Solvent extraction of base metals using bis((1-decylbenzimidazol-2-yl)methyl)amine (BDNNN) showed a lack of pH-metric separation of the metals. The extraction system was described quantitatively using the equilibria i...Solvent extraction of base metals using bis((1-decylbenzimidazol-2-yl)methyl)amine (BDNNN) showed a lack of pH-metric separation of the metals. The extraction system was described quantitatively using the equilibria involved to derive the mathematical explanation for the two linear log D vs pHe plots for each metal ion extraction curve, and coordination numbers could also be extracted from the two slopes. The lack of separation was attributed to the absence of stereochemical “tailor making” since the complexes isolated from the reaction of the ligand, bis((1H-benzimidazol- 2-yl)methyl)amine (NNN), with base metals suggested the formation of similar octahedral complex species from spectral and crystal structure evidence. The bis tridentate coordination observed was in agreement with information extracted from the extraction data. This investigation opens up an opportunity and an approach for the evaluation of amines as extractants but cautions against tridentate ligands.展开更多
Complexes [MCl 2{CH 3N(CH 2CH 2N[CDS1]CR 1R 2) 2}]((3, M=Co, R 1=H, R 2=Ph ; 4, M=Fe, R 1=H, \{R 2=Ph\}; 5, M=Co, R 1=R 2=Ph) were prepared and characterized by IR spectra and elemental analysis. The combination of ea...Complexes [MCl 2{CH 3N(CH 2CH 2N[CDS1]CR 1R 2) 2}]((3, M=Co, R 1=H, R 2=Ph ; 4, M=Fe, R 1=H, \{R 2=Ph\}; 5, M=Co, R 1=R 2=Ph) were prepared and characterized by IR spectra and elemental analysis. The combination of each of complexes 3-5 with ethylaluminoxane(EAO), respectively, was found to be moderately active for ethylene oligomerization to low carbon olefins. The activity of 113 kg oligomers·mol -1 Co·h -1 for complex 3(100 mol of EAO, 180 ℃ and 1 8 MPa ethylene) was observed with a selectivity of 93% to C 4-10 olefins, of which 96% were linear C4 10 olefins. The catalytic properties of complexes 3-5 were compared with those of analogous P,P coordinated complexes [MCl 2{CH 3N(CH 2CH 2PPh 2) 2}](1, M=Co; 2, \{M=\}Fe).展开更多
N-Methyl bis(2-(alkyloxy-alkylphosphoryloxy)ethyl)amines, which are abbreviated as PNPs, are a series of new skeleton chemicals belonging to schedule 2.B.04 chemicals of Chemical Weapons Convention (CWC). PNPs are imp...N-Methyl bis(2-(alkyloxy-alkylphosphoryloxy)ethyl)amines, which are abbreviated as PNPs, are a series of new skeleton chemicals belonging to schedule 2.B.04 chemicals of Chemical Weapons Convention (CWC). PNPs are important markers of chemical warfare agents because they are structurally relative to both nerve agents and N-mustards. In this study, fragmentation pathways of the most characteristic fragment ions in Q-TOF mass spectrometry were proposed based on the information from accurate mass and secondary fragmentations of product ions scan experiments. Results indicated that the base ion in LC/HRMS was the quasi-molecular ion [M+H]+. In LC-HRMS/MS, it was [M+H-CnH2n+1P(O)(OH)CmH2m+1O]+ fragment ion which was formed by losing an alkyloxy alkylphosphoryloxy group from the quasi-molecular ion. The diagnostic ion m/z84.0814 was identified as [C5H10N]+, which was the group of (CH2=CH)2N+(H)CH3. PNPs have two protonated centers. One is on the N atom, the other is on the O atom (P=O). O-n-propyl PNPs generally exhibited two fragmentation pathways. Firstly, the quasi-molecular ion [M+H]+ lost a propoxy alkylphosphoryloxy group to produce [R1P(OH+)(O-n-C3H7)OCH2CH2N(CH3)CH=CH2]+, which could be fragmented further to produce [C5H10N]+ ion. Secondly, [R1P(OH+)(O-n-C3H7) OCH=CH2]+ ions were produced from [M+H]+ and fragmented further to produce the abundant ions [R1P(OH+)(OH)OCH =CH2]. However, O-isopropyl PNPs characteristically produced weak fragment ions [M+H-C3H6]+, which were presumably formed via loss of CH3CH=CH2 from [M+H]+. Other PNPs showed similar fragmentation pathways as O-n-propyl PNPs. On the summarization of the MS fragmentation pathways of PNPs, LC-HRMS/MS quantitative and qualitative methods were developed and applied to analyze N-Methyl bis(2-(butoxy-methylphosphoryloxy)ethyl]amine in high background organic samples. The analytical results had successfully supported the sample preparation for the 33rd official proficiency test of Organization for Prohibition of Chemical Weapons (OPCW).展开更多
Lithium aluminium amide [LiAI（NHR）4] 5 obtained by treating the primary amine 4 with LiAlH4 could promote the ring opening of epoxide 2 and led to high regioselective product of racemic bis[2-（6-fluoro-2-chromanyl...Lithium aluminium amide [LiAI（NHR）4] 5 obtained by treating the primary amine 4 with LiAlH4 could promote the ring opening of epoxide 2 and led to high regioselective product of racemic bis[2-（6-fluoro-2-chromanyl）-2-hydroxyethyl]amine methanesulfonic acid salt 7.展开更多
The Zinc complex of N, N-bis (benzimidazol 2-yl-methy])amine has been synthesized and its crystal structure determined by X-ray diffraction method. The structure features of the complex are described.
