The title compound 2-ethoxy-spiro[2H-1,4,2-benzoxazaphosphorine-3（4H）,1＇-cycloheptane] 2-oxide （C15H22NO3P） was synthesized by the Mannich-type reaction of ο-amino-phenol with ethyl dichlorophosphinite and cyclo...The title compound 2-ethoxy-spiro[2H-1,4,2-benzoxazaphosphorine-3（4H）,1＇-cycloheptane] 2-oxide （C15H22NO3P） was synthesized by the Mannich-type reaction of ο-amino-phenol with ethyl dichlorophosphinite and cycloheptanone, and structurally characterized by single-crystal X-ray diffraction analysis. It crystallizes in orthorhombic, space group P212121 with a = 8.9840（12）, b = 9.2978（12）, c = 37.205（5） A, V= 3107.8（7） ,A^3, Z= 8, Mr = 295.31, Dc = 1.262 g/cm^3, F（000） = 1264, μ = 0.184 mm^-1, S = 1.026, the final R = 0.0502 and wR = 0.1017 for 3849 observed reflections with Ⅰ 〉 2σ（Ⅰ） and 378 variable parameters. The structure exhibits that the six-membered phosphorus heterocycle is in the envelope conformation.展开更多
The title compound, 2-（3-silatranylpropylamino）-4-dichlorophenyl-5,5-dimethyl- 1,3,2-dioxaphosphorinane-2-oxide （2（C20H33N2O6Psi）？C2H6O？CH4O, Mr = 991.20）, has been synthe- sized by the nucleophilic substituti...The title compound, 2-（3-silatranylpropylamino）-4-dichlorophenyl-5,5-dimethyl- 1,3,2-dioxaphosphorinane-2-oxide （2（C20H33N2O6Psi）？C2H6O？CH4O, Mr = 991.20）, has been synthe- sized by the nucleophilic substitution reaction of 2-chloro-4-phenyl-5,5-dimethyl-1,3,2-dioxa- phosphorinane-2-oxide with γ-aminopropylsilatrane, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P with a = 10.3783（15）, b = 11.2402（17）, c = 12.1675（18） ？, ？ = 70.653（4）, ？ = 82.908（4）, ？ = 85.690（4）？, V = 1328.1（3） ？3, Z = 1, Dc = 1.239 g/cm3, μ = 0.19 mm？1, F（000） = 532, the final R = 0.0640 and wR = 0.2090 for 3615 observed reflections with I 〉 2？（I）. The cyclic dioxaphosphorinane ring in the molecule adopts a thermodynamically stable cis conformation, while the silatrane fragment forms a cage-like structure in which there exists an intramolecular Si？N donor-acceptor bond. In the crystal structure, centrosymmetrically related molecules are linked by pairs of N–H？？？O hydrogen bonds into dimers, generating rings with graph-set motif R22（8）. Furthermore, a couple of O（7）–H（10）？？？O（3） hydrogen bonds were formed by O atom of P=O and H atom from hydroxyl in the solvent ethanol. Thermal property of the compound was also studied by means of thermogravimetry （TGA）. The thermal analysis and preliminary fireproofing test show that the title compound has good flame retardance.展开更多
The interaction between 4-（4-hydroxybut-2-ynyloxy）-3-（phenylsulfonyl）-1,2,5-oxadiazole-2-oxide （FB） and bovine serum albumin （BSA） was studied by spectroscopic methods including fluorescence and UV-Vis absorpt...The interaction between 4-（4-hydroxybut-2-ynyloxy）-3-（phenylsulfonyl）-1,2,5-oxadiazole-2-oxide （FB） and bovine serum albumin （BSA） was studied by spectroscopic methods including fluorescence and UV-Vis absorption spectroscopy. The quenching mechanism of fluorescence of BSA by FB was considered to be a dynamic quenching procedure. The number of binding sites n and apparent binding constant K were measured by fluorescence quenching method. The results indicate that there is FB molecular binding with BSA, and forming 1 ： 1 complex. The thermodynamic parameters such as △H, △G and △S, etc., were calculated, The results indicate that the binding reaction is mainly entropy-driven and hydrophobic forces play major role in the binding reaction, The distance r between donor （BSA） and acceptor （FB） was obtained according to Forster theory of non-radioactive energy transfer.展开更多
<正> The syntheses of a series of 2-[bis-(2-chloroethyl)amino]-6-alkoxylmethyl-tetrahydro-2H-1, 3, 2-oxazaphosphonne-2-oxide are described The structures of all target compounds have been determined by 1H NMR, M...<正> The syntheses of a series of 2-[bis-(2-chloroethyl)amino]-6-alkoxylmethyl-tetrahydro-2H-1, 3, 2-oxazaphosphonne-2-oxide are described The structures of all target compounds have been determined by 1H NMR, MS and elementary analysis, and their configurations and conformations have been studied by 31P NMR and X-ray diffraction analysis. The properties of NMR and MS of these compounds are discussed展开更多
