刚性氢化诺卜基双子季铵盐的合成与抗菌作用

doi:10.3969/j.issn.0253-2417.2020.06.010

摘要/Abstract

摘要：

由含氢化诺卜基的叔胺化合物与1，4-二溴(氯)化苄反应合成了6种新型含刚性碳氢链联结基的氢化诺卜基双子季铵盐，分别为二苄基-1，4-双(氢化诺卜基二甲基溴化铵)(3a)、二苄基-1，4-双(氢化诺卜基二乙基溴化铵)(3b)、二苄基-1，4-双(氢化诺卜基二正丙基溴化铵)(3c)、二苄基-1，4-双(氢化诺卜基二甲基氯化铵)(3d)、二苄基-1，4-双(氢化诺卜基二乙基氯化铵)(3e)和二苄基-1，4-双(氢化诺卜基二正丙基氯化铵)(3f)，通过红外光谱、质谱和核磁共振确证了合成的化合物为目标产物。采用菌丝生长速率法测定了新化合物对8种植物病原真菌的抑菌活性，结果表明：6种含刚性碳氢链联结基的氢化诺卜基双子季铵盐对所试的8种植物病原真菌的生长有很好的抑制作用，其中对七叶树壳梭孢菌抑菌的半数有效质量浓度(EC₅₀)值都低于10 mg/L，并且对彩绒革盖菌和西瓜枯萎病菌的EC₅₀值都低于百菌清对其的EC₅₀值；化合物3a、3b和3c对水稻纹枯病菌、油茶炭疽病菌、松枯梢病菌和七叶树壳梭孢菌的抑制效果随着连接基团的相对分子质量的增加而增强。化合物3f对油茶炭疽病菌有良好的抑菌活性，EC₅₀值为3.447 8 mg/L。

关键词: 氢化诺卜基, 双子季铵盐, 合成, 抑菌活性, 毒力回归方程

Abstract:

Six novel hydronopyl gemini quaternary ammonium salts containing rigid alkyl chain groups, namely dibenzyl-1, 4-bis(hydronopyl dimethyl ammonium bromide)(3a), dibenzyl-1, 4-bis(hydronopyl diethyl ammonium bromide)(3b), dibenzyl-1, 4-bis(hydronopyl di-n-propyl ammonium bromide)(3c), dibenzyl-1, 4-bis(hydronopyl dimethyl ammonium chloride)(3d), dibenzyl-1, 4-bis(hydronopyl diethyl ammonium chloride)(3e), and dibenzyl-1, 4-bis(hydronopyl di-n-propyl ammonium chloride)(3f) were synthesized from hydronopyl tertiary amine compounds and 1, 4-dibenzyl bromide(chloride), respectively. Their structures were confirmed by FT-IR, MS and NMR. The antifungal activities of the novel compounds against eight plant pathogens were evaluated by mycelium growth rate method. The results showed that six hydronopyl gemini quaternary ammonium salts containing rigid alkyl chain groups had obvious antifungal activities against 8 plant pathogenic fungi. Among them, the EC₅₀ values of all the compounds against Fusicoccum aesculi were lower than 10 mg/L, and the EC₅₀ values against Coriolus versicolor and Fusarium oxysporum were lower than that of chlorothalonil. The antifungal activities of compounds 3a, 3b and 3c against Rhizocyonia solani, Colletotrichum gloeosporioides, Sphaeropsis sapinea and Fusicoccum aesculi showed a rise as the molecular weight of linkers.Compound 3f had good antifungal activity against Colletotrichum gloeosporioides, and the EC₅₀ value was 3.447 8 mg/L.

Key words: hydronopyl, quaternary ammonium salt, synthesis, antifungal activity, toxic regression equation

中图分类号:

TQ351
O621

冯雪贞, 肖转泉, 范国荣, 秦金梦, 王宗德. 刚性氢化诺卜基双子季铵盐的合成与抗菌作用[J]. 林产化学与工业, 2020, 40(6): 77-84.

Xuezhen FENG, Zhuanquan XIAO, Guorong FAN, Jinmeng QIN, Zongde WANG. Synthesis and Antifungal Activity of Rigid Hydronopyl Gemini Quaternary Ammonium Salts[J]. Chemistry and Industry of Forest Products, 2020, 40(6): 77-84.

