盐酸美金刚中间体I的合成

以1,3-二甲基金刚烷和液溴为原料,不加任何溶剂,40℃反应24h,高收率,高纯度的生成盐酸美金刚重要中间体1-溴-3,5-二甲基金刚烷。     

金刚烷基Bola型表面活性剂的设计、合成及表面活性

以1,3-二溴金刚烷为起始原料,首先在Lewis酸催化作用下与苯酚发生傅-克烷基化反应生成1,3-二(4-羟苯基)金刚烷(DPAD);DPAD再经Williamson缩合反应和中和反应合成了新型金刚烷基Bola型表面活性剂1,3-二(4-(2-乙氧基磺酸钠)-苯基)金刚烷。采用IR、¹H NMR和元素分析等手段确定了各中间物及产物的结构,测试了1,3-二(4-(2-乙氧基磺酸钠)-苯基)金刚烷的表面活性。考察了关键反应步骤(Williamson缩合反应)溶剂、卤代磺烷基化试剂、反应温度、反应时间和物料比对产物收率的影响。在优化的反应条件下,1,3-二(4-(2-乙氧基磺酸钠)-苯基)金刚烷的总收率可达72%。     

一种适合工业化制备盐酸美金刚的方法

提供一种盐酸美金刚的制备方法,以1,3-二甲基金刚烷为起始物料,经Ritter反应、碱性水解、盐酸化成盐和用水重结晶得到盐酸美金刚原料药。     

盐酸美金刚胺的合成

采用1,3-二甲基金刚烷为原料,经氯化,与乙酰胺直接反应,水中析出物在丙三醇作溶剂下加入氢氧化钠反应,经乙酸乙酯萃取、浓缩、盐酸化得到盐酸美金刚胺,总收率76．1％。     

2,6-二甲基苯酚异构化反应研究

研究了三氯化铝催化2,6-二甲基酚的异构化反应，结果表明2,6-二甲基苯酚异构化合成附加值较高的二甲基苯酚混合物(包括2,5-二甲基苯酚、3,5-二甲基苯酚、2,3-二甲基苯酚、3,4-二甲基苯酚)是可行的，催化剂三氯化铝活性高，原料转化率>99%。主要考察了三氯化铝催化2,6-二甲基苯酚异构化反应合成2,5-二甲基苯酚、2,3-二甲基苯酚的效果，其中2,5-二甲基苯酚选择性可达95%以上，且2,6-二甲基苯酚转化率>83.5%。     

3-羟基-1-金刚烷甲基酮的合成及其工艺优化

以1-金刚烷甲酸为起始原料,经混酸(H_2SO_4/HNO_3)氧化得到3-羟基-1-金刚烷甲酸,经酰化、取代、脱羧得3-羟基-1-金刚烷甲基酮。考察了催化剂种类与用量、反应温度、反应时间、乙酰氯与3-羟基-1-金刚烷甲酸物质的量之比对3-羟基-1-金刚烷甲基酮收率的影响,确定了较佳的反应条件为:以吡啶为催化剂,n(吡啶)∶n(3-羟基-1-金刚烷甲酸)=1.5∶1,n(乙酰氯)∶n(3-羟基-1-金刚烷甲酸)=3.5∶1,反应温度为35℃,反应时间为3 h,在该条件下反应总收率约为70%(以1-金刚烷甲酸为基准)。     

新型1,3-茚满二酮类螺环化合物的合成与表征

以1,3-茚满二酮和取代苯甲醛为原料,通过Knoevenagel缩合反应生成2-芳基亚甲基-1,3-茚满二酮,然后2-芳基亚甲基-1,3-茚满二酮与4-氯代乙酰乙酸乙酯在催化剂作用下发生Michael/γ-Alkylation串联反应,获得了6个新型1,3-茚满二酮类螺环化合物。并且进行了催化剂、溶剂和温度的筛选,发现三乙胺为最优的催化剂,在室温下,以氯仿为溶剂,反应获得了最好的收率(98%)和非对映选择性(98∶2 dr)。产物的结构经1HNMR、13CNMR、HRMS确证。     

离子液体-铝盐催化蔗糖制乙酰丙酸甲酯

研究发现铝盐及铝盐与咪唑的复合盐催化剂可以在甲醇中催化蔗糖反应生成乙酰丙酸甲酯,尤其是在铝盐中加入1,3-二甲基咪唑的硫酸氢盐时,可以明显地提高乙酰丙酸甲酯的收率。本研究工作考察了B酸型的离子液体1,3-二甲基咪唑硫酸氢盐与各种铝盐的协同催化作用,同时研究了反应时间、反应温度和催化剂用量对乙酰丙酸甲酯收率的影响,优化了反应条件。在反应温度为140 ℃下反应3 h,使用0.500 g的1,3-二甲基咪唑硫酸氢盐和0.500 g的甲基磺酸铝作催化剂,乙酰丙酸甲酯的摩尔收率达到70%。     

