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1.
运用Micro-DSCⅢ微热量仪对3-硝基-1,2,4-三唑-5-酮(NTO)的二甲胺盐(DMANTO)测定比热容,拟合得到其比热容与热力学温度的关系式Cp(J/(ks·K))=2.8884×102+3.2774T和298.15K时标准摩尔热容221.74J/(mol·K).根据热容与热力学函数关系,计算了DMANTO以298.15K为基准在283~353K温区的焓、熵和吉布斯自由能,根据热容关系式及其热分解参数获得了其绝热至爆时间为13.45~13.67s.  相似文献   

2.
在甲苯溶剂中利用缓慢蒸发法得到1-(4-氯苯基)-4,4-二甲基-3-(1H-1,2,4-三唑基甲基)戊醇-3(戊唑醇)的单晶,通过 X射线单晶结构分析法测定其晶体结构,晶体属单斜晶系,空间群为P2(1)/c,晶胞参数为:a = 1.1645(1) nm,b = 1.6768(2) nm,c = 1.7478(2) nm,β= 92.055(2),Dcalc.= 1.199 g/cm3,Z = 4,F(000)= 264。运用密度泛函理论 (DFT) B3LYP得到其优化几何构型并得到其频率。计算得到的结构参数与相应的实验值十分接近。运用微热量仪对标题物进行比热容测定,在所测温度范围283~353 K内,比热容随温度呈稳定的线性变化,根据测定的比热容方程,计算出戊唑醇以298.15 K为基础在283~353 K温区的的热力学函数:焓、熵和吉布斯自由能。  相似文献   

3.
3-(3,4,5-三甲氧基苯基)-4-氨基-5-巯基-1,2,4-三唑与取代苄氯反应合成了九个新型3-(3,4,5-三甲氧基苯基)-4-氨基-5-取代苄巯基-1,2,4-三唑(2a~2i),其结构经1H NMR,IR和MS表征.初步生物活性测试结果表明,3-(3,4,5-三甲氧基苯基)-4-氨基-5-对氯苄巯基-1,2,4-三唑(2b)对半夏立枯病菌具有抑制活性.  相似文献   

4.
利用4-氨基-1,2,4-三唑与苦味酸的甲醇溶液制备了4-氨基-1,2,4-三唑苦味酸盐,并于室温下培养出单晶。通过X射线单晶结构分析法测定其晶体结构,晶体属于正交晶系,空间群为Pbcn,晶胞参数为:a=0.9207(3)nm,b=1.9874(6)nm,c=1.3304(4)nm,β=90°,V=2.434(5)nm3,Dc=1.709g/cm3,Z=8,F(000)=1280,R1=0.0584,wR2=0.1840。运用DSC测得配合物在298.15K时的标准摩尔比热容为484.39J/(mol.K),比热容与温度的关系式为:Cp(J/(g.K))=0.4435+3.6997×10-3T。  相似文献   

5.
利用4-氨基-1,2,4-三唑(4-ATZ)的乙醇溶液与乙酸锌的甲醇溶液合成了标题化合物Zn(4-ATZ)_2(CH_3COO)_2,并培养出单晶,通过X射线单晶结构分析法测定晶体结构,晶体属于正交晶系,空间群为Aba2,晶胞参数为:a=0.767 32(7)nm,b=1.66444(16)nm,c=1.09040(11)nm,V=1.3926(2)nm~3,D_c=1.936 g·cm~(-3),Z=4,F(000)=720,R_1=0.0246,wR_2=0.0675。运用Micro-DSCⅢ微热仪测定配合物的比热容,在283~353 K时,比热容随温度呈二次方关系,其关系式为:C_p/(J·g~(-1)·K~(-1))=-2.021915+1.749228×10~(-2)T-2.358752×10~(-5)T~2,298.15 K时配合物的标准摩尔比热容为385.62 J·mol~(-1)·K~(-1)。  相似文献   

