Silver nitrite, nitration

C22H2ftAgNgOi0.ft 5r Bis-(10-methylisoalloxazine)silver nitrite nitrate tetrahydrate, 39B, 802... 

Since aliphatic hydrocarbons (unlike aromatic hydrocarbons, p. 155) can be directly nitrated only under very special conditions, indirect methods are usually employed for the preparation of compounds such as nitroethane, CjHsNO. When ethyl iodide is heated with silver nitrite, two isomeric compounds are formed, and can be easily separated by fractional distillation. The first is the true ester, ethyl nitrite, C,HiONO, of b.p. 17° its identity is shown by the action of hot sodium hydroxide solution, which hydrolyses it, giving ethanol and... 

Silver nitrite. Warm concentrated solutions of silver nitrate (containing 48 g. of AgNOj) and potassium nitrite (containing 30 g. of KNOj) are mixed, and the mixture is allowed to cool. The silver nitrite which separates is filtered off and washed with water. It may be recrystallised from water at 70°, and is dried either in a vacuum desiccator or in an air oven at about 40° the yield is about 90 per cent. Silver nitrite should be stored in an tightly-stoppered amber bottle. 

Nitroethane and 1-(3,4 methylenedioxy) 2- nitropropane This method of producing the above mentioned nitro compounds is by far the best Ritter has come across yet The problem with standard nitroethane synthesis is that the -NO2 source most commonly used is silver nitrite (a la Merck Index citing). Needless to say, this is going to be an expensive compound to make as it is not available commercially but must be synthesized from costly silver nitrate. The other methods mentioned in Vogels 5th masterpiece... 

Silver Nitrite. Silver nitrite, AgN02, is prepared from silver nitrate and a soluble nitrite, or silver sulfate and barium nitrite. 

The synthetic applications of this reagent to the synthesis of nitroalkenes have been known since the 1960s.60 Nitration of alkenes with nitryl iodide, generated in situ from iodine and silver nitrite, is convenient for the synthesis of P-nitrostyrenes with various functional groups.61 This method is applied to the synthesis of ortho-methoxylated phenylisopropylamines, which are potent serotonine agonists (Eq. 2.31).62... 

Ethyl a-nitrobutyrate may be prepared in 75% yield by the reaction of silver nitrite with ethyl a-iodobutyrate.4 It has been prepared in 18% yield by nitration and subsequent decarboxylation of diethyl ethylmalonate.6 The present method offers the advantage of a direct preparation using sodium nitrite. 

Aromatic cation-radicals can also react with NOj", giving nitro compounds. Such reactions proceed either with a preliminary prepared cation-radical or starting from nncharged componnd if iodine and silver nitrite are added. As for mechanisms, two of them seem feasible—first, single electron transfer from the nitrite ion to a cation-radical and second, nitration of ArH with the NOj radical. This radical is quantitatively formed when iodine oxidizes silver nitrite in carbon tetrachloride (Neelmeyer 1904). 

A mixture of silver nitrite and iodine reacts with alkenes to give jS-nitroalkyl iodides, and therefore, provides a convenient route to a-nitroalkenes. Treatment of alkenes with ammonium nitrate and trifluoroacetic anhydride in the presence of ammonium bromide, followed by... 

When the reaction of methyl 5,6-dideoxy-2,3-di-0-p-tolylsulfonyl-a-L-arafoino-hex-5-enofuranoside with silver nitrite and iodine was performed in more-polar solvents, such as methanol and acetonitrile, a /3-iodo nitrate was produced, in addition to the C-iodo-C-nitro adduct 88 in methanol, the ratio of the two products was130 3 2. The /3-iodo nitrate was identical with the adduct obtained by the reaction of the alkene with silver nitrate and iodine in acetonitrile.132 The formation of the /3-iodo nitrate in the silver nitrite-iodine reaction in polar solvents may be due to the increased solubility of the silver nitrite the available nitrite ions could then be oxidized to nitrates. The positions of the iodo and nitrate groups in the adduct have not yet been established. 

Additional Exercises Calcium hydroxide from sodium hydroxide and calcium chloride silver nitrite from silver nitrate and sodium nitrite manganese sulfite, MnSChSHsO, from manganese chloride and sodium sulfite (adding a little S02 to the solution) mercuric iodide from potassium iodide and mercuric chloride. 

Silver Nitrite.—A warm concentrated aqueous solution of silver nitrate containing 24 gms. is mixed with a warm concentrated solution of potassium nitrite containing 15 gms. The mixture is allowed to cool and the silver nitrite which separates filtered off and rapidly washed with water. 

At a time when the only practicable methods for the preparation of nitromethane were the interaction of methyl iodide with silver nitrite and the Kolbe reaction from chloracetic acid, the explosive was far too expensive to merit consideration. The present cheap and large scale production of nitromethane by the vapor-phase nitration of methane and of ethane has altered the situation profoundly. Trimethylolnitromethane trinitrate is an explosive which can now be produced from coke, air, and natural gas. Nitromethane too has other interest for the manufacturer of explosives. It may be used as a component of liquid explosives, and it yields on reduction methylamine which is needed for the preparation of tetryl. 

B. C. Dutt and S. N. Sen found that when nitric oxide is passed into a suspension of barium dioxide in water, barium nitrite, not nitrate, is formed. P. Sabatier and J. B. Senderens observed no change when nitric oxide is passed over Cuprous Oxide at 500°. H. A. Auden and G. J. Fowler observed that dry nitric oxide and Silver oxide, at ordinary temp., form silver and silver nitrate P. Sabatier and J. B. Senderens also obtained silver and silver nitrite by passing nitric oxide into water with silver oxide in suspension. C. F. Schonbein found gold oxide is reduced by moist nitric oxide, forming nitrous acid. P. Sabatier and J. B. Senderens found that titanium sesquioxide forms white titanic oxide when heated in an atm. of nitric oxide and that stannous oxide below 500° burns in an atm. of nitric oxide, forming stannic oxide. If nitric oxide be passed into water with lead dioxide in suspension, the water is coloured, and in about 3 hrs., lead nitrite and nitrate are formed, and later, rhombic crystals of a basic nitrite. B. C. Dutt and S. N. Sen said that the nitrate is formed by the action of the dioxide on the nitrite. Lead dioxide is reduced to lead oxide by nitric oxide at 315°, and H. A. Auden and G. J. Fowler found that the reaction begins at 15°, when a basic lead nitrite is... 

The same salt was prepared by E. Peligot by adding barium nitrite to a soln. of silver nitrate. E. Mitsoherlioh, and V. Kohlschiitter and E. Eydmann added sodium nitrite to a soln. of silver nitrate, and crystallized the precipitated silver nitrite (and oxide) from its soln. in boiling water V. Meyer worked with potassium nitrite and silver nitrate J. Persoz melted equal parts of silver and potassium nitrates, and crystallized the silver nitrite from hot water. E. Priwoznik treated an excess of silver with nitric acid W. J. Russell, and A. R. Leeds passed hydrogen into a cone. soln. of silver nitrate and E. Divers heated silver nitrate in a current of nitric oxide. The aq. soln. decomposes below 100°, and J. Lang, and N. W. Fischer said that the losses are so great when the attempt is made to purify the salt by recrystallization, that it is better instead to wash the salt with a little cold water. A. Naumann and A. Rucker crystallized the salt from a soln. of nitrous acid. 

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