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• 近年来, 人类不断倡导农药向低毒、高效以及对环境友好的方向发展, 研究表明, 天然活性分子及其衍生物均有作用方式新颖、结构独特、对人畜低毒以及对环境友好等优点, 在农药的发展历程中有着重要意义^[1].

  1, 4-戊二烯-3-酮类化合物是一种重要的天然产物, 具有多种生物活性, 如杀虫^{[2, 3]}、抗病毒^[4]、抑菌^{[5, 6]}、消炎^{[7, 8]}和抗癌^[9~11]等, 因此, 该类化合物在农药领域一直是研究的热点.薛伟等^[12]将肟酯结构引入到1, 4-戊二烯-3-酮类化合物中, 设计合成了一系列1, 4-戊二烯-3-酮肟酯类衍生物.生物活性测试结果表明:在浓度为50 mg/L时, 该系列化合物对小麦赤霉病菌(Gibberella)、辣椒枯萎病菌(Fusarium oxysporium)和苹果腐烂病菌(Cytospora mandshurica)具有一定的抑制作用.张菊平等^[13]合成了一系列新型含苯并三嗪酮的1, 4-戊二烯-3-酮衍生物, 并对其进行抑柑橘溃疡病菌和烟草青枯病菌生物活性测试, 结果表明:在药剂浓度为100 μg/mL时, 部分化合物对上述两种病菌具有很好的抑制作用.

  三氮唑杂环作为一种重要的五元含氮化合物, 在医药和农药等领域都有着广泛的应用, 如抗癌^{[14, 15]}、抗细菌^{[16, 17]}、抗病毒^[18]、抗真菌^[19]和杀虫^[20]等, 在商品药物中三氮唑杂环类杀菌剂有:多效唑(Paclobutrazol)、丙环唑(Propiconazole)和亚胺唑(Imibenconazole)等^[21].闫柏任等^[22]合成一系列含1, 2, 4-三唑曼尼希碱的喹唑啉酮类衍生物, 生物活性测试结果表明:大部分化合物在200 μg/mL浓度下, 对柑橘溃疡病菌和水稻白叶枯病菌表现出较好的抑制活性.林桂汕等^[23]设计并合成了一系列桃金娘烯醛基2-酰基- 1, 2, 4-三唑-3-硫酮衍生物, 抑菌活性测试结果表明:在浓度为50 mg/L时, 部分目标化合物对玉米小斑病菌和苹果轮纹病菌表现出较好的抑菌活性.

  本文利用活性拼接原理, 将含硫醇的三唑引入到1, 4-戊二烯-3-酮结构中, 合成16个含硫醚三唑的1, 4-戊二烯-3-酮类化合物.并采用浊度法测试目标化合物的抑菌活性.

  1.   结果与讨论

  1.1   化合物的合成

  水合肼与二硫化碳反应得到中间体A, 其与醋酸反应生成中间体B; 对羟基苯甲醛与丙酮反应, 通过羟醛缩合得到中间体C, 其与取代醛再一次经羟醛缩合得到中间体D, D与1, 2-二溴乙烷发生取代反应生成中间体E, 最后与中间体B发生取代反应得到目标化合物F₁~F₁₆ (合成路线见Scheme 1).

  图式 1

  

  图式 1.  目标化合物F₁~F₁₆的合成路线

  Scheme 1.  Synthetic routes of target compounds F₁~F₁₆

  下载: 全尺寸图片 幻灯片

  1.2   化合物的结构表征

  以目标化合物F₃为例, 对其¹H NMR、HRMS的谱图特点进行讨论.在¹H NMR谱图中, δ 7.75出现双峰归属于含氧苯环上2'的氢, δ 7.73出现双峰归属于含氧苯环上6'的氢, δ 7.72出现双峰归属于1, 4-戊二烯-3-酮5位上烯键的氢, δ 7.68出现双峰归属于1, 4-戊二烯-3-酮1位上烯键的氢, δ 7.57出现双峰归属于含3, 4-二甲基苯环上6位的氢, δ 7.50出现双峰归属于含3, 4-二甲基苯环上5位的氢, δ 7.27出现单峰归属于含3, 4-二甲基苯环上2位的氢, δ 7.23出现双峰归属于含氧苯环上3'的氢, δ 7.20出现双峰归属于含氧苯环上5'的氢, δ 7.06出现双峰归属于1, 4-戊二烯-3-酮2位和4位上烯键的氢, δ 5.86出现单峰归属于三唑上氨基的氢, δ 4.34出现三峰归属于含氧上亚甲基的氢, δ 3.50出现三峰归属于含硫上亚甲基的氢, δ 2.30出现单峰归属于甲基的氢, δ 2.27出现单峰归属于甲基的氢, δ 2.26出现单峰归属于甲基的氢. 在HRMS谱图中, 目标产物的HRMS [M+H]⁺实测值和理论计算值是一致的, 误差均在±0.0030内, 进一步证实了目标化合物的结构.

  1.3   生物活性

  1.3.1   目标化合物的抑菌活性

  目标化合物F₁~F₁₆抑菌活性测试结果(表 1)表明, 所有化合物对柑橘溃疡病菌、水稻白叶枯病菌和烟草青枯病菌均有一定的抑制活性.其中浓度为100 μg/mL时, 化合物F₄、F₆、F₁₆等对柑橘溃疡病菌的抑制率超过对照药叶枯唑(59.5%), 化合物F₁、F₇、F₁₅等对水稻白叶枯病菌的抑制率超过对照药叶枯唑(56.0%), 化合物F₃、F₆对烟草青枯病菌的抑制率均超过对照药叶枯唑(61.1%).

