- Methylation of Some Cyclic Triphosphenium Ions
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Six cyclic triphosphenium ions, including examples of five-, six-, and seven-membered ring systems, have been successfully methylated by excess methyl triflate to form the corresponding di-cations. This has been unequivocally established by means of
- Dillon, Keith B.,Olivey, Richard J.
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- Methylphosphonium Tin Bromide: A 3D Perovskite Molecular Ferroelectric Semiconductor
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3D ABX3 organic–inorganic halide perovskite (OIHP) semiconductors like [CH3NH3]PbI3 have received great attention because of their various properties for wide applications. However, although a number of low-dimensional lead-based OIHP ferroelectric semiconductors have been documented, obtaining 3D ABX3 OIHP ferroelectric semiconductors is challenging. Herein, an A-site cation [CH3PH3]+ (methylphosphonium, MP) is employed to successfully obtain a lead-free 3D ABX3 OIHP ferroelectric semiconductor MPSnBr3, which shows clear above-room-temperature ferroelectricity and a direct bandgap of 2.62 eV. It is emphasized that MPSnBr3 is a multiaxial molecular ferroelectric with the number of ferroelectric polar axes being as many as 12, which is far more than those of the other OIHP ferroelectric semiconductors and even the classical inorganic perovskite ferroelectric semiconductors BiFeO3 (4 polar axes) and BaTiO3 (3 polar axes). MPSnBr3 is the first MP-based 3D ABX3 OIHP ferroelectric semiconductor. This finding throws light on the exploration of other excellent 3D ABX3 OIHP ferroelectric semiconductors with great application prospects.
- Chen, Xiao-Gang,Pan, Qiang,Song, Xian-Jiang,Xiong, Ren-Gen,Zhang, Han-Yue,Zhang, Tie,Zhang, Yi,Zhang, Zhi-Xu
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- Mass spectral study of the CWC-related S-alkyl methylphosphonochloridothioites/S,S′-dialkyl (alkyl′)methylphosphonodithioites under gas chromatography-mass spectrometry conditions
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A class of S-alkyl methylphosphonochloridothioites 3 (11 compounds), S,S′-dialkyl methylphosphonodithioites 4 (12 compounds) and S-alkyl S′-alkyl′ methylphosphonodithioites 5 (9 compounds) were synthesized and were analyzed using gas chromatography-electron ionization mass spectrometer (GC-EIMS). Generalized fragmentation pathways under experimental condition for synthesized compounds are proposed based on analysis of fragment ions of deuterated analogs and density functional theory (DFT) calculations. Results of the study were undertaken with a view to enrich the Organization for the Prohibition of Chemical Weapons (OPCW) Central Analytical Database (OCAD), which may be used for detection and identification of Chemical Weapons Convention (CWC)-related chemicals during on-site inspection and/or off-site analysis, such as OPCW proficiency tests.
- Saeidian, Hamid,Mirkhani, Valiollah,Faraz, Sajjad Mousavi,Sarabadani, Mansour,Naseri, Mohammad Taghi,Ashrafi, Davood,Mirjafary, Zohreh,Babri, Mehran
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- Method for synthesizing methyl phosphorus dichloride based on carbon microsphere loaded iron-nickel-cerium catalyst
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The invention discloses a method for synthesizing methyl phosphorus dichloride based on a carbon microsphere loaded iron-nickel-cerium catalyst. The method comprises the following steps: preparing impregnation liquid, preparing the carbon microsphere loaded iron-nickel-cerium catalyst and synthesizing the methyl phosphorus dichloride. According to the synthesis method, a carbon microsphere loaded iron-nickel-cerium catalyst is adopted, the loading amount of three elements of iron, nickel and cerium accounts for 0.2-1% of the total mass of a carbon microsphere carrier, and the molar ratio of iron-nickel-cerium atoms loaded into carbon microspheres is (49-62): (29-48): (3-9). According to the method, the reaction temperature is low, the temperature is 300-400 DEG C, the conversion rate of phosphorus trichloride is 20.4-30.1%, the yield of methyl phosphorus dichloride is 94.6-97.5%, the catalyst is solid, non-toxic and easy to separate from a reaction system, the service life is 2800-3400 hours, and 3.6-6.5 kg of methyl phosphorus dichloride can be produced by per gram of the carbon microsphere loaded iron-nickel-cerium catalyst.
