Synthesis of 2,3-epoxypinane by epoxidation of α-pinene with high selectivity

XU Xu,LIU Bing, TANG Nianhua, WANG Shifa

Journal of Nanjing Forestry University (Natural Sciences Edition) ›› 2013, Vol. 37 ›› Issue (01) : 96-100.

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Journal of Nanjing Forestry University (Natural Sciences Edition) ›› 2013, Vol. 37 ›› Issue (01) : 96-100. DOI: 10.3969/j.issn.1000-2006.2013.01.017

Synthesis of 2,3-epoxypinane by epoxidation of α-pinene with high selectivity

  • XU Xu1,LIU Bing2, TANG Nianhua1, WANG Shifa1*
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Abstract

2,3-epoxypinane was synthesized from α-pinene by epoxidation with high selectivity. Effects of concentration and dosage of peracetic acid, dosage of anhydrous sodium carbonate, solvent types, reaction temperature and reaction time on the conversion of α-pinene were investigated, respectively. Mean while the selectivity of 2,3-epoxypinane and chemical compositions of the products were investigated too. The most suitable reaction conditions were finally determined as follows: temperature 0-10 ℃, concentration of peracetic acid 2.0 mol/L, molar ratio of α-pinene and peracetic acid 1:1.1,molar ratio of α-pinene and Na2CO3 1:1.2, reaction time 2.0 h, using CHCl3 as the solvent and volume ratio of α-pinene and CHCl3 1:1.7. At this condition, conversion rate of α-pinene was above 99%, selectivity of 2,3-epoxypinane was more than 95%. The contents of the main impurities α-campholenic aldehyde and 3-pinonic in the final product were only 3.3% and 1.2% respectively.

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XU Xu,LIU Bing, TANG Nianhua, WANG Shifa. Synthesis of 2,3-epoxypinane by epoxidation of α-pinene with high selectivity[J]. Journal of Nanjing Forestry University (Natural Sciences Edition). 2013, 37(01): 96-100 https://doi.org/10.3969/j.issn.1000-2006.2013.01.017

References

[1] Bordoloi A, Lefebvre F, Halligudi S B. Organotin-oxometalate coordination polymer catalyzed oxyfunctionalization of monoterpenes[J]. Journal of Molecular Catalysis A: Chemical, 2007, 270(1-2):177-184.
[2] Silva J M, Vinhado F S, Mandelli D, et al. The chemical reactivity of some terpenes investigated by alumina catalyzed epoxidation with hydrogen peroxide and by DFT calculations[J]. Journal of Molecular Catralysis A: Chemical, 2006, 252(1-2):186-193.
[3] Tangestaninejad S, Habibi M H, Mirhhani V, et al. Readily prepared polymer-supported molybdenum carbonyls as novel reusable and highly active epoxidation catalysts[J]. Inorganic Chemistry Communications, 2006, 9(6):575-578.
[4] Saladino R, Andreoni A, Neri V, et al. A novel and efficient catalystic epoxidation of olefins and monoterpenes with microencapsulated Lewis base adducts of methyltrioxorhenium[J]. Tetrahedron, 2005, 61(5):1069-1073.
[5] Mirkhani V, Moghadam M, Tangestaninejad S. Host(nanocavity of zeolite-Y)-guest(manganese(III)salophen complex)nanocomposite materials: An efficient catalyst for biomimetic alkene epoxidation and alkane hydroxylation with sodium periodate[J]. Applied catalysis A: General, 2007, 321(1):49-57.
[6] Maksimchuk N V, Melgunov M S, Chesalov Y A,et al. Aerobic oxidations of α-pinene over cobalt-substituted polyoxometalate supported on amino-modified mesoporous silicates[J]. Journal of Catalysis, 2007, 246(2):241-248.
[7] 丁宗彪,陆文聪,王全瑞.以过碳酸钠为试剂制备环氧蒎烷的方法:中国,1422853A[P].2003-06-11. Ding Z B, Lu W C, Wang Q R. Method for preparing epoxy pinane using sodium percarbonate as reagent: CN1422853A[P]. 2003-06-11.
[8] Lavallee P, Bouthillier G. Efficient conversion of(1R,5R)-(+)-α-pinene to(1S,5R)-(-)-nopinone[J]. J Org Chem, 1986, 51(8):1362-1365.
[9] Castro J M, Palomino P J, Salido S, et al. Enantiospecific synthesis, separation and olfactory evaluation of all diastereomers of a homologue of the sandalwood odorant polysantol[J]. Tetrahedron, 2005, 61(47):11192-11203.
[10] 王宗德,陈金珠,宋湛谦.8-羟基别二氢葛缕醇甲酸酯及其合成方法和用作驱避剂:中国,1730459A[P].2006-02-08. Wang Z D, Chen J Z, Song Z Q. 8-hydroxyl-allo-dihydro-carvyl formate and its synthesis method and uses as repellent: CN1730459A[P]. 2006-02-08.
[11] 焦家俊,吴晓峰.过氧化氢的安全浓缩[J].化学世界,1997,4(1):12-15. Jiao J J, Wu X F. Safe concentration of hydrogen peroxide[J]. Chemical world, 1997, 4(1):12-15.
[12] 闫菊萍,关兰文.GB/T 6684—2002.化学试剂-30%过氧化氢[S].北京:中国标准出版社,2002. Yan J P, Guan L W. GB/T 6684—2002. Chemical Reagent -30% Hydrogen Peroxide[S]. Peiking:Standard Press of China, 2002.
[13] 胡延风,郭燕玲,王学敏.GB/T 19108—2003,过氧乙酸含量的测定[S].北京:中国标准出版社,2003. Hu Y F, Guo Y L, Wang X M. GB/T 19108—2003, Measurement of the Concentration of Hydrogen Peroxide[S]. Peiking: Standard Press of China, 2003.
[14] 王伟,周淑清,梁淑敏.过氧乙酸合成工艺的研究[J].黑龙江医药,2006,19(3):183-184. Wang W, Zhou S Q, Liang S M. Study on Process of Synthesis of Peracetic acid[J]. Heilongjiang Medicine Journal, 2006, 19(3):183-184.
[15] 王传虎,方荣生.过氧乙酸制备条件的选择及其稳定性的研究[J].中国消毒杂志,2006,23(2):100-102. Wang C H, Fang R S. Study on selection of conditions for preparing peracetic acid and its stability[J]. Chinese Journal of Disinfection, 2006, 23(2):100-102.
[16] 杨益琴,唐年华,刘兵,等.α-蒎烯合成N-烷基-N-(α-龙脑烯基)乙酰胺类化合物及香气特征[J].北京林业大学学报,2010,32(2):166-170. Yang Y Q, Tang N H, Liu B, et al. Synthesis and olfactory evaluation of N-alkyl-N-(α-campholenyl)acetamides from α-pinene[J]. Journal of Beijing Forestry University, 2010, 32(2):166-170.
[17] 刘兵,敖汪伟,杨杨,王石发.左旋β-蒎烯选择性氧化合成右旋诺蒎酮的研究[J].南京林业大学学报:自然科学版,2010,34(2):89-94. Liu B, Ao W W, Yang Y, Wang S F. Synthesis of(+)-nopinone from(-)-β-pinene by selective oxidation[J]. Journal of Nanjing Forestry University:Natural Sciences Edition, 2010, 34(2):89-94.
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