  表 1

  

  表 1  目标化合物F₁~F₁₆的抑菌活性(抑制率/%)^a

  Table 1.  Antibacterial activities (inhibition rate/%) of target compounds F₁~F₁₆

  下载: 导出CSV

  Compound	R	X. citri			X. oryzae			R. solanacearum
  		100 μg/mL	50 μg/mL		100 μg/mL	50 μg/mL		100 μg/mL	50 μg/mL
  F1	Ph	47.0±1.6	36.5±4.0		89.5±0.9	74.3±0.1		54.5±3.4	49.8±5.3
  F2	Thiophen-2-yl	42.4±2.3	39.0±5.0		34.7±0.6	1.5±0.2		32.8±2.1	28.3±0.1
  F3	3, 4-(CH3)2C6H3	57.4±4.1	41.9±2.7		17.7±0.8	10.6±1.4		75.9±1.5	62.4±0.4
  F4	4-NO2C6H4	72.3±5.3	62.8±2.8		58.0±0.5	41.6±1.2		51.6±0.1	47.9±0.5
  F5	4-ClC6H4	68.0±0.9	52.3±2.5		60.5±1.1	48.8±0.5		48.3±2.4	35.2±1.6
  F6	4-FC6H4	82.5±0.2	78.6±2.9		59.0±4.7	50.6±3.0		76.8±5.4	66.3±3.5
  F7	2, 4-(CH3O)2C6H3	71.3±0.9	63.5±0.4		70.0±0.4	62.9±0.9		53.2±0.6	50.0±3.2
  F8	3-NO2C6H4	66.9±6.4	57.1±1.1		60.1±1.6	51.7±1.8		50.5±3.8	41.7±5.2
  F9	2-ClC6H4	72.6±4.3	64.1±2.2		56.2±4.7	47.6±2.6		41.6±0.9	35.2±0.5
  F10	4-CH3OC6H4	70.9±2.9	64.5±5.4		61.7±0.9	57.4±2.6		48.3±2.5	32.4±3.5
  F11	4-Methylthiazol-5-yl	63.3±5.6	56.5±1.2		46.9±2.8	44.7±0.8		44.9±1.6	36.3±1.3
  F12	Furan-2-yl	55.3±1.3	48.1±2.5		68.6±4.2	56.7±0.2		37.4±0.7	23.2±4.8
  F13	3, 4-(CH3O)2C6H3	38.5±4.0	25.0±1.6		66.2±0.4	60.4±3.9		54.8±1.9	42.1±1.3
  F14	4-BrC6H4	73.6±6.1	65.8±2.7		62.2±0.7	54.9±0.4		50.2±0.1	47.1±7.2
  F15	2, 4-Cl2C6H3	56.7±2.4	45.7±4.9		61.7±0.4	54.9±0.6		55.9±1.1	42.4±0.6
  F16	4-CH3C6H4	77.4±4.0	68.7±1.4		53.0±1.9	44.6±0.6		51.0±1.8	33.9±2.3
  Bismerthiazolb	—	59.5±7.7	49.5±5.7		56.0±1.2	33.8±2.0		61.1±6.2	49.5±5.3
  a Average of three replicates; b The commercial bactericides (bismerthiazol) was used for comparison of antibacterial activity.

  1.3.2   目标化合物的抑植物病菌活性

  以商品药叶枯唑为对照药剂, 对部分化合物进行抑柑橘溃疡病菌、水稻白叶枯病菌和烟草青枯病菌的EC₅₀值测试, 结果列于表 2~4.由表 2可知, 所测目标化合物的柑橘溃疡病菌EC₅₀值均优于对照药叶枯唑, 其中化合物F₄、F₆、F₇、F₁₀、F₁₆的EC₅₀值分别为16.3、9.9、16.4、17.3、15.9 μg/mL, 优于对照药叶枯唑(54.9 μg/mL).由表 3可知, 所测目标化合物的水稻白叶枯病菌EC₅₀值均优于对照药叶枯唑, 其中化合物F₁、F₇、F₁₅的EC₅₀值分别为9.6、19.2、21.3 μg/mL, 优于对照药叶枯唑(69.3 μg/mL).由表 4可知, 所测目标化合物的烟草青枯病菌EC₅₀值均优于对照药叶枯唑, 其中化合物F₃、F₆的EC₅₀值分别为14.2、14.5 μg/mL, 优于对照药叶枯唑(82.6 μg/mL).

  表 2

  

  表 2  部分目标化合物对柑橘溃疡病菌的EC₅₀值^a

  Table 2.  EC₅₀ values of some compounds against X. citri

  下载: 导出CSV

  Compound	R	Toxic regression equation	r	EC50/(μg•mL-1)
  F4	4-O2NC6H4	y＝0.7252x+4.1219	0.9871	16.3±2.5
  F5	4-ClC6H4	y＝0.9076x+3.6020	0.9559	34.7±2.3
  F6	4-FC6H4	y＝0.9529x+4.0511	0.9581	9.9±2.1
  F7	2, 4-(CH3O)2C6H3	y＝0.6956x+4.1554	0.9889	16.4±1.0
  F8	3-O2NC6H4	y＝0.9427x+3.5545	0.9965	34.2±2.4
  F9	2-ClC6H4	y＝0.8344x+3.9314	0.9978	19.1±2.7
  F10	4-CH3OC6H4	y＝0.7527x+4.0683	0.9897	17.3±2.8
  F14	4-BrC6H4	y＝0.8865x+3.8683	0.9899	18.9±2.8
  F16	4-CH3C6H4	y＝0.9412x+3.8669	0.9965	15.9±1.9
  Bismerthiazola	—	y＝0.8357x+3.5466	0.9876	54.9±1.4
  a The commercial bactericides (bismerthiazol) was used for comparison of antibacterial activity.

  表 3

  

  表 3  部分目标化合物对水稻白叶枯病菌的EC₅₀值^a

  Table 3.  EC₅₀ values of some compounds against X. oryzae

  下载: 导出CSV

  Compound	R	Toxic regression equation	r	EC50/(μg•mL-1)
  F1	Ph	y＝1.0838x+3.9378	0.9488	9.6±1.9
  F5	4-ClC6H4	y＝0.7955x+3.7062	0.9066	42.3±0.5
  F7	2, 4-(CH3O)2C6H3	y＝0.8195x+3.9491	0.9250	19.2±0.8
  F8	3-O2NC6H4	y＝0.8219x+3.6715	0.9099	41.3±1.4
  F10	4-CH3OC6H4	y＝0.8897x+3.6013	0.9524	37.3±1.5
  F12	Furan-2-yl	y＝0.9935x+3.5123	0.9899	31.4±2.2
  F13	3, 4-(CH3O)2C6H3	y＝0.9779x+3.5713	0.9402	28.9±1.4
  F14	4-BrC6H4	y＝0.8431x+3.6698	0.9886	37.8±0.8
  F15	2, 4-Cl2C6H3	y＝0.4375x+4.4190	0.9756	21.3±0.8
  Bismerthiazola	—	y＝2.8364x+0.5935	0.9897	69.3±2.0
  a The commercial bactericides (bismerthiazol) was used for comparison of antibacterial activity.

