四氢芳樟基酰胺类化合物的合成及除草活性研究

doi:10.3969/j.issn.0253-2417.2023.03.011

Abstract

Abstract:

Seventeen tetrahydrolinalyl amides(2, 4a-4p) were designed and synthesized using tetrahydrolinalool as starting material. Their structures were characterized by FT-IR, ¹H NMR, ¹³C NMR and HRMS, then the herbicidal activities against Lolium perenne and Echinochloa crusgalli were evaluated. The results showed that the tetrahydrolinalyl amides exhibited certain growth inhibitory effects on L. perenne and E. crusgalli. Compounds 2, 4a, 4o showed the best pre-emergence herbicidal activity against L. perenne, where the inhibitory concentration 50%(IC₅₀) values for the root growth of L. perenne were 0.05, 0.05, and 0.04 mmol/L, respectively(weaker than that of the positive control glyphosate), and the IC₅₀ values for the shoot of L. perenne were 0.06, 0.05, and 0.05 mmol/L, respectively(stronger than that of glyphosate). The IC₅₀ values of compound 4b on root and shoot growth of E. crusgalli were 0.06 and 0.15 mmol/L(equal to that of glyphosate), respectively. The structure-activity relationship analysis showed that tetrahydrolinayl amides exhibited selectivity among different weed species. The compounds containing alkyl group showed higher herbicidal activity than that of benzene ring and furan ring. The herbicidal activity of compounds with electron-donating group on benzene ring was stronger than that with electron-withdrawing group, exhibiting better activity when it was located at the ortho- and meta-position of benzene ring.

Key words: tetrahydrolinalool, tetrahydrolinalyl amine, amides, herbicidal activity

CLC Number:

TQ35

Hongmei ZHANG, Jing WANG, Yuxiang CHEN, Shichao XU, Jianxin JIANG, Zhendong ZHAO. Synthesis and Herbicidal Activity of Tetrahydrolinalyl Amides[J]. Chemistry and Industry of Forest Products, 2023, 43(3): 89-100.

Figures/Tables 5

Fig.1

Table 1

The growth inhibition rate of tetrahydrolinalyl amides against growth of Lolium perenne"

化合物compound	不同浓度(mmol?L^-1)下的根长抑制率/% root growth inhibition rate at different concentration							不同浓度(mmol?L^-1)下的茎长抑制率/% shoot growth inhibition rate at different concentration
化合物compound	2.5	1.25	0.625	0.313	0.156	0.078	0.039	2.5	1.25	0.625	0.313	0.156	0.078	0.039
1	80.4	55.5	47.3	35.8	31.1	26.4	19.0	82.6	62.9	50.9	37.7	30.2	20.8	17.6
2	100.0	100.0	94.7	89.4	65.7	54.6	49.4	100.0	100.0	97.1	92.3	70.0	55.4	46.5
3	100.0	100.0	99.5	71.0	55.9	37.8	30.8	100.0	100.0	87.2	58.4	47.8	36.4	28.7
4a	97.9	96.3	91.2	82.0	72.4	58.1	43.4	100.0	96.7	93.6	86.5	76.2	58.7	47.5
4b	94.1	90.1	84.7	75.5	76.3	63.7	47.0	94.7	90.0	89.1	75.2	68.5	55.9	34.0
4c	92.3	81.3	70.6	58.3	46.5	38.9	32.2	93.9	79.1	72.9	61.3	48.5	42.3	31.0
4d	82.3	69.0	62.2	55.1	50.1	38.2	29.4	84.6	73.0	66.2	56.8	53.5	41.2	29.8
4e	100.0	98.1	89.5	62.5	46.6	31.8	25.2	100.0	98.5	89.2	67.2	52.0	49.0	42.2
4f	89.0	67.5	50.1	48.9	42.4	35.4	36.1	90.5	65.1	51.9	52.7	47.8	42.4	38.5
4g	98.9	98.5	84.7	69.3	62.1	48.2	44.4	98.8	98.0	88.0	72.0	65.9	52.5	47.5
4h	66.6	55.5	53.8	45.8	36.9	32.5	21.6	69.4	51.8	50.7	41.6	32.6	27.4	20.8
4i	75.1	65.6	58.2	40.5	35.9	30.2	27.6	76.9	67.2	57.2	39.9	37.7	24.9	19.5
4j	69.7	65.8	59.4	56.4	48.9	43.1	26.2	73.1	66.3	61.8	56.1	47.1	40.2	18.7
4k	48.6	38.3	35.5	28.9	21.8	15.2	6.7	55.8	43.0	42.3	39.4	30.3	21.5	8.5
4l	84.5	74.7	55.6	49.9	39.2	25.2	15.3	90.3	79.8	60.5	53.7	45.3	31.1	22.0
4m	69.6	60.2	43.2	34.3	32.6	22.9	19.3	71.8	61.4	50.8	38.5	33.1	25.2	19.8
4n	83.7	69.2	55.4	44.9	32.2	25.9	19.1	94.0	83.7	77.3	67.1	54.4	43.5	33.3
4o	94.4	85.1	79.5	73.8	68.2	63.9	56.8	95.0	84.2	76.0	68.6	62.3	58.1	52.2
4p	67.9	53.6	45.5	43.5	35.6	26.9	20.8	65.6	61.8	53.6	50.6	49.9	43.0	34.3
草甘膦glyphosate	100.0	100.0	95.7	87.8	76.1	68.6	57.8	100.0	99.5	93.6	82.3	55.0	40.2	37.8