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Paragraph 0014; 0016-0018; 0020-0022; 0024-0027
(2021/10/16)
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- Synthetic method for methylphosphorus dichloride
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The invention relates to a novel synthetic method for glufosinate ammonium intermediate methylphosphorus dichloride. The method is realized by the following technical solution: performing one-step reaction for 3-6 h by using aluminum powder, aluminum trichloride, chloromethane and phosphorus trichloride as raw materials at pressure of 0.3-1.0 MPa to directly obtain a ternary complex with a valencestate of +3, adding sodium chloride, and performing a reaction at 150 DEG C to obtain the methylphosphorus dichloride. According to the synthetic method adopted by the invention, the aluminum powderand the aluminum trichloride are used as the reaction raw materials, the yield can be up to 90% based on an aluminum element, and a utilization ratio of aluminum is improved; and a ternary complex reaction and a ligand reduction reaction are combined, so that the operation process is simplified, a generation amount of solid waste can be significantly reduced, and the production costs are effectively reduced.
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Paragraph 0024-0026; 0027-0029; 0030-0032; 0033-0041
(2019/05/15)
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- Method for preparing dichloro monoalkyl phosphine
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The invention discloses a method for preparing dichloro monoalkyl phosphine. When sodium chloride is used for decomplexing reaction of a binary complex of dichloro monoalkyl aluminum or alkyl aluminum sesquichloride and phosphorus trichloride, alkane solvents are added, the dissociated dichloro monoalkyl phosphine enters the alkane solvents, alkane solution of the dichloro monoalkyl phosphine and newly-generated NaAlCl4 solids are filtered and separated, mixture of the product dichloro monoalkyl phosphine and the alkane solvents can be distilled and separated and can also directly enter a next application process without separation, decomposition of traditional dichloro monoalkyl phosphine in high-temperature distillation is avoided, yield is improved, and waste residues are reduced.
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Paragraph 0060-0062
(2017/08/29)
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- PROCESS FOR PRODUCING METHYLDICHLOROPHOSPHANE
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The present invention primarily relates to a process for producing methyldichlorophosphane (MDP) by reaction of methane with PCl3 (phosphorus trichloride) in the presence of a catalytically active amount of a compound of formula SOxCl2, wherein the index x may take the value 1 (SOCl2, thionyl chloride) or 2 (SO2Cl2, sulphuryl chloride). The present invention further relates to particular mixtures that are particularly suitable for producing methyldichlorophosphane (MDP) in the context of the process according to the invention/that are formed when carrying out a process according to the invention.
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Paragraph 0062; 0067; 0068
(2017/11/16)
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- Green synthesis method of methyl phosphorus dichloride
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The invention discloses a green synthesis method of methyl phosphorus dichloride. The method comprises the following steps: by taking phosphorus pentachloride as a catalyst, heating phosphorus trichloride and phosphorus pentachloride into vapor, and preheating to 150-250 DEG C and mixing with methane and then entering a tubular reactor, and reacting for 0.1-1.0s under the conditions that the temperature is at 400-500 DEG C and the pressure is 0.3-1.2MPa, to obtain methyl phosphorus dichloride. After the catalyst is applied to methane and phosphorus trichloride to synthesize methyl phosphorus dichloride, the conversion rate of the phosphorus trichloride is effectively improved to 40%-50%, and the yield is 90%-95%; the adopted catalyst phosphorus pentachloride is decomposed into phosphorus trichloride and chlorine gas, the catalyst and the product is not required for separation, three wastes are not generated during the whole preparation, and all the materials are recycled, so that the resources are saved, the environment is beneficially protected, and the synthesis method is green.
