Beta-bromo-beta-nitrostyrene compound as well as preparation method and application thereof
By synthesizing β-bromo-β-nitrostyrene compounds, the problem of poor efficacy of existing pesticides against plant pathogenic fungi has been solved, providing a novel, highly efficient, and low-cost fungicide suitable for controlling diseases such as rice blast fungus and pyrophyllosis fungus.
Patent Information
- Application Number
- CN202410556779.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-05-07
- Publication Date
- 2025-11-07
AI Technical Summary
Existing technologies lack effective pesticides to inhibit plant pathogenic fungi, especially those that are ineffective against rice blast fungus, fruit rot fungus, and gray mold fungus.
We designed and synthesized β-bromo-β-nitrostyrene compounds, and prepared compounds with antibacterial activity by reacting them with liquid bromine in the presence of alkaline substances. These compounds were then applied in pesticides to control plant pathogenic fungi.
The compound exhibits significant inhibitory effects on various plant pathogenic fungi, such as rice blast fungus, fruit rot fungus, and gray mold fungus. Furthermore, the preparation method uses inexpensive and readily available raw materials and operates under mild reaction conditions, meeting the requirements of green chemistry.
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Figure CN120904053A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of chemical technology, in particular to a kind of β-bromo-β-nitrostyrene compound and its preparation method and application. BACKGROUND
[0002] Cinnamic acid is an important natural product, widely exists in cinnamon, propolis, fruits and vegetables, etc., is a natural antioxidant. A number of studies have shown that cinnamic acid has a wide range of biological activities, including anti-tumor, antioxidant, bactericidal, insecticidal, antiseptic and fresh-keeping, and due to their safety and low toxicity, has been widely used in many industries such as spices, food additives, cosmetics, etc. In the field of pesticide research, cinnamic acid and its derivatives have been confirmed to have inhibitory activity on a variety of plant pathogenic fungi, such as β-bromo-β-nitrostyrene, which shows good bactericidal activity. Therefore, we choose β-bromo-β-nitrostyrene as a lead structure for further optimization, hoping to obtain a new structure bactericide with application value in agriculture.
[0003] SUMMARY
[0004] The present application aims to at least solve one of the above-mentioned technical problems in the related art to some extent or at least provide a useful commercial option. To this end, the present application provides a β-bromo-β-nitrostyrene compound having good inhibitory effect on the growth of plant pathogenic fungi.
[0005] To achieve the above-mentioned purpose, the present application provides a β-bromo-β-nitrostyrene compound, which is a compound shown in formula I or a stereoisomer, geometric isomer, tautomer, racemate, nitroxide, hydrate, solvate and pharmaceutically acceptable salt of the compound shown in formula I,
[0006]
[0007] wherein R is a single substituent or multiple substituents at any position on the benzene ring, and R is selected from at least one of H, halogen, alkyl, alkoxy, haloalkyl or haloalkoxy; X is oxygen, and n is 0 or 1.
[0008] Preferably, the halogen is at least one of fluorine, chlorine, bromine or iodine.
[0009] Preferably, the alkyl group is C 1-10 alkyl, further preferably C 1-4 alkyl.
[0010] Preferably, the alkoxy group is C 1-6 alkoxy.
[0011] Preferably, R is selected from at least one of H, fluorine, chlorine, bromine, methyl, ethyl, propyl, methoxy, trifluoromethyl or trifluoromethoxy.
[0012] Preferably, the compound is one of the following compounds or a stereoisomer, a geometric isomer, a tautomer, a racemate, an oxime, a hydrate, a solvate and a pharmaceutically acceptable salt of the following compounds:
[0013]
[0014]
[0015]
[0016] The second aspect of the present application provides a method for preparing the compound as described above, which comprises: contacting a compound as shown in formula II with liquid bromine to obtain a compound as shown in formula I,
[0017]
[0018] wherein R and n are the same as defined above.
[0019] Preferably, the method comprises: dissolving the compound as shown in formula II and liquid bromine in a solvent in the presence of a basic substance, and performing a heating reaction under stirring to obtain the compound as shown in formula I.
[0020] Preferably, the basic substance is an organic base, and further preferably triethylamine and sodium acetate.
[0021] Preferably, the molar ratio of the compound as shown in formula II, liquid bromine and the base is 1: (1-1.5): (1-1.5).
[0022] Preferably, the solvent is one or more of dichloromethane, trichloromethane and chlorobenzene.
[0023] Preferably, the temperature of the heating reaction is 35-110°C.
[0024] Preferably, the time of the heating reaction is 4-12 hours.
[0025] The third aspect of the present application provides a pesticide containing the β-bromo-β-nitrostyrene compound as described above and the β-bromo-β-nitrostyrene compound prepared by the method as described above.
[0026] The fourth aspect of the present application provides a use of the β-bromo-β-nitrostyrene compound, the β-bromo-β-nitrostyrene compound prepared by the method, or the pesticide in the prevention and treatment of plant pathogenic fungi.
[0027] Preferably, the plant is at least one of rice, melon and fruit, pepper, or rape.
[0028] Preferably, the plant pathogenic fungi is at least one of Magnaporthe grisea, Pythium aphanidermatum, Botrytis cinerea, Fusarium graminearum, Rhizoctonia solani, Colletotrichum gloeosporioides, Phytophthora capsici, Alternaria alternata, Cercospora summerell, or Sclerotinia sclerotiorum.
[0029] The fifth aspect of the present application provides a method for preventing and treating plant pathogenic fungi, which comprises applying the β-bromo-β-nitrostyrene compound or the pesticide to a plant.
[0030] Preferably, the plant is at least one of rice, melon and fruit, pepper, or rape.
[0031] Preferably, the plant pathogenic fungi is at least one of Magnaporthe grisea, Pythium aphanidermatum, Botrytis cinerea, Fusarium graminearum, Rhizoctonia solani, Colletotrichum gloeosporioides, Phytophthora capsici, Alternaria alternata, Cercospora summerell, or Sclerotinia sclerotiorum.
[0032] The β-bromo-β-nitrostyrene compound provided by the present application has at least the following advantages:
[0033] 1. The compound has not been reported. The inventors design and actually synthesize analogues of the derivative β-bromo-β-nitrostyrene of natural product cinnamic acid as a lead structure, and especially discover a new structural compound having application value in agricultural fungi through exploration. The compound has important research significance and application value for developing new high-efficiency fungicides.
[0034] 2. The inventors accidentally discover that the compound can effectively inhibit the growth of plant pathogenic fungi.