  表 4

  

  表 4  部分目标化合物对烟草青枯病菌的EC₅₀值^a

  Table 4.  EC₅₀ values of some compounds against R. solanacearum

  下载: 导出CSV

  Compound	R	Toxic regression equation	r	EC50/(μg•mL-1)
  F3	3, 4-(CH3)2C6H3	y＝0.7267x+4.1628	0.9547	14.2±3.3
  F6	4-FC6H4	y＝0.8243x+4.0431	0.9917	14.5±4.9
  Bismerthiazola	—	y＝0.9991x+3.2599	0.9399	82.6±0.9
  a The commercial bactericides (bismerthiazol) was used for comparison of antibacterial activity.

  根据表 1~4数据可知, 大部分目标化合物具有较好的抑菌活性.构效关系分析表明:当取代基团为4-NO₂C₆H₄、4-FC₆H₄、4-CH₃OC₆H₄、4-CH₃C₆H₄时, 目标化合物对柑橘溃疡病菌表现出很好的抑制活性, 如F₄、F₆、F₁₀、F₁₆的EC₅₀值分别为16.3、9.9、17.3、15.9 μg/mL, 均优于对照药剂叶枯唑; 当取代基团为Ph、2, 4-(CH₃O)₂C₆H₃、3, 4-(CH₃O)₂C₆H₃、2, 4-Cl₂C₆H₃时, 目标化合物对水稻白叶枯病菌表现出很好的抑制活性, 如F₁、F₇、F₁₃、F₁₅的EC₅₀值分别为9.6、19.2、28.9、21.3 μg/mL, 均优于对照药剂叶枯唑; 当取代基团为3, 4-(CH₃)₂C₆H₃、4-FC₆H₄时, 目标化合物对烟草青枯病菌表现出很好的抑制活性, 如F₃、F₆的EC₅₀值分别为14.2、14.5 μg/mL, 均优于对照药剂叶枯唑.

  1.3.3   目标化合物F₆抑柑橘溃疡病菌(X. citri)作用机制研究^[24]

  通过扫描电镜观察柑橘溃疡病菌(X. citri)表面形态实验发现, 空白对照组菌体呈杆状, 大小均一, 形貌完整; 25 μg/mL F₆药液处理后细菌菌体两端出现细胞壁内陷, 菌体干瘪现象; 50 μg/mL F₆药液处理后菌体细胞壁出现不同程度的破裂, 细胞内容物外泄.

  2.   结论

  以对羟基苯甲醛、取代醛、1, 2-二溴乙烷和硫醇三唑等为原料, 经六步反应合成16个新型含硫醚三唑的1, 4-戊二烯-3-酮类衍生物.初步抑菌活性测试结果表明:化合物对柑橘溃疡病菌、水稻白叶枯病菌和烟草青枯病菌有一定的抑制作用.部分化合物对上述三种病菌的EC₅₀值优于对照药叶枯唑.扫描电镜实验表明:该类化合物对柑橘溃疡病菌的抑菌机制是通过破坏细菌的细胞膜结构, 导致细菌结构不完整, 从而达到抑菌的目的.

  图 1

  

  图 1.  在不同浓度化合物F₆孵育后柑橘溃疡病菌的扫描电镜图像

  Figure 1.  SEM images for X. citri after incubated in different concentration of compound F₆

  (a) c(F₆)＝0 μg/mL, (b) c(F₆)＝25 μg/mL, (c) c(F₆)＝50 μg/mL

  下载: 全尺寸图片 幻灯片

  3.   实验部分

  3.1   仪器与试剂

  Bruker ASCEND 400型(400 MHz)核磁共振波谱仪[四甲基硅烷(TMS)为内标, 瑞士Bruker公司]; Thermo Scientic Q Exactive高分辨质谱仪(HRMS, 赛默飞世尔科技有限公司); X-4型数字显微熔点测定仪(北京泰克仪器有限公司); Sartorius电子天平(德国赛多利斯集团); QY-20型三用紫外分析仪(上海市安亭电子仪器厂). 1, 2-二溴乙烷和取代醛购于上海泰坦科技股份有限公司; 水合肼、二硫化碳等试剂均为市售分析纯.中间体A、B的合成方法参照文献[25]; 中间体C、D、E的合成方法参照文献[26, 27].

  3.2   目标化合物F₁~F₁₆的合成

  在100 mL的单口圆底烧瓶中加入0.5 g中间体B (3.8 mmol)、1.3 g K₂CO₃ (9.6 mmol)和60 mL N, N-二甲基甲酰胺(DMF), 常温搅拌0.5 h, 然后缓慢加入1.1 g中间体E (3.2 mmol)的DMF溶液, 继续搅拌6~8 h.薄层色谱(TLC)跟踪反应, 当反应结束, 停止反应, 反应液用100 mL的水分散, 乙酸乙酯萃取(25 mL), 合并有机层, 用饱和食盐水洗涤(40 mL×3)、无水硫酸钠干燥、减压除去溶剂, 得粗产物, 经柱层析提纯得到目标化合物F₁~F₁₆.

  1-(4-(2-((4-氨基-5-甲基-4H-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-苯基-1, 4-戊二烯-3-酮(F₁):黄色固体, 收率60%. m.p. 130.2~131.4 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 7.80 (d, J=6.3 Hz, 2H), 7.76 (d, J=5.8 Hz, 2H), 7.72 (t, J=5.8 Hz, 2H), 7.46 (t, J=6.8 Hz, 1H), 7.42 (t, J=5.5 Hz, 2H), 7.31 (d, J=7.0 Hz, 1H), 7.20 (d, J=7.1 Hz, 1H), 7.07 (d, J=7.6 Hz, 1H), 7.02 (d, J=7.9 Hz, 1H), 5.87 (s, 2H), 4.32 (t, J=6.3 Hz, 2H), 3.49 (t, J=6.3 Hz, 2H), 2.28 (s, 3H); ¹³C NMR (100 MHz, DMSO-d₆) δ: 188.82, 160.58, 153.87, 151.15, 143.16, 142.74, 135.28, 130.95, 130.89, 129.45, 128.97, 128.05, 126.25, 124.01, 115.46, 66.82, 30.11, 10.25; ESI-HRMS calcd for C₂₂H₂₃O₂N₄S [M+H]⁺ 407.15362, found 407.15302.

