新型含胍基和季铵基团壳聚糖衍生物的合成

Synthesis of Novel Chitosan Derivatives Containing Guanidyl and Quaternary Ammonium Groups

N,N-二甲基-1,3-丙二胺与单氰胺经亲核加成反应制得中间体N,N-二甲基-N'-胍基-1,3-丙二胺(2);以壳聚糖为起始原料,依次与氯乙酸、环氧氯丙烷经取代反应制得N-(1-羟基-3-氯丙基)-羧甲基壳聚糖(4);4与2经季铵化反应合成了一系列含有胍基和季胺基团的羧甲基壳聚糖衍生物(5),其结构经1H NMR,IR和元素分析表征。研究了反应配比[γ=m(2)∶m(4)]和反应时间对5取代度的影响,结果表明,当γ为3∶1,反应时间为10 h时,取代度最高(73%)。

N,N-dimethyl-N＇-guanidyl-1,3-propyldiamine（ 2） was prepared by nucleophilic addition of 3-dimethylaminopropylamine with cyanamide. N-（ 1-hydroxyl-3-chloropropyl）-carboxymethyl chitosan（ 4） was prepared by substitution reaction of chitosan with chloroacetic acid then epichlorohydrin. The novel chitosan derivatives（ 5） containing guanidyl and quaternary ammonium groups were synthesized by quaterisation of 4 with 2. The structures were characterized by1 H NMR,IR and elemental analysis. The effects of raw material ration[γ = m（ 2） ∶ m（ 4） ] and reaction time on the degree of substitution（ DS） of the guanidyl and quaternary ammonium groups were investigated. The results showed that when γ was 3 ∶ 1,and the reaction time was 10 h,the largest DS was 73%.