CN1869032A - Coumarin kind compound and its preparation and application - Google Patents

Abstract

The invention discloses a coumarin compound and its preparation and application. The compound is shown in the general formula I: see the description for the definition of each substituent. The compounds of the present invention have excellent fungicidal activity, they have systemic activity and can be used as foliage and soil fungicides, and can be used to prevent and control diseases on various crops, and are particularly suitable for preventing and controlling the following plant diseases: grape downy mildew, Rice sheath blight, rice blast, tomato early blight, tomato late blight, wheat rust, wheat leaf spot, wheat powdery mildew, cucumber powdery mildew, cucumber downy mildew, cucumber gray mold, etc. The compound of the present invention also has good insecticidal activity and can be used to prevent and control pests on various crops. For example, it can be used to control armyworm, diamondback moth, peach aphid, Tetranychus cinnabarinus, Tetranychus urticae, ladybugs, pest mites and Culex palustris.

Description

A kind of coumarin compound and its preparation and application

technical field

The invention belongs to the field of agricultural insecticides and fungicides. Specifically, it relates to a coumarin compound and its preparation and application.

Background technique

The natural products coumarin and methoxyacrylate compounds are known biologically active compounds. Document JP04-182461 once disclosed the compound of following general formula:

The structural chemistry of compound 51 disclosed in this patent is as follows:

Before the present invention, the Chinese patent (application number is 200310105079.6) that we apply for relates to the benzopyrone derivatives shown in the following general formula as insecticide, fungicide:

In the formula: A is CH or N; B is O, S or NR ₉ ; R ₈ is hydrogen or (C ₁ -C ₁₂ ) alkyl; R ₁ and R ₂ are hydrogen, C ₁ -C ₁₂ alkyl or halogen C ₁ -C ₁₂ alkyl; R ₃ is hydrogen, C ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkyl or C ₁ -C ₁₂ alkoxy; R ₄ , R ₅ , R ₆ , R ₇ and R ₈ can be the same or different, and are hydrogen, halogen, cyano, nitro, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, alkynyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkylthio, C ₁ -C ₁₂ alkanesulfonyl, C ₁ -C ₁₂ alkylcarbonyl, C ₁ -C ₁₂ alkoxy C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxycarbonyl, C ₁ -C ₁₂ alkoxycarbonyl C ₁ -C ₁₂ alkyl, C ₁ -C 12 haloalkoxy C _{1 -C 12 alkyl} , optionally substituted amino C ₁ - C ₁₂ alkyl, optionally substituted aryloxy, optionally substituted aryl C ₁ -C ₁₂ alkyloxy, optionally substituted aryl, heteroaryl, optionally substituted aryl C ₁ -C ₁₂ alkyl, hetero Aryl C ₁ -C ₁₂ alkyl, heteroaryl C ₁ -C ₁₂ alkoxy, and groups represented by the following general formula: Wherein, R ₁₀ and R ₁₁ are hydrogen, optionally substituted alkyl, optionally substituted aryl, or optionally substituted aryl(C ₁ -C ₁₂ )alkyl.

However, the compounds disclosed in the above patents do not fall within the present invention.

Contents of the invention

The object of the present invention is to provide a novel coumarin compound which can control various diseases and insect pests in a very small dose, which can be applied in agriculture to prevent and control crop diseases and insect pests.

Technical scheme of the present invention is as follows:

The present invention provides a kind of coumarin compound, as shown in general formula I:

In the formula:

Q is selected from one of the following groups:

When Q=Q ₁ , Q ₂ or Q ₃ , R ₁ is selected from hydrogen or chlorine, R ₂ is selected from substituted pyridine, or R ₁ and R ₂ are connected to form a five-membered or six-membered ring; R ₃ is selected from hydrogen, Halogen, cyano, nitro, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ Alkylthio, C ₁ -C ₁₂ Alkylsulfonyl, C ₁ -C ₁₂ Alkylcarbonyl, C 1 -C ₁₂ Alkoxy C ₁ -C ₁₂ Alkyl, C _{1 -C 12} Alkoxy Carbonyl, C ₁ -C ₁₂ alkoxycarbonyl C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkoxy C ₁ -C ₁₂ alkyl, optionally substituted amino C ₁ -C ₁₂ alkyl, optionally substituted Aryloxy, optionally substituted aryl C ₁ -C ₁₂ alkyloxy, optionally substituted aryl, heteroaryl, optionally substituted aryl C ₁ -C ₁₂ alkyl, heteroaryl C ₁ -C ₁₂ alkane Base, heteroaryl C ₁ -C ₁₂ alkoxy;

When Q= _Q4 , R ₁ , R ₂ , and R ₃ may be the same or different, and are selected from hydrogen, halogen, cyano, nitro, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, C ₁ -C ₁₂ haloalkyl, C _{1 -C 12} alkoxy, C ₁ -C 12 alkylthio, C ₁ -C ₁₂ alkanesulfonyl, C ₁ -C ₁₂ alkylcarbonyl , C ₁ -C ₁₂ alkoxy C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxycarbonyl, C ₁ -C ₁₂ alkoxycarbonyl C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkane Oxygen C ₁ -C ₁₂ alkyl, optionally substituted amino C ₁ -C ₁₂ alkyl, optionally substituted aryloxy, optionally substituted aryl C ₁ -C ₁₂ alkyloxy, optionally substituted aryl, hetero Aryl, optionally substituted aryl C ₁ -C ₁₂ alkyl, heteroaryl C ₁ -C ₁₂ alkyl, heteroaryl C ₁ -C ₁₂ alkoxy, or R ₁ and R ₂ are connected to form a five-membered or six-membered ring;

and its stereoisomers.