[0035] 3. The method for preparing the compound has the advantages of cheap and readily available raw materials, mild reaction conditions, high product purity, low production cost, and is conducive to mass production. Moreover, the reaction operation process does not involve special reaction equipment, and meets the safety production and green chemistry requirements. DETAILED DESCRIPTION
[0036] The specific embodiments of the present application are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.
[0037] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not considered critical for the purposes of the application. The ranges should be interpreted as being inclusive of the recited values and the ranges between the recited values.
[0038] The first aspect of the present application provides a β-bromo-β-nitrostyrene compound, which is a compound represented by Formula I or a stereoisomer, a geometric isomer, a tautomer, a racemate, an oxime, a hydrate, a solvate, and a pharmaceutically acceptable salt of the compound represented by Formula I,
[0039]
[0040] wherein R is a single substituent or multiple substituents on the benzene ring at any position, and R is selected from at least one of H, halogen, alkyl, alkoxy, haloalkyl, or haloalkoxy; X is oxygen, and n is 0 or 1.
[0041] In the compound represented by Formula I, when there are multiple substituents on the benzene ring, each substituent can be the same or different. For example, when R represents two substituents on the benzene ring, the two substituents can both be halogen, alkyl, alkoxy, or one substituent can be halogen and the other substituent can be alkyl, or one substituent can be halogen and the other substituent can be alkoxy, or one substituent can be alkyl and the other substituent can be alkoxy.
[0042] In the present application, the haloalkyl refers to a group obtained by substituting at least one hydrogen atom in an alkyl group with a halogen, i.e., a halogen-substituted alkyl group; and the haloalkoxy refers to a group obtained by substituting at least one hydrogen atom in an alkoxy group with a halogen, i.e., a halogen-substituted alkoxy group.
[0043] The inventors have surprisingly found that the β-bromo-β-nitrostyrene compound provided by the present application can effectively inhibit the biological activity of a plant pathogenic fungus.
[0044] In specific embodiments, the halogen is at least one of fluorine, chlorine, bromine, or iodine, and the halogen described herein includes the halogen represented by R and the halogen in haloalkyl and haloalkoxy. In preferred embodiments, the halogen is at least one of fluorine, chlorine, or bromine.
[0045] In specific embodiments, the alkyl is C 1-10 alkyl, and the alkyl described herein includes the alkyl represented by R and the alkyl in haloalkyl. In preferred embodiments, the alkyl is C 1-4 alkyl.
[0046] In a specific embodiment, the alkoxy group is a C 1-6 Alkoxy, as used herein, includes alkoxy groups represented by R and alkoxy groups in haloalkoxy.
[0047] In a more preferred embodiment, R is selected from at least one of H, fluorine, chlorine, bromine, methyl, ethyl, propyl, methoxy, trifluoromethyl (-CF3) or trifluoromethoxy (-COF3).
[0048] In a more specific embodiment, the β-bromo-β-nitrostyrene compound is one of the following compounds or a stereoisomer, a geometric isomer, a tautomer, a racemate, an oxime, a hydrate, a solvate, and a pharmaceutically acceptable salt of the following compounds:
[0049]
[0050]
[0051]
[0052] The second aspect of the present application provides a method for preparing the compound described above, which comprises: contacting a compound shown in formula II with liquid bromine to obtain a compound shown in formula I, as shown in the following synthesis route,
[0053]
[0054] wherein R is the same as defined above.
[0055] In a specific embodiment, the method comprises: dissolving the compound shown in formula II and liquid bromine in a solvent in the presence of a basic substance, and heating under stirring to obtain the compound shown in formula I.
[0056] In a preferred embodiment, the basic substance is an organic base, and further preferably triethylamine and / or sodium acetate. The base is added during the reaction to eliminate one bromine atom added to the double bond.
[0057] In a preferred embodiment, the molar ratio of the compound shown in formula II, liquid bromine and base is 1: (1-1.5): (1-1.5). Under this condition, the compound shown in formula II can be completely reacted, the post-treatment is simple, and the target compound can be obtained with a higher yield.
[0058] In a preferred embodiment, the solvent is one or more of dichloromethane, chloroform and chlorobenzene.
[0059] In preferred embodiments, the heating reaction can be performed at a temperature of 35-110 °C, such as 35 °C, 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, or 110 °C.
[0060] In preferred embodiments, the heating reaction can be performed for a time period of 4-12 hours, such as 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, or 12 hours.
[0061] In a third aspect, the present application provides a pesticide comprising the β-bromo-β-nitrostyrene compound described above or the β-bromo-β-nitrostyrene compound prepared by the method described above, i.e., the pesticide comprises the compound of Formula I or a stereoisomer, a geometric isomer, a tautomer, a racemate, an N-oxide, a hydrate, a solvate, and a pharmaceutically acceptable salt of the compound of Formula I.
[0062] In a fourth aspect, the present application provides use of the β-bromo-β-nitrostyrene compound described above, the β-bromo-β-nitrostyrene compound prepared by the method described above, or the pesticide described above in controlling a plant pathogenic fungus. The inventors have found that the compounds described herein can be effectively used to inhibit the growth of a plant pathogenic fungus. According to the inventors’ experiments, representative compounds 1-41 provided herein show excellent fungicidal activity.
[0063] In preferred embodiments, the plant is at least one of rice, melon, fruit, pepper, or rape. In preferred embodiments, the plant pathogenic fungus is at least one of Magnaporthe grisea, Pythium aphanidermatum, Botrytis cinerea, Fusarium graminearum, Rhizoctonia solani, Colletotrichum gloeosporioides, Phytophthora capsici, Alternaria alternata, Alternaria solani, or Sclerotinia sclerotiorum.
[0064] In a fifth aspect, the present application provides a method for controlling a plant pathogenic fungus, the method comprising applying to a plant the β-bromo-β-nitrostyrene compound described above, the β-bromo-β-nitrostyrene compound prepared by the method described above, or the pesticide described above.
[0065] In preferred embodiments, the plant is at least one of rice, melon, fruit, pepper, or rape. In preferred embodiments, the plant pathogenic fungus is at least one of Magnaporthe grisea, Pythium aphanidermatum, Botrytis cinerea, Fusarium graminearum, Rhizoctonia solani, Colletotrichum gloeosporioides, Phytophthora capsici, Alternaria alternata, Alternaria solani, or Sclerotinia sclerotiorum.
