- Flexible diphosphonic acids for the isolation of uranyl hybrids with heterometallic UVI = O - ZnII cation-cation interactions
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A family of uranyl diphosphonates have been hydrothermally synthesized using various flexible diphosphonic acids and Zn(UO2)(OAc) 4·7H2O in the presence of bipy or phen. Single-crystal X-ray analyses indicate that these compounds represent the first examples of uranyl phosphonates with heterometallic UVI = O - Zn II cation-cation interactions.
- Tian, Tao,Yang, Weiting,Wang, Hao,Dang, Song,Sun, Zhong-Ming
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Read Online
- Turn-on fluorescence sensor for mono- and di-phosphonic acid derivatives using anthracene-based diamidine and its detection of amidinium-phosphonate and amidinium formation
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The fluorescence detection of di-phosphonic acid and mono-phosphonic acid derivatives using the anthracene-based diamidine 1 has been investigated. The diamidine 1 forms 1:1 and 1:2 complexes with the di-phosphonic acid and mono-phosphonic acid derivative
- Kusukawa, Takahiro,Nagano, Hitoshi,Nakaguchi, Keita,Takeshita, Shota,Harumoto, Yuya
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p. 465 - 476
(2018/01/03)
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- Whole ceramic-like microreactors from inorganic polymers for high temperature or/and high pressure chemical syntheses
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Two types of whole ceramic-like microreactors were fabricated from inorganic polymers, polysilsesquioxane (POSS) and polyvinylsilazane (PVSZ), that were embedded with either perfluoroalkoxy (PFA) tube or polystyrene (PS) film templates, and subsequently the templates were removed by physical removal (PFA tube) or thermal decomposition (PS). A POSS derived ceramic-like microreactor with a 10 cm long serpentine channel was obtained by an additional "selective blocking of microchannel" step and subsequent annealing at 300 °C for 1 h, while a PVSZ derived ceramic-like microreactor with a 14 cm long channel was yielded by a co-firing process of the PVSZ-PS composite at 500°C for 2 h that led to complete decomposition of the film template leaving a microchannel behind. The obtained whole ceramic-like microfluidic devices revealed excellent chemical and thermal stabilities in various solvents, and they were able to demonstrate unique chemical performance at high temperature or/and high pressure conditions such as Michaelis-Arbuzov rearrangement at 150-170°C, Wolff-Kishner reduction at 200°C, synthesis of super-paramagnetic Fe3O4 nanoparticles at 320°C and isomerisation of allyloxybenzene to 2-allylphenol (250°C and 400 psi). These economic ceramic-like microreactors fabricated by a facile non-lithographic method displayed excellent utility under challenging conditions that is superior to any plastic microreactors and comparable to glass and metal microreactors with high cost.
- Ren, Wurong,Perumal, Jayakumar,Wang, Jun,Wang, Hao,Sharma, Siddharth,Kim, Dong-Pyo
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p. 779 - 786
(2014/02/14)
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- Direct conversion of phosphonates to phosphine oxides: An improved synthetic route to phosphines including the first synthesis of methyl JohnPhos
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The synthesis of tertiary phosphine oxides from phosphonates was achieved reliably and in good to excellent yields using stoichiometric amounts of alkyl or aryl Grignard reagents and sodium trifluoromethanesulfonate (NaOTf). In the absence of the NaOTf additive, covalent coordination oligomers of magnesium and phosphorus species dominate the reaction, producing very low yields of phosphine oxide, but high conversions of the phosphonate starting material. Mechanistic studies revealed that a five-coordinate phosphorus species - not a phosphinate - is the reaction intermediate. A diverse array of phosphonates was converted to phosphine oxides using a variety of Grignard reagents for direct carbon-phosphorus functionalization. This new methodology especially simplifies the synthesis of dimethylphosphino (RPMe2)-type phosphines by using air-, water-, and silica-stable intermediates. To highlight this reaction, a new Buchwald-type ligand ([1,1′-biphenyl]-2-yldimethylphosphine, or methyl JohnPhos) and a classic bidentate phosphine, bis(diphenylphosphino)propane (dppp), were synthesized in excellent yields.
- Kendall, Alexander J.,Salazar, Chase A.,Martino, Patrick F.,Tyler, David R.