Table 1

Table 2

Table 3

Table 4

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化合物compound	不同浓度(mmol?L^-1)下的根长抑制率/% root growth inhibition rate at different concentration						不同浓度(mmol?L^-1)下的茎长抑制率/% shoot growth inhibition rate at different concentration
化合物compound	2.5	1.25	0.625	0.313	0.156	0.078	2.5	1.25	0.625	0.313	0.156	0.078
1	29.4	26.9	23.8	23.8	17.9	9.8	11.6	9.8	9.3	5.2	2.2	0
2	100.0	90.0	76.5	49.2	31.6	21.5	87.0	56.8	36.4	25.9	22.6	20.8
3	100.0	99.4	91.0	57.4	27.2	19.4	100.0	94.8	77.5	38.2	16.3	13.5
4a	77.8	74.0	68.6	56.1	48.3	33.8	59.5	58.0	51.3	44.3	33.6	23.6
4b	84.0	78.2	74.7	65.0	62.4	51.6	72.5	69.0	63.8	57.2	50.1	43.9
4c	52.8	43.9	35.2	33.3	28.8	22.0	41.0	29.2	26.0	15.3	16.4	10.4
4d	56.3	46.3	39.8	32.9	30.4	27.6	48.3	37.1	34.4	28.0	22.4	20.5
4e	58.7	51.3	45.7	31.8	27.4	22.9	48.2	41.5	38.2	23.5	14.0	11.1
4f	49.2	28.7	27.0	23.7	17.1	13.4	31.0	17.4	11.8	11.2	13.1	8.4
4g	37.6	31.1	28.8	24.6	19.6	13.2	34.5	29.5	26.8	18.9	12.6	6.7
4h	35.3	28.5	26.3	24.3	19.1	9.2	25.4	23.5	17.4	17.3	13.3	5.9
4i	46.3	40.5	39.8	30.8	24.2	19.2	42.1	35.5	33.2	29.2	22.9	18.9
4j	65.9	58.2	55.0	48.5	45.1	39.4	58.0	48.6	45.4	38.8	33.9	29.6
4k	46.6	36.7	25.8	21.0	17.3	11.1	38.3	29.9	26.8	24.9	15.3	10.7
4l	47.8	46.6	39.3	32.1	29.9	27.3	39.4	32.2	30.0	27.8	22.2	19.9
4m	28.5	24.2	17.0	12.0	12.5	6.7	25.7	19.0	9.9	9.0	5.3	6.9
4n	57.4	53.2	48.2	42.0	39.7	26.5	42.5	40.7	34.2	26.5	27.1	18.4
4o	77.6	75.7	66.3	59.4	57.7	53.5	51.9	54.0	48.7	41.6	36.8	29.5
4p	42.0	35.3	32.6	25.8	26.8	24.0	36.2	25.2	20.0	18.6	21.4	17.5
草甘膦glyphosate	100.0	99.8	92.3	83.9	79.6	69.5	97.5	91.9	77.2	64.0	54.1	38.5

