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

Coumarin kind compound and its preparation and application Download PDF

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CN1869032A
CN1869032A CNA2005100465141A CN200510046514A CN1869032A CN 1869032 A CN1869032 A CN 1869032A CN A2005100465141 A CNA2005100465141 A CN A2005100465141A CN 200510046514 A CN200510046514 A CN 200510046514A CN 1869032 A CN1869032 A CN 1869032A
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alkyl
alkoxy
hydrogen
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刘长令
李淼
关爱莹
张弘
李志念
叶天降
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Shenyang Research Institute of Chemical Industry Co Ltd
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Shenyang Research Institute of Chemical Industry Co Ltd
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Abstract

A coumarin-type compound with excellent bactericiding activity can be used to prevent and eliminate various diseases and pests of different agricultural crops, such as frosty mildew, rice blast, armyworm, plutella xylostella, etc. Its preparing process is also disclosed.

Description

A kind of coumarin kind compound and preparation thereof and application
Technical field
The invention belongs to agricultural insecticidal, sterilant field.Relate in particular to a kind of coumarin kind compound and preparation thereof and application.
Background technology
Natural product tonka bean camphor and methoxy acrylate compound all are compounds of known biologically active.Document JP 04-182461 once disclosed the compound of following general formula:
Figure A20051004651400041
The structural chemistry of disclosed compound 51 is as follows in this patent:
Before the present invention, the Chinese patent (application number is 200310105079.6) of our application relates to the benzopyrone analog derivative shown in the following general formula as desinsection, sterilant:
Figure A20051004651400043
In the formula: A is CH or N; B is O, S or NR 9R 8Be hydrogen or (C 1-C 12) alkyl; R 1, R 2Be hydrogen, C 1-C 12Alkyl or halo C 1-C 12Alkyl; R 3Be hydrogen, C 1-C 12Alkyl, halo C 1-C 12Alkyl or C 1-C 12Alkoxyl group; R 4, R 5, R 6, R 7, R 8Can be identical or different, be hydrogen, halogen, cyano group, nitro, C 1-C 12Alkyl, C 2-C 12Thiazolinyl, alkynyl, C 1-C 12Haloalkyl, C 1-C 12Alkoxyl group, C 1-C 12Alkylthio, C 1-C 12Alkane alkylsulfonyl, C 1-C 12Alkyl-carbonyl, C 1-C 12Alkoxy C 1-C 12Alkyl, C 1-C 12Alkoxy carbonyl, C 1-C 12Alkoxy carbonyl C 1-C 12Alkyl, C 1-C 12Halogenated alkoxy C 1-C 12Alkyl, any substituted amido C 1-C 12Alkyl, the aryloxy that replaces arbitrarily, any fragrant C that replaces 1-C 12Alkyl oxy, the aryl that replaces arbitrarily, heteroaryl, any aryl C that replaces 1-C 12Alkyl, heteroaryl C 1-C 12Alkyl, heteroaryl C 1-C 12The group that alkoxyl group and following general formula are represented: Wherein, R 10, R 11Be hydrogen, the alkyl that replaces arbitrarily, the aryl that replaces arbitrarily, any aryl (C that replaces 1-C 12) alkyl.
But the disclosed compound of above-mentioned patent does not fall into the present invention.
Summary of the invention
The object of the present invention is to provide a kind of novel coumarin compounds that just can control various disease and pests under very little dosage, it can be applicable to agricultural and goes up to prevent and treat disease and the insect pest of crop.