More preferred compounds in the present invention are: in general formula I

When Q=Q ₁ , Q ₂ or Q ₃ , R ₁ is selected from hydrogen or chlorine, R ₂ is selected from substituted pyridine, or R1 and R2 are connected to form a five-membered or six-membered ring; R3 is selected from hydrogen, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ ), alkoxycarbonyl C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkoxy C ₁ -C ₆ alkyl;

When Q= _Q4 , R ₁ , R ₂ , and R ₃ may be the same or different, and are selected from hydrogen, halogen, cyano, nitro, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ alkylcarbonyl , C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkoxycarbonyl C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkane Oxygen C ₁ -C ₆ alkyl, optionally substituted amino C ₁ -C ₆ alkyl, optionally substituted aryloxy, optionally substituted aryl C ₁ -C ₆ alkyloxy, optionally substituted aryl, hetero Aryl, optionally substituted aryl C ₁ -C ₆ alkyl, heteroaryl (C ₁ -C ₆ ) alkyl, heteroaryl C ₁ -C ₆ alkoxy, or R ₁ and R ₂ linked to form five or six-membered rings.

Further preferred compounds are: in general formula I

When Q=Q ₁ , Q ₂ or Q ₃ , R ₁ is selected from hydrogen or chlorine, R ₂ is selected from substituted pyridine, or R ₁ and R ₂ are connected to form a five-membered or six-membered ring, R ₃ is selected from hydrogen, Halogen, C ₁ -C ₆ alkyl;

When Q= _Q4 , R ₁ , R ₂ , and R ₃ may be the same or different, and are selected from hydrogen, chlorine, bromine, fluorine, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ - C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkanesulfonyl, C ₁ -C ₆ alkoxy C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkoxy C ₁ -C ₃ alkyl, substituted amino C ₁ -C ₃ alkyl, phenyl or substituted phenyl, benzyl or substituted benzyl, substituted pyridine, or R ₁ is linked to R ₂ into five- or six-membered rings.

A further preferred compound is: in general formula I

When Q=Q ₁ , Q ₂ or Q ₃ , R ₁ is selected from hydrogen, R ₂ is selected from chloropyridine or chloroalkoxypyridine, or R ₁ and R ₂ are connected to form a five-membered or six-membered ring, R ₃ is selected from hydrogen or methyl;

When Q= _Q4 , R ₁ , R ₂ , and R ₃ can be the same or different, and are selected from hydrogen, chlorine, bromine, fluorine, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, or R ₁ Linked with _R2 to form a five-membered or six-membered ring.

In the definition of compound I given above, the collective terms generally represent the following substituents:

The substituents in phenyl, phenoxy, benzyl and benzyloxy can be selected from hydrogen, alkyl, alkoxy, haloalkyl, haloalkoxy, halogen, nitro or CN, etc., and the number of substituents can be 1 ~5.

Halogen: refers to fluorine, chlorine, bromine and iodine.

Alkyl: straight chain or branched chain alkyl such as methyl, ethyl, propyl, isopropyl and tert-butyl.

Haloalkyl: Straight chain or branched chain alkyl in which hydrogen atoms may be partially or completely replaced by halogen atoms, for example, haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl group, difluoromethyl, trifluoromethyl.

Alkoxy: Straight or branched chain alkyl, bonded to the structure via an oxygen atom.

Halogenated alkoxy: Straight chain or branched alkoxy, the hydrogen atoms on these alkoxy can be partially or completely replaced by halogen atoms. For example, haloalkoxy such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy.

Alkenyl: Straight or branched chain with double bonds at any position, such as vinyl, allyl. Substituted alkenyl includes optionally substituted arylalkenyl.

Alkynyl: Straight chain or branched chain with triple bond at any position, such as ethynyl, propargyl. Substituted alkynyl groups include optionally substituted aralkynyl groups.

Aryl and the aryl moiety of arylalkyl, arylalkenyl, arylalkynyl, aryloxy or aryloxyalkyl include phenyl or naphthyl.

The heteroaryl group referred to in the present invention is a 5- or 6-membered ring containing one or more N, O, and S heteroatoms. For example pyridine, furan, pyrimidine, pyrazine, pyridazine, triazine, quinoline or benzofuran.

In the compounds of the present invention, stereoisomers (Z and E represent different configurations) can be formed due to different substituents linked by carbon-carbon double bonds and carbon-nitrogen double bonds. The compounds of the present invention include Z-isomers and E-isomers and mixtures thereof in any ratio.

The compounds listed in Table I below may be used to illustrate, but not limit, the invention.

