1638-86-4Relevant articles and documents
Co-ordination Kinetics of Some Aliphatic Amines towards the Photogenerated Transient 'CoH3'
Onishi, Masayoshi,Takaki, Isato,Hiraki, Katsuma,Oishi, Shigero
, p. 2675 - 2676 (1988)
Time-resolved adsorption spectra were observed after nitrogen-laser flash photolysis of toluene solutions of in the presence of some aliphatic amines, and second-order rate constants were evaluated for co-ordination of the amines to the co-ordinatively unsaturated transient 'CoHL3' photogenerated.The steric bulk of substituents on the amine nitrogens is a dominant factor in the magnitude of the constants.The CoHL3(amine) adducts were also formed upon continuoes photolysis with a high-pressure mercury lamp, and found to be stable at temperatures lower than -40 deg C, on the basis of their (31)P n.m.r. and visible absorption spectra.
Silver-Catalyzed Regioselective Phosphorylation of para-Quinone Methides with P(III)-Nucleophiles
Liu, Yu,Tang, Ke-Wen,Wong, Wai-Yeung,Xie, Jun,Xiong, Biquan,Xu, Shipan,Xu, Weifeng
, p. 14983 - 15003 (2021/11/12)
A simple and efficient method for the silver-catalyzed regioselective phosphorylation of para-quinone methides (p-QMs) with P(III)-nucleophiles (P(OR)3, ArP(OR)2, Ar2P-OR) has been established via Michaelis-Arbuzov-type reaction. A broad range of P(III)-nucleophiles and para-quinone methides are well tolerated under the mild conditions, giving the expected diarylmethyl-substituted organophosphorus compounds with good to excellent yields. Moreover, a series of corresponding enantiomers can be obtained by employing dialkyl arylphosphonite (ArP(OR)2) as substrates. The control experiments and 31P NMR tracking experiments were also performed to gain insights for the plausible reaction mechanism. This protocol may have significant implications for the formation of C(sp3)-P bonds in Michaelis-Arbuzov-type reactions.
Scalable Enantiomeric Separation of Dialkyl-Arylphosphine Oxides Based on Host–Guest Complexation with TADDOL-Derivatives, and their Recovery
Bagi, Péter,Fogassy, Elemér,Herbay, Réka,Holczbauer, Tamás,Keglevich, Gy?rgy,Mátrav?lgyi, Béla,Madarász, János,Székely, Gy?rgy,Varga, Bence
supporting information, (2020/03/23)
Several dialkyl-arylphosphine oxides were prepared, and the enantioseparation of the corresponding racemates was elaborated with host–guest complexation using TADDOL-derivatives. The crystallization conditions were optimized and two separate crystallization methods, one in organic solvent, and the other in water, were found to yield five examples of phosphine oxides with enantiomeric excess values higher than 94 %. A gram scale resolution was performed, and both enantiomers of the methyl-phenyl-propyl-phosphine oxide were separated with (R,R)- or (S,S)-spiro-TADDOL. The intermolecular interactions responsible for the enantiomeric recognition between the chiral host and guest molecules were investigated by single-crystal X-ray diffractional structural determinations. The similarities in the structural patterns of a few diastereomeric crystals were checked by powder X-ray diffraction, as well. Organic solvent nanofiltration (OSN) was used as a scalable technique for the decomposition of the corresponding phosphine oxide–spiro-TADDOL molecular complexes, and for the recovery of the phosphine oxide enantiomers and resolving agents.
New preparation method of first-class phenyl phosphine oxide initiator
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Paragraph 0049-0051, (2020/03/05)
The invention provides a new preparation method of a first-class phenyl phosphine oxide initiator. The method comprises the steps that (1) benzene and aluminum trichloride are added into a reaction vessel and stirred uniformly, then phosphorus trichloride is added, the temperature is slowly increased, and after a complete reaction, the temperature is reduced to room temperature; (2) a reaction mixture obtained in the step (1) is slowly added dropwise into a solvent containing a decomplexing agent, and the temperature is controlled for decomplexing; (3) a decomplexing product obtained in the step (2) is filtered to separate solids, and filtrate is subjected to pressure reduction distillation to obtain phenyl dialkoxy phosphine or diphenyl alkoxy phosphine; (4) a product obtained in the step(3) is dissolved in a benzene or methylbenzene solvent, and a trichloromethyl acetyl compound is added dropwise for a reaction; and (5) a solution obtained after the complete reaction in the step (4)is subjected to low-pressure desolvation, and light-yellow liquid or solid, namely the phenyl phosphine oxide initiator, is obtained through crystallization, suction filtering and drying. The methodhas the advantages that raw materials are easy to obtain, cost is low, operation is easy to perform, and mass production can be realized.
Efficient Synthesis of Phosphonamidates through One-Pot Sequential Reactions of Phosphonites with Iodine and Amines
Chen, Xunwei,Luo, Wenjun,Wang, Yanlin,Li, Zikang,Ma, Xiaorui,Peng, Ai-Yun
, p. 14474 - 14480 (2020/10/06)
A one-pot sequential strategy to construct phosphonamidates has been developed by generating phosphonites in situ from arylmagnesium bromides and triethyl phosphite followed by treatment with iodine and amines. A variety of phosphonamidates were obtained with good to excellent yields at room temperature from easily available materials.
