The total synthesis of 3,7 dimethyl 2 tridecanyl acetate,the active component of the sex pheromone of diprion pini,was investigated in this paper.The two key synthins blocks,2 methyl octan 1 yl lithium and 3,4 ...The total synthesis of 3,7 dimethyl 2 tridecanyl acetate,the active component of the sex pheromone of diprion pini,was investigated in this paper.The two key synthins blocks,2 methyl octan 1 yl lithium and 3,4 dimethyl γ butyrolactone,were obtained from diethyl malonate and 2,3 epoxybutane.2 Methyl octan 1 yl lithium reacted with 3,4 dimethyl γ butyrolactone to yield the ketoalcohol and then followed by Huang Minlong reduction to afford 3,7 dimethyl 2 tridecanol,acylated with acetic anhydide to give 3,7 dimethyl 2 tridecanyl acetate.展开更多
2,2'-Arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) 4l-s produced from reaction between dimedone with various aldehydes in acetonitrile using ZnO as a catalyst;whereas in the presence of ZnO-acetyl ...2,2'-Arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) 4l-s produced from reaction between dimedone with various aldehydes in acetonitrile using ZnO as a catalyst;whereas in the presence of ZnO-acetyl chloride catalysts the reaction is limited to give only 1,8-dioxo-octahydroxanthenes 3a-k in very good yields.展开更多
The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its...The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1- with a = 8.9438（4）, b = 11.6065（5）, c = 14.2215（6）A, α = 112.566（1）, β = 92.324（2）, γ = 102.91（1）°, V= 1315.65（10） A^3, Z = 2, Dc = 1.344 g/cm^3,μ（MoKa） = 0.282 mm^-1, λ = 0.71073 A, F（000） = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra- and intermolecular C（ 12）-H（12）…O（1） and C（28）-H（28）...O（1）# 1 hydrogen bonds were observed in the title compound.展开更多
The title compound N,N＇-bis（5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl） ethylene diamine （DPTDEDA, C12H26N2O4P2S2） was synthesized by the reaction of neopentyl glycol, phosphorus thio-chloride and 1,2-ethylene...The title compound N,N＇-bis（5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl） ethylene diamine （DPTDEDA, C12H26N2O4P2S2） was synthesized by the reaction of neopentyl glycol, phosphorus thio-chloride and 1,2-ethylenediamine, and characterized by elemental analysis, IR and ^1H NMR spectra. Its crystal structure was determined by single-crystal X-ray diffraction analysis and the thermal property was analyzed by TG analysis. The crystal structure belongs to monoclinic, space group P21/c, with a = 14.557（16）, b = 11.299（12）, c = 12.163（13）A,β = 98.707（19）^o, Dc = 1.305 g/cm^3, Z = 4, γ = 0.71073A,μ（MoKa） = 0.447 mm^-1, Mr = 388.41, V = 1977（4）A3, F（000） = 824, S = 1.107, the final R = 0.0478 and wR = 0.0810 for 1738 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the crystal structure is centrosymmetrically distributed through 1,2-ethylenediamine to join two distorted six-membered rings. The weak N-H…S interactions are observed and link the molecules into sheets. TG analysis shows that the title compound has good thermal stability and char-forming capability, which are required for an excellent intumescent fire retardant.展开更多
Eight rare earth metal （ Ⅲ ） complexes with 2- （ （（4,6-dimethyl）-2-pyrimidinyl） thio）-acetic acid, LnL3· n H2O [HL = 2-（（（4,6-dimethyl）-2-pyrimidinyl）thio）-acetic acid; Ln = La, Ce, Pr, Nd, Sm Eu, ...Eight rare earth metal （ Ⅲ ） complexes with 2- （ （（4,6-dimethyl）-2-pyrimidinyl） thio）-acetic acid, LnL3· n H2O [HL = 2-（（（4,6-dimethyl）-2-pyrimidinyl）thio）-acetic acid; Ln = La, Ce, Pr, Nd, Sm Eu, Gd, Tb; n = 4 or 5], were prepared and characterized by elemental analysis, complexometric titration, thermal analysis, conductivity, IR and ^1H- NMR. The results reveal that carboxyl group of the hgand coordinates with rare earth ions in bidentate mode after deprotonated. The water molecules exist as crystal water in the complexes. The anti-tumour activities of HL and some complexes were tested by both the MTT and SRB methods. The results show that the suppression ratios of some complexes against the tested tumour cells （HL-60 human leukemia cell lines, BGC-823 human gastric carcinoma cell lines, hela human cervix adenocarcinoma cell lines and Bel-7402 human hepatic carcinoma cell lines） are superior to HL.展开更多
