Reactions of selenium dichloride and dibromide with divinyl selenide: synthesis of novel selenium heterocycles and rearrangement of 2,6-dihalo-1,4-diselenanes

Потапов, В. А.; Амосова, С. В.; Volkova, K. A.; Пензик, М. В.; Albanov, A. I.

doi:10.1016/j.tetlet.2009.10.073

Cited by 52 publications

(10 citation statements)

References 34 publications

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Section: Short Communicationsmentioning

confidence: 99%

“…We were the first to reveal that freshly prepared selenium dichloride and selenium dibromide can be used in selective synthesis of organic selenides [3,4]. Reactions of selenium dichloride and dibromide with divinyl chalcogenides and their derivatives opened a synthetic route to new heterocyclic compounds [5][6][7][8][9][10].In continuation of our systematic studies on the chemical properties of selenium dihalides [3-10], we examined previously unknown addition of selenium dichloride to divinyl sulfone. It was found that the reaction occurs with high regioselectivity and leads to the formation of a new four-membered heterocyclic compound, 2,4-bis(chloromethyl)-1,3-thiaselenetane 1,1-dioxide (I).…”

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confidence: 99%

“…In continuation of our systematic studies on the chemical properties of selenium dihalides [3][4][5][6][7][8][9][10], we examined previously unknown addition of selenium dichloride to divinyl sulfone. It was found that the reaction occurs with high regioselectivity and leads to the formation of a new four-membered heterocyclic compound, 2,4-bis(chloromethyl)-1,3-thiaselenetane 1,1-dioxide (I).…”

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Synthesis of a new four-membered heterocycle by reaction of selenium dichloride with divinyl sulfone

2010

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SHORT COMMUNICATIONSSelenium dichloride and dibromide were not isolated as individual substances. It is known that selenium dichloride in solution exists in equilibrium with selenium tetrachloride and Se 2 Cl 2 , whereas the equilibrium of selenium dibromide in solution involves Se 2 Br 2 and bromine [1, 2]. We were the first to reveal that freshly prepared selenium dichloride and selenium dibromide can be used in selective synthesis of organic selenides [3,4]. Reactions of selenium dichloride and dibromide with divinyl chalcogenides and their derivatives opened a synthetic route to new heterocyclic compounds [5][6][7][8][9][10].In continuation of our systematic studies on the chemical properties of selenium dihalides [3-10], we examined previously unknown addition of selenium dichloride to divinyl sulfone. It was found that the reaction occurs with high regioselectivity and leads to the formation of a new four-membered heterocyclic compound, 2,4-bis(chloromethyl)-1,3-thiaselenetane 1,1-dioxide (I). The yield of compound I was 85%, calculated on the reacted divinyl sulfone, the conversion of the latter being 58%. sional correlation techniques, as well as by mass spectrometry and elemental analysis. According to the NMR data, compound I was isolated as a mixture of two diastereoisomers at a ratio of 2.5 : 1.2,4-Bis(chloromethyl)-1,3-thiaselenetane 1,1-dioxide (I). mp 76-77°C. Major diastereoisomer: 1 H NMR spectrum, δ, ppm: 3.91 d.d (2H, CH 2 Cl, 2 J = 11.8, 3 J = 7.1 Hz), 4.27 d.d (2H, CH 2 Cl, 2 J = 11.8, 3 J = 7.1 Hz), 5.52 d.d (2H, CHSe, 3 J = 7.1, 7.1 Hz). 13 C NMR spectrum, δ C , ppm: 41.39 (CH 2 Cl), 69.36 (CHSe). 77 Se NMR spectrum: δ Se 193 ppm. Minor diastereoisomer: 1 H NMR spectrum, δ, ppm: 3.93 d.d (2H, CH 2 Cl, 2 J = 11.9, 3 J = 7.7 Hz), 4.31 d.d (2H, CH 2 Cl, 2 J = 11.9, 3 J = 7.9 Hz), 5.54 d.d (2H, CHSe, 3 J = 7.7, 7.9 Hz). 13 C NMR spectrum, δ C , ppm: 41.63 (CH 2 Cl), 70.03 (CHSe). 77 Se NMR spectrum: δ Se 200 ppm. Mass spectrum, m/z (I rel , %): 268 (29)

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Section: Short Communicationsmentioning

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Synthesis of a new four-membered heterocycle by reaction of selenium dichloride with divinyl sulfone

