Ammonium polysulfide acids

Polythiodipropionic acids and their esters are prepared from acryUc acid or an acrylate with sulfur, hydrogen sulfide, and ammonium polysulfide (32). These polythio compounds are converted to the dithio analogs by reaction with an inorganic sulfite or cyanide. 

Agrochemical Products. Hydrazones of vanillin have been shown to have a herbicidal action similar to that of 2,4-D, and the zinc salts of dithiovanillic acid. Made by the reaction of vanillin and ammonium polysulfide in alcohoHc hydrochloric acid, dithiovanillic acid is a vulcanization inhibitor. 5-Hydroxymerciirivanillin, 5- a cetoxym erci iri va n ill in, and 5-ch1oromercurivani11in have been prepared and found to have disinfectant properties. 

Formazans are stable in alkaline solution. Alkaline hydrolysis of functionalities on formazans such as nitriles, esters, and amides leads to the acids (Section 7.3.1.1). The case of 3-nitroformazans (198) is unique. Reaction with hydroxide ion gives 3-hydroxy formazan (199) which can be readily oxidized to the tetrazolium betaine. In the presence of hydrosulfide, a reduction of the nitro group takes place giving 3-aminoformazan (200) with traces of the 3-mercaptoformazan (201), which by contrast is the main product when ammonium polysulfide is used (Scheme 30).45,346... 

Phenylacetamide has been obtained by a wide variety of reactions from benzyl cyanide with water at 250-260° 6 from benzyl cyanide with water and cadmium oxide at 240° 6 from benzyl cyanide with sulfuric acid 7 8 by saturation of an acetone solution of benzyl cyanide with potassium hydrosulfide 9 from benzyl cyanide with sodium peroxide 10 by electrolytic reduction of benzyl cyanide in sodium hydroxide 11 from ethyl phenyl-acetate with alcoholic 12 or aqueous 13 ammonia from phenyl-acetic acid with ammonium acetate 14 or urea 15 from diazoacetophenone with ammoniacal silver solution 16 from phenyl-acetic acid imino ether hydrochloride and water 17 from acetophenone with ammonium polysulfide at 215° 18 from benzoic acid 19 and by heating the ammonium salt of phenyl-acetic acid.20... 

The Willgerodt reaction, which involves heating ketones with ammonium polysulfide, is the most important route to carboxylic acids without degradation of the carbon chain. It applies especially to methyl and alkyl... 

The Kindler modification dodges heating in closed vessels under pressure by using, instead of aqueous ammonium polysulfide, a mixture of sulfur and morpholine. After being refluxed for 6-12 h, the ketone is converted into the thiomorpholide of the carboxylic acid. Subsequent alkaline hydrolysis yields the carboxylic acid as the final product [501, 503, 504, 1170]. 

Carbon disulfide is a valuable synthon (see Chapter 9, p. 147) which can be used for the synthesis of thiocarbonic acid derivatives. Thus, carbon disulfide reacts with ammonium polysulfide or hydrogen sulfide to give trithiocarbonic acid (70) or symmetrical esters (73) after reaction with an alkyl halide. With alkoxides or thiolates, carbon disulfide forms xanthates (77) or S-alkyl trithiocarbonates the latter by further treatment with alkyl, acyl or diazonium halides affords the derivatives (74)-(76) (Scheme 39). 

Willgerodt reaction. In its original form this reaction involved heating an aryl alkyl ketone in a sealed tube at 210-230° with an aqueous solution of yellow ammonium polysulfide, prepared by dissolving sulfur in ammonium sulfide solution. The product is an aryl substituted aliphatic aciil amide, together with some of the corresponding carboxylic acid and often the hydrocarbon. An example is the... 

Ammonium polysulfide (NH4>,S3 9080-17-6 yel unstab soln reac acids... 

The original Willgerodt Reaction conditions required high temperature and pressure, with use of ammonium polysulfide (NH4)2S and H2O to give either an amide or the ammonium salt of the corresponding acid. Kindler s modification, shown above, eliminated these problems and substituted Sg and a dry amine, most commonly morpholine. 

Conversion of aryl alkyl ketones to amides and/or the ammonium salts of the corresponding acids by aqueous ammonium polysulfide or by sulfur and a primary or secondary amine ... 

Ammonium polysulfide Carboxylic acid amides from a-subst. carboxylic acids... 

Dissolve Sn out of the sulfide precipitate with a minimum amount of ammonium polysulfide. Acidify the ammonium polysulfide with acetic acid, centrifuge the SnS2-... 

The name of Conrad Willgerodt is associated with a group of closely related reactions which have as a common feature the conversion of a carbonyl compound into an amide mth the same number of carbon atoms. The original process involved the reaction of an appropriately substituted alkyl aryl ketone with an aqueous solution of yellow ammonium polysulfide at an elevated temperature to form an aiyl-substituted aliphatic acid amide, ti ether with a smaller amount of the corresponding ammonium salt of the carboxylic acid. An example is the conversion of acetophenone into phenylacetamide and ammonium phenylacetate. ... 

The Kindler variation, - which promises to be more useful than the original Willgerodt procedure, consists in heating the ketone with approximately equimolecular amounts of sulfur and a dry amine instead of aqueous ammonium polysulfide. A thioamide is formed as the principal product and on hydrolysis with acid or alkali affords the carboxylic acid, usually in good yield. Generally a secondary aliphatic amine but sometimes a primary amine or even anhydrous ammonia is used the development of a method for the electrolytic reduction of the thioamides to amines extended the usefulness of the reaction as a new route to the synthesis of many important nitrogen bases. Early descriptions of this... 

It is of interest to note the behavior of molecules containing other functional groups. Carbinols form amides at somewhat higher tanpera-tures than the corresponding ketones, probably by way of unsaturated intermediates. Aldehydes are converted into the corresponding carboxylic acid amides when heated with aqueous ammonium polysulfide, > and they form substituted thioamides under conditions of the Kindler procedure. Aldimines likewise are converted to acid derivatives. Two imineS derived from methyl ketones and methylamine are reported to react with sulfur to form N-methylarylthioacetamides in a manner analogous to the reaction of methyl ketones in the presence of the amine. 

Phenylacetamide from Acetophenone (Use of Ammonium Polysulfide) An ammonium sulfide Elution is prepared by passing hydrogen sulfide into concentrated aqueous ammonia until the solution is saturated. A mixture of 2 g. of acetophenone with 10 g. of the colorless ammonium sulfide solution and 1 g. of sulfur is heated in a closed tube for four hours at 200-220°. After the reaction mixture has cooled, it is treated with sufficient hydrochloric acid to decompose the ammonium... 

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