[0066] Definitions and explanations
[0067] As used herein, “C1-10 "Alkyl" is understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having from 1 to 10 carbon atoms, preferably C 1-4 "Alkyl", in particular, the "C 1-10 "Alkyl" is understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having from 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. The alkyl group includes, but is not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl, 2-methylbutyl, 1 -methylbutyl, 1 -ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1 -dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1 -methylpentyl, 2-ethylbutyl, 1 -ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1 -dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl and isomers thereof. In particular, the group has 1, 2, 3, 4, 5 or 6 carbon atoms (i.e. "C 1-6 "Alkyl") such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, t-butyl, more particularly the group has 1, 2 or 3 carbon atoms (i.e. "C 1-3 "Alkyl") such as methyl, ethyl, n-propyl or isopropyl.
[0068] Unless otherwise indicated, the use of "compounds of the present application" and similar terms herein is intended to encompass the compounds of Formula (I) or a stereoisomer, geometric isomer, tautomer, racemic form, nitroso, hydrate, solvate, and pharmaceutically acceptable salt of the compounds of Formula (I).
[0069] The term "stereoisomers" as used herein includes compounds that are optical isomers resulting from the attachment of the molecule to one or more chiral atoms and compounds that are optical isomers resulting from restricted rotation about one or more bonds. The definition of the compounds of the present application encompasses all possible stereoisomers and mixtures thereof. Very specifically encompassed are racemic forms and separated optical isomers having specific activity. The racemic forms can be resolved into their separate optical isomers by physical methods, including, but not limited to, fractional crystallization, separation of diastereomeric derivatives, or separation by chiral column chromatography. The separate optical isomers can be obtained from the racemates by conventional methods, including, but not limited to, salt formation with an optically active acid, followed by crystallization.
[0070] The term "compound of formula I" and salts thereof as used in the present application can exist in their tautomeric forms, in which a hydrogen atom is transferred from one atom of a molecule to another atom of the same molecule, and the chemical bonds between the atoms are thereby rearranged. It should be understood that all tautomeric forms, where they can exist, are included within the scope of the present application. Furthermore, the compounds of formula I according to the present application can have trans isomers and cis isomers.
[0071] The term "pharmaceutically acceptable salts" as used in the present application means salts of the compounds of formula I with inorganic or organic acids.
[0072] The term "contacting" as used herein is to be given its broadest interpretation as encompassing any means by which at least two reactants can be brought into chemical reaction with each other, for example by mixing the two reactants under suitable conditions.
[0073] Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following and the accompanying drawings or can be learned by practice of the application.
[0074] The application will now be described in detail by way of reference only to the following Examples, which are not intended to limit the scope of the application. The starting materials and reagents used in the Examples are commercially available unless otherwise stated.
[0075] Example 1 is used to illustrate the preparation of compound 1
[0076]
[0077] Preparation of compound 1:
[0078] Into a 50 mL round bottom flask, 5 mmol of 4-biphenyl-β-nitrostyrene, 6 mmol of sodium acetate, 7.5 mmol of liquid bromine, 20 mL of chloroform were added in sequence, and the reaction was stirred at 80 °C. TLC was used to monitor the reaction in real time until the reaction was complete. After 4 h of reaction, 30 mL of saturated aqueous sodium thiosulfate solution was added to the system to remove residual liquid bromine, and extraction, drying, and recrystallization were performed to obtain a yellow solid. The yield was 85%, and the melting point (m.p.) was 148-151 °C.
[0079] 1 H NMR (400 MHz, CDC13, TMS) δ (ppm): 8.63 (s, 1H), 7.93 (d, J = 8.5 Hz, 2H), 7.66 (d, J = 8.4 Hz, 2H), 7.59-7.55 (m, 2H), 7.42 (t, J = 7.5 Hz, 2H), 7.35 (s, 1H); 13C NMR (101 MHz, CDC13, TMS) δ (ppm): 143.71, 138.55, 135.13, 130.59, 128.07, 128.03, 127.93, 127.40, 126.49, 126.15.
[0080] Compound 2-14 was prepared according to the similar procedure as compound 1, and the detailed preparation process was according to the synthetic route of the compounds of formula I described above.
[0081] Example 2
[0082]
[0083] The obtained pure product was yellow solid with a yield of 86% and m.p.: 126-128 °C.
[0084] 1 H NMR (400 MHz, CDC13, TMS) δ (ppm): 8.62 (s, 1H), 7.92 (dd, J = 8.4, 4.7 Hz, 2H), 7.64 (d, J = 8.4 Hz, 2H), 7.47 (t, J = 7.6 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 2.34 (d, J = 7.4 Hz, 3H); 13 C NMR (101 MHz, CDC13, TMS) δ (ppm): 143.68, 137.48, 135.62, 135.22, 130.62, 128.77, 127.59, 126.57, 126.44, 126.22, 20.18.
[0085] Example 3
[0086]
[0087] The obtained pure product was yellow solid with a yield of 83% and m.p.: 113-115 °C.
[0088] 1 H NMR (400 MHz, CDC13, TMS) δ (ppm): 8.63 (s, 1H), 7.92 (d, J = 8.4 Hz, 2H), 7.66 (d, J = 8.4 Hz, 2H), 7.55-7.50 (m, 2H), 7.47-7.42 (m, 2H), 1.30 (d, J = 5.2 Hz, 9H); 13CNMR (101 MHz, CDC13, TMS) δ (ppm): 150.69, 143.60, 138.90, 135.58, 135.23, 130.63, 127.61, 126.27, 125.81, 125.02, 33.66, 30.27.
[0089] Example 4
[0090]
[0091] The pure product obtained was a yellow solid with a yield of 79% and m.p.: 109-112°C.
[0092] 1 H NMR (400 MHz, CDC13, TMS) δ (ppm): 8.63 (s, 1H), 7.95 (d, J = 8.4 Hz, 2H), 7.66 (d, J = 7.3 Hz, 6H); 13 C NMR (101 MHz, CDC13, TMS) δ (ppm): 142.07, 141.98, 134.72, 130.60, 128.93, 127.40, 126.69, 126.49, 125.04, 125.00, 124.96, 124.93, 124.41, 121.71
[0093] Example 5
[0094]
[0095] The pure product obtained was a yellow solid with a yield of 92% and m.p.: 127-130°C.
[0096] 1 H NMR (400 MHz, CDC13, TMS) δ (ppm): 8.69 (s, 1H), 7.99 (d, J = 8.4 Hz, 2H), 7.69 (d, J = 8.4 Hz, 2H), 7.60-7.55 (m, 2H), 7.48-7.43 (m, 2H); 13 C NMR (101 MHz, CDC13, TMS) δ (ppm): 143.38, 138.02, 135.95, 134.66, 131.66, 130.12, 129.32, 129.28, 128.42, 127.36.
