334 Heterocyclic Chemistry ‘Thiirene-1-oxide 245 is prepared by the reaction of a,o’-dibromodibenzyl sulfoxide 244 with triethylamine”, The reaction of o,0-dichlorobenzyl sulfone 246 with an excess of base, triethylenediamine in dimethyl sulfoxide, at room temperature yields 2,3-diphenylthiirene-1,1-dioxide 247 (scheme-103). Br. oil Ces, CoHs, CoH CH — He \ / cots + (CoHs)N§ ——> ss Ss I I 4 ° 244 245 4 a Cols Cols wa yo i — CoH \ / ‘Cg, _() TED, (CH,),S0 ‘gf Gi) H,O. ‘e O 0, 246 247 Scheme-103 2 THREE-MEMBERED HETEROCYCLES WITH TWO HETEROATOMS Three-membered heterocycles with two heteroatoms are highly reactive and possess certain unusual properties because of the ring strain, These heterocycles, similer to three-membered heterocycles with one heteroatom, can also be prepared easily as compared to the larger rings because of the facile ring closure. These are interesting not only from their reactions point of view, but also from theoretical stand point of view. 2.1 Diaziridines 2.1.1 General Three-membered saturated heterocycles with one carbon atom and two nitrogen heteroatoms are known as diaziridines 248°",Three-Membered Heterocycles 335 248 Diaziridines are weak bases and form salts. The solubility in aqueous mineral acids decreases with increasing the chain length of the alkyl substituents. The nitrogen-inversion in diaziridine is retarded because of the increased rotational energy barrier resulting from the lone pair-lone pair interactions on the nitrogen atoms and thus diaziridine can be resolved into enantiomers. 2.1.2. Synthesi 2.1.2.1 Reaction of Ketones with Ammonia or Primary Amines Diaziridines are prepared by the reaction of ketones with ammonia or primary amines in the presence of an aminating agent (chloramine or hydroxylamine-O- sulfonic acid) (scheme-104)""5, NHy (ro or NHC or Np :NH2CI RNH, NH20SOsH Ww 252 Scheme-104 2.1.2.2 Reaction of Diazirines with Grignard Reagents The reaction of diazirines 283 with Grignard reagent provides diaziridines 255 (scheme-105)",336 Heterocyclic Chemistry N RM N—MgX. NH DC AS De] Oe N N-R N-R 253 (254 255 Scheme-105 2.1.2.3 Photochemical Method Diaziridines 257 can also be prepared by the electrocyclic ring closure of stabilized azomethine imides 256 in the presence of ultraviolet light. The reaction is reversed when diaziridine 257 is heated (scheme-106)"”. Scheme-106 Photolysis of A?-tetrazolines 258 also results in the formation of diaziridines 259 with the extrusion of N, (scheme-107)'*, N=N RIN NRE Se + MM R7 OH ROH 258 259 Scheme-107 2.1.3 Reactions Diaziridines are more stable than oxiranes. The diaziridine ring is stable to alkaline reagents, but hydrolyzed readily in acid solution. However, diaziridines undergo reactions involving the cleavage of C-N and N-N bonds and the retention of the ring. 2.1.3.1 Cleavage of N-N Bond (Reduction) Diaziridines are reduced to two molecules of amines with the cleavage of N-N bond (scheme-108)".