The title compound 1-（3-amino-[1,2,4]triazol-1-yl）-3,3-dimethyl-butan-2-one（3） was synthesized by Hofmann-alkylation reaction of 1-chloro-3,3-dimethyl-butan-2-one（1） and ~1H-[1,2,4]triazol-3-ylamine（2） with eq...The title compound 1-（3-amino-[1,2,4]triazol-1-yl）-3,3-dimethyl-butan-2-one（3） was synthesized by Hofmann-alkylation reaction of 1-chloro-3,3-dimethyl-butan-2-one（1） and ~1H-[1,2,4]triazol-3-ylamine（2） with equal amount of K_2CO_3 as acid acceptor. The structure of compound 3 was characterized by ~1H NMR, 13 C NMR, HRMS and single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group P21/n with a = 5.7227（8）, b = 27.924（4）, c = 6.2282（7） ？, β = 101.892（11）°, V = 973.9（2） ？~3, Z = 4, T = 180.00（10） K, μ（MoKα） = 0.087 mm^（-1）, Dc = 1.243 g/cm^3, 3832 reflections measured（3.648≤θ≤26.022°）, 1916 unique reflections（Rint = 0.0359, Rsigma = 0.0572） used in all calculations. The final R = 0.0557（I 〉 2σ（I）） and w R = 0.1276（all data）. Bioassay showed that 3 displayed excellent activity as plant growth regulator with inducing lateral root formation and enhancing primary root elongation at 0.27 mmol/L（50 ppm） in soybeen（He Feng-50）. Good water solubility was found with 50 mg in 1 m L of water. Therefore, application of 3 in agriculture is more environmentally friendly due to cosolvent-free condition, and results in improved abiotic-stress tolerance by affecting the root growth. And furthermore, it can be used as a precursor to investigate the function of regulating plant root growth.展开更多
The effect of 2-butyne-1, 4-diol on silver electrodeposition process from 5, 5-dimethyl hydantoin solutions was investigated by means of cyclic voltammetric measurement, scanning electron microscopy (SEM) and X-ray di...The effect of 2-butyne-1, 4-diol on silver electrodeposition process from 5, 5-dimethyl hydantoin solutions was investigated by means of cyclic voltammetric measurement, scanning electron microscopy (SEM) and X-ray diffraction (XRD). Cyclic voltammetric studies indicate that the reduction process of silver electrodeposition is influenced by adding 2-butyne-1, 4-diol. Owing to its adsorption on the electrode surface, 2-butyne-1, 4-diol moderately hinders the mass transfer of the silver complexed ions from the bulk solution to the outer limit of the electrode double layer and affects the electrocrystallization step. Scanning electron microscopy analysis reveals that the presence of 2-butyne-1, 4-diol in the electrolyte is beneficial and the silver deposits obtained are smoother, more compact and more leveled. X-ray diffraction analysis of the silver deposits obtained at 0.5 g·L-1 2-butyne-1, 4-diol indicated that the (110) plane is the most preferred plane and is not affected by the presence of 2-butyne-1, 4-diol in the electrolyte.展开更多
Electroanalytical techniques could be a reliable and promising alternative to classical and sophisticated methods because of their simplicity（small and portable）,easy use,the ability to deliver fast response with hi...Electroanalytical techniques could be a reliable and promising alternative to classical and sophisticated methods because of their simplicity（small and portable）,easy use,the ability to deliver fast response with high sensitivity and selectivity.A square wave voltammetric method was developed for the assessment of organophosphorus（OPs） compound impact on acetylcholinesterase（AChE） of Pheretima with 2,6-dimethyl-p-benzoquinone（2,6DMBQ） as a redox indicator.The substrate of acetylthiocholine is hydrolyzed by AChE and the produced thiocholine reacts with 2,6-DMBQ to give an obvious shift of electrochemical signal.The reduction peak of 2,6-DMBQ is located at around 0.18 V which is far away from the oxidation potential of possible interference components often present in biosample.The decreased rate of reduction current was related with the activity of AChE.The inhibition of parathion-methyl on AChE was assessed.The inhibiton rate of OPs on AChE activity increased quickly during the first 10 min inhibition,and after