[0097] Example 6
[0098]
[0099] The pure product obtained was a yellow solid with a yield of 78% and m.p.: 86-87°C.
[0100] 1 H NMR (400 MHz, CDC13, TMS) δ (ppm): 8.62 (s, 1H), 7.93 (d, J = 8.4 Hz, 2H), 7.65-7.56 (m, 4H), 7.26 (d, J = 8.2 Hz, 2H); 13 C NMR (101 MHz, CDC13, TMS) δ (ppm): 142.14, 137.26, 134.86, 130.61, 128.38, 127.57, 127.11, 126.57, 126.46, 120.72, 120.43.
[0101] Example 7
[0102]
[0103] The pure product obtained was a yellow solid with a yield of 85% and m.p.: 155-156°C.
[0104] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm): 8.87 (s, 1H), 8.10 (d, J = 8.3 Hz, 2H), 7.85 (d, J = 8.3 Hz, 2H), 7.75 (d, J = 8.6 Hz, 2H), 7.06 (t, J = 10.0 Hz, 2H), 3.81 (d, J = 6.3 Hz, 3H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm): 160.22, 143.56, 137.09, 132.31, 131.33, 128.82, 128.63, 127.77, 126.82, 115.04, 55.73.
[0105] Example 8
[0106]
[0107] The pure product obtained was a yellow solid with a yield of 82% and m.p. 108-110°C.
[0108] 1H NMR (400 MHz, DMSO-d6, TMS) δ (ppm): 8.87 (s, 1 H), 8.10 (d, J = 8.3 Hz, 2H), 7.85 (d, J = 8.3 Hz, 2H), 7.75 (d, J = 8.6 Hz, 2H), 7.06 (t, J = 10.0 Hz, 2H), 3.81 (d, J = 6.3 Hz, 3H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm): 156.50, 144.10, 138.63, 137.03, 132.15, 130.39, 128.11, 127.51, 127.47, 125.19, 21.46.
[0109] Example 9
[0110]
[0111] The pure product obtained was a yellow solid with a yield of 70% and m.p.: 158-160°C.
[0112] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm): 8.87 (s, 1 H), 8.10 (d, J = 8.3 Hz, 2H), 7.85 (d, J = 8.3 Hz, 2H), 7.75 (d, J = 8.6 Hz, 2H), 7.06 (t, J = 10.0 Hz, 2H), 3.81 (d, J = 6.3 Hz, 3H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm): 160.50, 137.18, 132.58, 131.29, 130.86, 130.28, 130.23, 130.20, 121.45, 121.42, 114.71, 112.39, 56.05
[0113] Example 10
[0114]
[0115] The pure product obtained was a yellow solid with a yield of 85% and m.p.: 116-118°C.
[0116] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm): 8.87 (s, 1 H), 8.10 (d, J = 8.3 Hz, 2H), 7.85 (d, J = 8.3 Hz, 2H), 7.75 (d, J = 8.6 Hz, 2H), 7.06 (t, J = 10.0 Hz, 2H), 3.81 (d, J = 6.3 Hz, 3H); 13C NMR (101 MHz, DMSO-d6, TMS) d (ppm): 161.70, 142.71, 136.93, 135.64, 132.20, 129.66, 129.58, 129.49, 128.30, 127.44, 116.56, 116.35.
[0117] Example 11
[0118]
[0119] The pure product obtained was a yellow solid with a yield of 75% and m.p.: 88-89°C.
[0120] 1 H NMR (400 MHz, DMSO-d6, TMS) d (ppm): 8.89 (s, 1H), 8.13 (d, J = 8.4 Hz, 2H), 7.93 (d, J = 8.4 Hz, 2H), 7.86 (s, 1H), 7.76 (d, J = 7.4 Hz, 1H), 7.57-7.48 (m, 2H); 13 C NMR (101 MHz, DMSO-d6, TMS) d (ppm): 142.09, 141.36, 136.83, 134.42, 132.15, 131.42, 130.39, 128.73, 128.64, 127.74, 127.15, 126.14.
[0121] Example 12
[0122]
[0123] The pure product obtained was a yellow solid with a yield of 84% and m.p.: 80-81°C.
[0124] 1 H NMR (400 MHz, DMSO-d6, TMS) d (ppm): 8.89 (s, 1H), 8.13 (d, J = 8.4 Hz, 2H), 7.93 (d, J = 8.4 Hz, 2H), 7.86 (s, 1H), 7.76 (d, J = 7.4 Hz, 1H), 7.57-7.48 (m, 2H); 13 C NMR (101 MHz, DMSO-d6, TMS) d (ppm): 142.09, 141.36, 136.83, 134.42, 132.15, 131.42, 130.39, 128.73, 128.64, 127.74, 127.15, 126.14.
[0125] Example 13
[0126]
[0127] The pure product obtained was a yellow solid with a yield of 72% and m.p.: 70-72°C.
[0128] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm): 8.88 (s, 1H), 8.12 (d, J = 8.3 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H), 7.62-7.54 (m, 2H), 7.39 (t, J = 7.6 Hz, 1H), 7.25 (d, J = 7.5 Hz, 1H), 2.40 (s, 3H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm): 143.95, 139.12, 138.80, 137.00, 132.18, 129.60, 129.57, 129.48, 128.17, 128.00, 127.48, 124.52, 21.56.
[0129] Example 14
[0130]
[0131] The pure product obtained was a yellow solid with a yield of 86% and m.p.: 137-140°C.
[0132] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm): 8.87 (d, J = 3.1 Hz, 1H), 8.12 (dd, J = 8.1, 2.8 Hz, 2H), 7.90 (d, J = 7.7 Hz, 2H), 7.77-7.68 (m, 4H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm): 142.41, 138.35, 136.87, 132.49, 132.21, 130.10, 129.48, 127.44, 127.43, 122.54.
[0133] Example 15
[0134]
[0135] Procedure for the preparation of compound 15:
[0136] To a 50 mL round bottom flask, 5 mmol of 4-biphenyl-β-nitroethene, 6 mmol of triethylamine, 5 mmol of liquid bromine, 20 mL of dichloromethane were added successively, the reaction was stirred at 35 °C, TLC was monitored in real time until the reaction was complete. After 6 h of reaction, 30 mL of saturated aqueous sodium thiosulfate solution was added to the system to remove residual liquid bromine, and the yellow solid was obtained by extraction, drying and recrystallization. Yield 75%, m.p.: 102-104 °C.
