Inspired by the anti-pancreatic promising results of our novel aminated cyclopropylmethylphosphonate compounds, an in vitro anti-prostate cancer activity exploration of these compounds was carried out on human prostat...Inspired by the anti-pancreatic promising results of our novel aminated cyclopropylmethylphosphonate compounds, an in vitro anti-prostate cancer activity exploration of these compounds was carried out on human prostate cancer cell line PC-3, and showed potent inhibiting activity at low micromolar concentrations (with an IC50 of approximately 45 μM).展开更多
Buoyed by the extensive research on the wide-range biological activities of aminophosphonates, a novel class of aminated (cyclopropylmethyl)phosphor-nates compounds was synthesized from diethyl ((1-(3-chloropropyl)cyc...Buoyed by the extensive research on the wide-range biological activities of aminophosphonates, a novel class of aminated (cyclopropylmethyl)phosphor-nates compounds was synthesized from diethyl ((1-(3-chloropropyl)cyclopropyl)methyl)phosphonate and various amines in the presence of Hunig’s base. Upon biological activity screening these compounds demonstrated encouraging anti-pancreatic cancer properties at low micromolar concentrations.展开更多
Copper catalyzed asymmetric formal [3＋2] cycloaddition of propargylic esters toβ‐keto phospho‐nates for the synthesis of chiral phosphonylated 2,3‐dihydrofurans was developed. By using a bulky and structurally ri...Copper catalyzed asymmetric formal [3＋2] cycloaddition of propargylic esters toβ‐keto phospho‐nates for the synthesis of chiral phosphonylated 2,3‐dihydrofurans was developed. By using a bulky and structurally rigid tridentate ketimine P,N,N ligand, a series of optically active phosphonylated 2,3‐dihydrofurans were prepared in high yield and up to 92%ee.展开更多
A series of novel L-amino acid esters prodrugs of acyclic nucleoside phosphonates was synthesized and their anti-HBV activity was evaluated in HepG2 2.2.15 cells. Compound 1d exhibited more potent anti-HBV activity an...A series of novel L-amino acid esters prodrugs of acyclic nucleoside phosphonates was synthesized and their anti-HBV activity was evaluated in HepG2 2.2.15 cells. Compound 1d exhibited more potent anti-HBV activity and lower cytotoxicity than those of adefovir dipivoxil with EC50 and CC50 values of 0.207 μmol/L and 2530 μmol/L, respectively.展开更多
The synthesis of thirteen new compounds α - [2 - (2, 4 -dichlorophenoxy) propionyloxy] alkyl phosphonates was described. The structures of these compounds were characterized by IR, 1H-NMR and MS.
l-Acetoxy allylic phosphonates rearrange regioselectively to γ-acetoxy α,β-unsaturated phosphonates under the catalysis of Pd(0). l-Acetoxy allylic phosphonates act as the precursors of phosphonatedπ-allylic catio...l-Acetoxy allylic phosphonates rearrange regioselectively to γ-acetoxy α,β-unsaturated phosphonates under the catalysis of Pd(0). l-Acetoxy allylic phosphonates act as the precursors of phosphonatedπ-allylic cations in palladium(0) catalyzed reactions[1]. The reactions of l-acetoxy allylic phosphonates under palladium(0) catalysis with nucleophiles have been reported. 1-4 These reactions are highly regio- and stereoselective. We wish to report here the palladium(0) catalyzed reaction of l-acetoxy allylic phosphonates in the absence of a nucleophile.展开更多
Fifteen title compounds 3a-0 were synthesized by condensation of 2chloro-benzothiazole with a-hydroxyphosphonates in good yields us- ing potassium iodide/tetrabutyl ammonium bromide as catalyst.All new com- pounds hav...Fifteen title compounds 3a-0 were synthesized by condensation of 2chloro-benzothiazole with a-hydroxyphosphonates in good yields us- ing potassium iodide/tetrabutyl ammonium bromide as catalyst.All new com- pounds have been identified by ~1H-NMR,IR and elemental analysis.展开更多