The title complex [Cu（ampym）（bapa）Cl]（ClO4） （C10H22Cl2CuN6O4） was synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The crystal crystallizes in the orthorhombic syst...The title complex [Cu（ampym）（bapa）Cl]（ClO4） （C10H22Cl2CuN6O4） was synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The crystal crystallizes in the orthorhombic system, space group Pna21 with a = 11.9904（12）, b = 15.9796（16）, c = 8.9 i 43（9） A^°, V = 1708.0（3）A^°3 Mr = 424.78, Z = 4, F（000） = 876, Dc = 1.652 g/cm^3, T = 293 K,μ =1 .619 mm^-1 and λ=0.71073 A^°. The structure was refined to R = 0.0240 and wR ： 0.0564 for 2905 observed reflections with I 〉 2σ（I）. Flack = 0.039（12）.展开更多
A novel PdC12/bis（2-pyridylmethyl）amine-based ligand （1） catalytic system, which is water-soluble and air-stable, has been successfully synthesized and applied for Suzuki-Miyaura cross-coupling reaction. In the pr...A novel PdC12/bis（2-pyridylmethyl）amine-based ligand （1） catalytic system, which is water-soluble and air-stable, has been successfully synthesized and applied for Suzuki-Miyaura cross-coupling reaction. In the presence of catalytic amount of PdCl2/1 system, arylboronic acids can couple with a wide range of aryl halides, including aryl bromides and aryl chlorides. The reactions proceed under mild conditions to give excellent yields, and a wide range of functionalities is tolerated.展开更多
文摘Solvent extraction of base metals using bis((1-decylbenzimidazol-2-yl)methyl)amine (BDNNN) showed a lack of pH-metric separation of the metals. The extraction system was described quantitatively using the equilibria involved to derive the mathematical explanation for the two linear log D vs pHe plots for each metal ion extraction curve, and coordination numbers could also be extracted from the two slopes. The lack of separation was attributed to the absence of stereochemical “tailor making” since the complexes isolated from the reaction of the ligand, bis((1H-benzimidazol- 2-yl)methyl)amine (NNN), with base metals suggested the formation of similar octahedral complex species from spectral and crystal structure evidence. The bis tridentate coordination observed was in agreement with information extracted from the extraction data. This investigation opens up an opportunity and an approach for the evaluation of amines as extractants but cautions against tridentate ligands.
基金Supported by the National Natural Science Foundation of China(No.2 0 1730 0 6 )
文摘Complexes [MCl 2{CH 3N(CH 2CH 2N[CDS1]CR 1R 2) 2}]((3, M=Co, R 1=H, R 2=Ph ; 4, M=Fe, R 1=H, \{R 2=Ph\}; 5, M=Co, R 1=R 2=Ph) were prepared and characterized by IR spectra and elemental analysis. The combination of each of complexes 3-5 with ethylaluminoxane(EAO), respectively, was found to be moderately active for ethylene oligomerization to low carbon olefins. The activity of 113 kg oligomers·mol -1 Co·h -1 for complex 3(100 mol of EAO, 180 ℃ and 1 8 MPa ethylene) was observed with a selectivity of 93% to C 4-10 olefins, of which 96% were linear C4 10 olefins. The catalytic properties of complexes 3-5 were compared with those of analogous P,P coordinated complexes [MCl 2{CH 3N(CH 2CH 2PPh 2) 2}](1, M=Co; 2, \{M=\}Fe).
