(Z)-/(E)-马鞭草烯酮肟醚的合成及抑菌活性

doi:10.3969/j.issn.0253-2417.2019.04.004

Abstract

Abstract:

Verbenone was prepared by selective oxidation of α-pinene at first. Then, by oximation of the carbonyl group (Z)-and(E)-verbenone oxime compounds were synthesized and separaed, followed by the nucleophilic substitution reaction to afford forty novel (Z)-and (E)-verbenone oxime ether compounds 4a-4t, including twenty couples of Z/E isomers. The structures of the target compounds were characterized by ¹H NMR, ¹³C NMR, FT-IR, UV-vis, and ESI-MS. The antifungal activities of the target compounds were evaluated. The results showed that, at the mass concentration of 50 mg/L, all the target products exhibited certain inhibition activities against the eight kinds of plant pathogens. Compound(E)-4r(R=2, 6-Cl) had inhibition rates of 77.8% against Physalospora piricola. Compound(E)-4s(R=2, 6-F) had inhibition rates of 72.7% against Rhizoctonia solani. Compound (E)-4n(R=p-CN) had inhibition rates of 70.8% against Helmithosporium maydis. Certain difference were found in inhibition activity of Z-E isomers against some plant pathogens. The CoMFA model(r²=0.992, q²=0.507) of (E)-verbenone oxime ether compounds for inhibiting Rhizoctonia solani was established for the study of 3D-QSAR, and the results could provide a basis for the design of potential lead compounds with higher activity.

Key words: α-pinene, verbenone, oxime ether, Z-E isomer, antifungal activity, 3D-QSAR

CLC Number:

TQ351

Xiaoyu WANG,Wengui DUAN,Guishan LIN,Guoqiang KANG,Minghao SHANG,Fuhou LEI. Synthesis and Antifungal Activity of (Z)-/(E)-Verbenone Oxime Ether Compounds[J]. Chemistry and Industry of Forest Products, 2019, 39(4): 27-34.

Figures/Tables 6

Table 1

Fig.1

Fig.2

Table 2

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Fig.4

References 23

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%
化合物 compounds	黄瓜枯萎病菌 Fusarium oxysporum	花生褐斑病菌 Cercospora arachidicola	苹果轮纹病菌 Physalos-pora piricola	番茄早疫病菌 Alternaria solani	小麦赤霉病菌 Gibberella zeae	水稻纹枯病菌 Rhizoctonia solani	玉米小斑病菌 Helmithos- porium maydis	西瓜炭疽病菌 Colletot-richum lagenarium
(Z)-4f	22.7	35.7	11.1	36.4	37.5	59.1	30.4	34.6
(E)-4f	18.2	14.3	61.1	36.4	25.0	57.6	26.1	19.2
(Z)-4n	23.8	35.7	66.7	63.2	45.0	57.5	29.2	29.4
(E)-4n	28.6	50.0	33.3	63.2	40.0	61.3	70.8	41.2
(Z)-4r	9.5	42.9	44.4	36.8	25.0	45.0	29.2	11.8
(E)-4r	18.2	28.6	77.8	9.1	41.7	68.2	39.1	42.3
(Z)-4s	19.0	50.0	50.0	52.6	45.0	55.0	41.7	35.3
(E)-4s	31.3	42.9	40.0	40.0	46.2	72.7	44.4	11.1
百菌清chlorothalonil	100.0	73.3	75.0	73.9	73.1	96.1	90.4	91.3

化合物compounds	CoMFA值CoMFA value	E_D	E_D′	残差residue
(E)-4a(R=H)	120	-2.77	-2.72	-0.05
(E)-4b(R= o-CH₃)	130	-2.38	-2.39	0.01
(E)-4c(R= m-CH₃)	128	-2.96	-2.96	0.00
(E)-4d(R=p-CH₃)	132	-2.19	-2.20	0.01
(E)-4e(R=o-OCH₃)	132	-2.53	-2.52	-0.01
(E)-4f(R=m-OCH₃)	132	-2.32	-2.32	0.00
(E)-4g(R=o-Cl)	128	-2.54	-2.50	-0.04
(E)-4h(R=m-Cl)	122	-2.44	-2.46	0.02
(E)-4i(R=p-Cl)	126	-2.49	-2.51	0.02
(E)-4j(R=o-NO₂)	132	-3.25	-3.27	0.02
(E)-4k(R=m-NO₂)	126	-2.43	-2.43	0.00
(E)-4l(R=p-NO₂)	132	-2.41	-2.42	0.01
(E)-4m(R=m-F)	120	-2.25	-2.31	0.06
(E)-4n(R=p-CN)	126	-2.25	-2.25	0.00
(E)-4o(R=p-SCH₃)	140	-2.35	-2.35	0.00
(E)-4p(R=p-vinyl)	132	-2.32	-2.32	0.00
(E)-4q(R=2, 6-CH₃)	138	-2.53	-2.55	0.02
(E)-4r(R=2, 6-Cl)	132	-2.18	-2.17	-0.01
(E)-4s(R=2, 6-F)	122	-2.04	-2.04	0.00
(E)-4t(R=3-Cl-4-F)	124	-2.40	-2.36	-0.04

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Synthesis and Antifungal Activity of (Z)-/(E)-Verbenone Oxime Ether Compounds

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