2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醛肟的合成
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摘要
以ω-甲酰基莰烯为主原料,与盐酸羟胺、三水合乙酸钠经亲核加成反应,合成目标化合物2-(3,3-二甲基双环[2. 2. 1]庚-2-亚基)乙醛肟。采用FT-IR、GC-MS、1H NMR和13C NMR等手段对产物进行了表征,确定了产物结构。探讨了溶剂及碱的种类、碱的用量、物料比、反应温度以及反应时间对原料转化率、产物选择性和产率的影响,得到了适宜的工艺条件为:碱为三水合乙酸钠,n(ω-甲酰基莰烯)∶n(盐酸羟胺)∶n(三水合乙酸钠)=1. 0∶1. 2∶2. 0,溶剂为20 m L的75%乙醇,反应温度为70℃,反应时间为2. 5 h。在上述条件下,产物的产率为83. 9%。
2-( 3,3-Dimethylbicyclo[2. 2. 1]heptan-2-ylidene) acetaldehyde oxime was synthesized by nucleophilic addition reaction of ω-formyl camphene with hydroxylamine hydrochloride and sodium acetate trihydrate.The structure of the product was identified by FT-IR,GC-MS、1 H and13 C NMR.The effects of types of solvent,different type of bases,dosage of base,material ratio,reaction temperature and reaction time on reaction rate and yield of the product were discussed.The optimum condition was obtained as follows:sodium acetate trihydrate as the base,n( ω-formyl camphene) ∶ n( hydroxylamine hydrochloride) ∶ n( sodium acetate trihydrate) =1. 0 ∶ 1. 2 ∶ 2. 0,solvent was 75% ethanol,the reaction temperature( 70℃),reaction time( 2. 5 h). Under the above condition,the product yield was 83. 9%.
2-( 3,3-Dimethylbicyclo[2. 2. 1]heptan-2-ylidene) acetaldehyde oxime was synthesized by nucleophilic addition reaction of ω-formyl camphene with hydroxylamine hydrochloride and sodium acetate trihydrate.The structure of the product was identified by FT-IR,GC-MS、1 H and13 C NMR.The effects of types of solvent,different type of bases,dosage of base,material ratio,reaction temperature and reaction time on reaction rate and yield of the product were discussed.The optimum condition was obtained as follows:sodium acetate trihydrate as the base,n( ω-formyl camphene) ∶ n( hydroxylamine hydrochloride) ∶ n( sodium acetate trihydrate) =1. 0 ∶ 1. 2 ∶ 2. 0,solvent was 75% ethanol,the reaction temperature( 70℃),reaction time( 2. 5 h). Under the above condition,the product yield was 83. 9%.
引文
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[2]肖转泉,钟平,金进良,等.ω-酰基莰烯系列化合物的合成、香气与分析[J].林产化学与工业,1992,(2):139-144.
[3]肖转泉.γ-异莰烷基醇及β-异莰烷基酮的合成[J].林产化学与工业,1992,(4):299-305.
[4]Michel T,Cokoja M,Kühn F E. Catalytic epoxidation of camphene using methyl Trioxorhen-ium(VII)as catalyst[J]. J Mol Catal A:Chem,2013,368-369:145-151.
[5]Bodrov A V,Nikitina L E,Startseva V A,et al.BF3-catalyzed addition of thiols to(+)-camphene[J]. Russ J Gen Chem,2013,83(1):80-86.
[6]Bahramian B,Mirkhani V,Tangestaninejad S,et al.Catalytie epoxidation of olefins and hydroxylation of alkanes with sodium periodate by water-soluble manganese(Ⅲ)salen[J].J Mol Catal A:Chem,2006,244(1-2):139-145.
[7]金霖霖,翁玉辉,范国荣,等.异莰烷基甲酸及其酯类的合成与结构分析[J].化学研究与应用,2016,28(11):1575-1 581.
[8]Zeng Y,Liu F.1,3-Dipolar cycloaddition in the synthesis of novel isoxazoline/pyrazole derivatives bearing 1,2,3-triazoles moiety[J].J Heterocycl Chem,2013,50(3):696-702.
[9]Jiang H,Yang J,Tang X,et al.Cu-catalyzed three-component cascade annulation reaction:an entry to functionalized pyridines[J].J Org Chem,2015,80(17):8 763-8 771.
[10]Ouyang G,Cai X J,Chen Z,et al.Synthesis and antiviral activities of pyrazole derivatives containing an oxime moiety[J]. J Agric Food Chem,2008,56(21):10 160-10167.
[11]McTier T L,Chubb N,Curtis M P,et al.Discovery of sarolaner:a novel,orally administered,broad-spectrum,isoxazoline ectoparasiticide for dogs[J]. Vet Parasitol,2016,222:2-11.
[12]杨吉春,吴峤,任兰会,等.除草剂开发的新进展[J].农药,2012,51(08):547-549,572.
[13]王积涛.有机化学[M].北京:高等教育出版社,2009:93-95.