Table 1

serial number R ₁ R ₂ R ₃ Q 1 h h h Q ₄ 2 h _CH3 h Q ₄ 3 h _{CH3 CH3} Q ₄ 4 h C ₆ H _{5 CH3} Q ₄ 5 _{CH3 CH3} h Q ₄ 6 _{CH3 CH3 CH3} Q ₄ 7 h CF ₃ h Q ₄ 8 h _CH3 h Q ₄ 9 h _CH3 h Q ₄ 10 Cl _CH3 h Q ₄ 11 h _CH2Cl h Q ₄ 12 Cl _CH2Cl h Q ₄ 13 Cl CH ₂ OCH ₃ h Q ₄ 14 Cl CH ₂ CH ₃ h Q ₄ 15 h CH ₂ CH _{3 CH3} Q ₄ 16 C ₂ H _{5 CH3} h Q ₄ 17 h CH ₂ OCH ₃ h Q ₄ 18 h _{CH2OC2H5 _ _} h Q ₄ 19 Cl _{CH2OC2H5 _ _} h Q ₄ 20 OCH ₃ CH ₂ OCH ₃ h Q ₄ twenty one N(CH ₃ ) _{2 CH3} h Q ₄ twenty two CN h h Q ₄ twenty three Cl _{CH3 CH3} Q ₄ twenty four h CH(CH ₃ ) ₂ h Q ₄ 25 C ₃ H _{7 CH3} h Q ₄ 26 nC ₄ H _{9 CH3} h Q ₄ 27 h tC ₄ H ₉ h Q ₄ 28 h 4-Cl-C ₆ H ₄ h Q ₄ 29 Cl 4-Cl-C ₆ H ₄ h Q ₄ 30 h 4-Cl-C ₆ H _{4 CH3} Q ₄ 31 Cl C ₆ H ₅ h Q ₄ 32 h CH ₂ CH ₃ h Q ₄ 33 h _{CH2C2H5 _ _} h Q ₄ 34 h _{CH2C2H5 _ _ CH3} Q ₄ 35 Cl _{CH2C2H5 _ _} h Q ₄ 36 _{CH3 CH2C2H5 _ _} h Q ₄ 37 h 4-FC ₆ H ₄ h Q ₄ 38 Cl 4-FC ₆ H ₄ h Q ₄ 39 h 4-FC ₆ H _{4 CH3} Q ₄ 40 h 4-CF ₃ -C ₆ H ₄ h Q ₄ 41 Cl 4-CF ₃ -C ₆ H ₄ h Q ₄ 42 Cl CH ₂ N(CH ₃ ) ₂ h Q ₄ 43 OCH ₃ C ₂ H ₅ h Q ₄ 44 OCH _{3 CH3} h Q ₄ 45 OC ₂ H _{5 CH3} h Q ₄ 46 h CH ₂ OCH ₂ CF ₃ h Q ₄ 47 Cl CH ₂ OCH ₂ CF ₃ h Q ₄ 48 F CF ₃ h Q ₄ 49 F _CH3 h Q ₄ 50 h CH ₂ N(CH ₃ ) ₂ h Q ₄ 51 h C ₆ H ₅ h Q ₄ 52 Cl nC ₄ H ₉ h Q ₄ 53 F nC ₄ H ₉ h Q ₄ 54 h _{CH2OCH2C6H5 _ _ _} h Q ₄ 55 OCH ₃ 4-Cl-C ₆ H ₅ h Q ₄ 56 F 4-Cl-C ₆ H ₅ h Q ₄ 57 CH ₃ S _CH3 h Q ₄ 58 _{CH3SO2 _ CH3} h Q ₄ 59 C ₂ H _{5 CH2C2H5 _ _} h Q ₄ 60 _{CH3SO2 _ CH2C2H5 _ _} h Q ₄ 61 h 4-NO ₂ -C ₆ H ₅ h Q ₄ 62 Cl 4-NO ₂ -C ₆ H ₅ h Q ₄ 63 h 4-NO ₂ -C ₆ H _{5 CH3} Q ₄ 64 _{PhCH2 CH3} h Q ₄ 65 _{PhCH2 CH3 CH3} Q ₄ 66 CF ₃ CH ₂ O C ₃ H ₇ h Q ₄ 67 h CH ₂ -Ph-4-Cl h Q ₄ 68 _CH3 CH ₂ -Ph-4-Cl h Q ₄ 69 C ₂ H ₅ CH ₂ -Ph-4-Cl h Q ₄ 70 CH ₂ -Ph-4-Cl _CH3 h Q ₄ 71 CH ₂ -Ph-4-Cl C ₂ H ₅ h Q ₄ 72 CH ₂ -Ph-4-Cl C ₃ H ₇ h Q ₄ 73 _CH3 CF ₃ h Q ₄ 74 Cl CF ₃ h Q ₄ 75 C ₂ H ₅ CF ₃ h Q ₄ 76 nC ₃ H ₇ CF ₃ h Q ₄ 77 nC ₄ H ₉ CF ₃ h Q ₄ 78 h _{CH2CH2 -} Ph-4-Cl h Q ₄ 79 _{CH2C2H5 _ _ CH2C2H5 _ _} h Q ₄ 80 h CH ₂ Bu h Q ₄ 81 _CH3 CH ₂ Bu h Q ₄ 82 nC ₃ H ₇ CH ₂ Bu h Q ₄ 83 CH ₂ Bu-t _CH3 h Q ₄ 84 _{CH2CH2 -} Ph-4-Cl _CH3 h Q ₄ 85 _{CH2CH2 -} Ph-4-Cl C ₂ H ₅ h Q ₄ 86 _{CH2CH2 -} Ph-4-Cl C ₃ H ₇ h Q ₄ 87 h 6-Cl-Pyridin-3-yl h Q ₁ 88 h 6-OCH ₂ CF ₃ -Pyridin-3-yl h Q ₁ 89 h 6-Cl-Pyridin-3-yl h Q ₂ 90 h 6-OCH ₂ CF ₃ -Pyridin-3-yl h Q ₂ 91 h 6-Cl-Pyridin-3-yl h Q ₃ 92 h 6-OCH ₂ CF ₃ -Pyridin-3-yl h Q ₃ 93 h 6-Cl-Pyridin-3-yl h Q ₄ 94 h 6-OCH ₂ CF ₃ -Pyridin-3-yl h Q ₄ 95 _{CH2CH2CH2 _ _} h Q ₄ 96 _{CH2CH2CH2 _ _ CH3} Q ₄ 97 _{CH2CH2CH2CH2 _ _ _} h Q ₄ 98 _{CH2CH2CH2CH2 _ _ _ CH3} Q ₄ 99 _{CH2CH2CH2 _ _} h Q ₁ 100 _{CH2CH2CH2 _ _ CH3} Q ₁ 101 _{CH2CH2CH2CH2 _ _ _} h Q ₁ 102 _{CH2CH2CH2CH2 _ _ _ CH3} Q ₁ 103 _{CH2CH2CH2 _ _} h Q ₂ 104 _{CH2CH2CH2 _ _ CH3} Q ₂ 105 _{CH2CH2CH2CH2 _ _ _} h Q ₂ 106 _{CH2CH2CH2CH2 _ _ _ CH3} Q ₂ 107 _{CH2CH2CH2 _ _} h Q ₃ 108 _{CH2CH2CH2 _ _ CH3} Q ₃ 109 _{CH2CH2CH2CH2 _ _ _} h Q ₃ 110 _{CH2CH2CH2CH2 _ _ _ CH3} Q ₃

