N-苄基丙烯酰胺的合成

以丙烯腈和苯甲醇为原料，浓硫酸作催化剂，合成了N-苄基丙烯酰胺（N-BAA）。考察了反应温度、反应时间和催化剂用量等因素对产物收率的影响，得出了最佳反应条件：n（丙烯腈）：n（苯甲醇）：n（浓硫酸）=3：1：1．2，反应时间3h，反应温度60℃。在最佳条件下，N-BAA的收率可达92％。每100g粗产物用10％氢氧化钠溶液提纯，精制产物纯度可达99．80％，熔点为64～65℃。通过红外光谱对产物结构进行了表征。     

Determining pheromone content of hairpencils from individual virgin males ofPseudaletia unipuncta (Haw.) (Lepidoptera: Noctuidae)

Levels of benzaldehyde recovered from virginPseudaletia unipuncta (Haw.) males were not influenced by (1) the time hairpencils remained in the solvent (1-72 hr), (2) anesthetization or agitation of males prior to excision of hairpencils, or (3) the time (photophase or scotophase) that hairpencils were excised. Thus the interindividual variability observed is not a methodological artifact. Most males had similar concentrations in both hairpencils, although in some cases only one hairpencil contained pheromone. In one case, a male with partially extruded hairpencils had no benzaldehyde at all. Neither pupal weight nor hairpencil length proved to be reliable indicators of pheromone content.Contribution No. 373, Département de biologie, Université Laval.     

8-R-9苄基-9H-嘌呤衍生物的合成研究

采用 (Ph3 P) 2 PdCl2 为催化剂 ,DMF为溶剂 ,对 8 碘 9 苄基 9H 嘌呤与有机锡试剂RSnBu3 (R=乙烯基、2 噻吩基、2 呋喃基、苯乙炔基和苯基等 )之间的Stille偶合反应进行了研究 ,合成出了5种 8位取代的嘌呤衍生物。在反应温度为 80℃ ,n(8 碘 9 苄基 9H 嘌呤 )∶n (RSnBu3 )∶n〔(Ph3 P) 2 PdCl2 〕 =1 0∶1 2∶0 0 5的较佳工艺条件下 ,产品收率 4 1%～ 91%。用1H NMR、13 C NMR和MS对产物进行了表征     

Studies on Catalytic Side-Chain Oxidation of Nitroaromatics to Aldehydes with Oxygen

The side-chain oxidation of 2-nitrotoluene in liquid phase in the presence of catalytic amount of manganese sulfate and stoichiometric amount of potassium hydroxide with oxygen was studied. In the most favorable conditions, over 80% of conversion of 2-nitrotoluene and 50% of selectivity to 2-nitrobenzaldehyde was achieved. Effects of the reaction parameters on the conversion of the reactant and the selectivity of the product were examined. These results, together with EPR spectroscopic study, show that a benzyl anion was formed in the early stage of the reaction, which was then converted to the final product via a free radical mechanism.     

PCC载体氧化剂的制备及应用研究

制备得到各种有代表性的氯铬酸吡啶(PCC)无机载体氧化试剂,以苯甲醇选择性氧化成苯甲醛为探针反应,考察了载体、反应条件对氧化反应效率的影响,控制各载体氧化剂中PCC的负载量均为1.8 mmol/g。室温下反应,搅拌时间为30 m in,苯甲醇的氧化反应产率为:分子筛65.8%,活性炭75.4%,氧化铝94.6%,硅胶96.9%,相同条件下PCC的产率为65.8%。硅胶是制备负载PCC的优良载体,在载体氧化剂对苯甲醇的氧化反应中,一定范围内增加反应时间和载体加入量都可以提高氧化产率。     

Mn/Ti-Zr复合氧化物催化苯甲酸甲酯选择性加氢

以硝酸锆和钛酸四丁酯为原料,采用共沉淀法制备Ti-Zr-O氧化物载体,采用浸渍法制备了Mn/Ti-Zr催化剂;采用XRD、N2物理吸附、H2-TPR、NH3-TPD和TG-DTA对Mn/Ti-Zr催化剂进行了表征,并考察了催化剂组成、结构和反应条件对苯甲酸甲酯（MB）加氢性能的影响,以及催化剂的长周期稳定性、失活和再生行为。结果表明：TiO2含量和Mn负载量分别为12% 和8% （二者均以Ti-Zr-O氧化物的质量为基准,下同）时制备的Mn/Ti-Zr催化剂性能最优,该催化剂在θ = 390 ℃, p = 1.0 MPa,n(H2)∶n(MB) = 9∶1和重时空速（WHSV）= 0.5 h-1的优化条件能够实现98.0% 的苯甲酸甲酯转化率和89.7%的苯甲醛和苯甲醇选择性;苯甲酸甲酯加氢反应的活性和选择性分别与Mn/Ti-Zr表面MnOx物种的氧化还原性和催化剂的酸性密切相关。此外,Mn/Ti-Zr催化剂具有良好的结构稳定性,在反应1000 h后仅因积碳而丧失11% 的活性,且轻微失活的催化剂可以通过焙烧恢复其初始活性和选择性。     

Solvent-free oxidation of benzyl alcohol with oxygen using zeolite-supported Au and Au–Pd catalysts

The oxidation of benzyl alcohol to benzaldehyde has been investigated in the absence of solvent using zeolite-supported Au and Au–Pd catalysts. Three zeolites were investigated, ZSM-5, zeolite β and zeolite Y, and these were contrasted with the titanoslicalite TS-1 and TiO₂ as supports. For the Au catalysts the best results are obtained with zeolite β as the support and the conversions were comparable or better than those observed with TiO₂ in terms of turn over frequencies. However, the selectivities observed with the acidic zeolites were lower than the non-acidic TS-1 and TiO₂. This is due to the subsequent reaction of benzaldehyde via acid catalysed reactions to give benzyl benzoate and its dibenzyl acetal, and, in some cases dibenzylether. Initial catalysts were evaluated with a gold loading of 2 wt% and increasing this to 4 wt% showed the expected increase in activity, indicating that there is scope to improve the performance of these catalysts. The most active catalysts were prepared by impregnation and catalysts prepared by deposition precipitation were considerably less active. Introduction of Pd into the catalyst improved the activity without significantly affecting the selectivity.     

S-苄基-L-半胱氨酸的合成

由溴化苄和L-半胱氨酸直接合成S-苄基-L-半胱氨酸,通过正交试验及统计分析,检验了各影响因子的显著性,确定了最佳工艺条件为：反应时间2.5h,反应温度45℃,原料配比n（溴化苄）：n（L-半胱氨酸）=1：1.在此条件下反应,摩尔产率可达到95%.     

乙酸苄酯的合成新工艺研究

报道了合成乙酸苄酯的新工艺 ,以有机溶剂丙酸丁酯作为反应介质 ,三乙胺为催化剂 ,合成了乙酸苄酯。产品收率可达 99 1%,产品纯度 >99 5 %,溶剂可反复回收使用。     

相转移催化氧化合成苯甲酸

研究了季铵盐CTAB催化高锰酸钾氧化氯化苄合成苯甲酸的反应。考察了CTAB用量、高锰酸钾用量、反应温度、反应时间对反应的影响。结果表明,合成苯甲酸的最优条件为:高锰酸钾与氯化苄的摩尔比为2∶1,CTAB的摩尔分数为氯化苄的8%,反应温度90℃,反应时间为3h,苯甲酸的产率可达89%。