1,4-二苯基-1,3-丁二烯的氰基蒽敏化光氧化反应

某些不能与单线态氧(~1O_2)起反应的烯烃、炔烃、硫醚和环氧化合物,在以氰基蒽为敏化剂的条件下,可发生经由光敏电子转移机理的氧化反应.近年来,Santamaria 等,Foote 等和我们都在研究这类反应.本文报道以9,10-二氰基蒽(DCA)为敏化剂、反,反-1,4-二苯基-1,3-丁二烯为反应物的电子转移光敏氧化反应,并讨论了反应机理.     

有机磷化合物的研究(LVII)——二苯(氧)基氯膦对肟基的自由基加成——合成1-氨基取代三烷基氧化膦及烷基膦酸酯的新途径

二苯基氯膦或二苯氧基氯膦对醛(酮)肟的反应可作为合成1-氨基烷基二苯基氧化膦或1-氨基烷基膦酸二苯酯的新方法,具有条件温和、操作方便及得率高的优点。EPR研究结果揭示了这类反应属自由基机理。     

共轭二烯在硅胶表面上的光氧化反应

本文选用了trans, trans-1,4-二苯基-1,3-丁二烯(DPB)分别与单重量态氧(^1O2)敏化剂亚甲基蓝(MB)或贫电子敏化剂9,10-二氰基蒽(DCA)共同吸附在硅胶表面上, 通过其光敏氧化反应来比较DPB吸附在硅胶表面与DPB在溶液中反应的异同.     

(2S,5S)-1-氮-3-氧-2,4,4-三苯基二环[3.3.0]辛烷衍生物的合成及表征

从不对称催化反应问世以来,人们一直在寻找高效、廉价、易制备的手性催化剂。Himto Nakano等人用(S)-二苯基脯胺醇和2-二苯膦基苯甲醛合成了手性化合物(2S,5S)-1-氮-3-氧-2-二苯膦基苯-4,4-二苯基二环[3．3．0]辛烷,并与钯络合来催化不对称反应。     

6,6‘—二（二苯基氧化膦甲基）—1,1’—氮氧化—2,2‘—联吡啶与…

合成了硝酸铒与四功能团含磷萃取剂６，６’－二（二苯基氧化膦甲基）－１，１’氮氧化－２，２’－联吡啶的配合物。用四圆衍射仪测定了配合物的晶体结构。金属离子周转的配位水分子已全部被取代。     

瑞香狼毒中灭蚜活性物质的结构鉴定

报道从瑞香狼毒(StellerachamaejasmeL.)根中发现分离到2个显示高农药活性化合物，能有效杀灭农业重要害虫蚜虫，经波谱及元素分析，确定其结构为1,5-二苯基-1-戊酮(1)和1,5-二苯基-2-烯-1-戊酮(2)。     

过硼酸钠对于有机物的氧化作用的研究 I:过硼酸钠对于芳胺和芳硫醚的氧化作用

研究了用过硼酸钠氧化邻位和对位硝基苯胺. 把胺基氧化成硝基、过硼酸钠还能氧化4-氨基-4'-硝基二苯基硫醚和2-氨基-2'-硝基二苯基硫醚. 得到4,4'-二硝基二苯砜和2,2'-二硝基二苯亚砜.     

1,2-二苯基乙烯基膦钯(Ⅱ)催化的 Sonograshira交叉偶联反应

合成了含有大位阻和富电子膦配体的1,2-二苯基乙烯基膦配体, 并研究了以1,2-二苯基乙烯基膦配体和二氯化二苯腈合钯(Ⅱ)为催化剂催化的Sonograshira交叉偶联反应.     

反式9, 10-二氢-9, 10-二苯基-9, 10-菲二醇包结性能的研究

合成了一种具有螯形结构的反式-9, 10-二氢-9, 10-二苯基-9,10-菲二醇(1)作为主体分子。它能与许多有机小分子化合物, 诸如DMF, DMSO, 吡啶, 哌啶, 喹啉, 异喹啉等形成包结化合物。本文还报道了这些包结化合物的IR, 粉末XRD的表征, 用^1H NMR谱测定了它们的分子摩尔比。DMF包结物的单晶四圆X衍射结果表明主体分子1与客体分子形成的包结物为配位笼状包合物。     

Complex Pd( Ⅱ ) with Vinyiphosphine and Its Application in Sonograshira Cross Coupling Reaction

合成了含有大位阻和富电子膦配体的1,2-二苯基乙烯基膦配体,并研究了以1,2-二苯基乙烯基膦配体和二氯化二苯腈合钯(Ⅱ)为催化剂催化的Sonograshira交叉偶联反应.     