that the value of inhibition rate approached to be constant.AChE lost almost 29.3% of activity after 10 min incubation with 1 μg/mL parathion-methyl and 67.5% of activity with 10 μg/mL parathion-methyl,while the activity that corresponds to 40 μg/mL parathion-methyl was nearly completely inhibited（94.9%）.Compared to cyclic voltammetry and amperometry,Square wave voltammetry（SWV） method is a high sensitive electroanalysis with fast scan-rate（only several seconds for one signal value） which is useful to prevent the electrodes from possible fouling or passivation.This method can be employed to assess the inhibition of organophosphate on AChE and investigate OPs impact on environmental animals.展开更多
Started from 5-hydroxy-2-pentanone, (R)(E)-3,7-dimethyl-2-octene-1,8-dioic acid, callosobruchusic acid, was synthesized via five steps with D-(-)-camphor sultam as the chiral auxiliary. It was of good optical purity a...Started from 5-hydroxy-2-pentanone, (R)(E)-3,7-dimethyl-2-octene-1,8-dioic acid, callosobruchusic acid, was synthesized via five steps with D-(-)-camphor sultam as the chiral auxiliary. It was of good optical purity and yield.展开更多
The title compound 3-bromo-5-（4-chlorophenyl）-4-cyanopyrrole-N,N-dimethyl-2-amide（3） was synthesized with 4-bromo-2-（4-chlorophenyl）-5-（trifluoromethyl）-1H-pyrrole-3-carbonitrile（1） and N,N-dimethylformamide...The title compound 3-bromo-5-（4-chlorophenyl）-4-cyanopyrrole-N,N-dimethyl-2-amide（3） was synthesized with 4-bromo-2-（4-chlorophenyl）-5-（trifluoromethyl）-1H-pyrrole-3-carbonitrile（1） and N,N-dimethylformamide（2） by the α-C acylation reaction catalyzed by potassium t-butoxide, and characterized by IR, 1H-NMR and X-ray single-crystal diffraction. It crystallizes in monoclinic, space group P2（1/n）with a = 12.789（2）, b = 13.783（2）, c = 17.980（3） °, β = 109.230（3）°, V = 2992.5 A3, Mr = 352.62, Dc = 1.565 mg/m3, Z = 8, m = 2.924 mm-1, F（000） = 1408, the final R = 0.0424 and w R = 0.0973 for 3518 observed reflections with I 〉 2σ（I）. A total of 23559 reflections were collected, of which 6242 were independent（Rint = 0.0566）. The insecticidal, herbicidal and antibacterial activities of compound 3 were determined, and the experimental results showed that the mortality of 3 at the concentration of 100 ppm on the Fipronil against Linnaeus was 76.6%, the growth inhibition rate of 3 against Cynodon Dactylon under the condition of 100 ppm was 35.8% and the inhibitory activity of 3 at the concentration of 25 ppm against Fusarium graminearum reached 50.9%. Hence, the title compound has the value of further research and application prospect.展开更多
基金Supported by Foundation for University Key Teacher by the Min-istry of Education
文摘The total synthesis of 3,7 dimethyl 2 tridecanyl acetate,the active component of the sex pheromone of diprion pini,was investigated in this paper.The two key synthins blocks,2 methyl octan 1 yl lithium and 3,4 dimethyl γ butyrolactone,were obtained from diethyl malonate and 2,3 epoxybutane.2 Methyl octan 1 yl lithium reacted with 3,4 dimethyl γ butyrolactone to yield the ketoalcohol and then followed by Huang Minlong reduction to afford 3,7 dimethyl 2 tridecanol,acylated with acetic anhydide to give 3,7 dimethyl 2 tridecanyl acetate.
基金support from the Research Council of University of Sistan and Baluchestan, Iran
文摘2,2'-Arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) 4l-s produced from reaction between dimedone with various aldehydes in acetonitrile using ZnO as a catalyst;whereas in the presence of ZnO-acetyl chloride catalysts the reaction is limited to give only 1,8-dioxo-octahydroxanthenes 3a-k in very good yields.
基金the Science Research Foundation of Henan Institute of Science and Technology (No. 06036)
文摘The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1- with a = 8.9438（4）, b = 11.6065（5）, c = 14.2215（6）A, α = 112.566（1）, β = 92.324（2）, γ = 102.91（1）°, V= 1315.65（10） A^3, Z = 2, Dc = 1.344 g/cm^3,μ（MoKa） = 0.282 mm^-1, λ = 0.71073 A, F（000） = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra- and intermolecular C（ 12）-H（12）…O（1） and C（28）-H（28）...O（1）# 1 hydrogen bonds were observed in the title compound.
