溶析结晶分离提纯2-氯-4，6-二硝基间苯二酚的方法

在室温条件下,首次利用溶析结晶方法对2-氯-4,6-二硝基间苯二酚进行分离提纯。选择乙醇为主溶剂,蒸馏水为析出剂。提纯产物用高效液相色谱、红外光谱、氢核磁共振、x射线衍射等手段进行测试表征。结果表明所得提纯产物是目的产物2-氯-4,6-二硝基间苯二酚晶体,纯度大于99．9％。     

2-氯-4，6-二硝基间苯二酚在乙醇／水混合溶剂中溶解度的研究

利用紫外吸收方法测得了2-氯-4,6-二硝基间苯二酚在乙醇／水混合溶剂中的溶解度,将实验溶解度数据和三参数经验模型相关联,通过系统的研究,证明三参数经验模型是合理的数学方程,可以准确地描述在乙醇／水混合溶剂中2一氯-4,6-二硝基间苯二酚溶解度变化规律,模型三参数（a,b和c）被确定。2-氯-4,6-二硝基间苯二酚在乙醇,水混合溶剂中的溶解度随温度的升高而增大;随水含量的升高而减小。     

2-氯-4,6-二硝基间苯二酚合成工艺研究

文章采用1,2,3-三氯苯为起始原料对合成PBO纤维单体4,6-二氨基间苯二酚的重要中间体2-氯-4,6-二硝基间苯二酚的合成方法进行了研究,并采用红外光谱法和氢核磁共振法对4,6-二硝基-1,2,3-三氯苯和2-氯-4,6-二硝基间苯二酚的结构进行了表征;采用正交试验法对4,6-二硝基-1,2,3-三氯苯碱性水解合成2-氯-4,6-二硝基间苯二酚的合成工艺进行了研究,确定了最佳工艺条件,在此条件下得到2-氯-4,6-二硝基间苯二酚的收率为95.3%。     

芴溶解度的测定及溶液结晶法提纯芴的工艺研究

在测定芴在甲醇、乙醇、正丁醇、甲苯、邻二甲苯中溶解度的基础上,确定正丁醇是溶液结晶法提纯芴的合适溶剂。介绍了采用溶液结晶法对工业芴的提纯分离的工艺过程及不同结晶条件对产品收率和纯度的影响,确定了利用溶液结晶提纯芴的最佳工艺条件,经提纯后可使芴的纯度由89.0%提高到96.6%或由95.0%提高到97.1%。     

TATB在1-乙基-3-甲基咪唑醋酸盐/二甲亚砜混合溶剂中的溶解度及结晶

研究了1-乙基-3-甲基咪唑醋酸盐([Emim]Ac)与二甲亚砜(DMSO)的质量比和溶解温度等对TATB溶解度的影响,用红外光谱(FTIR)、X射线衍射(XRD)、扫描电镜(SEM)、高效液相色谱(HPLC)和差示扫描量热(DSC)对结晶TATB的结构、形貌和热性能进行了表征。结果表明,[Emim]Ac与DMSO质量比为3∶7、温度为90℃时,TATB的溶解度为9.8g/100g。通过改变反溶剂醋酸的滴加速率能够控制TATB晶体的大小,形成的小颗粒镶嵌在大颗粒之间的晶体结构具有更好的热稳定性。     

2-氯-4,6-二甲基嘧啶的高效液相色谱分析

叙述采用反相高效液相色谱法，使用C18和紫外检测器分离测定2-氯-4，6-二甲基嘧啶。结果表明，其标准偏差为0．073，变异系数为0．044％，回收率为99．3％，线性相关系数为0．9993。     

LiBr在丙酮与水的混合溶剂中溶解度的测定与关联

使用静态法常压下分别测定了LiBr在不同质量百分比的丙酮与水的混合溶剂(水的质量分数为10％ ～40％)中293.15 ～323.15 K范围内的溶解度,并利用LIFAC模型及其参数推算了活度系数及溶解度,计算值与试验值的总平均绝对偏差和总平均相对偏差百分比分别是0.054 0和0.731 3％.结果表明,LIFAC模型可以用来预测LiBr在丙酮与水的混合溶剂中的溶解度.     