Phenylurea reacted with dichlorophenylphosphine and aldehydes or ketones by Mannich-type reaction in anhydrous benzene to give five-mem- bered phosphorous heterocyclic compounds.However.derivatives of α-ureidoalkylph...Phenylurea reacted with dichlorophenylphosphine and aldehydes or ketones by Mannich-type reaction in anhydrous benzene to give five-mem- bered phosphorous heterocyclic compounds.However.derivatives of α-ureidoalkylphosphonic acids were obtained as the reaction performed in glacial acetic acid.展开更多
Six coordination compounds of Pt(Ⅱ)L_2 and Ir(Ⅲ)L_3 type(where L is PT^-, 3Me-PT^-or 4Me-PT^-)are reported here.Four coordination compounds of the latter two ligands have never been reported before,while PT^-'s ...Six coordination compounds of Pt(Ⅱ)L_2 and Ir(Ⅲ)L_3 type(where L is PT^-, 3Me-PT^-or 4Me-PT^-)are reported here.Four coordination compounds of the latter two ligands have never been reported before,while PT^-'s were synthesized with H_2PtCl_6 and(NH_4)_3IrCl_6 respectively,which were different from the methods of Davidson et al.~1 and Sterinbrech^2.They were characterized by elemental analysis, UV,IR,~1HNMR and molar conductance.Their structural formulas have been determined,and the mechanism of synthetic reaction has been discussed.展开更多
The stability of the coordination compounds of the first transition series metal ions(Mn(Ⅱ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ)and Zn(Ⅱ))with 2-mercaptopyridine-1- oxide is reported.A coordination compound CoL_2 is synthesized and...The stability of the coordination compounds of the first transition series metal ions(Mn(Ⅱ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ)and Zn(Ⅱ))with 2-mercaptopyridine-1- oxide is reported.A coordination compound CoL_2 is synthesized and characterized for the first time.展开更多
This study preliminarily investigates the structure-activity relationships of novel [5,6]-fused ring energetic materials derived from the 6-nitro-7-azido-pyrazol [3,4-d][1,2,3]triazine 2-oxide(ICM-103) skeleton, empha...This study preliminarily investigates the structure-activity relationships of novel [5,6]-fused ring energetic materials derived from the 6-nitro-7-azido-pyrazol [3,4-d][1,2,3]triazine 2-oxide(ICM-103) skeleton, emphasizing the role of functional group substitution in tailoring key properties such as detonation performance and mechanical sensitivity. Strategic incorporation of nitrogen-rich substituents(e.g., hydrazine, guanidine) into the 1,2,3-triazine 2-oxide framework yielded compounds with diverse performance characteristics. Notably, compound 2 demonstrates energy performance(D = 8916 m·s^(-1) and P = 36.80 GPa) comparable to RDX, yet with lower mechanical sensitivity(IS = 37 J). Theoretical calculations show that the properties of the substituents themselves and their coupling with the molecular skeleton jointly determine the key properties of the target molecules. This study provides a framework for the customized design of energetic materials by linking the chemical properties of substituents with the performance parameters of target molecules. These findings highlight the potential of local molecular structural modification driven by structure-activity relationship analysis in promoting the development of next-generation energetic materials and lay a solid foundation for future research in this field.展开更多
Multifunctionalization reactions involving reactive intermediates offer powerful strategies for the rapid construction of complex molecules.Herein,we describe two trifunctionalization reactions of pyrazoleamide-derive...Multifunctionalization reactions involving reactive intermediates offer powerful strategies for the rapid construction of complex molecules.Herein,we describe two trifunctionalization reactions of pyrazoleamide-derived metal carbenes.Both transformations are proposed to proceed through a zwitterionic intermediate,formed via nucleophilic attack and pyrazole migration,followed by electrophilic trapping.This approach enables the efficient synthesis of 3-hydroxy-2-oxindole derivatives from isatins and amines in good yields,as well as chiralβ-aminoamide derivatives via a Rh/CPA co-catalytic system with excellent enantioselectivity.Importantly,both classes of compounds exhibited significant inhibitory activity against multiple tumor cell lines.展开更多
