阅读说明：本技术 苯乙酰胺类化合物的应用及杀藻剂 (Application of phenylacetamide compound and algicide ) 是由 冯玲玲 廖琴 韩强 王霞 刘红林 冯江涛 万坚 于 2018-08-07 设计创作，主要内容包括：本发明涉及农药及环境领域,公开了苯乙酰胺类化合物的应用及杀藻剂,具体公开了式(I)所示的苯乙酰胺类化合物在抑制藻类生长和/或杀灭藻类中的应用,以及公开了用于抑制藻类生长和/或杀灭藻类的杀藻剂,该杀藻剂的活性成分包括本发明的应用中所述的苯乙酰胺类化合物中的至少一种。将本发明的应用中所述的式(I)所示的苯乙酰胺类化合物用于抑制藻类生长和/或杀灭藻类时,具有高选择性、高抑制活性、毒性小的优点。<Image he="338" wi="700" file="DDA0001757472770000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention relates to the field of pesticides and environment, discloses application of phenylacetamide compounds and algicides, and particularly discloses application of the phenylacetamide compounds shown in a formula (I) in inhibiting the growth of algae and/or killing the algae, and an algicides for inhibiting the growth of the algae and/or killing the algae, wherein an active component of the algicides comprises at least one of the phenylacetamide compounds in the application. When the phenylacetamide compound shown in the formula (I) in the application is used for inhibiting the growth of algae and/or killing the algae, the phenylacetamide compound has the advantages of high selectivity, high inhibition activity and low toxicity.)

1. The application of the phenylacetamide compound shown in the formula (I) in inhibiting the growth of algae and/or killing the algae,

wherein, in the formula (I),

R¹、R²、R³、R⁴、R⁵and R⁶Each independently selected from H, C_1-12Alkyl of (C)_1-12Alkoxy, halogen, amino, nitro, hydroxy, C_1-12Alkyl hydroxy of, C_1-12Carboxyl, mercapto, sulfonic acid group, C substituted by 1 to 6 halogens_1-12The alkyl group of (a) is,

R⁷is a group represented by the following formula (I1) or formula (I2):

wherein, in the formulae (I1) and (I2), R¹¹、R²¹And R²²Each independently selected from H, C_1-12Alkyl of (C)_1-12Alkoxy, halogen, amino, nitro, hydroxy, C_1-12Alkyl hydroxy of, C_1-12Carboxyl, mercapto, sulfonic acid group, C substituted by 1 to 6 halogens_1-12Alkyl group of (1).

2. Use according to claim 1, wherein, in formula (I),

R¹、R²、R³、R⁴、R⁵and R⁶Each independently selected from H, C_1-8Alkyl of (C)_1-8Alkoxy, halogen, amino, nitro, hydroxy, C_1-8Alkyl hydroxy of, C_1-8Carboxyl group, mercapto group, sulfonic group, C substituted by 1 to 4 halogens_1-8The alkyl group of (a) is,

R⁷is a group represented by the following formula (I1) or formula (I2):

wherein, in the formulae (I1) and (I2), R¹¹、R²¹And R²²Each independently selected from H, C_1-8Alkyl of (C)_1-8Alkoxy, halogen, amino, nitro, hydroxy ofAmino group, C_1-8Alkyl hydroxy of, C_1-8Carboxyl group, mercapto group, sulfonic group, C substituted by 1 to 4 halogens_1-8Alkyl group of (1).

3. Use according to claim 1, wherein, in formula (I),

R¹、R²、R³、R⁴、R⁵and R⁶Each independently selected from H, C_1-6Alkyl of (C)_1-6Alkoxy, fluorine, chlorine, bromine, iodine, amino, nitro, hydroxyl, C_1-6Alkyl hydroxy of, C_1-6A carboxyl group, a mercapto group, a sulfonic acid group, C substituted with 1 to 3 halogens selected from fluorine, chlorine, bromine or iodine_1-6The alkyl group of (a) is,

R⁷is a group represented by the following formula (I1) or formula (I2):

wherein, in the formulae (I1) and (I2), R¹¹、R²¹And R²²Each independently selected from H, C_1-6Alkyl of (C)_1-6Alkoxy, fluorine, chlorine, bromine, iodine, amino, nitro, hydroxyl, amino, C_1-6Alkyl hydroxy of, C_1-6A carboxyl group, a mercapto group, a sulfonic acid group, C substituted with 1 to 3 halogens selected from fluorine, chlorine, bromine or iodine_1-6Alkyl group of (1).