Technical scheme of the present invention is as follows:
The invention provides a kind of coumarin kind compound, shown in general formula I:
In the formula:
Q is selected from one of following group:
Figure A20051004651400052
Work as Q=Q 1, Q 2Or Q 3The time, R 1Be selected from hydrogen or chlorine, R 2Be selected from the pyridine of replacement, or R 1With R 2Be connected to five yuan or six-ring; R 3Be selected from hydrogen, halogen, cyano group, nitro, C 1-C 12Alkyl, C 2-C 12Thiazolinyl, C 2-C 12Alkynyl, C 1-C 12Haloalkyl, C 1-C 12Alkoxyl group, C 1-C 12Alkylthio, C 1-C 12Alkane alkylsulfonyl, C 1-C 12Alkyl-carbonyl, C 1-C 12Alkoxy C 1-C 12Alkyl, C 1-C 12Alkoxy carbonyl, C 1-C 12Alkoxy carbonyl C 1-C 12Alkyl, C 1-C 12Halogenated alkoxy C 1-C 12Alkyl, any substituted amido C 1-C 12Alkyl, the aryloxy that replaces arbitrarily, any fragrant C that replaces 1-C 12Alkyl oxy, the aryl that replaces arbitrarily, heteroaryl, any aryl C that replaces 1-C 12Alkyl, heteroaryl C 1-C 12Alkyl, heteroaryl C 1-C 12Alkoxyl group;
Work as Q=Q 4The time, R 1, R 2, R 3Can be identical or different, be selected from hydrogen, halogen, cyano group, nitro, C respectively 1-C 12Alkyl, C 2-C 12Thiazolinyl, C 2-C 12Alkynyl, C 1-C 12Haloalkyl, C 1-C 12Alkoxyl group, C 1-C 12Alkylthio, C 1-C 12Alkane alkylsulfonyl, C 1-C 12Alkyl-carbonyl, C 1-C 12Alkoxy C 1-C 12Alkyl, C 1-C 12Alkoxy carbonyl, C 1-C 12Alkoxy carbonyl C 1-C 12Alkyl, C 1-C 12Halogenated alkoxy C 1-C 12Alkyl, any substituted amido C 1-C 12Alkyl, the aryloxy that replaces arbitrarily, any fragrant C that replaces 1-C 12Alkyl oxy, the aryl that replaces arbitrarily, heteroaryl, any aryl C that replaces 1-C 12Alkyl, heteroaryl C 1-C 12Alkyl, heteroaryl C 1-C 12Alkoxyl group, or R 1With R 2Be connected to five yuan or six-ring;
And steric isomer.
Comparatively preferred compound is among the present invention: in the general formula I
Work as Q=Q 1, Q 2Or Q 3The time, R 1Be selected from hydrogen or chlorine, R 2Be selected from the pyridine of replacement, or R1 and R2 are connected to five yuan or six-ring; R3 is selected from hydrogen, halogen, C 1-C 6Alkyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6Alkoxy C 1-C 6Alkyl, C 1-C 6Alkoxy carbonyl, C 1-C 6), alkoxy carbonyl C 1-C 6Alkyl, C 1-C 6Halogenated alkoxy C 1-C 6Alkyl;
Work as Q=Q 4The time, R 1, R 2, R 3Can be identical or different, be selected from hydrogen, halogen, cyano group, nitro, C respectively 1-C 6Alkyl, C 2-C 6Thiazolinyl, C 2-C 6Alkynyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6Alkane alkylsulfonyl, C 1-C 6Alkyl-carbonyl, C 1-C 6Alkoxy C 1-C 6Alkyl, C 1-C 6Alkoxy carbonyl, C 1-C 6Alkoxy carbonyl C 1-C 6Alkyl, C 1-C 6Halogenated alkoxy C 1-C 6Alkyl, any substituted amido C 1-C 6Alkyl, the aryloxy that replaces arbitrarily, any fragrant C that replaces 1-C 6Alkyl oxy, the aryl that replaces arbitrarily, heteroaryl, any aryl C that replaces 1-C 6Alkyl, heteroaryl (C 1-C 6) alkyl, heteroaryl C 1-C 6Alkoxyl group, or R 1With R 2Be connected to five yuan or six-ring.
