Sulfur bases

Production of nitric phosphates is not expected to expand rapidly ia the near future because the primary phosphate exporters, especially ia North Africa and the United States, have moved to ship upgraded materials, wet-process acid, and ammonium phosphates, ia preference to phosphate rock. The abundant supply of these materials should keep suppHers ia a strong competitive position for at least the short-range future. Moreover, the developiag countries, where nitric phosphates would seem to be appealing for most crops except rice, have already strongly committed to production of urea, a material that blends compatibly with sulfur-based phosphates but not with nitrates. 

Nonetheless, production and use of nitric phosphates ia Europe are continuing to grow. In general, nitric phosphate processes are somewhat more compHcated than sulfur-based processes and requite higher investment. In the past, several attempts have been made to estabHsh commercial acceptance of this type process ia the United States, but plant operations have been relatively short Hved because of low sulfur prices and resultant competition from sulfur-based processes. 

Wet-process acid is manufactured by the digestion of phosphate rock (calcium phosphate) with sulfuric acid. Depending on availabiHty, other acids such as hydrochloric may be used, but the sulfuric-based processes are by far the most prevalent. Phosphoric acid is separated from the resultant calcium sulfate slurry by filtration. To generate a filterable slurry and to enhance the P2O5 content of the acid, much of the acid filtrate is recycled to the reactor. 

Chevron Chemical Co. began commercial production of isophthahc acid in 1956. The sulfur-based oxidation of / -xylene in aqueous ammonia at about 320°C and 7,000—14,000 kPa produced the amide. This amide was then hydrolyzed with sulfuric acid to produce isophthahc acid at about 98% purity. Arco Chemical Co. began production in 1970 using air oxidation in acetic acid catalyzed by a cobalt salt and promoted by acetaldehyde at 100—150°C and 1400—2800 kPa (14—28 atm). The cmde isophthahc acid was dissolved and recrystallized to yield a product exceeding 99% purity. The Arco technology was not competitive and the plant was shut down in 1974. 

In mbber production, the thiol acts as a chain transfer agent, in which it functions as a hydrogen atom donor to one mbber chain, effectively finishing chain growth for that polymer chain. The sulfur-based radical then either terminates with another radical species or initiates another chain. The thiol is used up in this process. The length of the mbber polymer chain is a function of the thiol concentration. The higher the concentration, the shorter the mbber chain and the softer the mbber. An array of thiols have subsequendy been utilized in the production of many different polymers. Some of these apphcations are as foUow ... 

Depending on energy and raw material costs, the minimum economic carbon disulfide plant size is generaHy in the range of about 2000—5000 tons per year for an electric furnace process and 15,000—20,000 tons per year for a hydrocarbon-based process. A typical charcoal—sulfur facHity produces approximately 5000 tons per year. Hydrocarbon—sulfur plants tend be on the scale of 50,000—200,000 tons per year. It is estimated that 53 carbon disulfide plants existed throughout the world in 1991 as shown in Table 2. The production capacities of known hydrocarbon—sulfur based plants are Hsted in Table 3. The United States carbon disulfide capacity dropped sharply during 1991 when Akzo Chemicals closed down a 159,000 ton per year plant at Delaware City, Delaware (126). The United States carbon disulfide industry stiH accounts for about 12% of the total worldwide instaHed capacity. 

Double-Bond Cure Sites. The effectiveness of this kind of reactive site is obvious. It allows vulcanization with conventional organic accelerators and sulfur-based curing systems, besides vulcanization by peroxides. Fast and controllable vulcanizations are expected so double-bond cure sites represent a chance to avoid post-curing. Furthermore, blending with other diene elastomers, such as nitrile mbber [9003-18-3] is gready faciUtated. 

Three different covalent cure systems are commonly used sulfur-based or sulfur donor, peroxide, and maleimide. These systems rely on a cross-linking agent and one or more accelerators to develop high cross-link density. 

