995-32-4Relevant articles and documents
4-(diethoxy-phosphoryl)-2-methyl-but-2-enoate preparation method
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Paragraph 0076; 0077, (2020/01/25)
The invention discloses a 4-(diethoxy-phosphoryl)-2-methyl-but-2-enoate preparation method, which comprises: (a) carrying out an oxidation reaction on a pyruvic aldehyde aqueous solution to obtain a pyruvic acid/pyruvate aqueous solution; and (b) carrying out a reaction on the pyruvic acid/pyruvate aqueous solution and tetraethyl ethylene diphosphate, and performing an esterification reaction withan alcohol to obtain 4-(diethoxy-phosphoryl)-2-methyl-but-2-enoate. The method of the invention has advantages of cheap and easily available raw materials, simple operation of each step, high yield of the whole route, and high industrial application value.
Tri-n-butylphosphine-Catalyzed Phosphonoethylation Reactions of Hydrophosphoryl Compounds
Il’in,Antonova,Khusainova,Galkin
, p. 2207 - 2211 (2020/01/08)
An efficient method for the synthesis of 1,2-bisphosphoryl compounds based on the addition of hydrophosphoryl derivatives to O,O-diethyl vinylphosphonate was developed. The reaction proceeds in mild conditions under catalysis with tri-n-butylphosphine and leads to the formation of the corresponding target products with high yield.
A Universally Applicable Methodology for the Gram-Scale Synthesis of Primary, Secondary, and Tertiary Phosphines
Rinehart, N. Ian,Kendall, Alexander J.,Tyler, David R.
supporting information, p. 182 - 190 (2018/02/06)
Although organophosphine syntheses have been known for the better part of a century, the synthesis of phosphines still represents an arduous task for even veteran synthetic chemists. Phosphines as a class of compounds vary greatly in their air sensitivity, and the misconception that it is trivial or even easy for a novice chemist to attempt a seemingly straightforward synthesis can have disastrous results. To simplify the task, we have previously developed a methodology that uses benchtop intermediates to access a wide variety of phosphine oxides (an immediate precursor to phosphines). This synthetic approach saves the air-free handling until the last step (reduction to and isolation of the phosphine). Presented herein is a complete general procedure for the facile reduction of phosphonates, phosphinates, and phosphine oxides to primary, secondary, and tertiary phosphines using aluminum hydride reducing agents. The electrophilic reducing agents (iBu)2AlH and AlH3 were determined to be vastly superior to LiAlH4 for reduction selectivity and reactivity. Notably, it was determined that AlH3 is capable of reducing the exceptionally resistant tricyclohexylphosphine oxide, even though LiAlH4 and (iBu)2AlH were not. Using this new procedure, gram-scale reactions to synthesize a representative range of primary, secondary, and tertiary phosphines (including volatile phosphines) were achieved reproducibly with excellent yields and unmatched purity without the need for a purification step.
Preparing method of 2,6 11,15-tetramethyl2,4,6,8,10,12,14hexadecene heptaene dialdehyde
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Paragraph 0052; 0053; 0057; 0058; 0062; 0063, (2017/09/02)
The invention provides a preparing method of 2,6,11,15-tetramethyl 2,4,6,8,10,12,14 hexadecene heptaene dialdehyde. The preparing method comprises the first step of using 1,2-dihalogenated ethane as a raw material, making 1,2-dihalogenated ethane react with triethyl phosphite under the effect of a catalyst through Michaelis-Arbuzov to obtain tetraethyl ethylenebisphosphonate; the second step of making phosphonate react with pyruvic aldehyde dimethyl acetal under an alkali effect and through Horner-Wadsworth-Emmons to obtain 3-methyl-4,4-dimethoxy-2-butylene-1-diethyl phosphate; the third step of making 3-methyl-4,4-dimethoxy-2-butylene-1-diethyl phosphate directly react with 2,7-dimethyl-2,4,6-octatriene-1,8-dialdehyde through a 'one pot method' without separation to obtain 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-hexadecene heptaene dialdol methanol; the fourth step of making the acetal compound be subjected to hydrolysis protection under an acid condition to obtain the target compound 2,6,11,15-tetramethyl 2,4,6,8,10,12,14 hexadecene heptaene dialdehyde. According to the 'one pot method' processing technology, the raw materials are easy to obtain, and the preparing method is simple and coherent, simple in operation, mild in condition, good in yield, less in three wastes, and is thus suitable for industrialized production.