Further preferred compound is: in the general formula I
Work as Q=Q 1, Q 2Or Q 3The time, R 1Be selected from hydrogen or chlorine, R 2Be selected from the pyridine of replacement, or R 1With R 2Be connected to five yuan or six-ring, R 3Be selected from hydrogen, halogen, C 1-C 6Alkyl;
Work as Q=Q 4The time, R 1, R 2, R 3Can be identical or different, be selected from hydrogen, chlorine, bromine, fluorine, C respectively 1-C 6Alkyl, C 1-C 6Haloalkyl, C 1-C 6Alkyl-carbonyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6Alkane alkylsulfonyl, C 1-C 6Alkoxy C 1-C 3Alkyl, C 1-C 3Halogenated alkoxy C 1-C 3Alkyl, substituted amido C 1-C 3Alkyl, phenyl or substituted-phenyl, benzyl or substituted benzyl, substituted pyridines, or R 1With R 2Be connected to five yuan or six-ring.
Further preferred compound is: in the general formula I
Work as Q=Q 1, Q 2Or Q 3The time, R 1Be selected from hydrogen, R 2Be selected from chloro-pyridine or chlorinated alkoxy pyridine, or R 1With R 2Be connected to five yuan or six-ring, R 3Be selected from hydrogen or methyl;
Work as Q=Q 4The time, R 1, R 2, R 3Can be identical or different, be selected from hydrogen, chlorine, bromine, fluorine, C respectively 1-C 6Alkyl, C 1-C 6Haloalkyl, or R 1With R 2Be connected to five yuan or six-ring.
In the definition of the Compound I that provides above, compile the following substituting group of used term general proxy:
Substituting group can be selected from hydrogen, alkyl, alkoxyl group, haloalkyl, halogenated alkoxy, halogen, nitro or CN etc. in phenyl, phenoxy group, benzyl, the benzyloxy, and substituent number can be 1～5.
Halogen: refer to fluorine, chlorine, bromine and iodine.
Alkyl: straight or branched alkyl, for example methyl, ethyl, propyl group, sec.-propyl and the tertiary butyl.
Haloalkyl: the straight or branched alkyl, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen atom, for example, haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl.
Alkoxyl group: the straight or branched alkyl is connected on the structure through the Sauerstoffatom key.
Halogenated alkoxy: the straight or branched alkoxyl group, the hydrogen atom on these alkoxyl groups can partly or entirely be replaced by halogen atom.For example, halogenated alkoxy such as chlorine methoxyl group, dichloro methoxyl group, trichlorine methoxyl group, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, chlorine fluorine methoxyl group.
Alkenyl: straight or branched also can have two key, for example vinyl, allyl groups on any position.The substituted alkenyl base comprises the aromatic yl alkenyl of any replacement.
Alkynyl: straight or branched also can have triple bond on any position, for example ethynyl, propargyl.Substituted alkynyl comprises the sweet-smelling alkynyl of any replacement.
Aryl moiety in aryl and aralkyl, aromatic yl alkenyl, sweet-smelling alkynyl, aryloxy or the aryloxy alkyl comprises phenyl or naphthyl.
The indication heteroaryl is to contain one or more N, O, the heteroatomic 5 yuan of rings of S or 6 yuan of rings among the present invention.For example pyridine, furans, pyrimidine, pyrazine, pyridazine, triazine, quinoline or cumarone.
In compound of the present invention, because carbon-to-carbon double bond is connected different substituting groups and can forms steric isomer (representing different configurations with Z and E respectively) with the two keys of carbon-nitrogen.Compound of the present invention comprises the mixture of Z type isomer and E-isomer and any ratio thereof.
Can the present invention be described with the compound of listing in the following Table I, but not limit the present invention.
