簡介

甲基四氫鄰苯二甲酸酐是一種用于醫(yī)藥、聚合物、染料以及增塑劑的中間體[1]。藥物合成中的甲基四氫鄰苯二甲酸酐衍生物可通過苯酐單元的轉(zhuǎn)換而合成。通過苯酐單元的連續(xù)轉(zhuǎn)換可得到一系列碳環(huán)和雜環(huán)化合物。甲基四氫鄰苯二甲酸酐與氨或伯胺反應(yīng)得到甲基四氫鄰苯二甲酰亞胺,它具有抗高血壓和抗驚厥作用[2-3]。4-溴鄰苯二甲酰亞胺通過部分或全部還原得到相應(yīng)的4-溴苯并(C)呋咯酮和4-溴異二氫吲哚,它有治療精神病和抑郁癥作用。因此，甲基四氫鄰苯二甲酸酐在新藥合成方面發(fā)揮著重大作用[4]。

圖1 甲基四氫鄰苯二甲酸酐的結(jié)構(gòu)式。

合成

圖2 甲基四氫鄰苯二甲酸酐的合成路線[5]。

將3.7 g(0.015mol)4-溴鄰苯二甲酸酐加入50 ml含有少量(一滴)硫酸的醋酸溶液中,回流2 h后,將反應(yīng)混合物蒸干,得到4-溴鄰苯二甲酸酐粗品。再在粗品中加入2.8 g(0.015 mol)2-萘乙酸和50 mg無水醋酸鈉,將得到的固體混合物在通入氮的情況下加熱至275℃ ,反應(yīng)2 h后冷卻,得到褐色的固體反應(yīng)物,加入質(zhì)量分?jǐn)?shù)為10%的重碳酸鈉研磨并在真空中干燥。接著將干燥的固體混合物加入1 ml含有2.1 g(0.039 mol)甲醇鈉的甲醇溶液中,回流該溶液,1 h后,將反應(yīng)混合物蒸干后在水中溶解,再用醚將溶液多次萃取,用6 mol HCl將水層酸化,得到紅色的沉淀物,再在乙醇中重結(jié)晶得到2.5 g該產(chǎn)品甲基四氫鄰苯二甲酸酐(47%)。熔點180.5～ 181.5℃。合成路線如圖2所示。

應(yīng)用

普通的聚氨醋材料與大多數(shù)其它有機(jī)高分子材料一樣,在供給充足的熱量和氧時容易燃燒,尤其是用量大,應(yīng)用廣的聚氨酷泡沫塑料,表面積大,熱容量和導(dǎo)熱系數(shù)低。傳統(tǒng)應(yīng)用的聚氨酚膠粘劑多為多異氰酸酷溶劑膠和經(jīng)基聚氨醋溶劑膠，無溶劑雙組份反應(yīng)型膠粘劑已獲得逐步開發(fā)和應(yīng)用。其中，甲基四氫鄰苯二甲酸酐這類衍生物不僅具有反應(yīng)型阻燃劑通常具備的那些優(yōu)點,而且根據(jù)需要選用不同配方,可以獲得氧指數(shù)較高的聚氨酯材料。主要由于甲基四氫鄰苯二甲酸酐一系列的優(yōu)良性能,特別是具有柔韌性、抗剝離、耐磨、耐候好的低溫性能等[6-7]。目前廣泛應(yīng)用于建筑、木材加工、汽車、塑料加工、制鞋、低溫工程、磁帶、電子電器、型砂、機(jī)械緊固和修補(bǔ)以及家用粘接等方面[8-10]。

此外，甲基四氫鄰苯二甲酸酐經(jīng)過一系列連續(xù)反應(yīng)生成4-溴鄰苯二甲酰亞胺,然后生成5-溴鄰氨基苯甲酸的酰胺鹽,再通過酰胺的環(huán)化得到取代的喹唑啉酮[11]。根據(jù)最新公開的專利顯示,這些化合物有抗癌活性。另外，將甲基四氫鄰苯二甲酸酐與肼反應(yīng),再進(jìn)一步轉(zhuǎn)化可得到溴代2,3-二氮雜萘,其中某些化合物也有抗癌活性。以四苯基溴化物作催化劑, 甲基四氫鄰苯二甲酸酐與堿金屬碳酸鹽反應(yīng),制得OBPDA,或在銅催化劑存在下, 甲基四氫鄰苯二甲酸酐與堿金屬氟化物反應(yīng)制得OBP-DA,所用的溶劑為非質(zhì)子偶極溶劑,該溶劑有二甲基亞砜、二甲基甲酰胺和環(huán)丁砜等[12]。最近文獻(xiàn)報道其最新制備方法包括兩步反應(yīng):步: 甲基四氫鄰苯二甲酸酐與堿金屬氫氧化物反應(yīng)產(chǎn)生4-溴鄰苯二甲酸二堿金屬鹽,然后將其干燥;第二步:將干燥后的4-溴鄰苯二甲酸鹽與甲基四氫鄰苯二甲酸酐反應(yīng),用1,2-二氯苯作溶劑,四苯基溴化物作相轉(zhuǎn)移催化劑,所制得的4,4′-氧代雙鄰苯二甲酸酐(OBP-DA)被用在聚酰亞胺的生產(chǎn)中和在環(huán)氧樹脂中作添加劑[13]。4,4′-硫代雙鄰苯二甲酸酐則通過甲基四氫鄰苯二甲酸酐與堿金屬硫化物在非質(zhì)子偶極溶劑中制得。此種酐在聚酰亞胺生產(chǎn)中作為中間體被應(yīng)用在化工上行業(yè)[14]。