THE DIELS-ALDER REACTION OF DIPHENYL(1,2-PROPADIENYL)PHOSPHINE OXIDE AND DIPHENYL(1-PROPYNYL)PHOSPHINE OXIDE WITH CYCLOPENTADIENE

The Diels-Alder reaction of diphenyl(1,2-propadienyl)phosphine oxide 1 and diphenyl(1-propynyl)phosphine oxide 2 with cyclopentadiene is reported. 1 reacts smoothly at room temperature in the presence of one equivalent of aluminum trichloride to give the corresponding adducts endo 3a and exo 3b (90:10 ratio) whose structure was attributed on the basis of their ¹³C NMR spectra, whereas 2 is a poor dienophile, affording the corresponding adduct in low yield even under harsh conditions.     

Synthesis of diphenyl[alkyl(aryl)trimethylsiioxymethyl]phosphines

A series of previously unknown diphenyl[alkyl(aryl)trimethylsiloxymethyl]phosphines was prepared by the reaction of diphenyl(trimethylsilyl)phosphine with carbonyl compounds. The first complexes of these ligands with palladium chloride were prepared.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 754–756, April, 1994.     

Molecular structure of (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide. Synthesis of (3,5-diallylisocyanuratomethyl)phosphine sulfides

X-Ray study of the (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide showed that the phosphorylmethyl group is bonded to the nitrogen atom of the cycle. Reaction of the tris(chloromethyl)phosphine sulfide with sodium diallylisocyanurate gave (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide, and treatment of the tris(3,5-diallylisocyanuratomethyl)phosphine oxide with phosphorus pentasulfide gave a tris(3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1446–1448, August, 1993.     

Synthesis and characterization of arylene ether imide reactive oligomers and polymers containing diaryl alkyl phosphine oxide groups

The diamine monomer bis(m-aminophenyl) methyl phosphine oxide (DAMPO) was synthesized via nitration and reduction of diphenyl methyl phosphine oxide. Rigorous purification of this monomer enabled its utilization in the synthesis of high molecular weight poly(ether imide)s. Both thermoplastic materials and thermosetting systems, endcapped with either phthalic or phenylethynylphthalic anhydride, respectively, have been produced. Major emphasis has been placed on polyimides derived from 2,2′-bis(4-(3,4-dicarboxyphenoxy) phenyl) propane dian- hydride, also known as bisphenol-A dianhydride, or BPADA. High molecular weight homo- and copolyimides based on BPADA/DAMPO had glass transition temperature values in the range of 215–223°C, and were totally amorphous. They displayed higher modulus and tensile strength values than the polyetherimide control based on meta-phenylene diamine and also generated high TGA char yields in air. Phenylethynyl crosslinkable materials were effectively cured at 380°C to produce networks that are ductile, very solvent resistant and also generate high char yields, which suggest their possible utilization in fire resistant matrix systems. © 1998 John Wiley & Sons, Ltd.     

α-(2-噻唑基脲基)膦酸二苯酯的合成

报道了一种简便的合成取代脲基膦酸酯的通用的新方法。在二氯甲烷中,三乙胺为缚酸剂的条件下,α-氨基膦酸二苯酯与三聚光气反应形成α-异氰酸基膦酸酯2,2不经分离,直接与2-氨基(苯并)噻唑加成得到α-(2-噻唑基脲基)膦酸二苯酯3,产率55.0%-88.9%。     

Electrophilic and Nucleophilic Addition Reactions of α,β-Unsaturated Diphenylphosphoryl Compounds

Russian Journal of Organic Chemistry - Procedures were developed for the synthesis of diphenyl(prop-1-en-1-yl)phosphine oxide and cyclohex-1-en-1-yl(diphenyl)phosphine oxide by alkaline hydrolysis...     