  1-(4-(2-((4-氨基-5-甲基-4H-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-(噻吩-2-基)-1, 4-戊二烯-3-酮(F₂):黄色固体, 收率51%. m.p. 147.4~148.8 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 7.95 (d, J=5.8 Hz, 1H), 7.77 (d, J=5.9 Hz, 1H), 7.75 (d, J=5.5 Hz, 1H), 7.74 (d, J=5.8 Hz, 1H), 7.69 (d, J=5.9 Hz, 1H), 7.59 (d, J=6.4 Hz, 1H), 7.25 (d, J=5.9 Hz, 1H), 7.19 (t, J=7.5 Hz, 1H), 7.05 (d, J=7.2 Hz, 2H), 6.96 (d, J=6.8 Hz, 1H), 5.86 (s, 2H), 4.34 (t, J=6.4 Hz, 2H), 3.50 (t, J=6.3 Hz, 2H), 2.29 (s, 3H); ¹³C NMR (100 MHz, DMSO-d₆) δ: 188.12, 160.55, 153.84, 151.11, 142.75, 140.34, 135.69, 132.86, 130.95, 130.51, 129.21, 128.08, 125.23, 123.79, 115.44, 66.84, 30.16, 10.24; ESI-HRMS calcd for C₂₀H₂₁O₂N₄S₂ [M+H]⁺413.11004, found 413.10922.

  1-(4-(2-((4-氨基-5-甲基-4H-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-(3, 4-二甲基苯基)-1, 4-戊二烯-3-酮(F₃):黄色固体, 收率34%. m.p. 90.2~91.8 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 7.75 (d, J=6.1 Hz, 1H), 7.73 (d, J=5.4 Hz, 1H), 7.72 (d, J=6.6 Hz, 1H), 7.68 (d, J=5.9 Hz, 1H), 7.57 (d, J=6.4 Hz, 1H), 7.50 (d, J=6.8 Hz, 1H), 7.27 (s, 1H), 7.23 (d, J=5.8 Hz, 1H), 7.20 (d, J=7.0 Hz, 1H), 7.06 (d, J=7.8 Hz, 2H), 5.86 (s, 2H), 4.34 (t, J=6.4 Hz, 2H), 3.50 (t, J=6.4 Hz, 2H), 2.30 (s, 3H), 2.27 (s, 3H), 2.26 (s, 3H); ¹³C NMR (100 MHz, DMSO-d₆) δ: 188.76, 160.52, 153.84, 151.09, 143.00, 142.77, 139.78, 137.36, 132.87, 130.87, 130.56, 129.89, 128.12, 126.68, 125.19, 124.13, 115.48, 66.87, 30.22, 19.91, 19.79, 10.23; ESI-HRMS calcd for C₂₄H₂₇O₂N₄S[M+H]⁺ 435.18492, found 435.18408.

  1-(4-(2-((4-氨基-5-甲基-4H-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-(4-硝基苯基)-1, 4-戊二烯-3-酮(F₄):黄色固体, 收率: 34%. m.p. 137.2~138.5 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.33 (d, J=7.5 Hz, 2H), 8.10 (d, J=7.3 Hz, 2H), 7.87 (d, J=6.0 Hz, 2H), 7.80 (d, J=6.8 Hz, 2H), 7.59 (d, J=6.4 Hz, 1H), 7.26 (d, J=6.0 Hz, 1H), 7.11 (d, J=7.8 Hz, 2H), 5.90 (s, 2H), 4.38 (t, J=6.3 Hz, 2H), 3.54 (t, J=6.4 Hz, 2H), 2.33 (s, 3H); ¹³C NMR (100 MHz, DMSO-d₆)δ: 188.68, 160.77, 153.85, 151.11, 148.43, 144.05, 141.89, 139.92, 131.07, 129.94, 129.80, 127.93, 124.51, 124.02, 115.53, 66.87, 30.14, 10.24; ESI-HRMS calcd for C₂₂H₂₂O₄N₅S [M+H]⁺ 452.13870, found 452.13791.

  1-(4-(2-((4-氨基-5-甲基-4H-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-(4-氯苯基)-1, 4-戊二烯-3-酮(F₅):黄色固体, 收率: 54%. m.p. 165.8~167.1 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 7.84 (d, J=6.6 Hz, 2H), 7.78 (d, J=6.1 Hz, 2H), 7.75 (d, J=6.0 Hz, 1H), 7.54 (d, J=6.5 Hz, 2H), 7.39 (d, J=6.1 Hz, 1H), 7.22 (d, J=6.0 Hz, 1H), 7.08 (d, J=7.9 Hz, 2H), 7.04 (d, J=7.7 Hz, 1H), 5.89 (s, 2H), 4.36 (t, J=6.4 Hz, 2H), 3.52 (t, J=6.3 Hz, 2H), 2.31 (s, 3H); ¹³C NMR (100 MHz, DMSO-d₆)δ 188.74, 160.62, 153.85, 151.12, 143.36, 141.25, 135.33, 134.27, 130.95, 130.64, 129.49, 128.01, 126.82, 124.06, 115.49, 66.84, 30.14, 10.24; ESI-HRMS calcd for C₂₂H₂₂O₂N₄ClS [M+H]⁺ 441.11465, found 441.11404.

