微波条件下SiO_2/K_2CO_3促进的无溶剂法由肉桂醛/NH_2OH·HCl直接制备肉桂腈

以肉桂醛为原料,在无溶剂的条件下SiO2/K2CO3促进一步法直接制备肉桂腈。确定的最佳反应条件是:当肉桂醛∶盐酸羟胺∶碳酸钾=1∶1.5∶0.85(摩尔比),SiO2用量为每mmol肉桂醛0.3~0.4 g,室温下彻底研磨均匀后,以微波730 W火力加热4~5 min,制备效果最佳。在此条件下从肉桂醛制备肉桂腈的平均得率达90.3%。     

无溶剂条件下氧化锌催化合成肉桂腈

以ZnO为催化剂,在无溶剂条件下,肉桂醛和盐酸羟胺通过一步法合成了肉桂腈。ZnO催化合成肉桂腈的适宜反应条件为:n(肉桂醛)∶n(盐酸羟胺)=1∶1.5,催化剂用量为肉桂醛质量的6%,反应温度120℃,反应时间1 h,肉桂腈的收率可达90.2%。ZnO商业上容易得到,是一种环境友好催化剂。     

碱相转移催化脱水法合成肉桂腈的研究

研究了不同碱对肉桂醛肟的催化脱水效果及不同PTC的催化作用效果,并确定了使用KOH-TBAB催化脱水法合成肉桂腈的最佳反应条件。最佳反应条件为:TBAB的用量为6%(摩尔分数),KOH的用量为15%(摩尔分数),反应温度为124～126°C,反应时间为2.5h,在此条件下肉桂醛肟转化成肉桂腈的产率达90.3%。     

乙酐脱水法合成肉桂腈研究

以肉桂醛为原料 ,在 5 0 %的乙醇水溶液中制备肉桂醛肟 ,然后用乙酐在 12 4～ 12 6℃温度条件下脱水1h生成肉桂腈 ,产率达 90 .3%。     

Organometallic and coordination chemistry on phosphazenes. III. Synthesis, characterization, and electrochemical behavior of transition metal-cinnamonitrile cyclophosphazene derivatives

Hexakist 4-formylphenoxy cyclophosphazene (1) reacts with six equivalents of cyanomethylenetriphenylphosphorane to give hexakist 4-cinnamonitrile cyclotriphosphazene bearing 12 functional groups tsix nitriles and six olefins' able to coordinate up to 12 metals. In this way a series of polynuclear phosphazene metal derivatives (8–12) was prepared with different transition metals and in different oxidation states. Pt(0), Pt(II) and Rh(I). The analogous cinnamonitrile derivatives (3–7) were prepared and used as models for the characterization of corresponding phosphazene compounds. The redox properties of the complexes3–5 and8–10 as well as of the free cinnamonitrile2 and the free substituted cyclophosphazene1 have been investigated by cyclic voltammetry (CV) and controlled potential electrolysis (CPE) in aprotic media (THF, CH₂Cl₂, or NCMe 0.2M [NBu₄][BF₄]), at Pt electrodes. Cathodic processes have been detected only when the unsaturated C=C bond of the cinnamonitrile group is uncoordinated: hence, for compounds1. 4. and9. they are irreversible occur at potentialsE _p ^red ca. –1.3 to ca. –1.9V vs SCE which are less cathodic than that exhibited by the free cinnamonitrile (2:E _p ^red ca. –2.0 V vs SCE), and are believed to be centered at the electron-acceptor empty ^* (C=C) orbital of each of the cinnamonitrile groups present in the molecule. Anodic processes are displayed only by complexes3. 5. 8. and10 with at least one Pt(0) site: they are irreversible, conceivably centered at such a metal center, and occur at potentials (E _p ^bv ca. 0.7 1.2 V vs SCE) which are dependent on the electronic effects of the ligands, in particular the strong electron-withdrawing ability of the cyclophosphazene group. Complex10 undergoes dissociation in NCMe to form9 and possibly solvated [Pt(PPh₃)₂] species which adsorb at the electrode surface. No evidence for any redox process centered at the phosphazene ring has been found.Presented at the 1st Italian Workshop on Cyclo- and Poly(phosphazene) Materials, February 15–16, 1996, at the CNR Research Area in Padova, Italy.     

香料肉桂腈合成新工艺研究

采用一种新的合成方法,以苯甲醛和乙腈为原料,以氢氧化钾为碱催化剂,十二烷基三甲基氯化铵为相转移催化剂,并以乙腈作为溶剂来制备肉桂腈。针对催化剂用量、反应温度、反应时间等与缩合反应有关的影响因素进行了研究,从而确定了较好的缩合反应条件。试验结果表明：氢氧化钾对于此缩合反应是一个良好的碱性催化剂,十二烷基三甲基氯化铵是经济性最佳的相转移催化剂,而且反应时间短,后处理简单,收率高,可达到降低肉桂腈生产成本的要求,易于实现工业化。     

微波法合成肉桂腈研究

使用微波辐射加热法 ,以肉桂醛为原料 ,在 5 0 %乙醇水溶液中制备肉桂醛肟 ,进一步用乙酸酐使后者脱水生成肉桂腈 ,并用正交实验设计法确定了最佳脱水条件 ,在此条件下 ,从肉桂醛到肉桂腈的平均产率达 89.5 %。     

Nafion/SiO2催化合成肉桂腈的研究

应用新型固体酸催化剂Nafion／SiO2作为催化剂制备肉桂腈，对催化剂用量、反应温度和反应时间等对脱水反应的影响进行了研究，实验结果表明：Nafion／SiO2是肉桂醛肟脱水制备肉桂腈的良好催化剂，其反应时间短，后处理简单，催化剂用量少且可重复使用，收率高。脱水反应的最佳工艺条件为：催化剂用量为肉桂醛肟质量的10％，反应温度为120℃，反应时间为1h。