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Paragraph 0017; 0020; 0021; 0022; 0023; 0024; 0025-0042
(2017/07/22)
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- Synthesis method of glufosinate-ammonium intermediate methylphosphorus dichloride
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The invention discloses a synthesis method of glufosinate-ammonium intermediate methylphosphorus dichloride, belonging to the technical field of synthesis of a glufosinate-ammonium intermediate. The synthesis method comprises the following steps: by using methyl chloride, aluminum trichloride and phosphorus trichloride as raw materials, carrying out reaction under the pressure of 0.5-3.0 MPa for 6.5-10 hours to obtain a ternary complex, adding aluminum powder and sodium chloride, and carrying out reaction at a certain temperature to obtain the methylphosphorus dichloride. According to the method, the phosphorus trichloride is simultaneously used as the reactant and solvent; and the reaction pressure is enhanced, so that the methyl chloride gas sufficiently reacts with the solid and liquid phases without adding any other solvent, thereby enhancing the product purity, avoiding the problems of solvent separation, recovery and the like, reducing the phosphorus trichloride recovery difficulty, and greatly lowering the production cost.
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Paragraph 0012; 0013
(2017/01/05)
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- Synthesis and Herbicidal Activities of Sodium Methyl(α-(Substituted Phenoxyacetoxy)Alkyl)Phosphinates
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A series of sodium methyl(α-(substituted phenoxyacetoxy)alkyl)phosphinates was designed and synthesized. Their structures were confirmed by IR, 1H NMR and elemental analysis, and some of them were further confirmed by MS. The results of bioassay showed that most of title compounds exhibited moderate to good herbicidal activities against the root of barnyard grass and rape at 10～100 mg/L.
- Wang, Tao,Gao, Yujiao,Peng, Hao,He, Hongwu
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p. 972 - 977
(2015/08/04)
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- Synthesis and herbicidal activity of [(Substituted Phenoxyacetoxy) (Substituted Phenyl)Methyl](Methyl) phosphinates containing fluorine
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A series of [(substituted phenoxyacetoxy)(substituted phenyl)methyl] (methyl)phos- phinates containing fluorine were designed and synthesized. All the synthesized compounds were identified by elemental analysis, IR, 1H NMR, mass spectrometry. O-methyl [(2-fluorophenoxyacetoxy)(2,4- dichlorophenyl)methyl](methyl)phosphinate was further analyzed by X-ray single-crystal diffraction. Their herbicidal activity against a set of weed species was examined. Some of the compounds showed potential herbicidal activity, which provided some indications for further studies on structure modification. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.
- Deng, Xiaoyan,Liao, Guihong,Long, Qingwu,Gao, Yujiao,Peng, Hao,He, Hongwu
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p. 663 - 671
(2013/07/26)
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- Microsynthesis and electron ionization mass spectral studies of O(S)-alkyl N,N-dimethyl alkylphosphono(thiolo)thionoamidates for Chemical Weapons Convention verification
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RATIONALE The availability of mass spectra and interpretation skills are essential for unambiguous identification of the Chemical Weapons Convention (CWC)-related chemicals. The O(S)-alkyl N,N-dimethyl alkylphosphono(thiolo) thionoamidates are included in the list of scheduled CWC-related compounds, but there are very few spectra from these compounds in the literature. This paper examines these spectra and their mass spectral fragmentation routes. METHODS The title chemicals were prepared through microsynthetic protocols and were analyzed using electron ionization mass spectrometry with gas chromatography as a MS-inlet system. Structures of fragments were confirmed using analysis of fragment ions of deuterated analogs, tandem mass spectrometry and density functional theory (DFT) calculations. RESULTS Mass spectrometric studies revealed some interesting fragmentation pathways during the ionization process, such as alkene and amine elimination and McLafferty-type rearrangements. The most important fragmentation route of the chemicals is the thiono-thiolo rearrangement. DFT calculations are used to support MS results and to reveal relative preference formation of fragment ions. The retention indices (RIs) of all the studied compounds are also reported. CONCLUSIONS Mass spectra of the synthesized compounds were investigated with the aim to enrich the Organization for the Prohibition of Chemical Weapons (OPCW) Central Analytical Database (OCAD) which may be used for detection and identification of CWC-related chemicals during on-site inspection and/or off-site analysis such as OPCW proficiency tests. Copyright
- Saeidian, Hamdollah,Babri, Mehran,Abdoli, Morteza,Sarabadani, Mansour,Ashrafi, Davood,Naseri, Mohammad Taghi
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p. 2805 - 2814
(2013/01/15)
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- Synthesis and biological activity of α-oxo-2-pyridyl methyl phosphinates
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In an attempt to discover novel compounds with high activity and low toxicity, a series of new O,O-dimethyl-α-(substituted phenoxyacetoxy)-2- pyridyl methyl phosphinates, 5a-5h, have been designed and synthesized by the reaction of substituted phenoxyacetic chloride with 1-hydroxy-2-pyridyl methyl phosphinate, The structures of all new compounds were characterized by elementary analysis, IR, 1H NMR, and MS spectroscopies. The results of preliminary bioassay indicate that most of the target compounds have excellent inhibitory activities on barnyard grass and rape. Copyright Taylor & Francis Group, LLC.