  1-(4-(2-((4-氨基-5-甲基-4H-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-(4-氟苯基)-1, 4-戊二烯-3-酮(F₆):黄色固体, 收率: 50%. m.p. 122.5~123.7 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 7.87 (d, J=6.0 Hz, 1H), 7.85 (d, J=6.9 Hz, 1H), 7.80 (d, J=6.8 Hz, 1H), 7.75 (d, J=6.0 Hz, 3H), 7.34 (d, J=6.9 Hz, 1H), 7.30 (d, J=6.2 Hz, 2H), 7.20 (d, J=7.0 Hz, 1H), 7.06 (d, J=7.9 Hz, 2H), 5.86 (s, 2H), 4.34 (t, J=6.4 Hz, 2H), 3.51 (t, J=6.3 Hz, 2H), 2.30 (s, 3H); ¹³C NMR (100 MHz, DMSO-d₆) δ: 188.75, 160.59 (d, J=247.0 Hz), 153.84, 151.09, 143.15, 141.49, 131.98, 131.29, 130.90, 128.06, 126.13, 124.07, 116.58, 116.36, 115.50, 66.88, 30.21, 10.24; ESI-HRMS calcd for C₂₂H₂₂- O₂N₄FS [M+H]⁺ 425.14420, found 425.14322.

  1-(4-(2-((4-氨基-5-甲基-4H-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-(2, 4-二甲氧基苯基)-1, 4-戊二烯-3-酮(F₇):黄色固体, 收率: 31%. m.p. 132.5~134.1 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 7.89 (d, J=6.9 Hz, 1H), 7.73 (d, J=6.4 Hz, 2H), 7.67 (d, J=6.0 Hz, 1H), 7.58 (d, J=6.4 Hz, 1H), 7.24 (d, J=6.0 Hz, 1H), 7.15 (d, J=6.9 Hz, 1H), 7.08 (d, J=7.9 Hz, 1H), 7.04 (s, 1H), 6.73 (d, J=7.9 Hz, 1H), 6.63 (d, J=7.7 Hz, 1H), 5.86 (s, 2H), 4.35 (t, J=6.4 Hz, 2H), 3.90 (s, 3H), 3.84 (s, 3H), 3.50 (t, J=6.3 Hz, 2H), 2.30 (s, 3H); ¹³C NMR (100 MHz, DMSO-d₆) δ: 188.64, 163.33, 160.43, 160.31, 153.84, 151.10, 142.29, 137.52, 130.79, 130.48, 128.16, 124.90, 123.72, 116.42, 115.45, 106.77, 98.85, 66.84, 56.25, 55.99, 30.19, 10.24; ESI-HRMS calcd for C₂₄H₂₇O₄N₄S[M+H]⁺ 467.17475, found 467.17401.

  1-(4-(2-((4-氨基-5-甲基-4H-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-(3-硝基苯基)-1, 4-戊二烯-3-酮(F₈):黄色固体, 收率: 40%. m.p. 128.4~130.0 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.63 (s, 1H), 8.28 (d, J=7.9 Hz, 1H), 8.25 (d, J=7.7 Hz, 1H), 7.89 (t, J=7.1 Hz, 1H), 7.83 (d, J=6.9 Hz, 1H), 7.79 (d, J=6.1 Hz, 2H), 7.74 (d, J=6.0 Hz, 1H), 7.55 (d, J=6.5 Hz, 1H), 7.22 (d, J=6.0 Hz, 1H), 7.08 (d, J=7.9 Hz, 2H), 5.87 (s, 2H), 4.35 (t, J=6.4 Hz, 2H), 3.50 (t, J=6.3 Hz, 2H), 2.30 (s, 3H); ¹³C NMR (100 MHz, DMSO-d₆) δ: 188.73, 160.71, 153.85, 151.11, 148.83, 143.77, 140.21, 137.21, 134.89, 131.00, 130.91, 128.63, 127.98, 124.97, 123.97, 123.30, 115.51, 66.87, 30.16, 10.24; ESI-HRMS calcd for C₂₂H₂₂O₄N₅S [M+H]⁺452.13870, found 452.13766.

  1-(4-(2-((4-氨基-5-甲基-4H-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-(2-氯苯基)-1, 4-戊二烯-3-酮(F₉):黄色固体, 收率: 29%. m.p. 155.9~157.1 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.05 (d, J=7.9 Hz, 1H), 7.95 (d, J=6.1 Hz, 1H), 7.86 (d, J=6.1 Hz, 1H), 7.75 (d, J=6.0 Hz, 2H), 7.57 (d, J=6.4 Hz, 1H), 7.52 (t, J=6.3 Hz, 1H), 7.47 (t, J=6.6 Hz, 1H), 7.45 (d, J=6.0 Hz, 1H), 7.12 (d, J=7.9 Hz, 1H), 7.07 (d, J=7.7 Hz, 2H), 5.87 (s, 2H), 4.35 (t, J=6.4 Hz, 2H), 3.51 (t, J=6.3 Hz, 2H), 2.30 (s, 3H); ¹³C NMR (100 MHz, DMSO-d₆) δ: 188.49, 160.74, 153.85, 151.10, 144.02, 137.08, 134.61, 132.97, 132.22, 131.03, 130.54, 128.69, 128.21, 128.19, 127.92, 124.84, 115.53, 66.87, 30.17, 10.24; ESI-HRMS calcd for C₂₂H₂₂O₂N₄ClS [M+H]⁺ 441.11465, found 441.11404.

  1-(4-(2-((4-氨基-5-甲基-4H-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-(4-甲氧基苯基)-1, 4-戊二烯-3-酮(F₁₀):黄色固体, 收率: 62%. m.p. 138.3~139.9 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 7.76 (d, J=6.4 Hz, 3H), 7.74 (d, J=6.0 Hz, 2H), 7.71 (d, J=6.0 Hz, 1H), 7.22 (d, J=6.5 Hz, 1H), 7.18 (d, J=6.6 Hz, 1H), 7.06 (d, J=7.8 Hz, 2H), 7.03 (d, J=7.7 Hz, 2H), 5.87 (s, 2H), 4.34 (t, J=6.4 Hz, 2H), 3.82 (s, 3H), 3.51 (t, J=6.4 Hz, 2H), 2.29 (s, 3H); ¹³C NMR (100 MHz, DMSO-d₆) δ: 188.65, 161.66, 160.47, 153.86, 151.13, 142.74, 142.55, 130.84, 130.80, 128.13, 127.83, 124.09, 124.08, 115.44, 114.95, 66.81, 55.84, 30.11, 10.24; ESI-HRMS calcd for C₂₃H₂₅O₃N₄S [M+H]⁺437.16419, found 437.16360.

