Stannic chloride-induced unsymmetrical CSe bond cleavage of bis(N,N-dimethylcarbamoylseleno)methanes: Novel generation of selenoaldehydes

Abstract

Treatment of bis(N,N-dimethylcarbamoylseleno)

SnCl4‐Induced Unsymmetrical Cleavage of Bis(N,N‐diethylcarbamoyltelluro)‐arylmethanes: Generation of Tellurobenzaldehydes

“…Bis( N,N ‐dimethylcarbamoyl) ditelluride ( 1 ) was at first prepared in moderate yield by treating N,N ‐dimethylformamide (DMF) with sodium and elemental tellurium under heating followed by aerobic oxidation of the reaction mixture . Preparation of bis( N,N ‐diethylcarbamoyl) ditelluride ( 2 , R 1 = C 2 H 5 ) was also carried out by treating N,N ‐diethylformamide (DEF) with lithium metal and elemental tellurium through a similar procedure as shown in Scheme .…”

“…In the course of our studies on the novel generation of higher‐row chalcogenocarbonyl compounds, we previously reported a convenient preparation of stable ditelluroacetal derivatives A through the reaction of in situ generated tellurocarbamate ions with gem‐dihaloalkanes . Actually, such ditelluroacetals A are recognized as potent precursors for telluroaldehydes B in the light of their symmetrical structures with an easily removable electron‐withdrawing carbamoyl group on each tellurium atom, and compouds A are expected to undergo SnCl 4 ‐induced unsymmetrical C–Te bond cleavage to generate telluroaldehydes B through push–pull type removal of N,N ‐diethyltellurocarbamate in an analogous manner of our previous report on the generation of selenoaldehydes from bis( N,N ‐dimethylcarbamoylseleno)methanes . According to our expectation as mentioned above, we started our exploration on the reaction of A with SnCl 4 in the presence or absence of trapping agents.…”

Vibrational spectra, conformational properties and argon matrix photochemistry of diacetyl diselenide, CH3C(O)Se2C(O)CH3

“…On the other hand, bis(R‐carbonyl)diselenides, RC(O)SeSeC(O)R, reported to date correspond to compounds with aromatic (R–) substituents rather than aliphatic analogs, probably because of a higher thermal stability of aromatic species. Among the few reports of the aliphatic derivatives, the molecule [Me 2 NC(O)Se] 2 , for example, was used by Gong et al , as the starting reagent to obtain a series of new compounds of general formula Me 2 NC(O)SeRSeC(O)NMe 2 . Wang et al .…”

Formation of a Sterically Crowded 1,6,6αλ4-Triselenapentalene and 4H-Selenopyran-4-selones Fused with Two Bornane Skeletons Through the Reaction of d-Camphor p-Toluenesulfonylhydrazone With a Base and Elemental Selenium

“…In the course of our successive studies on the synthesis of higher-row chalcogenocarbonyl compounds, we have found a convenient synthesis of dialkenyl diselenides C through the reaction of ptoluenesulfonylhydrazones A, derived from ketones possessing an α-methylene group, with a base and elemental selenium. [18][19][20][21][22][23][24] The reaction was assumed to proceed through the in situ generated alkeneselenolate ions B via Bamford-Stevens type reaction of ptoluenesulfonylhydrazones [25][26][27][28][29][30][31][32][33] as shown in Scheme 1, and, therefore, the synthetic application of this sequence to the preparation of various selenium-containing heterocyclic compounds was keenly expected.…”