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supporting information
p. 6171 - 6178
(2015/02/19)
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- Substitution of the phosphonic acid and hydroxamic acid functionalities of the DXR inhibitor FR900098: An attempt to improve the activity against Mycobacterium tuberculosis
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Two series of FR900098/fosmidomycin analogs were synthesized and evaluated for MtDXR inhibition and Mycobacterium tuberculosis whole-cell activity. The design rationale of these compounds involved the exchange of either the phosphonic acid or the hydroxamic acid part for alternative acidic and metal-coordinating functionalities. The best inhibitors provided IC50 values in the micromolar range, with a best value of 41 μM.
- Andaloussi, Mounir,Lindh, Martin,Bj?rkelid, Christofer,Suresh, Surisetti,Wieckowska, Anna,Iyer, Harini,Karlén, Anders,Larhed, Mats
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scheme or table
p. 5403 - 5407
(2011/10/12)
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- Catalyst system and method for carbonylation
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The invention relates to a catalyst system for carbonylating olefinically or acetylenically unsaturated compounds with carbon monoxide and a nucleophile compound, containing (a) palladium; (b) a phosphine and (c) a polymer containing nitrogen which is soluble in the reaction mixture, with the exception of polyvinyl polymers with aromatic radicals containing nitrogen on the polymer chain. The invention also relates to a method for carbonylation in the presence of one such catalyst system.
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Page/Page column 9
(2008/06/13)
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- High yield synthesis of tetraethyl alkylenediphosphonates via the Michaelis-Arbuzov reaction
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A high-yield synthesis of tetraethyl alkylenediphosphonates was achieved via the Michaelis-Arbuzov reaction. Application of optimized reaction conditions for a series of homologous alkylenediphosphonates establishes the generality of the approach.
- Griffith, Julie A.,McCauley, David J.,Barrans Jr., Richard E.,Herlinger, Albert W.
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p. 4317 - 4323
(2007/10/03)
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- Medium-ring diphosphines from diphosphabicycloalkanes: stereoselective syntheses, structure and properties
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A series of 1,k+2-diphosphabicycloalkanes 2b-e are prepared by n-BuLi-promoted cyclisation of 1,ω-diphosphinoalkanes, followed by alkylation and cycloalkylation with 1,ω-dihaloalkanes.These compounds appear to be exclusively cis-isomers except 1,6-diphosphabicycloundecane 2e which is a 3:1 cis/trans mixture.Mono-quaternisation of cis-1,k+2-diphosphabicycloalkanes, followed by treatment of the mono-quaternary salts with alkyllithium or Grignard reagents produces cis-1,n-disubstituted-1,n-diphosphacycloalkanes 4 exclusively; examples containing 8-, 9- and 10-membered rings and a range of substituents on phosphorus are described.Di-quaternisation of 1,k+2-diphosphabicycloalkanes, followed by hydrolysis, yields the trans-isomers of 1,n-disubstituted-1,n-diphosphacycloalkane monooxides 6 exclusively; reduction of these with LiAlH4 in benzene gives largely trans-1,n-disubstituted-1,n-diphosphacycloalkanes 7, but is not completely stereoselective.The structure and properties of these diphosphacycloalkanes are discussed.He(I) photoelectron spectra of 1,5-diphosphabicyclooctane, 1,6-diphosphabicyclononane and 1,6-diphosphabicyclodecane show little evidence of interaction between phosphorus lone pairs, unlike the corresponding hydrazines.The medium-ring diphosphacycloalkanes, 1,5-dimethyl-1,5-diphosphacyclooctane and 1,6-dimethyl-1,6-diphosphacyclodecane also show little evidence of interaction between phosphorus lone pairs.
- Alder, Roger W.,Ganter, Christian,Gil, Michelle,Gleiter, Rolf,Harris, Christopher J.,et al.
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p. 1643 - 1656
(2007/10/03)
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- Cosmetic deodorant preparations containing alkane diphosphonic acid esters
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Alkane diphosphonic acid esters having the formula STR1 wherein R is a straight- or branched-chain alkyl radical having 1 to 6 carbon atoms; and n is an integer of 1 to 6 are deodorants in anhydrous cosmetic preparations for the suppression of body odor.
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