  1-(4-(2-((4-氨基-5-甲基-4h-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-(4-甲基噻唑-5-基)-1, 4-戊二烯-3-酮(f₁₁):黄色固体, 收率: 42%. m.p. 144.4~145.9 ℃; ¹h nmr (400 mhz, dmso-d₆) δ: 9.12 (s, 1h), 7.89 (d, j=6.5 hz, 1h), 7.76 (d, j=6.0 hz, 2h), 7.72 (d, j=7.9 hz, 1h), 7.26 (d, j=6.1 hz, 1h), 7.06 (d, j=7.8 hz, 2h), 6.91 (d, j=7.9 hz, 1h), 5.87 (s, 2h), 4.34 (t, j=6.4 hz, 2h), 3.50 (t, j=6.4 hz, 2h), 2.57 (s, 3h), 2.30 (s, 3h); ¹³c nmr (100 mhz, dmso-d₆) δ: 187.84, 160.63, 156.81, 155.35, 153.85, 151.11, 143.20, 132.03, 131.07, 129.22, 128.15, 128.02, 123.77, 115.44, 66.85, 30.15, 15.97, 10.24; esi- hrms calcd for c₂₀h₂₂o₂n₅s₂ [m+h]⁺ 428.12094, found 428.12033.

  1-(4-(2-((4-氨基-5-甲基-4H-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-(呋喃-2-基)-1, 4-戊二烯-3-酮(F₁₂):黄色固体, 收率: 50%. m.p. 150.4~151.9 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 7.91 (d, J=6.5 Hz, 1H), 7.76 (d, J=6.0 Hz, 2H), 7.69 (d, J=5.9 Hz, 1H), 7.60 (d, J=6.4 Hz, 1H), 7.23 (d, J=6.2 Hz, 1H), 7.05 (d, J=7.5 Hz, 2H), 7.01 (t, J=7.9 Hz, 1H), 6.97 (d, J=7.0 Hz, 1H), 6.69 (d, J=7.9 Hz, 1H), 5.88 (s, 2H), 4.34 (t, J=6.4 Hz, 2H), 3.51 (t, J=6.4 Hz, 2H), 2.30 (s, 3H); ¹³C NMR (100 MHz, DMSO-d₆) δ: 188.15, 160.55, 153.86, 151.51, 151.13, 146.51, 142.79, 130.97, 129.46, 128.05, 123.92, 123.46, 117.00, 115.42, 113.53, 66.82, 30.14, 10.24; ESI-HRMS calcd for C₂₀H₂₁O₃N₄S[M+H]⁺ 397.13289, found 397.13223.

  1-(4-(2-((4-氨基-5-甲基-4H-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-(3, 4-二甲氧基苯基)-1, 4-戊二烯-3-酮(F₁₃):黄色固体, 收率: 41%. m.p. 101.1~102.3 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 7.75 (d, J=6.1 Hz, 2H), 7.72 (d, J=5.5 Hz, 1H), 7.67 (d, J=5.9 Hz, 1H), 7.41 (s, 1H), 7.33 (d, J=7.0 Hz, 1H), 7.25 (d, J=6.9 Hz, 1H), 7.20 (d, J=6.9 Hz, 1H), 7.06 (d, J=7.8 Hz, 2H), 7.03 (d, J=7.6 Hz, 1H), 5.87 (s, 2H), 4.34 (t, J=6.4 Hz, 2H), 3.85 (s, 3H), 3.82 (s, 3H), 3.51 (t, J=6.3 Hz, 2H), 2.30 (s, 3H); ¹³C NMR (100 MHz, DMSO-d₆) δ: 188.63, 160.47, 153.85, 151.54, 151.12, 149.46, 143.23, 142.42, 130.82, 128.15, 128.04, 124.46, 123.97, 123.68, 115.45, 112.12, 110.98, 66.84, 56.08, 56.06, 30.17, 10.24; ESI-HRMS calcd for C₂₄H₂₇O₄N₄S[M+H]⁺ 467.17475, found 467.17389.

  1-(4-(2-((4-氨基-5-甲基-4H-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-(4-溴苯基)-1, 4-戊二烯-3-酮(F₁₄):黄色固体, 收率: 43%. m.p. 185.0~186.4 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 7.79 (d, J=6.1 Hz, 3H), 7.73 (d, J=5.5 Hz, 3H), 7.67 (d, J=5.8 Hz, 2H), 7.39 (d, J=6.1 Hz, 1H), 7.21 (d, J=6.8 Hz, 1H), 7.07 (d, J=7.7 Hz, 2H), 5.87 (s, 2H), 4.35 (t, J=6.4 Hz, 2H), 3.51 (t, J=6.4 Hz, 2H), 2.31 (s, 3H); ¹³C NMR (100 MHz, DMSO-d₆) δ: 188.74, 160.63, 153.84, 151.09, 143.36, 141.34, 134.61, 132.42, 130.94, 130.85, 128.03, 126.89, 124.18, 124.07, 115.50, 66.87, 30.19, 10.24; ESI-HRMS calcd for C₂₂H₂₂O₂N₄BrS[M+H]⁺ 485.06414, found 485.06293.

  1-(4-(2-((4-氨基-5-甲基-4H-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-(2, 4-二氯苯基)-1, 4-戊二烯-3-酮(F₁₅):黄色固体, 收率: 35%. m.p. 165.1~166.6 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.07 (d, J=7.8 Hz, 1H), 7.88 (d, J=6.1 Hz, 1H), 7.84 (d, J=6.6 Hz, 1H), 7.75 (d, J=6.1 Hz, 2H), 7.73 (s, 1H), 7.55 (d, J=6.4 Hz, 1H), 7.53 (d, J=6.4 Hz, 1H), 7.09 (d, J=7.9 Hz, 1H), 7.06 (d, J=7.8 Hz, 2H), 5.86 (s, 2H), 4.34 (t, J=6.4 Hz, 2H), 3.51 (t, J=6.3 Hz, 2H), 2.30 (s, 3H); ¹³C NMR (100 MHz, DMSO-d₆) δ: 188.39, 160.78, 153.84, 151.08, 144.20, 135.85, 135.81, 135.39, 132.08, 131.04, 130.01, 129.93, 128.68, 128.46, 127.90, 124.84, 115.55, 66.88, 30.19, 10.24; ESI-HRMS calcd for C₂₂H₂₁O₂N₄Cl₂S [M+H]⁺ 475.07568, found 475.07510.