4. Use according to claim 1, wherein, in formula (I),

R¹、R²、R³、R⁴、R⁵and R⁶Each independently selected from the group consisting of H, fluoro, chloro, bromo, iodo, nitro, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, cyclopentoxy, n-hexoxy, cyclohexyloxyHydroxy and trifluoromethyl;

R⁷is a group represented by the following formula (I1) or formula (I2):

wherein, in the formulae (I1) and (I2), R¹¹、R²¹And R²²Each independently selected from the group consisting of H, fluoro, chloro, bromo, iodo, nitro, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, amino, hydroxy, and trifluoromethyl; preferably, the first and second electrodes are formed of a metal,

in the formula (I), the compound represented by the formula (I),

R¹、R²、R³、R⁴、R⁵and R⁶Each independently selected from the group consisting of H, fluoro, chloro, bromo, iodo, nitro, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy, isopropoxy, hydroxy, and trifluoromethyl;

R⁷is a group represented by the following formula (I1):

wherein, in the formula (I1), R¹¹Selected from H and amino.

5. Use according to claim 1, wherein the phenylacetamide compound is at least one of the following compounds:

compound 1:

compound 3:

compound 5:

compound 7:

compound 9:

compound 11:

compound 13:

compound 15:compound 16:

compound 17:

compound 19:

6. use according to any one of claims 1 to 5, wherein each 1 x 10 is counted⁶Algae, wherein the dosage of the phenylacetamide compound shown in the formula (I) is 0.0001-100 micromoles; preferably 0.0005 to 5 micromoles; preferably 0.005 to 1 micromole.

7. The use of any one of claims 1 to 6, wherein the algae are red algae and blue algae.

8. The use according to claim 7, wherein the cyanobacteria is at least one of Synechocystis PCC 6803, anabaena, Synechocystis, Nostoc, Microcystis aeruginosa 905 and Microcystis aeruginosa 912.

9. An algicide for inhibiting the growth of and/or killing algae, the active ingredient of which comprises at least one of the phenylacetamide compounds described in the use according to any one of claims 1 to 8, in an amount of 0.01 to 100% by weight, based on the total weight of the algicide.

10. The algicide of claim 9, wherein the algicide is in a dosage form selected from the group consisting of a hydrating agent, a powder, an emulsion, a granule, and a suspension.

Technical Field

The invention relates to the field of pesticides and environment, in particular to application of phenylacetamide compounds in inhibiting growth of algae and/or killing algae and an algicide containing the phenylacetamide compounds.

Background

Due to the aggravation of human activities, the eutrophication degree of lakes in China and all over the world is increasingly improved, and the frequent outbreak of the cyanobacterial bloom is directly caused.

The blue algae bloom directly affects domestic water and industrial water in peripheral areas, seriously destroys ecological environment, brings huge economic loss to fishery production and tourism development and brings great hidden danger to public health.

The chemical algicide has the advantages of economy, high efficiency, convenience, quick response and the like, is an indispensable important component in an algae harm comprehensive treatment system, and is the most main prevention and control means for the emergency such as short-term quick treatment and control of algae harm and the like particularly during the large-scale outbreak of algae bloom.

The existing chemical algicides mainly comprise heavy metal compounds such as copper sulfate and complex compounds thereof; strong oxidants such as peroxide and potassium permanganate as algicides; herbicide algicides represented by diuron, prunetin and the like. However, these algicides have the problems of poor selectivity, large dosage and high toxicity to aquatic animals, aquatic plants, beneficial algae and the like, and the full play of the efficiency of preventing and controlling algae pests by using a chemical method is greatly limited.

Therefore, obtaining the inhibitor with good selectivity, low toxicity and good algae killing activity is an important development trend in the research of the modern chemical algae killing agent.

Disclosure of Invention

The invention aims to overcome the defects of low activity, poor selectivity and high toxicity of algicides provided by the prior art in the process of inhibiting the growth of algae and/or killing the algae, and provides the application of the phenylacetamide compound and the algicides containing the phenylacetamide compound, wherein the phenylacetamide compound has the advantages of high selectivity, high inhibition activity and low toxicity in the process of inhibiting the growth of the algae and/or killing the algae.

