Nitric acid, oxidation with

As Mach has found, oxidation of 2.4,6-tri-tert-butyl-X -phosphorin 24 in glacial acetic acid with a mixture of equal parts of cone, nitric and sulfuric acids yields 

The structure of the acid 83 is supported by elemental analysis. H-NMR shows only one doublet for the two (equivalent) protons at C—3 and C—5 (6 = 

By esterification with diazomethane two stereoisomeric methylesters 84 E and 84 Z were found. They could be separated by thin-layer chromatography m.p. 279 °C and 278 °C (sealed tube). The UV spectra are nearly the same, but the H-NMR spectra differ considerably (Table 10). 

In the tert.-butyl series no significant difference in the IR spectra of the two diastereoisomers can be detected. This is in a sharp contrast to the corresponding aryl series, i. e. 72 E and 72 Z, and must be influenced by the large hydrophobic tert.-butyl groups which prevent association by OH bridges. 

On the other hand the mass spectra of the two isomers differ very significantly only in the tert.-butyl series (Figs. 23 and 24). 

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The carboxylic acid produced m the greatest amounts is 1 4 benzenedicarboxylic acid (terephthahc acid) About 5 X 10 Ib/year is produced m the United States as a starting material for the preparation of polyester fibers One important process converts p xylene to terephthahc acid by oxidation with nitric acid... 

Since adipic acid has been produced in commercial quantities for almost 50 years, it is not surprising that many variations and improvements have been made to the basic cyclohexane process. In general, however, the commercially important processes stiU employ two major reaction stages. The first reaction stage is the production of the intermediates cyclohexanone [108-94-1] and cyclohexanol [108-93-0], usuaHy abbreviated as KA, KA oil, ol-one, or anone-anol. The KA (ketone, alcohol), after separation from unreacted cyclohexane (which is recycled) and reaction by-products, is then converted to adipic acid by oxidation with nitric acid. An important alternative to this use of KA is its use as an intermediate in the manufacture of caprolactam, the monomer for production of nylon-6 [25038-54-4]. The latter use of KA predominates by a substantial margin on a worldwide basis, but not in the United States. 

Reactions 8 and 9 are important steps for the Hquid-phase nitration of paraffins. The nitric oxide which is produced is oxidized with nitric acid to reform nitrogen dioxide, which continues the reaction. The process is compHcated by the presence of two Hquid phases consequentiy, the nitrogen oxides must transfer from one phase to another. A large interfacial area is needed between the two phases. 

Monosaccharides such as glucose and fmctose are the most suitable as starting materials. When starch is used, it is first hydrolyzed with oxahc acid or sulfuric acid into a monosaccharide, mainly glucose. It is then oxidized with nitric acid in an approximately 50% sulfuric acid solution at 63—85°C in the presence of a mixed catalyst of vanadium pentoxide and iron(III) sulfate. 

Insoluble iridium dioxide from the sodium peroxide fusion is dissolved in aqua regia, oxidized with nitric acid, and precipitated with ammonium chloride as impure ammonium hexachloroiridate(IV), To purify this salt, it is necessary to redissolve the compound and precipitate out the... 

Cyclohexanone shows most of the typical reactions of aUphatic ketones. It reacts with hydroxjiamine, phenyUiydrazine, semicarbazide, Grignard reagents, hydrogen cyanide, sodium bisulfite, etc, to form the usual addition products, and it undergoes the various condensation reactions that are typical of ketones having cx-methylene groups. Reduction converts cyclohexanone to cyclohexanol or cyclohexane, and oxidation with nitric acid converts cyclohexanone almost quantitatively to adipic acid. 

Suberic Acid. This acid is not produced commercially at this time. However, small quantities of high purity (98%) can be obtained from chemical supply houses. If a demand developed for suberic acid, the most economical method for its preparation would probably be based on one analogous to that developed for adipic and dodecanedioic acids air oxidation of cyclooctane to a mixture of cyclooctanone and cyclooctanol. This mixture is then further oxidized with nitric acid to give suberic acid (37). 

Alloxan forms an oxime (1007) which is the same compound, violuric acid, as that formed by nitrosation of barbituric acid likewise, a hydrazone and semicarbazone. Reduction of alloxan gives first alloxantin, usually formulated as (1008), and then dialuric acid (1004 R = OH) the steps are reversible on oxidation. Vigorous oxidation with nitric acid and alkaline hydrolysis both give imidazole derivatives (parabanic acid and alloxanic acid, respectively) and thence aliphatic products. Alloxan and o-phenylenediamine give the benzopteridine, alloxazine (1009) (61MI21300). 

Reaction.—. dA Fehling s solution to benzoin dissolved in alcohol. Benzil is formed and cuprous oxide precipitated. Benzil is also formed on oxidation with nitric acid. 

It yields, on oxidation with nitric acid, an acid having the odour of isovaleric acid. It is probably trycyclic. 

