Sodium acetate phenoxide

Another easily available palladium compound is PdCl2 however, it has low or no activity. The chloride ion in the coordination sphere of palladium seems to inhibit the coordination of two moles of butadiene to form the bis-77-allylic complex. However, PdCl2 can be used in the presence of an excess of bases, such as KOH, NaOH, sodium phenoxide, sodium acetate, potassium acetate, sodium methoxide, or tertiary amines. These bases deprive the chloride ion from the coordination sphere of palladium to form the active species. Thus, very stable and easily prepared... 

Rates of hydrolysis of diazoacetate ion in the presence of sodium acetate (plus a very small amount of acetic acid) or phenol—sodium phenoxide buffers are increased in comparison to rates without buffers at the same pH. The experimental data do not obey the simple equation... 

In the light of this mechanism, several well-known facts concerning diazonium coupling reactions are readily explicable. Sodium acetate or sodium carbonate is usually necessary for coupling to lower the acidity of the reaction mixture and to increase correspondingly the concentration of free base or phenoxide ion. There is little probability of reaction between diazonium and substituted anilinium ions since they are of like charge and the aromatic nucleus of the anilinium ion is deactivated ... 

Condensation of sodium phenoxide witli 2,2,2-trifluoroethyl iodide gives a product of direct substitution in a low yield, several other ethers are formed by eliminatton-addition reactions [7] Use of mesylate as a leaving group and hex amethyl phosphoramide (HMPA) as a solvent increases the yield of the substitution [S] Even chlorine can be replaced when the condensation is performed with potassium fluoride and acetic acid at a high temperature [9] (equations 6-8)... 

The rates of bromination of 3-nitrophenol in aqueous solution at 25 °C have been measured at various concentrations of perchloric acid and sodium bromide294. An increase in both caused a decrease in rate the latter again shows that Br is much less reactive than Br2, whilst the former shows that reaction occurs principally on the 3-nitrophenoxide ion and the difference from the observation for phenol in acetic acid (above p. 117) is undoubtedly partly due to the greater stability of the 3-nitrophenoxide relative to the phenoxide ion. The... 

Still another possibility in the base-catalyzed reactions of carbonyl compounds is alkylation or similar reaction at the oxygen atom. This is the predominant reaction of phenoxide ion, of course, but for enolates with less resonance stabilization it is exceptional and requires special conditions. Even phenolates react at carbon when the reagent is carbon dioxide, but this may be due merely to the instability of the alternative carbonic half ester. The association of enolate ions with a proton is evidently not very different from the association with metallic cations. Although the equilibrium mixture is about 92 % ketone, the sodium derivative of acetoacetic ester reacts with acetic acid in cold petroleum ether to give the enol. The Perkin ring closure reaction, which depends on C-alkylation, gives the alternative O-alkylation only when it is applied to the synthesis of a four membered ring ... 

Several chemical methods are used. In one method the mixture of aniline and quinoline is acylated either with acetic anhydride or with sulfochloride. The aniline forms a derivative and the quinoline remains unaffected. A second method treats the mixture with sodium nitrite and sulfuric acid. The aniline is converted into the diazonium salt and the quinoline forms the sulfate. The solution is made alkaline and steam-distilled the diazonium salt changes to sodium phenoxide, and quinoline is distilled. In the third method, the mixture is separated by means of hydrochloric acid and zinc chloride. Quinoline chlorozincate, (C9H7N)2H2ZnCl4, is sparingly soluble in water and is separated from the soluble anihne salt. 

Potassium nitronates, 950 Potassium nitrosodisulfonate, 940-942 Potassium permanganate, 713, 942-952 Potassium peroxymonosulfate. 952 Potassium persulfate, 952-954 silver-catalyzed, 954 Potassium phenoxide, 300 Potassium-sodium tartrate, 36 Potassium thiocyanate, 199, 378, 954 Potassium thiolacetate, 356,955-956 Potassium triacetylosmate, 955 Potassium triphenylmethide, see Triphenyl-methyl potassium Prednisolone, 997 21-acetate, 604... 

In diols containing both phenolic and alcoholic hydroxyl groups neutral conditions favour the acylation of the latter while the former are selectively acylated in the presence of triethylamine (ref. 57) doubtless due to the more nucleophilic phenoxide ion so formed, which is the basis of the Chattaway procedure originated many years ago. This is exemplified in the preferential formation in 95% yield of the phenolic acetate of estradiol in isopropanol containing 2.9 moles of sodium hydroxide in concentrated solution followed by the addition of 2.9 moles of acetic anhydride and then by stirring of the mixture for SOmins. at ambient temperature with maintenance of the pH at 7.8 (ref.58). 

The replacement of 5-chloro substituents by oxygen functions has been effected by the use of ethylene glycol and its homologs,125 126 glyddol (2-hydroxymethyloxiran),308 and sodium phenoxide.309 Prolonged treatment of 3-substituted 5-chloro-1,2,4-thiadiazoles with boiling acetic add yields the corresponding A2-l,2,4-thiadiazolin-5-ones.310... 

Kim [213] studied the effect of the coimter ion on the HKR of epiehlorhydrine, 1,2-epoxybutane, 1,2-epoxyhexane and epoxystyrene. The salen polymer catalyst were synthesized by eopolymerization of salen bearing chloromethyl groups with sodium phenoxide derivatives of hydroquinone, 1,3,5-trihydroxybenzene or l,l,l-tris(p-hydroxyphenyl)ethane in presence of A-methylpyrrolidine and NaH in THF (Sehemes 143 and 144). Co(lI) type polymeric chiral salen ligands were formed by reaction of the corresponding salen ligand with hydrous Co(ll) acetate. To obtained Co(IIl) polymeric chiral... 

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