文摘The title compound 2-ethoxy-spiro[2H-1,4,2-benzoxazaphosphorine-3（4H）,1＇-cycloheptane] 2-oxide （C15H22NO3P） was synthesized by the Mannich-type reaction of ο-amino-phenol with ethyl dichlorophosphinite and cycloheptanone, and structurally characterized by single-crystal X-ray diffraction analysis. It crystallizes in orthorhombic, space group P212121 with a = 8.9840（12）, b = 9.2978（12）, c = 37.205（5） A, V= 3107.8（7） ,A^3, Z= 8, Mr = 295.31, Dc = 1.262 g/cm^3, F（000） = 1264, μ = 0.184 mm^-1, S = 1.026, the final R = 0.0502 and wR = 0.1017 for 3849 observed reflections with Ⅰ 〉 2σ（Ⅰ） and 378 variable parameters. The structure exhibits that the six-membered phosphorus heterocycle is in the envelope conformation.
基金Supported by the Youth Foundation of Hubei Educational Committee(No.Q20151902)the State Undergraduate Innovative Training Program(No.201410517002)the Start-up Foundation for Doctor of Hubei University for Nationalities(No.MY2013B027)
文摘The title compound, 2-（3-silatranylpropylamino）-4-dichlorophenyl-5,5-dimethyl- 1,3,2-dioxaphosphorinane-2-oxide （2（C20H33N2O6Psi）？C2H6O？CH4O, Mr = 991.20）, has been synthe- sized by the nucleophilic substitution reaction of 2-chloro-4-phenyl-5,5-dimethyl-1,3,2-dioxa- phosphorinane-2-oxide with γ-aminopropylsilatrane, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P with a = 10.3783（15）, b = 11.2402（17）, c = 12.1675（18） ？, ？ = 70.653（4）, ？ = 82.908（4）, ？ = 85.690（4）？, V = 1328.1（3） ？3, Z = 1, Dc = 1.239 g/cm3, μ = 0.19 mm？1, F（000） = 532, the final R = 0.0640 and wR = 0.2090 for 3615 observed reflections with I 〉 2？（I）. The cyclic dioxaphosphorinane ring in the molecule adopts a thermodynamically stable cis conformation, while the silatrane fragment forms a cage-like structure in which there exists an intramolecular Si？N donor-acceptor bond. In the crystal structure, centrosymmetrically related molecules are linked by pairs of N–H？？？O hydrogen bonds into dimers, generating rings with graph-set motif R22（8）. Furthermore, a couple of O（7）–H（10）？？？O（3） hydrogen bonds were formed by O atom of P=O and H atom from hydroxyl in the solvent ethanol. Thermal property of the compound was also studied by means of thermogravimetry （TGA）. The thermal analysis and preliminary fireproofing test show that the title compound has good flame retardance.
基金Project supported by the National Natural Science Foundation of China （Nos. 30570015, 20373051 ）, the Natural Science Foundation of Hubei Province （Nos. 2006ABA333, 2005ABC002）, and the Science Foundation of Hubei Provincial Educational Department （No. D200528003）, and the Science Research Foundation of Chinese Ministry of Education （No. [2006]8IRT0543）.
文摘The interaction between 4-（4-hydroxybut-2-ynyloxy）-3-（phenylsulfonyl）-1,2,5-oxadiazole-2-oxide （FB） and bovine serum albumin （BSA） was studied by spectroscopic methods including fluorescence and UV-Vis absorption spectroscopy. The quenching mechanism of fluorescence of BSA by FB was considered to be a dynamic quenching procedure. The number of binding sites n and apparent binding constant K were measured by fluorescence quenching method. The results indicate that there is FB molecular binding with BSA, and forming 1 ： 1 complex. The thermodynamic parameters such as △H, △G and △S, etc., were calculated, The results indicate that the binding reaction is mainly entropy-driven and hydrophobic forces play major role in the binding reaction, The distance r between donor （BSA） and acceptor （FB） was obtained according to Forster theory of non-radioactive energy transfer.