基金This work was supported by the China Petroleum & Chemical Science and Technology Foundation (No. 205026) the Tianjin Science and Technology Plan Foundation (No. 06TXTJJC14400)
文摘The title compound N,N＇-bis（5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl） ethylene diamine （DPTDEDA, C12H26N2O4P2S2） was synthesized by the reaction of neopentyl glycol, phosphorus thio-chloride and 1,2-ethylenediamine, and characterized by elemental analysis, IR and ^1H NMR spectra. Its crystal structure was determined by single-crystal X-ray diffraction analysis and the thermal property was analyzed by TG analysis. The crystal structure belongs to monoclinic, space group P21/c, with a = 14.557（16）, b = 11.299（12）, c = 12.163（13）A,β = 98.707（19）^o, Dc = 1.305 g/cm^3, Z = 4, γ = 0.71073A,μ（MoKa） = 0.447 mm^-1, Mr = 388.41, V = 1977（4）A3, F（000） = 824, S = 1.107, the final R = 0.0478 and wR = 0.0810 for 1738 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the crystal structure is centrosymmetrically distributed through 1,2-ethylenediamine to join two distorted six-membered rings. The weak N-H…S interactions are observed and link the molecules into sheets. TG analysis shows that the title compound has good thermal stability and char-forming capability, which are required for an excellent intumescent fire retardant.
文摘Eight rare earth metal （ Ⅲ ） complexes with 2- （ （（4,6-dimethyl）-2-pyrimidinyl） thio）-acetic acid, LnL3· n H2O [HL = 2-（（（4,6-dimethyl）-2-pyrimidinyl）thio）-acetic acid; Ln = La, Ce, Pr, Nd, Sm Eu, Gd, Tb; n = 4 or 5], were prepared and characterized by elemental analysis, complexometric titration, thermal analysis, conductivity, IR and ^1H- NMR. The results reveal that carboxyl group of the hgand coordinates with rare earth ions in bidentate mode after deprotonated. The water molecules exist as crystal water in the complexes. The anti-tumour activities of HL and some complexes were tested by both the MTT and SRB methods. The results show that the suppression ratios of some complexes against the tested tumour cells （HL-60 human leukemia cell lines, BGC-823 human gastric carcinoma cell lines, hela human cervix adenocarcinoma cell lines and Bel-7402 human hepatic carcinoma cell lines） are superior to HL.
基金supported by the National Natural Science Foundation of China(No.2012BAD20B04)
文摘The title compound 1-（3-amino-[1,2,4]triazol-1-yl）-3,3-dimethyl-butan-2-one（3） was synthesized by Hofmann-alkylation reaction of 1-chloro-3,3-dimethyl-butan-2-one（1） and ~1H-[1,2,4]triazol-3-ylamine（2） with equal amount of K_2CO_3 as acid acceptor. The structure of compound 3 was characterized by ~1H NMR, 13 C NMR, HRMS and single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group P21/n with a = 5.7227（8）, b = 27.924（4）, c = 6.2282（7） ？, β = 101.892（11）°, V = 973.9（2） ？~3, Z = 4, T = 180.00（10） K, μ（MoKα） = 0.087 mm^（-1）, Dc = 1.243 g/cm^3, 3832 reflections measured（3.648≤θ≤26.022°）, 1916 unique reflections（Rint = 0.0359, Rsigma = 0.0572） used in all calculations. The final R = 0.0557（I 〉 2σ（I）） and w R = 0.1276（all data）. Bioassay showed that 3 displayed excellent activity as plant growth regulator with inducing lateral root formation and enhancing primary root elongation at 0.27 mmol/L（50 ppm） in soybeen（He Feng-50）. Good water solubility was found with 50 mg in 1 m L of water. Therefore, application of 3 in agriculture is more environmentally friendly due to cosolvent-free condition, and results in improved abiotic-stress tolerance by affecting the root growth. And furthermore, it can be used as a precursor to investigate the function of regulating plant root growth.