Crystallization kinetics and technology of 2-chloro-4,6-dinitro-resorcinol

The crystallization kinetics of 2-chloro-4,6-dinitro-resorcinol were studied by the method of intermittent dynamic analysis. The nucleation rate and crystal growth rate of 2-chloro-4,6-dinitro-resorcinol under three groups of conditions (27°C, 180 rpm; 33°C, 180 rpm; 33°C, 240 rpm) were estimated. The results show that, by increasing the temperature of the solution, both the nucleation rate and crystal growth rate increase. It is further found that, when the stirring rate increases, the nucleation rate increases and the crystal growth rate decreases. On the basis of the study of the crystallization kinetics, the effect of the operational parameters on the crystallization was studied. It is proved that, when the stirring rate is 180 rpm and the solution is cooled slowly to −8°C, the particle size of the crystals is even, the quality of the crystals is good, and the yield of the crystals is 40.6%. Published in Russian in Teoreticheskie Osnovy Khimicheskoi Tekhnologii, 2007, Vol. 41, No. 3, pp. 338–342. The text was submitted by the authors in English.     

超临界流体重结晶制备HMX微细颗粒和结晶速率的研究

Microparticle formation and crystallization rate of 1,3,5,7-tetranitro-l,3,5,7-tetraazacyclooctane (HMX) in acetone solution using supercritical carbon dioxide antisolvent (GAS) recrystallization were studied. Scanning electronic microscopy, X-ray diffraction and infrared radiation were used to examine particle size, crystallinity and chemical structure. The results show that β-HMX microparticle in different average size (2--9.5μm) and with narrow size distribution were obtained by controlling the expansibility, expansion speed, initial concentration and temperature during recrystallization of HMX. The formation of nuclei may be a main cause of consumption of solute when the solution is expanded rapidly enough and the equilibrium concentration is lower, in which almost monodisperse microparticle can be obtained.     

Antisolvent Crystallization of Roxithromycin and the Effect of Ultrasound

Antisolvent crystallization was performed to precipitate roxithromycin particles from organic solutions. Roxithromycin was dissolved in acetone at different concentrations and each solution was injected into an aqueous antisolvent leading to prompt particle formation. The effects of various experimental variables (solution injection rate, solution concentration, and temperature) on the particle size of roxithromycin were investigated. In addition to these variables, the effect of ultrasound on the resulting particle size was investigated by changing process parameters such as wave intensity (power output), sonication time, and the moment of ultrasonic application. When the drug solution was rapidly injected into the antisolvent, smaller crystals were obtained. Smaller crystals were obtained when solutions with high drug concentrations were used and also when the crystallization took place at lower temperatures. The particle size decreased with the increasing power output of ultrasound and with the increasing sonication time. It was also found that the ultrasonic wave induced the reduction of the particle size only when the ultrasound was applied to the solution at the initial stage of crystallization.     

7-氯-4,6-二硝基苯并氧化呋咱的合成与表征

以2-硝基-4-氯苯胺为原料,经氧化、环化、硝化,重排得7-氯-4,6-二硝基苯并氧化呋咱;用元素分析、核磁共振、红外光谱表征了其结构;研究了硝化反应温度和5-氯-苯并氧化呋咱与硝酸摩尔比对得率的影响.得出最佳硝化反应条件为:反应温度60℃,5-氯苯并氧化呋咱与硝酸的摩尔比为1∶10,得率为39%.     

2-氯-4,6-二硝基间苯二酚的结晶动力学研究

采用间歇动态法测定了2-氯-4,6-二硝基间苯二酚(CDNR)的结晶动力学参数,并回归了CDNR的结晶动力学方程,分析了结晶动力学的影响因素。通过回归结晶成核速率方程和生长速率方程的计算,得到了一定温度、一定搅拌速度下的成核、生长速率常数,温度27℃、搅拌速度180 r.min-1时成核速率常数和成长速率常数分别为9.17×106和2.17×10-12,温度33℃、搅拌速度240 r.min-1时成核速率常数和成长速率常数分别为2.02×108和7.10×10-12。     

对羟基苯甘氨酸在水-丙酮-硫酸混合溶剂中的溶解度及介稳区

分别采用恒温溶解法和变温溶解法测定了对羟基苯甘氨酸在水-丙酮-硫酸混合溶剂中的溶解度曲线和超溶解度曲线,利用激光监视装置检测测定系统中晶体的消失和产生,实验温度范围约为303~323K。随着混合溶剂中水的增加,溶解度略有增加;酸度增加,溶解度有较大幅度的增加。用经验方程二次多项式关联溶解度与温度的关系,计算的溶解度和实验值符合良好。测得的超溶解度曲线与溶解度曲线基本平行,介稳区宽度以最大过冷度表示约为1.5~2.4K,温度升高时介稳区宽度略有减少。溶剂中水含量或硫酸含量增加将使介稳区宽度变小;降低搅拌速度使介稳区明显变宽。实验结果可应用于优先结晶法拆分对羟基苯甘氨酸。     