文摘N-Methyl bis(2-(alkyloxy-alkylphosphoryloxy)ethyl)amines, which are abbreviated as PNPs, are a series of new skeleton chemicals belonging to schedule 2.B.04 chemicals of Chemical Weapons Convention (CWC). PNPs are important markers of chemical warfare agents because they are structurally relative to both nerve agents and N-mustards. In this study, fragmentation pathways of the most characteristic fragment ions in Q-TOF mass spectrometry were proposed based on the information from accurate mass and secondary fragmentations of product ions scan experiments. Results indicated that the base ion in LC/HRMS was the quasi-molecular ion [M+H]+. In LC-HRMS/MS, it was [M+H-CnH2n+1P(O)(OH)CmH2m+1O]+ fragment ion which was formed by losing an alkyloxy alkylphosphoryloxy group from the quasi-molecular ion. The diagnostic ion m/z84.0814 was identified as [C5H10N]+, which was the group of (CH2=CH)2N+(H)CH3. PNPs have two protonated centers. One is on the N atom, the other is on the O atom (P=O). O-n-propyl PNPs generally exhibited two fragmentation pathways. Firstly, the quasi-molecular ion [M+H]+ lost a propoxy alkylphosphoryloxy group to produce [R1P(OH+)(O-n-C3H7)OCH2CH2N(CH3)CH=CH2]+, which could be fragmented further to produce [C5H10N]+ ion. Secondly, [R1P(OH+)(O-n-C3H7) OCH=CH2]+ ions were produced from [M+H]+ and fragmented further to produce the abundant ions [R1P(OH+)(OH)OCH =CH2]. However, O-isopropyl PNPs characteristically produced weak fragment ions [M+H-C3H6]+, which were presumably formed via loss of CH3CH=CH2 from [M+H]+. Other PNPs showed similar fragmentation pathways as O-n-propyl PNPs. On the summarization of the MS fragmentation pathways of PNPs, LC-HRMS/MS quantitative and qualitative methods were developed and applied to analyze N-Methyl bis(2-(butoxy-methylphosphoryloxy)ethyl]amine in high background organic samples. The analytical results had successfully supported the sample preparation for the 33rd official proficiency test of Organization for Prohibition of Chemical Weapons (OPCW).
基金the National 863 Program(No.2003AA323030)the National Natural Science Foundation of China(No.50272069 and No.20472090)for financial support.
文摘Lithium aluminium amide [LiAI（NHR）4] 5 obtained by treating the primary amine 4 with LiAlH4 could promote the ring opening of epoxide 2 and led to high regioselective product of racemic bis[2-（6-fluoro-2-chromanyl）-2-hydroxyethyl]amine methanesulfonic acid salt 7.
基金the Key Discipline Fund of Tianjin Higher Education.
文摘The Zinc complex of N, N-bis (benzimidazol 2-yl-methy])amine has been synthesized and its crystal structure determined by X-ray diffraction method. The structure features of the complex are described.
基金This project was supported by the Foundation of Science Committee of Jiangsu province (BK2005045)
文摘The title complex [Cu（ampym）（bapa）Cl]（ClO4） （C10H22Cl2CuN6O4） was synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The crystal crystallizes in the orthorhombic system, space group Pna21 with a = 11.9904（12）, b = 15.9796（16）, c = 8.9 i 43（9） A^°, V = 1708.0（3）A^°3 Mr = 424.78, Z = 4, F（000） = 876, Dc = 1.652 g/cm^3, T = 293 K,μ =1 .619 mm^-1 and λ=0.71073 A^°. The structure was refined to R = 0.0240 and wR ： 0.0564 for 2905 observed reflections with I 〉 2σ（I）. Flack = 0.039（12）.
文摘A novel PdC12/bis（2-pyridylmethyl）amine-based ligand （1） catalytic system, which is water-soluble and air-stable, has been successfully synthesized and applied for Suzuki-Miyaura cross-coupling reaction. In the presence of catalytic amount of PdCl2/1 system, arylboronic acids can couple with a wide range of aryl halides, including aryl bromides and aryl chlorides. The reactions proceed under mild conditions to give excellent yields, and a wide range of functionalities is tolerated.
