Bicyclic chloroamine

The cis bicyclic chloroamine 313 reacted at a faster rate than the corresponding decalin system 313, (NCH3 replaced by CHj) and gave exclusively the cyclohexene iminium salt 314 while the chloroamine 315 reacted to give a mixture of other products. 

Not surprising, the most prevalent synthetic utility is the assembly of the pyrrolidine ring. N-Chloroamine 27 was obtained by treatment of N-methyl-2-cyclopentylethylamine (26) with N-chlorosuccinimide. Under classic Hofmann-Loffler-Freytag reaction conditions, 27 was rearranged either thermally or by UV irradiation in sulfuric acid to bicyclic amine... 

Other evidence advanced in favor of alkyl nitrenium ions came from Ag+ promoted isomerization and solvolysis of various cyclic and bicyclic A-chloroamines (e.g., A representative example is shown in Figure 13.12. It was argued... 

With this experience in hand, the amine hydrochloride IQ was transformed into the aminonitrile 2A as shown in Figure 4. This entire sequence was carried out on an approximate 0.5 mole scale via five separate reactions without isolation of intermediates to give a 67% overall yield of aminonitrile 1A based on amine IQ. Thus, the amine hydrochloride IQ was neutralized with concentrated potassium hydroxide, and the liberated free amine Q was taken up in ether. Treatment of this solution with N-chlorosuccinimide (NCS) gave a solution of the N-chloroamine 11. Further addition of ethanolic potassium hydroxide effected dehydrochlorination. The resultant bicyclic imine 12. in ethanolic ether was sequentially treated with aqueous sodium bisulfite and then solid sodium cyanide. The desired aminonitrile 1A was isolated as a distillable liquid. 

Surzur and Stella have utilized the radical bicyclization of ethylenic N-chloroamines to produce pyrrolizidines fimctionalized at C-2. Reaction of allylamine with l-bromopent-4-ene, followed by chlorination, gave the N-chloroamine (11). Treatment of 11 with aqueous acetic add and titanium(III)... 

Nelson s detailed investigation of one-electron oxidation of bicyclic amines and hydrazines continues CV studies show that /V -diacyl-hydrazines (19)30a and azabicyclooctanes (20a)30b gjVe long-lived radical cations comparison has been made between ease of electron loss and N inversion barriers in (20b) and related N-chloroamines 30c studies of the nitroxides (21) and related compounds show that ff-coupied transmission of positive charge from N to the CO in the radical cation is unimportant. 30d... 

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