Reaction of secondary phosphine chalcogenides with diallylamine

Diphenyl- or bis(2-phenylethyl)phosphine sulfides and -phosphine selenides react with diallylamine under radical initiation (UV or AIBN) to afford the corresponding diadducts and tetrahydropyrrolylmethyl phosphine chalcogenides. The yield and the ratio of the products depend on the structure of the starting secondary phosphine chalcogenides.     

Reaction of divinyl telluride with secondary phosphine chalcogenides

Divinyl telluride reacted with 2 equiv of diphenylphosphine sulfide in the presence of AIBN as radical initiator (63–68°C) to give the corresponding anti-Markovnikov adduct in 68% yield with high regioselectivity. Treatment of the addition product with aqueous hydrogen peroxide at room temperature afforded 71% of vinyldiphenylphosphine oxide. Radical addition of diphenylphosphine selenide to divinyl telluride (AIBN, 63–68°C) led to the formation of 1,1,3,3-tetraphenyldiphosphoxane 1,3-diselenide in 82% yield.     

Reaction of divinyl selenide with secondary phosphine chalcogenides

Under the conditions of free-radical initiation (AIBN, UV irradiation), divinyl selenide regioselectively reacts with secondary phosphine sulfides and phosphine selenides to afford, depending on the ratio of the reagents, mono- or diadducts mainly of the anti-Markownikoff structure. The conditions which allow obtaining the diadducts in up to 97% yield are found. By the example of 2-{[2-(diphenethylphosphoroselenoyl) ethyl]selanyl}ethyl(diphenethyl)phosphine selenide the diadducts were shown to react with aqueous hydrogen peroxide at 53–56°C to give vinyl(diphenethyl)phosphine oxide in 76% yield.     

Catalyst-free addition of secondary phosphine chalcogenides to pyrazolecarbaldehydes

1. Download : Download high-res image (84KB)
2. Download : Download full-size image

     

Chemoselective noncatalytic addition of secondary phosphine chalcogenides to citral

Addition of secondary phosphine oxides, phosphine sulfides and phosphine selenides to 3,7-dimethyl-2,6-octadienal (citral) (48–50°C, THF, argon) proceeds exclusively to the aldehyde group giving rise to new polyfunctional tertiary phosphine chalcogenides with diene and hydroxyl moieties in high preparative yield (up to 80%).     

Reaction of secondary phosphine oxides with acylacetylenes

Secondary phosphine oxides reacted with 1-alkanoyl-2-phenylacetylenes in chemoselective fashion under mild conditions (20°C, THF) in the absence of a catalyst (diphenylphosphine oxide) or in the presence of potassium hydroxide [bis(2-phenylethyl)phosphine oxide] to give 1-alkyl-1-diphenyl(or 2-phenylethyl)-phosphoryl-3-phenylprop-2-yn-1-ols in up to 96% yield. The reaction of diphenylphosphine oxide with 1-alkanoyl-2-phenylacetylenes in the system KOH-THF (20°C) afforded not only adducts at the carbonyl group but also products of double α,β-addition at the triple bond, 2,3-bis(diphenylphosphoryl)-3-phenylpropan-1-ones.     

Radical addition of secondary phosphine chalcogenides to allylamine: Atom-economic synthesis of aminopropylphosphine chalcogenides

Secondary phosphine sulfides and phosphine selenides react with allylamine under the conditions of radical initiation (UV or AIBN) to form the anti-Markovnikov adducts in up to 93 % yield.     

Chlorination of secondary phosphine chalcogenides with carbon tetrachloride in the absence of bases

The interaction of bis(2-phenylethyl)phosphine sulfide, bis(2-phenylethyl)phosphine selenide and bis[2-(2-phenyl)propyl]phosphine selenide with carbon tetrachloride under heating (80°C, 8–20 h) leads to the formation of the corresponding chlorophosphine chalcogenides with the yield of 80–90%.

     

Atom-sparing synthesis of tertiary diphosphine dichalcogenides from acetylenes and secondary phosphine chalcogenides

Secondary phosphine oxides and phosphine sulfides react with acetylene, methylacetylene, and phenylacetylene in the presence of strong bases (KOH-DMSO, KOH-THF) by the mechanism of double nucleophilic α,β-addition to form tertiary diphosphine dioxides and diphosphine disulfides in high yield (up to 97%).     