[0137] 1 H NMR (400 MHz, DMSO-d6) δ (ppm): 8.84 (s, 1H), 8.09 (d, J = 8.8 Hz, 2H), 7.52 (t, J = 6.0 Hz, 2H), 7.22-7.13 (m, 4H); 13 C NMR (101 MHz, DMSO-d6) δ (ppm): 160.28, 154.38, 136.75, 134.07, 130.70, 129.11, 127.22, 125.47, 122.19, 118.48.
[0138] Compounds 16-32 were prepared according to a procedure analogous to that of compound 15, following the synthetic route described above for the compounds of formula I.
[0139] Example 16
[0140]
[0141] The pure product obtained was a yellow solid with a yield of 85%, m.p.: 89-91 °C.
[0142] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm) 8.83 (s, 1H), 8.08 (d, J = 8.9 Hz, 2H), 7.69-7.64 (m, 1H), 7.46 (td, J = 7.8, 1.3 Hz, 1H), 7.36-7.30 (m, 2H), 7.07 (d, J = 8.8 Hz, 2H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm) 160.21, 150.33, 136.77, 134.09, 131.47, 129.70, 127.43, 127.11, 125.98, 125.20, 123.36, 117.16.
[0143] Example 17
[0144]
[0145] The pure product obtained was a yellow solid with a yield of 80% and m.p.: 116-118 °C.
[0146] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm) 8.83 (s, 1 H), 8.08 (d, J = 8.9 Hz, 2H), 7.30 (dt, J = 12.1, 2.8 Hz, 2H), 7.25-7.18 (m, 2H), 7.11 (d, J = 8.8 Hz, 2H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm) 161.07, 151.28, 136.82, 134.08, 126.98, 124.98, 122.65, 122.56, 117.81, 117.55, 117.32.
[0147] Example 18
[0148]
[0149] The pure product obtained was a yellow solid with a yield of 72% and m.p.: 58-60 °C.
[0150] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm) 8.83 (s, 1 H), 8.08 (d, J = 8.9 Hz, 2H), 7.30 (dt, J = 12.1, 2.8 Hz, 2H), 7.25-7.18 (m, 2H), 7.11 (d, J = 8.8 Hz, 2H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm) 161.07, 160.67, 158.27, 151.28, 136.82, 134.07, 126.98, 124.98, 122.64, 122.56, 117.81, 117.55, 117.32.
[0151] Example 19
[0152]
[0153] The pure product obtained was a yellow solid with a yield of 85% and m.p.: 102-104 °C.
[0154] 1H NMR (400 MHz, DMSO-d6, TMS) δ (ppm) 8.88 (s, 1 H), 8.12 (d, J = 8.4 Hz, 2H), 7.87 (d, J = 8.4 Hz, 2H), 7.79 (d, J = 8.3 Hz, 1 H), 7.73 - 7.71 (m, 2H), 7.52 - 7.47 (m, 2H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm) 160.08, 154.25, 135.95, 134.55, 131.12, 129.56, 127.88, 125.65, 124.32, 122.23, 118.76.
[0155] Example 20
[0156]
[0157] The pure product obtained was a yellow solid. Yield 92%, m.p.: 54-56°C.
[0158] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm) 8.82 (s, 1 H), 8.07 (d, J = 8.8 Hz, 2H), 7.33 (d, J = 8.5 Hz, 2H), 7.14 - 7.04 (m, 4H), 2.92 (dd, J = 13.8, 6.9 Hz, 1 H), 1.22 (d, J = 6.9 Hz, 6H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm) 161.12, 152.87, 147.73, 136.88, 134.08, 127.52, 126.80, 124.75, 120.06, 117.92, 34.67, 31.69.
[0159] Example 21
[0160]
[0161] The pure product obtained was a yellow solid. Yield 88%, m.p.: 61 -63°C.
[0162] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm) 8.82 (s, 1 H), 8.07 (d, J = 8.8 Hz, 2H), 7.33 (d, J = 8.5 Hz, 2H), 7.14 - 7.04 (m, 4H), 2.92 (dd, J = 13.8, 6.9 Hz, 1 H), 1.22 (d, J = 6.9 Hz, 6H); 13C NMR (101 MHz, DMSO-d6, TMS) δ (ppm) 161.19, 153.12, 145.49, 136.89, 134.08, 128.55, 126.80, 124.72, 120.45, 117.88, 33.32, 24.43.
[0163] Example 22
[0164]
[0165] The pure product obtained was a yellow solid in 78% yield, m.p.: 62-64 °C.
[0166] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm) 8.82 (d, J = 5.7 Hz, 1 H), 8.07 (d, J = 8.9 Hz, 2 H), 7.30 (d, J = 8.4 Hz, 2 H), 7.12 - 7.04 (m, 4 H), 2.63 (q, J = 7.6 Hz, 2 H), 1.20 (t, J = 7.6 Hz, 3 H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm) 161.19, 153.12, 145.49, 136.89, 134.08, 128.55, 126.80, 124.72, 120.45, 117.88, 33.32, 24.43.
[0167] Example 23
[0168]
[0169] The pure product obtained was a yellow solid in 78% yield, m.p.: 62-64 °C.
[0170] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm) 8.82 (d, J = 5.7 Hz, 1 H), 8.07 (d, J = 8.9 Hz, 2 H), 7.30 (d, J = 8.4 Hz, 2 H), 7.12 - 7.04 (m, 4 H), 2.63 (q, J = 7.6 Hz, 2 H), 1.20 (t, J = 7.6 Hz, 3 H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm) 161.19, 153.12, 145.49, 136.89, 134.08, 128.55, 126.80, 124.72, 120.45, 117.88, 33.32, 24.43.
[0171] Example 24
[0172]
[0173] The pure product obtained was a yellow solid with a yield of 75% and m.p.: 109-111 °C;
[0174] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm) 8.83 (s, 1 H), 8.08 (d, J = 8.9 Hz, 2 H), 7.86 (d, J = 2.5 Hz, 1 H), 7.53 (dd, J = 8.7, 2.5 Hz, 1 H), 7.35 (d, J = 8.7 Hz, 1 H), 7.12 (d, J = 8.8 Hz, 2 H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm) 159.81, 149.59, 136.69, 134.06, 130.90, 130.48, 129.71, 127.30, 127.10, 125.55, 124.47, 117.38.
