Miscellaneous Organic Oxidants

Experimental procedures have been described in which the desired reactions have been carried out either by whole microbial cells or by enzymes (1—3). These involve carbohydrates (qv) (4,5) steroids (qv), sterols, and bile acids (6—11) nonsteroid cycHc compounds (12) ahcycHc and alkane hydroxylations (13—16) alkaloids (7,17,18) various pharmaceuticals (qv) (19—21), including antibiotics (19—24) and miscellaneous natural products (25—27). Reviews of the microbial oxidation of aUphatic and aromatic hydrocarbons (qv) (28), monoterpenes (29,30), pesticides (qv) (31,32), lignin (qv) (33,34), flavors and fragrances (35), and other organic molecules (8,12,36,37) have been pubflshed (see Enzyp applications, industrial Enzyt s in organic synthesis Elavors AND spices). 

Photochemical elimination reactions include all those photoinduced reactions resulting in the loss of one or more fragments from the excited molecule. Loss of carbon monoxide from type I or a-cleavage of carbonyl compounds has been previously considered in Chapter 3. Other types of photoeliminations, to be discussed here, include loss of molecular nitrogen from azo, diazo, and azido compounds, loss of nitric oxide from organic nitrites, and loss of sulfur dioxide and other miscellaneous species. 

Table 6.2 shows the important applications of sodium hydroxide. Direct applications can be further broken down into pulp and paper (24%), soaps and detergents (10%), alumina (6%), petroleum (7%), textiles (5%), water treatment (5%), and miscellaneous (43%). Organic chemicals manufactured with sodium hydroxide are propylene oxide (23%), polycarbonate (5%), ethyleneamines (3%), epoxy resins (3%), and miscellaneous (66%). Inorganic chemicals manufactured are sodium and calcium hypochlorite (24%), sodium cyanide (10%), sulfur compounds (14%), and miscellaneous (52%). As you can see from the number of applications listed, and still the high percentages of miscellaneous uses, sodium hydroxide has a very diverse use profile. It is the chief industrial alkali. 

Abstract This chapter principally concerns oxidations of organic substrates containing N, O, S, P, As and Sb. Oxidations of amines are covered first, including primary amines to nitriles or amides secondary amines to imines or other products tertiary amines to N-oxides or other prodncts (Section 5.1) and the oxidation of amides (5.2). Oxidation of ethers to esters or lactones follows (5.3), then of sulfides to sulfoxides or sulfones (5.4) and of phosphines, arsine and stibines to their oxides (5.5). A final section (5.6) concerns such miscellaneous oxidations not covered by other sections in the book. 

Fluorine Miscellaneous materials, 4304 Magnesium perchlorate Cellulose, etc., 4078 /V-Meth yI morpholine oxide, 1991 Nitric acid Cellulose, 4430 Perchloric acid Cellulose and derivatives, 3992 Perchloric acid Hydrofluoric acid, Structural materials, 3992 Potassium chlorate Cellulose, 4011 Potassium nitrate Cellulose, 4645 Sodium chlorate Paper, etc., or Wood, 4033 Sodium nitrate Fibrous material, 4716 Sodium nitrite Wood, 4715 Sodium peroxide Fibrous materials, 4797 Zinc permanganate Cellulose, 4705 BLEACHING POWDER Wood perchlorates Organic matter See SUGARS... 

Organic isocyanates and isothiocyanates as well as nitric oxide insert similady (412). Carbon monoxide inserts to yield very stable acyltitamums (412,413). Miscellaneous Reactions of CpfTi Derivatives. Coupling of fluxional pentadienide ion with allyl bromide is regiospecificatly catalyzed by Cp2TiCl2 (414,415). In contrast, cuprous chloride gives the linear triene ... 

The 13 chapters of this book survey a range of fields of organic syntheses promoted by ruthenium catalysts, which involve hydrogenation, oxidation, various carbon-carbon bond formations, C-H activation, carbonylation, isomerization, bond-cleavage reaction, metathesis reaction, and miscellaneous nucleophilic and electrophilic reactions. 

Scheme 5.12. Miscellaneous oxidations of organic compounds over mixed bismuth-metal based catalysts.

The principles made use of in the design of the catalytic oxidation apiiaratns described for use in phthalic anhydride and maleic acid production may be applied to the design of apparatus for the oxidation to partial oxidation products of anthracene, toluene, and other organic compounds derived from coal-tar, petroleum, and miscellaneous sources. 

There are numerous applications for supported reagent catalysts in organic synthesis.3 4,6,7,15,21,22,43 These will be illustrated in sections on the important areas of partial oxidations, acid-catalysed reactions and base-catalysed reactions with other areas illustrated in a final miscellaneous section. 

The different applications have been classified by reaction type oxidation (sect. 2.1-2.3), hydrogenation (sect. 2.4), environmental (sect. 2.5) and miscellaneous (sect. 2.6). The environmental applications have been grouped together in view of the present relevance of this field. It includes total oxidation of organic compounds and CO, redox processes such as CO+NO reaction and NO/N2O decomposition. 

Alkyl Bound to Miscellaneous Elements. Several compounds in which alkyl is bound to a sulfur atom have become quite important in recent years for example, the mercaptans, such as amyl and ethyl mercaptan, are used as warning agents in natural gas because of their intense and disagreeable odor. Mercaptans are also employed in organic syntheses as, for instance, the manufacture of sulfonal by the condensation of ethyl mercaptan (ethanethiol) with acetone, followed by oxidation. In recent years a very considerable amount of mercaptan has been used for controlling the polymerization reaction between butadiene and styrene to form synthetic rubber (GR-S). 

The final results are given in Table 8. Note that the principal minerals add up to only 91.4% the remainder is assumed to be miscellaneous oxides, carbonates, or organic matter. 

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