CN106518817A - 对孟‑3‑烯‑1‑胺席夫碱衍生物及其制备方法与除草活性应用 - Google Patents

对孟‑3‑烯‑1‑胺席夫碱衍生物及其制备方法与除草活性应用 Download PDF

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CN106518817A
CN106518817A CN201610947955.7A CN201610947955A CN106518817A CN 106518817 A CN106518817 A CN 106518817A CN 201610947955 A CN201610947955 A CN 201610947955A CN 106518817 A CN106518817 A CN 106518817A
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alkene
meng
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赵振东
朱守记
徐士超
陈玉湘
李冬梅
毕良武
王婧
古研
卢彦菊
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Institute of Chemical Industry of Forest Products of CAF
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Abstract

本发明公开了一种对孟‑3‑烯‑1‑胺席夫碱衍生物及合成方法与除草活性应用。将对孟‑3‑烯‑1‑胺、醛溶入到有机溶剂中，搅拌，0℃～79℃反应。反应结束后，反应液经旋转蒸发除去溶剂，并经硅胶柱层析进一步纯化。本发明制备的系列对孟‑3‑烯‑1‑胺席夫碱衍生物对于一年生黑麦草生长具有良好的抑制作用。本发明的制备方法反应产物收率高，反应条件温和，原辅材料无毒，环境友好，反应过程简单易操作，可连续生产，十分有利于工业化生产。

Description

对孟-3-烯-1-胺席夫碱衍生物及其制备方法与除草活性应用
技术领域：
本发明涉及一类对孟-3-烯-1-胺席夫碱衍生物及其合成方法与除草活性应用，具体涉及利用对孟-3-烯-1-胺和醛在有机溶剂中通过亲核加成-消除一分子H2O来制备N-乙酰基-对孟-3-烯-1-胺的方法。
背景技术
单萜烯胺是一类具有生物活性的有机化合物，但挥发性较强，在应用过程中受到了限制。因此，对单萜烯胺进行结构修饰，以求获得具有挥发性差、生物活性强的衍生物的研究具有积极意义。但是，目前关于这方面的研究很少。
席夫碱主要是指含有亚胺或甲亚胺基团(-RC＝N-)的一类化合物。一般情况下，席夫碱是由胺和醛或酮通过亲核加成-消除反应得到。席夫碱类化合物及其金属配合物广泛应用于药学、催化、腐蚀以及光致变色等领域。尤其在药学领域，席夫碱具有除草、抑菌、抗病毒以及抗肿瘤等多种生物活性。如汤君等人合成的系列三唑席夫碱类化合物对稗草和油菜具有良好的除草活性(化学试剂,2014,36(7):589-593)。由于席夫碱类化合物具备以上各种特性，因此席夫碱的药理学和生理学活性，近年来一直是人们的研究对象。
发明内容
本发明的目的是提供一类对孟-3-烯-1-胺席夫碱衍生物及其制备方法与应用。该类物质具有环境友好、安全无毒的特点，合成方法具有易操作、反应条件温和、成本低、污染小等优点，易实现工业化。
本发明的技术方案为：一类对孟-3-烯-1-胺席夫碱衍生物，结构式为：
其中，的任意一种。
所述的对孟-3-烯-1-胺席夫碱衍生物的制备方法，将对孟-3-烯-1-胺和醛溶于有机溶剂中，搅拌反应，反应结束后，反应液经旋转蒸发除去溶剂乙醇得产物。
所述的醛RCHO中的中的任意一种。
反应温度控制在0℃～79℃或者加热回流反应。
反应时间为1h～100h。
反应液经旋转蒸发除去溶剂，并经硅胶柱层析进一步纯化。
所述的对孟-3-烯-1-胺席夫碱衍生物作为除草剂活性成分的应用。
所述的对孟-3-烯-1-胺席夫碱衍生物作为针对黑麦草的除草剂活性成分的应用。
有益效果
(1)本发明的对孟-3-烯-1-胺席夫碱衍生物为天然植物源产物，是天然单萜烯席夫碱类含氮衍生物，具有毒性低、安全性高、环境友好等特点。
(2)本发明反应条件温和，温度一般控制在0℃～79℃，常压下反应。
(3)本发明工艺过程简单，易操作，环境污染小，易实现工业化。
分析方法
