Sulfur and Phosphorus Compounds

Sulfur occurs directly beneath oxygen in the periodic table, and, like oxygen, it often exhibits a valence of two. Therefore, sulfur analogs of alcohols and ethers are often encountered. However, because sulfur is in the third period of the periodic table, it can also have a higher valence. Structures with four or six bonds to a sulfur are common. In organic chemistry the most important of these expanded valence compounds have the sulfur bonded to one or two extra oxygens. 

Similarly, phosphorus occurs directly beneath nitrogen in the periodic table and therefore often exhibits a valence of three. Again, structures with an expanded valence, having five bonds to the phosphorus, are common, especially when the extra bonds are to oxygen. This book is not concerned with all the possible sulfur and phosphorus compounds, nor does it spend much time on their nomenclature. Instead, it concentrates on those of most importance in organic chemistry and biochemistry. Let s begin with a discussion of some common sulfur compounds. 

3-Methyl-1 -butiinethiol 2-Butene-1-thiol Dimethyl sulfide 

A characteristic of organic sulfur compounds, especially volatile (low molecular mass) thiols, is their disagreeable odors. For example, 3-methyl-1-butanethiol and 2-butene-1-thiol are ingredients of a skunk s perfume, and methanethiol or ethanethiol is usually added, in small amounts, to natural gas, which is odorless by itself, so that leaks can be readily detected. The chemical properties of thiols and sulfides differ from those of alcohols and ethers in that thiols are somewhat stronger acids than alcohols and the sulfur atoms of these compounds are considerably more nucleophilic than the oxygen of their analogs. They are excellent nucleophiles in substitution reactions. 

Methanesultonyl chloride Cyclopentyl methanesul Innate (a sulfonyl chloride) (a sulfonate ester) 

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Typically, intense chemiluminescence in the UV/Vis spectral region requires highly exothermic reactions such as atomic or radical recombinations (e.g., S + S + M - S2 + M) or reactions of reduced species such as hydrogen atoms, olefins, and certain sulfur and phosphorus compounds with strong oxidants such as ozone, fluorine, and chlorine dioxide. Here we review the chemistry and applications of some of the most intense chemiluminescent reactions having either demonstrated or anticipated analytical utility. 

Organic compounds of sulfur and phosphorus are included in the section on reduction with sulfur and phosphorus compounds (p. 32, 35). 

Studies of the formation, chemical composition, and properties of deposits have shown that they consist of partially oxidized organic material, including more or less nitrogen, sulfur, and phosphorus. Compounds of iron, silicon, calcium, and other metals are present in small quantity, together with substantial amounts of lead oxides, sulfates, and halides from combustion of the antiknock fluid. The effects of these deposits are both physical and chemical in nature they may physically interfere with lubrication, heat transfer, gas flow, operation of valves and spark plugs chemically, they may bring about corrosion and oxidation. 

The use of -ous. -ic. per-, hypo-, ortho-, and meta- should be restricted to those compounds and to their derivatives their anions are named by changing -ous into -ite and -ic into -ate. In addition, and exceptionally, sulfur and phosphorus compounds lose the... 

Several recent reviews have included specific types of electrophilic cyclofunctionalization reactions.1 Important areas covered in these reviews are halolactonization u cyclofunctionalization of unsaturated hydroxy compounds to form tetrahydrofurans and tetrahydropyrans lb cyclofunctionalization of unsaturated amino compounds lc cyclofunctionalization of unsaturated sulfur and phosphorus compounds ld lf electrophilic heterocyclization of unconjugated dienes 1 synthesis of y-butyrolactones 1 h synthesis of functionalized dihydro- and tetrahydro-furans lj cyclofunctionalization using selenium reagents lk lm stereocontrol in synthesis of acyclic systems 1" stereoselectivity in cyclofunctionalizations lP and cyclofunctionalizations in the synthesis of a-methylenelactones.lq Previous reference works have also addressed this topic.2... 