Reactions of polystyryllithiums and model lithium carbanions with 9,10‐bis(halomethyl)anthracenes

The direct and nearly quantitative incorporation of 9,10‐anthracenylidene (AN) chromophores into polystyrene occurred via the reaction of polystyryllithium (PSLi) with 9,10‐bis(chloromethyl)anthracene (BCMA) at ?78 °C in tetrahydrofuran (THF)/ hexane containing between 30 and 40 vol % hexane. Although the reaction of PSLi and BCMA or 9,10‐bis(bromomethyl)anthracene (BBMA) in THF at ?78 °C gave nearly quantitative coupling, typically only 30–50% AN incorporation was observed, as determined by ultraviolet–visible spectrometry. Model coupling reactions of 3,3‐dimethyl‐1,1‐diphenyl‐1‐lithiobutane, (1,1,2,2‐tetramethyl)propylcyclopentadienyllithium, 9‐methylfluorenyllithium, and triphenylmethyllithium with BCMA or BBMA at ?78 °C in THF in nearly all cases gave several AN‐containing coupling products. This was consistent with lithium–halogen exchange leading to the linking of multiple AN groups. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3121–3129, 2001     

Miscibility and morphologies of poly(arylene ether phenyl phosphine oxide/sulfone) copolymer/vinyl ester resin mixtures and their cured networks

Nonreactive bisphenol A‐based poly(arylene ether triphenyl phosphine oxide/diphenyl sulfone) statistical copolymers and a poly(arylene ether triphenyl phosphine oxide) homopolymer, each having a number‐average molecular weight of about 20 kg/mol, were synthesized and solution‐blended with a commercial dimethacrylate vinyl ester resin. Free‐radical cured systems produced morphologies that were a function of both the amount of phosphonyl groups and the weight percentage of the copolymers. For example, highly hydrogen‐bonded poly(arylene ether phenyl phosphine oxide) homopolymer/vinyl ester resin mixtures were homogeneous in all proportions both before and after the formation of networks. Copolymers containing low amounts (≤30 mol %) of the phosphonyl groups displayed phase separation either before or during cure. The phase‐separated cured materials generally had phase‐inverted morphologies, such as a continuous thermoplastic copolymer phase and a particulate, discontinuous vinyl ester network phase, except for systems containing a very low copolymer content. The resin modified with a copolymer containing 30 mol % phosphine oxide comonomer showed improved fracture toughness, suggesting the importance of both phase separation and good adhesion between the thermoplastic polymer and the crosslinked vinyl ester filler phase. The results suggested that the copolymers with high amounts of phosphine oxide should be good candidates for interphase sizing materials between a vinyl ester matrix and high‐modulus carbon fibers for advanced composite systems. Copolymers with low amounts of phosphonyl groups can produce tough, vinyl ester‐reinforced plastics. The char yield increases with the concentration of bisphenol A poly(arylene ether phosphine oxide) content, suggesting enhanced fire resistance. The incorporation of thermoplastic copolymers sustains a high glass‐transition temperature but does not significantly affect the thermal degradation onset temperature. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2409–2421, 2000     

Synthesis and properties of phosphorus polyesters with systematically altered phosphorus environment

Monomers with phosphorus-containing substituents were incorporated into aromatic-aliphatic polyesters to develop polymeric halogen-free flame retardants as additives for poly(butylene terephthalate) (PBT). They were built into the polyester backbone of PBT substituting 1,4-butane diol as monomer by phosphorus-containing aromatic-aliphatic diols. Starting from 10-(2,5-bis(2-hydroxyethoxy)phenyl)-9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO-HQ-GE), the chemical structure of the phosphorus monomers was systematically varied resulting in new polymers with diphenyl phosphine oxide substituents and bridged phosphine oxide units. The polymers were prepared by transesterification polycondensation in the melt in lab-scale as well as in a 2.4 l-autoclave. The properties of the polyesters were determined and compared to the DOPO-based polyester with respect to the achieved molar mass and polydispersity, solid state structure, glass transition temperature, thermal stability and combustion behavior.It was found that the different phosphorus substituents lead to different glass transition temperatures. The polymers containing bridged phosphorus structural units showed higher glass transition temperatures T_g and resulted in higher char yields after thermal decomposition. Both phosphine oxide structures showed only one-step decomposition with a shoulder at the end of the step. In contrast, two separate steps were observed in the polyesters with DOPO-substituents. The results indicated that the phosphorus polyesters under discussion are suitable to adjust the flame retarding mechanism.