椰油酰胺丙基甜菜碱的合成与表征

以椰油酸甲酯、N,N-二甲基-1,3-丙二胺、氯乙酸和NaOH为原料,KOH为催化剂合成椰油酰胺丙基甜菜碱。考察了N,N-二甲基-1,3-丙二胺与椰油酸甲酯的投料比、催化剂用量、反应温度和反应时间对主反应椰油酰胺丙基二甲胺合成的影响。结果表明,较佳工艺条件为:n(N,N-二甲基-1,3-丙二胺)∶n(椰油酸甲酯)=1.15∶1,w(催化剂)=3.0%,反应温度为210℃,反应时间为25 min,此条件下椰油酸甲酯的转化率达到99.70%。采用红外光谱、质谱和高效液相色谱对目标产物结构进行了确认。     

连续法制备N,N-二甲基-1,3-丙二胺的工艺研究

以二甲胺和丙烯腈为原料,采用两步连续反应的方法对制备N,N-二甲基-1,3-丙二胺的工艺进行了研究,采用固定床反应器完成二甲胺与丙烯腈加成制备二甲氨基丙腈第1步反应和二甲氨基丙腈加氢制备N,N-二甲基-1,3-丙二胺第2步反应,并对反应工艺进行了优化。结果表明:第1步反应在空速为1.1 h~(-1),温度为30℃,压力为1.0 MPa,摩尔比为1∶1的条件下,丙烯腈的转化率和N,N-二甲基氨基丙腈选择性均能达99.5%以上;第2步反应固定床加氢还原采取逆流反应的方式,催化剂为DCF-1Raney-Ni催化剂,温度为70℃,压力为6.0 MPa,总空速为0.3 h~(-1),助催化剂为2.0%Na OH的甲醇溶液,Na OH质量分数为0.46%,二甲氨基丙腈的转化率与N,N-二甲基-1,3-丙二胺的选择性均达99.5%以上。     

PSA-PS在反-5-戊基-2-(4-氰基苯基)-1,3-二噁烷合成中的应用

以苯基磺酸官能化中孔硅基材料(PSA-PS)为催化剂,对氰基苯甲醛和2-戊基丙二醇为原料,催化合成了5-戊基-2-(4-氰基苯基)-1,3-二噁烷的顺、反混合物。并以同样的PSA-PS催化转型、重结晶后,得到反-5-戊基-2-(4-氰基苯基)-1,3-二噁烷纯品,收率83%。此外,在缩合反应中,对比对甲苯磺酸和氯化钙,使用PSA-PS催化可使反应时间缩短一半。PSA-PS在缩合、转型反应中可重复使用4次。     

2,6-萘二甲酸的合成研究

使用1,8-萘二甲酸酐为原料,采用亨克尔法,以碳酸锌做催化剂、萘和碘化钾为助剂,在二氧化碳气氛中进行反应,通过异构化反应制备2,6-萘二甲酸.探讨了反应温度、反应时间、催化剂用量、反应压力、搅拌速度、助催化剂和助剂用量对异构化转位反应的影响.结果表明:根据正交实验确定了1,8-萘二甲酸二钾盐异构化转位反应的较优工艺,各...     

二甲苯异构化催化剂的研究进展

介绍了EUO、SM-3和／MgAPSO-31等分子筛应用于二甲苯异构化催化剂的研究成果;总结和讨论了改性丝光沸石和ZSM-5分子筛对二甲苯异构化催化剂反应性能的影响;并对二甲苯异构化催化剂的发展前景进行了展望,提出了二甲苯异构化催化剂的研究方向应集中在保证催化剂活性和稳定性的同时改善选择性。     

负载AlCl_3催化剂合成挂式-三环[5.2.1.0~(2,6)]癸烷

采用液固反应法合成了负载AlCl3催化剂,用于催化桥式四氢双环戊二烯异构化合成挂式四氢双环戊二烯的反应。通过考察载体、负载量对催化剂活性的影响,选定SiO2作载体、负载量为60%的催化剂用于该反应;研究了负载催化剂用量、溶剂种类及反应时间对异构化反应的影响,得到了最佳反应条件:以挂式四氢双环戊二烯作溶剂,催化剂质量分数14%,反应时间2 h。在此条件下桥式四氢双环戊二烯的转化率为99%,挂式四氢双环戊二烯的选择性为97.9%。该过程反应后处理简单,环境友好。     

