CN114075254B - 一类壳寡糖衍生物杀线剂及其制备方法和应用 - Google Patents
一类壳寡糖衍生物杀线剂及其制备方法和应用 Download PDFInfo
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- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical class O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 title claims abstract description 29
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- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/18—Acyclic radicals, substituted by carbocyclic rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Plant Pathology (AREA)
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Abstract
本发明属于海洋化工工程技术，具体涉及一类壳寡糖衍生物杀线剂制备方法。本发明提供了一类结构新颖、杀线活性好、低毒的壳寡糖‑N‑（三氟丁烯基氧基）苯甲基‑N,N‑二甲基季铵盐衍生物及其制备方法。一类壳寡糖‑N‑（三氟丁烯基氧基）苯甲基‑N,N‑二甲基季铵盐衍生物衍生物通式如式I所示：
Description
技术领域
本发明属于海洋化工工程技术，具体涉及一类壳寡糖衍生物及其制备方法和应用。
背景技术
植物寄生线虫是我国农业作物病害的主要病原之一，农业寄生线虫主要寄生在植物根部，通过阻断营养、水分传输而影响植物生长。同时，线虫啃食植物组织也容易造成真菌、细菌等病原感染，形成并发症。由此，线虫病害每年都会给我国农业生产造成大量的经济损失。然而，化学防治作为线虫防治的主要手段仍存在许多问题。化学杀线剂大多是高毒、高残留品种，由于环境、生态要求而被禁用，而目前可供选择的仅有噻唑磷、威百亩等少数的种类，长期使用会造成耐药性及植物毒性。同时，这些杀线剂仅对动物病原有效，而对真菌等并发症作用不明显，作用方式单一。因此，迫切需要研发能够同时作用线虫、菌体的低毒多功效杀线剂，以提高防治效果，节约资源。
我国海洋面积辽阔，从丰富的海洋生物资源中开发农用生物活性物质，对我国蓝色经济、绿色农业发展具有重要意义。海洋生物资源中，海洋多糖由于特殊的生物活性，在食品、农业、工业、化妆等产业有广阔的开发前景。其中，几丁质是一种碱性多糖，在虾、蟹等节肢动物(甲壳纲、昆虫纲)的外壳中含量丰富。壳寡糖，是从中提取的一种寡糖，其具有促进作物生长、提高作免疫力的活性，同时多羟基和氨基使其容易通过改性获得特定生物活性，因此在农业领域有广阔的研究潜力。
三氟丁烯基是农药研发中的一类活性基团，其通过与其他杀线活性基团连用，能明显提高杀线活性，而酚酸（醛）结构就是一种杀线活性基团。植物源酚酸（醛）类物质与植物对各种病虫害的抗性有关。通过，将三氟丁烯基同酚酸结构结合能够获得良好的杀线活性。同时，季铵盐结构由于带正电荷，对许多菌类有很好的抑制活性。
因此，可将三氟丁烯基、酚酸、季胺结构相结合，同时接枝到壳寡糖上，同时获得杀线、抗菌等生物活性。同时兼具壳寡糖本身的低毒性、提高免疫力的活性，由此通过多重功效获得良好的线虫防治效果。
发明内容
本发明就是针对上述问题，提供了一类结构新颖、杀线活性好、低毒的壳寡糖衍生物及其制备方法和应用。
