Sodium /-butoxide

Double alkoxides of zirconium with alkah metals of the type MZr2(OR) have been obtained by reaction of alkah metal alkoxides with zirconium alkoxides (220). Although these usually are monomeric derivatives, the reaction between zirconium tetra-/-butoxide [1071 -76-7] and sodium /-butoxide was found (221) to form dimeric NaZr(OC(CH2)2) ]2. 

Treatment of the sodium salt of carbostyril with chlorodifluoro-methane and sodium <-butoxide in 1,2-dimethoxyethane gave the products of 0- (49) and iV -alkylation (50). ... 

Heating 3,4-bis(phenylsulfonyl)furoxan with a solution of sodium butoxide in butanol followed by reduction with trimethyl phosphite gives furazan 281 (Scheme 183). Compound 281 was converted into dialkoxy derivative 282 with the lithium salt of ( )-l-azabicyclo[2.2.2]octan-3-ol in 33% overall yield (96W012711, 97EUP773021, 98JMC379). 

Eight grams of the crude ester, which had been prepared from tosyl azide and sodium butoxide, then stored for four weeks at 0°C, was to be distilled at 0.2 mm Hg. On the bath reaching 70°C, there was a violent explosion. This was attributed to a toluenesulphonic acid autocatalysed elimination. However, presence of butyl azide as an impurity seems probable. 

Butyl S-methylthiolcarbonate has been prepared from sodium /-butoxide, carbonyl sulfide, and methyl iodide 3 and from methyl... 

Iverson and Sheppard (1977) have compared the method above, substituting sodium butoxide for sodium methoxide to H2S04 and boron trifluoride-catalyzed butyrolyses. Butyl esters were used by these and other investigators to improve the resolution of short chain esters and to reduce their volatility. They recommend the boron trifluoride method for preparation of butyl esters of milk fatty acids, although the other catalysts gave satisfactory results. Analysis of methyl esters resulted in lower values for the short chain fatty acids. 

Sodium butoxide Iodoethane Butyl ethyl ether (71%) Sodium... 

Finally, it has recently been shown that 2-(p-tolyl)benzoxazole reacts with Schiff s base (88) under the influence of sodium /-butoxide, giving /S-(2-phenylbenzoxazol-6-yl)-4-(benzoxazol-2-yl)styrene (89).53... 

Saigusa and Oda (196) have brominated polystyrene with N-bromo-succinimide in the presence of benzoyl peroxide 61% of the styrene units were brominated in the main chain. After dehydrohalogen-ation with sodium butoxide, the polymer contains 39% unchanged styrene units, 49% unsaturated groups, -CH=C-, and about 12%... 

A sodium butoxide solution is prepared in a flask attached to a reflux condenser by heating 23.5 g. of sodium with 300 ml. of commercial redistilled butyl alcohol (b. 115.5 to 117.5°C.). The resulting solution must be sufficiently free from color so as not to mask the effect of the indicator. The sodium dissolves rather slowly unless an elevated temperature is maintained. The brown color which is imparted to the warm alkaline solution as it is poured rapidly from the flask to the dropping funnel is not troublesome. 

Silicon, higher chlorides of, 42 Silicon tetrabromide, 38, 40 Silicon tetrachloride, 44 Silicopropane, octachloro, 44 Silicotungstic acid, 129 analysis, 131 ether complex, 131 Silver, metallic, 4 Silver chloride, reduction of, 3 Silver cyanamide, 98 Silver residues, purification of, 2 Sodium amalgam, 10 Sodium amide, 74 Sodium azide, purification of, 79 Sodium azidodithiocarbonate, 82 Sodium butoxide, 88 Sodium hypochlorite (solution), 90 Sodium iodate, 168 Sodium metaperiodate, 170 Sodium paraperiodate, chlorine method, 169 persulfate method, 170 Strontium amalgam, 11 Sulfur hexafluoride, 121 Sulfuryl chloride, 114... 

Sodium amide, 1 74, 2 80, 128, 134 Sodium amidophosphate (Na2P03NH2), 6 100 anhydrous, for preparation of tetrasodium imidodiphos-phate, 6 101 Sodium azide, 2 139 purification of, 1 79 Sodium azidodithiocarbonate, solution of, 1 82 Sodium butoxide, 1 88 Sodium carbonate, Na2C03, light, for preparation of chlorine (I) oxide, 5 159... 

Condensation of hydrazine with formaldehyde (37% solution) and hydrogen sulfide in water in the presence of a sodium butoxide-butanol buffer (pH 10.75-11.5) gives a mixture of products. The reactant ratio is an important factor in determining the product ratio and, when a 6 4 1 ratio of HCHO-H2S-H2NNH2 was used, the perhydro-A-(l,3-thiazet-3-yl)-l,3,5-dithiazine 48 was isolated in 5-6% yield in addition to other S,N-heterocycles (Equation 18) <2006RJ0145>. 

Concerning developments in the synthesis of 1,3-thiazetidine derivatives, it was recently shown that cyclothiomethyl-ation of phenyl hydrazine with formaldehyde and hydrogen sulfide in sodium butoxide medium produced A-phenyl(perhydro-l,3-thiazetidin-3-yl)amine in 22% yield <2006RCB1824>. 