固体杂多酸催化合成富马酸二甲酯

采用固体杂多酸磷钼酸为催化剂，溴酸盐为异构化剂，经顺酐一步合成了富马酸二甲酯，探讨了醇酐比、反应时间、催化剂的量、异构化剂的量以及异构化时间对合成DMF收率的影响，并确立了最佳反应条件。DMF收率达85％以上。     

Catalytic performance of MIL-100 (Fe,Cr) and MIL-101 (Fe,Cr) in the isomerization of endo- to exo-dicyclopentadiene

MIL-100 (Fe, Cr) and MIL-101 (Fe, Cr), metal-organic frameworks (MOFs), have been assessed in solvent-free isomerization of dicyclopentadiene (DCPD) from the endo- to exo-form. In the isomerization reaction, the conversion of endo-DCPD and selectivity for the exo-dimer strongly depend on the nature of the active metal center. The MIL-100 (Fe) catalyst possessing more acid sites shows the highest catalytic activity among the MILs and it was readily recoverable and reusable in subsequent reaction cycles for the isomerization. The effects of reaction parameters such as temperature, reaction time, and catalyst loading on the reactivity were also investigated.     

酸性离子液体催化甲基环戊烷异构化反应

以三级胺、盐酸和AlCl_3为主要原料制备了氯铝酸盐型酸性离子液体催化剂,并优化了催化剂的配比。考察了催化剂用量、反应温度、反应时间以及原料杂质等对甲基环戊烷异构反应的影响。结果表明,提高催化剂用量和反应温度可加快反应速率,在反应温度70℃,油剂比3.0,反应4 h后,环己烷的产率达到70%以上,微量杂质(正己烷和苯)几乎不影响甲基环戊烷的异构化反应。离子液体催化剂在补充活性组分AlCl_3的情况下可以实现循环使用。     

Application of kinetics and computational fluid dynamics in pinene isomerization

A reliable kinetic model to describe the effects of various factors on the reaction rate and selectivity of pinene isomerization is developed. Furthermore, computational fluid dynamics (CFD) is applied to simulate the solid- liquid dispersion in reactor. The catalyst TiM is obtained by improving the composition and structure of hydrated titanium dioxide. The kinetic equation of pinene isomerization is deduced based on reaction mechanism and catalyst deactivation model. The kinetic equation of pinene isomerization reaction is fitted, and the results show that the fitted equation is correlated with the experimental data. The rate and selectivity of pinene isomerization reaction are affected by the amount of catalyst, deactivation of catalyst, structure of catalyst, reaction temperature and water content of catalyst. The solid-liquid distribution of the reactor is calculated by computational fluid dynamics numerical simulation, and the solid-liquid dispersion in commercial scale reactor is more uniform than that in lab-scale reactor.     

Study on the pinene isomerization catalyzed by TiM

The isomerization reaction of pinene is one of the most important chemical reactions in the deep processing of pinene. The purpose of this study is to improve the performance of the metatitanic acid by composite. The composite metatitanic acid catalyst TiM was prepared by adding Mn elements in the preparation process. The catalytic performance of TiM was evaluated. Comparison of TiM and metatitanic acid catalyst (Ti-FGP), the reaction rate of TiM catalyst was faster, and after the reaction, the yield of camphene and tricyclene increased about 1%. The catalysts were characterized by an SEM, FT-IR and laser particle size analyzer. The results show that the pinene isomerization reaction requires the synergistic action of the Brönsted acid and Lewis acid. Brönsted acid has great influence on the activity of catalyst, and Lewis acid has a great influence on the selectivity of the catalyst. The structure and morphology of the catalyst have a certain effect on the selectivity of pinene isomerization reaction.     

Application of kinetics and computational fluid dynamics in pinene isomerization

A reliable kinetic model to describe the effects of various factors on the reaction rate and selectivity of pinene isomerization is developed. Furthermore, computational fluid dynamics(CFD) is applied to simulate the solid–liquid dispersion in reactor. The catalyst Ti M is obtained by improving the composition and structure of hydrated titanium dioxide. The kinetic equation of pinene isomerization is deduced based on reaction mechanism and catalyst deactivation model. The kinetic equation of pinene isomerization reaction is fitted, and the results show that the fitted equation is correlated with the experimental data. The rate and selectivity of pinene isomerization reaction are affected by the amount of catalyst, deactivation of catalyst, structure of catalyst, reaction temperature and water content of catalyst. The solid–liquid distribution of the reactor is calculated by computational fluid dynamics numerical simulation, and the solid–liquid dispersion in commercial scale reactor is more uniform than that in lab-scale reactor.