Acetic acid reaction with potassium

Vicinal iodo carboxylates may also be prepared from the reaction of olefins either with iodine and potassium iodate in acetic acid/ or with N-iodosuccinimide and a carboxylic acid in chloroform. " A number of new procedures for effecting the hydroxylation or acyloxylation of olefins in a manner similar to the Prevost or Woodward-Prevost reactions include the following iodo acetoxylation with iodine and potassium chlorate in acetic acid followed by acetolysis with potassium acetate reaction with iV-bromoacetamide and silver acetate in acetic acid reaction with thallium(III) acetate in acetic acid and reaction with iodine tris(trifluoroacetate) in pentane. ... 

Young et reported in 1951 that the solvolysis of a,a-dimethylallyl chloride in acetic acid buffered with potassium or lithium acetate is accompanied by partial isomerization to 7,7-dimethylallyl chloride, which solvolyzes only about an eighth as fast as its tertiary isomer. It was possible to calculate from the titrirnetric data rate coefficients for the isomerization reaction as well as for the two solvolysis reactions. Since neither the reaction rates nor the product compositions were influenced by added potassium chloride, it was concluded that the isomerization is intramolecular. This is the first documented example of internal return from a carbonium ion-anion pair, viz ... 

Solution A was prepared by dissolving potassium acetate in methanol Solution B was pre pared by adding potassium methoxide to acetic acid Reaction of methyl iodide either with solu tion A or with solution B gave the same major product Why" What was this product" ... 

Lead tetraacetate is added in small quantities, with stirring, to an ice-cold suspension of 11 g. of ethyl 3-(D-arabino-tetrahydroxybutyl)-5-methyl 4-furoate in 100 ml. of benzene plus 40 ml. of glacial acetic acid. Addition is stopped when there is a positive reaction with potassium iodide-starch paper. The mixture is stirred for a further ten minutes, filtered, and the benzene solution washed twice with water. The benzene layer is then dried with anhydrous sodium sulfate, filtered, and the filtrate evaporated to dryness. The residue (6 g.) is mixed with a solution of 7.5 g. of sodium hydroxide plus 20 g. of silver nitrate in 40 ml. of water, and heated for 40 minutes on a steam bath. The aqueous solution is filtered, acidified to Congo Red while being cooled with ice, and the crystals formed are removed by filtration, washed with ice-cold water, and dried over phosphorus pentoxide in the vacuum desiccator yield, 2.2 g. After recrystallization from water, the product has m. p. 234r-235°. 

There is surprisingly little reliable information on the sulfonation of benzo[6]thiophene or its derivatives. Benzo[6]thiophene is more readily sulfonated than naphthalene.699 Reaction with concentrated sulfuric acid at 80° gives a mixture of mono-, di-, and trisulfonic acids, reaction with 70% sulfuric acid at 80° gives a monosulfonic acid,699 and reaction with 18% oleum gives a disulfonic acid 86 in each case the orientation of the products is unknown. Treatment of benzo[6]thiophene with concentrated sulfuric acid in acetic anhydride at 20° gives 3-acetylbenzo[6]thiophene (ca. 10%) and a sulfonation product (isolated as the potassium salt), which was believed to be the 3-sulfonic acid.660 Recently, the sulfonation product has been shown to contain the 2- (8%) and 3-isomer (92%), by conversion into the sulfonyl chlorides and reduction to a separable mixture of 2- and 3-mercaptobenzo[6]thiophene.84... 

The enol acetate 77 of 3,4-dihydro-7-methoxy-5-methyl-l-(2l/)-naphthalenone was converted to the acid 78 by ozonolysis and hydrolysis and this by a Wittig reaction with a-methoxyethyltriphenyl-phosphonium chloride gave 79. Compound 79 was converted into 80 by a series of reactions, five in number, which in turn was converted into 81 by reaction with potassium in -butanol. The methyl ester of compound 81, one isomer of which was recognized as that having the correct stereo structure, was converted to 82 by heating with acetic anhydride and 10-camphorsulfonic acid. Subsequent steps involved ozonization, reaction with V,iV -carbonyldiimidazole, lactam formation, reaction with pyridinium bromide perbromide, reaction with sodium hydride, and a further series in which (+ )-oxodendrobine (83) was ultimately obtained. Reduction of the latter to ( )-dendrobine... 

Enolizable ketones were converted directly into their a-hydroxy dimethyl acetals upon reaction with DIB and methanolic potassium hydroxide at room temperature. If, during work up, there was acid treatment, then a-hydroxyketones were directly obtained. Numerous examples are known for such transformation, e.g. with 3-pentanone, acetophenones, 2,6-diacetylpyridine [16], tropan-3-one [17], -amino-ketones of great structural variety [18], etc. even a free radical reacted successfully in this way [19]. This conversion for an acetyl-oxazole served for the preparation of pyrimidine derivatives. 

Potassium iodide solution The addition of a nitrite solution to a solution of potassium iodide, followed by acidification with acetic acid or with dilute sulphuric acid, results in the liberation of iodine, which may be identified by the blue colour produced with starch paste. A similar result is obtained by dipping potassium iodide-starch paper moistened with a little dilute acid into the solution. An alternative method is to extract the liberated iodine with chloroform or carbon tetrachloride (see Section IV.16, reaction 4). 

Aliphatic nitroso compounds can be prepared from IV-alkylhydioxylamines oxidation widi bromine, chlorine or sodium hypochlorite in weakly acidic solution, reaction with potassium dichromate in acetic or sulfuric acid, and by oxidation widi yellow mercury(II) oxide in suspension in an organic solvent. Silver carbonate on Celite has also been used to prepare aliphatic nitroso compounds, such as ni-trosocyclohexane, in high yield from the corresponding hydroxylamines." Aqueous sodium periodate and tetraalkylanunonium periodates, which are soluble in organic solvents, are the reagents most commonly used for the oxidation of hydroxamic acids and IV-acylhydroxylamines to acylnitroso compounds... 

A mixture of 200 g. (3.45 moles) of propionaldehyde and 200 g. of ether is cooled to 0° in a flask equipped with a condenser, a dropping funnel, a thermometer, and a stirrer. Ten milliliters of a 15% aqueous solution of potassium hydroxide is added with vigorous stirring. The reaction mixture is cooled so that the temperature does not rise above 10-12°. When the mixture has cooled to about 6-8° another portion of potassium hydroxide solution is introduced in the same manner as before. Base is added in this way until there is no longer an evolution of heat upon addition. This requires 70-80 ml. of base solution and 35-40 minutes. The aqueous layer is separated and washed with ether. The combined ethereal solutions are washed with dilute aqueous acetic acid and with dilute sodium bicarbonate solution and then dried over anhydrous sodium sulfate. The ether is distilled off on a water bath, and the residue is distilled through a 25-cm. Vigreux column. At a pressure of 80-l(K) mm., there is first obtained a mixture of unreacted propionaldehyde and 2-methyl-2-pentenal. The propionaldol is collected at 84-86°/ll mm., and the yield is around 55-60%. 

Sulphonyl azides have been analysed by two processes release of nitrogen by reaction with triphenylphosphine and release of iodine by reaction with potassium iodide-acetic acid . 

Reaction with olefins.2 When ceric acetate is heated with styrene in glacial acetic acid containing 10% potassium acetate at 110° for 20 hr. the major product is the lactone (1), 70% yield. For the synthetic preparation of lactones, the more available ceric ammonium nitrate can be used in place of ceric acetate. 

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