In order to achieve the above object, the present invention provides, in a first aspect, the use of a phenylacetamide compound represented by the formula (I) for inhibiting the growth of algae and/or killing algae,

wherein, in the formula (I),

R¹、R²、R³、R⁴、R⁵and R⁶Each independently selected from H, C_1-12Alkyl of (C)_1-12Alkoxy, halogen, amino, nitro, hydroxy, C_1-12Alkyl hydroxy of, C_1-12Carboxyl, mercapto, sulfonic acid group, C substituted by 1 to 6 halogens_1-12The alkyl group of (a) is,

R⁷is a group represented by the following formula (I1) or formula (I2):

wherein, in the formulae (I1) and (I2), R¹¹、R²¹And R²²Each independently selected from H, C_1-12Alkyl of (C)_1-12Alkoxy, halogen, amino, nitro, hydroxy, C_1-12Alkyl hydroxy of, C_1-12Carboxyl, mercapto, sulfonic acid group, C substituted by 1 to 6 halogens_1-12Alkyl group of (1).

In a second aspect, the present invention provides an algicide for inhibiting the growth of algae and/or killing algae, wherein the active ingredient of the algicide comprises at least one of the phenylacetamide compounds described in the application of the first aspect, and the content of the phenylacetamide compounds is 0.01-100 wt% based on the total weight of the algicide.

When the phenylacetamide compound shown in the formula (I) in the application is used for inhibiting the growth of algae and/or killing the algae, the phenylacetamide compound has the advantages of high selectivity, high inhibition activity and low toxicity.

When the phenylacetamide compound shown in the formula (I) is used as an effective component of the algicide and applied to the comprehensive treatment of algal bloom, the high-selectivity, high-efficiency and obvious algae inhibiting and/or killing effect can be shown.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

As described above, the first aspect of the present invention provides the use of phenylacetamide compounds represented by the formula (I) for inhibiting the growth of algae and/or killing algae,

wherein, in the formula (I),

R¹、R²、R³、R⁴、R⁵and R⁶Each independently selected from H, C_1-12Alkyl of (C)_1-12Alkoxy, halogen, amino, nitro, hydroxy, C_1-12Alkyl hydroxy of, C_1-12Carboxyl, mercapto, sulfonic acid group, C substituted by 1 to 6 halogens_1-12The alkyl group of (a) is,

R⁷is a group represented by the following formula (I1) or formula (I2):

wherein, in the formulae (I1) and (I2), R¹¹、R²¹And R²²Each independently selected from H, C_1-12Alkyl of (C)_1-12Alkoxy, halogen, amino, nitro, hydroxy, amino, C_1-12Alkyl hydroxy of, C_1-12Carboxyl, mercapto, sulfonic acid group, C substituted by 1 to 6 halogens_1-12Alkyl group of (1).

“C_1-12The alkyl group of (a) means an alkyl group having 1 to 12 total carbon atoms, and includes a straight-chain alkyl group, a branched-chain alkyl group and a cyclic alkyl group, and may be, for example, a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group having 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11 or 12 total carbon atoms.

“C_1-12The "alkoxy group" of (a) represents an alkoxy group having 1 to 12 carbon atoms in total, and includes a linear alkoxy group and a branched alkoxy group, and may be, for example, a linear alkoxy group or a branched alkoxy group having 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms in total.

“C_1-12The "alkylhydroxy group" of (A) represents an alkyl group having a total number of carbon atoms of 1 to 12, including a straight chain or branched chain alkyl group, and C_1-12At least one H in the alkyl group of (a) is substituted by a hydroxyl group.

"C substituted by 1-6 halogens_1-12The "alkyl group" of (A) represents an alkyl group having a total number of carbon atoms of 1 to 12, including a straight chain or branched chain alkyl group, and the C_1-121-6H in the alkyl group of (A) are substituted by halogen atoms selected from halogen, e.g. C_1-121,2, 3,4, 5 or 6H in the alkyl group of (a) is substituted by any one or more halogen atoms selected from fluorine, chlorine, bromine and iodine.

“C_1-12The "carboxyl group" of (a) represents a carboxyl group having 1 to 12 carbon atoms in total, and includes a linear carboxyl group and a branched carboxyl group, and may be, for example, a linear carboxyl group or a branched carboxyl group having 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms in total.

