催化氧化合成δ-环戊内酯的工艺研究
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摘要
以环戊酮为原料,质量分数为30%过氧化氢为氧化剂,Sn/W-2-600为催化剂,环己烷为带水剂,丙酸为溶剂,负压条件下合成了δ-环戊内酯。经减压蒸馏的方式对实验产物进行提纯,并经FT IR表征分析。通过单因素和正交试验对δ-环戊内酯的合成工艺进行优化。结果表明最优条件为:环戊酮0.025mol,Sn/W-2-600用量为环戊酮质量的40%,n(过氧化氢)∶n(环戊酮)=1.5,n(丙酸)∶n(环戊酮)=13.5,反应时间4.5h,真空度为0.07 MPa,带水剂环己烷15mL。在此条件下,δ-环戊内酯的收率为72.26%。
δ-Valerolactone was synthesized from cyclopentanone using,30% aqueous hydrogen peroxide solution as oxidant,propionic acid as solvent and the composite metal oxide Sn/W-2-600 as catalyst.During the process,cyclohexane was used as water carrying agent and the whole device was under negative pressure conditions.The product was purified by vacuum distillation and then characterized and analyzed by FT IR.Through single-factor and orthogonal experiments,the synthesis technology was optimized.The optimal condtions were as follows:n(cyclopentanone)=0.025mol;the amount of catalyst was 40%;n(H2O2)∶n(cyclopentanone)=1.5;n(propionic acid)∶n(cyclopentanone)=13.5;the reaction time was4.5h,and the vacuum pressure was 0.07 MPa.Under these conditions,the yield ofδ-valerolactone could reach 72.26%.
δ-Valerolactone was synthesized from cyclopentanone using,30% aqueous hydrogen peroxide solution as oxidant,propionic acid as solvent and the composite metal oxide Sn/W-2-600 as catalyst.During the process,cyclohexane was used as water carrying agent and the whole device was under negative pressure conditions.The product was purified by vacuum distillation and then characterized and analyzed by FT IR.Through single-factor and orthogonal experiments,the synthesis technology was optimized.The optimal condtions were as follows:n(cyclopentanone)=0.025mol;the amount of catalyst was 40%;n(H2O2)∶n(cyclopentanone)=1.5;n(propionic acid)∶n(cyclopentanone)=13.5;the reaction time was4.5h,and the vacuum pressure was 0.07 MPa.Under these conditions,the yield ofδ-valerolactone could reach 72.26%.
引文
[1]ANTONIO H,ROBERTO M A,PEDRO R.An Easy Synthesisi of Pyranopyrimidines[J].Monatsh Chem,2006,137(11):1 421-1 430.
[2]GOODMAN M A,DETTY M R.Selenoxides as Catalysts for Epoxidation and Baeyer-Villiger Oxidation with Hydrogen Peroxide[J].Synlett,2006,(7):1 100-1 104.
[3]CHROBOK A.Baeyer-Villiger Oxidation of Ketones in Ionic Liquids Using Molecular Oxygen in the Presence of Benzaldehyde[J].Tetrahedron,2010,66(16):2 940-2 943.
[4]程丹.δ-环戊内酯以及其衍生物的合成研究[D].合肥:合肥工业大学,2007.
[5]李秀荣,毛建新,徐羽展,等.Baeyer-Villiger氧化反应催化体系的研究新进展[J].石油化工,2004,33(7):684-689.
[6]马振宏.杂多酸及SBA-15负载杂多酸催化环酮Baeyer-Villiger氧化反应研究[D].兰州:西北师范大学,2011.
[7]李静霞,黄靓,戴维林,等.高活性MgO/SnO2复合金属氧化物催化剂的合成及其在双氧水选择氧化环己酮制ε-己内酯反应中的应用[J].化学学报,2008,66(1):5-9.
[8]刘新奇,王佳,朱万坤,等.气相色谱内标法分析δ-戊内酯的含量[J].化学世界,2015,56(10):599-600,613.
[9]冯世宏,贾太轩,张震斌,等.δ-环戊内酯的制备及其光谱分析[J].光谱学与光谱分析,2015,35(10):2 810-2 813.
[10]朱万坤.H2O2间接催化氧化制备δ-戊内酯的新工艺研究[D].郑州:郑州大学,2014.
[11]吴培培.双氧水氧化环戊酮合成δ-环戊内酯的工艺研究[D].郑州:郑州大学,2015.
[12]王甲琴,王韧韧,李翠林,等.SnCl2·2H2O催化下H2O2对2-金刚烷酮的Baeyer-Villiger氧化[J].西北师范大学学报(自然科学版),2007,43(5):67-70.
[13]NOWAK I,FELICZAK A,NEKOKSOVA I,et al.Comparison of Oxidation Properties of Nb and Sn in Mesoporous Molecular Sieves[J].Appl Catal A:General,2007,321(1):40-48.
[14]杨志旺.锡化合物催化剂的合成及催化酮类BaeyerVilliger氧化反应研究[D].兰州:西北师范大学,2006.
[2]GOODMAN M A,DETTY M R.Selenoxides as Catalysts for Epoxidation and Baeyer-Villiger Oxidation with Hydrogen Peroxide[J].Synlett,2006,(7):1 100-1 104.
[3]CHROBOK A.Baeyer-Villiger Oxidation of Ketones in Ionic Liquids Using Molecular Oxygen in the Presence of Benzaldehyde[J].Tetrahedron,2010,66(16):2 940-2 943.
[4]程丹.δ-环戊内酯以及其衍生物的合成研究[D].合肥:合肥工业大学,2007.
[5]李秀荣,毛建新,徐羽展,等.Baeyer-Villiger氧化反应催化体系的研究新进展[J].石油化工,2004,33(7):684-689.
[6]马振宏.杂多酸及SBA-15负载杂多酸催化环酮Baeyer-Villiger氧化反应研究[D].兰州:西北师范大学,2011.
[7]李静霞,黄靓,戴维林,等.高活性MgO/SnO2复合金属氧化物催化剂的合成及其在双氧水选择氧化环己酮制ε-己内酯反应中的应用[J].化学学报,2008,66(1):5-9.
[8]刘新奇,王佳,朱万坤,等.气相色谱内标法分析δ-戊内酯的含量[J].化学世界,2015,56(10):599-600,613.
[9]冯世宏,贾太轩,张震斌,等.δ-环戊内酯的制备及其光谱分析[J].光谱学与光谱分析,2015,35(10):2 810-2 813.
[10]朱万坤.H2O2间接催化氧化制备δ-戊内酯的新工艺研究[D].郑州:郑州大学,2014.
[11]吴培培.双氧水氧化环戊酮合成δ-环戊内酯的工艺研究[D].郑州:郑州大学,2015.
[12]王甲琴,王韧韧,李翠林,等.SnCl2·2H2O催化下H2O2对2-金刚烷酮的Baeyer-Villiger氧化[J].西北师范大学学报(自然科学版),2007,43(5):67-70.
[13]NOWAK I,FELICZAK A,NEKOKSOVA I,et al.Comparison of Oxidation Properties of Nb and Sn in Mesoporous Molecular Sieves[J].Appl Catal A:General,2007,321(1):40-48.
[14]杨志旺.锡化合物催化剂的合成及催化酮类BaeyerVilliger氧化反应研究[D].兰州:西北师范大学,2006.