CN116082324A - 含杂环的1,2,4-噁二唑化合物及其制备方法和应用 - Google Patents
含杂环的1,2,4-噁二唑化合物及其制备方法和应用 Download PDFInfo
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- -1 Heterocyclic 1,2, 4-oxadiazole compound Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- GJNGXPDXRVXSEH-UHFFFAOYSA-N 4-chlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1 GJNGXPDXRVXSEH-UHFFFAOYSA-N 0.000 claims abstract description 7
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
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- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
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- IHNSIFFSNUQGQN-UHFFFAOYSA-N tioxazafen Chemical compound C1=CSC(C=2ON=C(N=2)C=2C=CC=CC=2)=C1 IHNSIFFSNUQGQN-UHFFFAOYSA-N 0.000 description 1
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- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
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Abstract
本发明公开了一种含杂环的1,2,4‑噁二唑化合物及其制备方法和应用,由对氯苯腈为原料合成应制得对氯苄胺肟,之后对氯苄胺肟与杂环酰氯反应制得新型含杂环的1,2,4‑噁二唑化合物。本发明制备方法简单、操作方便,制得的化合物在50ppm的浓度下具有一定的杀菌性和杀虫性。
Description
技术领域
本发明属于化学合成与药物应用技术领域,具体涉及一种含杂环的1,2,4-噁二唑化合物及其制备方法和应用。
背景技术
噁二唑可以作为药物分子组成的重要结构,并且具有明显的生物活性。而且噁二唑类化合物具有良好的热稳定性、化学稳定性及较高的电子亲和性;而被广泛的应用到医药,精细化工,农药等各方面。如1-2-4-噁二唑化合物具有杀虫、杀螨、杀菌、除草、抗菌的生物活性;1,2,4-噁二唑在新药创制中是较重要的杂环骨架,经常作为酯类和酰胺类的生物电子等排体,且1,2,4-噁二唑杂环结构的药物分子表现出多样的生物活性;但有关1,2,4-噁二唑类化合物在农用方面的研究相对较少,商品化的1,2,4-噁二唑杀线虫剂仅有Tioxazafen。
发明内容
本发明以对氯苯腈为原料合成的对氯苄胺肟为原料,通过引入杂环酰氯的方法,设计并合成了新颖的含杂环的1,2,4-噁二唑化合物,本发明的目的在于提供一种含杂环的1,2,4-噁二唑化合物及其制备方法和应用。
含杂环的1,2,4-噁二唑化合物,结构式如式(Ⅰ)所示:
式(I)中,取代基R为 取代基R1选自CH3、取代基R2取代或不取代,取代时R2选自CF3;取代基R3取代或不取代,取代时R3选自CF3、CHF2或Br;取代基R4取代或不取代,取代时R4为Cl;取代基R5取代或不取代,取代时R5选自Cl或Br;取代基R6取代或不取代,取代时R6为OCF3,取代基R7取代或不取代,取代时R7为Cl,取代基R8为C2H6或异丙基;取代基R9为CH3;取代基R10取代或不取代,取代时R10为OCHF2或CH3。