According to a first preferred embodiment, in formula (I),

R¹、R²、R³、R⁴、R⁵and R⁶Each independently selected from H, C_1-8Alkyl group of (A) or (B),C_1-8Alkoxy, halogen, amino, nitro, hydroxy, C_1-8Alkyl hydroxy of, C_1-8Carboxyl group, mercapto group, sulfonic group, C substituted by 1 to 4 halogens_1-8The alkyl group of (a) is,

R⁷is a group represented by the following formula (I1) or formula (I2):

wherein, in the formulae (I1) and (I2), R¹¹、R²¹And R²²Each independently selected from H, C_1-8Alkyl of (C)_1-8Alkoxy, halogen, amino, nitro, hydroxy, amino, C_1-8Alkyl hydroxy of, C_1-8Carboxyl group, mercapto group, sulfonic group, C substituted by 1 to 4 halogens_1-8Alkyl group of (1).

According to a second preferred embodiment, in formula (I),

R¹、R²、R³、R⁴、R⁵and R⁶Each independently selected from H, C_1-6Alkyl of (C)_1-6Alkoxy, fluorine, chlorine, bromine, iodine, amino, nitro, hydroxyl, C_1-6Alkyl hydroxy of, C_1-6A carboxyl group, a mercapto group, a sulfonic acid group, C substituted with 1 to 3 halogens selected from fluorine, chlorine, bromine or iodine_1-6The alkyl group of (a) is,

R⁷is a group represented by the following formula (I1) or formula (I2):

wherein, in the formulae (I1) and (I2), R¹¹、R²¹And R²²Each independently selected from H, C_1-6Alkyl of (C)_1-6Alkoxy, fluorine, chlorine, bromine, iodine, amino, nitro, hydroxyl, amino, C_1-6Alkyl hydroxy of, C_1-6A carboxyl group, a mercapto group, a sulfonic acid group, C substituted with 1 to 3 halogens selected from fluorine, chlorine, bromine or iodine_1-6Alkyl group of (1).

According to a third preferred embodiment, in formula (I),

R¹、R²、R³、R⁴、R⁵and R⁶Each independently selected from the group consisting of H, fluoro, chloro, bromo, iodo, nitro, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, cyclopentoxy, n-hexoxy, cyclohexyloxy, hydroxy, and trifluoromethyl;

R⁷is a group represented by the following formula (I1) or formula (I2):

wherein, in the formulae (I1) and (I2), R¹¹、R²¹And R²²Each independently selected from the group consisting of H, fluoro, chloro, bromo, iodo, nitro, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, hydroxy, amino, and trifluoromethyl.

According to a fourth preferred embodiment, in formula (I),

R¹、R²、R³、R⁴、R⁵and R⁶Each independently selected from the group consisting of H, fluoro, chloro, bromo, iodo, nitro, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy, isopropoxy, hydroxy, and trifluoromethyl;

R⁷is a group represented by the following formula (I1):

wherein, in the formula (I1), R¹¹Selected from H and amino.

According to a fifth preferred embodiment, the phenylacetamide-based compound is at least one of the following compounds:

preferably, for every 1 × 10⁶Algae, wherein the dosage of the phenylacetamide compound shown in the formula (I) is 0.0001-100 micromoles; more preferably 0.0005 to 5 micromolar; particularly preferably from 0.005 to 1. mu. mol.

Preferably, the algae are red algae and blue algae.

Preferably, the cyanobacteria is at least one of synechocystis PCC 6803, anabaena, nodularia, nostoc, microcystis aeruginosa 905 and microcystis aeruginosa 912.

As described above, the second aspect of the present invention provides an algicide for inhibiting the growth of algae and/or killing algae, wherein the active ingredient of the algicide comprises at least one of the phenylacetamide compounds described in the application of the first aspect of the present invention, and the content of the phenylacetamide compounds is 0.01 to 100 wt% based on the total weight of the algicide.

Preferably, in the algicide for inhibiting the growth of algae and/or killing algae according to the present invention, the phenylacetamide compound is contained in an amount of 1 to 90 wt% based on the total weight of the algicide.

Preferably, the algicide is in a dosage form selected from the group consisting of a hydrating agent, a powder, an emulsion, a granule and a suspension.

When the phenylacetamide compound represented by the formula (I) of the present invention is used as an active ingredient of an algicide, the compound can be mixed with a carrier or diluent acceptable in water to prepare various commonly used formulations, such as a hydrating agent, an emulsion, an aqueous solvent, a flowable agent, etc., and used as the algicide of the present invention.

In the present invention, the environmental conditions for applying the phenylacetamide compound are not particularly limited, and the phenylacetamide compound can be used under various conditions which are conventional in the art.