5-氯-2-甲基-2-乙基-4,6-二羟基苯并呋喃-3(2H)-酮的合成研究

以间苯三酚为起始原料,经氯代、酰化、选择性羟基保护、氧化环合和脱保护得到5-氯-2-甲基-2-乙基-4,6-二羟基苯并呋喃-3(2H)-酮,总收率为26.8%。其结构经ESI-MS、~1H NMR确证。     

Antisolvent Crystallization of Sulfa Drugs and the Effect of Process Parameters

Abstract

Three sulfa drugs (sulfathiazole, sulfamethizole, and sulfabenzamide) were crystallized using carbon dioxide and water as antisolvents, and the effects of the type of solvent, the crystallization temperature, and the antisolvent injection rate were investigated. Sulfathiazole crystallized in granulate form from acetone, but it was crystallized in acicular form from methanol. Sulfamethizole was crystallized in tabulate form from acetone and as plates from DMF. Sulfabenzamide was precipitated in the form of prisms from acetone and of aciculates from ethyl acetate. As the crystallization temperature increased from 30 to 50°C, the average particle size increased from 6.5 to 10.5 µm for sulfathiazole, 29.5 to 53.1 µm for sulfamethizole, and 33.0 to 59.8 µm for sulfabenzamide. The crystal habit tended to become more needle‐like as the antisolvent injection rate increased. Larger particles were produced when the antisolvent was changed from carbon dioxide to water.     

氯代特戊酰氯的合成方法研究

以特戊酰氯为原料,采用气相反应,利用自行设计的气相反应装置,成功地实现底物β-H的气相氯代,合成了氯代特戊酰氯。并对该反应的影响因素进行探讨,研究结果表明:当氯气流速为13～15cm3/min、反应时间130min、反应温度由104.5°C升至166°C时,无须光照,产品最高收率为85%。     

苯胺盐酸盐在乙醇-水体系中溶解度数据的测定和混合溶剂电解质模型

采用动态法测定了苯胺盐酸盐([HAE]Cl)在乙醇及乙醇-水溶液中288~348 K范围内的溶解度. 数据表明,苯胺盐酸盐在两个体系中的溶解度随温度升高而增大;当乙醇浓度大于30%(w)时,溶解度随乙醇浓度增大而迅速降低. 为研究苯胺盐酸盐在乙醇-水体系中的相平衡关系,用混合溶剂电解质NRTL模型对所测溶解度数据进行模拟计算,得到了[HAE]Cl与C6H5OH的相互作用能量参数,建立了[HAE]Cl-C6H5OH-H2O体系的混合溶剂电解质模型及其立体相图.     

碳酸丙烯酯复合溶剂研究

对碳酸丙烯酯复合溶剂脱碳进行了研究,开发出新型的复合溶剂：碳酸丙烯酯十二乙氨基乙醇。这种复合溶剂吸收二氧化碳的能力是纯碳酸丙烯酯的１．７２倍。实验选出其中两种最佳配比的复合溶剂进行动力学研究,获得其传质系数关联式,并考察了流体力学和温度对传质系数ＫＬ的影响。     

合成2-氯-5-三氯甲基吡啶新方法

叙述近年来国内外发展的新农药如氟虫腈、溴虫腈、七氟菊酯、四氟苯菊酯、氯氟吡氧乙酸、吡氟禾草灵等相关的含氟中间体的开发,包括对-三氟甲基苯胺、2,6-二氯-4-三氟甲基苯胺、2,6-二氯-4-三氟甲基苯肼、3,5-二氯-4-氨基-6-氟吡啶酚、2,3,5,6-四氟苄醇、2,3,5,6-四氟-4-甲基苄醇、2-氯-5-三氟甲基吡啶、2.3-二氯-5-三氟甲基吡啶和2-(对氯苯基)-5-(三氟甲基)吡咯-3-腈等合成方法和国内生产情况。 摘 要 改进了传统的气相法生产2-氯-5-三氯甲基吡啶,以较新颖的液相合成方法成功地合成出2-氯-5-三氯甲基吡啶,提高了产率,减少了反应时间,且条件较为温和,在化工生产中具有一定的指导意义,对于其他吡啶类化合物的氯化亦有一定的参考价值。     

蒽吡啶酮类溶剂染料的合成和溶解性能的研究

以4-溴-N-甲基-1,9-蒽吡啶酮为主要原料,采用不同的方法与十六种胺进行缩合得到相应的染料。对合成的染料进行了溶解度的测定,并对取代氨基与染料溶解度的关系进行了初步探讨。