3-(2-氧代-1,2-二氢喹啉-4-基)丙氨酸的合成研究

以丙二酸二乙酯为原料,经亚硝化、还原、乙酰化、缩合、水解、脱羧反应制得3-（2-氧代-1,2-二氢喹啉-4-基）丙氨酸,总收率为41.5%,含量为98.7%.合成工艺简单易操作,适合工业化生产.     

头孢托罗活性硫酯的合成工艺研究

优化了头孢托罗活性硫酯-(Z)-2-(5-氨基-1,2,4-噻二唑-3-基)-2-三苯甲氧亚胺基硫代乙酸(S-2-苯并噻唑)酯(2)的合成工艺。以3-氨基-5-乙酰胺基异噁唑(3)为原料,与特戊酰基异硫氰酸酯经重排反应,制得N-乙酰基-2-(5-特戊酰胺基-1,2,4-噻二唑-3-基)乙酰胺(5),收率为72%;采用亚硝酸异丙酯对中间体5进行肟化、然后与三苯基氯甲烷进行醚化制得(Z)-N-乙酰基-2-(5-特戊酰胺基-1,2,4-噻二唑-3-基)-2-三苯甲氧亚胺基乙酰胺(7a),收率为78%;7a经碱性水解,制得(Z)-2-(5-氨基-1,2,4-噻二唑-3-基)-2-三苯甲氧亚胺基乙酸(8),收率为65%;,在乙腈与甲苯的混合溶剂中,8与亚磷酸三乙酯、二苯并噻唑二硫醚混合反应,制得活性硫酯2,路线的总收率达24%。该合成工艺具有反应条件温和,操作简便,易于分离等优点,因而有较好的工业化应用前景。     

1，1′-硫代双（2－萘酚）的合成

以2-萘酚为主要原料,与二氯化硫在甲苯、乙酸乙酯组成的混合溶剂中反应,合成了抗氧剂1,1′-硫代双（2-萘酚）。确定的最佳反应条件为：溶剂为由甲苯、乙酸乙酯组成的混合溶剂,甲苯、乙酸乙酯重量比为3：2,溶剂与2－萘酚重量比为8：1,2－萘酚与二氯化硫物质的量比为2：1．03,反应温度10-20℃,反应时间3h,产品收率84．7％,纯度大于99．0％。     

3-(2-甲基-6-甲基硫代苯基)-4,5-二氢化异噁唑的合成研究

以2-(4,5-二氢异噁唑-3-基)-3-甲基苯胺为原料,铜为催化剂在无水的条件下经亚硝酸叔丁酯重氮化合成3-(2-甲基-6-甲基硫代苯基)-4,5-二氢化异噁唑。探索了反应温度、反应时间、催化剂的用量等因素对反应的影响,优化条件为反应温度为60℃,反应时间为1.5 h,n(2-(4,5-二氢异噁唑-3-基)-3-甲基苯胺)∶n(催化剂)=1∶3,反应收率为98.6%,产品结构经LC-MS、~1H NMR确证。     

4-[2-(4,6-二甲氧基嘧啶基)]-3-硫代脲酸苯酯合成工艺及生物活性研究

采用二步反应考察了4-[2-(4,6-二甲氧基嘧啶基)]-3-硫代脲酸苯酯合成的最优反应条件,通过氢谱(1H NMR)、红外光谱(IR)、元素分析和熔点测定,对所合成的产物进行结构分析。采用离体含毒介质法,对合成产物进行杀菌毒力活性的测定。结果表明,0.1 mol氯甲酸苯酯和0.2 mol硫氰酸钾,在乙酸乙酯中50℃反应2 h,滤去生成的氯化钾,加入4,6-二甲氧基嘧啶-2-胺0.08 mol,在60℃下反应4 h,产品总得率不低于75%。产品对植物病害菌有良好的抑制和杀灭作用。     

