Solubility of 4-(3,4-dichlorophenyl)-1-tetralone in eleven alcohols with the temperature range from 283K to 323K

The solubility of 4-(3,4-dichlorophenyl)-1-tetralone in eleven alcohols (methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, 2-butanol, 2-pentanol, 1,2-propanediol, 1,3-propanediol) was measured by using a laser technique with a temperature range from 283 K to 323 K, and at atmospheric pressure. For mono n-alcohols, the solubility is the lowest in methanol, increasing with the carbon chain of the alcohols. The results were correlated with a semi-empirical equation. The experimental solubility and correlation equation in this work can be used as essential data and models in the purification process of 4-(3,4-dichlorophenyl)-1-tetralone.     

4-(3,4-二氯苯基)-1-萘满酮合成述评

综述了4-(3，4-二氯苯基)-1-萘满酮的应用及合成方法，对不同路径的原料、催化剂及产率进行了介绍，并对这几种合成路径进行了比较。结果表明采用1-萘酚和邻二氯苯为原料，无水AlCl3作催化剂是一条理想和合成路线。     

Solubility of N-chloro succinimide in different pure solvents in the temperature range from 278.15 K to 333.15K

Solubility data were measured for N-chloro succinimide in pure n-butanol, ethyl acetate, acetone, isopropanol, tetrahydrofuran, acetonitrile and acetic anhydride at the temperature range between 278.15 K and 333.15 K under atmospheric pressure by gravimetric method. The solubility of N-chloro succinimide in those selected solvents increased with increasing temperature. The solubility data were correlated with the modified Apelblat equation and the van??t Hoff equation to obtain the model parameters. The experimental results could be useful for optimizing the process of purification of N-chloro succinimide in industry. Isopropanol could be the excellent solvent in the crystallization of N-chloro succinimide.     

N-(4-氯苯基)-N′-(3,4-二氯苯基)脲合成工艺研究

采用对氯苯胺和3,4-二氯苯基异氰酸酯合成了N-(4-氯苯基)-N′-(3,4-二氯苯基)脲,考察了溶剂用量、n(3,4-二氯苯基异氰酸酯)∶n(对氯苯胺)、反应时间和反应温度对反应的影响。实验表明:在溶剂邻二氯苯55mL,n(3,4-二氯苯基异氰酸酯)∶n(对氯苯胺)=1∶1,反应时间1h,反应温度145℃的工艺条件下,产品收率平均值达99.0%,熔点250~255℃(技术目标250~255℃),产品质量分数为99.7%,残留在产品中的对氯苯胺仅为32×10-6。     

手性中间体2,4-二氯-а-氯甲基苯甲醇的合成

[方法]2,4-二氯-α-氯甲基苯甲醇是重要的农药和医药中间体,可用于合成许多重要的农药和医药杀菌剂。以间二氯苯为起始原料,经傅克酰基化反应合成α-氯-2,4-二氯苯乙酮,再经手性催化还原得到α-氯-2,4-二氯苯乙醇。[结果]分别探讨了唑硼烷和唑铝烷催化体系的催化效果,由实验验证唑硼烷催化体系在室温下可使原料基本完全转化,ee值最高达98%。铝的催化效果一般,转化率和ee值均较低。[结论]该路线简单经济,反应条件温和,适合生产。     

Ultrasonic velocity measurements in isobutyric acid - water binary mixtures over the temperature range from 300.15 to 313.15 K

We measured the ultrasonic velocity, U, density, ρ, and viscosity, η in Isobutyric acid - water binary liquid mixtures over the entire composition range at temperatures ranging from 300.15 to 313.15 K under atmospheric pressure. The experimental data values were analyzed to determine, various acoustical parameters: adiabatic compressibility, β, acoustic impedance, Z, free length, L_f, free volume, V_f, molar volume, V_m, relaxation time, τ, absorption coefficient, α/f², internal pressure, π_i, Gibb’s free energy, ΔG, cohesive energy, CE, Wada’s constant, W, Rao’s constant, R_m and relative association, R_A. The variation of these parameters versus the mixture composition was explained on the basis of the intermolecular interactions between the components of the mixture.     