A series of di-n-hexyl alkyl phosphonates with bulky substituent on phosphorus was synthesized by PTC P-alkylation using crown ether.Upon saponification of the resulting di-n-hexyl alkylphosphonates in the presence of...A series of di-n-hexyl alkyl phosphonates with bulky substituent on phosphorus was synthesized by PTC P-alkylation using crown ether.Upon saponification of the resulting di-n-hexyl alkylphosphonates in the presence of crown ether or quaternary ammonium halide, corresponding mono-hexyl esters of alkyl phosphonic acids were prepared.Ultrasonic wave, as we found, can catalyze the reaction between dialkyl phosphite & metallic sodium and hydrolysis of dihexyl alkyl phosphonates.A series of di-t-alkyl phosphinic acids were synthesized by the reaction of Grignard reagent with PCl_3 followed by oxidation with 30% H_2O_2.It was found that the reaction between dibutyl phosphite and Grignard reagent of t-alkyl chloride is a new synthetic method for the preparation of mono-esters of highly hindered alkyl phosphonic acids.展开更多
Two novel transition metal phosphonate compounds, [Co（H2BDPP）（phen）]n 1 （BDPP = p-O3PCH2（C6H4）CH2PO3, phen = 1,10-phenanthroline） and [Pb3（BCP）2]n 2 （BCP = OOC（C6H4）CH2PO3）, have been synthesized and str...Two novel transition metal phosphonate compounds, [Co（H2BDPP）（phen）]n 1 （BDPP = p-O3PCH2（C6H4）CH2PO3, phen = 1,10-phenanthroline） and [Pb3（BCP）2]n 2 （BCP = OOC（C6H4）CH2PO3）, have been synthesized and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in the monoclinic system, space group C2/c with a = 21.169（4）, b = 12.001（2）, c = 7.6211（15）A, β = 98.03（3）°, V= 1917.2（6）A^3, C20H18N2O6P2Co, Mr = 505.22, Z = 8, De= 1.737 g/cm^3, p = 1.107 mm^-1, F（000） = 1020, the final R= 0.0450 and wR = 0.1306 for 2072 observed reflections （I 〉 2σ（I）. Compound 2 crystallizes in the monoclinic system, space group C2/c with a = 4.7167（9）, b = 18.753（2）, c = 22.781（3）A, β = 91.07（3）°, V= 2014.7（14）A^, C8H6O5PPb1.5, Mr = 523.88, Z = 8, Dc = 3.454 g/cm^3, p = 25.222 mm^-1, F（000） = 1856, the final R = 0.0441 and wR = 0.1906 for 2259 observed reflections （I 〉 2σ（I）. In compound 1, the 1D chain running along the c axis is bridged by four ligands （trans- HO3PCH2C6H4CH2PO3H） in four different directions to extend the structure into a three- dimensional network. In compound 2, the Pb（II） displays 4- and 5-coordination modes. There is a one-dimensional P-O-Pb band along the a axis formed by PO3 groups and Pb（II） cations. These bands are joined by μ2-O of -COO to yield two-dimensional inorganic P-O-Pb layers which are pillared by the OOCC6HaCH2PO3 ligands to form a three-dimensional network. Moreover, compound 2 displays a strong emission band attributed to the ligand-centered （LC） transition.展开更多
A new crystal of O,Oˊ-dipropyl-α-（2,4-dichlorolphenoxyacylamido）-α-（4-methoxyphenyl） methylphosphonates has been prepared at room temperature and characterized by elemental analysis and IR,MS,1H NMR spectra,13C...A new crystal of O,Oˊ-dipropyl-α-（2,4-dichlorolphenoxyacylamido）-α-（4-methoxyphenyl） methylphosphonates has been prepared at room temperature and characterized by elemental analysis and IR,MS,1H NMR spectra,13C NMR spectra and X-ray single-crystal determination.The complex crystallizes in triclinic,space group P1 with a = 7.858（2）,b = 12.621（4）,c = 12.621（4）,α = 96.17（3）,β = 90.960（3）,γ = 90.960（3）°,V = 1243.9（7）3,Dc = 1.346 Mg/m3,Z = 2,μ = 0.362 mm-1and F（000） = 528.展开更多
Iodine was found to be an efficient catalyst for the one pot synthesis of α-amino phosphonate from aldehydes, anilines and diethyl phosphite. The influences of the iodine loading, reaction solvent, the structure of a...Iodine was found to be an efficient catalyst for the one pot synthesis of α-amino phosphonate from aldehydes, anilines and diethyl phosphite. The influences of the iodine loading, reaction solvent, the structure of aldehyde and aniline on the reaction were studied.展开更多