The present invention also includes a preparation method of the compound of general formula I: the compound of general formula I is prepared by reacting the benzyl halide shown in formula II and the hydroxyl-containing coumarin compound shown in formula III under alkaline conditions:

Reaction 1:

In the formula: Q, R ₁ , R ₂ , R ₃ are as defined above, and Z is a leaving group, such as halogen (chlorine, bromine or iodine).

The compound of general formula I can be prepared in this way: in a suitable solvent, treat the 7-hydroxycoumarin compound shown in general formula III with a suitable base to form a salt, then add the compound of formula II, and react at an appropriate temperature After a certain period of time, the target product can be obtained after treatment.

Suitable solvents can be selected from tetrahydrofuran, acetonitrile, toluene, xylene, benzene, N,N-dimethylformamide, dimethyl sulfoxide, acetone or butanone, and the like.

Suitable bases may be selected from potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine or sodium hydride and the like.

The appropriate temperature refers to the temperature from room temperature to the boiling point of the solvent, usually 20-100°C.

The reaction time is 30 minutes to 20 hours, usually 1 to 10 hours.

The compound represented by general formula II can be prepared by known methods, see patents US4723034, US5554578, US6054592 and so on.

The 7-hydroxycoumarin compounds represented by the general formula III can refer to the literature J Med Chem.2001, 44: 664-671; Natural Product Research, 2003, 17 (2): 115-125; Chemistry of Natural Compounds, 2002 , 38(6): 532-538, etc. are prepared by reacting R ₂ COCHR ₁ CO ₂ CH ₃ (C ₂ H ₅ ) with substituted resorcinol in a suitable condensing agent (such as concentrated sulfuric acid, trifluoroacetic acid) have to.

The compounds of the present invention have excellent fungicidal activity, they have systemic activity and can be used as foliage and soil fungicides, and can be used to prevent and control diseases on various crops, and are particularly suitable for preventing and controlling the following plant diseases: grape downy mildew, Rice sheath blight, rice blast, tomato early blight, tomato late blight, wheat rust, wheat leaf spot, wheat powdery mildew, cucumber powdery mildew, cucumber downy mildew, cucumber gray mold, etc.

The compound of the present invention also has good insecticidal activity and can be used to prevent and control pests on various crops. For example, it can be used to control armyworm, diamondback moth, peach aphid, Tetranychus cinnabarinus, Tetranychus urticae, ladybugs, pest mites and Culex palustris. It has special effects on ladybugs and culex, and is especially suitable for the integrated control of pests.

The present invention also provides an insecticidal and bactericidal composition, which contains the compound of general formula I and an agriculturally acceptable carrier, and the weight percentage of active components in the composition is 0.1-99%.

The composition of the present invention may contain a single compound represented by general formula I or a mixture of several compounds.

The carrier in the composition of the present invention satisfies the following conditions: it is convenient to apply to the site to be treated after being formulated with the active ingredient, for example, it can be a plant, seed or soil; or it is convenient for storage, transportation or handling. Carriers can be solid or liquid, including substances that are usually gaseous but compressed into liquids. Carriers that are usually used in the preparation of insecticidal and fungicidal compositions can be used.

