The first separation and stereochemical determination of bis(α-hydroxyalkyl) phosphinic acids diastereoisomers

A separation of bis(α-hydroxyalkyl) phosphinic acid diastereoisomers is described. A novel method for the determination stereochemistry of bis(α-hydroxyalkyl) phosphinic acid diastereoisomers has been developed. The stereochemistry of one diastereoisomer was confirmed after converting to the corresponding methyl ester using trimethyl orthoformate.     

Fluorinated phosphorus compounds: Part 6. The synthesis of bis(fluoroalkyl) phosphites and bis(fluoroalkyl) phosphorohalidates

Reaction of phosphorus trichloride with tert-butanol and fluoroalcohols gave bis(fluoroalkyl) phosphites (R_FO)₂P(O)H in 42-89% yield, where R_F=HCF₂CH₂, H(CF₂)₂CH₂, H(CF₂)₄CH₂, CF₃CH₂, C₂F₅CH₂, C₃F₇CH₂, (CF₃)₂CH, (FCH₂)₂CH, CF₃(CH₃)₂C, (CF₃)₂CH₃C, CF₃CH₂CH₂, C₄F₉CH₂CH₂ and C₆F₁₃CH₂CH₂. Treatment of these with chlorine in dichloromethane gave the bis(fluoroalkyl) phosphorochloridates (R_FO)₂P(O)Cl in 49-96% yield. The chloridate (CF₃CH₂O)₂P(O)Cl was isolated in much lower yield from the interaction of thionyl chloride with bis(trifluoroethyl) phosphite. Heating the latter in dichloromethane with potassium fluoride and a catalytic amount of trifluoroacetic acid gave the corresponding fluoridate (CF₃CH₂O)₂P(O)F in 84% yield. Treatment of bis(trifluoroethyl) phosphite with bromine or iodine gave the bromidate (CF₃CH₂O)₂P(O)Br and iodidate (CF₃CH₂O)₂P(O)I in 51 and 46% yield, respectively. The iodidate is the first dialkyl phosphoroiodidate to have been isolated and characterised properly—its discovery lags behind the first isolation of a dialkyl phosphorochloridate by over 130 years. The fluoroalkyl phosphoryl compounds are generally more stable than known unfluorinated counterparts.     

Synthesis and characterization of [Zn(2,2′-bipy)]2(H2PO3)4: A neutral zinc phosphite cluster containing ZnO3N2 and H2PO3 units

The hydrothermal synthesis, crystal structure and some properties of a zinc phosphite with a neutral cluster, [Zn(2,2′-bipy)]₂(H₂PO₃)₄, are reported. This compound crystallizes in the triclinic system of space group P-1 (No. 2), a=8.3067(5) Å, b=8.9545(4) Å, c=10.0893(6) Å, α=95.448(2)°, β=99.7530(10)°, γ=103.461(2)°, V=712.23(7) ų, Z=1. The cluster consists of 4-membered rings formed by alternating ZnO₃N₂ square pyramids and H₂PO₃ pseudo pyramids, with two “hanging” H₂PO₃ groups attached to each of the Zn centers. The clusters are linked together by extensive multipoint hydrogen bonding involving the phosphite units to form a sheet-like structure. This compound represents the first example of zinc phosphite with P---OH bonds. An intense photoluminescence was observed from this compound upon photoexcitation at 388 nm.     

亚磷酸三乙酯硫化反应历程的GC/MS研究

用气相色谱-质谱联用技术研究了亚磷酸三乙酯和亚磷酸三苯酯与硫反应的机理.研究证明,硫与三价磷化合物的反应只发生在液相状态.     

Synthesis and Characterization of a Purely Inorganic Open‐framework Bimetallic Phosphite with Intersecting 12‐ and 16‐membered Ring Channels

A new three‐dimensional open‐framework cobalt‐zinc phosphite [Co(H₂O)₄Zn(HPO₃)₂]·H₂O ( 1 ), has been prepared under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction, XRD, IR and SQUID magnetometer. The compound crystallizes in the triclinic space group with a = 7.552(5), b = 7.671(5), c = 9.443(5) Å, α = 88.538(5)°, β = 89.109(5)°, γ = 87.056(5)°, V = 546.1(6) ų, Z = 2. The structure of 1 consists of corner‐shared (cs) four‐membered‐ring chains formed by alternating ZnO₄ tetrahedra and HPO₃ pseudopyramids, which are further linked through CoO₂(H₂O)₄ octahedra giving rise to a three‐dimensional (3‐D) neutral open‐framework with intersecting 12‐ and 16‐MR channels. The synthesis of system required the presence of L‐histidine which is not incorporated into the structure of the product. It is noteworthy that compound 1 represents the only known example of purely inorganic open‐framework cobalt‐zinc phosphite.     

