CN107417650B - N-(2-呋喃基)亚甲基-2-氰基-3-杂环基丙烯酰肼类衍生物及其应用 - Google Patents

N-(2-呋喃基)亚甲基-2-氰基-3-杂环基丙烯酰肼类衍生物及其应用 Download PDF

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CN107417650B
CN107417650B CN201710487694.XA CN201710487694A CN107417650B CN 107417650 B CN107417650 B CN 107417650B CN 201710487694 A CN201710487694 A CN 201710487694A CN 107417650 B CN107417650 B CN 107417650B
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徐志宏
杨建�
岳媛
严映坤
高扬
刘辉
唐孝荣
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Qidong Universal Gear Co ltd
Shanghai Ningjing Intellectual Property Agency Co ltd
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Abstract

本发明涉及杂环Schiff碱类化合物及其用途，特别涉及N‑(2‑呋喃基)亚甲基‑2‑氰基‑3‑杂环基丙烯酰肼类衍生物及其应用。本发明解决的技术问题是提供一种可作为抗氧化剂和农用杀虫剂使用的杂环Schiff碱类化合物，其结构式如式Ⅰ所示。本发明采用生物活性基团拼接原理，将杂环化合物引入Schiff碱类化合物中，发现了一些结构新颖、活性优异的活性化合物或活性先导化合物，从而为新型抗氧化剂及杀虫剂的创制奠定了较好的基础。

Description

N-(2-呋喃基)亚甲基-2-氰基-3-杂环基丙烯酰肼类衍生物及 其应用
技术领域
本发明涉及杂环Schiff碱类化合物及其用途，特别涉及N-(2-呋喃基)亚甲基-2-氰基-3-杂环基丙烯酰肼类衍生物及其应用。
背景技术
抗氧化剂能有效地延缓或抑制许多物质，特别是糖、脂、蛋白质、核酸等生物大分子的氧化变质，在许多领域都有着十分广泛的应用：(1)在食品加工方面，抗氧化剂能抑制油脂氧化，防止其酸败，常作为食品抗氧化添加剂；(2)在生命科学和医学领域，抗氧化剂能清除体内自由基，减缓机体过氧化状态的形成，预防和治疗自由基引起的各种疾病，提高机体免疫能力，从而保护人体健康；(3)在化学工业领域，抗氧化剂作为化工产品的稳定性添加剂，提高产品的抗氧化性能，从而延长其使用寿命。由于抗氧化剂在工农业生产及日常生活中都发挥着不可替代的作用，因此，高效、经济、低毒的抗氧化剂的研究与开发具有十分重要的意义。
另一方面，农药特别是杀虫剂的长期大量使用不仅污染了环境、破坏了生态平衡，还导致了严重的“3R”(残留、抗性和害虫再猖獗)和“三致”(致癌、致畸形和致突变)问题。这些问题引起了人类广泛的关注，如何有效地解决这些问题是人类面临的一项长期而艰巨的任务。这样，在农药面临着巨大的挑战，而人类又离不开农药的情况下，寻找对有害生物高效、对非靶标生物安全、在环境中易降解且降解产物对人类健康和生态环境安全的“环境和谐农药”或“绿色农药”已经成了农药研究的热点和前沿。
Schiff碱是指由伯胺与醛或酮发生缩合反应而生成的含有>C＝N-结构的一类有机化合物，既可以从天然产物中分离得到，也可以通过人工合成的方法获得。大量研究表明，Schiff碱类化合物在医学、催化、分析化学、腐蚀以及光致变色等领域都有着非常重要的作用。同时，Schiff碱类化合物还具有良好的生物活性，例如，杀虫、抗真菌、抗细菌、抗癌、抗寄生虫、除草等等。因此，近几十年来，人们对其研究和开发表现出了极大的兴趣，特别是在生物、医药、农药等领域更是受到了广泛的关注，并且不断有结构新颖、性能优异、作用方式独特、环境友好的品种问世。
近年来，在生物活性化合物的研究和开发过程中，杂环化合物显示出越来越重要的作用。由于其选择性好、活性高、用量少、毒性低以及在有害生物生理生化反应中的特异性而成为研究的主体。其中，呋喃、噻吩、吡啶、嘧啶、吡唑、咪唑、噻唑、三唑等化合物，因不断涌现出一些具有划时代意义的新颖药剂而引起人们的重视，也已成为生物活性化合物研究的热点和前沿。
