Potassium sulfide, reaction with

Ethylene carbonate, reaction with potassium thiocyanate, 42, 59 Ethylene sulfide, 42, S9 Ethyl formate, reaction with cyclo-hexylamine, 41, 14 Ethyl- -hexylamine, 43, 47 5-(2-Ethylhexyl)-l,2,3,4,5-pentachloro-cyclopentadiene, 43, 93 Ethylhydrazinium hydrogen oxalate,... 

The method described is adapted from the procedures of Kym 3 and Engelhardt, Latschinoff, and Malyscheff.4 Thio-benzoic acid has been prepared by the reaction of benzoyl chloride with potassium sulfide,4 hydrogen sulfide in pyridine,6 6 and magnesium bromide hydrosulfide.7 It is formed from dibenzoyl disulfide with potassium hydrosulfide,4 potassium hydroxide,4 8 and ammonia.9 It is also formed from dibenzoyl sulfide, from phenyl benzoate, and from benzoic anhydride with alcoholic potassium hydrosulfide.4 It has been obtained from dibenzoyl sulfide and hydrogen sulfide,10 carbon oxysulfide and phenyl-magnesium bromide,11 12 dibenzyl disulfide and sodium ethoxide,13 benzyl chloride and sulfur in the presence of potassium hydroxide,14 and benzylthiosulfuric acid and alkali.18 16... 

Haloalkyl phenyl sulfides produce cycloalkyl phenyl sulfides on treatment with base. The synthesis of cyclopropyl phenyl sulfides has attracted particular interest since these compounds can be metal-lated - - by Bu"Li in THF and the resulting 1-phenylthiocyclopropyllithium has been used for spiro-annelation of various cycloalkanones. - Thus, 3-chloro-l-phenylthiopropane leads to phenylthiocyclopropane on reaction with potassium amide in liquid ammonia (Scheme 7, entry a), but attempts to prepare 2-methylcyclopropyl phenyl sulfide from 3-chloro-l-phenylthiobutane by an analogous route failed in the cyclization step. Neither 3-mesyloxy- and 3-tosyloxy-l-phenylthiododecanes " nor 3-tosyloxy-l-phenylthiobutane produce cyclopropane derivatives either on reaction with LDA in THF (Scheme 7, entry b). Failure in these ring closure reactions has been attributed to inadequate car-... 

In one case the substituents on the nitrogen atoms were both phenyl.789 Two other methods of synthesis of the 3-pyrazolin-5-thiones have been reported. Michaelis992 has claimed the conversion of l,2-dimethyl-3-phenyl-3-pyrazolin-5-one to the thione analog by reaction with potassium hydrogen sulfide. Worrall1653 has reported the synthesis shown in eq. 150. 

A few halogenated 3-pyrazolin-5-thiones are known (Table XVIII). These are prepared from the methyl chlorides of 3- or 4,5-dichloro-pyrazole by reaction with sodium sulfide or potassium hydrogen sulfide.795,981 Michaelis988,992 has reported that 3-pyrazolin-5-selenones form dichlorides and di- and tetrabromides when treated with chlorine or bromine. No specific structures were suggested. 

BORIC ACID (10043-35-3) BH3O3 Aqueous boric acid is a weak acid incompatible with alkali carbonates hydroxides strong reducing agents, including metal hydrides, nitrides, sulfides, and alkali metals. Violent reaction with potassium metal. Contact with acetic anhydride forms a heat-sensitive explosive. On small fires, use water fog. 

CALCIUM SULFIDE (20548-54-3) CaS Reacts with moist air, water, steam, acids, and acid fiimes, producing toxic and flammable hydrogen sulfide gas. Violent reaction with strong oxidizers, chlorates, nitrates, lead dioxide with risk of fire and explosion. Explosive reaction with potassium nitrate, potassium chlorate. 

Bencarbazone 114 can be prepared in several steps from the nucleophilic displacement reaction of 2,4,5-trifluorobenzonitrile (110) with 4-methyl-3-tri-fiuoromethyl-l,2,4-triazolin-5-one (111) to give l-(4-cyano-2,5-difluorophenyl)-4-methyl-3-tri luoromethyl-l,2,4-triazolin-5-one (112). Reaction of 112 with ethane-sulfonamide in the presence of a base such as potassium carbonate gives 113, which on reaction with hydrogen sulfide gives bencarbazone (114) [116] (Scheme 3.5). 

Figure 33 shows the result of a separation procedure for lead, copper, iron and nickel carried out in this way. Copper is fixed as sulfide on the paper disk, iron and nickel washed into the ring zone and then revealed respectively in individual sectors by reaction with potassium cyanoferrate(II) and dimethylglyoxime. 

The common method for preparing CuNs is by reaction of a cuprous salt with sodium azide. Aqueous solution of cupric salt (sulfate) is reduced with potassium sulfide giving cuprous sulfide as precipitate which is then dissolved by addition of acetic acid. In the following step, sodium azide is added to the solution, precipitating CuNs [78,107]. 