Table 1
Figure A20051004651400071
Numbering R 1 R 2 R 3 Q
1 H H H Q 4
2 H CH 3 H Q 4
3 H CH 3 CH 3 Q 4
4 H C 6H 5 CH 3 Q 4
5 CH 3 CH 3 H Q 4
6 CH 3 CH 3 CH 3 Q 4
7 H CF 3 H Q 4
8 H CH 3 H Q 4
9 H CH 3 H Q 4
10 Cl CH 3 H Q 4
11 H CH 2Cl H Q 4
12 Cl CH 2Cl H Q 4
13 Cl CH 2OCH 3 H Q 4
14 Cl CH 2CH 3 H Q 4
15 H CH 2CH 3 CH 3 Q 4
16 C 2H 5 CH 3 H Q 4
17 H CH 2OCH 3 H Q 4
18 H CH 2OC 2H 5 H Q 4
19 Cl CH 2OC 2H 5 H Q 4
20 OCH 3 CH 2OCH 3 H Q 4
21 N(CH 3) 2 CH 3 H Q 4
22 CN H H Q 4
23 Cl CH 3 CH 3 Q 4
24 H CH(CH 3) 2 H Q 4
25 C 3H 7 CH 3 H Q 4
26 n-C 4H 9 CH 3 H Q 4
27 H tC 4H 9 H Q 4
28 H 4-Cl-C 6H 4 H Q 4
29 Cl 4-Cl-C 6H 4 H Q 4
30 H 4-Cl-C 6H 4 CH 3 Q 4
31 Cl C 6H 5 H Q 4
32 H CH 2CH 3 H Q 4
33 H CH 2C 2H 5 H Q 4
34 H CH 2C 2H 5 CH 3 Q 4
35 Cl CH 2C 2H 5 H Q 4
36 CH 3 CH 2C 2H 5 H Q 4
37 H 4-F-C 6H 4 H Q 4
38 Cl 4-F-C 6H 4 H Q 4
39 H 4-F-C 6H 4 CH 3 Q 4
40 H 4-CF 3-C 6H 4 H Q 4
41 Cl 4-CF 3-C 6H 4 H Q 4
42 Cl CH 2N(CH 3) 2 H Q 4
43 OCH 3 C 2H 5 H Q 4
44 OCH 3 CH 3 H Q 4
45 OC 2H 5 CH 3 H Q 4
46 H CH 2OCH 2CF 3 H Q 4
47 Cl CH 2OCH 2CF 3 H Q 4
48 F CF 3 H Q 4
49 F CH 3 H Q 4
50 H CH 2N(CH 3) 2 H Q 4
51 H C 6H 5 H Q 4
52 Cl n-C 4H 9 H Q 4
53 F n-C 4H 9 H Q 4
54 H CH 2OCH 2C 6H 5 H Q 4
55 OCH 3 4-Cl-C 6H 5 H Q 4
56 F 4-Cl-C 6H 5 H Q 4
57 CH 3S CH 3 H Q 4
58 CH 3SO 2 CH 3 H Q 4
59 C 2H 5 CH 2C 2H 5 H Q 4
60 CH 3SO 2 CH 2C 2H 5 H Q 4
61 H 4-NO 2-C 6H 5 H Q 4
62 Cl 4-NO 2-C 6H 5 H Q 4
63 H 4-NO 2-C 6H 5 CH 3 Q 4
64 PhCH 2 CH 3 H Q 4
65 PhCH 2 CH 3 CH 3 Q 4
66 CF 3CH 2O C 3H 7 H Q 4
67 H CH 2-Ph-4-Cl H Q 4
68 CH 3 CH 2-Ph-4-Cl H Q 4
69 C 2H 5 CH 2-Ph-4-Cl H Q 4
70 CH 2-Ph-4-Cl CH 3 H Q 4
71 CH 2-Ph-4-Cl C 2H 5 H Q 4
72 CH 2-Ph-4-Cl C 3H 7 H Q 4
73 CH 3 CF 3 H Q 4
74 Cl CF 3 H Q 4
75 C 2H 5 CF 3 H Q 4
76 n-C 3H 7 CF 3 H Q 4
77 n-C 4H 9 CF 3 H Q 4
78 H CH 2CH 2-Ph-4-Cl H Q 4
79 CH 2C 2H 5 CH 2C 2H 5 H Q 4
80 H CH 2Bu H Q 4
81 CH 3 CH 2Bu H Q 4
82 n-C 3H 7 CH 2Bu H Q 4
83 CH 2Bu-t CH 3 H Q 4
84 CH 2CH 2-Ph-4-Cl CH 3 H Q 4
85 CH 2CH 2-Ph-4-Cl C 2H 5 H Q 4
86 CH 2CH 2-Ph-4-Cl C 3H 7 H Q 4
87 H 6-Cl-Pyridin-3-yl H Q 1
88 H 6-OCH 2CF 3-Pyridin- 3-yl H Q 1
89 H 6-Cl-Pyridin-3-yl H Q 2
90 H 6-OCH 2CF 3-Pyridin- 3-yl H Q 2
91 H 6-Cl-Pyridin-3-yl H Q 3
92 H 6-OCH 2CF 3-Pyridin- 3-yl H Q 3
93 H 6-Cl-Pyridin-3-yl H Q 4
94 H 6-OCH 2CF 3-Pyridin- 3-yl H Q 4
95 CH 2CH 2CH 2 H Q 4
96 CH 2CH 2CH 2 CH 3 Q 4
97 CH 2CH 2CH 2CH 2 H Q 4
98 CH 2CH 2CH 2CH 2 CH 3 Q 4
99 CH 2CH 2CH 2 H Q 1
100 CH 2CH 2CH 2 CH 3 Q 1
101 CH 2CH 2CH 2CH 2 H Q 1
102 CH 2CH 2CH 2CH 2 CH 3 Q 1
103 CH 2CH 2CH 2 H Q 2