到目前为止，还未见有杂环Schiff碱类化合物作为抗氧化剂和农用杀虫剂使用的报道。
发明内容
本发明解决的技术问题是提供一种可作为抗氧化剂和农用杀虫剂使用的杂环Schiff碱类化合物。
本发明的N-(2-呋喃基)亚甲基-2-氰基-3-杂环基丙烯酰肼类衍生物，其结构式如式Ⅰ所示：
其中，R1为
R2为氢或C1-C4烷基；
R3为氢、C1-C4烷基或卤素；R4为氢、C1-C4烷基或卤素；X为O或S。
优选的，R1为R2为氢；R3为氢、C1-C4烷基或卤素；R4为氢、C1-C4烷基或卤素；X为O或S。
更优选的，R1为R2为氢。
另一种优选的，R1为R2为C1-C4烷基；R3为氢、C1-C4烷基或卤素；R4为氢、C1-C4烷基或卤素；X为O或S。
更优选R1为R2为甲基；R3为氢、C1-C4烷基或卤素；R4为氢、C1-C4烷基或卤素；X为O或S。
更优选R1为R2为甲基。
本发明还提供本发明化合物在制备抗氧化剂中的应用。
本发明的化合物，具有优异的抗氧化性能，可用作抗氧化剂。
本发明还提供本发明化合物在防治农业害虫中的应用。
本发明的化合物，也可用作杀虫剂，对粘虫、玉米螟、朱砂叶螨、淡色库蚊等农业害虫具有较好的毒杀活性。因此，优选所述农业害虫为粘虫、玉米螟、朱砂叶螨或淡色库蚊。
本发明采用生物活性基团拼接原理，将杂环化合物引入Schiff碱类化合物中，发现了一些结构新颖、活性优异的活性化合物或活性先导化合物，从而为新型抗氧化剂及杀虫剂的创制奠定了较好的基础。
具体实施方式
本发明提供结构式如式Ⅰ所示的化合物：
其中，R1为
R2为氢或C1-C4烷基；
R3为氢、C1-C4烷基或卤素；R4为氢、C1-C4烷基或卤素；X为O或S。
优选的，R1为R2为氢；R3为氢、C1-C4烷基或卤素；R4为氢、C1-C4烷基或卤素；X为O或S。更优选的，R1为 R2为氢。进一步优选R1为R2为氢。
另一种优选的，R1为R2为C1-C4烷基；R3为氢、C1-C4烷基或卤素；R4为氢、C1-C4烷基或卤素；X为O或S。更优选R1为R2为甲基；R3为氢、C1-C4烷基或卤素；R4为氢、C1-C4烷基或卤素；X为O或S。进一步优选R1为 R2为甲基；更优选R1为R2为甲基。
以下是本发明优选的结构式。
本发明的化合物，可以采用常规的制备方法得到。
本发明的化合物，具有优异的抗氧化性能，可用作抗氧化剂。
本发明的化合物，也可用作杀虫剂，对粘虫、玉米螟、朱砂叶螨、淡色库蚊等农业害虫具有较好的毒杀活性。
下面结合实施例对本发明的具体实施方式做进一步的描述，并不因此将本发明限制在所述的实施例范围之中。
实施例1化合物1～6的合成
合成原理：
1、化合物1的合成
(1)中间体的合成
将0.01mol的氰基乙酰肼置于三颈瓶中，加入15mL二氯甲烷作溶剂，3mL醋酸作催化剂，常温下搅拌。取0.01mol的糠醛加到5mL二氯甲烷中，充分溶解后，用恒压滴液漏斗逐滴加到三颈瓶中，反应5h，以薄层硅胶板(TLC)检测终点。将反应液置于烧杯中，用蒸馏水反复洗至中性。分液并减压蒸馏，抽滤后烘干，得到中间体。
(2)目标化合物的合成
取中间体0.01mol置于三颈瓶中，加入15mL无水乙醇作溶剂，3mL三乙胺作催化剂，于50℃的条件下搅拌。取0.01mol的糠醛加到5mL二氯甲烷中，充分溶解后，用恒压滴液漏斗逐滴加到三颈瓶中，反应1h。以薄层硅胶板(TLC)检测终点。反应完全后，将反应液倒入500mL烧杯中，加入300mL的石油醚并搅拌，有固体物质析出。将其抽滤并烘干后，用乙腈：无水乙醇＝1：10的混合溶液对粗产品重结晶，得到目标产物。
黄色晶体；IR(KBr)νmax(cm-1):3407,2211,1655,1561,1536,943；1H NMR(300MHz,DMSO-d6)δ(ppm):11.75(1H,s),8.34(1H,s),8.18(1H,s),8.08(1H,s),7.87(1H,s),7.45(1H,d,J＝3.6Hz),6.96(1H,s),6.86-6.85(1H,m),6.65(1H,s)；13C NMR(75MHz,DMSO-d6)δ(ppm):158.49(1C),149.57(2C),148.91(1C),146.03(1C),139.31(1C),137.22(1C),122.96(1C),116.26(1C),114.92(1C),114.50(1C),112.76(1C),99.94(1C)；HRMS(ESI)m/z:Calcd for C13H10N3O3[M+H]+:256.0717,Found:256.0714.