It is appropriate to include in this section the use of l,4-diodo-l,3-dienes, since these are at the same oxidation level as 1,3-diynes. The reaction of these with potassium sulfide using copper catalysis has been used to produce a range of di-, tri-, and tetraalkyl-substituted thiophenes, a selection of which is specified in Scheme 28 [48]. 

Reactions with Sulfur Compounds. Thiosuccinic anhydride [3194-60-3] is obtained by reaction of diethyl or diphenyl succinate [621-14-7] with potassium hydrogen sulfide followed by acidification (eq. 10). Thiosuccinic anhydride is also obtained from succinic anhydride and hydrogen sulfide under pressure (121). 

Uses. There may be some captive use of carbonyl sulfide for production of certain thiocarbamate herbicides (qv). One patent (38) describes the reaction of diethylamine with carbonyl sulfide to form a thiocarbamate salt which is then alkylated with 4-chloroben2yl haUde to produce 3 -(4-chloroben2yl) A[,A/-diethylthiocarbamate [28249-77-6] ie, benthiocarb [28249-77-6]. Carbonyl sulfide is also reported to be useful for the preparation of abphatic polyureas. In these preparations, potassium thiocyanate and sulfuric acid are used to first generate carbonyl sulfide, COS, which then reacts with a diamine ... 

If tin and sulfur are heated, a vigorous reaction takes place with the formation of tin sulfides. At 100—400°C, hydrogen sulfide reacts with tin, forming stannous sulfide however, at ordinary temperatures no reaction occurs. Stannous sulfide also forms from the reaction of tin with an aqueous solution of sulfur dioxide. Molten tin reacts with phosphoms, forming a phosphide. Aqueous solutions of the hydroxides and carbonates of sodium and potassium, especially when warm, attack tin. Stannates are produced by the action of strong sodium hydroxide and potassium hydroxide solutions on tin. Oxidizing agents, eg, sodium or potassium nitrate or nitrite, are used to prevent the formation of stannites and to promote the reactions. 

Vinyl chloride reacts with sulfides, thiols, alcohols, and oximes in basic media. Reaction with hydrated sodium sulfide [1313-82-2] in a mixture of dimethyl sulfoxide [67-68-5] (DMSO) and potassium hydroxide [1310-58-3], KOH, yields divinyl sulfide [627-51-0] and sulfur-containing heterocycles (27). Various vinyl sulfides can be obtained by reacting vinyl chloride with thiols in the presence of base (28). Vinyl ethers are produced in similar fashion, from the reaction of vinyl chloride with alcohols in the presence of a strong base (29,30). A variety of pyrroles and indoles have also been prepared by reacting vinyl chloride with different ketoximes or oximes in a mixture of DMSO and KOH (31). 

Potassium Permanganate. Probably the most widely used process for removing traces of hydrogen sulfide from carbon dioxide is to scmb the gas with an aqueous solution saturated with potassium permanganate [7722-64-7]. Sodium carbonate is added to the solution as buffer. The reaction is as foUows ... 

This dialkoxydiphenylsulfurane has been prepared by the reaction of diphenyl sulfide, 2,2,2-trifluoro-l-phenyl-l-(trifluoromethyl)ethyl hypochlorite, and potassium l,l,l,3,3,3-hexafluoro-2-phenyl-2-propanolate and by the reaction of diphenyl sulfide with 1 equivalent of chlorine and 2 equivalents of potassium 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanolate in diethyl ether. ... 

Perfluoroisobutylene and potassium sulfide give 2,4-bis[hexafluoroisopro-pylidene]-l,3-dithietane and a small amount of the bis(perfluoro-tcrr-butyl)trisul-fide. The trisulfide is the result of a reaction of the nascent perfluoro-rerr-butyl carbanion with sulfur. The same products in different yields are obtained with sulfur and cesium fluoride [i] (equation 2). 

Treatment of 3,4-dinitrofurazan with potassium thiocyanate in acetic acid at 10-20°C led to the corresponding thiocyanate 214 in 83% yield along with a small amount of 3-mercapto-4-nitrofurazan, whereas at 70-75°C the precursor was converted into a mixture of the disulfide 215 (38%) and tricycle 216 (27%). Thioether 217 was prepared in 78% yield by reaction of 3,4-dinitrofurazan and sodium sulfide (95MC25) (Scheme 145). 

The a -halosulfone, required for the Ramberg-Backlund reaction, can for example be prepared from a sulfide by reaction with thionyl chloride (or with N-chlorosuccinimide) to give an a-chlorosulfide, followed by oxidation to the sulfone—e.g. using m-chloroperbenzoic acid. As base for the Ramberg-Backlund reaction have been used alkoxides—e.g. potassium t-butoxide in an etheral solvent, as well as aqueous alkali hydroxide. In the latter case the use of a phase-transfer catalyst may be of advantage. ... 

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