104 CH 2CH 2CH 2 CH 3 Q 2
105 CH 2CH 2CH 2CH 2 H Q 2
106 CH 2CH 2CH 2CH 2 CH 3 Q 2
107 CH 2CH 2CH 2 H Q 3
108 CH 2CH 2CH 2 CH 3 Q 3
109 CH 2CH 2CH 2CH 2 H Q 3
110 CH 2CH 2CH 2CH 2 CH 3 Q 3
The present invention also comprises the preparation method of compound of Formula I: the compound of general formula I is reacted under alkaline condition by the coumarin kind compound of the hydroxyl shown in benzyl halogen shown in the formula II and the formula III and makes:
Reaction formula 1:
In the formula: Q, R 1, R 2, R 3Definition as above, Z is a leavings group, as halogen (chlorine, bromine or iodine).
Compound of Formula I can prepare like this: in appropriate solvent, form salt with the umbelliferone compounds shown in the suitable alkaline purification general formula III, the compound that adds formula II then behind reaction certain hour under the suitable temperature, handles promptly getting the purpose product.
Appropriate solvent can be selected from tetrahydrofuran (THF), acetonitrile, toluene, dimethylbenzene, benzene, N, dinethylformamide, methyl-sulphoxide, acetone or butanone etc.
Suitable alkali can be selected from potassium hydroxide, sodium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, triethylamine, pyridine or sodium hydride etc.
Suitable temperature refers to room temperature to the solvent boiling point temperature, is generally 20～100 ℃.
Reaction times is 30 minutes to 20 hours, common 1～10 hour.
Compound shown in the general formula I I can be made by currently known methods, referring to patent US4723034, US5554578, US6054592 etc.
But the umbelliferone compounds reference literature J Med Chem.2001 shown in the general formula III, 44:664-671; Natural Product Research, 2003,17 (2): 115-125; Chemistry of Natural Compounds, 2002,38 (6): 532-538 etc. are by R 2COCHR 1CO 2CH 3(C 2H 5) make with the Resorcinol that replaces reaction in suitable condensing agent (as the vitriol oil, trifluoroacetic acid).
Compound of the present invention has excellent fungicidal activity, they have systemic activity and can be used as the blade face and soil fungicides, can be applicable to the disease on the various crops of control, be particularly suitable for preventing and treating the following plants disease: downy mildew of garpe, rice sheath blight disease, rice blast, early blight of tomato, tomato late blight, wheat rust, speckled leaf blotch, wheat powdery mildew, powdery mildew of cucumber, cucumber downy mildew, gray mold of cucumber etc.