When distilled with phosphorus pentoxide, camphor yields cymene, and with iodine, carvacrol. Both of these bodies are para-derivatives of benzene. On oxidation with nitric acid camphor yields many acids, of which the chief are camphoric acid, CjgHjgO, camphanic acid, CjoHj O, and camphoronic acid, CgHj Og. The constitution of these acids has an important bearing on that of camphor. Many formulae have been suggested for camphor during the past few years, but that of Bredt is now universally accepted, and has received complete confirmation by Komppa s synthesis of camphoric acid. This synthesis confirms the formula for camphoric acid as—... 

Oxalic acid was formerly manufd by fusion of cellulose matter, eg sawdust, with Na hydroxide or by oxidation with nitric acid. It is now made by passing CO into coned Na hydroxide or by heating Na formate in the presence of Na hydroxide or Na carbonate (Refs 1 2)... 

Diphosphinomethane is a valuable intermediate to form methylene diphosphonic acid by oxidation with nitric acid (see Sec. IV). The alkali salts of methyl-enediphosphonic acid offer sequestering properties and are used as detergent builders. 

The oxidation of (S)-( + )-methylphenyl-n-propylphosphine with nitrogen tetroxide led to retention of configuration with considerable racemization, whereas oxidation with nitric acid gave the oxide with inversion of configuration. ... 

Hexenal is determined by photocolorimetry after oxidation with nitric acid. The yellow-orange oxidation product explodes on heating. 

Krishnamurty, K. V. et al., At. Abs. Newslett., 1976, 15, 68-70 When preparing soil and sediment samples for atomic absorption spectral analysis for trace metals, pre-oxidation with nitric acid before addition of hydrogen peroxide eliminates the danger of explosion. 

Two methylations of levan by means of dimethyl sulfate and potassium hydroxide (not sodium hydroxide) followed by one inethylation with methyl iodide and silver oxide yielded trimethyllevan in 88% yield. This was purified by solvent fractionation over-all yield 75%, m. p. 145-146°, OCHs 45.9%. Trimethyllevan, hydrolyzed by heating at 95° for twenty-four hours with a dilute solution of sulfuric acid gave a 98.5% yield of a crystalline trimethyl-D-fructose. The trimethyl-D-fructose was proved940 to be 1,3,4-trimethyl-D-fructofuranose since oxidation with nitric acid gave a 97% yield of a dimethyl-2-keto-D-gluco-saccharic acid which was identified as the crystalline diamide (95% yield). 

Pyrimidine oximes 286, 287, and 289 are oxidized with nitric acid to furoxanes 288 <2005RJC457, 2004CHE361> in the case of oximes 287 and 289, the reaction is accompanied by the hydrolysis of the oxime group in the 4-position of the starting pyrimidine (Scheme 74) <2005RJC457>. 

Deamination of 2-amino-2-deoxy-D-idonolactone (27) with nitrous acid led, after oxidation with nitric acid, to 2,5-anhydro-D-glucaric acid39,42 (28). As deamination of 2-amino-2-deoxy-D-idonic acid, followed by oxidation, gave 2,5-anhydro-D-idaric acid, the different behavior of the lactone 27 must be due to an attack on the incipient carbonium-ion at C-2 by a favorably disposed hydroxyl group in the molecule, such as at C-5. 

Dichloro-5,6-dicyano-l,4-benzoquinone is readily regenerated in good yield from the hydroquinone by oxidation with nitric acid.4... 

Other elements which occur in organic compounds, such as phosphorus, arsenic, other non-metals, and metals in organic combination, are detected by destroying the organic material by oxidation (with nitric acid in a sealed tube or by fusion with potassium nitrate or sodium peroxide) and then applying the usual tests. 

Possible alternatives to the ozonolysis process for production of brassylic acid include oxidation with nitric acid or with potassium permanganate these routes are feasible,[5] but yields were inferior to ozonolysis. 

Treatment of 5,6-dichloro-2,3-dimethyl- -benzoquinone with sodium sulfide followed by oxidation with nitric acid yields the thianthrene derivative (60). Sulfur extrusion from 60 with peracetic acid leads to 2,3,7,8-tetramethyl-l,4,6,9-dibenzothiophene tetrone (61) (overall yield 57%). ... 

The original procedure for the bromination-oxidation-reduction route used bromine in aqueous potassium hydroxide, followed by oxidation with nitric acid-hydrogen peroxide and reduction with alkaline ethanol. This procedure was improved by using NBS in aqueous sodium bicarbonate for the initial oxime bromination, followed by oxidation with nitric acid and final reduction of the Q -bromonitroalkane with sodium borohydride in methanol. It is possible to convert oximes to nitroalkanes via this procedure without isolating or purifying any of the intermediates. This procedure is reported to give yields of between 10 and 55 % for a range of oxime to nitroalkane conversions. ... 

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