Phosphorus hydrogen sulfide

The heat sensitivity (above) may explain the explosions which occur on contact of many readily oxidisable materials with this powerful oxidant. Such materials include ammonia, potassium arsenic, antimony sulfur, charcoal (adsorptive heating may also contribute) calcium phosphide, phosphine, phosphorus hydrogen sulfide, antimony sulfide, barium sulfide, mercury sulfide and tin sulfide [1], Various organic materials (paper, cork, rubber, turpentine, etc.) behave similarly [2]. Mixtures with hydrogen detonate on ignition [1]. 

Lead dioxide Aluminum carbide, hydrogen peroxide, hydrogen sulfide, hydroxylamine, ni-troalkanes, nitrogen compounds, nonmetal halides, peroxoformic acid, phosphorus, phosphorus trichloride, potassium, sulfur, sulfur dioxide, sulfides, tungsten, zirconium... 

A thioamide of isonicotinic acid has also shown tuberculostatic activity in the clinic. The additional substitution on the pyridine ring precludes its preparation from simple starting materials. Reaction of ethyl methyl ketone with ethyl oxalate leads to the ester-diketone, 12 (shown as its enol). Condensation of this with cyanoacetamide gives the substituted pyridone, 13, which contains both the ethyl and carboxyl groups in the desired position. The nitrile group is then excised by means of decarboxylative hydrolysis. Treatment of the pyridone (14) with phosphorus oxychloride converts that compound (after exposure to ethanol to take the acid chloride to the ester) to the chloro-pyridine, 15. The halogen is then removed by catalytic reduction (16). The ester at the 4 position is converted to the desired functionality by successive conversion to the amide (17), dehydration to the nitrile (18), and finally addition of hydrogen sulfide. There is thus obtained ethionamide (19)... 

Methyl-n-propyl ketone Cyanacetamide Phosphorus oxychloride Ammonia Hydrogen sulfide... 

The crystalline product produced by electrolytic oxidation of silver nitrate (and possibly as formulated) detonates feebly at 110°C. Mixtures with phosphorus and sulfur explode on impact, hydrogen sulfide ignites on contact and antimony trisulfide ignites when ground with the salt. 

Chlorine dioxide Ammonia, carbon monoxide, hydrogen, hydrogen sulfide, methane, mercury, nonmetals, phosphine, phosphorus pentachloride... 

Chromic(VI) acid Acetic acid, acetic anhydride, acetone, alcohols, alkali metals, ammonia, dimethylformamide, camphor, glycerol, hydrogen sulfide, phosphorus, pyridine, selenium, sulfur, turpentine, flammable liquids in general... 

Nitrites Nitrobenzene Nitroethane Nitrogen trichloride Organic nitrites in contact with ammonium salts, cyanides Nitric acid, nitrous oxide, silver perchlorate Hydroxides, hydrocarbons, metal oxides Ammonia, As, hydrogen sulfide, nitrogen dioxide, organic matter, ozone, phosphine, phosphorus, KCN, KOH, Se, dibutyl ether... 

The method described for the preparation of N-methyl-2-pyrrolidinethione is very similar to that of Peak and Stansfield 2 for the preparation of 4-thioacetylmorpholine. N-Methyl-2-pyrrolidinethione has also been prepared by the reaction of 2-chloro-N-methyl-A1-pyrrolinium chloride with hydrogen sulfide [yield 83% b.p. 144-145° (15 mm.)]3 and by heating N-methyl-2-pyrrolidinone with 2 equivalents of phosphorus pentasulfide in xylene [yield not reported b.p. 125-132° (10 mm.)].4 General procedures for the preparation of N,N-disubstituted thioamides have been reviewed.5, 6... 

Emits toxic fumes of nitrogen and phosphorus oxides when heated to decomposition (Lewis, 1990). Products reported from the combustion of malathion at 900 °C include carbon monoxide, carbon dioxide, chlorine, sulfur oxides, nitrogen oxides, hydrogen sulfide, and oxygen (Kennedy et al., 1972). 

There is very little information on the toxicity of phosphorus pentasulfide. Irritancy of the respiratory tract would be expected because the substance is rapidly hydrolyzed to phosphoric acid and hydrogen sulfide pulmonary irritation is expected at concentrations of lOmg/m ... 

Bromine reacts with phosphorus to form pbospborus tribromide, PBrs or phosphorus pentabromide, PBrs. The pentabromide forms in tbe presence of excess bromine. Bromine oxidizes hydrogen sulfide to sulfur ... 

This is often achieved from 1,4-dicarbonyl compounds in a procedure similar to that used to form furans but using phosphorus pentasulfide, or Lawesson s reagent (see below), to cause a transposition from carbonyl to thiocarbonyl groups, prior to cyclization and loss of hydrogen sulfide (Scheme 6.37). 

There are also methods where sulfur is used as the one-atom unit. Reagents include sulfur dichloride (Equation 79) <1983TL3203>, hydrogen sulfide (Equation 80) <1995RJC300>, and phosphorus pentasulfide (Equation 81) <2001T4195>. Elemental sulfur was used in the synthesis of 22 (Equation 82) <1985AXC1062>. 

Reactivity. Flammable polymerizes violently in the presence of trace amounts of metals or acids can react violently with acid anhydrides, alcohols, ketones, phenols, ammonia, hydrocyanic acid, hydrogen sulfide, halogens, phosphorus, isocyanates, strong alkalis and amines (American Conference of Governmental Industrial Hygienists, 1991)... 

The synthesis of 4//-thiopyrans from 1,5-dicarbonyl compounds consists of the cyclization of 1,5-dioxo precursors with hydrogen sulfide in the presence of protic acids or with various phosphorus polysulfides. 

There is a series of analogous cyclic thiuphosphoric acids with the formula (HS2P) thal may be prepared by the oxidation of red or white phosphorus with polysulfides under a variety of conditions. For example, the reaction of white phosphorus with a mixture of sulfur and hydrogen sulfide dissolved in triethylamine (which acts as a base) and chloroform opens the phosphorus cage to form the tectamerre cyclic anion ... 

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