Solubility and metastable zone width measurement of 3,4-bis(3-nitrofurazan-4-yl)furoxan (DNTF) in ethanol+water

The solubility and supersolubility of 3,4-bis(3-nitrofurazan-4-yl)furoxan (DNTF) in ethanol+water at different operation were determined by laser monitoring system under atmospheric pressure to study the metastable zone width (MSZW). The modified Apelblat equation was adopted to correlate the experimental solubility data, and the correlation result showed perfect consistent with the experimental data. The standard dissolution enthalpy, standard dissolution entropy and Gibbs energy were calculated according to the experimental solubil-ity data. The effect of the cooling rate, stirring rate, temperature and the concentration of ethanol+water on the MSZW was studied. It was found that the MSZW of DNTF increased with the increasing cooling rate, decreasing temperature, decreasing stirring rate and decreasing ratio of water. And the apparent nucleation order of DNTF in ethanol+water was calculated by the relationship between the cooling rate and the MSZW.     

Determination and correlation solubility of 4-nitroimidazole in twelve pure solvents from 278.15 K to 323.15 K

In this paper, the solubility of 4-nitroimidazole in twelve pure solvents (toluene, benzene, 1,4-dioxane, acetonitrile, ethyl acetate, acetone, GBL, ethanol, methanol, n-butanol, DMF and NMP) were determined by using the laser monitoring system from 278.15 K to 323.15 K under 101.1 kPa, which are 0.00018-0.00070, 0.00021-0.00073, 0.00034-0.00092, 0.00038-0.00142, 0.00047-0.00120, 0.00126-0.00303, 0.00225-0.00517, 0.00310-0.00724, 0.00467-0.00982, 0.00453-0.01940, 0.01947-0.04652, and 0.04670-0.07452, respectively. At constant temperature, the mole fraction solubility of 4-nitroimidazole were increased as the following order: toluene < benzene < 1,4-dioxane < (ethyl acetate or acetonitrile) < acetone < GBL < ethanol < (methanol or nbutanol) < DMF < NMP, and the solubility of 4-nitroimidazole in (ethyl acetate, acetonitrile) and (methanol, n-butanol) had an intersection point at 297.55 K and 281.85 K, respectively. The solubility of 4-nitroimidazole could be increased with increasing temperature in twelve pure solvents. The ideal model, modified Apelblat equation, polynomial empirical equation, and λh equation were used to correlate the experimental values. The experimental solubility values were employed to calculate the standard dissolution enthalpy, standard dissolution entropy and Gibbs energy. The dissolution of 4-nitroimidazole could be an endothermic process in twelve pure solvents. The determination and fitting solubility of 4-nitroimidazole have important guiding significance for the purification and crystallization of its preparation process.     

1-(5-(4-氯苯基)-1-(2,4-二氯苯基)-4-甲基-1H-吡唑-3-基)-3-(吡啶-3-基甲基)脲的合成

以5-(4-氯苯基)-1-(2,4-二氯苯基)-4-甲基-1H-吡唑-3-甲酸与二氯亚砜为起始原料,经酰氯化反应、酰胺反应、霍夫曼重排以及水解反应生成中间体5-(4-氯苯基)-1-(2,4-二氯苯基)-3-氨基-4-甲基-1H-吡唑,再经过与氯甲酸苯酯反应、胺酯交换反应得到标题化合物,其结构经1HNMR、MS谱确证,总收率26.9%。     

4-(3,4-二氯苯基)-3,4-二氢-1(2H)-萘酮的合成

邻二氯苯和丁二酸酐经付-克酰化制得,再经还原、付-克酰化和闭环等反应得到抗抑郁剂舍曲林的中间体4-(3,4-二氯苯基)-3,4-二氢-1(2H)-萘酮,总收率50%。第1步反应n(AlCl3):n(丁二酸酐)=2.2:1较为适宜。     

Solubility of 5-mercapto-1-methyltetrazole in pure solvents from (283 to 329) K

The solubility of 5-mercapto-1-methyltetrazole in pure solvents from (283 to 329) K was measured using a laser monitoring observation technique at atmospheric pressure. The solubility data were accurately correlated by a modified Apelblat equation. The calculated results of which are proved to show fine representation of experimental data.     

