The chemistry of 2,2-dichloro-3-p-nitrophenyl-1-phenyl aziridine, 6. Preparation of a stable aziridinyl C- anion, 3.

Synthesis and Reactivity of C-Heteroatom-Substituted Aziridines

“…2,2-Dichloroaziridine 283 bearing a naphthyl group at nitrogen was observed to be more reactive than 2,2-dichloroaziridine 162 with a phenyl group at nitrogen due to the larger electron-donating ability of the naphthyl ring in stabilizing the transition state . The effect of two chloro atoms combined with a 4-nitrophenyl group made the ring proton so acidic that it could be abstracted by sodium hydride in hexamethylphosphoramide (HMPA) or dimethoxyethane (DME) to generate a stable carbanion 287 . The quenching with D 2 O afforded the deuterated 2,2-dichloroaziridine 288 (Scheme ).…”

Oxiranyl Anions and Aziridinyl Anions

“…In 1972, Rubottom and Stevenson described for the first time the preparation of p -nitrophenyl-stabilized aziridinyl anion 326 from aziridine 325 and sodium hydride (Scheme ) . The aziridinyl anion 326 was the first example of a stable aziridinyl C-anion.…”

“…Moreover, reaction of 322 with several electrophiles (such as iodomethane and aldehydes) In 1972, Rubottom and Stevenson described for the first time the preparation of p-nitrophenyl-stabilized aziridinyl anion 326 from aziridine 325 and sodium hydride (Scheme 55). 82 The aziridinyl anion 326 was the first example of a stable aziridinyl C-anion. When 325 was treated with sodium hydride in HMPA (or DME) the anion 326 was formed as a bright purple solution.…”

Aziridinyl Anions: Generation, Reactivity, and Use in Modern Synthetic Chemistry

“…14 Another early preparation of aziridinyl anion was developed in 1972 by Rubottom and Stevenson who reported that the stable bright purple aziridinyl C-anion 6 could be generated at low temperature upon treatment of aziridine 5 with sodium hydride in HMPA. 15 The proposed aziridinyl C-anion proved to be stable upon warming to -10 °C and could be trapped with D 2 O (Scheme 3).…”