CN101289434A - 1,5-Difuryl pentadienone compound and its preparation method and fungicidal activity - Google Patents

Abstract

The invention relates to the preparation of a 1, 5-difuryl pentadiene ketones compound, which is the compound of the structural formula (I), wherein, R1 is fluoride atom, chlorine atom, bromine atom, methyl, ethyl, propyl and isopropyl; R2 is fluoride atom, chlorine atom, bromine atom, methyl, ethyl, propyl and isopropyl. The preparation can be applied to controlling plant diseases caused by bacteria or fungi.

Description

1,5-Difuryl pentadienone compound and its preparation method and fungicidal activity

technical field

The invention relates to the preparation of 1,5-difuryl pentadienone compounds, which can be applied to the prevention and treatment of plant diseases caused by bacteria or fungi.

Background technique

Plant diseases caused by plant bacteria or fungi are the great enemy of agricultural production. According to the statistics of the Food and Agriculture Organization of the United Nations (FAO), the average annual loss of production due to plant diseases is 10% to 15% of the total output. Due to the difficulty in prevention and control, it has caused great losses to agricultural production. For example, in 2007, the agricultural losses caused by plant diseases caused by plant bacteria or fungi in China amounted to 10 billion yuan.

In order to prevent and treat plant diseases caused by plant bacteria or fungi, people have carried out various researches. From the middle of the 1960s, humans have successfully developed the cis-butenamide fungicide wiltazol, which has a therapeutic effect on plant diseases, especially The broad-spectrum, high-efficiency, and low-toxic benzimidazole fungicides benomyl and carbendazim, etc., mark a major breakthrough in the use of chemical weapons to control plant diseases, bringing the chemical control of plant diseases and the development of fungicides into a new era. historical period. The emergence of systemic fungicides has stimulated the enthusiasm of humans to use a large number of chemical pesticides to prevent and control plant diseases. However, they also have different problems that limit their applications. For example, cycloflufenamide has poor systemic activity and cannot be well absorbed by tissues; triadimefon is a systemic therapeutic fungicide with a single action mechanism and site of action, and long-term and frequent use has caused serious diseases [Journal of Northwest A&F University (Natural Science Edition), 2005, 33, 233-236]; methoxyacrylate fungicides have a unique mechanism of action, but pathogens are prone to resistance.

Contents of the invention

The object of the present invention is to provide a 1,5-difuryl pentadienone compound, which can be applied to the prevention and treatment of plant diseases caused by bacteria or fungi.

The present invention is the compound of following structural formula (I):

in,

R ₁ is a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group;

R ₂ is a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group.

The compound of general formula (I) is prepared by aldol condensation reaction of various substituted 2-acetylfurans and substituted furan acrolein in a protic solvent such as ethanol.

In the formula, R ₁ and R ₂ have the same meaning as above.

The compound of general formula (I) has better control of plant diseases caused by bacteria or fungi.

The 1,5-difuryl pentadienone compound of the present invention is easy to synthesize, low in cost, has a good inhibitory effect on plant bacteria or plant fungi, and has a novel structure. There are no reports on compounds with better inhibitory effects. The design and synthesis of the invention meets the requirements of environmental friendliness and green chemistry.

The above-mentioned content of the present invention will be further described in detail below through specific embodiments. However, this should not be construed as a limitation of the present invention.

Detailed ways

The 1,5-difuryl pentadienone compounds in the following examples all come from the Institute of Pesticides and Crop Protection, Sichuan University, and the plant pathogens for testing come from Sichuan University, Chengdu Institute of Biology, Chinese Academy of Sciences, and China Common Microbial Strain The preservation center and the Sichuan Academy of Agricultural Sciences, the tested agricultural pests came from the experimental field of the Institute of Pesticides and Crop Protection, Sichuan University.

的制备Compound of Example 1

preparation of

5-Methylacetylfuran (10 mmol, 1.24 g) was dissolved in 10 ml of ethanol, and furan acrolein (10 mmol, 1.22 g) was added. Under the condition of constant stirring, NaOH powder (1 mmol, 0.040 g) was added several times, and stirred evenly. Keep the temperature of the reaction system at 0°C, after the addition is complete, continue the reaction at room temperature for 24 hours, add 100ml of water for dilution, a yellow solid precipitates, filter out the solid, wash it, dry it with infrared, and recrystallize it with absolute ethanol to obtain 1.58 g of pale yellow crystals, yield 69.30%.