6.
杜海堂  桑维钧  王慧 《有机化学》2012,31(8):1539-1542
以4-氨基-5-(3,4,5-三甲氧基苯基)-3-巯基-1,2,4-三唑为原料,环化得到6-巯基-3-(3,4,5-三甲氧基苯基)-1,2,4-三唑[3,4-b][1,3,4]噻二唑再与取代苄氯反应,得到9个6-取代苄硫基-3-(3,4,5-三甲氧基苯基)-1,2,4-三唑[3,4-b][1,3,4]噻二唑类衍生物3a~3i.其结构经IR,1H NMR,MS和元素分析确证.初步生物活性测试结果表明部分化合物有一定的杀菌活性.  相似文献   

7.
在无水乙醇中, 用吡咯烷二硫代氨基甲酸铵(APDTC)和1, 10-邻菲咯啉(o-phen·H2O)与YbCl3·3.84H2O作用, 合成了三元固态配合物, 确定它的组成为Yb[(C5H8NS2)3(C12H8N2)]. 用RD496-Ⅲ微量热计测定了298.15 K下水合氯化镱及两个配体在无水乙醇中的溶解焓, 两个配体醇溶液的混合焓及不同温度下标题化合物液相生成反应的焓变; 得到了液相生成反应的热力学参数(活化焓、活化熵和活化自由能)和动力学参数(速率常数、表观活化能、频率因子和反应级数); 通过合理的热化学循环, 求得了298.15 K时标题化合物的固相生成反应焓变; 推导了用该热量计测定固态物质比热容的计算式, 并测定了该配合物298.15 K的比热容.  相似文献   

8.
取代苯甲醛与4-氨基-5-(3,4,5-三甲氧基苯基)-1,2,4-三唑-3-硫酮(2)缩合生成5-(3,4,5-三甲氧基苯基)-4-取代苯基亚胺基-1,2,4-三唑-3-硫酮(3),再烷基加成化为新型5,6-2H-1,2,4-三唑[3,4-b][1,3,4]噻二嗪衍生物4.化合物结构经1HNMR 13C NMR,IR以及元素分析确认.采用噻唑兰(MTT)比色法进行化合物抑制人体前列腺癌细胞(PC3)体外活性测试,结果表明所合成的化合物具有不同程度的抑制PC3活性,其中化合物4a在10μmol·L-1浓度下对PC3的抑制率为75.9%.  相似文献   

9.
杜海堂  杜海军 《有机化学》2010,30(1):137-141
以3,4,5-三甲氧基苯甲酸为原料,通过4步反应得到4-氨基-5-(3,4,5-三甲氧基苯基)-3-巯基-1,2,4-三唑,再与取代芳酸反应,得到11个6-取代-3-(3,4,5-三甲氧基苯基)-1,2,4-三唑[3,4-b][1,3,4]噻二唑衍生物5a~5k。其结构经IR,1H NMR,MS和元素分析确证。初步生物活性测试结果表明部分化合物有一定的杀菌活性。  相似文献   

10.
N-(1,2,4-三唑)含氟肉桂醛亚胺的合成及生物活性   总被引:2,自引:0,他引:2  
含氟肉桂醛与4-氨基-5-(3,4,5-三甲氧基苯基)-1,2,4-三唑-3-硫酮(2)缩合生成5-(3,4,5-三甲氧基苯基)-4-取代苯基烯丙亚胺基-1,2,4-三唑-3-硫酮(3),再烷基化为新型含氟肉桂醛1,2,4-三唑亚胺(4).化合物结构经1HNMR,13CNMR,IR以及元素分析确认,并用X-ray单晶衍射测定了化合物4g的晶体结构,证实了分子中两个环外双键N=C和C=C均为E-式构型.初步生物活性测试结果表明,部分化合物具有抗植物病毒活性.  相似文献   

