Synthetic sulfides

Sofid sodium permanganate monohydrate has been shown to be a selective synthetic reagent (156). It is typically used in hexane for the heterogeneous oxidation of aldehydes, alcohols, and sulfides. Synthetic methodology based on crystal surfaces exhibited greater selectivity, higher yield, and easier work-up as compared to aqueous permanganate reactions. 

Chlorine Ammonia, acetylene, alcohols, alkanes, benzene, butadiene, carbon disulfide, dibutyl phthalate, ethers, fluorine, glycerol, hydrocarbons, hydrogen, sodium carbide, finely divided metals, metal acetylides and carbides, nitrogen compounds, nonmetals, nonmetal hydrides, phosphorus compounds, polychlorobi-phenyl, silicones, steel, sulfides, synthetic rubber, turpentine... 

Only a small part of the heavy spar extracted, less than 5%, is processed to barium chemicals (barium carbonate, barium sulfide, synthetic barium sulfate, barium chloride, barium hydroxide etc.). Over 90% is utilized in the extraction of crude oil and natural gas as suspensions in the drilling mud. Ca. 5% is used as a filler in the dye, paint, plastics and rubber industries and in the manufacture of glass. 

Caulking compound (liquid polymer poly sulfide synthetic rubber formula 112 for metal enclosures)... 

Two efficient syntheses of strained cyclophanes indicate the synthetic potential of allyl or benzyl sulfide intermediates, in which the combined nucleophilicity and redox activity of the sulfur atom can be used. The dibenzylic sulfides from xylylene dihalides and -dithiols can be methylated with dimethoxycarbenium tetrafiuoroborate (H. Meerwein, 1960 R.F. Borch, 1968, 1969 from trimethyl orthoformate and BFj, 3 4). The sulfonium salts are deprotonated and rearrange to methyl sulfides (Stevens rearrangement). Repeated methylation and Hofmann elimination yields double bonds (R.H. Mitchell, 1974). 

Historically, soda ash was produced by extracting the ashes of certain plants, such as Spanish barilla, and evaporating the resultant Hquor. The first large scale, commercial synthetic plant employed the LeBlanc (Nicolas LeBlanc (1742—1806)) process (5). In this process, salt (NaCl) reacts with sulfuric acid to produce sodium sulfate and hydrochloric acid. The sodium sulfate is then roasted with limestone and coal and the resulting sodium carbonate—calcium sulfide mixture (black ash) is leached with water to extract the sodium carbonate. The LeBlanc process was last used in 1916—1917 it was expensive and caused significant pollution. 

The principal classes of high performance fibers are derived from rigid-rod polymers, gel spun fibers, modified carbon fibers, synthetic vitreous fibers, and poly(phenyiene sulfide) fibers. 

Sulfite concentrations for scavenging oxygen ate typically in the 100— 300 mg/L range. Zinc compounds for sulfide scavenging ate used at concentrations of 1.4—14 kg/m (0.5—5 lb/bbl) synthetic magnetite concentrations range to 140 kg/m (50 lb/bbl) and higher if the need arises. 

Alternative synthetic routes to poly(arylene sulfide)s have been pubHshed (79—82). The general theme explored is the oxidative polymerization of diphenyl disulfide and its substituted analogues by using molecular oxygen as the oxidant, often catalyzed by a variety of reagents ... 

Although no consistently effective chemical repellent has been developed for vertebrate pests, some promising materials have been tested as repellents that are based on predator avoidance, specifically compounds from the secretions of predators. In 1995, synthetic sulfur compounds (two thietanes, a thiolane, and a substituted methyl sulfide, which were originally identified from the anal glands of the stoat, ferret, and red fox) suppressed browsing by the introduced AustraUan bmsh-tail opossum in New Zealand about as well as FEP (83). Suggestions were made that these compounds can be made more effective by the use of bitter compounds in a cocktail. 

Chemical pigments or synthetics may be metal compounds. A good example is white titanium dioxide. Other chemical pigments include cadmium sulfide colors, iron blue, and several synthetic versions of iron oxides. 

The highly ionic thaHic nitrate, which is soluble in alcohols, ethers, and carboxyhc acids, is also a very useful synthetic reagent. Oxidation of olefins, a,P-unsaturated carbonyl compounds, P-carbonyl sulfides, and a-nitrato ketones can aH be conveniently carried out in good yields (31,34—36). 

The effect of pH and the piC of the thiol has been discussed. This reaction is not of great synthetic interest, primarily because it yields a mixture of products, but it is of commercial consequence. It is also appHcable ia polysulfide synthesis, where the presence of small amounts of thiols can cause significant problems for the stabiUty of the polysulfide (51). A similar reaction between thiols and sulfides has also been described (52). In this instance, the process is heterogenous and acid-cataly2ed. 

The synthetic pigment is produced by one of several related procedures. The best quahty product is made by reaction of an aqueous solution of CdSO or CdCl with a solution of an alkaline metal sulfide or H2S. Zn, Se, or Hg may be added to the CdS to produce shade vatiations. After precipitation, the color is filtered, washed, and calcined in an inert atmosphere at 500—600°C. 

The mtroducuon of a tnfluoromethanethio group into an aromatic nng has a synthetic importance The reaction of tnfluoromethanethio copper with aryl bro mides and iodides provides a convenient route to the synthesis of aryltn fluoromethane sulfides The reaction is not sensitive to the type of substituents or the aromahc nucleus Selectivity can be achieved accordmg to the type of halogen or the aromatic rmg, because iodides react at lower temperatures than bromides, whereas chlondes do not react [f J] (equation 12) (Table 5)... 

The addition (150-157) of Grignard reagents, alkoxides, hydroxide, sulfides, cyanide, and enolate anions to pyridinium and isoquinolinium salts again provides a variety of cyclic enamines of potential synthetic use. 

Contrary to the expectation that a sulfur-containing substituent will be a catalyst poison, a phenylthio group serves as an effective selectivity control element in TMM cycloadditions. A single regioisomer (30) was obtained from the carbonate precursor (31) in good yield. The thermodynamically more stable sulfide (32) is readily accessible from (30) via a 1,3-sulfide shift catalyzed by PhSSPh. A wide array of synthetically useful intermediates could be prepared from the sulfides (30) and (32) with simple transformations (Scheme 2.10) [20]. 

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