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WO2024139260A1 - Dérivés d'allicine, leur procédé de préparation et leurs utilisations - Google Patents

Dérivés d'allicine, leur procédé de préparation et leurs utilisations Download PDF

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Publication number
WO2024139260A1
WO2024139260A1 PCT/CN2023/113516 CN2023113516W WO2024139260A1 WO 2024139260 A1 WO2024139260 A1 WO 2024139260A1 CN 2023113516 W CN2023113516 W CN 2023113516W WO 2024139260 A1 WO2024139260 A1 WO 2024139260A1
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Prior art keywords
allylthio
allicin
ethan
group
reaction
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Chinese (zh)
Inventor
李真真
陈庭倬
杨羚羚
朱洪江
廖立群
王周玉
周海伟
赵文娟
李岚
任丹
何其明
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Chengdu NewSun Crop Science Co Ltd
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Chengdu NewSun Crop Science Co Ltd
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Definitions

  • Allicin is an organic sulfur compound extracted from the bulb (garlic head) of garlic, a plant of the Allium family. It is also found in onions and other Allium plants. Its scientific name is diallyl thiosulfinate, and its chemical formula is C 6 H 10 OS 2 . The main active ingredients of allicin are diallyl trisulfate and diallyl disulfide.
  • Garlic extract is a natural plant-based pesticide. Compared with chemical pesticides, it has the advantages of being environmentally friendly and having less pesticide residues. It improves the application value of allicin and its derivatives in agricultural production and makes more contributions to solving global food security, food safety and environmental problems.
  • R 3 When R 3 is present, said R 3 is oxygen and the number of oxygen is 2 or 4, and said derivative is 3b or 3c;
  • the R 1 is a substituted phenyl group, substituted with one or more groups selected from the group consisting of fluorine, Bromine, chlorine, methoxy, amino, nitro, nitrile.
  • reaction molar ratio of compound 1 to compound 2 is 1:1 to 1:5.
  • the fourth object of the present invention is to provide the use of the above allicin derivatives or the above pesticide composition in the preparation of fungicides.
  • the fungus is any one or more of the following: Oomycetes of the Mastigomycetes, Pyromycetes, Coelomycetes, and Pedinomycetes of the Ascomycetes, and Trichosporons and Coelomycetes of the Ascomycetes.
  • Figures 12, 13, 14 and 15 are IC 50 graphs of allicin, Allicin-5, Allicin-15 and PA-16 against NDM-1, respectively;
  • Figures 21, 22, 23, 24, and 25 are IC 50 graphs of allicin, Allicin-5, Allicin-10, Allicin-15, and PA-16 against VIM-2, respectively;
  • the crude product was purified by column chromatography and eluted with pure petroleum ether to obtain the product, 2.52g yellow viscous liquid, with a yield of 52% and a purity of 84%.
  • the NMR spectrum of the prepared product is shown in Figure 5.
  • the prepared product is abbreviated as Allicin-13 below.
  • Example 10 The synthesis method of 2-allylthio-1-(4-methoxyphenyl)ethane-1-one is shown in Example 10. 1 mmol of 2-allylthio-1-(4-methoxyphenyl)ethane-1-one is dissolved in a mixed solvent (5 ml) of 30% H 2 O 2 : AcOH with a volume ratio of 4:1, and the reaction is carried out at room temperature for about 3 hours.
  • the reaction is terminated when the thioether raw material disappears as monitored by TCL, 20 ml of water is added, EA is extracted (10 ml, 3 times), the organic phases are combined, and then back-extracted with saturated brine (20 ml, 3 times), and then dried with anhydrous sodium sulfate and concentrated under reduced pressure to obtain a crude product.
  • the crude product is purified by column chromatography to obtain 2-allylsulfinyl-1-(4-methoxyphenyl)ethane-1-one (yield 73%, white solid).
  • the prepared product is abbreviated as Allicin-42 below.
  • Example 10 The synthesis method of 2-allylthio-1-(4-methoxyphenyl)ethane-1-one is shown in Example 10. 1 mmol of 2-allylthio-1-(4-methoxyphenyl)-1-one is dissolved in a mixed solvent (5 ml) of 30% H 2 O 2 :AcOH with a volume ratio of 4:1, and reacted at 80°C for about 2 hours.
  • the reaction is terminated when the thioether raw material disappears as monitored by TCL, 20 ml of water is added, EA is extracted (10 ml, 3 times), the organic phases are combined, and then back-extracted with saturated brine (20 ml, 3 times), and then dried with anhydrous sodium sulfate and concentrated under reduced pressure to obtain a crude product.
  • the crude product is washed with ether and water to obtain 2-allylsulfonyl-1-(4-methoxyphenyl)ethane-1-one (yield 81%, white solid).
  • the prepared product is abbreviated as Allicin-43 below.
  • step (1) Use a hole puncher to punch holes in concentric circles in the culture medium that has been successfully activated in step (1). Then inoculate the center of the culture medium and invert it in an incubator for culture. When the blank mycelium grows to cover 2/3 of the plate or the two bacterial circles grow to almost touch each other, use the cross method to measure the diameter of the colony, calculate the average diameter, and calculate the efficacy of the drug.
  • I mycelium growth inhibition rate
  • the medicament prepared by the allicin derivative prepared by the embodiment of the present invention, as well as allicin and Jianda were diluted to a certain multiple, and the effects on different pathogens were measured. All strains were obtained by sampling and separation in this laboratory, so there are some differences in the pathogenicity of the strains. The strains in different positions of different plants are marked in the present invention. The test results are shown in Table 1 and Figures 1-6.
  • a target compound with a sample concentration of 10 mM For a target compound with a sample concentration of 10 mM, mix it with DMSO at a volume ratio of 1:1, and shake it with a vortex shaker to obtain a 5 mM target compound solution. Take a 5 mM target compound solution and mix it with DMSO at a volume ratio of 1:10, and shake it with a vortex shaker to obtain a 0.5 mM target compound solution.
  • the 35 allicin structural derivatives under the general formula of the present invention such as Allicin-5, Allicin-10, Allicin-11, Allicin-12, Allicin-13, Allicin-15, etc., have the advantages of stronger antibacterial activity and wider antibacterial spectrum compared with allicin.
  • the allicin derivatives of the present invention can be used to prepare antibacterial agents; and the synthesis method of the present invention has the advantages of mild conditions and simple operation.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

