Synthesis of new heterocycles by oxidation of functionalized cyclic derivatives of bis(2-chlorovinyl) sulfide and selenide

(2E,6E)‐2,6‐Bis(organylchalogenylmethylidene) substituted 1,4‐dithiane 1,1,4,4‐tetraoxides and N‐organyl thiomorpholine 1‐oxides as new S‐oxide derivatives of bis(2‐organylchalcogenylvinyl) sulfides

“…In particular, the E,E ‐configuration of heterocycles 4a‐d is evidenced from vicinal spin‐spin coupling trans ‐constants ( 3 J CH = 8.1‐8.8 Hz) between the methylene carbons of 1,4‐dithiane framework and the vinyl protons of heterocycles 4a‐d methylidene groups. Similarly, the presence of vicinal trans ‐constants ( 3 J CH = 5.9 Hz) between the methylene carbons of the thiomorpholine framework and the vinyl protons of the methylidene moieties in heterocycles 5a‐c , 6a,b which match vicinal constants both in the parent heterocycles 2,3 and 2,6‐bis(chloromethylidene) substituted derivatives of N ‐organyl thiomorpholines points to retention of the E,E ‐configuration in the structures of heterocycles 5 , 6 .…”

“…Earlier, we have established that oxidation of (2 E ,6 E )‐2,6‐bis(chloromethylidene)‐1,4‐dithiane, N ‐ethyl‐ and N ‐(4‐acetylphenyl)‐(2 E ,6 E )‐2,6‐bis(chloromethylidene) thiomorpholines with hydrogen peroxide furnishes the corresponding (2 E ,6 E )‐2,6‐bis(chloromethylidene)‐1,4‐dithiane 1,1,4,4‐tetraoxide 1 , N ‐ethyl‐(2 E ,6 E )‐2,6‐bis(chloromethylidene) thiomorpholine 1‐oxide 2 , and N ‐(4‐acetylphenyl)‐(2 E ,6 E )‐2,6‐bis(chloromethylidene) thiomorpholine 1‐oxide 3 in which the chlorine atoms of chloromethylidene groups are located in the β‐position to the electron‐withdrawing S ‐oxide groups. Thus, in fact, these heterocycles represent bis(2‐chlorovinyl) sulfoxides and sulfone embedded into the rigid framework of six‐membered heterocycles, and the presence of S ‐oxide function should promote the nucleophilic vinylic substitution in these heterocycles.…”

“…[5,10] We have found that in the reaction of bis[(1E)-3-bromo-1-chloro-1-propen-2-yl] sulfone with primary amines in ethanol in the presence of NaHCO 3 or Na 2 CO 3 , heterocyclization is followed by the substitution with ethoxide ion of the chlorine atoms in chloromethylidene groups of the thiomorpholine 1,1-dioxide formed as the intermediate product to afford bis-ethoxymethylidene derivatives of thiomorpholine 1,1-dioxides. [11] Earlier, we have established that oxidation of (2E,6E)-2,6-bis(chloromethylidene)-1,4-dithiane, N-ethyl-and N-(4acetylphenyl)-(2E,6E)-2,6-bis(chloromethylidene) thiomorpholines with hydrogen peroxide furnishes the corresponding (2E,6E)-2,6-bis(chloromethylidene)-1,4-dithiane 1,1,4,4-tetraoxide 1, N-ethyl-(2E,6E)-2,6-bis(chloromethyli dene) thiomorpholine 1-oxide 2, and N-(4-acetylphenyl)-(2E,6E)-2,6-bis(chloromethylidene) thiomorpholine 1-oxide 3 [12] in which the chlorine atoms of chloromethylidene groups are located in the β-position to the electron-withdrawing S-oxide groups. Thus, in fact, these heterocycles represent bis(2-chlorovinyl) sulfoxides and sulfone embedded into the rigid framework of six-membered heterocycles, and the presence of S-oxide function should promote the nucleophilic vinylic substitution in these heterocycles.…”

Oxidation of E,E‐bis(3‐bromo‐1‐chloro‐1‐propen‐2‐yl) chalcogenides and use of E,E‐bis(3‐bromo‐1‐chloro‐1‐propen‐2‐yl)sulfone in heterocyclization with primary amines

“…It should be noted that N ‐organyl‐2( E ),6( E )‐bis(chloromethylidene) thiomorpholine‐1‐oxides were obtained recently by oxidation of N ‐organyl‐2( E ),6( E )‐bis(chloromethylidene) thiomorpholine with hydrogen peroxide in a mixture of chloroform and acetic acid . Further oxidation to N ‐organyl‐2( E ),6( E )‐bis(chloromethylidene) thiomorpholine‐1,1‐dioxides did not occur.…”

“…It should be noted that N-organyl-2(E),6(E)-bis(chloromethylidene) thiomorpholine-1-oxides were obtained recently by oxidation of N-organyl-2(E),6(E)-bis(chloromethylidene) thiomorpholine with hydrogen peroxide in a mixture of chloroform and acetic acid. [24] Further oxidation to Norganyl-2(E),6(E)-bis(chloromethylidene) thiomorpholine-1,1-dioxides did not occur. Thus, as presented in this article, heterocyclization of sulfone 3 under the influence of the primary amines in ethanol in the presence of Na 2 CO 3 or NaHCO 3 is currently the only method of synthesis of 2,6-bis(methylidene) derivatives of N-organyl thiomorpholine-1,1-dioxides.…”