Sodium n-butoxide

The phenol (Imol) in 5% aqueous NaOH is treated (while cooling) with benzoyl chloride (Imol) and the mixture is stirred in an ice bath until separation of the solid benzoyl derivative is complete. The derivative is filtered off, washed with alkali, then water, and dried (in a vacuum desiccator over NaOH). It is recrystalUsed from ethanol or dilute aqueous ethanol. The benzoylation can also be carried out in dry pyridine at low temperature ca 0°) instead of in NaOH solution, finally pouring the mixture into water and collecting the solid as above. The ester is hydrolysed by refluxing in an alcohol (for example, ethanol, n-butanol) containing two or three equivalents of the alkoxide of the corresponding alcohol (for example sodium ethoxide or sodium n-butoxide) and a few ca 5-10) millilitres of water, for half an hour to three hours. When hydrolysis is complete, an aliquot will remain clear on dilution with four to five times its volume of water. Most of the solvent is distilled off. The residue is diluted with cold water and acidified, and the phenol is steam distilled. The latter is collected from the distillate, dried and either fractionally distilled or recrystalUsed. 

Although quantitative yields of chloroform were found, low yields of trialkyl phosphite were produced and these decreased with time as the yields of trialkyl phosphate and dialkyl phosphate increased, e.g. in the reaction of sodium n-butoxide (0.06 mol) with phosphorus (0.009 mol) in 30 ml of methanol and 50 ml of n-butanol 47% of phosphite was produced in 3 h. together with 19% of phosphate and 7% of phosphonate. The product composition changed to 34%, 22% abd 21% respectively after 7 h. 

For the halogen-metal exchange reaction of bulkier halopyrimidines, steric hindrance retards the nucleophilic attack at the azomethine bond. As a consequence, halogen-metal exchange of 5-bromo-2,4-di-r-butoxypyrimidine (43) with n-BuLi could be carried out at -75 °C [20]. The resulting lithiated pyrimidine was then treated with n-butylborate followed by basic hydrolysis and acidification to provide 2,4-di-f-butoxy-5-pyrimidineboronic acid (44). 5-Bromopyrimidine 43 was prepared from 5-bromouracil in two steps consisting of a dehydroxy-halogenation with phosphorus oxychloride and an SnAt displacement with sodium r-butoxide. 

N-Bis(trimethylsilyl)acetamide, 34 Butyllithium, 56, 150, 157, 193, 322 sec-Butyllithium, 188 Butyllithium-Potassium t-butoxide, 56 Butyllithium-Sodium t-butoxide, 59 Butyllithium-Tetramethylethylene-diamine, 56, 57 t-Butylmagnesium bromide, 59 Butylpotassium-Tetramethylethylene-diamine, 59 Butylsodium, 59... 

Anionic polymerization behavior of 2-oxabicyelo[2.2.2]octan-3-one, an analogue of 54, is different from that described above. [55] Thus, the polymerization initiated with n-butyllithium propagates by alkoxide growing spedes, whereas the polymerization initiated by sodium rcrt-butoxide and sodium-potassium alloy propagates by both alkoxide and carboxylate growing species. The latter yields a polyester consisting of cis- and trans- 1,4-linked cyclohexane rings. 

Under continuous nitrogen flow, a reaction flask was dried with a propane torch flame and then cooled to ambient temperature. The flask was charged with 180 ml of toluene, palladium acetate (0.5 mmol), and tri-t-butylphosphine (2.0 mmol) and stirred at ambient temperature until a thick light yellow suspension was obtained. This mixture was then treated with 4-n-butylaniline (10 mmol), the Step 1 product (10 mmol), and sodium t-butoxide (22 mmol) and heated overnight at 80°C. The reaction mixture was poured into 1000 ml of methanol where a brownish precipitation slowly appeared, which was isolated by filtration. The brown solid was dissolved in 50 ml of CCI3H and re-precipitated in 500 ml of methanol, and the product was isolated in 45.0% yield as a brown powder having a M of 7728 daltons with a PDI of 2.12. 

Representative for the Palladium-Catalyzed Arylation of Amines with Aryl Chlorides using (f-BuljP/Pd (Reproduced with permission from [50]. 1999 American Chemical Society) In a dry box, aryl halide, amine, Pd(dba)j, (t-BuljP, and sodium fert-butoxide were weighed directly into a screw cap vial. A stir bar was added followed by 1.0-2.0 ml of toluene to give a purple mixture. The vial was removed from the dry box, and the mixture was stirred at room temperature. After 5.5 h, the reaction mixture was adsorbed onto sihca gel and chromatographed with 50% toluene/hexanes to give 242 mg (90%) of N-(4-cyano-phenyl)diphenylamine as a white solid. 

General Procedure for the N-Arylation of Indoles (Excerpted with permission from [119]. 2000 American Chemical Society) A Schlenk tube was charged with sodium ferf-butoxide (1.4 mmol), Pd2(dba)3 (0.005 mmol), and 4 (0.015 mmol). The Schlenk tube was fitted with a septum and attached to a Schlenk line. After the air atmosphere was replaced with argon, toluene (2 ml), aryl bromide (1.0 mmol), and the indole (1.2 mmol) were added. After the septum was replaced with a teflon valve, the reaction was sealed and heated to 80- 100°C with stirring until starting material was consumed as judged by GC analysis. The reaction mixture was cooled to room temperature, diluted with ether (20 ml), filtered, and concentrated. The crude reaction mixture was then purified by flash chromatography on silica gel. 

Sodium-f-Butanol-Tetrahydrofurane, 291 Sodium /-butoxide, 305 Sodium chloride-Dimethyl sulfoxide, 445 Sodium chloroacetate, 275 Sodium N-chloro-p-to/uenesulfonamide, 75, 445-446... 

Sodium ferf-butoxide in N,N-dimethylformamide at KXP was found to be very effective in promoting intramolecular displacements408 and 2,5 -anhydrothymidine was obtained directly from 5 -0-(methyl-sulfonyl)thymidine with these reagents. The same conditions have also been used to synthesize the anhydronucleosides 121 and 122 from a pseudouridine derivative408 and from a D-ribosyl derivative of 2,4-quinazolinedione.410 The same reagents with 3 -0-p-tolylsulfonyl-uridine gave mainly 1 -(2,3 -anhydro-y3-D-xylofuranosyl)uracil.408... 

N-Arylatwn. Secondary amines are arylated by ArCl under the following conditions heating with Ni(acac)2, 3,5,6,8-tetrabromo-l,10-phenanthroline, sodium t-butoxide, and PMHS in toluene at 130°. ... 

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