Flexible diphosphonic acids for the isolation of uranyl hybrids with heterometallic UVI = O - ZnII cation-cation interactions
Tian, Tao,Yang, Weiting,Wang, Hao,Dang, Song,Sun, Zhong-Ming
supporting information, p. 8288 - 8290 (2013/09/02)
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.
In vitro antitumor activity of the water soluble copper(I) complexes bearing the tris(hydroxymethyl)phosphine ligand
Marzano, Cristina,Gandin, Valentina,Pellei, Maura,Colavito, Davide,Papini, Grazia,Lobbia, Giancarlo Gioia,Del Giudice, Elda,Porchia, Marina,Tisato, Francesco,Santini, Carlo
, p. 798 - 808 (2008/09/19)
Monocationic hydrophilic complexes [Cu(thp)4]+ 3 and [Cu(bhpe)2]+ 4 were synthesized by ligand exchange reactions starting from the labile [Cu(CH3CN)4][PF 6] precursor in the presence of an excess of the relevant hydrophilic phosphine. Complexes 3 and 4 were tested against a panel of several human tumor cell lines. Complex 3 has been shown to be about 1 order of magnitude more cytotoxic than cisplatin. Chemosensitivity tests performed on cisplatin and multidrug resistance phenotypes suggested that complex 3 acts via a different mechanism of action than the reference drug. Different short-term proliferation assays suggested that lysosomal damage is an early cellular event associated with complex 3 cytotoxicity, probably mediated by an increased production of reactive oxygen species. Cytological stains and flow cytometric analyses indicated that the phosphine copper(I) complex is able to inhibit the growth of tumor cells via G2/M cell cycle arrest and paraptosis accompanied with the loss of mitochondrial transmembrane potential.
Palladium-catalyzed cross-coupling reactions of organocopper derivatives of methylphosphonic esters and amides with aryl and hetaryl iodides
Lukashev,Tarasenko,Beletskaya
, p. 172 - 178 (2007/10/03)
Copper derivatives of methylphosphonic amides are sufficiently stable thermally and can be used in palladium-catalyzed arylation reactions resulting in synthesis of previously unknown aryl- and hetaryl-methylphosphonic tetramethyldiamides in high yields.
Iodine atom transfer addition reaction of 1-iodoalkyl phosphonates to alkenes in the presence of α,α′-azoisobutyronitrile (AIBN): Mechanistic aspects
Balczewski,Mikolajczyk
, p. 659 - 663 (2007/10/03)
The objectives of this work were to elucidate the mechanistic pathway of the title reaction, which constitutes the first example of a radical iodine atom transfer addition reaction of non-fluorine-containing phosphonates, and to determine whether 2-iodo-2-methylpropionitrile, 8, can serve as a competing iodine donor with the starting diethyl 1-iodoalkyl phosphonates, 1a,b. The title reaction was found to proceed with AIBN as the sole radical initiator, not requiring poisonous tin reagents as co-initiators, and gave diethyl 3-iodoalkylphosphonates 3a-e (the final products of the propagation step, isolated in 59-95% yield), tetramethylsuccinodinitrile, 9, diethyl methylphosphonate, 4 and tetraethyl ethylenebisphosphonate 5 (all termination products, 0-10% yields). The radical character of this reaction was demonstrated using TEMPO as a radical trap. 8 (the intermediate of the initiation step), synthesized independently from AIBN and iodine, caused complete inhibition of the reaction when added to the reaction mixture, indicating that it does not behave as an iodine donor in the transfer stage, but rather as an inhibitor.
Kinetics of the synthesis of tetraethylethylenediphosphonate through NMR study
Azzouz, Abdelkrim,Didi, Mohamed-Amine
, p. 309 - 313 (2007/10/03)
The synthesis of tetraethylethylenediphosphonate (TEEDP) was investigated by means of 1H-NMR technique. The alkylenation process occurs via two steps. Some aspects of the reaction kinetics were discussed. The second step is ca. 1.7 times slower than the first one. TEEDP was synthesized via the intermediate formation of bromoethyl-diethylphosphonate. The first step is a 1st order reaction with respect to each reagent. Small TEEDP amounts were yielded in the first step suggesting the further reaction of the intermediate product with triethylphosphite. For both steps, the formation of the phosphonium ions (I and II) occurs more quickly than their decompositions.
High yield synthesis of tetraethyl alkylenediphosphonates via the Michaelis-Arbuzov reaction
Griffith, Julie A.,McCauley, David J.,Barrans Jr., Richard E.,Herlinger, Albert W.
, p. 4317 - 4323 (2007/10/03)
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.
