Beckmann rearrangement of oxime obtained from oleanolic acid. Structure elucidation of the initial oxime

被引：22

作者：

Bednarczyk-Cwynar, Barbara ^{[1
]}

Zaprutko, Lucjusz ^{[1
]}

Froelich, Anna ^{[1
]}

机构：

[1] Poznan Univ Med Sci, Fac Pharm, Dept Organ Chem, PL-60780 Poznan, Poland

来源：

JOURNAL OF MOLECULAR STRUCTURE | 2013年 / 1053卷

关键词：

Triterpenes; Oleanolic acid; Azaderivatives of oleanolic acid; Lactams; Beckmann rearrangement; TRITERPENES; RING; DERIVATIVES;

D O I：

10.1016/j.molstruc.2013.09.006

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Seven-membered A-lactam and A-nitrile of methyl oleanolate were synthesized from the corresponding oxime. Many reaction setups were tried to find the optimum conditions. The best results (the highest yield of the desired lactam along with total consumption of starting oxime) were obtained in pyridine with phosphoryl chloride as Lewis acid. The main product was obtained with the yield of about 60%. Mechanism of Beckmann rearrangement for the above triterpenic 3-oxime leading to normal and abnormal product (a lactam and a nitrile, respectively) was explained. The structures of both products were determined and fully characterized by spectral data. The stereoisomerism of the initial oxime was determined on the basis of Beckmann rearrangement product structure and X-ray analysis. (C) 2013 Elsevier B.V. All rights reserved.

引用

页码：115 / 121

页数：7

共 26 条

[1] Opening of the A ring in taraxast-20(30)-en-3-one oxime in the Beckmann reaction [J].

Akhmetova, V. R. ;

Shakurova, E. R. ;

Khalilov, L. M. .

RUSSIAN JOURNAL OF ORGANIC CHEMISTRY, 2009, 45 (04) :621-623

[2] Inhibition of α-glucosidase by oleanolic acid and its synthetic derivatives [J].

Ali, MS ;

Jahangir, M ;

ul Hussan, SS ;

Choudhary, MI .

PHYTOCHEMISTRY, 2002, 60 (03) :295-299

[3] TRANSFORMATIONS IN RING A OF METHYL GLYCYRRHETINATE [J].

ASKAM, V ;

BRADLEY, DM .

JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC, 1971, (10) :1895-&

[4] Synthesis of nonsteroidal drugs with anti-inflammatory and analgesic activities with zeolites and mesoporous molecular sieve catalysts [J].

Climent, MJ ;

Corma, A ;

Iborra, S .

JOURNAL OF CATALYSIS, 2005, 233 (02) :308-316

[5] GENERAL DEFINITION OF RING PUCKERING COORDINATES [J].

CREMER, D ;

POPLE, JA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1975, 97 (06) :1354-1358

[6] Silica supported MoO3:: a mild heterogeneous catalyst for the Beckmann rearrangement and its application to some sugar derived ketoximes [J].

Dongare, MK ;

Bhagwat, VV ;

Ramana, CV ;

Gurjar, MK .

TETRAHEDRON LETTERS, 2004, 45 (24) :4759-4762

[7] Synthesis of new glycyrrhetinic acid derived ring A azepanone, 29-urea and 29-hydroxamic acid derivatives as selective 11β-hydroxysteroid dehydrogenase 2 inhibitors [J].

Gaware, Rawindra ;

Khunt, Rupesh ;

Czollner, Laszlo ;

Stanetty, Christian ;

Da Cunha, Thierry ;

Kratschmar, Denise V. ;

Odermatt, Alex ;

Kosma, Paul ;

Jordis, Ulrich ;

Classen-Houben, Dirk .

BIOORGANIC & MEDICINAL CHEMISTRY, 2011, 19 (06) :1866-1880

[8] Evaluation of ursolic acid isolated from Ilex paraguariensis and derivatives on aromatase inhibition [J].

Gnoatto, Simone C. B. ;

Dassonville-Klimpt, Alexandra ;

Da Nascimento, Sophie ;

Galera, Philippe ;

Boumediene, Karim ;

Gosmann, Grace ;

Sonnet, Pascal ;

Moslemi, Safa .

EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY, 2008, 43 (09) :1865-1877

[9] A novel task-specific ionic liquid for Beckmann rearrangement: a simple and effective way for product separation [J].

Gui, JZ ;

Deng, YQ ;

Hu, ZD ;

Sun, ZL .

TETRAHEDRON LETTERS, 2004, 45 (12) :2681-2683

[10] Environmentally friendly Beckmann rearrangement of oximes catalyzed by metaboric acid in ionic liquids [J].

Guo, S ;

Deng, YQ .

CATALYSIS COMMUNICATIONS, 2005, 6 (03) :225-228

← 1 2 3 →