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

doi:10.3969/j.issn.0253-2417.2018.06.015

林产化学与工业 ›› 2018, Vol. 38 ›› Issue (6): 110-116.doi: 10.3969/j.issn.0253-2417.2018.06.015

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

黄静¹, 鲍涵², 张夏¹, 莫悦¹, 罗金岳¹, 刘祖广³

1. 南京林业大学化学工程学院, 江苏南京 210037;
2. 南京市金陵中学, 江苏南京 210005;
3. 广西林产化学与工程重点实验室, 广西南宁 530006

收稿日期:2018-07-26 出版日期:2018-12-25 发布日期:2018-12-27
通讯作者: 罗金岳,浙江余姚人,教授,研究领域为林产化学加工;E-mail:luojinyue@njfu.com.cn。 E-mail:luojinyue@njfu.com.cn
作者简介:黄静(1993-),女,安徽淮北人,硕士生;研究方向:精细有机合成;E-mail:2503622828@qq.com
基金资助:
广西林产化学与工程重点实验室一般项目（GXFC16-04）；江苏高校品牌专业建设工程项目（PPZY2015C221）

Synthesis and Characterization of 3'-(3,3-Dimethylbicyclo[2.2.1] hept-2-ylidene)-5'-phenyl-isoxazoline

HUANG Jing¹, BAO Han², ZHANG Xia¹, MO Yue¹, LUO Jinyue¹, LIU Zuguang³

1. College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China;
2. Jinling High School, Nanjing 210005, China;
3. Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Nanning 530006, China

Received:2018-07-26 Online:2018-12-25 Published:2018-12-27

摘要/Abstract

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¹³C 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%。

关键词: 莰烯醛肟, 环加成反应, 异噁唑啉化合物, 结构表征

Abstract: 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 ¹³C 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%.

Key words: camphene aldoxime, cycloaddition reaction, isoxazoline compound, structure characterization

中图分类号:

TQ35

黄静, 鲍涵, 张夏, 莫悦, 罗金岳, 刘祖广. 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[J]. 林产化学与工业, 2018, 38(6): 110-116.

HUANG Jing, BAO Han, ZHANG Xia, MO Yue, LUO Jinyue, LIU Zuguang. Synthesis and Characterization of 3'-(3,3-Dimethylbicyclo[2.2.1] hept-2-ylidene)-5'-phenyl-isoxazoline[J]. Chemistry and Industry of Forest Products, 2018, 38(6): 110-116.

参考文献

[1] 张平辉,郭利群,袁晓敏,等. 草酸二异龙脑酯的合成及其结构表征[J]. 林产化学与工业,2015,35(3):33-37. ZHANG P H,GUO L Q,YUAN X M,et al. Synthesis and structural characterization of diisobornyl oxalate[J]. Chemistry and Industry of Forest Products,2015,35(3):33-37.
[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 of ω-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. LÜ P,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-dihydro-isoxazoles[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.

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

Synthesis and Characterization of 3'-(3,3-Dimethylbicyclo[2.2.1] hept-2-ylidene)-5'-phenyl-isoxazoline

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 7

编辑推荐

Metrics

本文评价

关于本刊

投稿指南

在线期刊

相关单位

联系我们

[1]	刘丹丹, 韩唯凡, 蒋建新, 朱莉伟. 无患子果皮多糖微波提取工艺及抗氧化活性研究[J]. 林产化学与工业, 2018, 38(4): 109-116.
[2]	王鹏, 秦影, 傅英娟, 王兆江, 张凤山. 杨木自水解液中溶解木质素和胶体木质素的结构特征[J]. 林产化学与工业, 2017, 37(4): 59-66.
[3]	余星, 朱苗苗, 赵丽, 林中祥. 新型脱氢枞胺1,2,3-噻二唑衍生物的合成及表征[J]. 林产化学与工业, 2016, 36(1): 141-146.
[4]	黄曹兴, 何娟, 闵斗勇, 李鑫, 勇强. 毛竹竹青和竹黄半纤维素的提取与结构表征[J]. 林产化学与工业, 2015, 35(5): 29-36.
[5]	杨晓慧, 肖国民, 蒋剑春, 周永红. 木质素模型物紫丁香酚基丙三醇-β-愈创木基丙醚的合成与结构表征[J]. 林产化学与工业, 2015, 35(5): 65-70.
[6]	张平辉, 郭利群, 袁晓敏, 徐士超, 赵振东, 毕良武, 李冬梅. 草酸二异龙脑酯的合成及其结构表征[J]. 林产化学与工业, 2015, 35(3): 33-37.
[7]	王兆梅;李琳;胡松青;肖蕾. 微晶纤维素的定向硫酸酯化修饰及其结构表征[J]. 林产化学与工业, 2005, 25(3): 107-110.