Suitable solid carriers include natural and synthetic clays and silicates such as diatomaceous earth, talc, attapulgite, aluminum silicate (kaolin), montmorillonite and mica; calcium carbonate; calcium sulfate; ammonium sulfate; Silicon and synthetic calcium or aluminum silicates; elements such as carbon and sulfur; natural and synthetic resins such as benzofuran resins, polyvinyl chloride and styrene polymers and copolymers; solid polychlorinated phenols; bitumen; waxes such as Beeswax, paraffin.

Suitable liquid carriers include water; alcohols such as isopropanol and ethanol; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexyl ketone; ethers; aromatic hydrocarbons such as benzene, toluene, xylene; and mineral oil; chlorinated hydrocarbons such as carbon tetrachloride, perchlorethylene and trichlorethylene. Often, mixtures of these liquids are also suitable.

Insecticidal and fungicidal compositions are usually processed and transported in the form of concentrates, which are diluted by the user before application. The presence of a small amount of surfactant carrier aids in the dilution process. Thus, at least one carrier in compositions according to the invention is preferably a surfactant. For example the composition may contain at least two carriers, at least one of which is a surfactant.

A surfactant can be an emulsifying agent, a dispersing agent or a wetting agent; it can be a nonionic or an ionic surfactant. Examples of suitable surfactants include sodium or calcium salts of polyacrylic acid and lignosulfonic acid; condensation of fatty acids or fatty amines or amides with at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide things. Glycol, sorbitol, sucrose or pentaerythritol fatty acid esters and condensates of these esters with ethylene oxide and/or propylene oxide; fatty alcohols or alkylphenols such as p-octylphenol or p-octylcresol with epoxy Condensates of ethane and/or propylene oxide; sulfates and sulfonates of these condensation products; alkali metal or alkaline earth metal salts, preferably sodium salts, of sulfuric acid or sulfonates containing at least 10 carbon atoms in the molecule, For example, sodium laurate sulfate, sodium secondary alkyl sulfate, sodium sulfonated castor oil, sodium alkylaryl sulfonate, such as sodium dodecylbenzenesulfonate.

Examples of compositions according to the invention are wettable powders, powders, granules and solutions, emulsifiable concentrates, emulsions, suspension concentrates, aerosols and aerosols. Wettable powders usually contain 25, 50 or 75% by weight of active ingredients, and usually in addition to solid inert carriers, also contain 3-10% by weight of dispersants, and if necessary, 0-10% by weight of stabilizers and/or Or other additives such as penetrants or adhesives. Dusts can generally be formed as powder concentrates having a composition similar to wettable powders but without dispersants, which can be further diluted with a solid carrier to give compositions generally containing 0.5-10% by weight of active ingredient. Granules are usually prepared to have a size of 10 to 100 mesh (1.676-0.152 mm), and may be prepared by agglomeration or injection techniques. Usually granules contain 0.5-75% by weight of active ingredient and 0-10% by weight of additives such as stabilizers, surfactants, sustained-release modifiers. So-called "dry flowable powders" consist of relatively small granules having a relatively high concentration of active ingredient. Emulsifiable concentrates usually contain, in addition to solvents, co-solvents when required, 1-50% W/V active ingredients, 2-20% W/V emulsifiers and 0-20% W/V other additives such as stabilizers, penetrants agents and corrosion inhibitors. Suspension concentrates generally contain 10-75% by weight of active ingredient, 0.5-15% by weight of dispersant, 0.1-10% by weight of other additives such as defoamers, corrosion inhibitors, stabilizers, penetrants and adhesives.

Aqueous dispersions and emulsions, such as compositions obtained by diluting the wettable powders or concentrates according to the invention with water, are also within the scope of the invention. Said emulsions may be of the water-in-oil or oil-in-water type.

By adding one or more other fungicides to the composition, it can have a wider spectrum of activity than the compound of general formula I alone. Furthermore, other fungicides may have a synergistic effect on the fungicidal activity of the compounds of general formula I. It is also possible to mix the compound of general formula I with other insecticides, or simultaneously with another fungicide and other insecticides.

Detailed ways

The following specific examples are used to further illustrate the present invention.

Synthetic example

The preparation of example 1 compound 5

At room temperature, 0.2 g of 60% sodium hydride was added to the reaction flask, washed with petroleum ether, 30 ml of dry N,N-dimethylformamide was added thereto, stirred for half an hour, and 0.5 g of compound (III -1), continue to stir until no gas is released, add 0.8 g of compound (II-1), and continue to stir for 3 hours. The reaction mixture was poured into ice water, extracted three times with ethyl acetate, the combined extracts were washed three times with saturated brine, dried, filtered, and concentrated under reduced pressure to obtain 5 g of oily liquid. Column chromatography obtained 0.68 g of the title compound as a light yellow solid product, with a yield of 68%. Melting point: 131-133°C.

NMR data ( ¹ HNMR, 300MHz, internal standard TMS, solvent CDCl ₃ ) are as follows:

δppm 2.18(3H, s), 2.36(3H, s), 3.77(3H, s), 3.83(3H, s), 5.17(2H, s), 6.84-6.85(1H, d), 6.89-6.92(1H , m), 7.39 (3H, m), 7.48 (1H, m), 7.51 (1H, m).

