- Synthesis and Solubility of 5,5-Dimethyl-2-(phenyl(phenylamino)methyl)-1,3,2-dioxaphosphinane 2-oxide in Selected Solvents between 278.15 K and 347.15 K
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A flame retardant with enhanced phosphorus-nitrogen content, 5,5-dimethyl-2-(phenyl(phenylamino)methyl)-1,3,2-dioxaphosphinane 2-oxide (DPPO), was synthesized by the reaction of 5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide (DDPO) with N-benzylideneaniline. The structure of DPPO was characterized by nuclear magnetic resonance (1H NMR and 31P NMR) and Fourier transform infrared (FT-IR) spectroscopy. The thermal stability of DPPO was characterized by thermogravimetric analysis (TGA). The solubilities of DPPO were measured in different solvents including ethyl acetate, methanol, chloroform, acetonitrile, acetone, 1,2-dichloroethane, 1,4-dioxane, dichloromethane, tetrachloromethane, benzene, tetrahydrofuran, and isopropanol at temperature ranging from 278.15 to 347.15 K by the gravimetrical method. The mole fraction solubilities of DPPO in the above-mentioned organic solvents were correlated as the Apelblat equation, and the calculated values with equations shows good consistency with the experimental values. The root-mean-square deviation was less than 0.1%, and the average relative error was less than 0.04 in all of the experiments.
- Ma, Xiao,Zhao, Qianqiong,Liu, Qianwen,Xing, Yalin,Fan, Ruilan,Tian, Rongkai
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- Solubilities of 1,3,2-dioxaphosphorinane-2-methanol-α,5,5-trimethyl-α-phenyl-2-oxide in selected solvents between 278.15 k and 343.15 k
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The mole fraction solubilities of 1,3,2-dioxaphosphorinane-2-methanol-α,5,5-trimethyl-α-phenyl-2-oxide in different organic solvents including acetonitrile, acetone, ethyl acetate, 1,2-dichloroethane, methanol, ethanol, and chloroform were measured at a d
- Yuan, Yong,Fan, Rui-Lan,Guo, Lai,Chen, Cong-Yan,Zhao, Qian-Qiong
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- New synthetic route and characterisation of phosphorus and arsenic heterocyclic compounds
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Herein we report synthetic routes for the preparation of 2-chloro-1,3,2-dioxarsenane 1, O,O′-bis(5,5-dimethyl-1,3,2-dioxarsenane)-2,2-dimethyl-1,3-propanediol 3, 2-chloro-1,3,2-dioxaphosphorinane 4, and 2-fluoro-1,3,2-dioxaphosphorinane 5. The new synthetic routes described here have the advantage to be simple, very clean and to lead to the desired compounds in very good yields. Compound 2-fluoro-1,3,2-dioxarsenane 2 also was prepared in good yield and is described here for the first time. Compounds 1-5 were fully characterized on the basis of NMR spectroscopic studies. Semi-empirical structural studies have been carried out and the results show that 1 and 2 exist as a mixture of two conformers, whereas only one conformer for 4 and 5 have been found. Variable temperature 1H NMR studies reveal a fluxional behaviour for 1 and a mechanism for the inter-conversion between its two conformers is proposed.
- Matos, Robson M.,Gomes De Lima, Luiz Carlos,De Souza, Edward,Barcelos De Souza, Ana Lucia Americano,Gomes De Lima, Miriam Bernardes,Soares Raslan, Delio
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- Conformational equilibria of phosphoranes with 5-alkyl-substituted 1,3,2-dioxaphosphorinane rings attached diequatorially to five-coordinated phosphorus. Are boat/twist conformations populated?
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The conformational equilibria of 1,3,2-dioxaphosphorinanes 4-8, featuring diequatorial attachment of the ring to five-coordinate phosphorus, were perturbed by a series of substituents at C5 (Me, Ph, t-Bu). Unlike the analogous phosphoranes that feature equatorial/apical ring attachment and populate boat/twist conformations even when unbiased by ring substituents, no 1H NMR evidence could be found for population of a nonchair conformation, even in the presence of an axial 5-t-Bu (8). The failure to readily form boat/twist conformations also is contradictory to their known ease of population by 1,3,2-dioxaphosphorinanes containing three- or four-coordinate phosphorus. Both steric and stereoelectronic rationales are offered for this highly significant but hitherto unrecognized conformational property of 1,3,2-dioxaphosphorinane rings attached diequatorially to five-coordinate phosphorus. Perturbation of a chair-chair equilibrium (A ? B) was observed that allowed the determination of conformational energies (A values, kcal/mol, in C6D6) for the groups at C5: Me, 0.8; Ph, 1.6; t-Bu, 1.7. These values are similar to those for C5 substituents on 1,3-dioxane rings with the exception of 5-Ph (A value 1.0 kcal/mol for 1,3-dioxane). The similarity of the A values for the Ph and t-Bu substituents in the 1,3,2-dioxaphosphorinane ring is tentatively assigned to increased steric repulsions present when the 5-Ph is axial because of the apical P-O bond of the five-coordinate phosphorus.
