以分子氧(O_2)为氧化剂,在无溶剂条件下,研究了N-羟基邻苯二甲酰亚胺/乙酰丙酮亚钴(Ⅱ)体系对α-紫罗兰酮的催化氧化反应,分析了氧化产物,主要得到α-紫罗兰酮的烯丙位氧化产物5-氧代-α-紫罗兰酮,同时生成少量环氧α-紫罗兰酮及重排产物4-氧代-β-紫罗兰酮和环氧β-紫罗兰酮,提出了可能的反应机理,化合物的结构经IR、~1H NMR、MS和EA等测试技术得以表征;为了提高5-氧代-α-紫罗兰酮的选择性和催化氧化反应的转化率,优化了催化氧化反应的工艺条件:当反应温度为70 ℃,氧气压力为1.0 Mpa,N-羟基邻苯二甲酰亚胺和乙酰丙酮亚钴(Ⅱ)用量分别为α-紫罗兰酮的25%和1.0%,反应10 h,5-氧代-α-紫罗兰酮的产率达53.4%,反应转化率达95.0%以上,平行实验表明,实验重复性良好.
A practical catalytic method to oxidize α-ionone with molecular oxygen under normal pressure and temperature in the presence of catalyst iV-hydroxyphthalimide ( NHPI) combined with Co ( acac )_2 was developed, and the probable catalytic mechanism was proposed. Influences of the reaction conditions on the conversion of α-ionone and the selectivity of the major product(5-oxo-α-ionone) were investigated, the optimal technical parameters for 5-oxo-α-ionone were optimized. The results show that the primary products were 5-oxo-α-ionone, epoxy-α-ionone, as well as rearrangement products 4-oxo-β-ionone and epoxy-β-ionone, which were characterized by infrared spectroscopy, ~1H nuclear magnetic resonance spectroscopy, mass spectrometry and elemental analysis. The yield of 5-oxo-α-ionone and the conversion of α-ionone were 53. 4% and 95. 0% , respectively, under the conditions of 25% NHPI, 1.0% Co(acac)_2(in molar ratio), O_2 pressure of 1. 0 MPa, the reaction temperature at 70℃, and reaction time of 10 h, the procedure shows a good reprodu-cibility in the parallel experiments.
参考文献
| [1] | Punniyamurthy T,Velusamy S,Iqbal J.Chem Rev[J],2005,105(6):2 330 |
| [2] | Rajabi F,Karimi B.J Mol Cata A:Chem[J],2005,232(1):95 |
| [3] | Koguchi S,Kitazume T.Tetrahedron Lett[J],2006,47(16):2 797 |
| [4] | Coseri S,Mendenhal G D,Ingold K U.J Org Chem[J],2005,70(12):4 629 |
| [5] | Ishii Y,Sakaguchi S.Catal Surveys from Jap[J],1999,3(1):27 |
| [6] | Iwahama T,Sakaguchi S,Ishii Y.Chem Commun[J],1999,999(8):727 |
| [7] | Jiang S C,Wu Y,Li J,Li Z P,Liu H.Fragrance Flavor Cosmetic[J],2003,5(2):5 |
| [8] | Aleu J,Brenna E,Fuganti C.J Chem Soc,Perkin Trans[J],1999,(1):271 |
| [9] | Liu J,Colmenares L U,Liu R S M.Tetrahedron Lett[J],1997,38(49):8 495 |
| [10] | LUO Yi-Ming(罗一鸣),LIU Chang-Hui(刘长辉),TANG Rui-Ren(唐瑞仁).J Centl South Univ:Sci Technol(中南大学学报(自然科学版))[J],2006,37(3):5 21 |
| [11] | PENG Qian-Rong(彭黔荣),YANG Min(杨敏),XIE Ru-Gang(谢如刚).CN 1817 842A[P],2006 |
| [12] | ZHUO Guang-Lan(卓广澜),ZHAO Wei-Juan(赵伪娟),JIANG Xuan-Zhen(姜玄珍).Chinese J Org Chem(有机化学)[J],2004,24(8):962 |
| [13] | Hirai N,Sawatari N,Nakamura N,Sakag U S.J Org Chem[J],2003,68(17):6 587 |
| [14] | TANG Rui-Ren(唐瑞仁),LIU Chang-Hui(刘长辉),LUO Yi-Ming(罗一鸣).Chinese J App Chem(应用化学)[J],2006,23(7):718 |
| [15] | Sheldon R A,Arends I W C E.Adv Synth Catal[J],2004,346(6):1 051 |
| [16] | FAN Qian(范谦),LI Yao-Zhong(黎耀忠),HU Jia-Yuan(胡家元).Chem Res Appl(化学研究与应用)[J],2001,13(5):557 |
| [17] | Ishii Y,Sakaguchi.Catal Today[J],2006,117(1-3):105 |
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