文摘The effect of 2-butyne-1, 4-diol on silver electrodeposition process from 5, 5-dimethyl hydantoin solutions was investigated by means of cyclic voltammetric measurement, scanning electron microscopy (SEM) and X-ray diffraction (XRD). Cyclic voltammetric studies indicate that the reduction process of silver electrodeposition is influenced by adding 2-butyne-1, 4-diol. Owing to its adsorption on the electrode surface, 2-butyne-1, 4-diol moderately hinders the mass transfer of the silver complexed ions from the bulk solution to the outer limit of the electrode double layer and affects the electrocrystallization step. Scanning electron microscopy analysis reveals that the presence of 2-butyne-1, 4-diol in the electrolyte is beneficial and the silver deposits obtained are smoother, more compact and more leveled. X-ray diffraction analysis of the silver deposits obtained at 0.5 g·L-1 2-butyne-1, 4-diol indicated that the (110) plane is the most preferred plane and is not affected by the presence of 2-butyne-1, 4-diol in the electrolyte.
基金Supported by the Natural Science Foundation of Shanxi Province,China(No.20001057)
文摘Electroanalytical techniques could be a reliable and promising alternative to classical and sophisticated methods because of their simplicity（small and portable）,easy use,the ability to deliver fast response with high sensitivity and selectivity.A square wave voltammetric method was developed for the assessment of organophosphorus（OPs） compound impact on acetylcholinesterase（AChE） of Pheretima with 2,6-dimethyl-p-benzoquinone（2,6DMBQ） as a redox indicator.The substrate of acetylthiocholine is hydrolyzed by AChE and the produced thiocholine reacts with 2,6-DMBQ to give an obvious shift of electrochemical signal.The reduction peak of 2,6-DMBQ is located at around 0.18 V which is far away from the oxidation potential of possible interference components often present in biosample.The decreased rate of reduction current was related with the activity of AChE.The inhibition of parathion-methyl on AChE was assessed.The inhibiton rate of OPs on AChE activity increased quickly during the first 10 min inhibition,and after that the value of inhibition rate approached to be constant.AChE lost almost 29.3% of activity after 10 min incubation with 1 μg/mL parathion-methyl and 67.5% of activity with 10 μg/mL parathion-methyl,while the activity that corresponds to 40 μg/mL parathion-methyl was nearly completely inhibited（94.9%）.Compared to cyclic voltammetry and amperometry,Square wave voltammetry（SWV） method is a high sensitive electroanalysis with fast scan-rate（only several seconds for one signal value） which is useful to prevent the electrodes from possible fouling or passivation.This method can be employed to assess the inhibition of organophosphate on AChE and investigate OPs impact on environmental animals.
基金Supported by the National Natural Science Foundation of China( No. 2 9872 0 12)
文摘Started from 5-hydroxy-2-pentanone, (R)(E)-3,7-dimethyl-2-octene-1,8-dioic acid, callosobruchusic acid, was synthesized via five steps with D-(-)-camphor sultam as the chiral auxiliary. It was of good optical purity and yield.
基金supported by the National Natural Science Foundation of China(No.21272086)
文摘The title compound 3-bromo-5-（4-chlorophenyl）-4-cyanopyrrole-N,N-dimethyl-2-amide（3） was synthesized with 4-bromo-2-（4-chlorophenyl）-5-（trifluoromethyl）-1H-pyrrole-3-carbonitrile（1） and N,N-dimethylformamide（2） by the α-C acylation reaction catalyzed by potassium t-butoxide, and characterized by IR, 1H-NMR and X-ray single-crystal diffraction. It crystallizes in monoclinic, space group P2（1/n）with a = 12.789（2）, b = 13.783（2）, c = 17.980（3） °, β = 109.230（3）°, V = 2992.5 A3, Mr = 352.62, Dc = 1.565 mg/m3, Z = 8, m = 2.924 mm-1, F（000） = 1408, the final R = 0.0424 and w R = 0.0973 for 3518 observed reflections with I 〉 2σ（I）. A total of 23559 reflections were collected, of which 6242 were independent（Rint = 0.0566）. The insecticidal, herbicidal and antibacterial activities of compound 3 were determined, and the experimental results showed that the mortality of 3 at the concentration of 100 ppm on the Fipronil against Linnaeus was 76.6%, the growth inhibition rate of 3 against Cynodon Dactylon under the condition of 100 ppm was 35.8% and the inhibitory activity of 3 at the concentration of 25 ppm against Fusarium graminearum reached 50.9%. Hence, the title compound has the value of further research and application prospect.