Oxidative coupling of hydroxy- or aminoazobenzenes with secondary phosphine chalcogenides: Towards new media-responsive molecular switches

One or two chalcogenophosphinate groups were introduced to the azobenzene scaffold via the oxidative cross-coupling reaction of 4-amino-, 4-hydroxy- and 4,4′-dihydroxyazobenzenes with secondary phosphine chalcogenides using the CCl₄/Et₃N system under mild conditions in 41–95% yield. Cis-trans photoisomerization of the phosphorylated azobenzenes was reversibly controlled by alternating UV/Vis light irradiation. The chalcogenophosphinate group imparts the properties of media-responsive molecular photoswitches to the synthesized azobenzenes.     

Reaction of cluster niobium chalcogenides with n-butyllithium

Conclusions The reaction of cluster niobium chalcogenides with n-BuLi in hexane at 20°C has been studied. The phases obtained have been characterized by various physicochemical methods and are considered to be lithium intercalates based on the initial phases. The measured values of the Knight shifts of the lithium atoms in all the intercalates indicate a charge on these atoms close to +1.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1931–1933, September, 1987.     

Reactions of 2- and 4-pyrones with secondary phosphine chalcogenides: a facile synthesis of functional phosphorylated pyrones

The oxidative cross-coupling between 4-hydroxy-6-methyl-2-pyrone or 3-hydroxy-2-methyl-4-pyrone and secondary phosphine chalcogenides proceeds in CCl₄/Et₃N under mild conditions (20–52 °С, 0.75–10 h) through the hydroxyl group to give O-(6-methyl-2-oxo-2H-pyran-4-yl) diorganylphosphinochalcogenoates or O-(2-methyl-4-oxo-4H-pyran-3-yl) diorganylphosphinochalcogenoates, in high yields.     

Directed synthesis of tertiary phosphine chalcogenides with pyridine and hydroxy functions

Secondary phosphine chalcogenides react with pyridine-2-, pyridine-3-, and pyridine-4-carbaldehydes under mild noncatalytic conditions (22–43°C, 1–8.5 h) to form in 81–98% yield functional tertiary phosphine chalcogenides containing pyridine and hydroxy functions.     

Reaction of methyl iodide with organylethynyl silatranylmethyl chalcogenides

The reactivity of organylethynyl silatranylmethyl chalcogenides RC=CYCH₂Si(OCH₂CH₂)₃N (R=Ph, Me₃Si; Y=S, Se, Te) in the reaction with methyl iodide depending on the nature of the chalcogen Y, the substituent R at the triple bond, and the reaction conditions was studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2550–2551, December, 1998.     

Reaction of hydroxyflavones with secondary phosphine chalcogenides in the CCl4/Et3N system: synthesis of a new family of phosphorylated flavonoids

Flavonoids (3-hydroxy-, 3-hydroxy-4′-methoxy-, 3-hydroxy-7-methoxy-, and 5,7-dihydroxyflavones) react with secondary phosphine chalcogenides in the CCl₄/Et₃N redox system (50–52 °C, 3–5 h) to afford chemoselectively the corresponding chalcogenophosphinates of the hydroxyflavones in 65–82% yield.     

2,2,2-三氟卤乙烷和碳负离子的自由基亲核取代反应

主要研究2,2,2-三氟卤乙烷(碘、溴、氯、氟)和碳负离子的反应,在一定的温度下,以DMF作溶剂,除了2,2,2-三氟氟乙烷外,反应都得到了相应的2,2,2-三氟卤乙烷的衍生物以及碳负离子的偶联产物.该反应能被紫外光加速,能被对二硝基苯和对二苯酚阻止.因此,该反应是按S_RN1即自由基亲核取代反应机理进行.由于此反应能在黑暗中进行,所以它可能是通过热引发或自发引发来完成的.     

One-pot synthesis of ultra-branched mixed tetradentate tripodal phosphines and phosphine chalcogenides

Ultra-branched mixed tetradentate tripodal phosphines and phosphine chalcogenides have been synthesized by the exhaustive regioselective addition of secondary phosphines, phosphine sulfides and phosphine selenides to available tris(4-vinylbenzyl)phosphine oxide under free-radical conditions (UV irradiation or AIBN) in good to excellent yields.