11.
用苯胺、氨基氰、乙酰丙酮三种物质合成了杀菌剂嘧霉胺(C12N3H13).并用溶解量热法在常压、298.15K下,分别测定了苯胺、氨基氰、乙酰丙酮和嘧霉胺在混合溶剂(VDMF:VDMSO=2:1)中的溶解焓:ΔsHmΘ(C6NH7(l),298.15K)=-(12.48±0.16)kJmol-1、ΔsHmΘ(NH2CN(s),298.15K)=-(8.06±0.42)kJmol-1、ΔsHmΘ(CH3COCH2COCH3(l),298.15K)=(1.26±0.03)kJmol-1和ΔsHmΘ[C12N3H13(s),298.15K]=(13.84±0.12)kJmol-1.根据热化学原理求出了298.15K时,合成反应的标准反应热ΔrHmΘ=-(35.65±0.47)kJmol-1,以及嘧霉胺(C12N3H13(s))的标准摩尔生成焓ΔfHmΘ(C12N3H13(s),298.15K)=(198.5±1.5)kJmol-1;用TAMair微量热仪测定了嘧霉胺(C12N3H13(s))在301.15K时对灰葡萄孢菌作用的产热曲线,根据产热曲线求算了在嘧霉胺作用下,灰葡萄孢菌生长代谢的最大发热功率Pmax、最大产热功率的时间tmax、速率常数k和抑制率I等热动力学参数.结果表明:嘧霉胺在低浓度下对灰葡萄孢菌有刺激作用,高浓度下为抑制作用,即嘧霉胺对微生物的生长具有双向生物效应,也称为Hormsis效应.  相似文献   

12.
在水溶液中合成了5-氨基间苯二甲酸钠(1)和5-羟基间苯二甲酸钠(2)固态样品,元素分析和TG-DTG确定其组成符合C8H5O4NNa2·H2O(1)和C8H4O5Na2·H2O(2).用精密自动绝热热量计测定了它们在78~400K温区的低温热容,将实验值用最小二乘法拟合,得到热容随温度变化的多项式方程,用此方程进行数值积分,得到该温区内每隔5K的舒平热容值和各种热力学函数值.用RD496-2000型微热量计测定了样品在298.15K时的标准摩尔溶解焓分别为ΔsolHmθ(1,s)=-44.552±0.164kJmol-1和θΔsolHm(2,s)=-36.055±0.154kJmol-1,计算了其水合阴离子标准摩尔生成焓分别为θΔfHm(C8H5O4N2-,aq)=-684.56±1.67kJmol-1和ΔfHmθ(C8H4O52-,aq)=-1263.43±2.13kJmol-1.用RBC-II型精密转动弹热量计测定了样品的恒容燃烧热分别为ΔcU(1,s)=-13382.14±5.28Jg-1和ΔcU(2,s)=-10339.15±4.15Jg-1,计算了它们的标准摩尔燃烧焓和标准摩尔生成焓分别为ΔcHmθ(1,s)=-3252.90±1.28kJmol-1和θΔcHm(2,s)=-2522.64±1.01kJmol-1,ΔfHmθ(1,s)=-1406.46±1.66kJmol-1,θΔfHm(2,s)=-1993.79±1.46kJmol-1.  相似文献   

13.
The objective of this work is to study the behavior of an ionic liquid, 1-H-4-amino-1,2,4-triazolium nitrate, during thermal decomposition driven by an infrared laser (10.6 μm). The focus was to understand the initial decomposition reactions and subsequent reactions that lead to ring decomposition and eventually to ignition. A triple quadrupole mass spectrometer with molecular beam sampling was used to obtain gaseous decomposition species of the sample. The principal mass peaks that may contain multiple masses were analyzed through tandem mass techniques. The experiments were conducted at a laser heat flux of 100 W/cm2 in helium at 1 atm. To assist in interpreting the data, three other materials were also tested, 4-amino-1,2,4-triazolium hydrochloride, 4-amino-1,2,4-triazole, and 1-H-1,2,4-triazole. The results show that the most probable route to initiate the decomposition of the 1-H-4-amino-1,2,4-triazolium nitrate is through proton transfer from N1 site to the nitrate forming a neutral pair, nitric acid and amino-triazole. Subsequent reactions involve decomposition of the neutral pair and their interactions.  相似文献   

