Organophosphate analogues are commonly occurring structural features that are widely present in numerous natural substances, biologically active molecules and modern pharmaceutical compounds. The development of effici...Organophosphate analogues are commonly occurring structural features that are widely present in numerous natural substances, biologically active molecules and modern pharmaceutical compounds. The development of efficient strategies for the preparation of these analogues is still attractive but challenging in organophosphorus chemistry. In order to fill this gap, different new routes have been discovered including direct phosphonylation of alkyl radicals, indirect Arbuzov phosphonylation of alkyl radicals and nucleopilic phosphonylation of phosphorus. In this short review, we have attempted to summarize these recent developments for the synthesis of alkyl phosphonates in order to facilitate the development of green pharmacological alkyl phosphonates by emphasizing their variety of products, specificity and relevance, and providing the underlying mechanistic rationale whenever it is possible. We aim to provide readers with a comprehensive understanding of the current state of this field and contribute to future research.展开更多
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 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
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
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
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
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.
An efficient chlorination reaction of in situ generated(β-diazo-α,α-difluoroethyl)phosphonates has been achieved with hydrochloric acid as a chlorine source under mild and operationally convenient conditions.The re...An efficient chlorination reaction of in situ generated(β-diazo-α,α-difluoroethyl)phosphonates has been achieved with hydrochloric acid as a chlorine source under mild and operationally convenient conditions.The reaction does not need any catalyst and tolerates a wide scope of substrates,which affords the(β-chlorodifluoroethyl)phosphonate products in good to excellent yields.This reaction represents the first example of the halogenation of difluoroalkyl diazo compounds,and also provides an easy way for the synthesis of difluoromethylenephosphonate-containing compounds.展开更多
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
Three bench-stable difluoromethylene phosphonate hydrazones were prepared from simple diethyl(difluoromethyl)phosphonate within two steps in good yields. The [3 + 2] cycloaddition reaction of these diazo precursors wi...Three bench-stable difluoromethylene phosphonate hydrazones were prepared from simple diethyl(difluoromethyl)phosphonate within two steps in good yields. The [3 + 2] cycloaddition reaction of these diazo precursors with aryl diazonium salts has been accomplished under metal-free conditions with exclusive regioselectivity. This transformation provides practical access to a broad panel of 2-aryl-2 H-tetrazol-5-yl difluoromethylene phosphonates, including the corresponding derivatives of amino acid(phenylalanine) and drug cores(Pomalidomide and Lapatinib fragment).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
A series of mono L-amino acid ester, mono non-steroid anti-inflammation drug （NSAID）, carboxylic ester derivatives of acyclonucleoside phosphonates were prepared by using a ＂one pot synthesis＂ method and their in ...A series of mono L-amino acid ester, mono non-steroid anti-inflammation drug （NSAID）, carboxylic ester derivatives of acyclonucleoside phosphonates were prepared by using a ＂one pot synthesis＂ method and their in vitro anti-HBV activity were evaluated in HepG 2.2.15 cells. Compound 9a exhibited more potent anti-HBV activity and lower cytotoxicity than those of adefovir dipivoxil with IC50 and selective index （SI） values of 0.48μmol/L and 763.72, respectively.展开更多
The thermal decomposition of Ag NO_(3)is known to produce metallic Ag,but single-atomic dispersion is hard to achieve instead of the aggregation state of nanoparticles.Herein,we develop an efficient approach to therma...The thermal decomposition of Ag NO_(3)is known to produce metallic Ag,but single-atomic dispersion is hard to achieve instead of the aggregation state of nanoparticles.Herein,we develop an efficient approach to thermally generate and stabilize single Ag atoms via the coordination effect.Two desired Co-Ag phosphonates[Ag_(2)^(Ⅰ)Co_(2)^(Ⅲ)(notp H_(3))_2(NO_(3))]X[X=NO_(3)^(-)(1)or Cl O_(4)^(-)(2)]were synthesized by solid-phase grinding method or solution crystallization.Both crystal structures reveal slightly different packing arrangements of various lattice anions and identical one-dimensional(1-D)coordination chains,formed in each case by the coordination of Ag(Ⅰ)to the metalloligand Co(notp H_(3))and NO_(3)^(-) anion.The number of Ag(Ⅰ)ions connected to each NO_(3)^(-) anion reduces from 5 in bulk Ag NO_(3) to 2 in compounds 1 and 2,leading to the Ag NO_(3)component stepwise decomposition at a lower temperature(<300℃).During the thermal decomposition,the changes of supermolecular structures and Ag oxidation states were monitored by PXRD,IR and XAFS measurements.The most interesting finding is that 1 and 2 can retain chain structures and harvest Ag(0)atoms in the chain by controlling decomposition temperatures(220℃for 1 and 254℃for 2).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
基金support from the National Key R&D Program(2023YFD1700500)National Natural Science Foundation of China(22301093)the Fundamental Research Funds for the Central Universities and the Central China Normal University(CCNU).
