一种含蒽醌结构的红色可聚合染料单体的合成

Synthesis of A Red Dye Polymerizing Monomer Containing Anthraquinone

摘要:

在1,2-二氯乙烷介质中，用混酸将1,5-二氯蒽醌选择性硝化，制备出1,5-二氯-4-硝基蒽醌，后者与过量二乙醇胺进行亲核取代，形成一种含蒽醌发色母体结构的可聚合染料单体：1-(N,N-β-二羟乙基)氨基-5-氯-4-硝基蒽醌。通过单因素考察，找到1,5-二氯蒽醌选择性单硝化的较佳工艺条件：使用2:1混酸 [n(H2SO4) : n(HNO3) = 2.0 : 1.0]，投料比n(HNO3) : n(1,5-二氯蒽醌) = 2.00 : 1.00，反应温度20℃，反应时间4 h，单硝化收率达到95%；同样，在n(二乙醇胺) : n(1,5-二氯-4-硝基蒽醌) = 5.00 : 1.00，反应温度40℃，反应时间10 h 等条件下，目标分子收率达81.5 %，最大可见吸收波长（DMF）?max 1 = 393.5 nm，??max 2 = 514.6 nm。用 MS、NMR等方法表征了单硝化产物与目标分子的化学结构。

Abstract:

1,5-dichloroanthraquinone was nitrated with mixed acid in 1,2-dichloroethane to form 1,5-di chloro-4-nitroanthraquinone, followed by nucleophilic displacing the chlorine atom located opposite the nitro group with an excess of diethanolamine to give a red dye polymerizing monomer containing anthraquinone: 1-[N,N-β-dihydroxyethyl)]amino-5-chloro-4-nitroanthraquinone. It has been found that the optimum process technology of synthesizing 1,5-dichloro-4-nitroanthra-quinine and 1-[N,N-β-di- hydroxyethyl)]amino-5-chloro-4-nitroanthraquinone via investigating some different factors effecting the synthetic process, of which 1,5-dichloro-4-nitroanthraquinone will be obtained in 95% at the foll- owing optimum conditions: n(HNO3) : n(1,5-dichloroan-thraquinone) = 2.00 : 1.00, mixed acid [n(H2SO4) : n(HNO3) = 2.0 : 1.0], reaction temperature 20℃, and reaction time 4h. And 1-[N,N-β-di- hydroxyethyl)]amino-5-chloro-4-nitroanthraquinone will be obtained with ?max1 = 393.5 nm, ?max2 = 514.6 nm, and the yield of 81.5% at the following optimum conditions: n(diethanolamine) : n(1,5-dichloro-4-nitroanthraquinone) = 5.00 : 1.00，reaction temperature 40℃, and reaction time 10h. The chemical structures of the two obtained compounds were characterized with melting point, MS, and 1H NMR.