Reactions of N,NA-diisopropyl-thiourea（abbreviated as L1） with CuC l2 and Cu Br2 afforded the trimeric（L1Cu Cl）3（1） and（L1Cu Br）3（2）, respectively, featuring the sulfur bridged Cu3S3 six-membered ring each a...Reactions of N,NA-diisopropyl-thiourea（abbreviated as L1） with CuC l2 and Cu Br2 afforded the trimeric（L1Cu Cl）3（1） and（L1Cu Br）3（2）, respectively, featuring the sulfur bridged Cu3S3 six-membered ring each as the core structure. During the reaction, Cu（Ⅱ） was reduced to Cu（I）. Similarly, the reactions of L1 with Cu Cl and Cu Br gave the same products as those by L1 with respective Cu Cl2 and Cu Br2. In contrast, treatment of 1,3-diisopropyl-4,5-dimethylimidazole-2（3H）-thione（L2） with Cu I led to the formation of sulfur and iodide mixed-bridged complex [（L2）4（Cu I）5]（3）, in which two co-vertice Cu3S2 I six-membered rings were fused by an iodide atom. Compounds obtained were characterized by 1H NMR and 13 C spectroscopy, elemental analysis, and single-crystal X-ray diffraction. 2 belongs to the monoclinic system, space group P21/c with a = 19.6009（10）, b = 11.5069（6）, c = 17.1744（9） A, β = 109.062（3）o, V = 3661.2（3） A3, C21H48Br3Cu3N6S3, Mr = 911.18, Z = 4, Dc = 1.653 Mg/m^3, μ（Mo Kα） = 5.192 mm–1, F（000） = 1824, S = 1.030, the final R = 0.0374 and w R = 0.0808 for 4988 observed reflections（I 2σ（I）） and R = 0.0726 and wR = 0.0916 for all data. 3·2THF belongs to the monoclinic system, space group I2/a with a = 19.7335（6）, b = 13.3544（4）, c = 29.6355（11） A, β = 105.415（2）o, V = 7528.9（4） A3, C52H96Cu5I5N8O2S4, Mr = 1945.81, Z = 4, Dc = 1.717 Mg/m^3, μ（Mo Kα） = 3.589 mm–1, F（000） = 3816, S = 1.034, the final R = 0.0325 and w R = 0.0810 for 5704 observed reflections（I 2σ（I）） and R = 0.0447 and wR = 0.0910 for all data.展开更多
The title compound S-（＋）-N＇-tertbutylaminocarbonyl-N-[3-methyl-2-（4-chlorophenyl）butyryl] thiourea has been synthesized and its crystal structure was determined by singlecrystal X-ray diffraction analysis. There...The title compound S-（＋）-N＇-tertbutylaminocarbonyl-N-[3-methyl-2-（4-chlorophenyl）butyryl] thiourea has been synthesized and its crystal structure was determined by singlecrystal X-ray diffraction analysis. There exist intramolecular N（2）-H（2A）…O（1）, C（17）-H（17A）… O（2） and N（3）-H（3A）…S（1） hydrogen bonds as well as intermolecular N-H…O interaction between the carbonyl and amidogen groups. Crystallographic data： CITH24ClN3O2S, Mr = 369.90, monoclinic, space group C2/c with a = 22.9922（19）, b = 14.4844（12）, c = 12.4618（11） A, β = 92.608（2）°, V = 4145.8（6） ]k3, Z = 8, Dc = 1.185 g/cm^3, F（000） = 1568, g（MoKa） = 0.298 mm^-1, R = 0.0578 and wR = 0.1308.展开更多
A novel diamine monomer, pyridine-2, 6-bis（（4-aminophenyl）thioureido）carbonyl（PATC） was synthesized efficiently and polymerized with various aromatic dianhydrides. Consequently, poly（pyridine thiourea-imide）s...A novel diamine monomer, pyridine-2, 6-bis（（4-aminophenyl）thioureido）carbonyl（PATC） was synthesized efficiently and polymerized with various aromatic dianhydrides. Consequently, poly（pyridine thiourea-imide）s（PPTIs） with good thermal properties and flame retardancy were fabricated. The structures of PATC and PPTIs were characterized by FTIR, 1H-NMR, 13C-NMR spectroscopy along with elemental analysis, crystallinity, organosolubility, inherent viscosity and gel permeation chromatographic measurements. PPTIs containing C=S, CONH and meta substituted pyridine moieties in the polymer backbone showed amorphous nature and were readily soluble in highly polar organic solvents and even in less polar solvents such as tetrahydrofuran（THF）. Polymers had inherent viscosities in the range of 0.91-1.16 d L/g and molecular weight was found between 68000-77000 g/mol. The electrical properties of the PPTIs were estimated in terms of dielectric constant over a range of frequencies. Their thermal stability was determined by 10% weight loss temperature found in the range of 519-563 °C under inert atmosphere. The glass transition temperature of the polyimides varied between 247 °C and 267 °C. The flame retardant properties of PPTIs were investigated in terms of limiting oxygen index（LOI） which was found in the range of 38.26-39.95. Introduction of thiourea in the polymer backbone is an effective way to improve the thermal stability and flame retardancy. Thus PATC can be considered as an excellent candidate for the synthesis of high performance polymers.展开更多