- Wang, Tao,He, Hong Wu
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scheme or table
p. 1884 - 1891
(2009/09/06)
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- Synthesis of stable N′,N′,N″,N″-tetramethylguanidine-Substituted σ4(P)- and σ3(P)-organophosphorus compounds with N-protonated P-N bonds the first σ3-phosphorus-substituted ammonium salts
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The dependence of the protolytic decomposition rate of phosphorus amides on the substituents at phosphorus is decribed. On treatment with HCl, the N′,N′,N″,N″-tetramethylguanidine(= TMG)-substituted σ4(P) compounds 5 and 9 formed salts that were protonated at the imino nitrogen atoms and were completely stable in the solid state, and surprisingly stable in solution. Even with a large excess of HCl, only the imino nitrogen atom underwent protonation, with formation of HCl2- as a counter anion, without cleavage of the P-N bond. The basicity of the imino nitrogen atom also protected σ3(P) species from electrophilic attack, and the ionic compounds 12, 14, and 20c were formed, providing examples of the first stable σ3(P) amides with one or two protonated P-N bonds. Such unusual stability is associated with steric protection by the Ph3C (= trityl) group and charge delocalization over the TMG-moiety. In contrast, MeP(TMG)2 was unstable towards HCl, whereas treatment with HSbF6 led to the phosphonium salt 24, where protonation had occurred at phosphorus. The same result was obtained when triphenylmethylphosphonous dichloride 1 was allowed to react with 3 equivalents of HTMG, forming the stable phosphonium salt 19, soluble in water, which was converted to the bicationic species 20c upon treatment with HCl. - The basicity of the tritylated phosphorus compounds was found to increase in the order 5 3N · 3 HF caused rapid conversion of compound 6 to 25, the nucleophilic attack of fluoride ion at phosphorus could not be prevented by the stabilizing effects mentioned. - All compounds were investigated by 1H- and 31P-NMR spectroscopy. The crystal structures of compounds 5, Ph3CP(=O)-(H)TMG,and 6, [5 · 2 HCl], were determined; 6 is protonated at the imino nitrogen, leading to a longer P-N bond [5: 161.6(2), 6: 168.7(2) pm], and the counterion is HCl2-. In the structure of 20c, [Ph3CP(TMG)2] · 3 HCl, the cation is protonated at both imino N atoms and the counterions are Cl- and HCl2- (one of each).
- Plack, Volker,Mu?nchenberg, Jochen,Tho?nnessen, Holger,Jones, Peter G.,Schmutzler, Reinhard
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p. 865 - 875
(2007/10/03)
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- Manufacturing method for alkyldihalogenophosphines
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A manufacturing method for an alkyldihalogenophosphine uses an alkyl halide and a trihalide of phosphorus as starting materials. A reaction product which is formed by an FC reaction is reduced by yellow phosphorus in the presence of iodine, whereby an alkyldihalogenophosphine is manufactured. A high-purity alkyldihalogenophosphine can be manufactured with a high yield by using an excess amount of a trihalide of phosphorus, which can act as a reaction solvent.