2、化合物2的合成
(1)中间体的合成
将0.01mol的氰基乙酰肼置于三颈瓶中，加入15mL二氯甲烷作溶剂，3mL醋酸作催化剂，常温下搅拌。取0.01mol的糠醛加到5mL二氯甲烷中，充分溶解后，用恒压滴液漏斗逐滴加到三颈瓶中，反应5h，以薄层硅胶板(TLC)检测终点。将反应液置于烧杯中，用蒸馏水反复洗至中性。分液并减压蒸馏，抽滤后烘干，得到中间体。
(2)目标化合物的合成
取中间体0.01mol置于三颈瓶中，加入15mL无水乙醇作溶剂，3mL三乙胺作催化剂，于50℃的条件下搅拌。取0.01mol的5-溴噻吩-2-甲醛加到5mL二氯甲烷中，充分溶解后，用恒压滴液漏斗逐滴加到三颈瓶中，反应1h，以薄层硅胶板(TLC)检测终点。反应完全后，将反应液倒入500mL烧杯中，加入300mL的石油醚并搅拌，有固体物质析出。将其抽滤并烘干后，用乙腈：无水乙醇＝1：10的混合溶液对粗产品重结晶，得到目标产物。
黄色粉末；IR(KBr)νmax(cm-1):3431,2207,1680,1625,1540,934；1H NMR(300MHz,DMSO-d6)δ(ppm):11.79(1H,s),8.46(1H,s),8.33(1H,s),7.87(1H,s),7.80(1H,d,J＝3.6Hz),7.51(1H,d,J＝3.6Hz),6.97(1H,s),6.65(1H,s)；13C NMR(75MHz,DMSO-d6)δ(ppm):157.97(1C),149.43(1C),145.94(1C),144.44(1C),139.82(1C),139.32(1C),137.87(1C),132.39(1C),122.37(1C),116.54(1C),114.91(1C),112.66(1C),101.22(1C)；HRMS(ESI)m/z:Calcd for C13H9BrN3O2S[M+H]+:349.9593,Found:349.9589.
3、化合物3的合成
(1)中间体的合成
将0.01mol的氰基乙酰肼置于三颈瓶中，加入15mL二氯甲烷作溶剂，3mL醋酸作催化剂，常温下搅拌。取0.01mol的5-甲基糠醛加到5mL二氯甲烷中，充分溶解后，用恒压滴液漏斗逐滴加到三颈瓶中，反应5h，以薄层硅胶板(TLC)检测终点。将反应液置于烧杯中，用蒸馏水反复洗至中性。分液并减压蒸馏，抽滤后烘干，得到中间体。
(2)目标化合物的合成
取中间体0.01mol置于三颈瓶中，加入15mL无水乙醇作溶剂，3mL三乙胺作催化剂，于50℃的条件下搅拌。取0.01mol的糠醛加到5mL二氯甲烷中，充分溶解后，用恒压滴液漏斗逐滴加到三颈瓶中，反应1h，以薄层硅胶板(TLC)检测终点。反应完全后，将反应液倒入500mL烧杯中，加入300mL的石油醚并搅拌，有固体物质析出。将其抽滤并烘干后，用乙腈：无水乙醇＝1：10的混合溶液对粗产品重结晶，得到目标产物。
橙色晶体；IR(KBr)νmax(cm-1):3438,2213,1685,1610,1548,933；1H NMR(400MHz,DMSO-d6)δ(ppm):11.66(1H,s),8.24(1H,s),8.17(1H,s),8.08(1H,s),7.44(1H,d,J＝3.6Hz),6.86-6.85(2H,m),6.28(1H,d,J＝2.4Hz),2.35(3H,s)；13C NMR(100MHz,DMSO-d6)δ(ppm):158.37(1C),155.51(1C),149.49(1C),148.92(1C),148.06(1C),139.18(1C),137.09(1C),122.79(1C),116.83(1C),116.27(1C),114.45(1C),109.17(1C),100.02(1C),13.94(1C)；HRMS(ESI)m/z:Calcd for C14H12N3O3[M+H]+:270.0873,Found:270.0869.