In the present invention, there is no particular limitation on the method for preparing the phenylacetamide compound represented by the formula (I), and those skilled in the art can prepare the phenylacetamide compound represented by the formula (I) according to the present invention by various methods known in the art.

The present invention illustratively lists the preparation of phenylacetamides of formula (I) by the following method:

synthesis of chloroacetamidobenzene compounds: the chloracetyl chloride is contacted with 1, 2-dichloroethane solution of substituted or unsubstituted aniline, heated to room temperature and then refluxed, and precipitates are separated out after being cooled to the room temperature, and the pure product is obtained after suction filtration, drying and recrystallization.

Synthesis of target compound: adding chloroacetamidobenzene compounds and NaI into ethanol, stirring to obtain a mixture, adding mercaptothiadiazole compounds or mercaptoimidazole compounds into aqueous solution of NaOH, finally dropwise adding the mixture into the aqueous solution, stirring at normal temperature, monitoring by TLC, performing reduced pressure distillation and desolventization after the reaction is finished, extracting the obtained residue with water/dichloromethane, desolventizing, and recrystallizing with ethanol to obtain a pure target product.

The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available without specific description.

Preparation example

Preparation of compound 1:

the first step is as follows: adding chloroacetyl chloride (50mmol) into 1, 2-dichloroethane solution (100mL) of aniline (20mmol) dropwise at 0 ℃, heating to room temperature, refluxing for 3.5h (TLC monitoring), cooling to room temperature, precipitating a large amount of precipitate, performing suction filtration, drying, and recrystallizing with 1, 2-dichloroethane to obtain a pure product.

The second step is that: adding 2-chloro-N-phenyl acetamide (4.9mmol) and NaI (1.5mmol) into ethanol (10mL), stirring to obtain a mixture, adding 2-mercapto-1, 3, 4-thiadiazole (5.85mmol) into an aqueous solution (2.5mL) of NaOH (7.0mmol), finally dropwise adding the mixture into the aqueous solution, stirring at normal temperature, reacting for about 1.0h (TLC monitoring), performing reduced pressure distillation and desolventization after the reaction is finished, extracting the obtained residue with water/dichloromethane, then extracting with dichloromethane (15X 2mL) twice from the aqueous phase after liquid separation, combining organic phases, desolventizing, and recrystallizing with ethanol to obtain a pure target product.

Compound 1:¹H NMR(600MHz,DMSO-d₆)δ(ppm)10.42(s,1H),9.53(s,1H),7.60(d,J＝7.8Hz,2H),7.33(t,J＝7.8Hz,2H),7.08(t,J＝7.3Hz,1H),4.36(s,2H)；¹³C NMR(151MHz,DMSO-d₆))δ(ppm)165.54,165.41,154.67,139.11,129.25,124.01,119.53,38.75；MS(EI):m/z＝251.10[M]⁺.

the preparation of compounds 2 to 20 was carried out using a similar preparation method to that of compound 1.

Compound 2: c₁₀H₈FN₃OS₂

¹H NMR(600MHz,DMSO-d₆)δ(ppm)10.50(s,1H),9.55(s,1H),7.64(dd,J＝8.8,5.0Hz,2H),7.18(t,J＝8.8Hz,2H),4.36(s,2H)；¹³C NMR(151MHz,DMSO-d₆)δ(ppm)165.52,165.38,159.38,157.78,154.71,154.60,135.48,135.46,121.41,121.36,115.89,115.75,38.60；MS(EI):m/z＝269.07[M]⁺.

Compound 3: c₁₀H₈ClN₃OS₂

¹H NMR(400MHz,DMSO-d₆)δ(ppm)10.54(s,1H),9.52(s,1H),7.62(d,J＝8.6Hz,2H),7.38(d,J＝8.5Hz,2H),4.34(s,2H)；¹³C NMR(151MHz,DMSO-d₆)δ(ppm)165.73,165.28,154.66,138.05,129.14,127.61,121.08,38.68；MS(EI):m/z＝285.00[M]⁺.

Compound 4: c₁₀H₈BrN₃OS₂

¹H NMR(400MHz,DMSO-d₆)δ(ppm)10.52(s,1H),9.51(s,1H),7.56(d,J＝8.9Hz,2H),7.49(d,J＝8.9Hz,2H),4.34(s,2H)；¹³C NMR(151MHz,DMSO-d₆)δ(ppm)165.73,165.22,154.70,154.54,138.43,132.01,121.46,115.64,38.70；MS(EI):m/z＝329.01[M-1]⁺,331.05[M+1]⁺.

