Nitrations ketones, nitric acid

Oxonium nitrates have been known since 1835 [72]. They were originally described as addition compounds of aldehydes and ketones with nitric acid [72, 73], Reddelien [74], who carried out particularly extensive studies, represented the... 

Note Polar solvent soluble in water, ketones, organic halides, alcohols, ether, and many oils highly flammable narcotic by inhalation incompatible with strong oxidizers, nitrates, nitric acid, reducing agents. Synonyms ethyl methyl ketone, 2-butanone, MEK, methyl acetone. 

Stewart compiled a table of extraction data for a large number of ethers, alcohols, ketones, etc, for Pu in the tri-, quadri-and hexavalant oxidation states from ammonium nitrate-nitric acid mixtures. These data are reproduced in their entirety as Tables IV-21, and IV-22, to show the variety of compounds tried and to indicate the types of compounds which are efficient as Pu extractants. In general, the ability of these compounds to extract correlates with the basicity of the oxygen, nitrogen or other functional group. Thus, electronegative substituents invariably decrease the extractibility of Pu (see e. g. diethyl ether vs dichlorodiethyl-ether). 

Oxo Ion Salts. Salts of 0x0 ions, eg, nitrate, sulfate, perchlorate, hydroxide, iodate, phosphate, and oxalate, are readily obtained from aqueous solution. Thorium nitrate is readily formed by dissolution of thorium hydroxide in nitric acid from which, depending on the pH of solution, crystalline Th(N02)4 5H20 [33088-17 ] or Th(N02)4 4H20 [33088-16-3] can be obtained (23). Thorium nitrate is very soluble in water and in a host of oxygen-containing organic solvents, including alcohols, ethers, esters, and ketones. Hydrated thorium sulfate, Th(S0 2 H20, where n = 9, 8, 6, or 4, is... 

The transformations (1) lead to unstable alkyl nitrates, which can detonate very easily. The reactions (2) lead to more or less complete oxidations of the organic molecule. The formation of aldehydes is purely theoretical since they are more oxidisable than alcohols and therefore are not part of the oxidation process by nitric acid. On the other hand, a ketone can form with a secondary alcohol. With tertiary alcohols, carboxylic acid is the only possible outcome of the partial oxidation, which is caused by the breaking of C-C bonds. When the oxidation is out of control, it is likely to have a complete oxidation. Finally, with heavy metal... 

Nitration of ketones or enol ethers provides a useful method for the preparation of a-nitro ketones. Direct nitration of ketones with HN03 suffers from the formation of a variety of oxidative by-products. Alternatively, the conversion of ketones into their enolates, enol acetates, or enol ethers, followed by nitration with conventional nitrating agents such as acyl nitrates, gives a-nitro ketones (see Ref. 79, a 1980 review). The nitration of enol acetates of alkylated cyclohexanones with concentrated nitric acid in acetic anhydride at 15-22 °C leads to mixtures of cis- and rrans-substituted 2-nitrocyclohexanones in 75-92% yield. 4-Monoalkylated acetoxy-cyclohexanes give mainly m-compounds, and 3-monoalkylated ones yield fra/w-compounds (Eq. 2.40).80... 

Symmetrical and unsymmetrical benzoins have been rapidly oxidized to benzils in high yields using solid reagent systems, copper(II) sulfate-alumina [105] or Oxone-wet alumina [105, 106] under the influence of microwaves (Scheme 6.32). Conventionally, the oxidative transformation of a-hydroxy ketones to 1,2-diketones is accomplished by reagents such as nitric acid, Fehling s solution, thallium(III) nitrate (TTN), ytterbium(III) nitrate, ammonium chlorochromate-alumina and dayfen. In addition to the extended reaction time, most of these processes suffer from drawbacks such as the use of corrosive acids and toxic metals that generate undesirable waste products. 

Iodoform Iodomethane Iron disulfide Isothiourea Ketones Lactonitrile Lead Acetone, lithium, mercury(II) oxide, mercury(I) chloride, silver nitrate Silver chlorite, sodium Water, powdered pyrites Acrylaldehyde, hydrogen peroxide, nitric acid Aldehydes, nitric acid, perchloric acid Oxidizing materials Ammonium nitrate, chlorine trifluoride, hydrogen peroxide, sodium azide and carbide, zirconium, oxidants... 

