Synthesis of new macrocyclic aminomethylphosphines based on 4,4"-diaminodiphenylmethane and its derivatives

The reaction of bis(hydroxymethyl)phenylphosphine with 4,4"-diaminodiphenylmethane in DMF afforded 1,1",5,5"-bis[methylenedi(p-phenylene)]di(3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) (1) whose structure was established by X-ray diffraction analysis. Sulfurization and oxidation of macrocyclic tetraphosphine 1 gave rise to products 2 and 3, respectively, compound 3 being obtained as a stable hexahydrate. The reaction of bis(hydroxymethyl)phenylphosphine with bis(4-N-methylaminophenyl)methane in DMF followed by sulfurization yielded monocyclic bis{methylenedi[p-phenylene(N-methyl)aminomethyl]}di(P-phenyl)phosphine sulfide (4).     

(-)-双(薄荷基甲酰基)苯基氧化膦的合成及在自由基光聚合中的螺旋选择性

以苯基二氯化膦和薄荷基甲酸为原料, 合成了一种手性双酰基膦氧化物光引发剂(-)-双(薄荷基甲酰基)苯基氧化膦. 采用核磁共振谱、 质谱及元素分析确定了该化合物的结构, 并测定了其螺旋诱导能力. 结果表明, (-)-BMPPO在引发自由基光聚合大位阻的单体甲基丙烯酸-1-苯基二苯并环庚酯(PDBSMA)的反应中具有螺旋选择性. 所得聚合物具有高度全同结构并显示出光学活性, 说明该聚合物形成了稳定的单手性螺旋链构象. 降低单体与引发剂的投料比及提高聚合温度有利于增加反应的螺旋选择性. 在手性薄荷醇溶剂中, 由(2,4,6-三甲基苯甲酰基)二苯基氧化膦(TPO)引发单体PDBSMA的光聚合反应也具有螺旋选择性, 但螺旋选择性很小.     

Two-fragment α-adrenolytics

A method for the synthesis of hypotensive alkyl(phenyl)[ω-(N-phenylpiperazino)alkyl]-phosphine oxides by reacting alkyl(ω-haloalkyl)phenylphosphine oxides withN-phenylpiperazine was elaborated. Phenyl[γ-(N-phenylpiperazino)propyl]propylphosphine oxide reacts with alkyl halides to give [γ-(N-alkyl-N′-phenylpiperazinio)propyl]phenyl(propyl)oxophosphine halides. For Part 1 see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 488–492, March, 2000.     

The photoelectron spectrum and conformation of phenylphosphine and phenylarsine

He(I) and He(II) photoelectron spectra of phenylphosphine and phenylarsine have been investigated and assigned. The rotational barrier of the phosphino group has been investigated at the MP2/6-31G(d,p)//MP2/6-31G(d,p) and HF/6-31G(d,p)//HF/6-31G(d,p) levels of theory, and that of the arsino group at the HF/6-31G(d,p)//6-31G(d,p) levels of theory. The rotational barrier of the two molecules is nearly the same. The energy difference between the two possible conformers of the molecules is low (1.5 kJ/mol at the MP2/6-31G(d,p) level of theory), allowing nearly free rotation about the P-C bond. The photoelectron spectrum cannot be interpreted by considering the most stable rotamer, but all possible conformers should be taken into account. The present interpretation is consistent with the smalln _p - interaction concluded from other investigations. The rotational barrier ofo-phosphinophenol is significantly larger than for phenylphosphine, and the photoelectron spectrum of this compound can be interpreted by considering a single conformer, and no appreciable interaction between the -system of the ring and the phosphorus lone pair.     

Cyclic(arylene ether) oligomers containing the phenylphosphine oxide moiety

A series of cyclic(arylene ether) oligomers containing the phenylphosphine oxide moiety has been synthesized by reaction of bis(4-fluorophenyl)phenylphosphineoxide with dihydroxy compounds 1a–d as well as 1,2-dihydro-4-(4-hydroxyphenyl) (2H)phthalazin-1-one in DMF in the presence of anhydrous K₂CO₃ under high dilution conditions. These cyclic oligomers are amorphous and have high solubility in organic solvents. The MALDI-TOF-MS technique has been used as a powerful tool to analyze these cyclic systems. The cyclic(arylene ether) oligomers readily undergo anionic ring-opening polymerization in the melt at 350°C by using potassium 4,4′-biphenoxide as the initiator, affording linear, high molecular weight poly(arylene ether)s containing the phenylphosphine oxide moiety. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 519–526, 1998     