图/表 3

图1

表1

双子季铵盐对8种植物病原真菌的抑菌活性1)"

化合物 compounds	质量浓度/(mg·L^-1) mass concn.	抑菌率antifungal activity/%
化合物 compounds	质量浓度/(mg·L^-1) mass concn.	A	B	C	D	E	F	G	H
3a	200	96.30	75.12	76.83	100.00	100.00	81.38	100.00	97.59
	100	74.34	66.43	62.76	100.00	98.68	65.62	100.00	95.44
	50	65.08	53.38	50.44	100.00	97.11	56.45	100.00	84.99
	25	56.61	33.57	41.64	65.48	90.89	40.69	100.00	61.39
	12.5	39.68	20.77	27.27	54.76	80.77	24.93	97.96	35.39
	6.25	—	—	—	—	—	—	85.24	—
	3.13	—	—	—	—	—	—	80.31	—
	1.56	—	—	—	—	—	—	—	—
3b	200	91.08	74.80	68.68	100.00	100.00	76.00	100.00	98.36
	100	79.18	67.19	64.21	100.00	98.40	64.00	100.00	94.39
	50	67.28	53.54	52.63	100.00	96.28	54.13	100.00	86.92
	25	54.69	41.47	38.42	100.00	93.48	38.13	100.00	82.24
	12.5	38.67	24.41	28.42	100.00	82.71	17.87	91.98	68.69
	6.25	—	—	—	66.19	—	—	50.13	—
	3.13	—	—	—	37.65	—	—	30.03	—
	1.56	—	—	—	21.58	—	—	—	—
3c	200	96.82	72.19	70.39	100.00	98.79	71.34	100.00	90.11
	100	90.19	66.57	60.61	99.53	98.79	70.73	100.00	81.59
	50	84.35	65.17	45.25	98.25	97.34	65.24	100.00	65.93
	25	68.70	47.19	32.40	93.57	94.93	61.59	98.04	67.31
	12.5	38.00	36.52	15.64	53.22	87.68	54.27	87.11	50.55
	6.25	—	—	—	—	—	—	82.07	—
	3.13	—	—	—	—	—	—	80.67	—
	1.56	—	—	—	—	—	—	—	—
3d	200	93.85	66.67	56.36	100.00	100.00	69.55	100.00	95.39
	100	83.59	65.21	42.60	100.00	96.49	39.10	100.00	91.26
	50	74.36	34.31	23.64	82.31	92.97	27.76	100.00	78.16
	25	53.85	16.30	20.52	68.8	81.97	23.88	89.98	66.75
	12.5	26.92	8.52	12.21	58.97	33.26	16.42	41.56	49.03
	6.25	—	—	—	—	—	—	—	—
	3.13	—	—	—	—	—	—	—	—
	1.56	—	—	—	—	—	—	—	—
3e	200	89.18	86.36	51.98	100.00	100.00	93.08	100.00	96.77
	100	75.26	61.54	39.55	100.00	95.86	79.83	100.00	89.85
	50	58.51	40.09	23.16	100.00	90.75	72.91	92.96	77.42
	25	30.15	21.21	16.38	57.38	76.64	44.38	66.58	37.97
	12.5	4.64	7.46	15.82	38.81	57.18	27.09	22.86	32.75
	6.25	—	—	—	—	—	—	—	—
	3.13	—	—	—	—	—	—	—	—
	1.56	—	—	—	—	—	—	—	—
3f	200	92.92	91.09	60	100	96.59	58.24	100	93.96
	100	88.99	80.62	41.18	100.00	94.23	41.18	96.82	89.37
	50	66.96	78.84	27.65	60.61	90.03	27.65	89.55	78.26
	25	63.03	73.72	22.35	45.95	76.38	22.35	33.86	34.54
	12.5	29.47	55.46	15.88	40.26	52.49	15.88	7.95	27.54
	6.25	—	—	—	—	—	—	—	—
	3.13	—	—	—	—	—	—	—	—
	1.56	—	—	—	—	—	—	—	—
百菌清 chlorothalonil	200	91.40	59.83	71.14	73.20	61.86	56.85	87.89	45.07
	100	80.23	57.89	69.30	65.75	61.58	49.75	84.47	41.49
	50	76.51	56.23	50.89	60.22	57.63	44.92	76.58	38.21
	25	75.93	54.02	23.93	58.29	57.06	24.37	74.47	36.72
	12.5	64.88	45.15	18.71	57.46	55.93	15.74	58.16	33.73
	6.25	—	—	—	—	—	—	—	—
	3.13	—	—	—	—	—	—	—	—
	1.56	—	—	—	—	—	—	—	—