采取气相峰面积归一化法对产物进行分析，气相条件：岛津GC-2014AF，载气N2压力为0.6MPa，空气压力为0.6MPa，H2压力为0.6MPa，采取程序升温，升温程序为：70℃(保持2min，速率3℃/min)→100℃(保持0min，速率10℃/min)→270℃(保持2min)。
附图说明
图1为本发明对孟-3-烯-1-胺与糠醛反应产物的红外光谱(FT-IR)图。
图2为本发明对孟-3-烯-1-胺与糠醛反应产物的1H核磁共振(1H NMR)分析图谱。
图3为本发明对孟-3-烯-1-胺与糠醛反应产物的13C核磁共振(13C NMR)分析图谱。
图4为本发明对孟-3-烯-1-胺与糠醛反应产物的红外光谱(FT-IR)图。
具体实施方案
本发明采用的对孟-3-烯-1-胺席夫碱衍生物的合成方法，由以下步骤组成：
(1)将对孟-3-烯-1-胺和醛溶于有机溶剂中，并搅拌。
(2)温度在0℃～79℃或加热回流。
(3)反应时间在1h～100h。
(4)反应结束后，反应液经旋转蒸发除去溶剂，并经硅胶柱层析进一步纯化。
(5)采用培养皿种子萌发法测定对孟-3-烯-1-胺席夫碱衍生物对黑麦草的芽前除草活性。
对孟-3-烯-1-胺席夫碱衍生物的合成反应式为：
B1：R＝B2：R＝B3：R＝B4：R＝B5：R＝B6：R＝B7：R＝
该类化合物对一年生黑麦草具有较强的除草活性。化合物B1、B2、B3、B4、B5和B6对一年生黑麦草根长的IC50分别为0.29mmol/L、0.23mmol/L、0.29mmol/L、0.29mmol/L、0.23mmol/L和0.33mmol/L；对一年生黑麦草茎长的IC50分别为0.41mmol/L、0.32mmol/L、0.43mmol/L、0.37mmol/L和0.34mmol/L。B7对一年生黑麦草的除草活性比传统除草剂草甘膦强，其对一年生黑麦草根长和茎长的IC50分别远小于0.14mmol/L和0.31mmol/L。而草甘膦对一年生黑麦草根长和茎长的IC50分别为0.14mmol/L和0.41mmol/L。该类化合物在作为以除草活性为代表的农药方面具有广阔的应用前景。
下面结合具体实施例对本发明进行进一步说明：
实施例1
往装有温度计、冷凝管的100mL三口烧瓶中加入4mmol对孟-3-烯-1-胺(自制，其制备方法参见赵振东等的专利ZL 201610454509.2，3-对孟烯-1-胺及其制备方法与生物活性应用，2016.06.21，下同。)、4.8mmol糠醛和20mL无水乙醇，搅拌，室温反应2h。反应液经浓缩、真空干燥后得0.93g(3.92mmol)黄色油状粘稠物(B1)，含量为97.4％，收率为98.0％。
化合物B1的HR-MS、FT-IR、ESI+-MS、1H NMR及13C NMR等谱学表征数据如下：
FT-IR(cm-1):2958.4,2921.5(s,νC-H)；1641.7(s,νN＝C)；1483.8,1370.1(m,δC-H)；1015.4(s,νC-O).ESI+-MS(45eV,m/z):232.12[M+H]+,137.15[M+H-Furan-CH＝NH]+,96.09[M+H-α-Terpinene]+.HR-MS(ESI)for C15H22NO,calcd.232.1696,found 232.1713[M+H]+,Δ＝3.15ppm,DBE＝6.1H NMR(DMSO,500MHz),δH 8.06(1H,s,1-N＝CH),7.78(1H,d,J＝0.5Hz,H-Furan),6.86(1H,d,J＝1.65Hz,H-Furan),6.58(1H,dd,J＝3.25,1.75Hz,H-Furan),5.37(1H,t,3-H),2.13-2.21(2H,m,5-Ha,8-H),2.03-2.07(1H,m,2-Ha),1.93-2.0(1H,m,5-He),1.84-1.89(1H,m,2-He),1.71-1.76(1H,m,6-Ha),1.56-1.60(1H,m,6-He),1.15(3H,s,7-H),0.95(3H,d,J＝0.73Hz,10-H),0.94(3H,d,J＝0.73Hz,9-H).13C NMR(DMSO,500MHz),δC152.82(1-N＝CH),145.46(C-Furan),145.17(C-Furan),142.60(4-C),116.65(3-C),113.82(C-Furan),112.17(C-Furan),58.20(1-C),36.82(6-C),34.69(2-C),34.56(8-C),26.72(7-C),23.71(5-C),21.70(9-C),21.68(10-C).
