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樟脑酸基酰腙类化合物的合成及其抑菌、除草活性研究

Synthesis, Antibacterial and Herbicidal Evaluation of Camphoric Acid-based Acylhydrazone Compounds

  • 摘要: 以樟脑酸为原料,先经过脱水反应制备樟脑酸酐,再与水合肼酰化制备N-氨基樟脑酰亚胺,然后分别与多氟取代苯甲醛、噻吩甲醛和呋喃甲醛缩合得到12个新型的樟脑酸基酰腙化合物4a~4l。利用傅里叶变换-红外光谱(FT-IR)、核磁共振(1H NMR和13C NMR)以及电喷雾-质谱(ESI-MS)等对化合物进行结构表征。抑菌活性测试表明:质量浓度50 mg/L时,5-二氟苯基樟脑酸基酰腙(4i)、2-三氟甲基苯基樟脑酸基酰腙(4a)和2, 3-二氟苯基樟脑酸基酰腙(4d)对苹果轮纹病菌的抑制率分别为90.6%、85.4%和82.2%。除草活性测试表明:质量浓度100 mg/L时,3-三氟甲基苯基樟脑酸基酰腙(4b)、3, 4-二氟苯基樟脑酸基酰腙(4h)和3-噻吩基樟脑酸基酰腙(4k)对油菜胚根的生长抑制率分别为94.7%、95.6%和80.6%。其中化合物4i综合效果最好,50 mg/L时对苹果轮纹病菌的抑制率90.6%(活性级别为A级), 100 mg/L时对油菜胚根的生长抑制率75.6%(活性级别为B级)。

     

    Abstract: Camphoric anhydride (2) was prepared via dehydration reaction using camphoric acid (1) as starting material. N-aminocamphorimide (3) was prepared by the acylation of compound 2 with hydrazine hydrate. And then, 12 novel camphoric acid-based acylhydrazone compounds 4a-4l were synthesized by the condensation reaction between N-aminocamphorimide and polyfluoro-substituted benzaldehyde, thiophene-carbaldehyde or furaldehyde. The target compounds were characterized by means of Fourier transform infrared spectroscopy(FT-IR), nuclear magnetic resonance(1H NMR and 13C NMR) and electrospray ionization-mass spectrometry(ESI-MS). The preliminary bioassay showed that 3, 5-difluorophenyl camphoric acid-based acylhydrazone (4i), 2-trifluoromethylphenyl camphoric acid-based acylhydrazone (4a) and 2, 3-difluorophenyl camphoric acid-based acylhydrazone (4d) exhibited excellent antifungal activities with the inhibition ratios of 90.6%, 85.4% and 82.2% against Botryosphaeria berengeriana at the mass concentration of 50 mg/L. Herbicidal evaluation results showed that most of the compounds had certain inhibitory effects on the growth of rape radicle at 100 mg/L. Among them, the growth inhibition rates of compounds 3-trifluoromethylphenyl camphoric acid-based acylhydrazone (4b), 3, 4-difluorophenyl camphoric acid-based acylhydrazone (4h) and 3-thienyl camphoric acid-based acylhydrazone (4k) on the radicle of rape(Brassica campestris) were 94.7%, 95.6% and 80.6%, respectively. Compound 4i has the best overall effect, the inhibition ratio of 90.6% against B.dothidea at 50 mg/L (the activity level was A grade); the root growth inhibition rate of on root of rape (B. campestris) was 75.6% at 100 mg/L (the activity level was B grade).

     

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