. In cases where overlap has been observed it has proved possible to identify both components from the mass spectrum of the mixture. The crude alkaloid extracts are treated with trimethylsilyldiethylamine to form volatile TMS derivatives of the hydroxylated components. The presence of a free phenolic or hydroxyl group is then detected by an ion with m/e 73 [(CH3)3Si+]. Positional isomers [e.g., erysovine (5) and erysodine (7)] are resolved although a- and /1-erythroidine are not. The presence of fi-erythroidine (60) can be estimated since it shows some enol content under the silylation conditions and gives rise to a monotrimisyl derivative with m/e 345 (15). 

V-trimethylsilyldiethylamine) (/V-trimethylsilylimidazole) TMSI > TMSDEA > TMCS/pyridine... 

N-Trimethylsilyldiethylamine (TMSDEA) is a strongly basic silylating reagent and is particulady usehil for derivatizing low molecular weight acids. The reaction by-product, diethylamine, is volatile enough to be easily removed from the reaction medium. 

SCHMIDT DEGRADATION Sodium azide. SILYLATION Trimethylsilyldiethylamine. SIMMONS-SMITH REAGENT, which see. SOMMELET REACTION Hexamethylenetetramine. 

Trimethylpyridine, 61, 62 N-Trimethylsilylamides, 204 Trimethylsilyl azide, 276, 542 Trimethylsilylcarbene, 544 Trimethylsilyl cyanide, 542-543 Trimethylsilyldiazomethane, 543-544 Trimethylsilyldiethylamine, 544-545 Trimethylsilyl enol ethers, 125, 538 N-(Trimethylsilyl)glycine trimethyl silyl... 

Trimethyl phosphite, 110, 315—316 Trimethylsilyl azide, 316 Trimethylsilyldiethylamine, 317 Trimethylsilyl enol ethers, 310-311 Trimethylsilyl ethers, 24 Trimethylsilylimidazole, 148 Trimethylsulfonium iodide, 124... 

Reaction with trimethylsilyldiethylamine Trimethylsilyl esters of N-trimethylsilylamino acid 28, 29... 

Coad [82] on the formation of derivatives in the column by consecutive insertion into it of (1) a sample of the compound to be analysed and (2) a reagent, suggested using this method to form TMS derivatives. The method was applied to the analysis of polyols, acids and oxyacids. As the donor of the TMS group a mixture of N,0-bis(trimethylsilyl)-acetamide, trimethylsilyldiethylamine and hexamethyldisilazine was used. Fig. 1.14 shows a chromatogram of the TMS derivatives of polyols, obtained in the analysis of a mixture of polyols performed in accordance with the method proposed by Esposito... 

Amino acids from the hydrochlorides. Amino acids can be liberated from the hydrochlorides or hydrobromides by treatment with trimethylsilyldiethylamine in DMF or with bis(trimethylsilyl)acetamide (1, 61 2, 30 3, 23-24) in THF. Average yields exceed 96%. 

Typical vapor phase silylating agents used in top surfaee imaging systems include dimethylsilyldimethylamine (DMSDMA), trimethylsilyldimethylamine (TMSDMA), and trimethylsilyldiethylamine (TMSDEA). Typical liquid phase silylating agents used in top surfaee imaging systems inelude 1,1,33,5,5-hexamethylcyclotrisilazane and bis(dimethylamino)dimethylsilane with N-methyl-2- pyrrolidone (NMP) as a diffusion promoter. Typical polymer resins include polyvinyl phenol and novolac/diazoquinone polymer resins. 

Preparation of Phosphonic Acid Chlorides. Disilyl esters of phosphonic acids react with oxalyl chloride-DMF to give the phosphonyl chlorides and silyl chlorides under mild conditions (eq (>) Prior treatment of an acid-sensitive phosphonate monoester with Trimethylsilyldiethylamine was used to minimize exposure to HCl (eq 7). ... 

Trimethylsilyldiethylamine as Halosilane Equivalent. Tri-methylsilyldiethylamine has recently found applications in preparation (in situ) of difficult-to-handle and highly moisture-sensitive iodosilanes and bromosilanes. This method has been used for a variety of synthetic transformations, including cleavage of cyclic ethers, cyclic acetals, and oxazolidines. The conversion of esters to carboxylic acids may also be accomplished with trimethylsi-lyldiethylamine as shown in the following examples. It may be suggested that other reactions of iodosilane and bromosilane can be carried out by means of trimethylsilyldiethylamine. 

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