  1-(4-(2-((4-氨基-5-甲基-4H-1, 2, 4-三唑-3-基)硫基)乙氧基)苯基)-5-(4-甲基苯基)-1, 4-戊二烯-3-酮(F₁₆):黄色固体, 收率: 63%. m.p. 169.0~170.8 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 7.77 (d, J=6.0 Hz, 1H), 7.75 (d, J=6.1 Hz, 2H), 7.73 (d, J=5.5 Hz, 1H), 7.69 (d, J=5.9 Hz, 2H), 7.30 (d, J=6.0 Hz, 2H), 7.27 (d, J=6.2 Hz, 1H), 7.22 (d, J=6.0 Hz, 1H), 7.07 (d, J=7.7 Hz, 2H), 5.87 (s, 2H), 4.35 (t, J=6.4 Hz, 2H), 3.51 (t, J=6.4 Hz, 2H), 2.36 (s, 3H), 2.31 (s, 3H); ¹³C NMR (100 MHz, DMSO-d₆) δ: 188.77, 160.54, 153.84, 151.10, 142.88, 142.78, 140.90, 132.55, 130.89, 130.07, 128.98, 128.11, 125.34, 124.11, 115.47, 66.86, 30.19, 21.55, 10.24; ESI-HRMS calcd for C₂₃H₂₅O₂N₄S [M+H]⁺ 421.16927, found 421.16855.

  3.3   目标化合物的抑菌活性测试

  采用浊度法, 以柑橘溃疡病菌、水稻白叶枯病菌和烟草青枯病菌为测试对象, 以叶枯唑为实验对照药剂, 在100和50 μg/mL浓度下, 测试目标化合物的体外抑菌活性^[28].

  将柑橘溃疡病菌、水稻白叶枯病菌和烟草青枯病菌放在营养琼脂培养基(NA, 5.0 g蛋白胨, 1.0 g酵母粉, 3.0 g牛肉膏, 10.0 g葡萄糖, 15.0 g琼脂和1000 mL二次水)固体培养基上培养, 然后置于26~28 ℃的恒温细菌培养箱中培养至长出单菌落.选取适量的黄色单菌落, 将其放到营养肉汤培养基(NB, 5.0 g蛋白胨, 1.0 g酵母粉, 3.0 g牛肉膏, 10.0 g葡萄糖和1000 mL二次水)液体培养基中, 在26~28 ℃、180 r/min恒温摇床中振荡培养到对数生长期备用.

  将化合物和对照药剂配制为100和50μg/mL浓度, 分别取1 mL加入到装有4 mL NB液体培养基的试管中, 再分别量取40 μL含有柑橘溃疡病菌、水稻白叶枯病菌和烟草青枯病菌的NB液体培养基加入试管中, 于26~28 ℃、180 r/min恒温摇床振荡培养24 h.在分光光度计上, 测定595 nm波长处加药无菌NB液体培养基的OD₅₉₅值, 以及测定各个浓度的菌液OD₅₉₅值.

  校正OD₅₉₅值＝含菌培养基OD₅₉₅－无菌培养基OD₅₉₅

  抑制率(%)＝(校正后对照培养基菌液OD₅₉₅－校正含药培养基OD₅₉₅)/校正后对照培养基菌液OD值×100%.

  3.4   扫描电镜成像实验

  量取1.5 mL生长至对数期的柑橘溃疡病菌(X. citri)菌液于2 mL离心管中, 低速离心(6000 r/min)约1 min, 使细菌离心成团, 加入1 mL磷酸盐缓冲溶液(PBS, pH＝7.2)以洗去培养基, 然后再加入1.5 mL PBS缓冲溶液, 用枪头轻轻重悬, 最后加入目标化合物F₆药液使其浓度分别为25和50 μg/mL, 空白对照补加二甲基亚砜(DMSO) 10 μL, 室温孵育8~10 h^[24].

  吸取孵育后菌液1 mL于2 mL离心管中低速离心(6000 r/min)约1 min, 使细菌离心成团, 弃去上清液, 沉淀菌体用1 mL PBS溶液洗涤3次以洗去药剂; 加入1 mL 2.5%戊二醛固定液固定8~10 h或过夜(4 ℃), 弃去固定液, 再用1 mL PBS溶液洗涤3次以洗去戊二醛; 菌体分别用1 mL 30%、50%、70%、90%、100% (3次)乙醇依次进行脱水置换(每次置换约10~15 min), 脱水后样品置于冷冻干燥机冷冻干燥2 h; 干燥菌体粉末经粘样、喷金后进行扫描电镜(Nova Nano SEM 450)测试.

  辅助材料(Supporting Information)中间体和目标化合物的¹ H NMR, ¹³ C NMR, HRMS谱图.这些材料可以免费从本刊网站(http://sioc-journal.cn/)上下载.

  
  
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• 

  图式 1  目标化合物F₁~F₁₆的合成路线

  Scheme 1  Synthetic routes of target compounds F₁~F₁₆

  下载: 全尺寸图片 幻灯片
  

  图 1  在不同浓度化合物F₆孵育后柑橘溃疡病菌的扫描电镜图像

  Figure 1  SEM images for X. citri after incubated in different concentration of compound F₆

  (a) c(F₆)＝0 μg/mL, (b) c(F₆)＝25 μg/mL, (c) c(F₆)＝50 μg/mL

  下载: 全尺寸图片 幻灯片

  表 1  目标化合物F₁~F₁₆的抑菌活性(抑制率/%)^a

  Table 1.  Antibacterial activities (inhibition rate/%) of target compounds F₁~F₁₆