2-氧代环己烷基磺酸盐的合成

[目的]2-氧代环己烷基磺酸盐是合成N-(2-三氟甲基-4-氯苯基)-2-氧代环己烷基磺酰胺(L-13)的重要中间体,为了进一步提高其收率和纯度,研究了2-氧代环己烷基磺酸盐合成的反应条件。同时研究了用五氧化二磷与硫酸反应制备三氧化硫的条件。[结果]合成2-氧代环己烷基磺酸盐的最佳投料摩尔比是三氧化硫∶二氧六环∶环己酮为1∶1.1∶1.1,最佳反应温度-15~-20℃,最佳反应时间为4 h,溶剂的用量是三氧化硫∶二氯乙烷为1 g∶5.06 mL。在后处理过程中用氢氧化钙除掉硫酸,经碱中和生成的磺酸钾盐的质量要好于磺酸钠盐。[结论]投料比、反应温度、溶剂用量和后处理方法对2-氧代环己烷基磺酸盐的收率和品质影响很大,磺酸钾盐的收率可达71.2%,其能够满足L-13的合成要求。     

水相合成S-正辛基-5,5-二苯基-2-硫代海因的绿色工艺

以5,5-二苯基-2-硫代海因和溴代正辛烷为原料，在碱水溶液中相转移催化合成S-正辛基-5,5-二苯基-2-硫代海因，考察溴代正辛烷用量、氢氧化钾用量、相转移剂种类和用量以及反应时间对产率的影响。确定较佳工艺条件为：5,5-二苯基-2-硫代海因50 mmol，溴代正辛烷55 mmol，氢氧化钾50 mmol，十八叔胺0.2 g，水50 mL，回流反应4 h，可得到高纯度S-正辛基- 5,5- 二苯 基-2 -硫代海因，产率达85%。产品结构经IR、¹H NMR、13C NMR及MS进行了表征。     

3,3-二甲氧基丙腈的合成

以2—氯—3—苯硫砜基丙腈[Ⅰ]为原料经过消除和加成二步反应合成3,3—二甲氧基丙腈[Ⅱ]。[Ⅰ]在0℃～20℃脱HCl得3—苯硫砜基丙烯[Ⅲ],收率为88%。[Ⅲ]在甲醇溶液中以甲醇钠为催化剂反应得[Ⅱ],收率98%。消除反应的创新处在于用四氢呋喃代替乙醚,节省大量溶剂,收率有所提高,加成反应的创新处是增大甲醇钠的投料比,优化反应条件。     

2,3-环硫-1-(2-呋喃基)-3-苯基-1-酮的合成

以1-(2-呋喃基)-3-苯基-2-丙烯-1-酮(FPPO)、过氧化氢、硫脲为原料,以四丁基溴化铵为催化剂,采用一锅法合成2,3-环硫-1-(2-呋喃基)-3-苯基-1-酮(TFPO)。通过单因素实验,考察了时间、温度、氧化剂用量、催化剂用量等对TFPO产率的影响,进一步利用正交实验优化法对合成TFPO的工艺参数进行优化。结果表明,合成TFPO较佳的工艺条件为:环氧化温度为5℃,硫化时间为2 h,硫化温度为35℃,n(硫脲)∶n(FPPO)=1∶1,催化剂用量为15.5%(以FPPO物质的量为基准计算得到,下同)。在该条件下,TFPO产率为85.8%。采用FTIR、1HNMR和13CNMR确认了TFPO的结构,应用TGA、UV测试了TFPO的性能。TGA测试结果显示,TFPO的耐热温度为160℃,展现出良好的热稳定性。紫外测试结果表明,TFPO的透光率可达90%以上,具有优异的透光性能。     

微波辐射固相合成5-(取代吲哚基-3-次甲基)(硫代)巴比妥酸

在无溶剂、无催化剂、微波辐射条件下,取代吲哚-3-甲醛与(硫代)巴比妥酸通过Knoevenagel缩合反应,合成了一系列5-(取代吲哚基-3-次甲基)(硫代)巴比妥酸。最佳反应条件为:n(吲哚-3-甲醛)∶n(巴比妥酸)=1.2∶1.0,微波辐射时间8 min,微波功率500 W,产率68.4%～82.8%。     