The preparation of example 2 compound 49

At room temperature, the mixed solution containing 0.85 gram of anhydrous potassium carbonate, 0.6 gram of compound (III-2), 0.93 gram of compound (II-1) in 20 ml of butanone was heated under reflux and stirred for 5 hours, and the reaction mixture was poured into Extracted in ice water three times with ethyl acetate, combined the extracts, washed three times with saturated brine, dried, filtered, and concentrated under reduced pressure to obtain a yellow solid as a crude product. Column chromatography with a mixture of ethyl acetate and petroleum ether (1:2) yielded 0.89 g of the title compound as a solid, with a yield of 75%. Melting point: 83-85°C.

NMR data ( ¹ HNMR, 300MHz, internal standard TMS, solvent CDCl ₃ ) are as follows:

δppm 2.37(3H, s), 3.77(3H, s), 3.84(3H, s), 5.18(2H, s), 6.88-6.89(1H, d), 7.39(1H, m), 7.41(3H, m ), 7.45(1H, m), 7.48(1H, m).

The preparation of example 3 compound 106

At room temperature, the mixed solution containing 0.3 gram of anhydrous potassium carbonate, 0.22 gram of compound (III-3), 0.30 gram of compound (II-2) in 10 ml of butanone was heated under reflux and stirred for 5 hours, and the reaction mixture was poured into Extracted in ice water three times with ethyl acetate, combined the extracts, washed three times with saturated brine, dried, filtered, and concentrated under reduced pressure to obtain a yellow solid as a crude product. Column chromatography with a mixture of ethyl acetate and petroleum ether (1:2) gave 0.18 g of the title compound as a solid.

The preparation of example 4 compound 110

Stir 0.52 g of compound 106 and twice the molar ratio of methylamine in 50 ml of methanol at room temperature overnight, concentrate and extract twice with ethyl acetate, wash the combined extracts with water three times, then wash twice with saturated brine, and dry , filtered and concentrated to obtain 0.48 g of the title compound. Yield 92%.

Other compounds were synthesized according to the above method.

The physical properties and NMR data ( ¹ HNMR, 300MHz, internal standard TMS, solvent CDCl ₃ ) of some compounds are as follows:

Compound 6: The melting point is 144-146°C. δppm 2.19(3H, s), 2.36(3H, s), 3.40(3H, s), 3.76(3H, s), 3.83(3H, s), 5.21(2H, s), 6.87-6.88(1H, d ), 7.36-7.40 (4H, m), 7.41 (1H, m).

Compound 10: The melting point is 139-141°C. δppm 2.55(3H,s), 3.77(3H,s), 3.83(3H,s), 5.19(2H,s), 6.87-6.88(1H,d), 6.99(1H,dd), 7.39-7.41(3H , m), 7.52-7.54 (2H, m).

Compound 26: oil δppm 0.94 (3H, t), 1.44 (4H, m), 2.37 (3H, s), 2.63 (2H, t), 3.76 (3H, s), 3.81 (3H, s) 5.17 (2H , s), 6.83-6.84 (1H, d), 6.89-6.92 (1H, dd), 7.39 (3H, m), 7.48-7.51 (1H, d), 7.57 (1H, m).

Compound 95: The melting point is 177-179°C. δppm 2.20(2H, m), 2.89(2H, t), 3.04(2H, t), 3.77(3H, s), 3.83(3H, s), 5.18(2H, s), 6.91(2H, m), 7.33 (1H, m), 7.38 (3H, m), 7.57 (1H, m).

Compound 96: The melting point is 150-151°C. δppm 2.19(2H, t), 2.42(3H, s), 2.90(2H, t), 3.02(2H, t), 3.75(3H, s), 3.82(3H, s), 5.21(2H, s), 6.85 (1H, d), 7.23 (1H, m), 7.39 (3H, m), 7.62 (1H, m).

Compound 97: The melting point is 160-161°C. δppm 1.82(4H, m), 2.57(2H, t), 2.73(2H, t), 3.77(3H, s), 3.83(3H, s), 5.17(2H, s), 6.85(1H, d), 6.84 (1H, dd), 7.39 (3H, m), 7.44 (1H, m), 7.57 (1H, m).

Compound 98: The melting point is 167-169°C. δppm 1.81(4H, m), 2.39(3H, s), 2.57(2H, t), 2.74(2H, t), 3.75(3H, s), 3.82(3H, s), 5.20(2H, s), 6.84 (1H, d), 7.34 (1H, d), 7.39 (3H, m), 7.62 (1H, m).

Compound 99: The melting point is 140-142°C. δppm 2.21(2H, m), 2.89(2H, t), 3.03(2H, t), 3.76(3H, s), 3.85(3H, s), 5.06(2H, s), 6.85(2H, m), 7.23 (1H, m), 7.36 (3H, m), 7.55 (1H, m), 7.61 (1H, s).

Compound 100: The melting point is 190-192°C. δppm 2.21(2H, t), 2.87(3H, s), 2.92(2H, t), 3.02(2H, m), 3.71(3H, s), 3.84(3H, s), 5.07(2H, s), 6.75 (1H, d), 7.20 (2H, m), 7.33 (2H, m), 7.53 (1H, m), 7.61 (1H, s).