  Compound	R	X. citri			X. oryzae			R. solanacearum
  		100 μg/mL	50 μg/mL		100 μg/mL	50 μg/mL		100 μg/mL	50 μg/mL
  F1	Ph	47.0±1.6	36.5±4.0		89.5±0.9	74.3±0.1		54.5±3.4	49.8±5.3
  F2	Thiophen-2-yl	42.4±2.3	39.0±5.0		34.7±0.6	1.5±0.2		32.8±2.1	28.3±0.1
  F3	3, 4-(CH3)2C6H3	57.4±4.1	41.9±2.7		17.7±0.8	10.6±1.4		75.9±1.5	62.4±0.4
  F4	4-NO2C6H4	72.3±5.3	62.8±2.8		58.0±0.5	41.6±1.2		51.6±0.1	47.9±0.5
  F5	4-ClC6H4	68.0±0.9	52.3±2.5		60.5±1.1	48.8±0.5		48.3±2.4	35.2±1.6
  F6	4-FC6H4	82.5±0.2	78.6±2.9		59.0±4.7	50.6±3.0		76.8±5.4	66.3±3.5
  F7	2, 4-(CH3O)2C6H3	71.3±0.9	63.5±0.4		70.0±0.4	62.9±0.9		53.2±0.6	50.0±3.2
  F8	3-NO2C6H4	66.9±6.4	57.1±1.1		60.1±1.6	51.7±1.8		50.5±3.8	41.7±5.2
  F9	2-ClC6H4	72.6±4.3	64.1±2.2		56.2±4.7	47.6±2.6		41.6±0.9	35.2±0.5
  F10	4-CH3OC6H4	70.9±2.9	64.5±5.4		61.7±0.9	57.4±2.6		48.3±2.5	32.4±3.5
  F11	4-Methylthiazol-5-yl	63.3±5.6	56.5±1.2		46.9±2.8	44.7±0.8		44.9±1.6	36.3±1.3
  F12	Furan-2-yl	55.3±1.3	48.1±2.5		68.6±4.2	56.7±0.2		37.4±0.7	23.2±4.8
  F13	3, 4-(CH3O)2C6H3	38.5±4.0	25.0±1.6		66.2±0.4	60.4±3.9		54.8±1.9	42.1±1.3
  F14	4-BrC6H4	73.6±6.1	65.8±2.7		62.2±0.7	54.9±0.4		50.2±0.1	47.1±7.2
  F15	2, 4-Cl2C6H3	56.7±2.4	45.7±4.9		61.7±0.4	54.9±0.6		55.9±1.1	42.4±0.6
  F16	4-CH3C6H4	77.4±4.0	68.7±1.4		53.0±1.9	44.6±0.6		51.0±1.8	33.9±2.3
  Bismerthiazolb	—	59.5±7.7	49.5±5.7		56.0±1.2	33.8±2.0		61.1±6.2	49.5±5.3
  a Average of three replicates; b The commercial bactericides (bismerthiazol) was used for comparison of antibacterial activity.

  下载: 导出CSV

  表 2  部分目标化合物对柑橘溃疡病菌的EC₅₀值^a

  Table 2.  EC₅₀ values of some compounds against X. citri

  Compound	R	Toxic regression equation	r	EC50/(μg•mL-1)
  F4	4-O2NC6H4	y＝0.7252x+4.1219	0.9871	16.3±2.5
  F5	4-ClC6H4	y＝0.9076x+3.6020	0.9559	34.7±2.3
  F6	4-FC6H4	y＝0.9529x+4.0511	0.9581	9.9±2.1
  F7	2, 4-(CH3O)2C6H3	y＝0.6956x+4.1554	0.9889	16.4±1.0
  F8	3-O2NC6H4	y＝0.9427x+3.5545	0.9965	34.2±2.4
  F9	2-ClC6H4	y＝0.8344x+3.9314	0.9978	19.1±2.7
  F10	4-CH3OC6H4	y＝0.7527x+4.0683	0.9897	17.3±2.8
  F14	4-BrC6H4	y＝0.8865x+3.8683	0.9899	18.9±2.8
  F16	4-CH3C6H4	y＝0.9412x+3.8669	0.9965	15.9±1.9
  Bismerthiazola	—	y＝0.8357x+3.5466	0.9876	54.9±1.4
  a The commercial bactericides (bismerthiazol) was used for comparison of antibacterial activity.

  下载: 导出CSV

  表 3  部分目标化合物对水稻白叶枯病菌的EC₅₀值^a

  Table 3.  EC₅₀ values of some compounds against X. oryzae

  Compound	R	Toxic regression equation	r	EC50/(μg•mL-1)
  F1	Ph	y＝1.0838x+3.9378	0.9488	9.6±1.9
  F5	4-ClC6H4	y＝0.7955x+3.7062	0.9066	42.3±0.5
  F7	2, 4-(CH3O)2C6H3	y＝0.8195x+3.9491	0.9250	19.2±0.8
  F8	3-O2NC6H4	y＝0.8219x+3.6715	0.9099	41.3±1.4
  F10	4-CH3OC6H4	y＝0.8897x+3.6013	0.9524	37.3±1.5
  F12	Furan-2-yl	y＝0.9935x+3.5123	0.9899	31.4±2.2
  F13	3, 4-(CH3O)2C6H3	y＝0.9779x+3.5713	0.9402	28.9±1.4
  F14	4-BrC6H4	y＝0.8431x+3.6698	0.9886	37.8±0.8
  F15	2, 4-Cl2C6H3	y＝0.4375x+4.4190	0.9756	21.3±0.8
  Bismerthiazola	—	y＝2.8364x+0.5935	0.9897	69.3±2.0
  a The commercial bactericides (bismerthiazol) was used for comparison of antibacterial activity.

  下载: 导出CSV

  表 4  部分目标化合物对烟草青枯病菌的EC₅₀值^a

  Table 4.  EC₅₀ values of some compounds against R. solanacearum

  Compound	R	Toxic regression equation	r	EC50/(μg•mL-1)
  F3	3, 4-(CH3)2C6H3	y＝0.7267x+4.1628	0.9547	14.2±3.3
  F6	4-FC6H4	y＝0.8243x+4.0431	0.9917	14.5±4.9
  Bismerthiazola	—	y＝0.9991x+3.2599	0.9399	82.6±0.9
  a The commercial bactericides (bismerthiazol) was used for comparison of antibacterial activity.

  下载: 导出CSV
•