The extractive separation properties and the extractive regularity of the lanthanide elements by five di(2-ethylhexyl)alkyl phosphonates with various alkyl structure:di(2-ethylhexyl)chloromethyl phosphonate CH_2ClP(O)...The extractive separation properties and the extractive regularity of the lanthanide elements by five di(2-ethylhexyl)alkyl phosphonates with various alkyl structure:di(2-ethylhexyl)chloromethyl phosphonate CH_2ClP(O) (OC_8H_(17)-i)_2(1),di(2-ethylhexyl)β-chloroethyl phosphonate ClCH_2CH_2P(O) (OC_8H_(17)-i)_2 (2),di(2-ethylhexyl)α-chloroethyl phosphonate CH_3CHClP(O)(OC_8H_(17)-i)_2 (3),and corresponding di(2-ethylhexyl)methyl phosphonate CH_3P(O)(OC_8H_(17)-i)_2 (4),di(2-ethylhexyl)ethyl phosphonate C_2H_5P(O) (OC_8H_(17)-i)_2 (5),in nitrate system have been studied.The coordination compounds were prepared. The structure of these extractants and their coordination compounds were further explored by IR and ^(31)P NMR spectra.展开更多
Traditional treatment processes cannot completely remove phosphonates in circulating cooling water by one-step method. Herein, we designed peroxymonosulfate/UV irradiation/hydrated zirconium oxide(PMS/UV/HZO) coupling...Traditional treatment processes cannot completely remove phosphonates in circulating cooling water by one-step method. Herein, we designed peroxymonosulfate/UV irradiation/hydrated zirconium oxide(PMS/UV/HZO) coupling process to enhance the phosphonates removal. In particular, nitrilotrismethylenephosphonic acid(NTMP) removal efficiency by PMS/UV/HZO process was much higher than that of PMS/UV process, UV/HZO process and other processes in comparison experiments. Specifically,almost 97.2% NTMP in water was degraded, and the total phosphorous(TP) reduced from 9.3 mg/L to 0.26 mg/L at pH 7 within 180 min. TP removal efficiency still reached above 90% after 5 cycles adsorptiondesorption of HZO. Moreover, Cl^(-), NO_(3)-and SO_(4)^(2-)ions all had negligible effect on NTMP removal. During the process, NTMP was first destroyed to form phosphates and other intermediates by the reactive oxygen species(ROS), then phosphates were in situ immobilized via HZO adsorption. Sulfate radical(SO_(4)^(·-))has been confirmed to be the major ROS in the reaction system by quenching experiment and electron paramagnetic resonance(EPR) characterization. And the excellent selective adsorption capacity of HZO for phosphate produced was attributed to the strong inner-sphere coordination between H_(2)PO_(4)-/HPO_(4)^(2-)and Zr-OH on the surface of HZO. These results suggest that PMS/UV/HZO process is a promising technique for enhanced phosphonates decontamination.展开更多
Chiral phosphine-containing skeletons play a pivotal role in bioactive natural products, pharmaceuticals, chiral catalysts, and ligands. Despite considerable progress has been made in the synthesis of chiral phosphoru...Chiral phosphine-containing skeletons play a pivotal role in bioactive natural products, pharmaceuticals, chiral catalysts, and ligands. Despite considerable progress has been made in the synthesis of chiral phosphorus compounds, the development of facile and modular methods to access chiral allylic phosphorus compounds remains challenging due to the simultaneous control required for reactivity, enantioselectivity, and stereoselectivity. Herein, we present a general and modular platform to achieve the asymmetric reductive cross-coupling of α-bromophosphonates and vinyl bromides, enabling the synthesis of highly valuable chiral allylic phosphonate products with remarkable yields, enantioselectivities, and stereoselectivities.展开更多
Rational design of efficient pH-universal hydrogen evolution reaction catalysts to enable large-scale hydrogen production via electrochemical water splitting is of great significance,yet a challenging task.Herein,Ru a...Rational design of efficient pH-universal hydrogen evolution reaction catalysts to enable large-scale hydrogen production via electrochemical water splitting is of great significance,yet a challenging task.Herein,Ru atoms in the Ru_(2)P structure were replaced with M=Co,Ni,or Mo to produce M_(2-x)Ru_(x)P nanocrystals.The metals show strong site preference,with Co and Ni occupying the tetrahedral sites and Ru the square pyramidal sites of the CoRuP and NiRuP Ru_(2)P-type structures.The presence of Co or Ni in the tetrahedral sites leads to charge redistribution for Ru and,according to density functional theory calculations,a significant increase in the Ru d-band centers.As a result,the