Synthesis and Fungicidal Activity of Novel 3,7-Dimethylocta-2,6-dienamides and 3,7-Dimethyl-6,7-dihydroxyoct-2-enamides

doi:10.6023/cjoc202105009

Abstract

A series of novel (Z)- and (E)-3,7-dimethylocta-2,6-dienamides and optical (6R or 6S)-3,7-dimethyl-6,7-dihydroxyoct-2-enamides were designed and synthesized using (Z)- and (E)-geraniols as raw materials, respectively. Their structures were characterized by IR, ¹H NMR, ¹³C NMR and HR-ESI-MS spectra. The preliminary bioassay results indicated that some compounds exhibit certain in vitro fungicidal activities against Rhizoctonia solani and Sclerotinia sclerotiorum at the concentration of 50 µg/mL. For example, (Z)-N-(2-(4-chlorophenyl)phenyl)-3,7-dimethylocta-2,6-dienamide (5d), (6S,2Z)-N-(2- (4-chlorophenyl)phenyl)-3,7-dimethyl-6,7-dihydroxyoct-2-enamide (7g) and (6S,2Z)-N-(2-(4-chlorophenyl)phenyl)-3,7-dimethyl-6,7-dihydroxyoct-2-enamide (7h) have EC₅₀ values of 46.3, 38.1 and 40.6 µg/mL against S. sclerotiorum, and (Z)-N-(4-tert-butyl-benzyl)-3,7-dimethylocta-2,6-dienamide (5b) has an EC₅₀ value of 20.5 µg/mL against R. solani, respectively. The in vivo efficacy of (Z)-N-(2-chloro-4-trifluromethylphenyl)-3,7-dimethylocta-2,6-dienamide (5c), (E)-N-(2-chloro- 4-trifluromethylphenyl)-3,7-dimethylocta-2,6-dienamide (5g) and (6S,2E)-N-(2-chloro-4-trifluromethylphenyl)-3,7-dimethyl- 6,7-dihydroxyoct-2-enamide (7m) at the concentration of 400 µg/mL were in the range of 50%~100% against Pseudoperonospora cubensis and Erysiphe graminis. They have a potential to be optimized for improving the fungicidal activity.

Key words: 3,7-dimethylocta-2,6-dienamide, 3,7-dimethyl-6,7-dihydroxyoct-2-enamide, Sharpless asymmetric dihydroxylation, fungicidal activity

Cite this article

Weiwei Wang, Yihao Li, Xinlei Liu, Yu Zhao, Mingan Wang. Synthesis and Fungicidal Activity of Novel 3,7-Dimethylocta-2,6-dienamides and 3,7-Dimethyl-6,7-dihydroxyoct-2-enamides[J]. Chinese Journal of Organic Chemistry, 2021, 41(9): 3717-3725.

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化合物	构型	R¹R²	水稻纹枯菌	辣椒疫霉菌	油菜菌核菌	黄瓜灰霉菌	棉花立枯菌
5a	2Z	Morpholino	18.3	12.5	6.3	11.3	7.5
5b	2Z	4-t-BuC₆H₄CH₂, H	60.6	10.0	30.6	30.6	10.0
5c	2Z	2-Cl-4-CF₃C₆H₄, H	51.1	2.5	0	15.6	14.4
5d	2Z	2-(4-Cl-C₆H₄)C₆H₄, H	37.8	6.3	65.6	23.1	8.1
5e	2E	Morpholino	43.3	17.5	0	33.8	8.8
5f	2E	4-t-ButC₆H₄CH₂, H	41.1	9.4	48.8	36.3	11.3
5g	2E	2-Cl-4-CF₃C₆H₄, H	31.1	0	15.6	10.0	11.3
5h	2E	2-(4-Cl-C₆H₄)C₆H₄, H	35.6	3.8	0	10.0	11.9
7a	2Z,6S	Morpholino	41.1	10.0	8.1	6.3	12.5
7b	2Z,6R	Morpholino	43.3	11.3	49.4	12.5	12.5
7c	2Z,6S	4-t-ButC₆H₄CH₂, H	28.9	14.4	27.5	43.1	9.4
7d	2Z,6R	4-t-ButC₆H₄CH₂, H	23.3	13.8	21.3	34.4	16.3
7e	2Z,6S	2-Cl-4-CF₃C₆H₄, H	41.1	21.3	54.4	35.6	18.8
7f	2Z,6R	2-Cl-4-CF₃C₆H₄, H	29.4	15.0	27.5	11.9	17.5
7g	2Z,6S	2-(4-Cl-C₆H₄)C₆H₄, H	30.0	28.1	71.3	51.3	8.1
7h	2Z,6R	2-(4-Cl-C₆H₄)C₆H₄, H	53.9	25.6	61.3	40.6	9.4
7i	2E,6S	Morpholino	23.9	8.1	29.4	36.9	5.0
7j	2E,6R	Morpholino	34.4	8.8	58.8	30.6	0
7k	2E,6S	4-t-ButC₆H₄CH₂, H	25.6	12.5	12.5	30.0	10.0
7l	2E,6R	4-t-ButC₆H₄CH₂, H	39.4	18.8	29.4	27.5	10.0
7m	2E,6S	2-Cl-4-CF₃C₆H₄, H	41.7	27.5	51.3	22.5	23.8
7n	2E,6R	2-Cl-4-CF₃C₆H₄, H	38.9	26.9	54.4	26.3	17.5
7o	2E,6S	2-(4-Cl-C₆H₄)C₆H₄, H	21.7	10.0	12.5	12.5	0
7p	2E,6R	2-(4-Cl-C₆H₄)C₆H₄, H	32.2	13.1	34.4	25.6	16.9
R-1			71.8	66.4	81.8	72.0	80.2
丁吡吗啉			61.6	100	74.4	68.1	37.2
烯酰吗啉			14.6	100	15.0	9.4	20.9