4、化合物4的合成
(1)中间体的合成
将0.01mol的氰基乙酰肼置于三颈瓶中，加入15mL二氯甲烷作溶剂，3mL醋酸作催化剂，常温下搅拌。取0.01mol的5-甲基糠醛加到5mL二氯甲烷中，充分溶解后，用恒压滴液漏斗逐滴加到三颈瓶中，反应5h，以薄层硅胶板(TLC)检测终点。将反应液置于烧杯中，用蒸馏水反复洗至中性。分液并减压蒸馏，抽滤后烘干，得到中间体。
(2)目标化合物的合成
取中间体0.01mol置于三颈瓶中，加入15mL无水乙醇作溶剂，3mL三乙胺作催化剂，于50℃的条件下搅拌。取0.01mol的5-甲基糠醛加到5mL二氯甲烷中，充分溶解后，用恒压滴液漏斗逐滴加到三颈瓶中，反应1h，以薄层硅胶板(TLC)检测终点。反应完全后，将反应液倒入500mL烧杯中，加入300mL的石油醚并搅拌，有固体物质析出。将其抽滤并烘干后，用乙腈：无水乙醇＝1：10的混合溶液对粗产品重结晶，得到目标产物。
橙色晶体，IR(KBr)νmax(cm-1):3424,2208,1672,1604,1546,940；1H NMR(400MHz,DMSO-d6)δ(ppm):11.59(1H,s),8.24(1H,s),7.98(1H,s),7.37(1H,d,J＝3.2Hz),6.84(1H,d,J＝3.2Hz),6.53(1H,d,J＝3.2Hz),6.28(1H,d,J＝2.8Hz),2.44(3H,s),2.35(3H,s)；13CNMR(100MHz,DMSO-d6)δ(ppm):159.84(1C),158.65(1C),155.41(1C),148.13(1C),147.77(1C),138.96(1C),136.66(1C),124.82(1C),116.64(1C),116.50(1C),111.56(1C),109.15(1C),97.78(1C),14.33(1C),13.95(1C)；HRMS(ESI)m/z:Calcd for C15H14N3O3[M+H]+:284.1030,Found:284.1024.
5、化合物5的合成
(1)中间体的合成
将0.01mol的氰基乙酰肼置于三颈瓶中，加入15mL二氯甲烷作溶剂，3mL醋酸作催化剂，常温下搅拌。取0.01mol的5-甲基糠醛加到5mL二氯甲烷中，充分溶解后，用恒压滴液漏斗逐滴加到三颈瓶中，反应5h，以薄层硅胶板(TLC)检测终点。将反应液置于烧杯中，用蒸馏水反复洗至中性。分液并减压蒸馏，抽滤后烘干，得到中间体。
(2)目标化合物的合成
取中间体0.01mol置于三颈瓶中，加入15mL无水乙醇作溶剂，3mL三乙胺作催化剂，于50℃的条件下搅拌。取0.01mol的5-溴噻吩-2-甲醛加到5mL二氯甲烷中，充分溶解后，用恒压滴液漏斗逐滴加到三颈瓶中，反应1h，以薄层硅胶板(TLC)检测终点。反应完全后，将反应液倒入500mL烧杯中，加入300mL的石油醚并搅拌，有固体物质析出。将其抽滤并烘干后，用乙腈：无水乙醇＝1：10的混合溶液对粗产品重结晶，得到目标产物。
黄色粉末；IR(KBr)νmax(cm-1):3444,2208,1627,1587,1553,970；1H NMR(400MHz,DMSO-d6)δ(ppm):11.72(1H,s),8.47(1H,s),8.23(1H,s),7.81(1H,d,J＝3.6Hz),7.52(1H,d,J＝3.6Hz),6.86(1H,s),6.29(1H,s),2.36(3H,s)；13C NMR(100MHz,DMSO-d6)δ(ppm):157.97(1C),155.62(1C),148.01(1C),144.42(1C),139.87(1C),139.29(1C),138.02(1C),132.50(1C),122.40(1C),116.99(1C),116.72(1C),109.22(1C),101.40(1C),13.99(1C)；HRMS(ESI)m/z:Calcd for C14H11BrN3O2S[M+H]+:363.9750,Found:363.9750.