化合物compound	根root			茎shoot
化合物compound	毒力回归方程toxicity regression equations	R	IC₅₀/(mmol?L^-1)	毒力回归方程toxicity regression equations	R	IC₅₀/(mmol?L^-1)
1	y=5.223 8+0.850 1x	0.956 4	0.55	y=5.321 8+1.000 6x	0.979 4	0.48
2	y=6.851 0+1.460 1x	0.964 4	0.05	y=7.186 5+1.746 3x	0.977 0	0.06
3	y=7.372 8+2.331 6x	0.899 0	0.10	y=6.136 0+1.314 2x	0.946 8	0.14
4a	y=6.590 8+1.248 3x	0.998 6	0.05	y=6.747 8+1.310 0x	0.998 0	0.05
4b	y=6.243 7+0.856 4x	0.983 1	0.04	y=6.263 9+1.080 0x	0.985 3	0.07
4c	y=5.836 6+1.024 4x	0.984 4	0.15	y=5.887 1+1.042 0x	0.978 8	0.14
4d	y=5.524 0+0.748 2x	0.988 9	0.20	y=5.620 9+0.788 9x	0.990 1	0.16
4e	y=6.604 4+1.831 8x	0.967 9	0.13	y=6.610 2+1.520 2x	0.931 7	0.09
4f	y=5.500 2+0.782 6x	0.895 7	0.23	y=5.546 0+0.720 3x	0.862 8	0.17
4g	y=6.618 5+1.475 8x	0.956 6	0.08	y=6.627 1+1.388 9x	0.969 0	0.07
4h	y=5.169 8+0.623 8x	0.988 4	0.53	y=5.127 6+0.678 9x	0.984 7	0.65
4i	y=5.311 9+0.738 6x	0.977 8	0.38	y=5.344 8+0.892 9x	0.992 2	0.41
4j	y=5.361 9+0.579 7x	0.963 8	0.24	y=5.413 1+0.738 6x	0.955 5	0.28
4k	y=4.722 7+0.742 4x	0.976 2	2.36	y=4.912 7+0.723 9x	0.942 1	1.32
4l	y=5.530 2+1.091 3x	0.993 8	0.33	y=5.713 0+1.097 7x	0.986 7	0.22
4m	y=5.118 5+0.761 7x	0.980 3	0.70	y=5.204 3+0.789 0x	0.994 6	0.55
4n	y=5.437 0+1.004 1x	0.989 5	0.37	y=5.995 9+1.056 4x	0.993 2	0.11
4o	y=6.085 4+0.708 8x	0.964 5	0.03	y=6.035 2+0.801 8x	0.950 0	0.05
4p	y=5.112 7+0.652 9x	0.986 7	0.67	y=5.239 6+0.410 9x	0.978 8	0.26
草甘膦glyphosate	y=6.851 0+1.236 0x	0.983 7	0.03	y=7.043 8+1.949 9x	0.965 3	0.09

化合物compound	根root			茎shoot
化合物compound	毒力回归方程toxicity regression equations	R	IC₅₀/(mmol?L^-1)	毒力回归方程toxicity regression quations	R	IC₅₀/(mmol?L^-1)
1	y=4.357 9+0.442 9x	0.913 1	28.17	y=3.643 5+0.654 6x	0.932 2	118.13
2	y=6.039 7+1.775 8x	0.989 6	0.26	y=5.219 4+1.211 8x	0.912 2	0.66
3	y=6.973 5+2.889 5x	0.976 4	0.21	y=6.206 6+2.390 2x	0.971 5	0.31
4a	y=5.544 0+0.788 3x	0.985 3	0.20	y=5.095 4+0.650 2x	0.973 7	0.71
4b	y=5.746 8+0.611 3x	0.991 6	0.06	y=5.428 2+0.513 3x	0.996 6	0.15
4c	y=4.813 4+0.520 2x	0.985 2	2.28	y=4.450 0+0.648 2x	0.971 5	7.05
4d	y=4.884 9+0.494 6x	0.976 3	1.71	y=4.691 1+0.510 3x	0.984 3	4.03
4e	y=4.959 5+0.671 5x	0.989 1	1.15	y=4.702 2+0.844 7x	0.980 1	2.25
4f	y=4.564 2+0.636 4x	0.951 8	4.84	y=4.112 2+0.474 0x	0.863 2	74.63
4g	y=4.504 4+0.495 6x	0.982 4	10.00	y=4.408 1+0.719 5x	0.975 6	6.65
4h	y=4.446 6+0.544 6x	0.934 6	10.38	y=4.201 0+0.539 1x	0.934 6	30.34
4i	y=4.741 5+0.522 9x	0.981 8	3.12	y=4.626 5+0.439 9x	0.991 2	7.06
4j	y=5.205 2+0.431 6x	0.993 7	0.33	y=4.970 8+0.474 4x	0.992 8	1.15
4k	y=4.583 2+0.725 5x	0.992 3	3.75	y=4.479 9+0.595 4x	0.974 3	7.48
4l	y=4.808 8+0.404 5x	0.979 0	2.97	y=4.554 0+0.366 0x	0.986 0	16.55
4m	y=4.201 9+0.590 8x	0.976 8	22.44	y=4.006 5+0.609 6x	0.928 2	42.65
4n	y=5.032 0+0.498 7x	0.968 2	0.86	y=4.670 0+0.465 1x	0.971 0	5.12
4o	y=5.569 1+0.478 8x	0.974 0	0.06	y=4.986 8+0.420 0x	0.958 0	1.07
4p	y=4.613 2+0.335 7x	0.961 4	14.20	y=4.365 0+0.316 2x	0.832 5	101.89
草甘膦glyphosate	y=7.221 4+1.772 0x	0.908 7	0.06	y=6.235 0+1.474 5x	0.987 7	0.15

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Synthesis and Herbicidal Activity of Tetrahydrolinalyl Amides

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