1,3-二氰硫基-2-N,N-二甲氨基丙烷制备研究

以3-氯丙烯为原料,通过和二甲胺水溶液进行缩合反应,再用氯气进行双键加成反应,最后同硫氰化钠反应生成了农药杀螟丹的中间体1,3-二氰硫基-2-N,N-二甲氨基丙烷。最终产物纯度为99%以上。     

2－羟基－3－烯丙氧基－1－丙烷磺酸盐的合成

用合成的１－氯－２－羟基－３－烯丙氧基丙烷中间体，经磺化作用，制得２－羟基－３－烯丙氧基－１－丙烷磺酸盐（ＨＡＰＳ）。经元素分析、红外光谱分析和核磁共振谱分析，确证了ＨＡＰＳ的结构。     

2,2-二甲氧基丙烷的合成研究

简述了 2 ,2 -二甲氧基丙烷的合成方法 ,着重介绍了以丙二醇和丙酮为原料经 2 ,2 ,4-三甲基 - 1,3-二氧环戊烷合成了 2 ,2 -二甲氧基丙烷的新方法 ,两步反应总收率 6 3.7%。此外对实验结果及反应所用催化剂、分水剂等做了讨论。     

BiOCl催化剂的丙烷氧化脱氢催化性能

以_L-赖氨酸为模板剂,采用沉淀法制备了BiOCl催化剂,对催化剂进行了X射线衍射、N₂吸附-脱附和H₂-TPR等表征,并测试了BiOCl催化剂对丙烷氧化脱氢制丙烯反应的催化性能。结果表明,制备的BiOCl催化剂为四面体结构,500 ℃焙烧3 h后,催化剂比表面积为11.2 m²·g^-1,未完全还原氧物种的含量较多。随着反应温度升高,丙烷转化率和丙烯选择性增加,丙烷转化率为20%时,丙烯选择性达64.5%。     

MoO3/ZrO2催化剂的丙烷氧化脱氢制丙烯催化性能

以十六烷基三甲基溴化铵为表面活性剂,采用溶剂热法制备系列MoO_3/ZrO_2催化剂,采用H2-TPR、N_2吸附-脱附、X射线衍射等对其进行表征,并评价MoO_3/ZrO_2催化剂的丙烷氧化脱氢制丙烯催化性能。结果表明,MoO_3负载于ZrO_2载体上制备的催化剂催化活性增加,MoO_3负载质量分数为20%的MoO_3/ZrO_2催化剂,在反应温度为600℃时,丙烷转化率27.45%,丙烯选择性44.78%,丙稀收率12.29%。     

SBA-15 grafted with 3-aminopropyl triethoxysilane in supercritical propane for CO2 capture

Supercritical propane (SC-propane) was found to be a promising solvent for grafting (3-aminopropyl)triethoxysilane (APS) onto synthesized SBA-15 for CO₂ capture. The influence of operating conditions in SC-propane for CO₂ adsorption at different pressures (8.3–13.8 MPa), temperatures (85–120 °C), and periods of time (4–16 h) were evaluated. The CO₂ adsorption conditions under different partial pressures, temperatures and moisture were evaluated. The results showed a reduction in pore characteristics and an increased amount of grafted APS with increasing pressure and temperature after grafting. After grafting in SC-propane at 11.0 MPa and various temperatures for 16 h, a 3–20% increase in the amount of grafted APS and a 6–49% increase in the CO₂ adsorption capacity over the toluene refluxing was observed. The time required for grafting in SC-propane could be reduced while maintaining higher nitrogen content and CO₂ adsorption capacity compared with grafting in toluene refluxing.     