參考文獻(xiàn)

[1] J. Chen, G. Wu, S. Huo, Z. Kong, Synthesis and characterization of curing reaction of epoxy resin obtained from anacardic acids, Linchan Huaxue Yu Gongye 40(4) (2020) 41-46.

[2] Y. Chen, A kind of thermosetting resin composition, prepreg, metal-clad laminated board and printed-circuit board, Shengyi Technology Co., Ltd., Peop. Rep. China . 2017, p. 18pp.

[3] Y. Chen, Thermosetting resin composition, pre-preg, metal foil-coated laminated board, and printed circuit board, Shengyi Technology Co., Ltd., Peop. Rep. China . 2017, p. 34pp.

[4] B.S.S. Guimaraes, E.L. Guiguer, O. Bianchi, L.B. Canto, Non-isothermal cure kinetics of an anhydride-cured cycloaliphatic/aromatic epoxy system in the presence of a reactive diluent, Thermochim. Acta 717 (2022) 179351.

[5] Z. Li, Adhesive for wafer protective film, and its preparation method, Guangdong Laier New Material Technology Co., Ltd., Peop. Rep. China . 2019, p. 12pp.

[6] K. Liu, Q. Li, B. Yang, J. Chen, Z. Li, Y. Xing, L. Wang, B. Zhou, H. Zhao, T. Huang, L. Zhang, H. Zhang, T. Zhao, X. Xu, J. Song, Silicon carbide composite ceramic slurry pump and production process thereof, Hanjiang Hongyuan Xiangyang Silicon Carbide Special Ceramics Co., Ltd., Peop. Rep. China . 2019, p. 22pp.

[7] J. Ma, C. Chen, C. Cui, J. He, R. Huang, S. Yang, Z. Chu, Phosphorus-containing epoxy resin composition, and prepreg and laminate prepared from the same applied as printed circuit board for electronic instruments, Suzhou Shengyi Sci. Tech Co., Ltd., Peop. Rep. China . 2019, p. 11pp.

[8] Y. Shen, Preparation method of solvent type weather-proof epoxy coating, Panjin Qunyi Pipeline Anticorrosion Co., Ltd., Peop. Rep. China . 2017, p. 6pp.

[9] S. Wan, H. He, Sialidase substrate, and kit containing the same and application thereof in testing bacterial vaginosis, Hefei Huajin Bio-tech Co., Ltd., Peop. Rep. China . 2022, p. 27pp.

[10] H. Wu, Q. Xie, Q. Duan, J. Yan, K. Yin, Plasma fluorination of BaTiO3 for enhancement of interfacial adhesion and surface insulation of epoxy resin, J. Mater. Sci. 55(4) (2020) 1499-1510.

[11] D. Yao, H. Dong, D. Lv, X. Liu, H. Wu, D. Zhang, C. Yang, J. Li, T. Feng, Aerogel composite foam core material for thermal insulation board and preparation method thereof, Henan Fanrui Composite Materials Institute Co., Ltd., Peop. Rep. China . 2020, p. 5pp.

[12] P. Zhao, Bi-component polyureide based building sealant and preparation method thereof, Beijing Oriental Yuhong Waterproof Technology Co., Ltd., Peop. Rep. China . 2019, p. 10pp.

[13] Y. Zhao, K. Yang, J. Bai, W. Chen, X. Wang, Y. He, Fluorine-modified epoxy resin for improving surface flashover voltage and its preparation method, Hefei University of Technology, Peop. Rep. China . 2019, p. 9pp.

[14] X. Zhong, Carbon fiber composite material for new-energy automobile and preparation method thereof, Hefei Xianjie New Energy Technology Co., Ltd., Peop. Rep. China . 2019, p. 8pp.