表1

表2

双子季铵盐对8种植物病原真菌的毒力回归方程及EC50"

化合物 compounds	菌种 strain	毒力回归方程 y=a+bx	相关系数 correlation cofficient(R²)	EC₅₀/(mg·L^-1)
3a	A	y=2.9595+1.5227x	0.9412	21.8798
	B	y=2.826+1.2736x	0.9932	50.9367
	C	y=3.2377+1.0672x	0.9957	44.8089
	D	y=-0.0024+4.7711x	0.8739	11.1809
	E	y=2.1016+3.0387x	0.8956	8.9918
	F	y=2.9783+1.254x	0.9955	40.9418
	G	y=3.3259+4.0687x	0.9362	2.5790
	H	y=-3.271+4.6076x	0.9905	17.5174
3b	A	y=3.2517+1.3157x	0.9962	21.3235
	B	y=3.1492+1.1239x	0.9924	44.3332
	C	y=3.4454+0.9212x	0.9895	48.7176
	D	y=2.3985+5.6099x	0.9222	2.9090
	E	y=2.3405+2.9055x	0.8729	8.2292
	F	y=2.7798+1.3004x	0.9859	50.9710
	G	y=2.2441+4.6725x	0.9127	3.8888
	H	y=-4.0172+1.3151x	0.9894	5.5892
3c	A	y=3.000+1.6901x	0.9881	15.2525
	B	y=3.8637+0.7856x	0.9584	27.9617
	C	y=2.6904+1.2676x	0.9922	66.3911
	D	y=1.1004+3.6262x	0.9596	11.8959
	E	y=5.2643+0.9319x	0.9592	0.5204
	F	y=4.7241+0.3863x	0.9732	5.1762
	G	y=5.4964+1.0537x	0.9584	0.3380
	H	y=3.9192+0.9964x	0.9657	12.1522
3d	A	y=3.1182+1.7261x	0.9927	12.3085
	B	y=2.3018+1.6532x	0.9766	42.8616
	C	y=2.9276+1.0916x	0.9833	32.0185
	D	y=0.8013+4.6694x	0.9067	7.9285
	E	y=1.2911+3.9072x	0.9268	8.8971
	F	y=3.0074+1.1332x	0.9420	57.3422
	G	y=1.6443+4.6992x	0.8937	5.1773
	H	y=3.8298+1.4418x	0.9968	6.4801
3e	A	y=1.7188+2.3375x	0.9820	25.3326
	B	y=1.914+2.0498x	0.9974	32.0264
	C	y=3.1059+0.9358x	0.9627	105.7067
	D	y=0.837+5.1099x	0.8779	6.5267
	E	y=1.8499+3.5364x	0.8921	7.7759
	F	y=3.0387+1.7143x	0.9911	13.9341
	G	y=-0.2258+5.3345x	0.9596	9.5416
	H	y=2.7633+2.0443x	0.9818	6.5267
3f	A	y=3.3042+1.6319x	0.9740	10.9431
	B	y=4.5273+0.8794x	0.9605	3.4478
	C	y=3.1223+1.0109x	0.9801	72.0246
	D	y=-0.2579+5.1805x	0.8936	10.3499
	E	y=4.0593+1.4544x	0.9780	4.4341
	F	y=3.1554+0.9808x	0.9838	76.0021
	G	y=-0.7494+5.0122x	0.9685	14.0310
	H	y=2.7584+1.9733x	0.9702	13.6769
百菌清 chlorothalonil	A	y=4.6122+0.7020x	0.9330	3.5676
	B	y=4.6428+0.2790x	0.9215	19.0705
	C	y=2.5805+1.3637x	0.9663	59.4580
	D	y=4.7391+0.3514x	0.9324	5.5245
	E	y=4.9851+0.1401x	0.9495	1.2772
	F	y=3.0509+0.9517x	0.9688	106.5451
	G	y=4.4659+0.7584x	0.9730	5.0601
	H	y=4.3162+0.2379x	0.9926	748.3247

表2

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