含乙烯功能团的β环糊精单体的合成与表征

Synthesis and Characterization of the β-cyclodextrinmonomers with Vinyl Functional Groups

为提高含双键β-环糊精单体的制备效率及丰富其种类,本文通过酰胺化反应和亲核反应合成三种分子中含乙烯功能团的β-环糊精单体。具体方法如下:利用单-6-对甲基苯磺酰-β-环糊精酯(β-CD-6-OTs)和乙二胺(EDA)反应引入活泼氨基,再以1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDCI)和1-羟基苯并三唑(HOBT)为活化剂,N,N-二异丙基乙胺(DIPEA)为缚酸剂,分别与丙烯酸、丁香酸衍生物发生酰胺化反应,制得分子中含双键的β-环糊精单体;以NaH为催化剂,3-溴丙烯为化学改性剂,合成分子中含烯丙基的β-环糊精衍生物;利用质谱、红外光谱以及核磁共振氢谱对三种单体的结构进行表征。结果表明,在室温条件下,分别按照β-CD-6-E(1.0 eq)、AAc/SA-AC(1.2 eq)、HOBT(1.2 eq)、DIPEA(3.3 eq)、EDCI(1.5 eq)和β-CD(1.0 eq)、NaH(20 eq)、3-溴丙烯(2.9 eq)的投料比进行酰胺化反应和亲核反应。表征结果表明,双键均键合至β-环糊精分子中,得到了单取代产物6-丙烯酰乙二胺-β-环糊精(β-CD-6-EA)和6-丙烯酰化丁香酸-β-环糊精(β-CD-6-SA-AC),和以双取代为主的6-O-烯丙基-β-环糊精(Allyl-β-CD)。因此,利用改进后的方法制备含双键环糊精单体,不仅操作简单、效率高,还增加了可聚合环糊精单体的种类和数量,为今后制备各种功能的环糊精高聚物提供了应用基础和思路。

In this paper,three kinds of β-cyclodextrin monomers with vinyl functional groups were synthesized by amidation reaction and necleophilic reaction to improve the preparation efficiency and enrich the monomers.The definite means were as follows： Firstly,the active aminogroups was introduced by the reaction of single-6-p-methylbenzene sulfonyl-β-cyclodextrin（ β-CD-6-OTs） and ethylenediamine（ EDA）.Secondly,the target compounds were synthesized via amidation reaction using1-（ 3-dimethylaminopropyl）-3-ethylenediamine hydrochloride（ EDCI）/1-hydroxybenzotriazole（ HOBT） as their activating agent and N,N-diisopropylamine（ DIPEA） as their acid-binding agent. Using NaH as the catalyst and 3-allyl bromideas the chemistry modifier,the β-cyclodextrinderivative（ Allyl-β-CD） was synthesized. The structure of compounds was further confirmed by mass spectrum,fourier transform infrared spectrometer,and1 H-nuclear magnetic resonance spectra. The results showed that amination and nucleophilic reactions were carried out in accordance with the input ratios of β-CD-6-E（ 1.0 eq）,AAc/SA-AC（ 1.2 eq）,HOBT（ 1.2 eq）,DIPEA（ 3.3 eq）,EDCI（ 1.5 eq） and β-CD（ 1.0 eq）,NaH（ 20 eq）,and3-bromopropylene（ 2.9）,respectively,under the room temperature conditions. Characterization results showed that the double bond was bonded to the β-cyclodextrin,obtaining single-6-acryloyl ethylenediamine-β-cyclodextrin（ β-CD-6-EA）,single-6-acryloyl syringic acid-β-cyclodextrin（ β-CD-6-SA-AC） and disubstituted 6-o-allyl-β-Cyclodextrin（ Allyl-β-CD）.Then,the improved method was used to prepare β-cyclodextrin monomers with vinyl functional groups,which was not only easy to operate and efficient,but also increased the variety and quantity of polymerizable cyclodextrin monomers,which would provide the application basis and ideas for the preparation of various functional cyclodextrin polymers in the future.