为了实现本发明的上述目的，本发明采用如下技术方案为：
1. 壳寡糖衍生物为N-（三氟丁烯基氧基）苯甲基-N,N-二甲基壳寡糖季铵盐衍生物，通式如式I所示：
式中n=2-30，t=2，R=H。
2. 壳寡糖衍生物的制备方法为：
（1）单或多羟基苯甲醛在水或醇中，在碱的存在下，与O-乙酰壳寡糖在常温下反应6~10 h，然后经过滤、醇洗、索式提取、烘干等步骤，得O-乙酰壳寡糖-羟基苯甲醛希夫碱衍生物；其中，以壳寡糖单元结构为基准，壳寡糖、醛、碱、O-乙酰壳寡糖的摩尔比为1:1~1.5:0.1~0.5；所述单或多羟基苯甲醛原料为3-羟基苯甲醛、4-羟基苯甲醛、2,4-二羟基苯甲醛、3,4-二羟基苯甲醛、2,3,4-三羟基苯甲醛或3,4,5-三羟基苯甲醛；碱为氢氧化钠或氢氧化钾；醇为乙醇或甲醇；壳寡糖骨架的分子量为300-5000；
（2）将步骤（1）中的O-乙酰壳寡糖-羟基苯甲醛希夫碱衍生物置入碱性有机溶剂，加入4-溴-1,1,2-三氟-1-丁烯、缚酸剂，于60~70℃反应12-24 h，反应后经过滤、醇洗、烘干，得O-乙酰基壳寡糖-（O-三氟丁烯基）羟基苯甲醛希夫碱衍生物；其中，以壳寡糖单糖为基准，壳寡糖希夫碱、缚酸剂、4-溴-1,1,2-三氟-1-丁烯的摩尔比为1:1~1.5:1~1.5；碱性溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、吡啶等，缚酸剂为吡啶、三乙胺、氨水等；
（3）将步骤（2）中的O-乙酰基壳寡糖-（O-三氟丁烯基）羟基苯甲醛希夫碱衍生物置于水与有机溶剂的混合溶液中，加入还原剂，常温反应3~4 h，过滤，滤液加入醇析出沉淀，再经过滤、醇洗、烘干等步骤，得O-乙酰基-N-（O-三氟丁烯基）羟基苯甲氧基壳寡糖衍生物；其中，以壳寡糖单糖为基准，衍生物与还原剂的摩尔比为1:3~5；还原剂为硼氢化钠、氰基硼氢化钠等；有机溶剂为甲醇、乙腈，与水的体积比为1:3；
（4）将步骤（3）中的O-乙酰基-N-（O-三氟丁烯基）羟基苯甲氧基壳寡糖衍生物置于有机溶剂中，加入少量硫酸钠、适量硫酸二甲酯，回流反应6~10 h；减压蒸馏除掉有机溶剂，再加入醇，继续减压蒸馏，得O-乙酰基-N-（O-三氟丁烯基）羟基苯甲氧基-N,N-二甲基壳寡糖季铵盐衍生物粗产物；其中，以壳寡糖单糖为基准，衍生物与硫酸钠、硫酸二甲酯的摩尔比为1：0.1~0.5:1.5~2。所述有机溶剂为氯仿、四氯甲烷等；醇为甲醇、乙醇等；
（5）将步骤（4）中的O-乙酰基-N-（O-三氟丁烯基）羟基苯甲氧基-N,N-二甲基壳寡糖季铵盐衍生物粗产物置于醇或水中，加入适量碱，回流3~4 h，减压蒸馏除掉有机溶剂，再水溶、透析、冻干，即得N-（O-三氟丁烯基）羟基苯甲氧基-N,N-二甲基壳寡糖季铵盐衍生物；其中，以壳寡糖单糖为基准，衍生物、碱的摩尔比为1:2~4，碱为氢氧化钠或氢氧化钾，醇为甲醇或乙醇。
本发明的优点
三氟丁烯基类农药是农业上一大杀虫、杀线类农药，其与其他活性基团结合，会发挥协同增效作用；季胺类活性基团由于带正电荷，具有较强的抗菌活性；将两者结合共同接枝到壳寡糖上，即可增强杀线活性，也可增强对线虫侵染所引起菌类复合病起到抑制作用；同时兼具壳寡糖本身的促免疫、调节生长活性。所合成的衍生物兼具多重功效，在线虫防治过程中具有较强应用性。
附图说明
图1是COSDTQA核磁氢谱。
具体实施方式
下面结合说明书附图对本发明作进一步说明，并且本发明的保护范围不仅局限于以下实施例。
实施例1 N,N-二甲基-N-（4-三氟丁烯基-2,3-二羟基）-苯甲基壳寡糖季铵盐的制备