A number of cement materials are used with brick. Standard are phenolic and furan resins, polyesters, sulfur, silicate, and epoxy-based materials. Carbon-filled polyesters and furanes are good against nonoxidizing acids, salts, and solvents. Silica-filled resins should not be used against hydrofluoric or fluosihcic acids. Sulfur-based cements are limited to 93°C (200°F), while resins can be used to about 180°C (350°F). The sodium silicate-based cements are good against acids to 400°C (750°F). 

Hydrochloric acid/stannous chloride. Modifications of the standard HC1 cleaning program to aid control corrosion of exposed steel include the addition of HF, as discussed earlier, but also stannous chloride. Where the cleaning program is likely to remove considerable volumes of rust and magnetite, even in the presence of a nitrogen- and sulfur-based proprietary corrosion inhibitor, rapid corrosion of exposed steel may develop. This is because the ferric ions (Fe3+) released from ferric oxide act to reduce the exposed steel to ferrous ions (Fe2+). 

Another difference between diese catalysts is found in dieir functional group tolerance. Catalysts such as 12 are more robust to most functionalities (except sulfur and phosphorus), moisture, oxygen, and impurities, enabling them to easily polymerize dienes containing functional groups such as esters, alcohols, and ketones.9 On die other hand, catalyst 14 is more tolerant of sulfur-based functionalities.7 The researcher must choose die appropriate catalyst by considering the chemical interactions between monomer and catalyst as well as the reaction conditions needed. 

Since sulfur-based S03/air is becoming the predominant route for the manufacture of anionic surfactants, little attention will be paid to other, less versatile processes in this chapter. 

There are four main sulfonation reactor configurations applied worldwide to produce all kinds of top quality anionic surfactants from sulfur-based S03/air as the sulfonating agent. All these systems have proven and documented experience ... 

HNO3 (nitric acid) gas, aqueous, solid phases HNO2 (nitrous acid) gas, aqueous phases Sulfur based ... 

Earlier studies (162) on synthetic iron-sulfur-based clusters showed that protons bind to the bridging sulfur atoms and increase the rate of substitution at the metal atoms. FeMoco exhibits similar behavior, with protonation causing considerable acceleration in the... 

Besides macrocyclic benzoic acids [33] (see above), investigations have also been carried out on compounds with intra-annular sulfur-based acidic groups, sulfinic acids [43] (Skowronska-Ptasinska et al., 1987) and sulfonic acids [45] (van Eerden et al., 1989). 

Iron(III) complexes of 2-acetylpyridine Af-oxide iV-methyl- and 3-azabicyclo[3.2.2.]nonylthiosemicarbazone, 24 and 25, respectively, have been isolated from both iron(III) perchlorate and chloride [117], The perchlorate salt yields low spin, octahedral, monovalent, cationic complexes involving two deprotonated, tridentate thiosemicarbazone ligands coordinated via the N-oxide oxygen, azomethine nitrogen and thiol sulfur based on infrared spectral studies. Their powder ESR g-values are included in Table 1 and indicate that bonding is less covalent than for the analogous thiosemicarbazones prepared from 2-acetylpyridine, 3a and 4. Starting with iron (III) chloride, compounds with the same cations, but with tetrachloroferrate(III) anions, were isolated. 

The S-methyldithiocarbazates of both 2-formylquinoline, 18, and 1-formyliso-quinoline, 19, yield diamagnetic green [FeL2] complexes from iron(II) sulfate [131]. Coordination for both complexes is via the ring nitrogen, azomethine nitrogen and thiol sulfur based on infrared studies. 

Copper(II) complexes of 2,6-lutidylphenylketone thiosemicarbazone, 38, have been prepared from copper(II) chloride and copper(II) bromide [186]. Similar to 2-pyridyl thiosemicarbazones, 38-H coordinates via the ring nitrogen, the azomethine nitrogen and the thiol sulfur based on infrared spectral assignments. Magnetic susceptibilities and electron spin resonance spectra indicate dimeric complexes and both are formulated as [Cu(38-H)A]2 with bridging sulfur atoms. The electronic spectra of both halide complexes show band maxima at 14500-14200 cm with shoulders at 12100 cm S which is consistent with a square pyramidal stereochemistry for a dimeric copper(II) center. 

