催化氢化还原法制备的N,N-双烷基化壳聚糖
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摘要
以十二烷基磺酸钠为相转移剂,月桂醛与壳聚糖反应生成西夫碱,再通过钯碳(Pd/C)催化氢化还原西夫碱制备N,N-双十二烷基化壳聚糖衍生物.通过试验分析催化氢化反应时间、反应温度、Pd/C催化剂用量等因素对烷基化取代度的影响,并用元素分析、红外光谱、核磁共振氢谱等对产物进行表征.正交试验结果表明:催化氢化制备N,N-双十二烷基化壳聚糖的最佳催化氢化反应时间为24 h,反应温度为30℃,Pd/C催化剂的用量占壳聚糖总量的1%,制得的N,N-双十二烷基化壳聚糖的烷基化取代度为189%.
Sodium dodecyl sulfonate was used as the phase transfer agent to react lauraldehyde with chitosan to generate schiff base. Then N,N-dialkyl chitosan derivatives were prepared by palladium carbon(Pd/C) catalytic hydrogenation reduction of schiff base. The effects of catalytic hydrogenation reaction time, reaction temperature, Pd/C catalyst dosage on the degree of alkylation substitution were studied. The products were characterized by elemental analysis, infrared spectroscopy and ~1H NMR spectroscopy. Orthogonal experiment results show that the best catalytic hydrogenation reaction conditions for the catalytic hydrogenation preparation of N,N-dialkyl chitosan are: reaction time 24 h, reaction temperature 30 ℃, Pd/C catalyst 1% of the total amount of chitosan. And the alkylation degree of N,N-dialkyl chitosan is 189%.
Sodium dodecyl sulfonate was used as the phase transfer agent to react lauraldehyde with chitosan to generate schiff base. Then N,N-dialkyl chitosan derivatives were prepared by palladium carbon(Pd/C) catalytic hydrogenation reduction of schiff base. The effects of catalytic hydrogenation reaction time, reaction temperature, Pd/C catalyst dosage on the degree of alkylation substitution were studied. The products were characterized by elemental analysis, infrared spectroscopy and ~1H NMR spectroscopy. Orthogonal experiment results show that the best catalytic hydrogenation reaction conditions for the catalytic hydrogenation preparation of N,N-dialkyl chitosan are: reaction time 24 h, reaction temperature 30 ℃, Pd/C catalyst 1% of the total amount of chitosan. And the alkylation degree of N,N-dialkyl chitosan is 189%.
引文
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[3] LI Mingchun,SU Sheng,XIN Meihua,et al.Relationship between N,N-dialkyl chitosan monolayer and corresponding vesicle[J].Journal of Colloid and Interface Science,2007,311(1):285-288.DOI:10.1016/j.jcis.2006.12.082.
[4] 洪键淞,辛梅华,李明春,等.N-甲基N,N-双十二烷基壳聚糖盐酸盐的合成及自组装囊泡性能[J].化工进展,2014,33(2):423-428.DOI:10.3969/j.issn.1000-6613.2014.02.027.
[5] HUO Meirong,ZHANG Yong,ZHOU Jianping,et al.Formation,microstructure,biodistribution and absence of toxicity of polymeric micelles formed by N-octyl-N,O-carboxymethyl chitosan[J].Carbohydrate polymers,2011,83(4):1959-1969.DOI:10.1016/j.carbpol.2010.10.073.
[6] RAFAEL D,SCHMITT C C,NEUMANN M G.Syntheses and characterization of amphiphilic quaternary ammonium chitosan derivatives[J].Carbohydrate polymers,2016,147(20):97-103.DOI:10.1016/j.carbpol.2016.03.083.
[7] HUO Meirong,ZHANG Yong,ZHOU Jianping,et al.Synthesis and characterization of low-toxic amphiphilic chitosan derivatives and their application as micelle carrier for antitumor drug[J].International Journal of Pharmaceutics,2010,394(1):162-173.DOI:10.1016/j.ijpharm.2010.05.001.
[8] 张晓林,李明春,辛梅华,等.N,N-双十二烷基-3,6-O-磺丙基壳聚糖对紫杉醇的增溶作用[J].化工进展,2012,31(12):2748-2752.DOI:10.16085/j.issn.1000-6613.2012.12.026.
[9] 曾皓月,王之,方美娟,等.pDNA-巯基壳聚糖纳米粒的制备及Box-Behnken效应面法工艺优化[J].华侨大学学报(自然科学版),2017,38(5):676-681.DOI:10.11830/ISSN.1000-5013.201703054.
[10] 王晓燕.N烷基壳聚糖纤维的制备及其凝血性能研究[D].天津:天津工业大学,2018.
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[12] LIU Chong,YUAN Jing,ZHANG Jian,et al.Rh-catalyzed asymmetric hydrogenation of beta-branched enol esters for the synthesis of beta-chiral primary alcohols[J].Organic Letters,2018,20(1):108-111.DOI:10.1021/acs.orglett.7b03469.
[13] LI Jing,MA Yujie,LU Yufei,et al.Synthesis of enantiopure γ-lactones via a ruPHOX-ru catalyzed asymmetric hydrogenation of γ-keto acids[J].Advanced Synthesis and Catalysis,2019,365(5):1-9.DOI:10.1002/adsc.2018 01186.
[14] GRAHAM W P,LI Hao,PRANAW K,et al.Rapid synthesis of rhodium-palladium alloy nanocatalysts[J].Chem Cat Chem,2018,10(1):329-333.DOI:10.1002/cctc.201701133.
[15] GUO Miao,LI He,REN Yiqi,et al.Improving catalytic hydrogenation performance of Pd nanoparticles by electronic modulation using phosphine ligands[J].ACS Catalysis,2018,8(7):6476-6485.DOI:10.1021/acscatal.8b00872.
[16] SUN Xiaohui,SUAREZ A I,OSADCHII D,et al.Single cobalt sites in mesoporous N-doped carbon matrix for selective catalytic hydrogenation of nitroarenes[J].Journal of Catalysis,2018,357:20-28.DOI:10.1016/j.jcat.2017.10.030.
[17] BAUER H,ALONSO M,FARBER C,et al.Imine hydrogenation with simple alkaline earth metal catalysts[J].Nature Catalysis,2018,1(1):40-47.DOI:10.1038/s41929-017-0006-0.
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[19] 赵博文.纳米Pd基催化剂的可控制备及其在维生素E关键中间体:炔醇选择性加氢中的应用研究[D].杭州:浙江大学,2018.
[20] LIU Qili,ZHANG Jianxin,LI Dong,et al.Inhibition of amphiphilic N-Alkyl-O-carboxymethyl chitosan derivatives on alternaria macrospora[J].Biomed Research International,2018,2018:5236324.DOI:10.1155/2018/5236324.