文摘Organophosphate analogues are commonly occurring structural features that are widely present in numerous natural substances, biologically active molecules and modern pharmaceutical compounds. The development of efficient strategies for the preparation of these analogues is still attractive but challenging in organophosphorus chemistry. In order to fill this gap, different new routes have been discovered including direct phosphonylation of alkyl radicals, indirect Arbuzov phosphonylation of alkyl radicals and nucleopilic phosphonylation of phosphorus. In this short review, we have attempted to summarize these recent developments for the synthesis of alkyl phosphonates in order to facilitate the development of green pharmacological alkyl phosphonates by emphasizing their variety of products, specificity and relevance, and providing the underlying mechanistic rationale whenever it is possible. We aim to provide readers with a comprehensive understanding of the current state of this field and contribute to future research.
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.
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.
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.
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.
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.
基金supports from the National Natural Science Foundation of China (No. 21761132021)German Research Foundation (No. RO362/74–1)Qin Lan project from Jiangsu Province for JLH is also acknowledged
文摘An efficient chlorination reaction of in situ generated(β-diazo-α,α-difluoroethyl)phosphonates has been achieved with hydrochloric acid as a chlorine source under mild and operationally convenient conditions.The reaction does not need any catalyst and tolerates a wide scope of substrates,which affords the(β-chlorodifluoroethyl)phosphonate products in good to excellent yields.This reaction represents the first example of the halogenation of difluoroalkyl diazo compounds,and also provides an easy way for the synthesis of difluoromethylenephosphonate-containing compounds.
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 National Natural Science Foundation of China (Nos.21772142,21901181 and 21961142015)the National Key Research and Development Program of China (No.2019YFA0905100)+1 种基金Tianjin Municipal Science & Technology Commission (No.19JCQNJC04700)the CNRS in France。
文摘Three bench-stable difluoromethylene phosphonate hydrazones were prepared from simple diethyl(difluoromethyl)phosphonate within two steps in good yields. The [3 + 2] cycloaddition reaction of these diazo precursors with aryl diazonium salts has been accomplished under metal-free conditions with exclusive regioselectivity. This transformation provides practical access to a broad panel of 2-aryl-2 H-tetrazol-5-yl difluoromethylene phosphonates, including the corresponding derivatives of amino acid(phenylalanine) and drug cores(Pomalidomide and Lapatinib fragment).
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supported by the National Natural Science Foundation of China(Nos.20962004,81260473)Projects of Guizhou Science and Technology Department(Nos.2013-3031,2012-3013)Excellent Youth Scientific Talents Foundation of Guizhou(No.2013-45)
文摘A series of mono L-amino acid ester, mono non-steroid anti-inflammation drug （NSAID）, carboxylic ester derivatives of acyclonucleoside phosphonates were prepared by using a ＂one pot synthesis＂ method and their in vitro anti-HBV activity were evaluated in HepG 2.2.15 cells. Compound 9a exhibited more potent anti-HBV activity and lower cytotoxicity than those of adefovir dipivoxil with IC50 and selective index （SI） values of 0.48μmol/L and 763.72, respectively.
基金the National Natural Science Foundation of China(Nos.21671098,21731003)the Fundamental Research Funds for the Central Universities(Nos.14380151,14380206)is acknowledged。
文摘The thermal decomposition of Ag NO_(3)is known to produce metallic Ag,but single-atomic dispersion is hard to achieve instead of the aggregation state of nanoparticles.Herein,we develop an efficient approach to thermally generate and stabilize single Ag atoms via the coordination effect.Two desired Co-Ag phosphonates[Ag_(2)^(Ⅰ)Co_(2)^(Ⅲ)(notp H_(3))_2(NO_(3))]X[X=NO_(3)^(-)(1)or Cl O_(4)^(-)(2)]were synthesized by solid-phase grinding method or solution crystallization.Both crystal structures reveal slightly different packing arrangements of various lattice anions and identical one-dimensional(1-D)coordination chains,formed in each case by the coordination of Ag(Ⅰ)to the metalloligand Co(notp H_(3))and NO_(3)^(-) anion.The number of Ag(Ⅰ)ions connected to each NO_(3)^(-) anion reduces from 5 in bulk Ag NO_(3) to 2 in compounds 1 and 2,leading to the Ag NO_(3)component stepwise decomposition at a lower temperature(<300℃).During the thermal decomposition,the changes of supermolecular structures and Ag oxidation states were monitored by PXRD,IR and XAFS measurements.The most interesting finding is that 1 and 2 can retain chain structures and harvest Ag(0)atoms in the chain by controlling decomposition temperatures(220℃for 1 and 254℃for 2).
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.