14.
The thermal decomposition behavior of 3,4,5-triamino-1,2,4-triazole dinitramide was measured using a C-500 type Calvet microcalorimeter at four different temperatures under atmospheric pressure. The apparent activation energy and pre-exponential factor of the exothermic decomposition reaction are 165.57 kJ mol−1 and 1018.04 s−1, respectively. The critical temperature of thermal explosion is 431.71 K. The entropy of activation (ΔS ), enthalpy of activation (ΔH ), and free energy of activation (ΔG ) are 97.19 J mol−1 K−1, 161.90 kJ mol−1, and 118.98 kJ mol−1, respectively. The self-accelerating decomposition temperature (T SADT) is 422.28 K. The specific heat capacity of 3,4,5-triamino-1,2,4-triazole dinitramide was determined with a micro-DSC method and a theoretical calculation method. Specific heat capacity (J g−1 K−1) equation is C p = 0.252 + 3.131 × 10−3  T (283.1 K < T < 353.2 K). The molar heat capacity of 3,4,5-triamino-1,2,4-triazole dinitramide is 264.52 J mol−1 K−1 at 298.15 K. The adiabatic time-to-explosion of 3,4,5-triamino-1,2,4-triazole dinitramide is calculated to be a certain value between 123.36 and 128.56 s.  相似文献   

15.
以二次蒸馏水为溶剂,合成了2-吡嗪羧酸银(Ag(pyza)(s)),并利用X-射线单晶衍射法表征了其晶体结构.根据晶体结构数据计算得到2-吡嗪羧酸银的晶格能为554.10 kJ/mol.利用TG/DSC热分析技术研究了该化合物的热分解过程;用精密自动绝热热量计测量了其在78~378 K温区的低温热容;通过最小二乘法拟合得到了摩尔热容随折合温度变化的多项式方程,利用此方程计算出该化合物的舒平热容和各种热力学函数.通过设计合理的热化学循环,利用等温环境溶解-反应热量计分别测定了所设计热化学反应的反应物和产物在选定溶剂中的溶解焓,通过计算得到反应的反应焓为:?(31.919±0.526)kJ/mol.利用Hess定律计算出2-吡嗪羧酸银的标准摩尔生成焓为:?(243.659±1.298)kJ/mol.利用紫外-可见光谱仪对反应物和产物溶解所得溶液分别进行测量,从而证实了所设计热化学循环的可靠性.  相似文献   

16.
Twelve novel energetic salts 1a-f and 2a-f with nitrodicyanomethanide and dinitrocyanomethanide anions paired with 1,5-diamino-4-methyltetrazolium, 1,4-dimethyl-5-aminotetrazolium 1,4,5-trimethyltetrazolium, 1-methyl-4-amino-1,2,4-triazolium, 1,4-dimethyltriazolium, and 1,3-dimethylimidazolium have been prepared through metathesis reactions of equivalent silver(I) salts with corresponding iodide salts in acetonitrile. Key physical properties, such as melting point, thermal stability and density, were measured. The relationship between their structures and these properties was determined. The structures of 1,5-diamino-4-methyltetrazolium-based salts 1a and 2a were further confirmed by single-crystal X-ray analysis. The densities and standard enthalpies of formation for these energetic salts were calculated. All of the salts possess higher enthalpies of formation than the nitrate analogues.  相似文献   

17.
Results of a molecular dynamics study of several triazolium-based ionic liquids are reported. Triazolium cations include 1,2,4-triazolium, 1,2,3-triazolium, 4-amino-1,2,4-triazolium, and 1-methyl-4-amino-1,2,4-triazolium. Each cation was paired with a nitrate or perchlorate anion. These materials are part of a class of ionic compounds that have been synthesized recently but for which little physical property data are available. Properties of the more common ionic liquid, 1-n-butyl-3-methylimidazolium nitrate, are also computed and compared with the properties of the triazolium-based compounds. A molecular mechanics force field was developed for these materials using a mix of ab initio calculations and parameter fitting using the molecular compound 1H-1,2,4-triazole as a basis for the triazolium cations. Liquid-phase properties that were computed include heat capacities, cohesive energy densities, gravimetric densities/molar volumes as a function of temperature and pressure, self-diffusivities, rotational time constants, and various pair correlation functions. In the solid phase, heat capacities and lattice parameters were computed. Of all of these properties, only lattice parameters have been measured experimentally (and only for four of the triazolium compounds). The agreement with the experimental crystal structures was good. When compared with that of the imidazolium-based ionic liquid, the triazolium-based materials have much smaller molar volumes, higher cohesive energy densities, and larger specific heat capacities. They also tend to be less compressible, have a higher gravimetric density, and have faster rotational dynamics but similar translational dynamics.  相似文献   

