594-30-9Relevant articles and documents
CO2-activated NaClO-5H2O enabled smooth oxygen transfer to iodoarene: A highly practical synthesis of iodosylarene
Miyamoto, Kazunori,Watanabe, Yuichiro,Takagi, Taisei,Okada, Tomohide,Toyama, Takashi,Imamura, Shinji,Uchiyama, Masanobu
, (2021/05/27)
A safe, rapid, and environmentally friendly synthesis of iodosylarene (ArIO) has been developed using NaClO under a carbon dioxide (CO2) atmosphere. Exposure of iodoarene to NaClO-5H2O in acetonitrile under CO2 (1 atm) resulted in the clean formation of ArIO within 10 minutes in high yield. The absence of a base in this method enables the direct use of in-situ-generated iodosylarene not only for a variety of oxidative transformations (synthesis of sulfilimine, pentavalent bismuth, benzyne adduct, etc.), but also for the synthesis of iodonium ylide and imino-λ3-iodane in one pot.
A Direct S0→Tn Transition in the Photoreaction of Heavy-Atom-Containing Molecules
Kuribara, Takahito,Matsumoto, Koki,Muranaka, Atsuya,Nagasawa, Sho,Nakajima, Masaya,Nemoto, Tetsuhiro,Uchiyama, Masanobu
supporting information, p. 6847 - 6852 (2020/03/23)
According to the Grotthuss–Draper law, light must be absorbed by a substrate to initiate a photoreaction. There have been several reports, however, on the promotion of photoreactions using hypervalent iodine during irradiation with light from a non-absorbing region. This contradiction gave rise to a mystery regarding photoreactions involving hypervalent iodine. We demonstrated that the photoactivation of hypervalent iodine with light from the apparently non-absorbing region proceeds via a direct S0→Tn transition, which has been considered a forbidden process. Spectroscopic, computational, and synthetic experimental results support this conclusion. Moreover, the photoactivation mode could be extended to monovalent iodine and bromine, as well as bismuth(III)-containing molecules, providing new possibilities for studying photoreactions that involve heavy-atom-containing molecules.
BISMUTH PERFLUOROALKYLPHOSPHINATES AS LEWIS ACID CATALYSTS
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Paragraph 0092, (2018/10/19)
The invention relates to bismuth perfluoroalkylphosphinates as Lewis acid catalysts, the compounds, and processes for the preparation thereof. [in-line-formulae]ArxBi[OP(O)(Rf)2]3-x??(Ia),[/in-line-formulae] [in-line-formulae]Ar3Bi[OP(O)(Rf)2]2??(Ib).[/in-line-formulae]
Bismuth Perfluoroalkylphosphinates: New Catalysts for Application in Organic Syntheses
Solyntjes, Sven,Neumann, Beate,Stammler, Hans-Georg,Ignat'ev, Nikolai,Hoge, Berthold
, p. 1568 - 1575 (2017/02/10)
Commercially available BiPh3was treated with perfluoroalkylphosphinic acids [for example, (C2F5)2P(O)OH] to generate novel, highly Lewis acidic bismuth(III) perfluoroalkylphosphinates of the type PhxBi[RF2PO2]3?x(x=0, 1, 2) (RF=-C2F5, -C4F9). The first bismuth(V) perfluoroalkylphosphinate, Ph3Bi[(C2F5)2PO2]2, was synthesized from Ph3BiCl2and Ag[(C2F5)2PO2]. Examples for the successful application of the catalytically active bismuth(III) and bismuth(V) phosphinates in carbon–carbon bond forming reactions, such as Friedel–Crafts acylation and alkylation, Diels–Alder, Strecker and Mannich reaction, are presented.
Effect of π-accepting substituent on the reactivity and spectroscopic characteristics of triarylbismuthanes and triarylbismuth dihalides
Rahman, A.F.M. Mustafizur,Murafuji, Toshihiro,Ishibashi, Motoko,Miyoshi, Youhei,Sugihara, Yoshikazu
, p. 3395 - 3401 (2007/10/03)
Competitive chlorination of p-substituted triarylbismuthanes 1 [(p-XC6H4)3 Bi; a: X = OMe, c: Cl, d: CO2Et, e: CF3, f: CN, g: NO2] and trimesitylbismuthane (2,4,6-Me3C6H2) 3Bi 1h by sulfuryl chloride was carried out against 1b (X = H) and the effect of these substituents on the formation of triarylbismuth dichlorides 2 was studied. The relative ratios 2/2b decreased with increasing electron-withdrawing ability of the substituents (2a/2b = 53/47, 2c/2b = 33/67, 2d/2b = 35/65, 2e/2b = 29/71, 2f/2b = 16/84, 2g/2b = 0/100, 2h/2b = 46/54), indicating a lowering of reactivity of the lone pair on the bismuth atom. Pd-Catalyzed degradation of 2a-g and their difluorides 3 giving biaryls 4 was promoted by the electron-withdrawing p-substituents in the equatorial aryl groups but suppressed by the more electronegative fluorine atoms in the apical positions. This is in fairly good accord with the stability of the trigonal bipyramidal geometry. The 13 study of 1-3 showed that the signals due to the ipso carbons (C1) attached to the bismuth atom shift downfield with increasing electron-withdrawing nature of the p-substituents. No such tendency was observed in other aromatic ring carbons. The electronic effect on the C1 atoms, similar to that on the chlorination of 1 and degradation of 2 and 3, indicates the significant participation of the C1 atoms in these reactions through the Bi-C1 bonds.
Unexpected Formation of Triarylbismuth Diformates in the Oxidation of Triarylbismuthines with Ozone at Low Temperatures
Suzuki, Hitomi,Ikegami, Tohru,Matano, Yoshihiro,Azuma, Nagao
, p. 2411 - 2416 (2007/10/02)
Oxidation of triphenylbismuthine 1 with ozone in toluene at -78 deg C gave, unexpectedly, a high yield of triphenylbismuth diformate 3, which was also obtainable as a minor product by a similar oxidation in ethyl acetate and acetone.An X-ray crystallographic study revealed that compound 3 has C2 symmetry, the geometry around the bismuth atom being best described as a distorted trigonal bipyramid as a result of strong intramolecular interaction between the bismuth and carbonyl oxygen atoms.Treatment of compound 3 with aqueous sodium acetate or halides readily converted it into the corresponding triphenylbismuth diacetate 5 or dihalides 7 - 9.