intrinsic activity of CoRuP and NiRuP increases considerably compared to Ru_(2)P in both acidic and alkaline media.The effect is not observed for MoRuP,in which Mo prefers to occupy the pyramidal sites.In particular,CoRuP shows state-of-the-art activity,outperforming Ru_(2)P with Pt-like activity in 0.5 M H_(2)SO_(4)(η10=12.3 mV;η100=52 mV;turnover frequency(TOF)=4.7 s^(-1)).It remains extraordinarily active in alkaline conditions(η10=12.9 mV;η100=43.5 mV)with a TOF of 4.5 s^(-1),which is 4x higher than that of Ru_(2)P and 10x that of Pt/C.Further increase in the Co content does not lead to drastic loss of activity,especially in alkaline medium,where,for example,the TOF of Co_(1.9)Ru_(0.1)P remains comparable to that of Ru_(2)P and higher than that of Pt/C,highlighting the viability of the adopted approach to prepare cost-efficient catalysts.展开更多
A series of novel mono（2,2,2-trifluoroethyl） esters,mono L-amino acid ester prodrugs of acyclic nucleoside phosphonates was synthesized and their in vitro anti-HBVactivity was evaluated in HepG 2 2.2.15 cells.Compou...A series of novel mono（2,2,2-trifluoroethyl） esters,mono L-amino acid ester prodrugs of acyclic nucleoside phosphonates was synthesized and their in vitro anti-HBVactivity was evaluated in HepG 2 2.2.15 cells.Compound 1d exhibited more potent anti-HBV activity and lower cytotoxicity than those of adefovir dipivoxil and alamifovir（MCC-478） with EC_（50） and CC_（50） values of 0.01μmol/L and 8000μmol/L respectively.展开更多
<正> With phosphoric formic acid (PFA) and its analog,phosphonoacetic acid (PAA),as the lead compounds,α-amino phosphonates were introduced into PFA and PAA.The derivatives oi N-( alkoxycarbonyl-aikoxyphosphony...<正> With phosphoric formic acid (PFA) and its analog,phosphonoacetic acid (PAA),as the lead compounds,α-amino phosphonates were introduced into PFA and PAA.The derivatives oi N-( alkoxycarbonyl-aikoxyphosphonyl)-α-arnino phosphonates (Ⅰ) and N-(alkoxycarbonyl-methyt-alkoxyphosphonyl)-α-amino phosphonates (Ⅱ) with the N-terminal of amino phosphonates bonding to phosphorus atom of PFA and PAA were synthesized via the reaction of the corresponding phosphonyl chloride with a-amino phosphonates in the presence of a base.The 31P NMK spectra of Ⅰ and Ⅱwere determined.It is found that the coupling constants 3Jpp with R3 being alkyl group were lower than those with R3 being (substituted) phenyl,and this result was discussed.The preliminary bioassay showed that some of the compounds Ⅰ and Ⅱhave better activities against tobacco mosaic virus (TMV).The inhibitory was higher than that of DHT (2,4-dioxyhexahydro-1,3,5-triazine).In addition,some of the compounds showed the activity against cancer cells.展开更多
Main observation and conclusion An efficient Lewis acid enabled ketones phosphonylation to synthesize vinylphosphonates has been developed.This method relays on ketone hydrophosphonylation/α-hydroxy phosphonates unim...Main observation and conclusion An efficient Lewis acid enabled ketones phosphonylation to synthesize vinylphosphonates has been developed.This method relays on ketone hydrophosphonylation/α-hydroxy phosphonates unimolecular elimination(E1)dehydration cascade reaction sequence.展开更多
A novel and efficient procedure for the synthesis of alkyl phosphonates through one pot condensation of alkyl halide and trialkyl /aryl phosphite in the presence of Amberlyst-15 as catalyst under solvent free conditio...A novel and efficient procedure for the synthesis of alkyl phosphonates through one pot condensation of alkyl halide and trialkyl /aryl phosphite in the presence of Amberlyst-15 as catalyst under solvent free conditions was applied.It demonstrated several advantages such as good yields of products,simple operation,convenient separation and inexpensive catalyst.展开更多