6、化合物6的合成
(1)中间体的合成
将0.01mol的氰基乙酰肼置于三颈瓶中，加入15mL二氯甲烷作溶剂，3mL醋酸作催化剂，常温下搅拌。取0.01mol的5-甲基糠醛加到5mL二氯甲烷中，充分溶解后，用恒压滴液漏斗逐滴加到三颈瓶中，反应5h，以薄层硅胶板(TLC)检测终点。将反应液置于烧杯中，用蒸馏水反复洗至中性。分液并减压蒸馏，抽滤后烘干，得到中间体。
(2)目标化合物的合成
取中间体0.01mol置于三颈瓶中，加入15mL无水乙醇作溶剂，3mL三乙胺作催化剂，于50℃的条件下搅拌。取0.01mol的2-呋喃基丙烯醛加到5mL二氯甲烷中，充分溶解后，用恒压滴液漏斗逐滴加到三颈瓶中，反应1h，以薄层硅胶板(TLC)检测终点。反应完全后，将反应液倒入500mL烧杯中，加入300mL的石油醚并搅拌，有固体物质析出。将其抽滤并烘干后，用乙腈：无水乙醇＝1：10的混合溶液对粗产品重结晶，得到目标产物。
褐色晶体；IR(KBr)νmax(cm-1):3447,2204,1680,1621,1549,920；1H NMR(400MHz,DMSO-d6)δ(ppm):11.66(1H,s),8.22(1H,s),8.09(1H,d,J＝11.6Hz),7.95(1H,s),7.43(1H,d,J＝14.8Hz),7.03-6.93(2H,m),6.85(1H,s),6.71(1H,s),6.28(1H,s),2.35(3H,s)；13C NMR(100MHz,DMSO-d6)δ(ppm):158.11(1C),155.49(1C),152.41(1C),151.61(1C),148.10(1C),147.34(1C),138.99(1C),133.76(1C),120.81(1C),117.46(1C),116.77(1C),115.66(1C),113.88(1C),109.18(1C),105.56(1C),13.96(1C)；HRMS(ESI)m/z:Calcd forC16H14N3O3[M+H]+:296.1030,Found:296.1029.
