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

Abstract

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

CLC Number:

TQ351
O621

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.

Figures/Tables 3

Fig.1

Table 1

Antifungal activity of gemini quaternary ammonium salts against 8 plant pathogenic fungi"

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	—	—	—	—	—	—	—	—

Table 1

Table 2

Toxic regression equation and EC50 of gemini quaternary ammonium salts against 8 plant pathogenic fungi"

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

Table 2

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Synthesis and Antifungal Activity of Rigid Hydronopyl Gemini Quaternary Ammonium Salts

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