Compound 5: c₁₀H₈IN₃OS₂

¹H NMR(600MHz,DMSO-d₆)δ(ppm)10.50(s,1H),9.49(s,1H),7.63(d,J＝8.6Hz,2H),7.40(d,J＝8.6Hz,2H),4.30(s,2H)；¹³C NMR(151MHz,DMSO-d₆)δ(ppm)165.73,165.27,154.69,154.54,138.92,137.84,121.75,87.58,38.78；MS(EI):m/z＝377.05[M]⁺.

Compound 6: c₁₀H₈N₄O₃S₂

¹H NMR(400MHz,DMSO-d₆)δ(ppm)10.98(s,1H),9.51(s,1H),8.22(d,J＝8.4Hz,2H),7.82(d,J＝8.5Hz,2H),4.40(s,2H)；¹³C NMR(151MHz,DMSO-d₆)δ(ppm)166.63,165.03,154.83,154.67,145.15,142.81,125.44,119.25,38.70；MS(EI):m/z＝296.10[M]⁺.

Compound 7: c₁₁H₈N₃OS₂

¹H NMR(400MHz,DMSO-d₆)δ(ppm)10.87(s,1H),9.53(s,1H),7.82(d,J＝8.3Hz,2H),7.67(d,J＝8.4Hz,2H),4.41(s,2H)；¹³C NMR(151MHz,DMSO-d₆)δ(ppm)166.34,165.27,154.82,142.72,127.42,126.61,126.59,125.62,124.31,124.10,123.88,123.82,123.67,122.02,38.72；MS(EI):m/z＝319.10[M]⁺.

Compound 8: c₁₁H₁₁N₃O₂S₂

¹H NMR(600MHz,DMSO-d₆)δ(ppm)10.34(s,1H),9.53(s,1H),7.51(d,J＝8.5Hz,2H),6.90(d,J＝8.4Hz,2H),4.32(s,2H),3.72(s,3H)；¹³C NMR(151MHz,DMSO-d₆)δ(ppm)160.39,159.88,150.68,149.63,149.47,127.14,115.95,109.19,50.42,33.54；MS(EI):m/z＝281.03[M]⁺.

Compound 9: c₁₁H₁₁N₃O₂S₂

¹H NMR(600MHz,DMSO-d₆)δ(ppm)9.68(s,1H),9.55(s,1H),8.00(d,J＝7.9Hz,1H),7.09(t,J＝7.7Hz,1H),7.05(d,J＝8.0Hz,1H),6.91(t,J＝7.6Hz,1H),4.40(s,2H),3.84(s,3H)；¹³C NMR(151MHz,DMSO-d₆)δ(ppm)160.79,160.45,149.76,149.58,144.52,122.23,119.89,116.50,115.57,106.43,50.96,33.39；MS(EI):m/z＝281.00[M]⁺.

Compound 10: c₁₀H₉N₃O₂S₂

¹H NMR(400MHz,DMSO-d₆)δ(ppm)10.12(s,1H),9.50(s,1H),9.23(s,1H),7.36(d,J＝8.4Hz,2H),6.72(d,J＝8.4Hz,2H),4.27(s,2H)；¹³C NMR(151MHz,DMSO-d₆)δ(ppm)165.55,164.79,154.68,154.58,154.02,130.75,121.37,115.59,38.66；MS(EI):m/z＝267.02[M]⁺.

Compound 11: c₁₁H₈N₃F₃OS₂

¹H NMR(400MHz,DMSO-d₆)δ(ppm)10.87(s,1H),9.53(s,1H),7.82(d,J＝8.3Hz,2H),7.67(d,J＝8.4Hz,2H),4.41(s,2H)；¹³C NMR(151MHz,DMSO-d₆)δ(ppm)166.34,165.27,154.82,142.72,127.42,126.61,126.59,125.62,124.31,124.10,123.88,123.82,123.67,122.02,38.72；MS(EI):m/z＝319.10[M]⁺.

Compound 12: c₁₀H₈N₃ClOS₂

¹H NMR(600MHz,DMSO-d₆)δ(ppm)10.00(s,1H),9.57(s,1H),7.81(d,J＝7.9Hz,1H),7.51(d,J＝8.0Hz,1H),7.34(t,J＝7.7Hz,1H),7.20(t,J＝7.6Hz,1H),4.45(s,2H)；¹³CNMR(151MHz,DMSO-d₆)δ(ppm)166.34,165.34,154.84,154.73,134.90,129.93,127.89,126.83,126.40,125.89,38.25；MS(EI):m/z＝285.05[M]⁺.

