Dinitrogen tetroxide reactions with

Dinitrogen tetroxide has a highly exothermic reaction with boron trichloride. 

Dinitrogen tetroxide gives rise to a violent reaction with dimethyisulphoxide. This reaction can lead to a detonation. The same happens when using nitric acid that contains less than 14% of water. In both cases, the reaction should form dimethylsulphone. 

A reaction of dinitrogen tetroxide with acetonitrile in the presence of indium was carried out. The technician wanted to accelerate the process by stirring the medium, causing ils detonation. This accident was put down to the vioient oxidation of the acetonitrile accumulated, by nitrogen oxide catalysed by indium. 

Nitrosation, of amides with dinitrogen tetroxide, 47, 46 of N phenylglycine, 46, 96 p-Nitrosodimethylamhne, reaction with o nitrobenzylpyndimum bro mide, 46,82 

The reaction of alkynes with dinitrogen tetroxide is less synthetically useful as a route to nitro compounds. The reaction of 3-hexyne with dinitrogen tetroxide yields a mixture of cis- and fran -3,4-dinitro-3-hexene (4.5% and 13% respectively), 4,4-dinitro-3-hexanone (8%), 3,4-hexanedione (16%) and propanoic acid (6%). 2-Butyne forms a mixture containing both cis- and fran -2,3-dinitro-2-butene (7 % and 34 % respectively). "  

The reaction of a-nitroalkenes with nitrogen dioxide or its dimer, dinitrogen tetroxide, has been used to synthesize polynitroalkanes. Thus, the reaction of dinitrogen tetroxide with 2,3-dinitro-2-butene (6) and 3,4-dinitro-3-hexene is reported to yield 2,2,3,3-tetranitrobutane (7, 25 %) and 3,3,4,4-tetranitrohexane (32 %) respectively.  

Thioanisole, oxidation, by dinitrogen tetroxide, 46,80 by hydrogen peroxide, 46, 80 by lead tetraacetate, 46, 80 reaction with sodium metaperiodate to form methyl phenyl sulfoxide, 46,78 

The reactions of diazoesters with hydrochloric and sulfuric acids, triphenylphosphine, and dinitrogen tetroxide resulted in aryl chloroacetates, bis(aryloxycarbonylmethyl) sulfates, triphenylphosphoranylidenehydrazones of aryl 2-oxoethanoates, and iV-oxides of diaryl l,2,5-oxadiazole-3,4-dicarboxylates <1999RJO 666>. 

Dinitrogen tetroxide reacts with simple alcohols in the gas and liquid phase to yield the corresponding nitrite ester as the major product together with trace amounts of oxidation products (Equation 3.4). This is the case for neat reactions and those conducted in methylene chloride between subambient and ambient temperatures. 

Nitrogen dioxide forms an equilibrium with dinitrogen tetroxide. When it is cold, the equilibrium favours the second compound. Depending on the thermal conditions, the dangerous reactions will involve one or the other of these two compounds. Their endothermic character makes them hardly stable. 

The photochemical reaction of Re2(CO)io with PMePhg seems to fit into this two-equilibrium scheme fairly well, and so represents a recently discovered example of substitution at M2(CO)io without metal-metal bond cleavage. Dinitrogen tetroxide reacts with Re2(CO)io to cleave the metal-metal bond and give ultimately Re(N03)(C0)5, by the following sequence  

In the photolysis of difiuorodiazirine (218) a singlet carbene was also observed (65JA758). Reactions of the difiuorocarbene were especially studied with partners which are too reactive to be used in the presence of conventional carbene precursors, such as molecular chlorine and iodine, dinitrogen tetroxide, nitryl chloride, carboxylic acids and sulfonic acids. Thus chlorine, trifiuoroacetic acid and trifiuoromethanesulfonic acid reacted with difiuorodiazirine under the conditions of its photolysis to form compounds (237)-(239) (64JHC233). 

Many other reactions of ethylene oxide are only of laboratory significance. These iaclude nucleophilic additions of amides, alkaU metal organic compounds, and pyridinyl alcohols (93), and electrophilic reactions with orthoformates, acetals, titanium tetrachloride, sulfenyl chlorides, halo-silanes, and dinitrogen tetroxide (94). 

C. By Oxidation.—This year s literature has been notable for attempts to study the details of certain phosphine oxidation reactions. In one such investigation nitric acid was found to oxidize phosphines, or phosphine sulphides, to phosphine oxides with inversion of configuration at phosphorus, whereas dinitrogen tetroxide, in the absence of acid, was found to oxidize the same compounds with predominant retention. The partial racemization observed with the latter reagent was probably due to the racemization of the oxides, since methylphenyl-n-propylphosphine oxide 

Recently, nitration of organolithiums and Grignards with N204 has been developed for the preparation of certain kinds of nitro compounds (Eqs. 2.14 and 2.15).31 The success of this process depends on the reaction conditions (low temperature) and the structure of substrates. For example, 3-nitrothiophene can be obtained in 70% overall yield from 3-bromothiophene this is far superior to the older method. 3-Nitroveratrole cannot be prepared usefully by classical electrophilic nitration of veratrole, but it can now be prepared by direct o>7/ o-lithiation followed by low-temperature N204 nitration. The mechanism is believed to proceed by dinitrogen tetroxide oxidation of the anion to a radical, followed by the radical s combination. 

The catalysed nitration of phenol gives chiefly 0- and />-nitrophenol, (< 0-1% of w-nitrophenol is formed), with small quantities of dinitrated compound and condensed products. The ortho para ratio is very dependent on the conditions of reaction and the concentration of nitrous acid. Thus, in aqueous solution containing sulphuric acid (i 75 mol 1 ) and nitric acid (0-5 mol 1 ), the proportion of oriha-substitution decreases from 73 % to 9 % as the concentration of nitrous acid is varied from o-i mol l i. However, when acetic acid is the solvent the proportion of ortAo-substitution changes from 44 % to 74 % on the introduction of dinitrogen tetroxide (4-5 mol 1 ). 

The Ponzio reaction provides a useful route to gem-dinitro compounds and involves treating oximes with a solution of nitrogen dioxide or its dimer in diethyl ether or a chlorinated solvent. The Ponzio reaction works best for aromatic oximes where the synthesis of many substituted aryldinitromethanes have been reported. Compound (56), an isomer of TNT, is formed from the reaction of dinitrogen tetroxide with the oxime of benzaldehyde (55) followed by mononitration of the aromatic ring with mixed acid. Yields are usually much lower for aliphatic aldoximes and ketoximes. " The parent carbonyl compound of the oxime is usually the major by-product in these reactions. 

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