Preparation of O-Protected Cyanohydrins by Aerobic Oxidation of α-Substituted Malononitriles in the Presence of Diarylphosphine Oxides
Zhang, Dapeng,Lian, Mingming,Liu, Jia,Tang, Shukun,Liu, Guangzhi,Ma, Cunfei,Meng, Qingwei,Peng, Haisheng,Zhu, Daling
supporting information, p. 2597 - 2601 (2019/04/17)
A mild, reagent-cyanide-free, and efficient synthesis of O-phosphinoyl-protected cyanohydrins from readily available α-substituted malononitriles was realized using diarylphosphine oxides in the presence of O2. Mechanistic studies indicated that in addition to the initial aerobic oxidation of the malononitrile derivative notable features of this process include the formation of a tetrahedral intermediate and a subsequent intramolecular rearrangement. The phosphinoyl-protecting group can be removed by alcoholysis or by reduction with DIBAL-H.
Aryl(dimethylaminomethyl)phosphinic Acid Esters: Syntheses, Structures, and Reactions with Halogen Hydrogen Acids, Tin Halides, and Trimethyl Halosilanes
Lutter, Michael,Jurkschat, Klaus
, p. 3481 - 3490 (2018/08/21)
This paper reports the synthesis of the aryl(iodomethyl)phosphinic acid ethyl esters, Ar(ICH2)P(O)OEt (Ar = Ph, Ar = mesityl), which, via dimethyamination, are converted to the corresponding aryl(dimethylaminomethyl)phosphinic acid ethyl esters, Ar(Me2NCH2)P(O)OEt (Ar = Ph, Ar = mesityl). Upon reaction with hydrogen chloride, compound Me2NCH2(Ph)P(O)OEt forms its hydrochloride salt as a crystalline material. Depending on the reaction conditions, treatment of Me2NCH2(Ph)P(O)OEt with SnCl2 gave either [Me2HNCH2(Ph)P(O)OEt][SnCl3] or the mixed-valent dinuclear tin salt [{Me2HNCH2(Ph)P(O)O}4SnCl2][SnCl3]2, as its dichloromethane solvate. The reaction of Me2NCH2(Mes)P(O)OEt with SiMe3I gives the diorgano bis(trimethylsiloxy)phosphinium iodide [Me2NCH2(Mes)P(OSiMe3)2]I, as its toluene solvate. In solution, it is involved in an equilibrium with Me2NCH2(Mes)P(O)OSiMe3 and SiMe3I. From the hydrolysis of [Me2NCH2(Mes)P(OSiMe3)2]I, the hydrogen iodide derivative [Me2HNCH2(Mes)P(O)OH]I was obtained as three different solvates. [Me2NCH2(Mes)P(OSiMe3)2]I reacted with SnF2 to give a product mixture from which the mixed-valent tin compound [{SnII2Me2NCH2(Mes)P(O)2}4SnIVF2]I2, was isolated. The compounds were characterized by NMR and IR spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction analysis.
Preparation method for catalytically compounding benzyl phosphonate by using basic ionic liquid
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Paragraph 0042; 0044; 0045; 0062, (2018/01/12)
The invention belongs to the technical field of organic synthesis and relates to a preparation method for benzyl phosphonate as a key intermediate of an acyl phosphine oxide type photoinitiator. According to the method, benzene, phosphorus trichloride and alkyl alcohol are taken as main raw materials and are compounded into benzyl phosphonate through two-step reaction. The preparation method is characterized in that a target product is generated through the low-temperature reaction of the dichlorophenyl phosphine and alcohol under the condition of a gemini basic ionic liquid catalyst in the second step reaction, the reaction temperature is controlled within -10 DEG C to 10 DEG C, the dichlorophenyl phosphine is dropwise added and then the mixture reacts for 0.5-7 hours under a stirring condition after the temperature is increased to 30-50 DEG C. The preparation method has the advantages of low cost, simple and convenient after-treatment, high yield, and the like, and is suitable for industrial production.
Identification of the Privileged Position in the Imidazo[1,2-a]pyridine Ring of Phosphonocarboxylates for Development of Rab Geranylgeranyl Transferase (RGGT) Inhibitors
Ka?mierczak, Aleksandra,Kusy, Damian,Niinivehmas, Sanna P.,Gmach, Joanna,Joachimiak, ?ukasz,Pentik?inen, Olli T.,Gendaszewska-Darmach, Edyta,B?azewska, Katarzyna M.
supporting information, p. 8781 - 8800 (2017/11/15)
Members of the Rab GTPase family are master regulators of vesicle trafficking. When disregulated, they are associated with a number of pathological states. The inhibition of RGGT, an enzyme responsible for post-translational geranylgeranylation of Rab GTPases represents one way to control the activity of these proteins. Because the number of molecules modulating RGGT is limited, we combined molecular modeling with biological assays to ascertain how modifications of phosphonocarboxylates, the first reported RGGT inhibitors, rationally improve understanding of their structure-activity relationship. We have identified the privileged position in the core scaffold of the imidazo[1,2-a]pyridine ring, which can be modified without compromising compounds' potency. Thus modified compounds are micromolar inhibitors of Rab11A prenylation, simultaneously being inactive against Rap1A/Rap1B modification, with the ability to inhibit proliferation of the HeLa cancer cell line. These findings were rationalized by molecular docking, which recognized interaction of phosphonic and carboxylic groups as decisive in phosphonocarboxylate localization in the RGGT binding site.
McKenna reaction - Which oxygen attacks bromotrimethylsilane?
Blazewska, Katarzyna M.
, p. 408 - 412 (2014/01/17)
The first experimental proof of the course of silylation in the McKenna reaction, one of the most widely used reactions for the synthesis of organophosphorus acids, is presented. The reaction (in acetonitrile) proceeds via an attack of the terminal oxygen from the dialkyl phosphonate on the silicon atom in bromotrimethylsilane. Isotopically enriched diethyl phenylphosphonates (Pi - 17O or Pi - 18O) were used as the model compounds. The location of the isotopic tracers was detected using 31P and 17O NMR spectroscopy.