Examples of the so-called chaperon effect involving interaction between the electrophile and an appropriate substituent at the a-position in an alkyl chain prior to ring substitution at the ortAo-position have been explored in nitrations involving dilute solutions of nitric acid in dichloromethane. Aldehydic or ketonic carbonyl groups are most effective, but carboxyl, alkoxycarboxyl, and amide groups also work well. l-Phenylpropan-2-one, for example, forms 85% of l-(2-nitrophenyl)propan-2-one (5). 

Dave and co-workers have reported a successful synthesis of 2,2,4,4-tetranitroadamantane (117) which uses the mono-protected diketone (113) as a key intermediate. In this synthesis (113) is converted to the oxime (114) and then treated with ammonium nitrate and nitric acid in methylene chloride to yield the em-dinitro derivative (115). This nitration-oxidation step also removes the acetal-protecting group to leave the second ketone group free. Formation of the oxime (116) from ketone (115), followed by a similar nitration-oxidation with nitric acid and ammonium nitrate, yields 2,2,4,4-tetranitroadamantane (117). In this synthesis the protection strategy enables each carbonyl group to be treated separately and thus prevents the problem of internal nitroso dimer formation. 

Axenrod and co-workers reported a synthesis of TNAZ (18) starting from 3-amino-l,2-propanediol (28). Treatment of (28) with two equivalents of p-toluenesulfonyl chloride in the presence of pyridine yields the ditosylate (29), which on further protection as a TBS derivative, followed by treatment with lithium hydride in THF, induces ring closure to the azetidine (31) in excellent yield. Removal of the TBS protecting group from (31) with acetic acid at elevated temperature is followed by oxidation of the alcohol (32) to the ketone (33). Treatment of the ketone (33) with hydroxylamine hydrochloride in aqueous sodium acetate yields the oxime (34). The synthesis of TNAZ (18) is completed on treatment of the oxime (34) with pure nitric acid in methylene chloride, a reaction leading to oxidation-nitration of the oxime group to em-dinitro functionality and nitrolysis of the A-tosyl bond. This synthesis provides TNAZ in yields of 17-21 % over the seven steps. 

C14H18N2O5, Mr 294.31, mp 137 °C, does not occur in nature. It forms yellowish crystals with a sweet, very persistent, slightly animal musk odor. Musk ketone is prepared by Friedel Crafts acetylation of l,3-dimethyl-5-tert-butylbenzene, and nitration of the resulting 2,6-dimethyl-4-/cr/-butylacetophenone with nitric acid. 

Electrophiles such as halogen attack 4-thiopyrones in position 3 while alkylation occurs on the exocyclic oxygen or sulfur atom to form a thiopyrylium cation. Nitration with nitric acid is unsuccessful because the acid protonates the ketone and the thiopyrylium produced is no longer nucleophilic (Scheme 18). 

Aromatic aldehydes and ketones have been extensively reported from alkaline nitrobenzene oxidations but not from oxygen or nitric acid oxidations. A number of nitrophenols and nitrated aromatic acids have been... 

Periodic acid test. (For 1,2-glycols and a-hydroxyaldehydes and ketones, Section 4.2.55, p. 454). Add 1 drop (0.05 ml) of concentrated nitric acid to 2.0 ml of a 0.5 per cent aqueous solution of paraperiodic acid (H5IOe) contained in a small test tube and shake well. Then introduce 1 drop or a small crystal of the compound. Shake the mixture for 15 seconds and add 1-2 drops of 5 per cent aqueous silver nitrate. The immediate production of a white precipitate (silver iodate) constitutes a positive test and indicates that the organic compound has been oxidised by the periodic acid. The test is based upon the fact that silver iodate is sparingly soluble in dilute nitric acid whereas silver periodate is very soluble if too much nitric acid is present the silver iodate will not precipitate. 

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