- Selective P?C(sp3) Bond Cleavage and Radical Alkynylation of α-Phosphorus Alcohols by Photoredox Catalysis
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Herein the first P?C(sp3) bond cleavage and radical alkynylation of α-phosphorus alcohols to construct phosphonoalkynes is reported. The phosphorus radical is generated upon P?C bond cleavage reaction via the alkoxyl radical through photoredox catalysis with cyclic iodine(III) reagents. Various arylphosphinoyl-, alkylphosphinoyl-, phosphonate-, and phosphonic amide alcohols serve as radical phosphorus precursors to construct phosphonoalkynes for the first time.
- Jia, Kunfang,Li, Junzhao,Chen, Yiyun
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p. 3174 - 3177
(2018/02/09)
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- Phosphono-replaced methyl alcohol derivative, and preparation method and application thereof
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The invention discloses a phosphono-replaced methyl alcohol derivative, and a preparation method and application thereof. The phosphono-replaced methyl alcohol derivative has the advantages that a (hetero) aryl methyl alcohol derivate serves as an initiator, and raw materials are easy to get and have great varieties; products obtained according to the preparation method have various types and wide application ranges, and serve as ligands which coordinate with rhodium to obtain various aldehydes through catalyzed synthesis; the phosphono-replaced (hetero) aryl methyl alcohol can be transformed into phosphonic compounds conveniently; the phosphonic compounds serving as photoinitiators can be widely applied to production of high polymer materials, paint, binders, adhesive tapes and the like. The preparation method has the advantages that reactions are achieved in the air, reaction conditions are mild, yield of target products is high, pollution is small, reaction operations and post-treatment processes are simple, and the preparation method is suitable for industrial production.
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Paragraph 0021; 0022
(2017/08/28)
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- Push-pull acylo-phosphine oxides for two-photon-induced polymerization
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The two-step method for the synthesis of acyl-phosphine oxides from aromatic aldehydes was optimized giving the products in 52-97% overall yield. Linear and nonlinear optical properties of series of acyl-phosphine oxides possessing substituents with different electron-donating ability were investigated. Two-photon absorption cross sections (σ2) of push-pull acyl-phosphine oxide was determined as 9GM via z-scan measurements with femtosecond laser pulses. Using acyl-phosphine oxides possessing dipolar structure as initiators, 3D nanopatterns were successfully fabricated by two-photon initiated polymerization. These compounds also initiate classical photopolymerization when excited with UV radiation.
- Nazir, Rashid,Danilevicius, Paulius,Gray, David,Farsari, Maria,Gryko, Daniel T.
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p. 7239 - 7244
(2013/10/21)
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- Phosphorus compounds as photoinitiators for radicalic polymerization
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p-Methoxybenzoyldialkylphosphonates, where alkyl = methyl, ethyl and p-methoxy-benzoyldiphenylphosphine oxide were synthesized by Michaelis-Arbuzov reaction. These compounds were used as photoinitiators for radicalic polymerization of acrylic monomers. Th
- Macarie, Lavinia,Ilia,Iliescu, Smaranda,Popa, Adriana,Dehelean,Manoviciu,Petrean,Abadie
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p. 165/[421]-173/[429]
(2007/10/03)
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- Investigations about the Electronic Influences on the Reactivity of Aroyl- and Acyldiphenylphosphanes and their Resulting Products
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The air sensitive aroyl- and acyldiphenylphosphanes RC(O)-PPh2 (2a - i) are obtained by reaction of the acyl chlorides RC(O)Cl (1a - i) with (CH3)3Si-PPh2 in petroleum ether.On access of water 2a - i are hydrolysed immediately.Starting from η5-C5H5Mn(CO)2THF (3x), BrMn(CO)5 (3y) and 2c - f the stable complexes LnMn-PPh2-C(O)R (4cx,dx,ey,fx) are formed. 1b - d, f - i can be transformed into the phosphane oxides RC(O)-P(O)Ph2 (5b - d, f - i) by Arbusov reaction with Ph2POCH3.From the oxides 5b - d, f and water, by a one pot reaction of 2b - d, f with HP(O)Ph2 andoxygen, or by the action of HP(O)Ph2 on 5a, f, the phosphinates -CHR (6a - d, f) are formed. 6a is produced also in form of the picolinium chloride 6a'.The electronic influences of the different aroyl residues on the reactivity of the aroylphosphanes 2c, d, f are investigated on the basis of the electronic and i.r. spectra of 4cx, dx, fx.The unusual stability of the methoxy compound 5f can be traced back to the strong +M effect of the 4-methoxybenzoyl residue.
- Lindner, Ekkehard,Huebner, Dieter
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p. 2574 - 2590
(2007/10/02)
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