3'-(3,3-二甲基双环[2.2.1]庚-2-亚基)-5'-苯基-异噁唑啉的合成与表征
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摘要
以2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醛肟(莰烯醛肟)和苯乙烯为原料,通过环加成反应合成了未见报道的3'-(3,3-二甲基双环[2.2.1]庚-2-亚基)-5'-苯基-异噁唑啉,并采用FT-IR、GC-MS、~1H NMR以及~(13)C NMR等手段对产物进行表征,确定了产物结构。探讨了溶剂种类、催化剂种类及用量、氧化剂过硫酸氢钾复合盐(Oxone)用量、苯乙烯用量以及反应时间对反应转化率和得率的影响,得到适宜的工艺条件为:50%甲醇为溶剂,氯化钾为催化剂,n(莰烯醛肟)∶n(氯化钾)∶n(Oxone)∶n(苯乙烯)=1.0∶0.5∶1.5∶2.0,反应时间10 h,在此条件下,产物得率为88.07%。
The unreported 3'-( 3,3-dimethylbicyclo[2.2.1]hept-2-ylidene)-5'-phenyl-isoxazoline was synthesized by cycloaddition reaction of 2-( 3,3-dimethylbicyclo[2.2.1]heptan-2-ylidene) acetaldehyde oxime( camphene aldoxime,CAO) and syrene. The structure of the product was identified by FT-IR,GC-MS,~1H NMR and ~(13)C NMR. The effects of the types of solvent,type and dosage of catalyst,amount of oxidant Oxone,dosage of syrene and reaction time on reaction rate and product yield were discussed. The optimum conditions were obtained as follows: potassium chloride as the catalyst,50% methanol as solvent,n( camphene aldoxime) ∶ n( potassium chloride) ∶ n( Oxone) ∶ n( syrene) = 1.0 ∶0.5 ∶1.5 ∶2.0,reaction time 10 h. Under the above conditions,the product yield was 88.07%.
The unreported 3'-( 3,3-dimethylbicyclo[2.2.1]hept-2-ylidene)-5'-phenyl-isoxazoline was synthesized by cycloaddition reaction of 2-( 3,3-dimethylbicyclo[2.2.1]heptan-2-ylidene) acetaldehyde oxime( camphene aldoxime,CAO) and syrene. The structure of the product was identified by FT-IR,GC-MS,~1H NMR and ~(13)C NMR. The effects of the types of solvent,type and dosage of catalyst,amount of oxidant Oxone,dosage of syrene and reaction time on reaction rate and product yield were discussed. The optimum conditions were obtained as follows: potassium chloride as the catalyst,50% methanol as solvent,n( camphene aldoxime) ∶ n( potassium chloride) ∶ n( Oxone) ∶ n( syrene) = 1.0 ∶0.5 ∶1.5 ∶2.0,reaction time 10 h. Under the above conditions,the product yield was 88.07%.
引文
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[2]林中祥,顾阳.微波辐射下莰烯与乙醇的加成反应[J].南京林业大学学报:自然科学版,2001,25(5):21-24.LIN Z X,GU Y. The reaction of camphene with ethyl alcohol under microwave irradiation[J]. Journal of Nanjing Forestry University:Natural Sciences Edition,2001,25(5):21-24.
[3]肖转泉.莰烯醛的反应研究及在合成上的应用Ⅱ—与甲基烷基酮的缩合反应[J].江西师范大学学报:自然科学版,1992,16(2):106-111.XIAO Z Q. Study on the reactions ofω-formylcamphene and its applications to synthesis.Ⅱ:Condensation reactions with methyl alkyl ketones[J]. Journal of Jiangxi Normal University:Natural Sciences Edition,1992,16(2):106-111.
[4]周调调,刘六军,白杨,等.固体酸催化莰烯与邻甲酚的选择性烷基化反应[J].现代化工,2011,31(S2):69-72.ZHOU T T,LIU L J,BAI Y,et al. Study on selective alkylation of camphene with o-cresol over solid acidcatalyst[J]. Modern Chemical Industry,2011,31(S2):69-72.
[5]周调调.以莰烯为原料合成檀香型香料[D].北京:北京林业大学硕士学位论文,2012.ZHOU T T. Study on synthesis of sandalwood-like perfume from camphene[D]. Beijing:Master Degree Thesis of Beijing Forestry University,2012.
[6]BHARATE S B,BHUTANI K K,KHAN S I,et al. Biomimetic synthesis,antimicrobial,antileishmanial and antimalarial activities of euglobals and their analogues[J]. Bioorganic&Medicinal Chemistry,2006,14(6):1750-1760.
[7]BHARATE S B,KHAN S I,TEKWANI B L,et al. S-Euglobals:Biomimetic synthesis,antileishmanial,antimalarial,and antimicrobial activities[J]. Bioorganic&Medicinal Chemistry,2008,16(3):1328-1336.
[8]HEASLEY B. Isoxazole functionalization technologies enable construction of tetracycline derivatives[J]. Angewandte Chemie International Edition,2011,50(37):8474-8477.
[9]吕萍,姬文娟,韦伟,等.含三氟甲基异噁唑啉类化合物的合成及杀虫活性[J].农药学学报,2013,15(2):135-139.LP,JI W J,WEI W,et al. Synthesis and insecticidal activity of trifluorome thylisoxazoline compounds[J]. Chinese Journal of Pesticide Science,2013,15(2):135-139.
[10]郑彩云,吴建伟,何心伟,等.新型二茂铁异噁唑啉衍生物的合成及其电化学性能[J].合成化学,2009,17(1):91-94.ZHENG C Y,WU J W,HE X W,et al. Synthesis of novel ferrocenyl isoxazoline derivatives and their electrochemical performance[J]. Chinese Journal of Synthetic Chemistry,2009,17(1):91-94.
[11]KORANNE P S,TSUJIHARA T,ARAI M A,et al. Design and synthesis of chiral hybrid spiro(isoxazole-isoxazoline)ligands[J].Tetrahedron:Asymmetry,2007,18(8):919-923.
[12]ARMSTRONG S K,COLLINGTON E W,KNIGHT J G,et al. A new method for stereoselective homoallylic amine synthesis[J]. Journal of the Chemical Society Perkin Transactions 1,1993(13):1433-1447.
[13]GI H J,XIANG Y,SCHINAZI R F,et al. Synthesis of dihydroisoxazole nucleoside and nucleotide analogs[J]. The Journal of Organic Chemistry,1997,62(1):88-92.
[14]CHIACCHIO U,RESCIFINA A,CORSARO A,et al. Diastereoselective and enantioselective synthesis of 4'-aza analogues of 2',3'-dide oxynucleosides[J]. Tetrahedron:Asymmetry,2000,11(10):2045-2048.
[15]YE Y,ZHENG Y,XU G Y,et al. Rection of nitrile oxides with vinylphonate:A facile,regioselective approach to 5-phosphonyl-4,5-dihydroisoxazoles[J]. Heteroatom Chemistry,2003,14(3):254-257.
[16]YOSHIMURA A,ZHU C J,MIDDLETON K R,et al. Hypoiodite mediated synthesis of isoxazoline from aldoximes and alkenes using catalytic KI and Oxone as the terminal oxidant[J]. Chemical Conmmunications,2013,49(42):4800-4802.
[17]HAN L Q,ZHANG B J,ZHU M,et al. An environmentally benign synthesis of isoxazolines and isoxazoles mediated by potassium chloride in water[J]. Tetrahedron Letters,2014,55(14):2308-2311.