实施例2
往装有温度计、冷凝管的100mL三口烧瓶中加入4mmol对孟-3-烯-1-胺、6mmol 2-吡咯-甲醛和20mL无水乙醇，搅拌，室温反应42h得粗产物，产率为65.4％(GC)。反应液浓缩后，经硅胶柱层析分离、真空干燥后得黄色油状粘稠物0.40g(B2，1.74mmol)，收率为43.5％。
化合物B2的HR-MS、FT-IR、ESI+-MS、1H NMR及13C NMR等谱学表征数据如下：
FT-IR(cm-1):3229.7(w,νN-H)；2957.1,2921.5(s,νC-H)；1630.6(s,νN＝C)；1419.9(m,δC-H)；1031.0(s,νC-N).ESI+-MS(45eV,m/z):231.17[M+H]+,137.19[M+H-Pyrrole-CH＝NH]+,95.17[M+H-α-Terpinene]+.HRMS(ESI)for C15H23N2,calcd.231.1856,found231.1842[M+H]+,Δ＝5.83ppm,DBE＝6.1H-NMR(DMSO,500MHz),δH 8.02(1H,s,1-N＝CH),6.84(1H,s,H-Pyrrole),6.41(1H,dd,J＝3.30,1.30Hz,H-Pyrrole),6.10(1H,t,J＝2.98Hz,H-Pyrrole),5.40(1H,t,3-H),2.15-2.23(2H,m,5-Ha,8-H),2.05-2.08(1H,m,2-Ha),1.89-2.0(2H,m,2-He,5-He),1.72-1.77(1H,m,6-Ha),1.57-1.62(1H,m,6-He),1.16(3H,s,7-H),0.98(3H,d,J＝1.80Hz,10-H),0.96(3H,d,J＝1.80Hz,9-H).13C NMR(DMSO,500MHz),δC 147.25(1-N＝CH),142.64(4-C),131.25(C-Pyrrole),122.0(C-Pyrrole),116.93(3-C),113.43(C-Pyrrole),109.14(C-Pyrrole),57.34(1-C),37.23(6-C),34.84(2-C),34.69(8-C),27.21(7-C),23.84(5-C),21.83(9-C),21.80(10-C).
实施例3
往装有温度计、冷凝管的100mL三口烧瓶中加入4mmol对孟-3-烯-1-胺、8mmol噻吩-2-甲醛和20mL无水乙醇，搅拌，室温反应96h。反应液经浓缩、90℃真空干燥去除未反应完的噻吩-2-甲醛后得0.99g(3.93mmol)黄色固体(B3)，含量为98.3％)，收率为98.3％。
化合物B3的HR-MS、FT-IR、ESI+-MS、1H NMR及13C NMR等谱学表征数据如下：
FT-IR(cm-1):2957.6,2921.6(s,νC-H)；1630.4(s,νN＝C)；1430.7(m,δC-H).ESI+-MS(45eV,m/z):248.11[M+H]+,137.18[M+H-Thiophene-CH＝NH]+,112.10[M+H-α-Terpinene]+.HRMS(ESI)for C15H22NS,calcd 248.1467,found 248.1478[M+H]+,Δ＝4.22ppm,DBE＝6.1H-NMR(DMSO,500MHz),δH 8.38(1H,s,1-N＝CH),7.61(1H,d,J＝5.0Hz,H-Thiophene),7.44(1H,d,J＝3.55Hz,H-Thiophene),7.13(1H,dd,J＝4.95,3.60Hz,H-Thiophene),5.38(1H,t,3-H),2.14-2.22(2H,m,5-Ha,8-H),2.05-2.09(1H,m,2-Ha),1.88-1.99(2H,m,2-He,5-He),1.71-1.76(1H,m,6-Ha),1.56-1.61(1H,m,6-He),1.17(3H,s,7-H),0.96(6H,d,J＝6.90Hz,9-H,10-H).13C NMR(DMSO,500MHz),δC 150.13(1-N＝CH),144.24(C-Thiophene),142.68(4-C),131.06(C-Thiophene),129.21(C-Thiophene),128.04(C-pyrrole),116.69(3-C),57.96(1-C),37.04(6-C),34.74(2-C,8-C),26.84(7-C),23.74(5-C),21.78(9-C,10-C).