How to optimize and regulate the distribution of phosphoric acid in matrix,and pursuing the improved electrochemical performance and service lifetime of high temperature proton exchange membrane(HT-PEMs)fuel cell are ...How to optimize and regulate the distribution of phosphoric acid in matrix,and pursuing the improved electrochemical performance and service lifetime of high temperature proton exchange membrane(HT-PEMs)fuel cell are significant challenges.Herein,bifunctional poly(p-terphenyl-co-isatin piperidinium)copolymer with tethered phosphonic acid(t-PA)and intrinsic tertiary amine base groups are firstly prepared and investigated as HT-PEMs.The distinctive architecture of the copolymer provides a well-designed platform for rapid proton transport.Protons not only transports through the hydrogen bond network formed by the adsorbed free phosphoric acid(f-PA)anchored by the tertiary amine base groups,but also rely upon the proton channel constructed by the ionic cluster formed by the t-PA aggregation.Thorough the design of the structure,the bifunctional copolymers with lower PA uptake level(<100%)display prominent proton conductivities and peak power densities(99 mS cm^(-1),812 mW cm^(-2)at 160℃),along with lower PA leaching and higher voltage stability,which is a top leading result in disclosed literature.The results demonstrate that the design of intermolecular acid-base-pairs can improve the proton conductivity without sacrificing the intrinsic chemical stability or mechanical property of the thin membrane,realizing win-win demands between the mechanical robustness and electrochemical properties of HT-PEMs.展开更多
文摘Inspired by the anti-pancreatic promising results of our novel aminated cyclopropylmethylphosphonate compounds, an in vitro anti-prostate cancer activity exploration of these compounds was carried out on human prostate cancer cell line PC-3, and showed potent inhibiting activity at low micromolar concentrations (with an IC50 of approximately 45 μM).
文摘Buoyed by the extensive research on the wide-range biological activities of aminophosphonates, a novel class of aminated (cyclopropylmethyl)phosphor-nates compounds was synthesized from diethyl ((1-(3-chloropropyl)cyclopropyl)methyl)phosphonate and various amines in the presence of Hunig’s base. Upon biological activity screening these compounds demonstrated encouraging anti-pancreatic cancer properties at low micromolar concentrations.
基金supported by the National Natural Science Foundation of China (21403022,21572226)the Natural Science Foundation of Liaoning Province of China (2015020194)~~
文摘Copper catalyzed asymmetric formal [3＋2] cycloaddition of propargylic esters toβ‐keto phospho‐nates for the synthesis of chiral phosphonylated 2,3‐dihydrofurans was developed. By using a bulky and structurally rigid tridentate ketimine P,N,N ligand, a series of optically active phosphonylated 2,3‐dihydrofurans were prepared in high yield and up to 92%ee.
文摘A series of novel L-amino acid esters prodrugs of acyclic nucleoside phosphonates was synthesized and their anti-HBV activity was evaluated in HepG2 2.2.15 cells. Compound 1d exhibited more potent anti-HBV activity and lower cytotoxicity than those of adefovir dipivoxil with EC50 and CC50 values of 0.207 μmol/L and 2530 μmol/L, respectively.
文摘The synthesis of thirteen new compounds α - [2 - (2, 4 -dichlorophenoxy) propionyloxy] alkyl phosphonates was described. The structures of these compounds were characterized by IR, 1H-NMR and MS.
文摘l-Acetoxy allylic phosphonates rearrange regioselectively to γ-acetoxy α,β-unsaturated phosphonates under the catalysis of Pd(0). l-Acetoxy allylic phosphonates act as the precursors of phosphonatedπ-allylic cations in palladium(0) catalyzed reactions[1]. The reactions of l-acetoxy allylic phosphonates under palladium(0) catalysis with nucleophiles have been reported. 1-4 These reactions are highly regio- and stereoselective. We wish to report here the palladium(0) catalyzed reaction of l-acetoxy allylic phosphonates in the absence of a nucleophile.
文摘Fifteen title compounds 3a-0 were synthesized by condensation of 2chloro-benzothiazole with a-hydroxyphosphonates in good yields us- ing potassium iodide/tetrabutyl ammonium bromide as catalyst.All new com- pounds have been identified by ~1H-NMR,IR and elemental analysis.
基金Project Supported by National Science Foundation of China.