- Huang, Yande,Bentrude, Wesley G.
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- Phosphate-phosphonate preparation method
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The invention relates to a phosphate-phosphonate preparation method, which comprises the following steps: performing condensation and dehydration reaction on neopentyl phosphite and alcohol phosphonate in the presence of an esterification catalyst, then adding ozone for oxidation, and distilling a solvent under reduced pressure to obtain the phosphate-phosphonate, the neopentyl phosphite being generated by hydrolyzing neopentyl phosphorochloridite. According to the method, use of a triethylamine acid binding agent is avoided, so that problems about recovery and pollution of a large amount of triethylamine hydrochloride are reduced; the mild ozone is adopted as an oxidizer, so that simplicity and convenience are ensured, explosion dangers of hydrogen peroxide are avoided, the reaction condition is mild and easy to control, and the ozone subjected to aftertreatment can be conveniently and rapidly treated directly by illumination; time for oxidation reaction is greatly shortened, the reaction temperature is low, and the purity and the yield of an obtained product are high, and are greatly improved compared with those achieved by a conventional process.
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Paragraph 0086; 0087; 0088; 0089; 0090-0093
(2019/01/08)
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- Synthese et etude conformationnelle par RMN (1H, 13C, 31P) et DFT des cycloalcoxyphosphinallenes et des hydrazones β-cycloalcoxyphosphonatees
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The addition of hydrazine and its derivatives to cycloalkoxyphosphinallenes leads to β-(5,5-dialkyl-2-oxo-1,3,2-dioxaphosphoranyl)-hydrazones in good yields. The structure of the obtained compounds were elucidated by the NMR (1H, 13C
- Salah, Nessrine,Arfaoui, Youssef,Bahri, Mohamed,Efrit, Mohamed Lotfi,Akacha, Azaiez Ben
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p. 609 - 622
(2013/07/26)
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- Allenylphosphonates/allenylphosphine oxides as intermediates/precursors for intramolecular cyclization leading to phosphorus-based indenes, indenones, benzofurans, and isochromenes
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Utilizing internally available functional groups, a simple protocol for the efficient synthesis of phosphorus-based indenes, indenones, benzofurans, and isochromenes via intramolecular cyclization of allene intermediates/precursors is generated; the latter intermediates/precursors are conveniently obtained through aldehyde-, alkylidene-, and hydroxyl-functionalized propargyl alcohols and PIII-Cl precursors. The structures of key products have been unequivocally confirmed by X-ray crystallography.
- Sajna,Kumara Swamy
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body text
p. 5345 - 5356
(2012/08/27)
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- METHOD FOR PRODUCING PHOSPHORUS COMPOUND HAVING PHOSPHATE-PHOSPHONATE BOND
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A novel process for preparing in a high purity and in a high yield phosphorus compounds having a phosphate-phosphonate bond within one molecule, along with only a small amount of a by-product, without being restricted by the kind of a phosphonate having an alcoholic hydroxyl group which is a raw material, without using a catalyst such as magnesium chloride, but only using a nitrogen-containing basic compound.
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Page/Page column 9; 11-13
(2008/06/13)
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- Cyclic chlorophosphites as scaffolds for the one-pot synthesis of α-aminophosphonates under solvent-free conditions
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New α-aminophosphonates of the type (OCH2CMe 2CH2O)P(O)CH(NHCO2R)(R′) [6a-i, 7a-e, and 8a-c] have been synthesized in high yields by a three-component reaction using (OCH2CMe2CH2O)PCl (3), benzamide (or urethane or benzyl carbamate), and an aldehyde without using any catalyst under solvent-free conditions. This route can be readily adapted for bis-aminophosphonates as well as optically active binaphthoxy α-aminophosphonates; it also tolerates the phenolic -OH group as shown by the synthesis of hydroxy functionalized aminophosphonates. Partial hydrolysis of compounds 7a-d leads to products in which the phosphorinane ring is cleaved first. Compounds (OCH2CMe2CH2O)P(O)CH[NHC(O)Ph] (9-anthryl) (6f) and optically pure (R,S)-(-)-(C20H 12O2)P(O)CH(NHCO2Et)(Ph) (14a) were characterized by X-ray crystallography.