Oxidation of sulfur and phosphorus compounds. The peroxide has been used to oxidize the sulfide (2) to the corresponding sulfone in 83% yield without attack of the double bond. Geranyl phenyl sulfide is oxidized to the corresponding sulfone in Ninular yield.4 Trialkylphosphines and phosphites are oxidized to the corresponding oxides in high yield.5... 

Selective to sulfur and phosphorus compounds more selective than NPD to compounds containing phosphorus Flame photometric detector Organophosphorus pesticides (EPA 8141) Sulfur compounds may interfere with organophosphorus pesticides. 

Reoplex 400 0 200 I MeCI 364 619 449 647 671 Polypropylene glycol adipate) for aromatics, heterocycles, vitamins, sulfur and phosphorus compounds... 

When sulfur and phosphorus compounds are burned in an FDD-type flame, chemiluminescent species are produced that produce light at 393 nm (sulfur) and 526 nm (phosphorous). An optical interference filter passes the appropriate light to a photomultiplier tube, a sensitive photon detector. These detectors are known as flame photometric detectors (FPD).. ... 

The response of the flame photometric detector is due to chemiluminescence subsequent to combustion of certain organic molecules in an energetic flame. The initial work on this principle by Brody and Chaney [109] was primarily concerned with selective detection of sulfur and phosphorus compounds, although detection of other elements is also feasible with different optical filters. 

Although determinations of sulfur and phosphorus compounds constitute the main applications of the FPD, there are 20 emitters that produce analytically useful signals. Nitrogen-containing... 

Figure 5 Cross-sectional view of a flame photometric detector. (Reproduced with permission from Patterson PL, Howe RL, and Abushumays A (1978) Dual-flame photometric detector for sulfur and phosphorus compounds in gas chromatographic effluents. Anal cal Chemistry 50 339-344.)...

Ions determined in food samples can be divided into nitrogen, sulfur and phosphorus compounds, halides, and inorganic and organic cations. For health purposes, the determination of nitrogen compounds such as nitrite, nitrate, ammonium, and biogenic amines is of great importance. Nitrates are naturally present in many foodstuffs, noticeably... 

Oxidation of Alcohols, Sulfur, and Phosphorus Compounds as well as Si-Si and Si-H Bonds. Bis(trimethylsilyl) peroxide acts as an effective oxidant for alcohols in the presence of p3tri-dinium dichromate or RuCLlPPhsls complex as the catalyst in CH2CI2. By this method, primary allylic and benzylic alcohols can be selectively oxidized to a-enals in the presence of a secondary alcohol. 

The function of an antioxidant is to divert the peroxy radicals and thus prevent a chain process. Other antioxidants function by reacting with potential initiators, and thus retard oxidative degradation by preventing initiation of chains. Many sulfur and phosphorus compounds are believed to function in the latter way. The hydroperoxide products from autoxidation are potential chain initiators. This fact gives autoxidations the potential of being autocatalytic, since the more oxidation product is formed, the higher the initiator concentration. Divalent sulfur compounds and trivalent phosphorus compounds can reduce hydroperoxides, yielding stable products ... 

Traditional organic sulfur and phosphorus compounds, such as zinc dialkyl (or diaryl) dithiophosphate (ZDDP), tricresyl phosphate (TCP) and sulfurised isobutylene (SIB), have been proved to have good AW and EP properties and achieved wide application. However, these AW/EP additives are chemically more or less reactive, and have lower resistance to heat and oxidation than most modern base oils, and cannot be used to formulate oils for high-temperature applications. The more powerful EP additives usually have some corrosive effect... 

Use Mostly selective for sulfur and phosphorus compounds (e.g., pesticides). Detection of sulfur compounds in a complex matrix. 

Biologically active components of the organic soil fraction include polysaccharides, amino sugars, nucleotides, and organic sulfur and phosphorus compounds. Humus, a water-insoluble material that biodegrades very slowly, makes up (he bulk of soil organic matter. The organic compounds in soil are summarized in Table 18.1. 

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