文摘A series of di-n-hexyl alkyl phosphonates with bulky substituent on phosphorus was synthesized by PTC P-alkylation using crown ether.Upon saponification of the resulting di-n-hexyl alkylphosphonates in the presence of crown ether or quaternary ammonium halide, corresponding mono-hexyl esters of alkyl phosphonic acids were prepared.Ultrasonic wave, as we found, can catalyze the reaction between dialkyl phosphite & metallic sodium and hydrolysis of dihexyl alkyl phosphonates.A series of di-t-alkyl phosphinic acids were synthesized by the reaction of Grignard reagent with PCl_3 followed by oxidation with 30% H_2O_2.It was found that the reaction between dibutyl phosphite and Grignard reagent of t-alkyl chloride is a new synthetic method for the preparation of mono-esters of highly hindered alkyl phosphonic acids.
基金supported by the State Key Laboratory of Structural Chemistry, National Natural Science Foundation of China (20873021)the Young Talent Programmed of Fujian Province (No. 2006F3072)
文摘Two novel transition metal phosphonate compounds, [Co（H2BDPP）（phen）]n 1 （BDPP = p-O3PCH2（C6H4）CH2PO3, phen = 1,10-phenanthroline） and [Pb3（BCP）2]n 2 （BCP = OOC（C6H4）CH2PO3）, have been synthesized and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in the monoclinic system, space group C2/c with a = 21.169（4）, b = 12.001（2）, c = 7.6211（15）A, β = 98.03（3）°, V= 1917.2（6）A^3, C20H18N2O6P2Co, Mr = 505.22, Z = 8, De= 1.737 g/cm^3, p = 1.107 mm^-1, F（000） = 1020, the final R= 0.0450 and wR = 0.1306 for 2072 observed reflections （I 〉 2σ（I）. Compound 2 crystallizes in the monoclinic system, space group C2/c with a = 4.7167（9）, b = 18.753（2）, c = 22.781（3）A, β = 91.07（3）°, V= 2014.7（14）A^, C8H6O5PPb1.5, Mr = 523.88, Z = 8, Dc = 3.454 g/cm^3, p = 25.222 mm^-1, F（000） = 1856, the final R = 0.0441 and wR = 0.1906 for 2259 observed reflections （I 〉 2σ（I）. In compound 1, the 1D chain running along the c axis is bridged by four ligands （trans- HO3PCH2C6H4CH2PO3H） in four different directions to extend the structure into a three- dimensional network. In compound 2, the Pb（II） displays 4- and 5-coordination modes. There is a one-dimensional P-O-Pb band along the a axis formed by PO3 groups and Pb（II） cations. These bands are joined by μ2-O of -COO to yield two-dimensional inorganic P-O-Pb layers which are pillared by the OOCC6HaCH2PO3 ligands to form a three-dimensional network. Moreover, compound 2 displays a strong emission band attributed to the ligand-centered （LC） transition.
基金supported by the National Basic Research Program of China(2010CB126100)
文摘A new crystal of O,Oˊ-dipropyl-α-（2,4-dichlorolphenoxyacylamido）-α-（4-methoxyphenyl） methylphosphonates has been prepared at room temperature and characterized by elemental analysis and IR,MS,1H NMR spectra,13C NMR spectra and X-ray single-crystal determination.The complex crystallizes in triclinic,space group P1 with a = 7.858（2）,b = 12.621（4）,c = 12.621（4）,α = 96.17（3）,β = 90.960（3）,γ = 90.960（3）°,V = 1243.9（7）3,Dc = 1.346 Mg/m3,Z = 2,μ = 0.362 mm-1and F（000） = 528.
基金Financial support for this research was provided by the National Natural Science Foundation of China （No.20472061） and Sun Yat-sen University.
文摘Iodine was found to be an efficient catalyst for the one pot synthesis of α-amino phosphonate from aldehydes, anilines and diethyl phosphite. The influences of the iodine loading, reaction solvent, the structure of aldehyde and aniline on the reaction were studied.
文摘The extractive separation properties and the extractive regularity of the lanthanide elements by five di(2-ethylhexyl)alkyl phosphonates with various alkyl structure:di(2-ethylhexyl)chloromethyl phosphonate CH_2ClP(O) (OC_8H_(17)-i)_2(1),di(2-ethylhexyl)β-chloroethyl phosphonate ClCH_2CH_2P(O) (OC_8H_(17)-i)_2 (2),di(2-ethylhexyl)α-chloroethyl phosphonate CH_3CHClP(O)(OC_8H_(17)-i)_2 (3),and corresponding di(2-ethylhexyl)methyl phosphonate CH_3P(O)(OC_8H_(17)-i)_2 (4),di(2-ethylhexyl)ethyl phosphonate C_2H_5P(O) (OC_8H_(17)-i)_2 (5),in nitrate system have been studied.The coordination compounds were prepared. The structure of these extractants and their coordination compounds were further explored by IR and ^(31)P NMR spectra.
