羟基酪醇快速硝基化及产物波谱表征

doi:10.11707/j.1001-7488.20180414

Abstract

Abstract: [Objective] Hydroxytyrosol (HT), belongs to polyphenolic compounds, was widely distributed in olive fruit. Its nitration process is very important for the field of forest products processing industry. Since the traditional method with mixture of concentrated sulfuric acid and nitric acid was easy to make phenolic compound oxidation, and is not an environmentally friendly process. It is thus imperative to find a new fast way to make it nitration, unveiling the product chemical structure by classic multiple spectroscopies in the meantime.[Method] By means of being mixed with NaNO₂ under the condition of weak acid and room temperature, hydroxytyrosol was nitrated quickly. The nitro product was characterized by Uv-vis, FTIR, HPLC-MS, ¹HNMR and ¹³CNMR.[Result] It was observed that this reaction can be finished in 10 min with pH 3.8 (HAC-NaAC butter solution), achieving yield conversion 99.5%. Also, the maximum adsorption wavelengths of nitro-hydroxytyrosol were 245, 296 and 346 nm by Uv-vis spectrophotometer. Phenolic hydroxyl (wavenumber 3 359 cm^-1) of hydroxytyrosol as a reactant in the reaction process did not change, and nitro group (wavenumber 1 557 and 1 405 cm^-1) was introduced into hydroxytyrosol by the results of FTIR. The chemical structure of reaction product was further confirmed by HPLC-MS, ¹HNMR and ¹³CNMR, giving rise to a MW 199 and nitro group linked into para-position of phenolic hydroxyl in hydroxytyrosol.[Conclusion] By means of mild operation conditions (room temperature, pH 3.8 and 10 min), mixing with NaNO₂ as a cheap and accessible industrial raw material, hydroxytyrosol is very easy to get nitrated quickly and the nitro group in the product single-located in para-position of phenolic hydroxyl. These will provide a new path for nitro-phenol preparation to replace a traditional method using mixed strong acids, being of an importance.

Key words: hydroxytyrosol, nitration reaction, product, spectroscopy characterization

CLC Number:

S785
TQ917

Xie Pujun, Huang Lixin, Zhang Caihong, Ding Shasha, Deng Yejun. A Fast Nitration Reaction of Hydroxytyrosol and Characterization on Its products with Spectroscopy[J]. Scientia Silvae Sinicae, 2018, 54(4): 121-127.