[0175] Example 25
[0176]
[0177] The pure product obtained was a yellow solid with a yield of 74% and m.p.: 83-84 °C.
[0178] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm) 8.84 (s, 1 H), 8.10 (d, J = 8.8 Hz, 2 H), 7.48 (t, J = 8.1 Hz, 1 H), 7.32 (d, J = 8.0 Hz, 1 H), 7.26 (t, J = 2.1 Hz, 1 H), 7.20 (d, J = 8.8 Hz, 2 H), 7.12 (dd, J = 8.2, 2.2 Hz, 1 H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm) 159.86, 156.57, 136.72, 134.67, 134.07, 132.23, 127.36, 125.77, 125.18, 120.33, 118.92, 118.82.
[0179] Example 26
[0180]
[0181] The pure product obtained was a yellow solid with a yield of 82% and m.p.: 58-60 °C.
[0182] 1H NMR (400 MHz, DMSO-d6, TMS) δ (ppm) 8.81 (s, 1 H), 8.07 (d, J = 8.8 Hz, 2 H), 7.27 (d, J = 8.3 Hz, 2 H), 7.07 (dd, J = 16.4, 8.6 Hz, 4 H), 2.34 (d, J = 8.0 Hz, 3 H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm) 161.29, 152.88, 136.89, 134.63, 134.07, 131.21, 126.77, 124.66, 120.56, 117.76, 20.84.
[0183] Example 27
[0184]
[0185] The pure product obtained was a yellow solid in 76% yield, m.p.: 45-48 °C.
[0186] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm) 8.86-8.80 (m, 1 H), 8.09 (t, J = 10.0 Hz, 2 H), 7.44-7.36 (m, 1 H), 7.33-7.27 (m, 1 H), 7.24-7.13 (m, 1 H), 7.10-6.97 (m, 3 H), 2.14 (s, 3 H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm) 161.12, 152.79, 136.92, 134.20, 132.32, 130.29, 128.34, 126.66, 126.02, 124.41, 121.39, 116.89, 16.15.
[0187] Example 28
[0188]
[0189] The pure product obtained was a yellow solid in 80% yield, m.p.: 83-87 °C.
[0190] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm) 8.83 (s, 1 H), 8.07 (s, 2 H), 7.64 (d, J = 7.9 Hz, 1 H), 7.35-7.05 (m, 4 H), 6.92 (s, 1 H), 2.35 (s, 3 H); 13C NMR (101 MHz, DMSO-d6, TMS) d (ppm) 160.35, 154.77, 140.11, 136.75, 134.21, 134.08, 127.09, 125.30, 122.98, 119.85, 119.76, 118.37, 22.97.
[0191] Example 29
[0192]
[0193] The pure product obtained was a yellow solid in 86% yield, m.p.: 44-46 °C.
[0194] 1 H NMR (400 MHz, DMSO-d6, TMS) d (ppm) 8.81 (s, 1H), 8.06 (d, J = 8.7 Hz, 2H), 7.12 (d, J = 8.9 Hz, 2H), 7.04 (dd, J = 12.1, 8.9 Hz, 4H), 3.78 (s, 3H); 13 C NMR (101 MHz, DMSO-d6, TMS) d (ppm) 161.91, 156.92, 148.17, 136.92, 134.07, 126.62, 124.36, 122.16, 117.24, 115.79, 55.93.
[0195] Example 30
[0196]
[0197] The pure product obtained was a yellow solid in 72% yield, m.p.: 99-103 °C;
[0198] 1 H NMR (400 MHz, DMSO-d6, TMS) d (ppm) 8.84 (s, 1H), 8.09 (d, J = 8.8 Hz, 2H), 7.63 - 7.58 (m, 1H), 7.47 (t, J = 8.1 Hz, 1H), 7.30 (d, J = 8.2 Hz, 1H), 7.15 (d, J = 8.7 Hz, 2H); 13 C NMR (101 MHz, DMSO-d6, TMS) d (ppm) 159.64, 152.08, 136.69, 134.10, 133.58, 131.41, 129.88, 127.67, 125.71, 121.62, 117.97, 117.58.
[0199] Example 31
[0200]
[0201] The pure product obtained was a yellow solid with a yield of 77% and m.p.: 80-83°C.
[0202] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm) 8.83 (s, 1H), 8.08 (d, J = 8.6 Hz, 2H), 7.74-7.66 (m, 1H), 7.46-7.30 (m, 2H), 7.07 (d, J = 8.6 Hz, 2H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm) 159.86, 156.57, 136.81, 134.67, 134.25, 132.23, 127.36, 125.77, 125.18, 120.34, 118.92, 118.81.
[0203] Example 32
[0204]
[0205] The pure product obtained was a yellow solid with a yield of 75% and m.p.: 104-107°C.
[0206] 1 H NMR (400 MHz, DMSO-d6, TMS) δ (ppm) 8.83 (s, 1H), 8.07 (d, J = 8.7 Hz, 2H), 7.49 (s, 1H), 7.37-7.31 (m, 1H), 7.08 (dd, J = 19.2, 8.6 Hz, 3H), 2.14 (s, 3H); 13 C NMR (101 MHz, DMSO-d6, TMS) δ (ppm) 160.66, 151.84, 136.83, 134.18, 132.77, 131.81, 129.60, 128.08, 126.90, 124.83, 122.98, 117.15, 16.01.
[0207] Example 33
[0208]
[0209] Preparation of compound 33:
[0210] To a solution of 5 mmol of 4-biphenyl-β-nitrostyrene, 7.5 mmol of sodium acetate, 5 mmol of liquid bromine, 20 mL of chlorobenzene in a 50 mL round bottom flask, the reaction was heated and stirred at 110 °C, monitored by TLC until the reaction was complete. After 12 h of reaction, the system was added 30 mL of saturated aqueous sodium thiosulfate solution to remove the residual liquid bromine, extracted, dried, recrystallized to obtain a yellow solid. Yield 81 %, m.p.: 113-115 °C.
[0211] 1 H NMR (400 MHz, DMSO-d6) δ (ppm): 8.93 (s, 1 H), 8.10 (d, J = 7.7 Hz, 1 H), 7.51 (t, J = 7.8 Hz, 1 H), 7.25 (t, J = 7.6 Hz, 1 H), 7.10 (d, J = 9.0 Hz, 2 H), 7.01 (d, J = 9.0 Hz, 2 H), 6.79 (d, J = 8.3 Hz, 1 H), 3.77 (s, 3 H); 13 C NMR (101 MHz, DMSO-d6) δ (ppm): 157.97, 156.76, 148.97, 133.97, 132.03, 130.05, 129.95, 123.01, 121.76, 120.86, 116.79, 115.75, 55.94.