试验例1本发明化合物杀虫活性的测定
1.供试害虫
粘虫3龄幼虫，玉米螟3龄幼虫，朱砂叶螨成螨，淡色库蚊3龄幼虫，它们均为室内常年累代饲养的敏感品系。
2.粘虫的测定方法
将待测样品溶解于二甲亚砜并用0.1％吐温-80水溶液稀释成一定的浓度，以不加待测样品的相应溶液为阴性对照。将玉米叶片剪成2×4cm的小段，在待测溶液中浸5s后拿开，沥干后放入底部铺有滤纸的培养皿(6cm)中，接入15头3龄幼虫，再将其放置在温度为22～24℃，相对湿度为60％，光照时间为14:10h的实验室中继续饲养，24h后记录死亡情况，每一实验重复3次，并用下列公式计算校正死亡率：
3.玉米螟的测定方法
将待测样品溶解于二甲亚砜并用0.1％吐温-80水溶液稀释成一定的浓度，以不加待测样品的相应溶液为阴性对照。把玉米嫩穗和嫩苞叶切成小段，在待测溶液中浸10s后拿开，沥干后放入直径为6cm，高9cm的玻璃培养皿中，接入15头大小整齐、健康的玉米螟3龄幼虫，再将其放置在温度为22～24℃，相对湿度为60％，光照时间为14:10h的实验室中继续饲养，24h后记录死亡情况，每一实验重复3次，并用下列公式计算校正死亡率：
4.朱砂叶螨的测定方法
将待测样品溶解于二甲亚砜并用0.1％吐温-80水溶液稀释成一定的浓度，以不加待测样品的相应溶液为阴性对照。采集虫口密度大的菜豆叶，仔细挑选使健康的成螨(30～50头)留在叶面上，将带虫的菜豆叶浸入待测溶液5s后拿开，沥干后放入底部铺有滤纸的培养皿(6cm)中，放置在温度为22～24℃，相对湿度为60％，光照时间为14:10h的实验室中继续饲养，24h后记录死亡情况，每一实验重复3次，并用下列公式计算校正死亡率：
5.淡色库蚊的测定方法
采用世界卫生组织推荐的方法，将待测样品溶解于二甲亚砜并用0.1％吐温-80水溶液稀释成一定的浓度，以不加待测样品的相应溶液为阴性对照。取每种溶液1mL，分别加入到装有99mL蒸馏水和20头淡色库蚊3龄幼虫的118mL蜡质纸杯中，将这些纸杯放置在温度为22～24℃，相对湿度为60％，光照时间为14:10h的实验室中继续饲养，24h后记录死亡情况，每一实验重复3次，并用下列公式计算校正死亡率：
6.试验结果
本发明化合物的杀虫结果见表1。
表1
a：三次重复的平均值。
从上表1可知本发明化合物对这些害虫均有较好的毒杀活性。
试验例2本发明化合物的抗氧化性能的测定
1.仪器与试剂
721B型分光光度计，1，1-二苯基-2-苦基肼(DPPH)，95％乙醇。
2.测定步骤
(1)DPPH及样品溶液的配制
用分析天平准确称取0.0130克DPPH，用95％乙醇定容至500mL容量瓶中，得到浓度为26mg/L的溶液；准确称取0.0100g待测样品，用95％乙醇定容至100mL容量瓶中，得到浓度为100mg/L的样品溶液。
(2)在10mL锥形瓶中依次加入4mL的DPPH溶液和1mL95％乙醇溶液，混匀反应稳定后，以95％乙醇为参比溶液，在λmax＝518nm处测定其吸光度值，记为A0。
(3)在10mL锥形瓶中依次加入4mL的DPPH溶液和1mL待测溶液，摇匀，在室温下反应40min稳定后，以95％乙醇为参比溶液，在波长λmax＝518nm处测定其吸光度值，记为AS。每一实验重复三次，并用下列公式计算抗氧化剂的自由基清除率Y(％)：
3.抗氧化性能的测定结果
表2在浓度为100mg/L时，化合物对DPPH自由基的清除率
化合物 清除率<sup>a</sup>(％)
化合物1 93.5
化合物2 90.6
化合物3 85.6
化合物4 87.9
化合物5 86.4
化合物6 92.3
a：三次重复的平均值。
从上表2可知，本发明化合物对DPPH自由基的清除率都在85％以上，即它们都有较好的抗氧化性能。

Claims (9)

1.结构式如式Ⅰ所示的化合物：
其中，R1为
R2为氢或C1-C4烷基；
R3为氢、C1-C4烷基或卤素；R4为氢、C1-C4烷基或卤素；X为O或S。
2.根据权利要求1所述的化合物，其特征在于：R2为氢。
3.根据权利要求2所述的化合物，其特征在于：R1为
4.根据权利要求1所述的化合物，其特征在于：R2为C1-C4烷基。
5.根据权利要求4所述的化合物，其特征在于：R2为甲基。
6.根据权利要求5所述的化合物，其特征在于：R1为
7.根据权利要求1所述的化合物，其特征在于，其结构式如下：
8.权利要求1～7任一项所述的化合物在防治农业害虫中的应用。
9.根据权利要求8所述的化合物在防治农业害虫中的应用，其特征在于：所述农业害虫为粘虫、玉米螟、朱砂叶螨或淡色库蚊。
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