References

曹海华. 2013. 紫外光谱在化合物结构分析中的应用. 内蒙古石油化工, 39(8):34-36.
(Cao H H. 2013. Compound structure analysis with ultraviolet spectrum. Inner Mongo Petrochem, 39(8):34-36.[in Chinese])
冯柏成, 韩德彰, 吴祖望, 等. 2006. 3,4-亚甲二氧基硝基苯合成和晶体结构.大连理工大学学报, 46(4):488-490.
(Feng B C, Han D Z, Wu Z W, et al. 2006. Synthesis and crystal structure of 3, 4-methylenedioxy-nitrobenzene. J Dalian Univ Technol, 46(4):488-490.[in Chinese])
隽英华, 武志杰, 陈利军. 2009.基于紫外吸收光谱的酚类衍生物含量检测研究. 光谱学与光谱分析, 29(8):2232-2235.
(Juan Y H, Wu Z J, Chen L J. 2009. Study of Determination of phenol derivatives based on ultraviolet absorption spectra. Spectrosc Spect Ana, 29(8):2232-2235.[in Chinese])
李改云, 朱显超, 邹献武, 等. 2014. 微波辅助杨木快速苯酚液化及产物表征. 林业科学, 50(11):115-121.
(Li G Y, Zhu X C, Zou X W, et al. 2014. Rapid wood liquefaction with phenol by microwave heating and product characterization. Scientia Silvae Sinicae, 50(11):115-121.[in Chinese])
刘艳珠, 李永绣, 李霞, 等. 2010. 硝酸铁对水杨酸甲酯的硝化及位置选择性. 应用化学, 27(4):432-436.
(Liu Y Z,Li Y X,Li X,et al. 2010. Nitration reaction between methyl salicylate and iron(Ⅲ) nitrate and its regioselectivity. Chin J Appl Chem, 27(4):432-436.[in Chinese])
王晓飞, 李辰, 郑媛媛, 等. 2011.油橄榄叶多酚类成分研究. 中草药, 42(5):848-851.
(Wang X F, Li C, Zheng Y Y, et al. 2011. Polyphenols from leaves of Olea europaea. Chin Tradit Herb Drugs, 42(5):848-851.[in Chinese])
原姣姣, 叶建中, 王成章, 等. 2015. 油橄榄羟基酪醇的生物合成及其衍生物研究进展. 林产化学与工业, 35(2):154-162.
(Yuan J J, Ye J Z, Wang C Z, et al. 2015, Advance in biosynthesis and biological activities of olive hydroxytyrosol and its derivatives, Chem Ind Fore Prod, 35(2):154-162.[in Chinese])
Bisignano G, Tomaino A, Lo Cascio R, et al. 1999. On the in-vitro antimicrobial activity of oleuropein and hydroxytyrosol. J Pharm Pharmacol, 51(8):971-974.
Bonifácio M J, Sutcliffe J S, Torrão L, et al. 2014. Brain and peripheral pharmacokinetics of levodopa in the cynomolgusmonkey following administration of opicapone, a third generation nitrocatechol COMT inhibitor. Neuropharmaco, 77:334-341.
Çırak Ç, Sert Y, Ucun F. 2013. Effect of intermolecular hydrogen bonding, vibrational analysis and molecular structure of 4-chlorobenzothioamide. Spectrochimica Acta A:Molecular and Biomolecular Spectroscopy, 113:130-136.
Conlon D A, Lynch J E, Hartner F W, et al. 1996. Nitrous acid-catalyzed nitration of 4-bromo-2,5-dichlorophenol:observation of an unusually facile rearrangement of a 4-bromo-2-nitrophenol during nitration. J Org Chem, 61(18):6425-6429.
Cornard J P, Merlin J C. 2005. Molecular structure and spectroscopic properties of 4-nitrocatecholat different pH:UV-visible, Raman, DFT and TD-DFT calculations. Chem Phys, 309(2/3):239-249.
De Leonardis A, Macciola V, Lembo G. et al. 2007. Studies on oxidative stabilization of lard by natural antioxidants recovered from olive-oil mill wastewater. Food Chem, 100(3):998-1004.
Dega-Szafran Z, Katrusiak A, Szafran M. 2005. Molecular structure of the complex of n-methylmorpholine betaine with 2,4-dinitrophenol. J Mol Struct, 741(1/3):1-9.
Firouzabadi H, Iranpoor N, Zolfigol M A. 1998. Dinitrogen tetroxide complexes of iron (Ⅲ) and copper (Ⅱ) nitrates as new versatile reagents for organic synthesis. efficient and elective oxidation of sulfides to their corresponding sulfoxides under mild conditions. Synth Commun, 71(9):377-385.
Hill D E, Vasdev N, Holland J P. 2015. Evaluating the accuracy of density functional theory for calculating ¹H and ¹³C NMR chemical shifts in drug molecules. Comput Theor Chem, 1051:1161-172.
Jemai H, El Feki A, Sayadi S. 2009. Antidiabetic and antioxidant effects of hydroxytyrosol and oleuropein from olive leaves in alloxan-diabetic rats. J Agric Food Chem, 57(19):8798-8804.
Kono Y, Shibata H, Kodama Y. et al. 1995. The suppression of the N-nitrosating reaction by chlorogenic acid. Biochem J, 312(3):947-953.
Napolitano A, Camera E, Picardo M, et al. 2002. Reaction of hydro(pero)xy derivatives of polyunsaturated fatty acids/esters with nitrite ions under acidic conditions. Unusual nitrosative breakdown of methyl 13-hydro(pero)xyoctadeca-9,11-dienoate to a novel 4-nitro-2-oximinoalk-3-enal product. J Org Chem, 67(4):1125-1132.
Owen R W, Haubner R, Hull W E, et al. 2004. Olive and olive oil in cancer prevention. Eur J Cancer Prev, 13(4):319-326.
Pereira-Caro G, Andrés M, Laura B, et al. 2009. Antioxidant activity evaluation of alkyl hydroxytyrosyl ethers, a new class of hydroxytyrosol derivatives. Food Chem, 115(1):86-91.
Slatnar A, Mikulic-Petkovsek M, Stampar F, et al. 2014. HPLC-MSn identification and quantification of phenolic compound sinhazelnut kernels, oil and bagasse pellets. Food Res Int, 64:783-789.
Tamiri T, Rozin R, Lemberger N, et al. 2009. Urea nitrate, an exceptionally easy-to-make improvised explosive:studies towards trace characterization. Anal Bioanal Chem, 395(2):421-428.
Uyama H, Kurioka H, Kaneko I, et al. 1994. Synthesis of a new family of phenol resin by enzymatic oxidative polymerization. Chem Lett, 23(3):423-426.
Witanowski M, Biedrzycka Z, Sicinska W, et al. 2002. A study of solvent polarity and hydrogen bonding effects on the nitrogen NMR shieldings of N-nitramines and ab initio calculations of the nitrogen shieldings of C-nitro, N-nitro and O-nitro systems. J Mol Struct, 602-603:199-207.

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A Fast Nitration Reaction of Hydroxytyrosol and Characterization on Its products with Spectroscopy

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