一种含杂环的1,2,4-噁二唑化合物的制备方法,包括如下步骤:
1)以无水乙醇为溶剂,将对氯苯腈与盐酸羟胺在碳酸钠存在的条件下反应,生成如式(Ⅱ)所示的化合物;
2)以冰乙酸为溶剂,三乙胺碱性条件下加入步骤1)得到的如式(Ⅱ)所示的化合物与杂环酰氯反应生成如式(Ⅰ)所示的含杂环的1,2,4-噁二唑化合物;
其反应过程如下:
进一步地,步骤1)中合成如式(Ⅱ)所示的化合物时,对氯苯腈与盐酸羟胺的物质的量比为1:2。
进一步地,步骤2)中合成如式(Ⅰ)所示的含杂环的1,2,4-噁二唑化合物时,如式(Ⅱ)所示的化合物与杂环酰氯的物质的量比为1:1.1-1:1.2。
所述的含杂环的1,2,4-噁二唑化合物在制备杀菌剂和杀虫剂中的应用。
本发明的有益效果在于:
1)本发明制备方法简单、操作方便,所得产物的结构经核磁氢谱进行了确认,并对所得的18个目标产物进行了杀菌活性测试,结果表明:在50ppm下18个化合物均具有一定活性。Ⅰ-5、Ⅰ-9和Ⅰ-12对辣椒疫霉病菌的抑制率都达到了64.5%。Ⅰ-17、Ⅰ-18对黄瓜灰霉病菌的抑制率分别达到了60%、53.3%。Ⅰ-5对水稻稻瘟病菌的抑制率达到54.5%。Ⅰ-14对油菜菌核病菌、黄瓜灰霉病菌和水稻纹枯病菌的抑制率达到了66.7%、63.3%和53%。Ⅰ-13对油菜菌核病菌和水稻纹枯病菌的抑制率均达到了75%,对黄瓜灰霉病菌和苹果轮纹病菌的抑制率在61%以上,对小麦赤霉病菌的抑制率达到54.2%。
2)本发明含杂环的1,2,4-噁二唑化合物对粘虫、蚊幼虫具有一定的杀虫活性。Ⅰ-1、Ⅰ-4、Ⅰ-12、Ⅰ-13和Ⅰ-16在500ppm下作用于粘虫造成的死亡率均达到了100%,但在200ppm下它们对粘虫造成的死亡率降为65%、0、25%、35%、30%,Ⅰ-1杀粘虫活性最好。
Ⅰ-4在10ppm、5ppm、2ppm下作用于蚊幼虫造成的死亡率均达到了100%,但在1ppm下它对蚊幼虫造成的死亡率降为45%。Ⅰ-13在10ppm、5ppm、2ppm、1ppm、0.5ppm下作用于蚊幼虫造成的死亡率均达到了100%,但在0.25ppm下它对蚊幼虫造成的死亡率降为65%。
具体实施方式
下面结合具体实施例对本发明作进一步说明,但本发明的保护范围并不限于此。
反应过程如下:
实施例1如式(Ⅱ)所示化合物的制备
在100mL圆底烧瓶中加入碳酸钠(5.8g,55.0mmol)溶液,再加入10mL无水乙醇和对氯苯腈18(6.9g,50.0mmol),常温搅拌,搅拌均匀后分批加入盐酸羟胺(7.0g,100.0mmol),继续常温搅拌2h,升温回流反应4h,等到反应液冷却后抽滤除去碳酸钠,滤液减压旋转蒸发除去溶剂,得到中间体Ⅱ(4-氯苄胺肟)粗品7.7g,收率90%
实施例2 -19化合物Ⅰ-1~Ⅰ-18的制备
在50mL圆底烧瓶中加入中间体Ⅱ(0.3g,1.7mmol)然后加入10mL冰乙酸和1mL三乙胺,搅拌均匀后,滴加1.9mmol杂环酰氯(取代基R如表1所示),室温搅拌2h,升温回流反应4h,TLC(VEA/VPE=1/1)跟踪反应,等到反应结束后停止加热,冷却至常温后加水即可析出固体,抽滤烘干得到目标化合物Ⅰ-1~Ⅰ-18。具体数据见表1和表2。
表1含杂环的1,2,4-噁二唑化合物理化数据
表2含杂环的1,2,4-噁二唑化合物氢谱数据
实施例20杀菌活性测试
试验方法
(1)试验对象:番茄早疫病菌(Alternariasolani)、小麦赤霉病菌(FusaHumgraminearum Sehw)、水稻稻瘟病菌(Pyricularia Grisea)、辣椒疫霉病菌(Phytophthoracapsici Leonian)、油菜菌核病菌(Sclerotinia sclerotiorum(Lib.)de Bary)、黄瓜灰霉病菌(Botrytis cinerea)、水稻纹枯病菌(Thanatephoruscucumeris)、黄瓜枯萎病菌(Fusarium oxysporum.sp.cucumebrium Owen)、花生褐斑病菌(Cercospora arachidicolaHori)、苹果轮纹病菌(Botryosphaeria dothidea)。