Cure system (species) Sulfur-based phthalimide (PVI)... 

Act to decompose hydroperoxides into stable molecules such as alcohols and ethers, before they can react with light to form free radicals. Main chemical classes are trivalent phosphorous compounds and thio-synergists (esters of thiodipropionic acid). Sulfur-based organic antioxidants decompose hydroperoxides by non-radical reactions. Typical peroxide decomposers are Irgafos 168, Ultranox 626, Irganox PS 800 and others. 

Second only to sulfur-based systems, nitrogen complexes are relatively well represented in the structural literature with 41 complexes reported. Of these, 25 are with I2 as the electron acceptor, 11 are with the interhalogen IC1, three are with Br2, and two are with IBr. As expected, in every case the halogen bond forms between the nitrogen and the softest halogen atom, i.e., iodine, in all of the complexes except those with dibromine. Most N I2 complexes, and all N Br2, N IBr, and N IC1 complexes are simple adducts, mode A. Exceptions for the diiodine complexes include bridging mode (B) observed for diazines, such as pyrazine [86], tetramethylpyrazine [86], phenazine, and quinoxaline [87], and for 9-chloroacridine [89] and the 1 1 complex of diiodine with hexamethylenetetramine [144] and amphoteric bridging mode (BA) observed for 2,2 -bipyridine [85], acridine [89], 9-chloroacridine [89], and 2,3,5,6-tetra-2/-pyridylpyrazine [91]. The occurrence of both B and BA complexes with 9-chloroacridine, and of B and A complexes and an... 

With 112 structurally characterized complexes, sulfur-based electrons are by far the most commonly encountered. This is attributed to its importance in antithyroid drugs, as described above. The majority of these complexes... 

The addition of perfluoroalkyl iodides to simple olefins has been quite successful under aqueous conditions to synthesize fluorinated hydrocarbons.119 In addition to carbon-based radicals, other radicals such as sulfur-based radicals, generated from RSH-type precursors (R = alkyl, acyl) with AIBN, also smoothly add to a-allylglycines protected at none, one, or both of the amino acid functions (NH2 and/or CO2H). Optimal results were obtained when both the unsaturated amino... 

Gayo KM, Suto MJ. Traceless linker Oxidative activation and displacement of a sulfur-based linker. Tetrahedron Lett 1997 38 211-214. 

The C-3 and C-5 position of BODIPY core skeleton is one of the most important points for the substitution to tune photophysical properties, including absorption and/or emission maxima as well as fluorescence quantum yields. First of all, the introduction of amine-based (15d-15g) or sulfur-based (15b-15c) nucleophiles can... 

Figure 1 (a) Structures of common sulfur-based amino acids and tripeptides, (b) Structures of nucleic acid... 

Enantiomers of a chiral compound show many different physiological responses, including those of odor and taste2 and it has long been known that enantiomers of some sulfur-containing compounds may have different odors. The examples discussed here are for sulfur-containing compounds where the chirality is based on carbon. While certain compounds can show sulfur-based chirality, there are apparently no known cases where enantiomers dependent on sulfur chirality exhibit different odors. 

In recent years, the amount of research time devoted to materials chemistry has risen almost exponentially and sulfur-based radicals, such as the charge-transfer salts based upon TTF (tetrathiafulvalene), have played an important role in these developments. These TTF derivatives will not be discussed here but are dealt with elsewhere in this book. Instead we focus on recent developments in the area of group 15/16 free radicals. Up until the latter end of the last century, these radicals posed fundamental questions regarding the structure and bonding in main group chemistry. Now, in many cases, their thermodynamic and kinetic stability allows them to be used in the construction of molecular magnets and conductors. In this overview we will focus on the synthesis and characterisation of these radicals with a particular emphasis on their physical properties. 

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