1809-20-7Relevant articles and documents
Way to Enforce Selectivity via Steric Hindrance: Improvement of Am(III)/Eu(III) Solvent Extraction by Loaded Diphosphonic Acid Esters
Matveev, Petr I.,Huang, Pin-Wen,Kirsanova, Anna A.,Ananyev, Ivan V.,Sumyanova, Tsagana B.,Kharcheva, Anastasia V.,Khvorostinin, Evgenii Yu.,Petrov, Vladimir G.,Shi, Wei-Qun,Kalmykov, Stepan N.,Borisova, Nataliya E.
, p. 14563 - 14581 (2021/10/12)
Hybrid donor extractants are a promising class of compounds for the separation of trivalent actinides and lanthanides. Here, we investigated a series of sterically loaded diphosphonate ligands based on bipyridine (BiPy-PO-iPr and BiPy-PO-cHex) and phenant
Copper-Catalyzed C?P Cross-Coupling of (Cyclo)alkenyl/Aryl Bromides and Secondary Phosphine Oxides with in situ Halogen Exchange
Stankevi?, Marek,Wo?nicki, Pawe?
supporting information, p. 3484 - 3491 (2021/07/22)
An efficient protocol for concurrent tandem halogen exchange/C?P cross-coupling of cycloalkenyl bromides and secondary phosphine oxides has been developed. The catalytic system is based on cheap and air-stable copper(I) iodide as the precatalyst, commercially available N,N’-dimethylethylenediamine as the ligand, and Cs2CO3 or K2CO3 as the base. The use of sodium iodide as an additive reduces the excessive use of organic bromides to near-stoichiometric by promoting the in situ transformation to the corresponding iodides. Diarylphosphine oxides undergo cycloalkenylation with 35–99 % yields and dicyclohexylphosphine oxide with 30–53 % yields. In the case of acyclic alkenyl bromides the cross-coupling products undergo conjugate addition of diphenylphosphine oxide and satisfying yields are observed only for internal olefins. In the case of aryl bromides satisfying yields (43–72 %) are observed only for sterically unhindered arenes or arenes possessing an ortho-directing group. Cycloalkenylphosphine oxides prepared in the cross-coupling reaction undergo base-catalyzed and base-promoted conjugate addition to give bis(phosphinoyl)cycloalkanes.
Reaction of sodium N-benzylideneglycinate with dialkyl chlorophosphites in the presence of water
Dimukhametov, Mudaris N.,Mironov, Vladimir F.,Islamov, Daut R.,Litvinov, Igor A.,Gnezdilov, Oleg I.,Danilova, Yuliya V.
, p. 107 - 109 (2021/02/16)
The outcome of reaction of sodium N-benzylideneglycinate containing water in its crystal lattice with dialkyl chlorophosphites depends on the mode of addition of the latter. Upon the simultaneous mixing of the reactants, 1,4-bis[α-(dialkoxyphosphoryl)benz
METHOD FOR PRODUCING ORGANOPHOSPHORUS COMPOUND
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Paragraph 0085; 0090; 0091; 0094; 0095, (2020/05/02)
PROBLEM TO BE SOLVED: To provide a method for producing an organophosphorus compound which has excellent energy efficiency without containing a halogenated alkyl or a by-product derived from a halogenated alkyl. SOLUTION: There is provided a method for producing an organophosphorus compound by reacting a trivalent organophosphorus compound represented by the following general formula (1) in the presence of a super strong acid and/or at least one acid catalyst containing a solid superstrong acid catalyst to generate a pentavalent organophosphorus compound represented by the following general formula. (where Z1 represents OR2 or R2; Z2 represents OR3 or R3; R1, R2 and R3 represent an alkyl group, an alkenyl group or the like; when R2 and R3 are an alkyl group or the like, R2 and R3 may be bonded to each other to form a cyclic structure; and R1 may be a hydrogen atom.) SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
Water determines the products: An unexpected Br?nsted acid-catalyzed PO-R cleavage of P(iii) esters selectively producing P(O)-H and P(O)-R compounds
Li, Chunya,Wang, Qi,Zhang, Jian-Qiu,Ye, Jingjing,Xie, Ju,Xu, Qing,Han, Li-Biao
supporting information, p. 2916 - 2922 (2019/06/18)
Water is found able to determine the selectivity of Br?nsted acid-catalyzed C-O cleavage reactions of trialkyl phosphites: with water, the reaction quickly takes place at room temperature to afford quantitative yields of H-phosphonates; without water, the reaction selectively affords alkylphosphonates in high yields, providing a novel halide-free alternative to the famous Michaelis-Arbuzov reaction. This method is general as it can be readily extended to phosphonites and phosphinites and a large scale reaction with much lower loading of the catalyst, enabling a simple, efficient, and practical preparation of the corresponding organophosphorus compounds. Experimental findings in control reactions and substrate extension as well as preliminary theoretical calculation of the possible transition states all suggest that the monomolecular mechanism is preferred.
Nickel-Catalyzed Hydrophosphonylation and Hydrogenation of Aromatic Nitriles Assisted by Lewis Acid
Islas, Rosa E.,García, Juventino J.
