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

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(1HNMR和13CNMR)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50mg/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100mg/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,50mg/L时对苹果轮纹病菌的抑制率90.6%(活性级别为A级),100mg/L时对油菜胚根的生长抑制率75.6%(活性级别为B级)。

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( 1 H NMR and 13 C 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% and82. 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 radicleat 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).