[0212] Compounds 34-41 were prepared according to a procedure analogous to that of compound 33, following the synthetic routes described previously for the compounds of formula I.
[0213] Example 34
[0214]
[0215] The pure product obtained was a yellow solid with a yield of 84 %, m.p.: 116-117 °C.
[0216] 1 H NMR (400 MHz, DMSO-d6) δ (ppm): 8.93 (s, 1 H), 8.10 (d, J = 7.7 Hz, 1 H), 7.51 (t, J = 7.8 Hz, 1 H), 7.25 (t, J = 7.6 Hz, 1 H), 7.10 (d, J = 9.0 Hz, 2 H), 7.01 (d, J = 9.0 Hz, 2 H), 6.79 (d, J = 8.3 Hz, 1 H), 3.77 (s, 3 H); 13CNMR (101 MHz, DMSO-d6) δ (ppm): 160.48, 158.09, 157.11, 152.08, 134.00, 131.96, 130.35, 130.10, 123.69, 122.07, 121.98, 121.47, 117.62, 117.47, 117.24.
[0217] Example 35
[0218]
[0219] The pure product obtained was a yellow solid in 88% yield, m.p.: 126-128°C.
[0220] 1 H NMR (400 MHz, DMSO-d6) δ (ppm): 8.81 (s, 1 H), 8.11 (d, J = 7.8 Hz, 1 H), 7.60 (t, J = 9.9 Hz, 3H), 7.35 (t, J = 7.6 Hz, 1 H), 7.07 (d, J = 8.7 Hz, 2H), 7.00 (d, J = 8.2 Hz, 1 H); 13 CNMR (101 MHz, DMSO-d6) δ (ppm): 156.13, 155.78, 143.42, 134.04, 133.55, 133.09, 131.85, 130.21, 124.37, 122.15, 121.82, 118.79, 116.72.
[0221] Example 36
[0222]
[0223] The pure product obtained was a yellow solid in 74% yield, m.p.: 107-108°C.
[0224] 1 H NMR (400 MHz, DMSO-d6) δ (ppm): 8.91 (s, 1 H), 8.13 (d, J = 7.8 Hz, 1 H), 7.65 (dd, J = 8.0, 1.2 Hz, 1 H), 7.55 (dd, J = 11.4, 4.3 Hz, 1 H), 7.49 - 7.41 (m, 1 H), 7.32 (dt, J = 7.6, 5.5 Hz, 2H), 7.26 (d, J = 8.0 Hz, 1 H), 6.78 (d, J = 8.2 Hz, 1 H); 13C NMR (101 MHz, DMSO-d6) d (ppm): 156.31, 151.01, 134.06, 131.48, 131.43, 130.56, 130.16, 129.63, 127.15, 125.51, 123.90, 122.79, 120.96, 116.69.
[0225] Example 37
[0226]
[0227] The pure product obtained was a yellow solid in 82% yield, m.p.: 76-78 °C.
[0228] 1 H NMR (400 MHz, DMSO-d6) d (ppm): 8.81 (s, 1 H), 8.10 (d, J = 7.3 Hz, 1 H), 7.63-7.56 (m, 1 H), 7.46 (t, J = 8.2 Hz, 1 H), 7.37 (t, J = 7.6 Hz, 1 H), 7.28 (d, J = 8.0 Hz, 1 H), 7.20 (s, 1 H), 7.10-7.01 (m, 2 H); 13 C NMR (101 MHz, DMSO-d6) d (ppm): 157.36, 155.84, 134.64, 134.04, 132.16, 131.91, 130.69, 130.25, 124.87, 124.59, 122.35, 119.65, 119.06, 118.25.
[0229] Example 38
[0230]
[0231] The pure product obtained was a yellow solid in 72% yield, m.p.: 54-56 °C.
[0232] 1 H NMR (400 MHz, DMSO-d6) d (ppm): 8.80 (s, 1 H), 8.08 (d, J = 7.4 Hz, 1 H), 7.61 -7.49 (m, 2 H), 7.32 (t, J = 7.4 Hz, 1 H), 7.13 (d, J = 2.1 Hz, 1 H), 6.97-6.81 (m, 2 H), 2.31 (s, 3 H); 13C NMR (101 MHz, DMSO-d6) d (ppm): 156.26, 155.56, 139.98, 134.00, 133.94, 131.77, 130.46, 130.08, 124.12, 122.27, 121.88, 119.32, 119.10, 118.51, 22.90.
[0233] Example 39
[0234]
[0235] The pure product obtained was a yellow solid with a yield of 70% and m.p.: 102-105°C.
[0236] 1 H NMR (400 MHz, DMSO-d6) d (ppm): 8.83 (s, 1 H), 8.11 (d, J = 7.9 Hz, 1 H), 7.56 (dd, J = 11.4, 4.3 Hz, 1 H), 7.49 (d, J = 8.9 Hz, 2 H), 7.35 (t, J = 7.4 Hz, 1 H), 7.13 (d, J = 8.9 Hz, 2 H), 6.98 (d, J = 8.1 Hz, 1 H); 13 C NMR (101 MHz, DMSO-d6) d (ppm): 156.27, 155.22, 134.03, 131.86, 130.62, 130.57, 130.20, 128.79, 124.28, 122.06, 121.48, 118.64.
[0237] Example 40
[0238]
[0239] The pure product obtained was a yellow solid with a yield of 76% and m.p.: 62-64°C.
[0240] 1 H NMR (400 MHz, DMSO-d6) d (ppm): 8.94 (s, 1 H), 8.12 (d, J = 7.6 Hz, 1 H), 7.57-7.47 (m, 1 H), 7.37 (d, J = 7.4 Hz, 1 H), 7.27 (t, J = 7.6 Hz, 2 H), 7.21-7.15 (m, 1 H), 6.98 (d, J = 7.9 Hz, 1 H), 6.70 (d, J = 8.3 Hz, 1 H), 2.20 (d, J = 23.5 Hz, 3 H); 13C NMR (101 MHz, DMSO-d6) d (ppm): 156.98, 153.54, 134.04, 132.19, 131.69, 130.00, 129.77, 128.21, 125.59, 123.10, 120.66, 120.50, 116.44, 16.11.
[0241] Example 41
[0242]
[0243] The obtained pure product was a yellow solid with a yield of 75% and m.p.: 109-111 °C.
