1‐Amino‐2‐methylindoline is a precursor used in the synthesis of antihypertension drugs. It reacts with monochloramine to lead to the formation of 1‐amino‐2‐methylindole and azo(2‐methyl)indoline. These new products have been isolated and characterized by microanalysis, uv, gc/ms, ir, and 1H/13C nmr. The reaction leads to the transient formation of an indolic aminonitrene. 1‐Amino‐2‐methylindole formation proceeds in strongly alkaline medium by rearrangement of a diaziridine intermediate. In neutral or slightly alkaline medium, one obtains a precipitate of tetrazene type (‐N‐N=N‐N‐), the azo(2‐methyl)indoline. The study of the thermochemical properties shows that tetrazene decomposes towards 150 °C to give the 1,1′‐bi(2‐methyl)indoline. The stability of the starting reagents and products was the subject of a systematic investigation. A reaction mechanism is proposed.
The formation of 3-azabicyclo [3,3,0]oct-2-ene in the course of the synthesis of 3,0]octane using the Raschig process results from the following two consecutive reactions: chlorine transfer between the monochloramine and the 3-azabicyclo[3,3,0]octane followed by a dehydrohalogenation of the substituted haloamine. The kinetics of the reaction were studied by HPLC and UV as a function of temperature (15 to 44ЊC), and the concentrations of NaOH (0.1 to ) and the chlorinated derivative (1 to ). Ϫ33.6 J mol K ene were determined. IR, NMR, and ES/MS analysis show dimerization of the water-soluble monomer into a white insoluble dimer.
High-grade chloramine is prepared in batch and in continuous mode starting from mixed ammoniacal solutions and hypochlorite at hundred chlorometric degrees.
3,4‐Diazabicyclo[4.3.0]non‐2‐ene and N,N'‐azo‐3‐azabicyclo[3.3.0]octane are the main products of the oxidation of N‐amino‐3‐azabicyclo[3.3.0]octane by chloramine. These new compounds have been isolated and characterized. A structural study has been performed with the goal of establishing the cis—trans configuration at the bicyclic junction. Multinuclear proton decoupling carried out on the endocyclic hydrazone has allowed the determination of the coupling constant of the bridgehead hydrogens. A low temperature conformational study shows splitting of the 13C signal of the carbon atom located α with respect to the ammonia nitrogen. This result, consistent with a cis structure, was confirmed by a nmr analysis conducted on the solid tetrazene derivative. The X‐ray data collection on a single cyrstal of the tetrazene has permitted us to determine the crystallographic properties of this compound. Data processing by direct methods reveals that the geometry of the molecule presents a cis configuration for the bicyclic bridge link and a trans one for the azo group, confirming thus the main results obtained by nmr studies.
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