Reaction with active nitrogen

Table III. Changes in Activity of 14C-Labeled Propylenes upon Reaction with Active Nitrogen ...

Chemiluminescent Reactions of Active Nitrogen with Hydrocarbons... 

Figure 6 CN(B22+ —> X2i ) emission in the reaction of active nitrogen with hydrocar-...

The base-catalyzed condensation of azides with activated methylene compounds is a well-established route to IJT-triazoles. In particular, it is the best route to triazoles bearing a 5-amino or hydroxy substituent and an aryl or carbonyl-containing function in the 4-position. The addition is regiospecific. The reaction is a stepwise one, since anomerism of glycosyl azides has been observed in their reaction with activated methylene compounds, indicating the presence of an intermediate. The mechanism can be envisaged as a nucleophilic attack by the car-banion on the terminal nitrogen of the azide, followed by cyclization to a... 

Fig. 4-5. Yields of HCN and 14N15N from the reaction of active nitrogen with 15NO-C2H4 mixtures ranging in composition from pure C2H4 to pure 15NO. The symbols ( ) and (O) represent experiments in which the ethylene flow rate was maintained at values in excess of titration end point while increasing increments of nitric oxide were added. The symbols ( ) and ( ) correspond to experiments in which nitric oxide flow rates were held at values in excess of titration end point while various amounts of ethylene were added (from Fersht and Back139 with permission of the National Research Council of Canada).

The most reliable results were obtained by Levy and Winkler (68) who investigated five different methods of terminating the reaction of active nitrogen with ethylene in the temperature range 22-400°C. The... 

Dimethyl sulfide is toxic and possesses a very bad odour. Particularly, in reactions with activated DMSO on a very big scale, it may be advisable to destroy the dimethyl sulfide, generated during the reaction, by purging the reaction mixture with a nitrogen flow, and scrubbing the resulting gaseous mixture with aqueous NaOCl.5... 

Two important reactions of arene oxides in animal tissue are (1) detoxification and (2) formation of conjugates of arene oxides with purine pyrimidine bases of DNA. For both of these reactions to take place, the arene oxide should have a certain intrinsic stability to survive an aromatization reaction. Reaction with the thiolate bond of glutathione is responsible for detoxification, whereas the extent of involvement of arene oxides in the nucleophilic reactions with nonpolarized nitrogen bases of DNA is directly related to their carcinogenic activity. 

The 5-benzyl derivative of 3-vinylindole 211 reacted with methyl male-ate and fumarate (89CPB1999) in a sealed glass tube at 100°C under a nitrogen atmosphere, giving the unstable 212, the structure of which was identified by transformation to 213 via reaction with active Mn02. 

The reaction is akin to the Ritter reaction, with activation achieved by nitration, rather than proton-ation, and the products accordingly retain the nitro group. Additions to 1-phenylcyclohexene (59%) and to franr-stilbene (72%) are stereospecific (trans) cfr-stilbene gives the expected tfireo product (39%) plus some erythro (6%). Reactions of nitrogen dioxide with alkenes are very complex and rarely use-ful. A recent mechanistic paper gives many key references. " Addition of NjOs is occasionally usefiil, as with dicyclopentadiene (Scheme 49). ... 

Selenium nitride, SeN, is formed by the reaction of selenium or selenium chlorides Se2Cl2 or SeCLi with active nitrogen prodnced by a high freqnency discharge. To date, only the electron band spectra have been investigated. 

Some controversy exists over the reactive species produced when nitrogen is passed through an R.f. or microwave discharge. Verbeke and Winkler investigated the reactions of active nitrogen with nitric oxide and ethylene and found that the amount of nitric oxide removed was greater than the maximum amount of HCN produced from ethylene. To account for this difference they postulated that vibrationally excited molecules were decomposing nitric oxide, viz. 

Freeman and Winkler studied the reaction of active nitrogen with ammonia their results indicate that the participation of species other than atomic nitrogen... 

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