取10g O-乙酰壳寡糖溶于150mL蒸馏水中，加入1g氢氧化钠，常温搅拌数分钟，加入2,3,4-三羟基苯甲醛，常温反应10h，抽滤，滤饼先后用水、无水乙醇洗涤，经60℃烘干，得5.3g O-乙酰壳寡糖-（2,3,4-三羟基）苯甲醛希夫碱（AcCOSTBA）。
取4g AcCOSTBA 于50mL N,N-二甲基甲酰胺中，加入5mL吡啶，滴加2.9mL 4-溴-1,1,2-三氟-1-丁烯，升温至70℃反应10h。反应结束，降至室温，过滤，滤饼用无水乙醇洗涤，得3.6g O-乙酰壳寡糖-（4-O-三氟丁烯基氧基-2,3-三羟基）苯甲醛希夫碱（AcCOSTBABF）。
取AcCOSTBABF（1.05g）于蒸馏水/乙醇混合液（V:V=3:1）中，加入10%硼氢化钠溶液（10mL），常温反应4h，过滤。收集滤液，加入乙醇析出沉淀，过滤，滤饼用无水乙醇洗涤，60℃烘干，得灰白色固体O-乙酰基-N-（4-O-三氟丁烯基-2,3-二羟基）-苯甲基壳寡糖（COSTTBM），产量为1g。
取1g AcCOSTTBM与1-甲基-2-吡咯烷酮中，浸泡12h，依次加入1.5g 碘化钠、2mL碘甲烷、0.2mL氢氧化钠溶液（4 M），60℃反应24h。过滤，滤饼用无水乙醇洗涤，60℃烘干，得O-乙酰基-N,N-二甲基-N-（4-O-三氟丁烯基-2,3-二羟基）-苯甲基壳寡糖季铵盐（AcCOSDTQA）。
取0.9g AcCOSDTQA于无水乙醇中，加入0.7g氢氧化钠，于60℃反应4h，经透析、冷冻干燥，即得0.3g N,N-二甲基-N-（4-O-三氟丁烯基-2,3-二羟基）-苯甲基壳寡糖季铵盐（COSDTQA, 3-1）。
如图1所示，COSDTQA有多个亚甲基峰，首先是三氟丁烯基O–CH2和C＝C–CH2，分别位于δ3.23ppm和δ2.30ppm，还原后的苯亚甲基在δ3.37ppm，与之相连的是季胺化的甲基，出峰在2.70ppm。另外，δ7.75ppm为苯环上的羟基峰。综上，所有氢谱峰对应COSDTQA的结构，证明其合成成功。同时，根据各氢峰的积分，计算可得三氟丁烯基、苯亚甲基、季胺基的取代度分别为34.4%、38.9%和19.8%。
壳寡糖衍生物杀线活性测定
采用浸虫法测定样品对南方根结线虫（ Meloidogyne incognita）的杀线活性。测试在4个样品浓度下进行：2.0mg/mL、1.0mg/mL、0.5mg/mL、0.25mg/mL。
实验以相同0.008mg/mL的噻唑磷药剂（溶剂为1%的吐温20）为阳性对照，以蒸馏水为空白对照。方法参照农业部标准 NY/T 1833.1-2009, 具体步骤如下：
将被感染线虫的植物根部组织剪成小段，置于1%次氯酸钠溶液中震荡4min，依次通过200目、500目筛，用水洗涤，收集根结线虫虫卵，置于铺有一层滤纸的培养皿汇中，25℃黑暗环境中孵化3d，收集二龄幼虫（J2），配成悬浮液。配制2mg/mL的样品母液，依次稀释至1.0mg/mL、0.5mg/mL、0.25mg/mL。吸取制备好的J2悬浮液20μL（约50条）加入到96孔板中，然后用移液器从低浓度到高浓度，依次吸取药液及对照100μL分别加到96孔板中，加盖于25℃恒温培养。每处理4次重复，于24h、48h、72h后，用解剖镜下观测J2死亡情况，统计死亡率。
样品对J2的杀灭活性，用校正死亡率表示：
实验结果见表1
植物毒性评价
衍生物对种子萌发和根伸长的影响来评估衍生物的植物毒性。选取10个均匀饱满的黄瓜种子，放入一个直径为90 mm、内衬滤纸的培养皿中。然后，加入4 mL样品溶液（0.5和1.0 mg/mL）。将种子放在25.0±2.0℃黑暗中培育。48 h后，测定种子发芽率和胚根伸长。每个处理重复三次，蒸馏水作为空白对照。发芽指数（GI）用以下公式计算：
其中，下标S和C分别代表样品处理组和空白对照组的结果。RL和GS分别表示种子的胚根长度和萌发种子的数目。当GI超过1时，衍生物被认为没有植物毒性。
