7-溴-9,10-二甲基-9,10-二氢-9,10-环氧蒽-2-甲酸甲酯的合成  

Synthesis of methyl 7-bromo-9,10-dimethyl-9,10-dihydro-9,10-epoxyanthracene-2-carboxylate

作　　者：杜漠 赵梅梅 杨莎[1] 仝红娟 DU Mo;ZHAO Mei-mei;YANG Sha;TONG Hong-juan(School of Pharmacy,Shaanxi Institute of International Trade&Commerce,Xianyang 712046,China;Xianyang Key Laboratory of Molecular Imaging and Drug Synthesis,Xianyang 712046,China)

机构地区：[1]陕西国际商贸学院医药学院,陕西咸阳712046 [2]咸阳市分子影像与药物合成重点实验室,陕西咸阳712046

出　　处：《化学工程师》2023年第2期5-7,20,共4页Chemical Engineer

基　　金：陕西省教育厅专项科研计划项目(22JK0277);咸阳市分子影像与药物合成重点实验室项目(2021QXNL-PT-0008)。

摘　　要：本文报道7-溴-9,10-二甲基-9,10-二氢-9,10-环氧蒽-2-甲酸甲酯(1)的合成。首先,1,2,4-三溴苯(2)与2,5-二甲基呋喃(3)发生Diels-Alder反应得到6-溴-1,4-二甲基-1,4-二氢-1,4-环氧萘(4),然后中间体4与3,6-二(吡啶-2-基)-1,2,4,5-四嗪(5)发生逆Diels-Alder反应得到5-溴-1,3-二甲基异苯并呋喃(6),最后,中间体6与[5-(甲氧羰基)-2-(三甲基硅)苯基](苯基)碘鎓三氟甲烷磺酸盐(7)原位发生Diels-Alder反应得到目标化合物1,中间体4及产物1结构通过1H NMR、MS进行表征。考察了合成6-溴-1,4-二甲基-1,4-二氢-1,4-环氧萘(4)的反应条件,发现当物料摩尔比为n_((3))∶n_((2))=5∶1、正丁基锂用量为n((n-Bu Li))∶n_((2))=1.2∶1、反应40min时,中间体4的收率最高达到75.1%。Methyl 7-bromo-9,10-dimethyl-9,10-dihydro-9,10-epoxyanthracene-2-carboxylate(1)was synthesized.Firstly,6-bromo-1,4-dimethyl-1,4-dihydro-1,4-epoxynaphthalene(4)was obtained by the Diels-Alder reaction of 1,2,4-tribromobenzene(2)with 2,5-dimethylfuran(3).Then,5-bromo-1,3-dimethylisobenzofuran(6)was produced by the reverse Diels-Alder reaction of intermediate 4 with 3,6-di(pyridin-2-yl)-1,2,4,5-tetrazine(5).Finally,the target compound 1 was obtained by the Diels-Alder reaction of intermediate 6 reacts in situ with(5-(methoxycarbonyl)-2-(trimethylsilyl)phenyl)(phenyl)iodonium trifluoromethanesulfonate(7).The structures of intermediate 4 and product 1 were characterized by~1H NMR and MS.The reaction conditions for the synthesis of compound 4 were investigated,it was found that the highest yield of intermediate 4 was 75.1%when the molar ratio of material was n_((3))∶n_((2))=5∶1,the dosage of n-BuLi was n(n-Bu Li)∶n_((2))=1.2∶1 and the reaction time was 40min.

关 键 词：氧桥环化合物 DIELS-ALDER反应 苯炔 合成 

分 类 号：TQ463[化学工程—制药化工]