Compound 101: The melting point is 114-116°C. δppm 1.82(4H, m), 2.57(2H, t), 2.73(2H, t), 3.73(3H, s), 3.88(3H, s), 5.02(2H, s), 6.81(1H, d), 6.87 (1H, dd), 7.20 (1H, m), 7.36 (2H, m), 7.44 (1H, m), 7.53 (1H, m), 7.63 (1H, s).

Compound 102: The melting point is 170-172°C. δppm 1.81(4H, m), 2.36(3H, s), 2.57(2H, t), 2.73(2H, t), 3.71(3H, s), 3.84(3H, s), 5.07(2H, s), 6.75 (1H, d), 7.19 (1H, m), 7.34 (3H, m), 7.53 (1H, m), 7.61 (1H, s).

Preparation Examples (the addition of active components in the formula is metered after 100 percent, and all percentages are percentages by weight)

Example 5 40% EC

Compound 5 (content 97.6%) 40%

Phosphorous acid 10%

Ethoxylated Triglycerides 15%

Cyclohexanone make up to 100%

Phosphorous acid was dissolved in cyclohexanone, and compound 5 and ethoxylated triglyceride were added to obtain a clear solution.

Example 6 60% wettable powder

Compound 6 (content 98.4%) 60%

Sodium dodecyl naphthalene sulfonate 2%

Sodium Lignosulfonate 9%

Kaolin to make up to 100%

The components (all solids) were mixed together and pulverized in a pulverizer until the granules were on par.

Example 7 40% aqueous suspension

Compound 26 (content 97.6%) 40%

Sodium dodecyl naphthalene sulfonate 4%

Hemicellulose 2%

Propylene oxide 8%

Water make up to 100%

Compound 26 was pulverized in a ball mill (1 mm beads) with 80% addition of water and sodium dodecyl naphthalenesulfonate. The other ingredients were dissolved in the remaining water and then the other ingredients were added with stirring.

Example 8 25% suspension-emulsion concentrate

Compound 98 (content 96.2%) 25%

Lauryl Alcohol Polyethylene Glycol Phosphate (Emulsifier 1) 4%

Ethoxylated Triglycerides (Emulsifier 2) 2%

Calcium dodecylbenzenesulfonate (emulsifier 3) 1.5%

Methylene oxide ethylene oxide copolymer (dispersant) 2.5%

Cyclohexanone (Solvent 1) 30%

Alkylaryl fraction (boiling point > 200°C) (solvent 2) Make up to 100%

Compound 98 was dissolved in 80% solvent, then emulsifier and dispersant were added, and the mixture was stirred thoroughly. The mixture was pulverized in a ball mill (1 mm beads) before adding the rest of the solvent.

Bioactivity assay

Example 9 Determination of Bactericidal Activity

Various fungal diseases of plants were tested with the compounds of the present invention. The test method is as follows:

The living pot method was adopted. The original drug of the compound to be tested was dissolved in a small amount of acetone, and diluted to the required concentration with water containing 0.1% Tween 80. Spray application on the plant test material, and carry out disease inoculation 24 hours later. After inoculation, the plants are placed in a constant temperature and humidity incubator to allow the infection to continue, and the evaluation and investigation will be carried out after the control is fully diseased (usually within a week).

Some test results are as follows:

When 400ppm, to cucumber downy mildew (Pseudoperonospora cubenis) control effect is 100% have compound 5,99,101 etc.; Control effect greater than 90% has compound 6,10 etc.; 98 etc.

At 400ppm, compounds 97, 99, etc. have 100% control effect on Botrytis cinerea; compound 101, etc. have control effect greater than 85%.

Compounds 6 and 26 have a control effect of more than 85% on rice sheath blight (Rhizoctonia solani) at 200 ppm.

At 200ppm, the control effect on wheat powdery mildew (BLumeria graminis) is 100% with compounds 5, 101, etc.; greater than 95% with compound 10, etc.

Bioactivity assay

Example 10 Determination of insecticidal and acaricidal activity

Insecticidal activity tests were carried out on several insects and acarids using the compounds of the present invention. The method of determination is as follows:

After the new compound was dissolved in a mixed solvent of acetone/methanol (1:1), it was diluted to the desired concentration with water containing 0.1% Tween 80.

Targeting armyworm (Leucania separata), diamondback moth (Plutella xylostella) and 2nd instar larvae of Culex pippenspallens, green peach aphid (Myzus persicae), and cinnabar spider mite (Tetranychus cinnabarinus) using airbrush spray and immersion Insecticidal activity was determined by the method (Culex larvae), the pressure of the airbrush spray treatment was 10psi (about 0.7kg/cm ² ), and the spray volume was 0.5ml. Mortality of the target was investigated 2-3 days after treatment.

Some test results are as follows:

When the concentration of the drug solution is 600ppm, the mortality rate of the compound 99 etc. to the tested target Culex pisciatus reaches 100%.

When the concentration of the drug solution is 600ppm, compound 98 also shows considerable activity against armyworm, diamondback moth and green peach aphid, which is greater than 50%.