如表1所示，壳寡糖季铵盐衍生物能够明显提高壳寡糖的杀线活性，同时在24h时，0.41mg/mL的浓度下，对根结线虫J2的杀灭活性在50%以上。尽管，相同浓度时，活性仍低于噻唑磷。但是，所得衍生物为多糖衍生物，在取得相同作用效果时，需要更高的浓度，这是预料中的。同时，壳寡糖衍生物具有促植物生长作用，即更低的植物毒性。另外，壳寡糖季铵盐类具有良好所得杀菌活性，因此所得衍生物具有多重功效，由此，将在线虫防治过程中获得良好的效果。因此，本发明为利用海洋生物活性物质开发新型生物杀线剂提供了一条新的思路。
Claims (3)
1.一类壳寡糖衍生物，其特征在于：N-（三氟丁烯基氧基）苯甲基-N,N-二甲基壳寡糖季铵盐衍生物通式如式I所示：
式中n=2-30，t=2，R=H。
2.根据权利要求1所述的壳寡糖衍生物的制备方法，其特征在于：
（1）多羟基苯甲醛在水或醇中，在碱的存在下，与O-乙酰壳寡糖在常温下反应6~10h，然后经过滤、醇洗、索式提取、烘干步骤，得O-乙酰壳寡糖-羟基苯甲醛希夫碱衍生物；其中，以壳寡糖单元结构为基准，O-乙酰壳寡糖、醛、碱的摩尔比为1:1~1.5:0.1~0.5；所述多羟基苯甲醛原料为2,3,4-三羟基苯甲醛或3,4,5-三羟基苯甲醛；碱为氢氧化钠或氢氧化钾；醇为乙醇或甲醇；壳寡糖骨架的分子量为300-5000；
（2）将步骤（1）中的O-乙酰壳寡糖-羟基苯甲醛希夫碱衍生物置入碱性有机溶剂，加入4-溴-1,1,2-三氟-1-丁烯、缚酸剂，于60~70℃反应12-24h，反应后经过滤、醇洗、烘干，得O-乙酰基壳寡糖-（O-三氟丁烯基）羟基苯甲醛希夫碱衍生物；其中，以壳寡糖单元结构为基准，壳寡糖希夫碱、缚酸剂、4-溴-1,1,2-三氟-1-丁烯的摩尔比为1:1~1.5:1~1.5；所述碱性溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或吡啶，缚酸剂为吡啶、三乙胺或氨水；
（3）将步骤（2）中的O-乙酰基壳寡糖-（O-三氟丁烯基）羟基苯甲醛希夫碱衍生物置于水与有机溶剂的混合溶液中，加入还原剂，常温反应3~4h，过滤，滤液加入醇析出沉淀，再经过滤、醇洗、烘干步骤，得O-乙酰基-N-（O-三氟丁烯基）羟基苯甲氧基壳寡糖衍生物；其中，以壳寡糖单元结构为基准，衍生物与还原剂的摩尔比为1:3~5；所述还原剂为硼氢化钠或氰基硼氢化钠；有机溶剂为甲醇或乙腈，与水的体积比为1:3；
（4）将步骤（3）中的O-乙酰基-N-（O-三氟丁烯基）羟基苯甲氧基壳寡糖衍生物置于有机溶剂中，加入少量硫酸钠、适量硫酸二甲酯，回流反应6~10h；减压蒸馏除掉有机溶剂，再加入醇，继续减压蒸馏，得O-乙酰基-N-（O-三氟丁烯基）羟基苯甲氧基-N,N-二甲基壳寡糖季铵盐衍生物粗产物；其中，以壳寡糖单糖为基准，衍生物与硫酸钠、硫酸二甲酯的摩尔比为1:0.1~0.5:1.5~2；所述有机溶剂为氯仿或四氯甲烷；醇为甲醇或乙醇；
（5）将步骤（4）中的O-乙酰基-N-（O-三氟丁烯基）羟基苯甲氧基-N,N-二甲基壳寡糖季铵盐衍生物粗产物置于醇或水中，加入适量碱，回流3~4h，减压蒸馏除掉有机溶剂，再水溶、透析、冻干，即得N-（O-三氟丁烯基）羟基苯甲氧基-N,N-二甲基壳寡糖季铵盐衍生物；其中，以壳寡糖单糖为基准，衍生物、碱的摩尔比为1:2~4；所述醇为甲醇或乙醇；碱为氢氧化钠、氢氧化钾。
3.根据权利要求1所述的壳寡糖衍生物的应用，其特征在于：所述通式I所示N-（三氟丁烯基氧基）苯甲基-N,N-二甲基壳寡糖季铵盐衍生物在制备杀线剂及杀菌剂中应用。
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