基金the National Natural Science Foundation of China (No. 52000102)the Natural Science Foundation of Jiangsu Province (No. BK20190689) for offering financial support to this research。
文摘Traditional treatment processes cannot completely remove phosphonates in circulating cooling water by one-step method. Herein, we designed peroxymonosulfate/UV irradiation/hydrated zirconium oxide(PMS/UV/HZO) coupling process to enhance the phosphonates removal. In particular, nitrilotrismethylenephosphonic acid(NTMP) removal efficiency by PMS/UV/HZO process was much higher than that of PMS/UV process, UV/HZO process and other processes in comparison experiments. Specifically,almost 97.2% NTMP in water was degraded, and the total phosphorous(TP) reduced from 9.3 mg/L to 0.26 mg/L at pH 7 within 180 min. TP removal efficiency still reached above 90% after 5 cycles adsorptiondesorption of HZO. Moreover, Cl^(-), NO_(3)-and SO_(4)^(2-)ions all had negligible effect on NTMP removal. During the process, NTMP was first destroyed to form phosphates and other intermediates by the reactive oxygen species(ROS), then phosphates were in situ immobilized via HZO adsorption. Sulfate radical(SO_(4)^(·-))has been confirmed to be the major ROS in the reaction system by quenching experiment and electron paramagnetic resonance(EPR) characterization. And the excellent selective adsorption capacity of HZO for phosphate produced was attributed to the strong inner-sphere coordination between H_(2)PO_(4)-/HPO_(4)^(2-)and Zr-OH on the surface of HZO. These results suggest that PMS/UV/HZO process is a promising technique for enhanced phosphonates decontamination.
基金supported by the National Natural Science Foundation of China (22071183)the Science and Technology Commission of Shanghai Municipality (19DZ2271500)。
文摘Chiral phosphine-containing skeletons play a pivotal role in bioactive natural products, pharmaceuticals, chiral catalysts, and ligands. Despite considerable progress has been made in the synthesis of chiral phosphorus compounds, the development of facile and modular methods to access chiral allylic phosphorus compounds remains challenging due to the simultaneous control required for reactivity, enantioselectivity, and stereoselectivity. Herein, we present a general and modular platform to achieve the asymmetric reductive cross-coupling of α-bromophosphonates and vinyl bromides, enabling the synthesis of highly valuable chiral allylic phosphonate products with remarkable yields, enantioselectivities, and stereoselectivities.
文摘Rational design of efficient pH-universal hydrogen evolution reaction catalysts to enable large-scale hydrogen production via electrochemical water splitting is of great significance,yet a challenging task.Herein,Ru atoms in the Ru_(2)P structure were replaced with M=Co,Ni,or Mo to produce M_(2-x)Ru_(x)P nanocrystals.The metals show strong site preference,with Co and Ni occupying the tetrahedral sites and Ru the square pyramidal sites of the CoRuP and NiRuP Ru_(2)P-type structures.The presence of Co or Ni in the tetrahedral sites leads to charge redistribution for Ru and,according to density functional theory calculations,a significant increase in the Ru d-band centers.As a result,the intrinsic activity of CoRuP and NiRuP increases considerably compared to Ru_(2)P in both acidic and alkaline media.The effect is not observed for MoRuP,in which Mo prefers to occupy the pyramidal sites.In particular,CoRuP shows state-of-the-art activity,outperforming Ru_(2)P with Pt-like activity in 0.5 M H_(2)SO_(4)(η10=12.3 mV;η100=52 mV;turnover frequency(TOF)=4.7 s^(-1)).It remains extraordinarily active in alkaline conditions(η10=12.9 mV;η100=43.5 mV)with a TOF of 4.5 s^(-1),which is 4x higher than that of Ru_(2)P and 10x that of Pt/C.Further increase in the Co content does not lead to drastic loss of activity,especially in alkaline medium,where,for example,the TOF of Co_(1.9)Ru_(0.1)P remains comparable to that of Ru_(2)P and higher than that of Pt/C,highlighting the viability of the adopted approach to prepare cost-efficient catalysts.