18.
Enthalpies of dissolution of L-proline in water were measured calorimetrically at 283–313 K. The experimental temperature of dissolution of proline in water at the studied temperatures was shown to be almost independent of its concentration over the range 0.01–0.11 mol/kg. Standard enthalpies of dissolution and standard heat capacities of dissolution were calculated over this temperature range. The heat capacity of dissolution was ascertained to increase in the row glycine, proline, and alanine. The partial molar heat capacity of proline in water was determined and compared with the values obtained by extrapolation of the apparent heat capacities. The changes in entropy and reduced enthalpy and the Gibbs energy over the temperature range from 273 to 323 K were determined using familiar thermodynamic relations. The data for glycine and alanine were compared.  相似文献   

19.
采用均匀沉淀法,在20%的乙醇水溶液中,用水杨酸、维生素B3与稀土硝酸盐合成了一类新的稀土三元配合物.通过元素分析、化学分析、摩尔电导、红外光谱、紫外光谱、热重-微分热重分析等手段对配合物的结构和性质进行表征,确定了它们的组成通式为[RE(C7H5O3)2(C6H4NO2)·H2O](RE=La,Ce,Nd).维生素B3吡啶环上的N原子和水杨酸的酚羟基均未参与配位,两种配体均是脱质子后以羧酸根与RE3+离子配位,且成键以离子性为主,兼有部分共价性.在298.15 K,用精密的溶解-反应热量计分别测量了配位反应相关各物质的溶解焓,根据盖斯(Hess)定律求得合成反应的标准摩尔反应焓r mHФ分别为:(180.61±0.72)、(187.25±0.68)和(185.61±0.26)kJ/mol.进而求出配合物的标准摩尔生成焓为:f mHФ[La(C7H5O3)2(C6H4NO2)·H2O(s),298.15 K]=-(2493.9±2.9)、f mHФ[Ce(C7H5O3)2(C6H4NO2)·H2O(s),298.15 K]=-(2441.0±2.8)和f mHФ[Nd(C7H5O3)2(C6H4NO2)·H2O(s),298.15 K]=-(2463.1±2.9)kJ/mol.  相似文献   

20.
Energetic salts based on dipicrylamine and its amino derivative were synthesized. All salts were fully characterized by multinuclear NMR spectroscopy ((1)H, (13)C), vibrational spectroscopy (IR), and elemental analysis. Ethylenediammonium di-DPA (DPA=dipicrylamine) and 1,3-diaminoguanidinium DPA were further confirmed by single-crystal X-ray diffraction. These salts exhibit reasonable physical properties, such as high densities (1.71-1.81 g cm(-3)), good thermal stabilities (T(d) =155-285 °C), and low solubilities in water. The impact sensitivity of 1-methyl-3,4,5-triamino-1,2,4-triazolium DPA is lower than that of 2,4,6-trinitrotoluene (TNT), and for some other energetic salts their impact sensitivities are comparable to that of TNT. Based on experimental densities and theoretical calculations carried out by using the Gaussian 03 suite of programs, all the salts have calculated detonation pressures (22.5-27.8 GPa) and velocities (7226-7917 m s(-1)) that exceed those of conventional TNT. The toxicities of these salts measured by luminescent bacteria toxicity tests are much lower than that of TNT, and two binary eutectic mixtures with melting points that fall between 70 and 100 °C were identified.  相似文献   

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