实施例4
往装有温度计、冷凝管的100mL三口烧瓶中加入3mmol对孟-3-烯-1-胺、4.5mmol4-咪唑甲醛和20mL无水乙醇，搅拌，加热回流22h(GC产率为98.08％)。反应液浓缩后得0.746g粗产物，并用乙醚洗涤一次，干燥后得0.48g产品(2.08mmol)微黄色固体(B4)，含量为100％，收率为69.5％。
化合物B4的熔点及HR-MS、FT-IR、ESI+-MS、1H NMR、13C NMR等谱学表征数据如下：
熔点m.p.:106.5-108.4℃；FT-IR(cm-1):3118.9(w,νN-H)；3015.9(w,ν＝C-H)；2959.9,2918.4,2836.9(s,νC-H)；1645.4(s,νN＝C)；1446.3,1364.8(m,δC-H)；1113.5(s,νC-N).ESI+-MS(45eV,m/z):232.13[M+H]+,137.13[M+H-Imidazole-CH＝NH]+,107.08[M+H-α-Terpinene]+.HRMS(ESI)for C14H22N3,calcd 232.1808,found 232.1819[M+H]+,Δ＝4.73ppm,DBE＝6.1H-NMR(DMSO,500MHz),δH 8.14(1H,s,1-N＝CH),7.70(1H,s,H-Imidazole),7.39(1H,s,H-Imidazole),5.39(1H,t,3-H),2.14-2.23(2H,m,2-Ha,8-H),2.05-2.08(1H,m,5-Ha),1.87-1.99(2H,m,2-He,5-He),1.72-1.77(1H,m,6-Ha),1.57-1.62(1H,m,6-He),1.16(3H,s,7-H),0.96(6H,d,J＝6.80Hz,9-H,10-H).
实施例5
往装有温度计、冷凝管的100mL三口烧瓶中加入4mmol对孟-3-烯-1-胺、6mmol 2-吡啶甲醛和20mL无水乙醇，搅拌，加热回流19h(GC产率为99.35％)。反应液浓缩后得1.315g粗产物，并经硅胶柱层析分离纯化得0.75g(B5，3.10mmol)黄色油状粘稠物(上柱前，硅胶用石油醚-三乙胺溶液(V60～90℃石油醚︰V三乙胺＝2︰1)浸泡2h，洗脱剂为10％乙酸乙酯-石油醚溶液)，收率为77.5％。
化合物B5的HR-MS、FT-IR、ESI+-MS、1H-NMR、13C-NMR等谱学表征数据如下：
FT-IR(cm-1):3051.3(w,ν＝C-H)；2958.1,2922.2(s,νC-H)；1643.6(s,νN＝C)；1434.3(s,δC-H).ESI+-MS(45eV,m/z):243.12[M+H]+,137.15[M+H-Pyridine-CH＝NH]+,107.08[M+H-α-Terpinene]+.HRMS(ESI)for C16H23N2,calcd.243.1856,found 243.1863[M+H]+,Δ＝3.01ppm,DBE＝7.1H-NMR(DMSO,500MHz),δH 8.64(1H,d,J＝4.75Hz,H-Pyridine),8.24(1H,s,1-N＝CH),7.97(1H,d,J＝7.90Hz,H-Pyridine),7.87(1H,m,H-Pyridine),7.44-7.47(1H,m,H-pyrrole),5.42(1H,t,3-H),2.25-2.28(1H,m,2-Ha),2.12-2.21(2H,m,5-Ha,8-H),1.97-2.02(1H,m,2-He),1.87-1.93(1H,m,5-He),1.79-1.83(1H,m,6-Ha),1.62-1.68(1H,m,6-He),1.22(3H,s,7-H),0.96(3H,d,J＝1.55Hz,10-H),0.95(3H,d,J＝1.55Hz,9-H).13C NMR(DMSO,500MHz),δC 157.24(C-Pyridine),155.37(1-N＝CH),149.71(C-Pyridine),142.75(4-C),137.24(C-Pyridine),125.34(C-Pyridine),120.45(C-Pyridine),116.59(3-C),58.47(1-C),36.72(6-C),34.69(2-C),34.57(8-C),26.95(7-C),23.66(5-C),21.80(9-C),21.75(10-C).