(2)试验处理:各待测化合物用DMSO溶解成1%EC母液备用。采用抑菌圈法,评价待测化合物在50ppm剂量下对试验靶标的室内杀菌活性,另设清水对照(QCK)。
(3)试验方法:用移液枪吸取150微升上述配置的EC母液,溶于2.85mL的吐温水中,配成待测化合物的有效浓度为500ppm的药液。用移液枪吸取1ml药液放入已灭菌的培养皿中,再放入9ml的PDA培养基,摇匀,冷却。用打孔器打取圆形菌饼后用接种针挑至培养皿中央,然后将培养皿置于培养箱27℃中培养,48h后测量菌落直径。菌落纯生长量为菌落平均直径与菌饼直径的差值,抑菌率(%)计算方法参照如下公式。
活性测试结果如表3所示:
表3含杂环的1,2,4-噁二唑化合物杀菌活性
在50ppm下含杂环的1,2,4-噁二唑化合物均具有一定活性。Ⅰ-5、Ⅰ-9和Ⅰ-12对辣椒疫霉病菌的抑制率都达到了64.5%。Ⅰ-17、Ⅰ-18对黄瓜灰霉病菌的抑制率分别达到了60%、53.3%。Ⅰ-5对水稻稻瘟病菌的抑制率达到54.5%。Ⅰ-14对油菜菌核病菌、黄瓜灰霉病菌和水稻纹枯病菌的抑制率达到了66.7%、63.3%和53%。总体来看,Ⅰ-13杀菌活性是该系列最佳,对油菜菌核病菌和水稻纹枯病菌的抑制率均达到了75%,对黄瓜灰霉病菌和苹果轮纹病菌的抑制率在61%以上,对小麦赤霉病菌的抑制率达到了54.2%。
实施例21杀虫活性测试
试验方法
(1)试验对象:
试验靶标:二龄粘虫、一龄蚊幼虫仪器设备:电子天平、浸虫笼、容量瓶、培养皿、烧杯、移液管(移液枪)、镊子、滤纸、记号笔、秒表等。
(2)实验制剂:
试验化合物Ⅰ-1-Ⅰ-18在DMSO或乙醇中稀释,制成500ppm的原液,并稀释为200ppm、10ppm、5ppm、2ppm、1ppm、0.5ppm、0.25ppm。
(3)实验方法:
分别将二龄粘虫浸入500ppm药液10s、一龄蚊幼虫浸入10ppm药液10s,然后用滤纸吸去多余药液,将昆虫转移至正常条件下饲养,每处理重复三次,每重复浸虫20头,并设有机溶剂处理作为空白对照。在24小时时记录昆虫生命状况,一个有机体对吸管的尖端探测没有反应即判定它已死亡。二龄粘虫死亡率达到100%的处理继续测试200ppm下的杀虫活性。一龄蚊幼虫死亡率达到100%的处理继续测试5ppm下的杀虫活性,以此类推。
死亡率(%)计算方法参照如下公式进行计算。
如果空白对照死亡率小于5%,无需校正;如果对照死亡率在5-20%,应进行校正;如果空白对照死亡率大于20%,重做试验。杀虫活性测试结果如表4所示:
表4含杂环的1,2,4-噁二唑化合物杀虫活性
含杂环的1,2,4-噁二唑化合物对粘虫、蚊幼虫具有一定的杀虫活性。在500ppm下Ⅰ-1、Ⅰ-4、Ⅰ-12、Ⅰ-13和Ⅰ-16化合物作用于粘虫造成的死亡率均达到了100%,但在200ppm下它们对粘虫造成的死亡率降为65%、0、25%、35%、30%,Ⅰ-1杀粘虫活性最好。Ⅰ-4在10ppm、5ppm、2ppm下作用于蚊幼虫造成的死亡率均达到了100%,但在1ppm下它对蚊幼虫造成的死亡率降为45%。Ⅰ-13在10ppm、5ppm、2ppm、1ppm、0.5ppm下作用于蚊幼虫造成的死亡率均达到了100%,但在0.25ppm下它对蚊幼虫造成的死亡率降为65%。
本说明书所述的内容仅仅是对发明构思实现形式的列举,本发明的保护范围不应当被视为仅限于实施例所陈述的具体形式,本发明的保护范围也仅仅于本领域技术人员根据本发明构思所能够想到的等同技术手段。
Claims (5)
3.根据权利要求2所述的含杂环的1,2,4-噁二唑化合物的制备方法,其特征在于步骤1)中合成如式(Ⅱ)所示的化合物时,对氯苯腈与盐酸羟胺的物质的量比为1:2。
4.根据权利要求2所述的含杂环的1,2,4-噁二唑化合物的制备方法,其特征在于步骤2)中合成如式(Ⅰ)所示的化合物时,如式(Ⅱ)所示的化合物与杂环酰氯的物质的量比为1:1.1-1:1.2。
5.一种根据权利要求1所述的含杂环的1,2,4-噁二唑化合物在制备杀菌剂和杀虫剂中的应用。
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