2010

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“…We perform systematic studies on reactions of selenium halides with acetylenes [2,4,5] and its derivatives, such as divinyl sulfide [6][7][8][9][10], divinyl sulfone [11][12][13][14], and divinyl selenide [15][16][17][18]. Stereoselective methods of synthesis of (E,E)-bis(2-halovinyl) selenides were developed on the basis of reactions of selenium halides with acetylene [4,5].…”

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Reaction of diselenium dichloride with acetylene

2011

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“…Reactions of selenium dichloride and selenium dibromide with compounds possessing two double [4][5][6][7][8][9][10][11][12][13][14][15][16][17] or triple bonds [1][2][3] provide efficient methods for the synthesis of new heterocyclic systems [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. Reactions of selenium dichloride and selenium dibromide with divinyl sulfide [4][5][6][7][8][9], divinyl sulfone [10][11][12][13], and divinyl selenide [14][15][16][17] afforded previously unknown four-, five-, and six-membered heterocycles containing two chalcogen atoms.…”

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Reaction of selenium dichloride with allyl phenyl ether

2011

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SHORT COMMUNICATIONSIn the recent years, a new synthetic approach to organoselenium compounds on the basis of selenium dichloride and selenium dibromide is extensively developed . Reactions of selenium dichloride and selenium dibromide with compounds possessing two double [4][5][6][7][8][9][10][11][12][13][14][15][16][17] or triple bonds [1-3] provide efficient methods for the synthesis of new heterocyclic systems [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. Reactions of selenium dichloride and selenium dibromide with divinyl sulfide [4][5][6][7][8][9], divinyl sulfone [10][11][12][13], and divinyl selenide [14-17] afforded previously unknown four-, five-, and six-membered heterocycles containing two chalcogen atoms.We recently showed that selenium dihalides can act as electrophilic reagents in electrophilic aromatic substitution processes. Bis(4-methoxyphenyl) selenide was synthesized in high yield by reaction of selecnium dichloride with methoxybenzene [21]. The reaction was carried out by heating the reactants in boiling chloroform. An important condition ensuring successful reaction is the use of arene activated by an alkoxy group. Insofar as selenium dichloride is capable of both adding at a double bond and acting as electrophile, a combination of these reactions could lead to fused heterocyclic compounds.In fact, by reaction of selenium dichloride with allyl phenyl ether we obtained a new heterocyclic compound, 3-chloromethyl-2,3-dihydro-1,4-benzoxaselenine (I) in 75% yield. The reaction was carried out with equimolar amounts of the reactants in chloroform. The best result was obtained by mixing the reactants at low temperature (-60°C) with subsequent heating of the reaction mixture to 50-60°C. Presumably, the addition of selenium dichloride at the allyl group occurs at low temperature, whereas the second step, electrophilic aromatic replacement, requires elevated temperature (50-60°C). The reaction is regio-and stereoselective. This may be due to formation of intermediate seleniranium ion A; attack by chloride ion on the latter at the methylene carbon atom with formation of anti-Markovnikov adduct B is more favorable.The structure of compound I was determined by 1 H, 13 C (including JMOD technique), and 77 Se NMR spectroscopy, mass spectrometry, and elemental analysis. The coupling constant between the selenium atom and CH carbon atom in the propyl fragment corresponds to direct Se-C interaction ( 1 J C,Se ), which indicates that selenium adds to the central carbon atom of the allyl group.It should be noted that Migalina et al. [22] previously described the reaction of selenium tetrachloride with allyl phenyl ether, which did not lead to cyclization product but afforded the corresponding open-chain Markovnikov adduct, dichlorobis(2-chloro-3-phenoxypropyl)-λ 4 -selane.Thus we were the first to demonstrate that addition of selenium dichloride at double bond can be accompanied by electrophilic aromatic substitution with formation of fused heterocyclic system.3-Chloromethyl-2,3-dihydro-1,4...

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Reactions of selenium dichloride and dibromide with divinyl selenide: synthesis of novel selenium heterocycles and rearrangement of 2,6-dihalo-1,4-diselenanes

Cited by 52 publications

References 34 publications

Synthesis of a new four-membered heterocycle by reaction of selenium dichloride with divinyl sulfone

Synthesis of a new four-membered heterocycle by reaction of selenium dichloride with divinyl sulfone

Reaction of diselenium dichloride with acetylene

Reaction of selenium dichloride with allyl phenyl ether

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