Compound 13: c₁₁H₁₁N₃OS₂

¹H NMR(600MHz,DMSO-d₆)δ(ppm)9.73(s,1H),9.54(s,1H),7.40(d,J＝7.8Hz,1H),7.21(d,J＝7.3Hz,1H),7.16(t,J＝7.5Hz,1H),7.09(t,J＝7.3Hz,1H),4.35(s,2H),2.19(s,3H)；¹³C NMR(151MHz,DMSO-d₆)δ(ppm)165.74,165.41,154.64,136.18,131.96,130.72,126.36,125.81,125.10,38.17,18.10；MS(EI):m/z＝265.01[M]⁺.

Compound 14: c₁₀H₈N₃ClOS₂

¹H NMR(600MHz,DMSO-d₆)δ(ppm)10.64(s,1H),9.56(s,1H),7.86(s,1H),7.49(d,J＝8.2Hz,1H),7.37(t,J＝8.1Hz,1H),7.15(d,J＝7.9Hz,1H),4.41(s,2H)；¹³C NMR(151MHz,DMSO-d₆)δ(ppm)166.00,165.24,154.69,154.59,140.51,133.64,130.86,123.72,119.08,117.93,38.70；MS(EI):m/z＝285.04[M]⁺.

Compound 15: c₁₁H₁₁N₃OS₂

¹H NMR(600MHz,DMSO-d₆)δ(ppm)10.31(s,1H),9.52(s,1H),7.42(s,1H),7.35(d,J＝8.0Hz,1H),7.20(t,J＝7.8Hz,1H),6.89(d,J＝7.4Hz,1H),4.31(s,2H),2.28(s,3H)；¹³CNMR(151MHz,DMSO-d₆)δ(ppm)165.44,165.41,154.64,154.53,139.02,138.43,129.04,124.70,120.04,116.73,38.76,21.55；MS(EI):m/z＝265.11[M]⁺.

Compound 16: c₁₁H₁₁N₃FOS₂

¹H NMR(600MHz,CDCl₃)δ(ppm)9.12(s,1H),9.08(s,1H),7.77(dd,J＝8.3,5.5Hz,1H),6.86(d,J＝8.7Hz,2H),4.15(s,2H),2.20(s,3H)；¹³C NMR(151MHz,CDCl₃)δ(ppm)166.01,165.89,160.18,158.55,152.04,131.68,131.63,131.25,131.23,124.13,124.07,116.65,116.50,112.68,112.54,36.80,17.65；MS(EI):m/z＝283.02[M]⁺.

Compound 17: c₁₁H₁₁N₃ClOS₂

¹H NMR(600MHz,DMSO-d₆)δ(ppm)10.11(s,1H),9.56(s,1H),7.43(d,J＝8.5Hz,1H),7.31(s,1H),7.22(d,J＝8.5Hz,1H),4.40(s,2H),2.22(s,3H)；¹³C NMR(151MHz,DMSO-d₆)δ(ppm)166.00,165.35,154.73,135.29,134.29,130.28,129.56,126.53,126.26,38.19,17.96；MS(EI):m/z＝299.04[M]⁺.

Compound 18: c₁₁H₁₁N₃BrOS₂

¹H NMR(600MHz,DMSO-d₆)δ(ppm)10.08(s,1H),9.56(s,1H),7.43(s,1H),7.39(d,J＝8.5Hz,1H),7.35(d,J＝8.6Hz,1H),4.40(s,2H),2.22(s,3H)；¹³C NMR(151MHz,DMSO-d₆)δ(ppm)165.99,165.46,154.82,154.71,135.79,134.74,133.11,129.11,126.88,117.79,38.21,18.02；MS(EI):m/z＝343.01[M-1]⁺,345.02[M+1]⁺.

Compound 19: c₁₀H₉N₄ClOS₂

¹H NMR(600MHz,dmso)δ10.31(d,J＝47.5Hz,1H),7.47(dd,J＝19.6,8.2Hz,2H),7.19(d,J＝4.5Hz,2H),4.08(s,1H),3.36(s,2H),2.88–2.80(m,1H),2.51(s,1H),1.18(d,J＝6.5Hz,6H).¹³C NMR(151MHz,dmso)δ172.01(s),158.12(s),150.27(s),148.73(s),144.95(s),143.14(s),133.29(d,J＝44.3Hz),125.85(s),124.17(s),39.44(d,J＝13.4Hz),30.59(s).