Claims (8)

1. A coumarin compound, as shown in general formula I: In the formula: Q is selected from one of the following groups: When Q=Q ₁ , Q ₂ or Q ₃ , R ₁ is selected from hydrogen or chlorine, R ₂ is selected from substituted pyridine, or R ₁ and R ₂ are connected to form a five-membered or six-membered ring; R ₃ is selected from hydrogen, Halogen, cyano, nitro, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, C ₁ -C ₁₂ haloalkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ Alkylthio, C ₁ -C ₁₂ Alkylsulfonyl, C ₁ -C ₁₂ Alkylcarbonyl, C ₁ -C ₁₂ Alkoxy C ₁ -C ₁₂ Alkyl, C ₁ -C ₁₂ Alkoxy Carbonyl, C ₁ -C ₁₂ alkoxycarbonyl C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkoxy C ₁ -C ₁₂ alkyl, optionally substituted amino C ₁ -C ₁₂ alkyl, optionally substituted Aryloxy, optionally substituted aryl C ₁ -C ₁₂ alkyloxy, optionally substituted aryl, heteroaryl, optionally substituted aryl C ₁ -C ₁₂ alkyl, heteroaryl C ₁ -C ₁₂ alkane Base, heteroaryl C ₁ -C ₁₂ alkoxy; When Q= _Q4 , R ₁ , R ₂ , and R ₃ may be the same or different, and are selected from hydrogen, halogen, cyano, nitro, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, C ₁ -C ₁₂ haloalkyl, C _{1 -C 12} alkoxy, C ₁ -C 12 alkylthio, C ₁ -C ₁₂ alkanesulfonyl, C ₁ -C ₁₂ alkylcarbonyl , C ₁ -C ₁₂ alkoxy C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxycarbonyl, C ₁ -C ₁₂ alkoxycarbonyl C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkane Oxygen C ₁ -C ₁₂ alkyl, optionally substituted amino C ₁ -C ₁₂ alkyl, optionally substituted aryloxy, optionally substituted aryl C ₁ -C ₁₂ alkyloxy, optionally substituted aryl, hetero Aryl, optionally substituted aryl C ₁ -C ₁₂ alkyl, heteroaryl C ₁ -C ₁₂ alkyl, heteroaryl C ₁ -C ₁₂ alkoxy, or R ₁ and R ₂ are connected to form a five-membered or six-membered ring; and its stereoisomers. 2. The compound according to claim 1, characterized in that: in general formula I When Q=Q ₁ , Q ₂ or Q ₃ , R ₁ is selected from hydrogen or chlorine, R ₂ is selected from substituted pyridine, or R1 and R2 are connected to form a five-membered or six-membered ring; R3 is selected from hydrogen, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ ), alkoxycarbonyl C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkoxy C ₁ -C ₆ alkyl; When Q= _Q4 , R ₁ , R ₂ , and R ₃ may be the same or different, and are selected from hydrogen, halogen, cyano, nitro, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ alkylcarbonyl , C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkoxycarbonyl C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkane Oxygen C ₁ -C ₆ alkyl, optionally substituted amino C ₁ -C ₆ alkyl, optionally substituted aryloxy, optionally substituted aryl C ₁ -C ₆ alkyloxy, optionally substituted aryl, hetero Aryl, optionally substituted aryl C ₁ -C ₆ alkyl, heteroaryl (C ₁ -C ₆ ) alkyl, heteroaryl C ₁ -C ₆ alkoxy, or R ₁ and R ₂ linked to form five or six-membered rings. 3. The compound according to claim 2, characterized in that: in general formula I When Q=Q ₁ , Q ₂ or Q ₃ , R ₁ is selected from hydrogen or chlorine, R ₂ is selected from substituted pyridine, or R ₁ and R ₂ are connected to form a five-membered or six-membered ring, R ₃ is selected from hydrogen, Halogen, C ₁ -C ₆ alkyl; When Q= _Q4 , R ₁ , R ₂ , and R ₃ may be the same or different, and are selected from hydrogen, chlorine, bromine, fluorine, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ - C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkanesulfonyl, C ₁ -C ₆ alkoxy C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkoxy C ₁ -C ₃ alkyl, substituted amino C ₁ -C ₃ alkyl, phenyl or substituted phenyl, benzyl or substituted benzyl, substituted pyridine, or R ₁ is linked to R ₂ into five- or six-membered rings. 4. The compound according to claim 3, characterized in that: in general formula I When Q=Q ₁ , Q ₂ or Q ₃ , R ₁ is selected from hydrogen, R ₂ is selected from chloropyridine or chloroalkoxypyridine, or R ₁ and R ₂ are connected to form a five-membered or six-membered ring, R ₃ is selected from hydrogen or methyl; When Q= _Q4 , R ₁ , R ₂ , and R ₃ can be the same or different, and are selected from hydrogen, chlorine, bromine, fluorine, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, or R ₁ Linked with _R2 to form a five-membered or six-membered ring. 5. The compound according to any one of claims 1-4, characterized in that: the compound of general formula I is composed of benzyl halide shown in formula II and hydroxyl-containing coumarin compound shown in formula III in base React under neutral conditions to obtain:

In the formula, Z is a leaving group selected from chlorine, bromine or iodine. 6. The use of the compound as claimed in claim 1 in controlling pests on crops. 7. The application of the compound as claimed in claim 1 in the control of pathogens on crops. 8. An insecticidal and bactericidal composition, characterized in that: the composition contains the compound of formula I as claimed in claim 1, and the weight percentage of the active ingredient is 0.1-99%.