实施例6
往装有温度计、冷凝管的100mL三口烧瓶中加入4mmol对孟-3-烯-1-胺、6mmol苯甲醛和20mL无水乙醇，搅拌，加热回流7h(GC产率为92.24％)。反应液浓缩后得1.248g粗产物，80℃真空干燥后得0.88g产品(B6，3.65mmol)黄色油状粘稠物，收率为91.2％。
FT-IR(cm-1):3025(w,ν＝C-H)；2960,2925(s,νC-H)；1643(s,νN＝C)；1450(s,δC-H).ESI+-MS(45eV,m/z):242.10[M+H]+,137.11[M+H–Ph-CH＝NH]+,106.08[M+H–α-Terpinene]+.1HNMR(DMSO-d6,500MHz),δH 8.27(1H,s,1-N＝CH),7.75-7.77(2H,m,H-Ph),7.42-7.43(3H,m,H-Ph),5.40(1H,t,3-H),2.25(1H,d,J＝17.8Hz,2-Ha),2.14-2.20(1H,m,8-H),2.09(1H,d,J＝17.4Hz,2-He),1.89-2.00(2H,m,5-Ha,6-Ha),1.76-1.81(1H,m,5-He),1.59-1.66(1H,m,6-He),1.20(3H,s,7-H),0.96(6H,d,J＝6.9Hz,9-H,10-H).13C NMR(DMSO-d6,125MHz),δC155.77(1-N＝CH),142.66(4-C),137.40(C-Ph),130.60(C-Ph),128.89(C-Ph),128.10(C-Ph),116.75(3-C),57.95(1-C),37.12(6-C),34.82(2-C),34.73(8-C),26.82(7-C),23.77(5-C),21.76(10-C),21.75(9-C).
实施例7
往装有温度计、冷凝管的100mL三口烧瓶中加入4mmol对孟-3-烯-1-胺、5.5mmol2,6-二氯苯甲醛和20mL无水乙醇，搅拌，加热回流19h(GC产率为86.42％)。反应液浓缩后得1.475g粗产物，经硅胶柱层析分离、真空干燥后得黄色油状粘稠物1.09g(B7，3.53mmol)，收率为88.2％。
FT-IR(cm-1):3055(w,ν＝C-H)；2960,2925(s,νC-H)；1652(s,νC＝C)；1430(s,δC-H).ESI+-MS(45eV,m/z):309.98[M+H]+,137.10[M+H–Ar-CH＝NH]+,173.93[M+H–α-Terpinene]+.HRMS(ESI)for C17H22Cl2N,calcd.310.1124,found 310.1120[M+H]+,Δ＝1.23ppm,DBE＝7.1H NMR(DMSO-d6,500MHz),δH 8.26(1H,s,1-N＝CH),7.48(2H,d,J＝8.4Hz,H-Ar),7.40(1H,t,J＝8.1Hz,H-Ar),5.37(1H,t,3-H),2.28(1H,d,J＝17.8Hz,2-Ha),2.11-2.19(2H,m,2-He,8-H),1.94-2.03(2H,m,5-Ha,6-Ha),1.82-1.87(1H,m,5-He),1.61-1.66(1H,m,6-He),1.22(3H,s,7-H),0.96(6H,dd,J＝6.8,2.1Hz,9-H,10-H).13C NMR(DMSO-d6,125MHz),δC 152.44(1-N＝CH),142.87(4-C),136.32(C-Ar),133.81(C-Ar),131.12(C-Ar),129.11(C-Ar),129.07(C-Ar),116.23(3-C),59.51(1-C),36.26(6-C),34.70(2-C),34.30(8-C),27.59(7-C),23.61(5-C),21.77(10-C),21.61(9-C).