, p. 1337 - 1345 (2019/02/01)
In this paper, we describe the catalytic hydrophosphonylation of several aromatic nitriles used to synthesize α-aminophosphonates (α-APs) using commercially available trialkyl phosphites (P(OR)3, R=Et, iPr, Bu,) and simple and inexpensive nickel chloride (NiCl2.6H2O) as the catalytic precursor. The use of triethylborane (Et3B) as a Lewis acid (LA) was mandatory in order to successfully perform H-phosphite moiety incorporation at the CN bond of non-activated benzonitriles (BN) derivatives. Interestingly, when a highly activated BN such as 2,3,4,5,6-pentafluorobenzonitrile (BN-g) was employed, it was possible to perform the reaction in the absence of an LA using milder reaction conditions. Also, we found that using HP(O)(OiPr)2 as a starting material afforded the aminobisphosphonate derivative with better selectivity than using the method involving P(OiPr)3 as the initial reagent. Remarkably, when using HP(O)(OiPr)2 with an excess of Et3B, the reaction's selectivity completely changed to yield N-benzyl- benzylimine (BBI) and 2,4,5-triphenylimidazole.
Catalytic Phosphite Hydrolysis under Neutral Reaction Conditions
Oberhauser, Werner,Manca, Gabriele
supporting information, p. 4824 - 4827 (2018/05/17)
Cationic phosphametallocene-based platinum(II) aqua complexes were used as efficient precatalysts for the hydrolysis of aromatic and aliphatic tertiary phosphites under neutral reaction conditions at room temperature, leading to the selective cleavage of one P-O bond of the phosphite. NMR labeling experiments combined with stoichiometric model reactions and theoretical density functional theory calculations, performed with the appropriate model compounds, shed light on the operative catalytic cycle, which comprises intramolecular water molecule transfer to the cis-coordinated phosphite molecule.
Synthesis and structure-activity relationships study of α-aminophosphonate derivatives containing a quinoline moiety
Zhu, Xi-Feng,Zhang, Jing,Sun, Shuo,Guo, Yan-Chun,Cao, Shu-Xia,Zhao, Yu-Fen
, p. 1514 - 1518 (2017/07/17)
Two series of α-aminophosphonate derivatives containing a quinoline moiety have been designed and synthesized by introducing bioactive quinoline scaffold to α-aminophosphonate. The in vitro cytotoxic activities of target compounds were first investigated against two human cancer cell lines including Eca109 and Huh7 by MTT assay. Results revealed that most of target compounds exhibited moderate to high antitumor activities against the tested cancer cell lines and some demonstrated more potent inhibitory activities compared with Sunitinib. Among them, compounds 4b2 and 4b4 containing methyl-substituted aniline group were found to be more active than Sunitinib against both of two cancer cell lines, with IC50 in the range of 2.26?μmol/L–7.46?μmol/L.
Hydrophosphonylation of Alkynes with Trialkyl Phosphites Catalyzed by Nickel
Islas, Rosa E.,García, Juventino J.
, p. 4125 - 4131 (2017/10/09)
The use of simple and inexpensive NiCl2?6 H2O as a catalyst precursor for C?P bond formation in the presence of commercially available trialkyl phosphites (P(OR)3, R=Et, iPr, Bu, SiMe3) along with several alkynes is presented. Control experiments showed the in situ formation of (RO)2P(O)H as the species that undergo the addition into the C≡C bond at the alkynes to yield the product of P?H addition. The hydrophosphonylation of diphenylacetylene with P(OEt)3, P(OiPr)3, and P(OSiMe3)3 proceeds in high yields (>92 %) without the need of a specific solvent or ligand. This method is useful for the preparation of organophosphonates for both phenylacetylene as a terminal alkyne model and internal alkynes in yields that range from good to modest.
Method of preparing kitazin
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Paragraph 0053-0055, (2017/06/29)
The invention discloses a method for preparing iprobenfos. The method comprises the following steps: (1) by taking phosphorus trichloride and isopropanol as esterification raw materials, performing deacidification reaction, thereby preparing O,O-diisopropyl phosphite; (2) removing residual 2-chloropropane; (3) reacting O,O-diisopropyl phosphite with sulfur and sodium hydroxide at low temperature in the presence of a solvent, thereby generating O,O-diisopropyl sulfo-sodium phosphate; (4) removing the solvent and filtering; (5) reacting O,O-diisopropyl sulfo-sodium phosphate with benzyl chloride, filtering, and separating the liquid, thereby preparing iprobenfos crude raw oil; (6) washing with water, crystallizing, filtering, and removing the solvent, thereby preparing a iprobenfos active compound. According to the method, as the sodium hydroxide is adopted to prepare salt at low temperature, the decomposition of O,O-diisopropyl phosphite is reduced, the impurities are reduced, no ammonia nitrogen wastewater is generated, and as 2-chloropropane of O,O-diisopropyl phosphite is removed, the generation of a byproduct thiophosphoric acid triisopropyl ester is reduced, and the quality of iprobenfos is improved.