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- Preparation and -Cycloaddition of Methylthio-chlorophosphanes RP(Cl)SMe (R = Me, Et, Ph)
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The methylthio-chlorophosphanes RP(Cl)SMe are prepared in good yields (62-65percent) by condensation reactions of the corresponding dichlorophosphanes RPCl2 with methanethiol in the presence of trimethylamine (molar ratio 1:1:1). 1 and 3 have been used to produce 3-phospholene sulfides in a one-pot process by reaction with 1,3-dienes at 70 to 100 deg C.Reaction proceeds via -cycloadducts, which in suitable cases can be isolated and used for the preparation of the corresponding 3-phospholene oxides.New compounds were characterized by elemental analysis and spectroscopic investigations (NMR, MS). - Keywords: Methylthio-chlorophosphanes, 3-Phospholene Sulfides and Oxides, Mass Spectra, NMR Spectra
- Apitz, Joerg,Grobe, Joseph,Le Van, Duc
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p. 257 - 260
(2007/10/02)
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- Gas-Phase Infrared Spectra of the Unstable Phosphaalkenes CF2=PH, CF2=PCF3, and CH2=PCl: The C=P Stretching Vibration and Force Constant.
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Gas-phase infrared spectra of the unstable phosphaalkenes CF2=PH, CF2=PCF3, and CH2=PCl and their deuteriated species have been measured and vibrational assignments have been made.The C=P stretching bands are observed at 1349.5, 1350.2, and 1365.3 cm-1 for CF2=PH, CF2=PD, and CF2=PCF3, respectively, and at 979.7 and 847.9 cm-1 for CH2=PCl and CD2=PCl, respectively.Normal coordinates were treated for these molecules.For the fluorophosphaalkenes, the C=P stretching mode is highly coupled with the CF2 symmetric stretching mode; one of the coupled vibrations is shifted to higher wavenumber of about 1350 cm-1 and the other to lower wavenumber of about 730 cm-1.For CH2=PCl, the C=P stretching vibration of 979.7 cm-1 is almost negligibly perturbed by other vibrational modes, so that it gives an almost intrinsic C=P stretching wavenumber.For CD2=PCl, the C=P stretching mode is coupled largely with the CD2 scissoring mode.The band intensities of the C=P stretching vibration have also been discussed.The C=P stretching force constant was determined to be 562-668 N m-1.The values for the carbon-phosphorus force constants of the double and triple bonds are roughly two and three times, respectively, as large as the value for the single bond, and the values for the carbon-phosphorus bonds are about half the values for the corresponding carbon-nitrogen bonds.
- Ohno, Keiichi,Kurita, Eiichi,Kawamura, Masanobu,Matsuura, Hiroatsu
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p. 5614 - 5620
(2007/10/02)
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- Synthesis and transformations of phosphorus imidazolidines (1,3-diaza-2-phospholidines)
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Four new derivatives of the phosphorus imidazolidine ring system have been prepared by animation of dichlorophosphines with variously N,N′-disubstituted ethylenediamines. The nmr spectra of the N-CH3 substituted rings show a sharp doublet for these protons and a multiplet for the methylene bridge protons, while the N-phenyl derivatives show a sharp doublet for the methylene bridge protons at 60 and 100 MHz contrary to expectations on the basis of the pyramidal stereochemistry of phosphorus(III). These observations are interpreted in terms of the stereochemistry and dynamics of the diazaphos-pholidine heterocycles. The phosphorus imidazolidines are transformed to their boron analogs in an exothermic reaction with phenylboron dichloride with the release of dichlorophosphine, but the reaction is not reversible. Treatment of the phosphorus ring with arsenic trichloride yields a solid whose mass spectrum shows a peak at the highest mass corresponding to the ten-membered ring dimer of the known arsenic imidazolidine.
- Das,Zuckerman
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p. 1028 - 1030
(2007/10/08)
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