NaNj Sodium azide, 1 79 2 139 NaOCSodium butoxide, 1 88 NaOj Sodium superoxide 4 82 Na202-8H20 Sodium peroxide, 3 1 NbFt Niobium (V) fluoride, 3 179 NdClj Neodymium chloride, 1 32 Nd2(C2O4)2 10H2O Neodymiumox-alate, 2 60... 

Butyl S-methylthiolcarbonate has been prepared from sodium /-butoxide, carbonyl sulfide, and methyl iodide 1 and from methyl chlorothiolformate and /-butyl alcohol.4 /-Butyl phenyl carbonate has been prepared from phenyl chloroformate and /-butyl alcohol.6 6... 

The analogous reaction of unsaturated lactones and lactams is strongly accelerated in the presence of alcohols which protonate the copper enolate formed in the conjugate reduction.281 This protocol was used in an enantioselective synthesis of the antidepressant (—)-paroxetine 324. Here, the key step was the conjugate reduction of the lactam 322 by PMHS in the presence of /-amylalcohol and catalytic amounts of CuCl2, ( S)- -tol-BINAP, and sodium /-butoxide, giving the product 323 with 90% yield and 90% ee (Scheme 90).281 The second chirality center was installed by diastereoselective alkylation of 323. 

N Sodium Butoxide Transfer 9.62 g of sodium butox-ide solution (50% in butanol) into a 100-mL volumetric flask, dilute to volume with 1-butanol, and mix. 

Procedure For each sample (hexane blank, Standard Reference Solution, and Sample Solution) to be assayed, pipet 5.0 mL of solution into a clean 8-mL clear glass vial. Add 0.5 mL of 0.5 N sodium butoxide, seal, and shake vigorously. The solution will turn yellow. For the hexane blank and the Sample Solutions only, allow the solution to stand for 2 min. Neutralize the mixture by adding 1.0 mL of 0.5 N hydrochloric acid. Seal the vial, and shake well until the solution is clear. Check the pH with pH paper. The solution should be acidic. If it is not, the column will degrade. 

N sodium butoxide and 0.5 N hydrochloric acid, respectively, for the Standard Reference Solution. 

Formamidine reacts with a-hydroxyketones95 and a-haloketones62 to yield oxazoles and imidazoles. Normally the formamidine is liberated from its hydrochloride by the addition of sodium butoxide in n-butanol. It is interesting to note that in the reaction with a-hydroxyketones, the aliphatic acyloins yielded mainly imidazoles (35-68% yield), whereas the benzoins gave mainly oxazoles (67-80%).95 Unlike formamidine, acetamidine and benzamidine react with both aliphatic acyloins and with benzoins to yield imidazoles exclusively.65 Bredereck65 explains the reactions as follows ... 

Butyl phosphate has been prepared by the action of phosphorus oxychloride upon -butyl alcohol, aluminum butoxide, or sodium butoxide. The above procedure is similar to one that has been used for the preparation of alkyl phosphites. ... 

The conversion of o- and p-nitroethylbenzenes with /-butyl nitrite and sodium /-butoxide into the corresponding nitroacetophenone oximes is accomplished in 67-74% yields. ... 

Esters of aliphatic and aromatic sulfonic acids are conveniently prepared in high yields from alcohols and sulfonyl halides. A basic medium is required. By substituting sodium butoxide for sodium hydroxide in butanol, the yield of n-butyl p-toluenesulfonate is increased from 54% to 98%. Ethyl benzenesulfonate and nuclear-substituted derivatives carrying bromo, methoxyl, and nirro groups are prepared from the corresponding sulfonyl chlorides by treatment with sodium ethoxide in absolute ethanol the yields are 74-81%. Pyridine is by far the most popular basic medium for this reaction. Alcohols (C -Cjj) react at 0-10° in 80-90% yields, and various phenols can be converted to aryl sulfonates in this base. "... 

When amidines or guanidines cyclize in the presence of a-functionalized carbonyl reagents they form imidazoles with a variety of 1-, 2-, 4- and 5-substituents [1, 2]. Formamldine will react with a-hydroxy- [8] or a-halogenoketones [9], to give mixtures of oxazolcs and imidazoles. Usually, the formamidine is liberated from its hydrochloride by treatment with sodium butoxide in butanol. When the two-carbon synthon is an a-hydroxyketone the aliphatic members mainly form imidazoles (35-70%), while benzoins give oxazoles (67-80%) preferentially [8], The competing pathways are shown in Scheme 4.3.1. 

Although numerous methods are known for the synthesis of carbamates of primary and secondary alcohols, they are not satisfactory for the preparation of carbamates of tertiary alcohols /-Butyl carbamate was first obtained by reaction of sodium /-butoxide with phosgene and tbionyl chloride at —60°, followed by reaction with concentrated aqueous ammonia, the overall yield was less than 20%. This procedure, however, was found to be unsuitable for the preparation of carbamates of other tertiary alcohols. Carbamates have been prepared by the... 

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