二阶非线性光学材料中间体DAMNS的合成研究

Study on synthesis of an intermediate DAMNS of Second-Order Nonlinear Optical Materials

系统研究了新型二阶非线性光学材料中间体E-2,5-二乙酰氨基-4’-甲氧基-4-硝基二苯乙烯(DAMNS)的制备工艺,以2,5-二氨基甲苯(2,5-TDA)为原料,经乙酰化,硝化及缩合反应得到目标产物,并利用IR和NMR对DAMNS进行了结构表征.研究结果表明:2,5-TDA的二乙酰化和硝化以两步反应一锅法的原位合成工艺为优选,它以乙酸为溶剂,乙酐为酰化剂,97%硝酸为硝化剂,制得质量分数为96.32%,收率为71.03%的2,5-二乙酰氨基-4-硝基甲苯(DANT),然后以DMSO为溶剂,哌啶为催化剂,在分子筛粉末存在下,DANT和对甲氧基苯甲醛(MBA)经Wittig缩合反应,制得中间体DAMNS,收率71.23%,精制得到质量分数为98.89%的DAMNS.

The synthesis of the intermediate. E-2,5-diacetamido-4 ＇-methoxy-4-nitrostilbene （DAMNS） of Second-Order Nonlinear Optical Materials were studied systematically. Starting with the raw material-2,5-diaminotoluene, the title compound was prepared via acetylation, nitration and condensation. The structure of the product was characterized by IR and NMR. The influences of various reaction conditions on the yield were investigated, and the optimal reaction conditions were as follows： An efficient one-pot synthesis of acetylation and nitration were employed with acetic acid as solvent, acetic anhydride as acetylation reagent, 97% nitric acid as nitration reagent. The HPLC of DANT is 96. 32% and the yield is 71. 03%. Condensation： DMSO as solvent, Piperidine as catalyst, Condensation reaction of DANT and MBA to get DAMNS in the existence of Molecular sieve, the yield is 71.23%, then refining to get 98.89M DAMNS.