Compound 20: c₁₀H₁₀N₄OS₂

¹H NMR(600MHz,dmso)δ10.46(s,1H),9.52(s,1H),7.96(s,1H),7.36–7.22(m,2H),4.31(d,J＝23.5Hz,2H),3.38(s,2H).¹³C NMR(151MHz,dmso)δ165.07(s),154.34(d,J＝14.9Hz),139.15(s),129.25(s),114.41(s),109.99(s),103.46(s).

Test example 1

Synechocystis PCC 6803 and Microcystis aeruginosa 912 are the most important model algae among cyanobacteria.

The synechocystis PCC 6803 and the microcystis aeruginosa 912 are selected as living experiment objects to be used for testing the effect of the phenylacetamide compounds on inhibiting the growth of algae.

Respectively culturing synechocystis PCC 6803 and microcystis aeruginosa 912 in the same amount in BG-11 liquid culture medium containing compounds with different concentrations, and culturing in artificial climate incubator. Controlling the temperature of the incubator to be 28 +/-1 ℃, the humidity to be 60 percent, and the light intensity to be 8000lx, 12h (illumination): 12h (dark).

The specific operation is as follows:

pre-culturing a batch of Synechocystis PCC 6803 and Microcystis aeruginosa 912, growing to late log phase, and measuring OD₇₃₀Inoculation ofStandby;

diluting the logarithmic phase algae solution with fresh BG-11 culture medium to obtain inoculated algae solution, and controlling the cell concentration of algae to about 1 × 10⁶Per mL, algae growth inhibition experiment;

the compounds were weighed in advance, dissolved in DMSO, and compound solutions of different concentrations (concentrations: 0, 0.01, 0.03, 0.1, 0.3, 1,3, and 10mM, respectively) were prepared.

To each well of the 96-well plate, 200. mu.L of the diluted inoculated algal solution was added, and then 2. mu.L of each of the compounds shown in Table 1 was added to the well, at final concentrations of 0, 0.003, 0.01, 0.03, 0.1, 0.3, 1,3, 10, 30 and 100. mu.M, respectively. Setting a blank control (adding DMSO into an algae liquid system) without a compound and a background control (a compound system prepared by dissolving DMSO) with a phenylacetamide compound;

culturing in artificial climate incubator for 6 days, and measuring OD with enzyme-labeling instrument₇₃₀Calculating the inhibition rate of phenylacetamide compounds with different concentrations according to formula 1;

equation 1: inhibition%₇₃₀- (Experimental group OD)₇₃₀-phenylacetamide compound background control OD₇₃₀)]Blank control OD₇₃₀×100％；

Plotting the concentration of the phenylacetamide compound as an abscissa and the inhibition rate calculated by the formula 1 as an ordinate, and fitting the plotting by using a formula logistic in Origin to obtain the EC of the phenylacetamide compound₅₀The results are shown in Table 1.

TABLE 1

Comparative test example 1

This comparative test example was conducted in a similar manner to test example 1, except that copper sulfate, which is an algicide of the prior art, was used in this comparative test example instead of the phenylacetamide compound of test example 1 to inhibit the growth of Synechocystis PCC 6803 and Microcystis aeruginosa 912, and the inhibition was calculated using formula 2 under the same conditions, and the results are shown in Table 2.

Equation 2: percent inhibition [ (% OD of control group without compound addition)₇₃₀Blank control OD₇₃₀)]Experimental group OD₇₃₀Blank control OD₇₃₀)]/(control OD without Compound addition)₇₃₀Blank control OD₇₃₀)]×100％；

The results show that the inhibition rate and the killing effect of the phenylacetamide compound on the blue algae are even higher than those of copper sulfate used in the prior art, and the phenylacetamide compound has wide application prospect.

In addition, the invention adopts a mode of spraying the stem and leaf after seedling, and the compounds shown in the table 1 are respectively applied to mustard, chickweed, chenopodium quinoa, alopecurus nobilis, blue grass and club grass at the dosage of 150gai/ha for treatment, and as a result, the compounds have no killing or inhibiting activity on the mustard, the chickweed, the chenopodium quinoa, the alopecurus nobilis, the blue grass and the club grass, which shows that the compounds have the advantage of high selectivity when inhibiting the growth of algae and/or killing the algae.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.