288.15K-308.15K(Poloxamerl88+乙醇/丙酮+水)三元体系的密度和黏度

The densities and viscosities of ternary systems(Poloxamer 188+ethanol/acetone+water)were meas- ured at 288.15,293.15,298.15,303.15,308.15 K and atmospheric pressure for different mass fractions of Poloxamer 188(0 to 0.02)in aqueous solution and different solvent volume fractions of ethanol/acetone(0 to 0.3)in Poloxamer 188 aqueous solution.The densities were measured by a pycnometer,while the viscosities were measured using two Ubbelohde capillary viscometers.The correlations of density and viscosity of these ternary systems are obtained by fitting the experimental data at different temperatures,mass fractions and volume fractions.     

Thermodynamic properties of metamizol monohydrate in pure and binary solvents at temperatures from (283.15 to 313.15)K

The thermodynamic properties of metamizol monohydrate in pure solvents (methanol,ethanol,n-propanol and isopropanol) and two binary mixed solvent systems including (methanol + ethanol) and (methanol +isopropanol) were measured from 283.15 K to 313.15 K by gravimetric method under atmospheric pressure thought as 0.1 MPa.The modified Apelblat equation,the CNIBS/R-K equation,the Hybrid model and the NRTL model were used to correlate the solubility of metamizol monohydrate,respectively.The results show that the solubility of metamizol monohydrate in all the tested solvents increases with the rising temperature which means that it has temperature dependence.What's more,the effects of solvent components of the binary solvent mixtures on solubility were discussed,it illustrates that the increasing of the molar fraction of methanol gives the system a greater dissolving power.Furthermore,according to the NRTL model,the enthalpy,the Gibbs energy and the entropy of the mixing process were also obtained and discussed.     

1-(4-甲基苯基)乙醇的合成工艺研究

采用乙酰氯为酰化剂、三氯化铝催化甲苯的傅-克酰基化反应制备4-甲基苯乙酮,然后采用固定床将其在CuO-NiO-MnO2/SiO2铜基催化剂上连续催化加氢制备1-(4-甲基苯基)乙醇。研究结果表明,以二氯甲烷作溶剂,n(AlCl3)∶n(甲苯)∶n(乙酰氯)=1.1∶1∶1.1时,反应时间1h,反应温度0℃,甲苯的转化率达100%,4-甲基苯乙酮的收率为99.5%,纯度可达99.2%。然后在铜基催化剂CuO-NiO-MnO2/SiO2的催化下,氢气压力2.0MPa,反应温度100℃,n(H2)∶n(4-甲基苯乙酮)=30∶1,液空速为0.30h-1的条件下,4-甲基苯乙酮加氢制备1-(4-甲基苯基)乙醇,4-甲基苯乙酮的转化率为100%,1-(4-甲基苯基)乙醇的收率为97.6%。     

Solubility measurement,correlation and thermodynamic properties of 2,3,4-trichloro-1,5-dinitrobenzene in fifteen mono-solvents at temperatures from 278.15 to 323.15 K

The solubility of 2,3,4-trichloro-1,5-dinitrobenzene(TCDNB) was measured by a laser dynamic method over the temperature range from 278.15 K to 323.15 K under 0.1 MPa in fifteen mono-solvents(methanol,ethanol, isopropanol, n-butanol, toluene, dichloromethane, chloroform, tetrachloromethane, 1,2-dichloroethane, acetone, ethyl acetate, acetonitrile, N-methylpyrrolidone(NMP), N,Ndimethylformamide dimethyl sulfoxide(DMF), dimethyl sulfoxide(DMSO). The solubility of TCDNB could be increased with incre...     

Volumetric study of aqueous solutions of poly(ethylene glycol) from 283.15 to 313.15 K and at 0.1 MPa

Density measurements of binary aqueous solutions of poly(ethylene glycol), with a nominal average molecular weight of 6000, were used to determine the specific volumes of the solutions with solute‐to‐solvent mass ratios (mass of the solute/mass of the solvent) of 0.0483–0.5493 and at seven different temperatures (283.15, 285.15, 293.15, 298.15, 303.15, 308.15, and 313.15 K). The difference between the specific volume of a solution and the specific volume of a pure solvent, at a given temperature, was expanded by a virial‐type equation, in terms of the solute concentration. The first‐order coefficient was the partial specific volume of a solute at infinite dilution. The higher order coefficients corresponded to the contribution of pairs, triplets, and higher order solute aggregates according to the constant‐pressure theory of solutions. The functional dependence of the virial coefficients on the temperature was examined in terms of solute–solute and solute–solvent interactions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2685–2689, 2004     