¹ H-NMR (400MHz, CDCl ₃ ): 2.43 (3H, s), 6.19-6.20 (1H, m), 6.45-6.49 (2H, m), 6.76 (1H, d, J=15.2Hz), 6.86- 6.94(2H, m), 7.17(1H, d, J=3.2Hz), 7.45(1H, s), 7.53～7.60(1H, m)

Example 21, Determination of the Bactericidal Activity of 5-Difuryl Pentadienone Compounds to Phytopathogenic Bacteria and Fungi

1 tested plant pathogenic bacteria

1.1 Plant pathogenic bacteria tested

Xanthomonas oryzae pv.oryzae, Xanthomonas campestris pv. malvacearum, Pantoea stewartii subsp. stewartii, Pseudomonas solanacearum pv.tabaci, potato Soft rot fungus (Erwinia carotovora subsp. carotovora), ginger blast fungus (Ralstonia solanacearum), cabbage black rot fungus (Xanthomonas campestris pv. Campestris), cabbage soft rot fungus (Erwinia aroideae).

1.2 Plant pathogenic fungi tested

Piricularia oryzae Cav, Rhizoctonia solani, Fusarium graminearum, Bipolaris maydis, Phytophthora infestans, Tobacco anthracnose ( Colletotrichum nicotianae), Alternaria brassicae, Botrytis cirerea.

2 Experimental method:

2.11, Determination of antibacterial activity of 5-difuryl pentadienone compounds against plant pathogenic bacteria

Determination of colony inhibition rate (%) by growth rate method:

The phytopathogenic bacteria described in 1.1 were diluted to a certain concentration respectively, and added to 1,5-difuryl pentadienone compound liquid culture medium (the final concentration of 1,5-difuryl pentadienone compound adopts A series of 1,5-difuryl pentadienone compound concentration gradient medium was prepared by the double dilution method of the test tube), and each series was inoculated with a suspension of test bacteria, and each concentration was repeated 3 times, and sterile Water was used as blank control. After culturing at 35-38°C for 18-24 hours, use the serial dilution method to count the bacteria, and calculate the colony inhibition rate according to the number of colonies. The formula is as follows:

2. Determination of the antibacterial activity of 2.21,5-difuryl pentadienone compounds against plant pathogenic fungi

Determination of mycelia relative inhibition rate (%) by toxic medium method:

First, dilute the 1,5-difuryl pentadienone compound with sterile water and then mix it with the PDA medium. The final concentration of the 1,5-difuryl pentadienone compound adopts the double dilution method , to make a series of drug-containing plates with uniform thickness, use sterile water as a blank control, and repeat each treatment 3 times. After the medium is solidified, connect the phytopathogenic fungus test bacteria cake on the solidified medium, and cultivate it at 27-28°C for 3-5 days. The diameter of the bacteria cake is 0.4cm. silk growth inhibition rate.

3 Experimental results

1,5-difuryl pentadienone compounds to the antibacterial activity assay results of the plant pathogenic bacteria (see Table 1). From the results in Table 1, it can be known that 1,5-difuryl pentadienone compounds have a good inhibitory effect on plant pathogenic bacteria.

The relative inhibitory rate (%) of table 1 embodiment 1 compound to phytopathogenic bacteria when 50mg/L

Strains Colony inhibition rate (%) Strains Colony inhibition rate (%) Xanthomonas oryzae 100 Xanthomonas cotton 85.37 corn bacterial wilt 90.31 Tobacco solanacearum 96.30 Potato soft rot 88.64 Cabbage soft rot 100 Cabbage black rot fungus 73.25 Zingiberella zingiberi 46.28

The following are the test results of the inhibitory activity of 1,5-difuryl pentadienone compounds on plant pathogenic fungi (see Table 2). It can be seen from the results in Table 2 that 1,5-difuryl pentadienone compounds also have a good inhibitory effect on plant pathogenic fungi.

Table 2 embodiment 1 compound at 50mg/L to the relative inhibitory rate (%) of phytopathogenic fungus

Strains Relative inhibition rate (%) Strains Relative inhibition rate (%) Magnaporthe grisea 100 Rice sheath blight 100 Fusarium tritici 68.30 Pseudomonas maize 90.38 Black spot fungus of cabbage 87.34 Phytophthora infestans 79.30 Botrytis cinerea 98.36 tobacco anthracnose 79.69

In summary, the 1,5-difuryl pentadienone compounds of the present invention have good broad-spectrum bactericidal activity on plant pathogenic bacteria, and they will be developed into stable, efficient, non-toxic novel green pesticides with Broad prospects.

Claims (3)

1, a kind of 1,5-difuryl pentadiene ketone compounds is characterized in that it is the compound of structure (I):

Wherein,

R ₁Be fluorine atom, chlorine atom, bromine atoms, methyl, ethyl, propyl group, sec.-propyl;

R ₂Be fluorine atom, chlorine atom, bromine atoms, methyl, ethyl, propyl group, sec.-propyl.

2, according to the synthetic method of compound shown in the claim 1, its reaction is:

3, according to claim 11,5-difuryl pentadiene ketone compounds is used, and it is characterized in that its application in control bacterium or fungus-caused Plant diseases.