基金supported by the Research Fund for Teachers of Central South University(2013JSJJ007)the Science and Technology Planning Project of Hunan Province(2013FJ2003)
文摘Reactions of N,NA-diisopropyl-thiourea（abbreviated as L1） with CuC l2 and Cu Br2 afforded the trimeric（L1Cu Cl）3（1） and（L1Cu Br）3（2）, respectively, featuring the sulfur bridged Cu3S3 six-membered ring each as the core structure. During the reaction, Cu（Ⅱ） was reduced to Cu（I）. Similarly, the reactions of L1 with Cu Cl and Cu Br gave the same products as those by L1 with respective Cu Cl2 and Cu Br2. In contrast, treatment of 1,3-diisopropyl-4,5-dimethylimidazole-2（3H）-thione（L2） with Cu I led to the formation of sulfur and iodide mixed-bridged complex [（L2）4（Cu I）5]（3）, in which two co-vertice Cu3S2 I six-membered rings were fused by an iodide atom. Compounds obtained were characterized by 1H NMR and 13 C spectroscopy, elemental analysis, and single-crystal X-ray diffraction. 2 belongs to the monoclinic system, space group P21/c with a = 19.6009（10）, b = 11.5069（6）, c = 17.1744（9） A, β = 109.062（3）o, V = 3661.2（3） A3, C21H48Br3Cu3N6S3, Mr = 911.18, Z = 4, Dc = 1.653 Mg/m^3, μ（Mo Kα） = 5.192 mm–1, F（000） = 1824, S = 1.030, the final R = 0.0374 and w R = 0.0808 for 4988 observed reflections（I 2σ（I）） and R = 0.0726 and wR = 0.0916 for all data. 3·2THF belongs to the monoclinic system, space group I2/a with a = 19.7335（6）, b = 13.3544（4）, c = 29.6355（11） A, β = 105.415（2）o, V = 7528.9（4） A3, C52H96Cu5I5N8O2S4, Mr = 1945.81, Z = 4, Dc = 1.717 Mg/m^3, μ（Mo Kα） = 3.589 mm–1, F（000） = 3816, S = 1.034, the final R = 0.0325 and w R = 0.0810 for 5704 observed reflections（I 2σ（I）） and R = 0.0447 and wR = 0.0910 for all data.
基金This work was supported by the National Key Technologies R & D Programs of China (No. 2004BA-308A22-8)
文摘The title compound S-（＋）-N＇-tertbutylaminocarbonyl-N-[3-methyl-2-（4-chlorophenyl）butyryl] thiourea has been synthesized and its crystal structure was determined by singlecrystal X-ray diffraction analysis. There exist intramolecular N（2）-H（2A）…O（1）, C（17）-H（17A）… O（2） and N（3）-H（3A）…S（1） hydrogen bonds as well as intermolecular N-H…O interaction between the carbonyl and amidogen groups. Crystallographic data： CITH24ClN3O2S, Mr = 369.90, monoclinic, space group C2/c with a = 22.9922（19）, b = 14.4844（12）, c = 12.4618（11） A, β = 92.608（2）°, V = 4145.8（6） ]k3, Z = 8, Dc = 1.185 g/cm^3, F（000） = 1568, g（MoKa） = 0.298 mm^-1, R = 0.0578 and wR = 0.1308.
基金financially supported by the Higher Education Commission of Pakistan(HEC)under the Indigenous 5000 PhD Fellowship Scheme Batch-IV
文摘A novel diamine monomer, pyridine-2, 6-bis（（4-aminophenyl）thioureido）carbonyl（PATC） was synthesized efficiently and polymerized with various aromatic dianhydrides. Consequently, poly（pyridine thiourea-imide）s（PPTIs） with good thermal properties and flame retardancy were fabricated. The structures of PATC and PPTIs were characterized by FTIR, 1H-NMR, 13C-NMR spectroscopy along with elemental analysis, crystallinity, organosolubility, inherent viscosity and gel permeation chromatographic measurements. PPTIs containing C=S, CONH and meta substituted pyridine moieties in the polymer backbone showed amorphous nature and were readily soluble in highly polar organic solvents and even in less polar solvents such as tetrahydrofuran（THF）. Polymers had inherent viscosities in the range of 0.91-1.16 d L/g and molecular weight was found between 68000-77000 g/mol. The electrical properties of the PPTIs were estimated in terms of dielectric constant over a range of frequencies. Their thermal stability was determined by 10% weight loss temperature found in the range of 519-563 °C under inert atmosphere. The glass transition temperature of the polyimides varied between 247 °C and 267 °C. The flame retardant properties of PPTIs were investigated in terms of limiting oxygen index（LOI） which was found in the range of 38.26-39.95. Introduction of thiourea in the polymer backbone is an effective way to improve the thermal stability and flame retardancy. Thus PATC can be considered as an excellent candidate for the synthesis of high performance polymers.