实施例8
对孟-3-烯-1-胺席夫碱衍生物除草活性测试：采用培养皿种子萌发法，供试草种为一年生黑麦草种子(百绿集团)。
称取1mmol对孟-3-烯-1-胺席夫碱衍生物到100mL容量瓶中，用0.25mL DMF溶解，滴加一滴吐温80，并用蒸馏水稀释至刻度，得到浓度为10mmol/L的溶液作为母液。采用二倍稀释法，配置成一系列浓度(稀释液中DMF和吐温80的浓度和母液一致)。
先将一年生黑麦草种子用蒸馏水浸泡15h。在培养皿(φ9cm)底部放一张滤纸，标上标签，分别加入10mL上述对应浓度的样品溶液，加等量的水、DMF与吐温80的混合液作为空白对照。每个培养皿中加入10粒种子，置于培养箱中，25℃培养5d。实验数据由DPS软件进行处理分析。
式中：
y—根长或茎长抑制率
x2—对照根长或茎长
x1—处理后根长或茎长
实例8测定结果如表1和表2所示。
表1对孟-3-烯-1-胺席夫碱对一年生黑麦草的芽前除草活性
a浓度(mmol·L-1)；b抑制率(％)
表2对孟-3-烯-1-胺席夫碱对一年生黑麦草的毒力回归方程分析及IC50和IC90

Claims (9)

1.一类对孟-3-烯-1-胺席夫碱衍生物，其特征在于，结构式为：
其中，的任意一种。
2.权利要求1所述的对孟-3-烯-1-胺席夫碱衍生物的制备方法，其特征在于，将对孟-3-烯-1-胺和醛溶于有机溶剂中，搅拌反应，反应结束后，反应液经旋转蒸发除去溶剂乙醇得产物。
3.根据权利要求2所述的一种对孟-3-烯-1-胺席夫碱衍生物的制备方法，其特征在于，所述的醛RCHO中的中的任意一种。
4.根据权利要求2所述的对孟-3-烯-1-胺席夫碱衍生物的制备方法，其特征在于，所述的有机溶剂为甲醇、乙醇、四氢呋喃、二甲基甲酰胺、二甲基亚砜、二氯甲烷等中的任意一种或二种及以上组成的混合物。
5.根据权利要求2所述的一种对孟-3-烯-1-胺席夫碱衍生物的制备方法，其特征在于，反应温度控制在0℃～79℃或者加热回流反应。
6.根据权利要求2所述的一种对孟-3-烯-1-胺席夫碱衍生物的制备方法，其特征在于，反应时间为1h～100h。
7.根据权利要求2所述的一种对孟-3-烯-1-胺席夫碱衍生物的制备方法，其特征在于，反应液经旋转蒸发除去溶剂，并经硅胶柱层析进一步纯化。
8.权利要求1所述的对孟-3-烯-1-胺席夫碱衍生物作为除草剂活性成分的应用。
9.权利要求1所述的对孟-3-烯-1-胺席夫碱衍生物作为针对黑麦草的除草剂活性成分的应用。
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CN110105224B (zh) * 2019-06-06 2022-05-03 中国林业科学研究院林产化学工业研究所 3-对䓝烯-1-仲胺类化合物及其制备方法与除草应用
CN111205193A (zh) * 2020-02-21 2020-05-29 中国林业科学研究院林产化学工业研究所 一种紫苏胺衍生物的制备方法及应用
CN111217708A (zh) * 2020-02-21 2020-06-02 中国林业科学研究院林产化学工业研究所 一种烃基紫苏胺衍生物的制备方法与除草应用
CN111217708B (zh) * 2020-02-21 2022-07-26 中国林业科学研究院林产化学工业研究所 一种烃基紫苏胺衍生物的制备方法与除草应用

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