[0244] 1 H NMR (400 MHz, DMSO-d6) d (ppm): 8.88 (s, 1H), 8.11 (d, J = 7.8 Hz, 1H), 7.53 (t, J = 7.8 Hz, 1H), 7.32-7.22 (m, 3H), 7.01 (t, J = 9.9 Hz, 2H), 6.86 (d, J = 8.3 Hz, 1H), 2.31 (s, 3H); 13 C NMR (101 MHz, DMSO-d6) d (ppm): 157.24, 153.83, 134.26, 133.99, 131.94, 131.13, 130.18, 130.01, 123.50, 121.45, 119.90, 117.80, 20.77.
[0245] Example 42
[0246] Bactericidal activity experiment
[0247] Test materials: Pyricularia oryzae, Pythium aphanidermatum, Botrytis cinerea, Fusarium graminearum, Rhizoctonia solani, Guignardia bidwellii, Sclerotinia sclerotiorum.
[0248] Test method: The compound of the present application was dissolved in DMSO to prepare a series of drug solutions (concentration 50 ppm), which were added to the potato culture medium after melting and cooling to about 45°C to prepare the required drug-containing plates. The colony edge of each strain colony pre-cultured on PDA plate medium was punched into a 5 mm diameter fungus cake and inoculated on drug-containing plates with different concentrations, and cultured at 25°C in the dark. When the colony diameter of the control reached more than 80% of the diameter of the culture dish, the colony diameter was measured by cross method, and each treatment was repeated 3 times, with DMSO solution as a blank control. The inhibition percentage (%) of mycelial growth of each drug concentration was calculated according to the following formula, and the results are shown in Tables 1-6:
[0249]
[0250] Table 1 Bactericidal activity data of compounds 1-14 (test concentration 50 μg / mL)
[0251]
[0252] Table 2 Bactericidal activity EC of compounds 1-14 50 values (μg / mL)
[0253]
[0254]
[0255] Table 3 Bactericidal activity data of compounds 15-32 (test concentration 50 μg / mL)
[0256]
[0257] Table 4 Bactericidal activity EC of compounds 15-32 50 values (μg / mL)
[0258]
[0259]
[0260] Table 5 Bactericidal activity data of compounds 33-41 (test concentration 50 μg / mL)
[0261]
[0262] Table 6 Bactericidal activity EC of compounds 33-41 50 values (μg / mL)
[0263]
[0264] From the results of Tables 1-6, it can be seen that most of the compounds in the present application have excellent antifungal activity, and some of the compounds can be used to prevent and treat various plant pathogenic fungi, such as Rhizoctonia solani, Colletotrichum gloeosporioides, Pyricularia grisea, Phytophthora capsici, and the like.
[0265] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed in the present application and fall within the protection scope of the present application.
Claims
1. A β-bromo-β-nitrostyrene compound, characterized by, The compound is a compound shown in formula I or a stereoisomer, a geometric isomer, a tautomer, a racemate, an oxime, a hydrate, a solvate and a pharmaceutically acceptable salt of the compound shown in formula I, wherein R is a single substituent or multiple substituents at any position of the benzene ring, and R is at least one selected from H, halogen, alkyl, alkoxy, haloalkyl or haloalkoxy; X is oxygen, and n is 0 or 1.
2. The compound of claim 1, wherein The halogen is at least one selected from fluorine, chlorine, bromine or iodine; Preferably, the alkyl group is C 1-10 alkyl, further preferably C 1-4 alkyl; Preferably, said alkoxy group is a C 1-6 alkoxy group.
3. The compound of claim 1 or 2, wherein R is at least one selected from H, fluorine, chlorine, bromine, methyl, ethyl, butyl, methoxy, trifluoromethyl or trifluoromethoxy.
4. The compound of claim 1 or 2, wherein The compound is a compound shown in formula I or a stereoisomer, a geometric isomer, a tautomer, a racemate, an oxime, a hydrate, a solvate and a pharmaceutically acceptable salt of the compound shown in formula I, 5. A process for the preparation of a compound according to any one of claims 1 to 4, characterized in that, The method comprises: contacting a compound shown in formula II with liquid bromine to obtain a compound shown in formula I, wherein R and n are the same as defined in any one of claims 1 to 4.
6. The method of claim 5, wherein, The method comprises: dissolving the compound shown in formula II and liquid bromine in a solvent in the presence of a basic substance, and performing a heating reaction under stirring to obtain a compound shown in formula I; Preferably, the basic substance is an organic base, and further preferably triethylamine and / or sodium acetate; Preferably, the molar ratio of the compound shown in formula II, liquid bromine and base is 1:(1-1.5):(1-1.5); Preferably, the solvent is one or two or more selected from dichloromethane, trichloromethane and chlorobenzene; Preferably, the temperature of the heating reaction is 35-110°C; Preferably, the time of the heating reaction is 4-12 hours.
7. A pesticide, characterized by comprising: The pesticide contains the β-bromo-β-nitrostyrene compound according to any one of claims 1 to 4 and the β-bromo-β-nitrostyrene compound prepared by the method according to claim 5 or 6.
8. Use of the β-bromo-β-nitrostyrene compound according to any one of claims 1 to 4, the β-bromo-β-nitrostyrene compound prepared by the method according to claim 5 or 6 or the pesticide according to claim 7 in controlling plant pathogenic fungi.
9. Use according to claim 8, characterized in that, The plant is at least one selected from rice, melon, fruit, pepper and rape; Preferably, the pathogenic fungi are at least one selected from Pyricularia oryzae, Pythium aphanidermatum, Botrytis cinerea, Fusarium graminearum, Rhizoctonia solani, Colletotrichum gloeosporioides, Phytophthora capsici, Mycosphaerella pinodes, Podosphaera xanthii and Sclerotinia sclerotiorum.
10. A method for controlling plant pathogenic fungi, characterized in that, The method comprises: applying the β-bromo-β-nitrostyrene compound according to any one of claims 1 to 4, the β-bromo-β-nitrostyrene compound prepared by the method according to claim 5 or 6 or the pesticide according to claim 7 to a plant; Preferably, the plant is at least one selected from rice, melon, fruit, pepper and rape; Preferably, the pathogenic fungi are at least one selected from Pyricularia oryzae, Pythium aphanidermatum, Botrytis cinerea, Fusarium graminearum, Rhizoctonia solani, Colletotrichum gloeosporioides, Phytophthora capsici, Mycosphaerella pinodes, Podosphaera xanthii and Sclerotinia sclerotiorum.