La présente invention divulgue des dérivés d'allicine, leur procédé de préparation et leurs utilisations. La formule structurale des dérivés d'allicine est représentée par (I), dans laquelle R1 est un groupe substitué ou non substitué choisi dans le groupe suivant : phényle, aryle hétérocyclique azoté, aryle hétérocyclique soufré, cycloalkyle, aryle cyclique fusionné, benzopyranyle, époxyalkyle, pyrimidinyle et un groupe morpholino azote ; la substitution se référant à une substitution par un ou plusieurs groupes dans le groupe suivant : fluoro, chloro, bromo, alcoxyle, amino, halogénoalcoxyle, alkylsulfonyle, un groupe nitrile, benzyloxy, nitro, aminosulfonyle et phényle ; lorsque R2 est présent, R2 est hydrogène ou méthyle ; et lorsque R3 est présent, R3 est oxygène et le nombre d'atomes d'oxygène est 2 ou 4 ; et R2 et R3 ne sont pas présents en même temps. Les dérivés d'allicine selon la présente invention ont un effet relativement bon de lutte sur des microbes pathogènes qui ont une résistance aux médicaments par rapport aux microbicides existants, et ont une activité antimicrobienne élevée et un spectre antimicrobien plus large. Le dérivé peut être utilisé pour préparer des microbicides agricoles et des médicaments pour inhiber des enzymes bactériennes.
PCT/CN2023/113516 2022-12-26 2023-08-17 Dérivés d'allicine, leur procédé de préparation et leurs utilisations Ceased WO2024139260A1 (fr)

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WO2003031420A1 (fr) * 2001-10-05 2003-04-17 Bayer Cropscience Ag Derives d'isothiazole
CN113784958A (zh) * 2019-04-08 2021-12-10 Pi工业有限公司 用于控制或预防植物病原性真菌的新型噁二唑化合物

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LV15139B (lv) * 2016-04-22 2017-03-20 Rīgas Tehniskā Universitāte Sulfonu sintēzes paņēmiens no kālija aliltrifluorborātiem

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WO2003031420A1 (fr) * 2001-10-05 2003-04-17 Bayer Cropscience Ag Derives d'isothiazole
CN113784958A (zh) * 2019-04-08 2021-12-10 Pi工业有限公司 用于控制或预防植物病原性真菌的新型噁二唑化合物

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