基金supported by the grants from the National Natural Science Foundation of China(No.20962004)the Provincial Social Development Foundation of Guizhou,China(No.QKHSYZ[2009]3081)+1 种基金Provincial Special Assistant Foundation for High-level Talents of Guizhou,China(No.TZJF-2009-36)Science and Technology Foundation of Guizhou Province,China(No.QKHJZ[2008]2140)
文摘A series of novel mono（2,2,2-trifluoroethyl） esters,mono L-amino acid ester prodrugs of acyclic nucleoside phosphonates was synthesized and their in vitro anti-HBVactivity was evaluated in HepG 2 2.2.15 cells.Compound 1d exhibited more potent anti-HBV activity and lower cytotoxicity than those of adefovir dipivoxil and alamifovir（MCC-478） with EC_（50） and CC_（50） values of 0.01μmol/L and 8000μmol/L respectively.
基金Project supported by the National Natural Science Foundation of China
文摘<正> With phosphoric formic acid (PFA) and its analog,phosphonoacetic acid (PAA),as the lead compounds,α-amino phosphonates were introduced into PFA and PAA.The derivatives oi N-( alkoxycarbonyl-aikoxyphosphonyl)-α-arnino phosphonates (Ⅰ) and N-(alkoxycarbonyl-methyt-alkoxyphosphonyl)-α-amino phosphonates (Ⅱ) with the N-terminal of amino phosphonates bonding to phosphorus atom of PFA and PAA were synthesized via the reaction of the corresponding phosphonyl chloride with a-amino phosphonates in the presence of a base.The 31P NMK spectra of Ⅰ and Ⅱwere determined.It is found that the coupling constants 3Jpp with R3 being alkyl group were lower than those with R3 being (substituted) phenyl,and this result was discussed.The preliminary bioassay showed that some of the compounds Ⅰ and Ⅱhave better activities against tobacco mosaic virus (TMV).The inhibitory was higher than that of DHT (2,4-dioxyhexahydro-1,3,5-triazine).In addition,some of the compounds showed the activity against cancer cells.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21762038 and 21968032)the Fundamental Research Funds for the Central Universities(Nos.31920190077 and 31920190015)+2 种基金the Innovation and Entrepreneurship Talent Project of Lanzhou(No.2019-RC-21)the Scientific Research Foundation of Northwest University for Nationalities(No.xbmuyjrc 201603)the Organic Chemistry Innovation Groups.The authors thank Dr.Gang-Wei Wang for helpful discussions.
文摘Main observation and conclusion An efficient Lewis acid enabled ketones phosphonylation to synthesize vinylphosphonates has been developed.This method relays on ketone hydrophosphonylation/α-hydroxy phosphonates unimolecular elimination(E1)dehydration cascade reaction sequence.
基金BRNS.BARC,Mumbai for providing financial assistance(2010/37C/26/BRNS/1424)
文摘A novel and efficient procedure for the synthesis of alkyl phosphonates through one pot condensation of alkyl halide and trialkyl /aryl phosphite in the presence of Amberlyst-15 as catalyst under solvent free conditions was applied.It demonstrated several advantages such as good yields of products,simple operation,convenient separation and inexpensive catalyst.
基金supported by the National Key Research and Development Program(2018YFA0702002)the National Key Research and Development Program(Japan-China Joint Research Program)(2017YFE0197900)
文摘How to optimize and regulate the distribution of phosphoric acid in matrix,and pursuing the improved electrochemical performance and service lifetime of high temperature proton exchange membrane(HT-PEMs)fuel cell are significant challenges.Herein,bifunctional poly(p-terphenyl-co-isatin piperidinium)copolymer with tethered phosphonic acid(t-PA)and intrinsic tertiary amine base groups are firstly prepared and investigated as HT-PEMs.The distinctive architecture of the copolymer provides a well-designed platform for rapid proton transport.Protons not only transports through the hydrogen bond network formed by the adsorbed free phosphoric acid(f-PA)anchored by the tertiary amine base groups,but also rely upon the proton channel constructed by the ionic cluster formed by the t-PA aggregation.Thorough the design of the structure,the bifunctional copolymers with lower PA uptake level(<100%)display prominent proton conductivities and peak power densities(99 mS cm^(-1),812 mW cm^(-2)at 160℃),along with lower PA leaching and higher voltage stability,which is a top leading result in disclosed literature.The results demonstrate that the design of intermolecular acid-base-pairs can improve the proton conductivity without sacrificing the intrinsic chemical stability or mechanical property of the thin membrane,realizing win-win demands between the mechanical robustness and electrochemical properties of HT-PEMs.
