茴脑基双酰肼类化合物的合成及其植物病原菌抑制活性研究

doi:10.3969/j.issn.0253-2417.2022.03.016

摘要/Abstract

摘要：

以茴脑氧化得到的茴香醛为原料，经与丙酸酐的Perkin缩合反应，制备保持有茴脑中苯丙素类C6-C3活性结构单元的羧酸，再经酯化、肼解和N-酰化反应，合成得到19个茴脑基双酰肼化合物(6a~6s)。采用FT-IR、¹H NMR、¹³C NMR和ESI-MS对目标化合物结构进行了表征，并测试了目标化合物对8种植物病原菌的抑制活性。研究结果表明：在质量浓度50 mg/L时，目标化合物对8种植物病原菌均显示出一定的抑菌活性，其中，化合物6a(R=H)、6f(R=m-Cl)、6o(R=p-I)、6p(R=p-OH)和6q(R=p-t-Bu)对苹果轮纹病菌的抑制率分别为94.8%、96.1%、91.7%、96.1%和91.7%，均为A级活性水平，远优于阳性对照百菌清。化合物6f(R=m-Cl)和6p(R=p-OH)值得进一步研究。

关键词: 茴脑, 茴香醛, 双酰肼, 抑菌活性, 合成

Abstract:

Anethole-based carboxylic acid, which maintained the phenylpropanoid C6-C3 active structural unit in anethole, was prepared by Perkin condensation reaction of propionic anhydride with anisaldehyde obtained by the oxidation of anethole. Then, nineteen anethole-based diacylhydrazine compounds(6a-6s) were synthesized via esterification, hydrazinolysis, and N-acylation reactions. All the target compounds were characterized by FT-IR, ¹H NMR, ¹³C NMR, and ESI-MS. Their antifungal activity against eight tested plant pathogens was also evaluated. The results showed that, the target compounds showed certain antifungal activity against the eight tested plant pathogens, at the mass concentration of 50 mg/L. Among them, compounds 6a(R=H), 6f(R=m-Cl), 6o(R=p-I), 6p(R=p-OH), and 6q(R=p-t-Bu) had inhibition rates of 94.8%, 96.1%, 91.7%, 96.1%, and 91.7% against Physalospora piricola(all in A-class activity level), which were much better than that of the positive control chlorothalonil. Compounds 6f(R=m-Cl) and 6p(R=p-OH) were worthy of further investigation.

Key words: anethole, anisaldehyde, diacylhydrazine, antifungal activity, synthesis

中图分类号:

TQ351

范钟天, 段文贵, 林桂汕, 陈铭, 黄媚. 茴脑基双酰肼类化合物的合成及其植物病原菌抑制活性研究[J]. 林产化学与工业, 2022, 42(3): 117-125.

Zhongtian FAN, Wengui DUAN, Guishan LIN, Ming CHEN, Mei HUANG. Synthesis of Anethole-based Diacylhydrazine Compounds and Their Antifungal Activity Against Plant Pathogens[J]. Chemistry and Industry of Forest Products, 2022, 42(3): 117-125.

图/表 2

图1

表1

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化合物 compound	抑制率inhibitory rate/%
化合物 compound	黄瓜枯萎病菌 F. oxysporum	花生褐斑病菌 C. arachidicola	苹果轮纹病菌 P. piricola	番茄早疫病菌 A. solani	小麦赤霉病菌 F. graminearum	水稻纹枯病菌 R. solani	玉米小斑病菌 H. maydis	西瓜炭疽病菌 C. lagenarium
6a	50.7	44.3	94.8	53.6	34.1	66.1	56.8	49.2
6b	23.0	80.0	53.5	63.8	58.3	13.7	22.8	31.6
6c	37.8	80.0	64.3	66.4	64.8	17.3	37.7	31.6
6d	23.6	26.7	36.9	28.2	32.6	43.9	24.3	23.6
6e	21.1	74.3	79.6	84.1	49.3	14.9	31.3	27.6
6f	32.2	64.3	96.1	79.0	65.2	14.9	39.8	31.6
6g	23.6	30.8	25.4	19.1	29.4	43.9	19.5	23.6
6h	28.2	18.3	17.7	19.1	35.8	27.7	19.5	14.5
6i	14.5	30.8	25.4	28.2	42.3	35.8	24.3	14.5
6j	19.1	18.3	17.7	19.1	19.7	32.6	24.3	14.5
6k	14.5	18.3	25.4	19.1	48.7	19.7	19.5	23.6
6l	32.2	52.9	75.2	53.6	41.0	19.8	22.8	35.5
6m	32.2	55.7	85.2	75.2	57.9	16.1	12.1	27.6
6n	32.2	74.3	44.8	76.4	56.6	17.3	33.4	27.6
6o	26.7	52.9	91.7	56.2	47.9	19.8	37.7	27.6
6p	43.3	67.1	96.1	63.8	41.0	16.1	35.5	39.4
6q	39.6	64.3	91.7	63.8	54.5	12.4	48.3	43.3
6r	28.2	35.0	29.2	37.3	48.7	35.8	14.8	19.1
6s	14.5	18.3	19.6	37.3	39.0	40.6	24.3	14.5
百菌清 chlorothalonil	100.0	73.3	75.0	73.9	73.1	96.1	90.4	91.3

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