化合物	构型	R¹R²	水稻纹枯菌	辣椒疫霉菌	油菜菌核菌	黄瓜灰霉菌	棉花立枯菌
5a	2Z	Morpholino	18.3	12.5	6.3	11.3	7.5
5b	2Z	4-t-BuC₆H₄CH₂, H	60.6	10.0	30.6	30.6	10.0
5c	2Z	2-Cl-4-CF₃C₆H₄, H	51.1	2.5	0	15.6	14.4
5d	2Z	2-(4-Cl-C₆H₄)C₆H₄, H	37.8	6.3	65.6	23.1	8.1
5e	2E	Morpholino	43.3	17.5	0	33.8	8.8
5f	2E	4-t-ButC₆H₄CH₂, H	41.1	9.4	48.8	36.3	11.3
5g	2E	2-Cl-4-CF₃C₆H₄, H	31.1	0	15.6	10.0	11.3
5h	2E	2-(4-Cl-C₆H₄)C₆H₄, H	35.6	3.8	0	10.0	11.9
7a	2Z,6S	Morpholino	41.1	10.0	8.1	6.3	12.5
7b	2Z,6R	Morpholino	43.3	11.3	49.4	12.5	12.5
7c	2Z,6S	4-t-ButC₆H₄CH₂, H	28.9	14.4	27.5	43.1	9.4
7d	2Z,6R	4-t-ButC₆H₄CH₂, H	23.3	13.8	21.3	34.4	16.3
7e	2Z,6S	2-Cl-4-CF₃C₆H₄, H	41.1	21.3	54.4	35.6	18.8
7f	2Z,6R	2-Cl-4-CF₃C₆H₄, H	29.4	15.0	27.5	11.9	17.5
7g	2Z,6S	2-(4-Cl-C₆H₄)C₆H₄, H	30.0	28.1	71.3	51.3	8.1
7h	2Z,6R	2-(4-Cl-C₆H₄)C₆H₄, H	53.9	25.6	61.3	40.6	9.4
7i	2E,6S	Morpholino	23.9	8.1	29.4	36.9	5.0
7j	2E,6R	Morpholino	34.4	8.8	58.8	30.6	0
7k	2E,6S	4-t-ButC₆H₄CH₂, H	25.6	12.5	12.5	30.0	10.0
7l	2E,6R	4-t-ButC₆H₄CH₂, H	39.4	18.8	29.4	27.5	10.0
7m	2E,6S	2-Cl-4-CF₃C₆H₄, H	41.7	27.5	51.3	22.5	23.8
7n	2E,6R	2-Cl-4-CF₃C₆H₄, H	38.9	26.9	54.4	26.3	17.5
7o	2E,6S	2-(4-Cl-C₆H₄)C₆H₄, H	21.7	10.0	12.5	12.5	0
7p	2E,6R	2-(4-Cl-C₆H₄)C₆H₄, H	32.2	13.1	34.4	25.6	16.9
R-1			71.8	66.4	81.8	72.0	80.2
丁吡吗啉			61.6	100	74.4	68.1	37.2
烯酰吗啉			14.6	100	15.0	9.4	20.9

化合物	黄瓜霜霉病	小麦白粉病	化合物	黄瓜霜霉病	小麦白粉病	玉米锈病	苹果炭疽病
5a	0	0	7f	0	0	0	0
5b	0	0	7g	0	0	0	0
5c	85	80	7h	0	0	0	0
5d	0	0	7i	0	0	0	0
5e	0	0	7j	0	0	0	0
5f	0	0	7k	0	0	0	0
5g	85	100	7l	0	0	0	0
5h	0	0	7m	50	70	0	0
7a	0	0	7n	0	0	0	0
7b	0	0	7o	0	0	0	0
7c	0	0	7p	0	0	0	0
7d	0	0	(Z,R)-2^[19]	100	100	60	65
7e	0	0	(Z,S)-2^[19]	100	100	80	100

化合物	黄瓜霜霉病	小麦白粉病	化合物	黄瓜霜霉病	小麦白粉病	玉米锈病	苹果炭疽病
5a	0	0	7f	0	0	0	0
5b	0	0	7g	0	0	0	0
5c	85	80	7h	0	0	0	0
5d	0	0	7i	0	0	0	0
5e	0	0	7j	0	0	0	0
5f	0	0	7k	0	0	0	0
5g	85	100	7l	0	0	0	0
5h	0	0	7m	50	70	0	0
7a	0	0	7n	0	0	0	0
7b	0	0	7o	0	0	0	0
7c	0	0	7p	0	0	0	0
7d	0	0	(Z,R)-2^[19]	100	100	60	65
7e	0	0	(Z,S)-2^[19]	100	100	80	100

3,7-二甲基辛-2,6-二烯酰胺和3,7-二甲基-6,7-二羟基辛-2-烯酰胺的合成及杀菌活性