Propane Oxidative Dehydrogenation over Metal Pyrophosphates Catalysts

Metal pyrophosphates (M–P₂O₇, where M is V, Zr, Cr, Mg, Mn, Ni or Ce) have been found to catalyze the oxidative dehydrogenation of propane to propene. The reaction was conducted at 1 atm, 450–550°C and feed flowrate of 75 cm³/min (20 cm³/min propane, 5 cm³/min oxygen and the balance is helium). All catalysts showed increase in degrees of conversion and decrease in olefins selectivity with increase in reaction temperature. At 550°C, MnP₂O₇ exhibited the highest activity (40.7% conversion) and total olefins (C₃H₆ and C₂H₄) yield (29.3%). The other catalysts, indicated by their respective metals, may be ranked (based on olefins yield) as V (16.9%) < Cr (17.5%) < Ce (25.1%) < Zr (26.2%) < Ni (26.8%) < Mg (27.9%). The reactivity of the lattice oxygen was estimated from energy of formation of the corresponding metal oxides. Correlation between the selectivity to propene and the standard energy of formation was attempted. Although there was no clear correlation, the result suggested that the lattice oxygen play a key role in the selectivity-determining step.     

水热处理对氧化铝载体物化性质及丙烷脱氢性能的影响

采用水热处理对γ-Al2O3载体改性,并进行XRD、N2物理吸附-脱附、热重、NH3-TPD及H2-TPR表征。结果表明,γ-Al2O3经过"再水合-焙烧"过程,晶型变好,表面总酸量降低,Pt-Al2O3相互作用增加,提高了Pt Sn K/Al2O3催化剂的丙烷脱氢转化率、选择性及稳定性。其中,140℃处理4 h时,氧化铝负载的Pt Sn K催化剂表现出最优的丙烷脱氢性能,100 h内平均转化率为33.6%,平均选择性97.3%,失活参数为15.9%。     

Synergistic mechanism of isolated Fe3+ and highly dispersed Ptδ+ over zeolite for boosting propane dehydrogenation

Pt-based catalysts have been widely investigated in propane dehydrogenation (PDH) owing to their high activity in C H activation, while it suffers from Pt sintering and coke deposition. We develop a transition metal Fe and zeolite support synergistic-modified method to realize the highly dispersed and stable Pt species inside zeolite over Pt/Fe-silicate-1. And it shows the excellent PDH performance with propylene generation rate of 51.6 mol C₃H₆ g_Pt⁻¹ h⁻¹ and low deactivation rate constant k_d of 0.017 h⁻¹ as well as a high TOF_Pt of 37.6 s⁻¹ at 550°C. The systematic characterizations reveal the isolated Fe³⁺ species could significantly improve Pt dispersity and regulate Pt electronic density to realize a more positive Pt^δ+ species inside Silicalite-1 pore. And the further in situ DRIFTS experiments demonstrate that the synergistic effect between the appropriate acidic Fe sites and the highly dispersed Pt^δ+ species around Fe species are responsible for the superior PDH performance.     

Dual-function catalysis in propane dehydrogenation over Pt1–Ga2O3 catalyst: Insights from a microkinetic analysis

The kinetics of propane dehydrogenation over single-Pt-atom-doped Ga₂O₃ catalyst has been examined by combining density functional theory calculations and microkinetic analysis. The doping of Pt not only can improve the selectivity of the Ga₂O₃ catalyst by hindering the deep dehydrogenation reactions but also helps to achieve a long-term stability by improving the resistance of Ga₂O₃ to hydrogen reduction. Microkinetic analysis indicates that upon Pt doping the turnover frequency for propane consumption is increased by a factor of 2.8 under typical operating conditions, as compared to the data on the pristine Ga₂O₃ surface. The calculated results suggest that the Pt₁–Ga₂O₃ catalyst shows a bifunctional character in this reaction where the Pt–O site brings about dehydrogenation while the Ga–O site is active for desorbing H₂, which provides a beautiful explanation for the previous experimental observation that even trace amounts of Pt can dramatically improve the catalytic performance of Ga₂O₃.