基金Project supported by the National Natural Science Foundation of China and the Postdoctor Science Foundation
文摘<正> The syntheses of a series of 2-[bis-(2-chloroethyl)amino]-6-alkoxylmethyl-tetrahydro-2H-1, 3, 2-oxazaphosphonne-2-oxide are described The structures of all target compounds have been determined by 1H NMR, MS and elementary analysis, and their configurations and conformations have been studied by 31P NMR and X-ray diffraction analysis. The properties of NMR and MS of these compounds are discussed
基金the National Natural Science Foundation of People's Republic of China:
文摘Phenylurea reacted with dichlorophenylphosphine and aldehydes or ketones by Mannich-type reaction in anhydrous benzene to give five-mem- bered phosphorous heterocyclic compounds.However.derivatives of α-ureidoalkylphosphonic acids were obtained as the reaction performed in glacial acetic acid.
文摘Six coordination compounds of Pt(Ⅱ)L_2 and Ir(Ⅲ)L_3 type(where L is PT^-, 3Me-PT^-or 4Me-PT^-)are reported here.Four coordination compounds of the latter two ligands have never been reported before,while PT^-'s were synthesized with H_2PtCl_6 and(NH_4)_3IrCl_6 respectively,which were different from the methods of Davidson et al.~1 and Sterinbrech^2.They were characterized by elemental analysis, UV,IR,~1HNMR and molar conductance.Their structural formulas have been determined,and the mechanism of synthetic reaction has been discussed.
文摘The stability of the coordination compounds of the first transition series metal ions(Mn(Ⅱ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ)and Zn(Ⅱ))with 2-mercaptopyridine-1- oxide is reported.A coordination compound CoL_2 is synthesized and characterized for the first time.
基金financial support from the National Natural Science Foundation of China (Grant No.22375190)。
文摘This study preliminarily investigates the structure-activity relationships of novel [5,6]-fused ring energetic materials derived from the 6-nitro-7-azido-pyrazol [3,4-d][1,2,3]triazine 2-oxide(ICM-103) skeleton, emphasizing the role of functional group substitution in tailoring key properties such as detonation performance and mechanical sensitivity. Strategic incorporation of nitrogen-rich substituents(e.g., hydrazine, guanidine) into the 1,2,3-triazine 2-oxide framework yielded compounds with diverse performance characteristics. Notably, compound 2 demonstrates energy performance(D = 8916 m·s^(-1) and P = 36.80 GPa) comparable to RDX, yet with lower mechanical sensitivity(IS = 37 J). Theoretical calculations show that the properties of the substituents themselves and their coupling with the molecular skeleton jointly determine the key properties of the target molecules. This study provides a framework for the customized design of energetic materials by linking the chemical properties of substituents with the performance parameters of target molecules. These findings highlight the potential of local molecular structural modification driven by structure-activity relationship analysis in promoting the development of next-generation energetic materials and lay a solid foundation for future research in this field.
基金the National Natural Science Foundation of China(92256301)Guangdong Provincial Key Laboratory of Chiralmoleculeand Drug Discovery(2023B1212060022)+2 种基金Natural Science Foundation of Guangdong Province(2023A1515011486)Key-Area Research and Development Program of Guangdong Province(2022B1111050003,2022B1111070004)the open project of the Key Laboratory of Xinjiang Native Medicinal and Edible Plant Resources Chemistry(KSUZDSYS202401)is greatly acknowledged.
文摘Multifunctionalization reactions involving reactive intermediates offer powerful strategies for the rapid construction of complex molecules.Herein,we describe two trifunctionalization reactions of pyrazoleamide-derived metal carbenes.Both transformations are proposed to proceed through a zwitterionic intermediate,formed via nucleophilic attack and pyrazole migration,followed by electrophilic trapping.This approach enables the efficient synthesis of 3-hydroxy-2-oxindole derivatives from isatins and amines in good yields,as well as chiralβ-aminoamide derivatives via a Rh/CPA co-catalytic system with excellent enantioselectivity.Importantly,both classes of compounds exhibited significant inhibitory activity against multiple tumor cell lines.