Reactions of 4-ethoxy-l,l,l-trifluoro-3-buten-2-one with phosphorous nucleophiles: Diethyl phosphite, tributyl phosphine and tris(diethylamino) phosphine

The reaction of (E)-4-ethoxy-l,l,l-trifluoro-3-buten-2-one EtOCHCHCOCF₃1 with diethyl phosphite (EtO)₂P(O)H 2 afforded a 1:1 cis- and trans-mixture of diethyl(l-trifluomethyl-3-ethoxy)allyl-phosphate EtO-CHCH-CH(CF₃)OP(O)(OEt)₂3 via the 1,2-λ⁵-oxaphosphol-4-ene intermediate. While tributyl phosphine Bu₃P added to 1 giving the double addition product Bu₃P⁺CH₂-C⁻(COCF₃)-CHCH-COCF₃5. Its resonance structure was fully identified by spectral methods and single crystal X-ray diffraction analysis. More strong phosphorous nucleophile tris(diethylamino) phosphine (Et₂N)₃P reacted with 1 to give the known compound (E)-4-(diethylamino)-l,l,l-trifluoro-3-buten-2-one Et₂N-CHCH-COCF₃10 in good yield.     

Electromembrane extraction of polar basic drugs from plasma with pure bis(2-ethylhexyl) phosphite as supported liquid membrane

Electromembrane extraction (EME) of polar basic drugs from human plasma was investigated for the first time using pure bis(2-ethylhexyl) phosphite (DEHPi) as the supported liquid membrane (SLM). The polar basic drugs metaraminol, benzamidine, sotalol, phenylpropanolamine, ephedrine, and trimethoprim were selected as model analytes, and were extracted from 300 μL of human plasma, through 10 μL of DEHPi as SLM, and into 100 μL of 10 mM formic acid as acceptor solution. The extraction potential across the SLM was 100 V, and extractions were performed for 20 min. After EME, the acceptor solutions were analyzed by high-performance liquid chromatography-ultraviolet detection (HPLC-UV). In contrast to other SLMs reported for polar basic drugs in the literature, the SLM of DEHPi was highly stable in contact with plasma, and the system-current across the SLM was easily kept below 50 μA. Thus, electrolysis in the sample and acceptor solution was kept at an acceptable level with no detrimental consequences. For the polar model analytes, representing a log P range from −0.40 to 1.32, recoveries in the range 25–91% were obtained from human plasma. Strong hydrogen bonding and dipole interactions were probably responsible for efficient transfer of the model analytes into the SLM, and this is the first report on efficient EME of highly polar analytes without using any ionic carrier in the SLM.     

Multicatalytic synthesis of 1,2-dihydroisoquinolin-1-ylphosphonates via a tandem four-component reaction

A tandem four-component reaction of 2-bromobenzaldehyde, alkyne, amine, and diethyl phosphite catalyzed by the combination of palladium and copper salts provides a facile and efficient route to 1,2-dihydroisoquinolin-1-ylphosphonate. A cascade Sonogashira-intramolecular cyclization-nucleophilic addition may be involved in the reaction process.     

亚磷酸三苯酯臭氧化合物分解产生单重态氧的研究

This letter reports a study on producing gas-phase O2（a1Δ）by decomposition of triphenyl phosphite ozonide（（C6H5O）3 PO3,TPPO3）under a number of reaction conditions. For the first time,the cooperative emission at wavelengths 634 and 703 nm of O2（a1Δ）generated by TPPO3 decomposition are observed. Specifically,under the condition of catalyzed decomposition by pyridine of TPPO3 solution in CFCl3 at low temperature,the emission spectrum is the same as that from the basic hydrogen peroxide plus chlorine reaction. This shows the feasibility of developing a new source for singlet delta oxygen. However,in the experiments of spontaneous decomposition of solid TPPO3 and thermal decomposition of TPPO3 solution on a high temperature surface,the spectra have a wide emission background around the 634 and 703 nm peaks,which indicates the production of some excited species than O2（a1Δ）. Besides,there are about 2%-3% CO and 1. 5%-2% CO2 in the gaseous products together with a small amount of insoluble in acetone solid product,which imply that other than the formation of O2（a1Δ）and TPPO by unimolecular decomposition of TPPO3,more complicated reactions may take place. The study of the reaction mechanism,the optimization of the expertise of O2（a1Δ）generation by TPPO3 decomposition as well as measurement of absolute concentration of O2（a1Δ）are under way.     

Asymmetric Synthesis of α-Amino Phosphonic Acids Employing the Condensation of Nitrones with Phosphite Derivatives

Abstract

Chiral α-amino phosphonic acid derivatives were synthesized by condensing an enantiomerically homogeneous diazasilyl phosphite with a series of prochiral nitrones. The reactions proceed under mild conditions with moderate to high enantioselectivities and good yields.