- Swamy, K. C. Kumara,Kumaraswamy, Sudha,Kumar, K. Senthil,Muthiah
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p. 3347 - 3351
(2007/10/03)
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- 2-TRICHLOROSILYL-1,3,2-DIHETEROPHOSPHORINANES
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Synthesis, study of steric structure and chemical features of new 2-trichlorosilyl-1,3,2-diaza- and dioxaphosphorinanes are reported.The main step for the synthesis of these compounds is the reaction of the corresponding cyclic hydrides with silicon tetrachloride.Key words: 2-H-1,3,2-diheterophosphorinane; silylation; 2-trichlorosilyl-1,3,2-diaza- and -dioxaphosphorinanes; 31P and 29Si NMR data.
- Nifantyev, E. E.,Maslennikova, V. I.,Vasyanina, L. K.,Bekker, A. R.,Nesterenko, N. B.
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p. 243 - 248
(2007/10/02)
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- Dioxaphosphorinane compounds and polyolefin compositions stabilized therewith
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Disclosed are novel cyclic phosphite compounds having the formula wherein R1 is hydrogen, alkyl or aralkyl; R2 is hydrogen or alkyl; R3 is alkyl or aryl; and R4 and R5 each is alkyl. Also disclosed are polyolefin compositions stabilized with one or more of the above compounds.
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- 2-Alkyl-5,5-dimethyl-1,3,2-dioxaphosphorinan-2-ones α-Lithiated Carbanions. Synthesis, Stability, and Conformation
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The preparation and a conformational study of lithiated 2-alkyl-5,5-dimethyl-1,3,2-dioxaphosphorinan-2-ones (2) in THF-hexane are described.These anions are present as two rapidly interconverting species with the P=O bond either axial (2a) or equatorial (2e).They are thermally unstable, but can be stabilised by the presence of one equivalent of LiBr or of lithium di-isopropylamide.A 31P NMR study of the self condensation of the carbanions (2) showed that the phosphorus atom in the axial conformation (2a) is more electrophilic than in the equatorial one (2e).An X-ray structural study of 2,5,5-trimethyl-1,3,2-dioxaphosphorinan-2-one is described.
- Patois, Carl,Ricard, Louis,Savignac, Philippe
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p. 1577 - 1581
(2007/10/02)
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- DIALKYL THIOPHOSPHONATE DERIVATIVES OF TRIORGANOTIN(IV)
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The reaction of triorganotin chlorides with sodium dialkyl thiophosphites proceeds to completion on refluxing the reactants in a 1:1 molar ratio for about ten hours.Similar reactions of triorganotin chloride with dialkyl thiophosphonate do not give comparable yields in the presence of triethylamine.The products formed are colorless volatile liquids having pungent odour, are miscible with common organic solvents and are found to be monomeric.Exposure of these compounds to atmospheric oxygen the thiophosphite linkage was oxidized to a thiophosphate linkage.These complexes have been characterized by elemental analyses, molecular weight determination, IR, 1H NMR and 31P NMR spectral data.Key words: Dialkyl thiophosphonate; 2-thiono-1,3,2-dioxa-4,4',6-trimethyl-phosphorinane; triorganotin dialkyl thiophosphite.
- Nagar, P. N.
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p. 177 - 182
(2007/10/02)
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- Preparation of a 2-aralkyl-5,5-dialkyl-1,3,2-dioxaphosphorinan-2-one from 2-aralkoxy-5,5-dialkyl-1,3,2-dioxaphosphorinane
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A process for preparing a 2-aralkyl-5,5-dialkyl-1,3,2-dioxaphosphorinan-2-one by heating a 2-aralkyloxy-5,5-dialkyl-1,3,2-dioxaphosphorinane such as the novel 2-benzyloxy-5,5-dimethyl-1,3,2-dioxaphosphorinane, with a catalytic quantity of an aralkyl halide. The aralkyl halide can be recovered and recycled.
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