Sodium terf-butoxide

Mol (9.6 or 11.3 g) of powdered sodium or potassium f-butoxide and 50 ml of hexane or pentane are placed into the flask. The mixture is cooled to — 70 °C and a solution of 0.10 mol of butyllithium in 70 ml of hexane is added over a few seconds with efficient stirring. The suspension is then cooled to —40 °C and 0.10 mol of TMEDA is added in one portion. In the case of sodium terf-butoxide a homogeneous solution is formed, the addition of TMEDA to the BuLi-potassium teH-butoxide mixture results in a fine suspension. The mixtures are kept below — 30 °C since at 0 °C or higher the TMEDA is attacked by the base. 

Shibasaki s heterobimetallic complexes, active in the asymmetric aldol reaction (see Section 7.1) provide the opportunity to activate both the nucleophile and Michael acceptor. Whilst the aluminium lithium bis-BlNOL complex (ALB) (11.28) does not catalyse conjugate addition of a-phosphonate ester (11.29) with cyclopentenone (11.30) by itself, addition of sodium terf-butoxide allows a highly enantioselective reaction to take place. A postulated model for enantioinduction in this process involves simultaneous binding of the metallated nucleophile and acceptor to the catalyst by interaction with a BINAP oxygen and the aluminium centre respectively. Heterobimetallic complexes have also been used to catalyse the addition of a-nitroesters and malonatesto Michael acceptors. 

Exposure of compound 16, a substance that can be obtained in a straightforward manner from glycine, to sodium tert-butoxide furnishes an enolate that undergoes conversion to 8 upon treatment with terf-butyl formate. It was anticipated that the phthalimido and tert-butyl ester protecting groups in 8 could be removed easily and selectively under anhydrous conditions at a later stage in the synthesis. 

The preparatively useful and simple N-alkylation procedure that utilizes a combination of carboxylic acid and sodium borohydride has been applied to carbazole giving an efficient 9-ethylation. Also of preparative importance is the use of thallous ethoxide as base in dimethylformamide-ether 9-methyl-, 9-ethyl-, n-propyl-, n-butyl-, benzyl-, and n-allylcarbazoles were efficiently produced, as well as 9,9 -dicarbazolylalkanes using C3, C4, and Cg dihalides. 2-Acetyl- and 2-vinylcarbazole were also efficiently 9-ethylated by this route. Another more recent approach to N-alkylation of carbazole utilizes potassium terf-butoxide in the presence of a catalytic quantity of 18-crown-6 9-methylcarbazole was prepared in high yield. ... 

Poly(difluorosilylene), 4324 Potassium antimonide, 4668 Potassium terf-butoxide, 1645 Potassium cyclopentadienide, 1840 Potassium diethylamide, 1679 Potassium octacyanodicobaltate(8—), 2875 Potassium—sodium alloy, 4641... 

Carbethoxy-7,7-diphenyIvinylacetic acid has been prepared in 58-62% yield by the condensation of benzophenone with diethyl succinate in the presence of sodium ethoxide.1 The procedure described here is a modification involving the use of potassium terf.-butoxide as the condensing agent.2... 

Recently, the bis(methylthio)methylene imine of pseudoephedrine glycinamide was shown to undergo diastereoselective alkylation at 23 °C with lithium terf-butoxide or sodium ethoxide as base and various alkyl halides as electrophiles (eq 21 ). This procedure was used to prepare enantiomerically enriched a-amino acids. 

Potassium terf-butoxide,1-5-32 sodium hydride,6 butyllithium1 have all been used for this purpose. The alkyl(aryl)sulfanylcarbene (carbenoid) thus generated undergoes addition, often effectively, across the double bond of alkenes,1,25 enol ethers,6 ketene acetals1 and enamines.3,4 The use of chloromethyl phenyl sulfide, oxirane, tetraethylammonium bromide as a catalyst and an alkene gave phenylsulfanylcyclopropanes in rather low yield.7 For the synthesis of... 

ALCOOL ETHYLIQUE (French) (64-17-5) Forms explosive mixture with air [flash point 55°F/13°C 68°F/20 C (80%) 72°F/22°C (60%) 79°F/26°C (40%)]. Reacts, possibly violently, with strong oxidizers, bases, acetic anhydride, acetyl bromide, acetyl chloride, aliphatic amines, bromine peniafluoride, calcium oxide, cesium oxide, chloryl perchlorate, disulfuryl difluoride, ethylene glycol methyl ether, iodine heptafluoride, isocyanates, nitrosyl perchlorate, perchlorates, platinum, potassium-terf-butoxide, potassium, potassium oxide, potassium peroxide, phosphorus(III) oxide, silver nitrate, silver oxide, sulfuric acid, oleum, sodium, sodium hydrazide, sodium peroxide, sulfinyl cyanamide, tetrachlorosilane,. s-tri-azine-2,4,6-triol, triethoxydialuminum tribromide, triethylaluminum, uranium fluoride, xenon tetrafluoride. Mixture with mercury nitrate(Il) forms explosive mercury fulminate. Forms explosive complexes with perchlorates, magnesium perchlorate (forms ethyl perchlorate), silver perchlorate. Flow or agitation of substance may generate electrostatic charges due to low conductivity. 

The carbonyl compounds that can undergo this condensation include aliphatic, aromatic, and <%,/ -unsaturated aldehydes, aliphatic, saturated carbo-cyclic, and aromatic ketones, diketones, oxo esters, and cyano ketones. Sodium ethoxide and potassium terf-butoxide are the condensing agents generally used. 

Carbon tetrachloride is a noncombustible liquid. Explosion may occur when this compound is mixed with alkali metals such as sodium, potassium, lithium, or their alloys or finely divided aluminum, magnesium, calcium, barium, beryllium, and other metals on heating or impact. Reactions with hydrides of boron or silicon, such as diborane, disilane, trisilane, or tetrasilane, can be explosively violent. When mixed with dimethyl formamide and heated, carbon tetrachloride may explode (Kittila 1967). Its mixture with potassium terf-butoxide may ignite. Its reaction with fluorine or a halogen fluoride is generally vigorous and may become violent on heating. A violent reaction occurs with hypochlorites. 

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