Synthesis of new linear polymers containing phosphorus atom in the main chain by the radical polyaddition: Addition polymers of phenylphosphine with 1,4-divinylbenzene or 1,4-diisopropenylbenzene and their properties

A polyaddition of phenylphosphine (PH) to 1,4-divinylbenzene (DVB) or 1,4-diisopropenylbenzene (DIPB) was carried out by radical initiations or UV irradiation at 60–80°C in toluene under a nitrogen atmosphere. The soluble polymer with higher molecular weight () was obtained in a high yield with AIBN initiator for 95 h in the presence of 5% excess of PH to DVB (monomer feed ratio [DVB]₀/[PH]₀ = 1/1.05). On the other hand, a polyaddition of PH to DIPB proceeded much slower than the case of DVB, but the high polymer was obtained in a high yield by choosing polyaddition conditions such as polyaddition temperature and initiator concentration. From ¹H-NMR, IR analyses, and phosphorus content of the polymers, it was characterized that both polymers have the alternating structure consisting of PH and DVB or DIPB units in 1 : 1 ratio. The glass transition and decomposition temperatures of both polymers under a nitrogen atmosphere were almost similar: 15–30°C and 380–385°C, respectively; but, the polymers were oxidized by heating under an atmosphere of air. The polymers had a self-extinguishing property and the polymer blend of the flammable polymers such as polystyrene and polyethylene with the phosphorus-containing polymers exhibited an excellent flame resistance. © 1994 John Wiley & Sons, Inc.     

含三苯基膦聚醚醚酮酮的结构与性能

以双[4-(对氟苯甲酰基)苯基]苯基氧化膦和对苯二酚(HQ)为单体, 合成了新型主链含三苯基膦结构的聚醚醚酮酮, 并对聚合物的结构和性能进行了表征.     

The effect of low earth orbit atomic oxygen exposure on phenylphosphine oxide-containing poly(arylene ether)s

Unoriented thin films of phenylphosphine oxide-containing poly(arylene ether)s were exposed to low Earth orbit aboard the space shuttle Atlantis (STS-51) as part of a flight experiment designated Limited Duration Candidate Exposure (LDCE 4–5). The samples were exposed to primarily atomic oxygen (!10,\7×10¹⁹ atoms/cm²). Based on post-flight analyses using atomic force microscopy, X-ray photoelectron spectroscopy, gel permeation chromatogrpahy and weight loss data, it was proposed that atomic oxygen exposure of these materials produces a phosphate layer at the surface of the samples, apparently by the reaction of atomic oxygen with the phosphorus in the polymer backbone. Ground-based oxygen plasma exposure experiments have previously shown that this phosphate layer provides a barrier against further attack by atomic oxygen [1]. The results obtained from these analyses compare favorably with those obtained from samples exposed to an oxygen plasma in ground-based exposure experiments [1]. © 1998 John Wiley & Sons, Ltd.     

Phosphonyl/hydroxyl hydrogen bonding–induced miscibility of poly(arylene ether phosphine oxide/sulfone) statistical copolymers with poly(hydroxy ether) (phenoxy resin): Synthesis and characterization

High molecular weight bisphenol A or hydroquinone‐based poly(arylene ether phosphine oxide/sulfone) homopolymer or statistical copolymers were synthesized and characterized by thermal analysis, gel permeation chromatography, and intrinsic viscosity. Miscibility studies of blends of these copolymers with a (bisphenol A)‐epichlorohydrin based poly(hydroxy ether), termed phenoxy resin, were conducted by infrared spectroscopy, dynamic mechanical analysis, and differential scanning calorimetry. All of the data are consistent with strong hydrogen bonding between the phosphonyl groups of the copolymers and the pendent hydroxyl groups of the phenoxy resin as the miscibility‐inducing mechanism. Complete miscibility at all blend compositions was achieved with as little as 20 mol % of phosphine oxide units in the bisphenol A poly(arylene ether phosphine oxide/sulfone) copolymer. Single glass transition temperatures (T_g) from about 100 to 200°C were achieved. Replacement of bisphenol A by hydroquinone in the copolymer synthesis did not significantly affect blend miscibilities. Examination of the data within the framework of four existing blend T_g composition equations revealed T_g elevation attributable to phosphonyl/hydroxyl hydrogen bonding interactions. Because of the structural similarities of phenoxy, epoxy, and vinylester resins, the new poly(arylene ether phosphine oxide/sulfone) copolymers should find many applications as impact‐improving and interphase materials in thermoplastics and thermoset composite blend compositions. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1849–1862, 1999