5-甲氧羰基-4-(4-甲氧苯基)-6-甲基-3,4-二氢嘧啶-2-酮的合成

在固体酸的催化下,茴香醛、乙酰乙酸甲酯与脲进行环化缩合,一步合成了5－甲氧羰基－4－（4－甲氧苯基）－6－甲基－3,4－二氢嘧啶－2－（1H）酮,通过改变各种实验因素,找到了合成标题化合的最佳实验条件。即茴香醛0.05mol,乙酰乙酸甲酯0.06mol.脲0.75 mol,NH2SO3H1.5g,无水乙醇为溶剂,反应时间为0．6h,选用此实验条件收率可达95％以上。     

298 K时三元体系MeSO4-(NH4)2SO4-H2O的相平衡

用等温溶解平衡法研究了298 K时MeSO4-(NH4)2SO4-H2O三元体系的溶解度,并绘制了平衡相图. 结果表明,在MnSO4-(NH4)2SO4-H2O体系中,有MnSO4×H2O, (NH4)2Mn(SO4)2×6H2O和(NH4)2SO4 3条饱和曲线,组成为MnSO4×H2O和(NH4)2Mn(SO4)2×6H2O及(NH4)2Mn(SO4)2×6H2O和(NH4)2SO4的2个共饱和点,以及平衡固相为(NH4)2SO4, (NH4)2Mn(SO4)2×6H2O和MnSO4×H2O的3个纯盐结晶区. 在ZnSO4-(NH4)2SO4-H2O体系中,有(NH4)2Zn(SO4)2×6H2O, ZnSO4×7H2O与(NH4)2SO4 3条饱和曲线,组成为(NH4)2Zn(SO4)2×6H2O和ZnSO4×7H2O及(NH4)2SO4和(NH4)2Zn(SO4)2×6H2O的2个共饱和点,以及平衡固相为(NH4)2Zn(SO4)2×6H2O, ZnSO4×7H2O和(NH4)2SO4的3个纯盐结晶区. 在(NH4)2SO4-FeSO4-H2O体系中,有(NH4)2Fe(SO4)2×6H2O, FeSO4×7H2O和(NH4)2SO4的3条饱和曲线,组成为(NH4)2Fe(SO4)2×6H2O和FeSO4×7H2O及(NH4)2Fe(SO4)2×6H2O和(NH4)2SO4的2个共饱和点,以及平衡固相为(NH4)2Fe(SO4)2×6H2O, FeSO4×7H2O和(NH4)2SO4的3个纯盐结晶区. 研究结果既为含Fe2+, Mn2+和Zn2+溶液的复盐沉淀深度净化提供了理论指导,同时也为四元体系的研究奠定了基础.     

3,4-二氢-4-(1-哌啶甲基)-5H-1-苯并氧杂-5-酮盐酸盐的合成及其生物活性研究

α,β-不饱和环戊酮的Mannich碱和α,β-不饱和环己酮的Mannich碱具有显著的抗炎活性,为了寻求新的具有抗炎活性的环酮类化合物,设计了3,4-二氢-4-(1-哌啶甲基)-5H-1-苯并氧杂-5-酮盐酸盐作为目标化合物。以苯酚、γ-丁内酯、甲醛和哌啶等原料合成了目标化合物,并利用熔点、红外光谱、核磁共振氢谱等手段确定了其结构。采用二甲苯致小鼠耳肿胀法,测定了该化合物的抗炎活性,实验结果表明在200mg/kg剂量下该化合物对二甲苯所致小鼠耳肿胀的抑制率为54.5%。采用Born's比浊法测定了该化合物的抗血小板聚集活性,实验结果表明该化合物的抗血小板聚集活性比噻氯匹啶强约23倍。     

Solubilities of norfloxacin in ethanol, 1‐propanol,acetone, and chloroform from 294.15 to 318.15 K

The solubilities of norfloxacin in ethanol, 1‐propanol, acetone, and chloroform have been determined from 294.15 to 318.15 K by a static equilibrium method. The experimental results showed that the solubilities of norfloxacin in ethanol, 1‐propanol, acetone, and chloroform were all small, and increased slightly with the increase of the temperature, respectively. Under the same temperature, the decrease order of solubility of norfloxacin in the different solvents is 1‐propanol, chloroform, ethanol, and acetone. The experimental data were correlated with the modified Apelblat equation.