Compound of the present invention has excellent insecticidal activity simultaneously, can be used for preventing and treating various pest on crop.For example can be used for preventing and treating mythimna separata, small cabbage moth, black peach aphid, carmine spider mite, Tetranychus urticae, ladybug, evil mite and culex pipiens pollens.Especially ladybug and culex pipiens pollens there are special efficacy, are particularly suitable for integrated control insect.
The present invention also provides a kind of desinsection, fungicidal composition, contains upward acceptable carrier of compound of Formula I and agricultural in the said composition, and the weight percentage of active ingredient is 0.1-99% in the composition.
Composition of the present invention can contain the simplification compound shown in the general formula I or the mixture of several compounds.
Carrier system in the present composition satisfies the material of following condition: being convenient to be applied to pending site after it and activeconstituents are prepared, for example can be plant, seed or soil; Perhaps help storing, transport or operation.Carrier can be solid or liquid, comprises the material that is generally gas but has been compressed into liquid, and used carrier all can use in preparation desinsection, fungicidal composition usually.
Suitable solid carrier comprises natural and synthetic clay and silicate, for example diatomite, talcum, attapulgite, pure aluminium silicate (kaolin), montmorillonite and mica; Lime carbonate; Calcium sulfate; Ammonium sulfate; Synthetic silicon oxide and synthetic calcium silicate or pure aluminium silicate; Element such as carbon and sulphur; Natural and synthetic resin such as coumarone resin, polyvinyl chloride and styrene polymer and multipolymer; Solid polystream phenol; Pitch; Wax such as beeswax, paraffin.
Suitable liquid vehicle comprises water; Alcohol is as Virahol and ethanol; Ketone such as acetone, methyl ethyl ketone, methyl isopropyl Ketone, cyclohexyl ketone; Ether; Aromatic hydrocarbons such as benzene,toluene,xylene; Petroleum fractions such as kerosene and mineral oil; Hydrochloric ether such as tetracol phenixin, tetrachloroethylene and trieline.Usually, these mixtures of liquids also are suitable.
Desinsection, fungicidal composition are processed into the form of enriched material usually and are used for transportation with this, by the user it are diluted before using.Having of a spot of supporting surfactant helps dilution.Like this, according to having preferably tensio-active agent of a kind of carrier in the composition of the present invention at least.For example composition can contain at least two kinds of carriers, and wherein at least a is tensio-active agent.
Tensio-active agent can be emulsifying agent, dispersion agent or wetting agent; It can be non-ionic or the ionic tensio-active agent.The example of suitable tensio-active agent comprises the sodium salt or the calcium salt of polyacrylic acid and lignosulfonic acid; Contain the lipid acid of at least 12 carbon atoms or the condenses of aliphatic amide or acid amides and oxyethane and/or propylene oxide in the molecule.The condenses of glycol, sorbyl alcohol, sucrose or pentaerythritol fatty ester and these esters and oxyethane and/or propylene oxide; Fatty Alcohol(C12-C14 and C12-C18) or alkylphenol such as paraoctyl phenol or to the condenses of octyl group cresylol and oxyethane and/or propylene oxide; The vitriol of these condensation products and sulfonate; In molecule, contain the sulfuric acid of 10 carbon atoms or the basic metal or the alkaline earth salt of sulphonate at least, particular certain cancers, sulfuric acid laurate sodium for example, the secondary alkyl ester sodium of sulfuric acid, the sulfonated castor oil sodium salt, alkyl aryl sulfonic acid ester sodium is as pelopon A.
The example of composition of the present invention is wettable powder, pulvis, granule and solution, emulsible enriching agent, emulsion, suspension enriching agent, aerosol and smoke substance.Wettable powder contains 25,50 or 75% weight activeconstituents usually, and usually except that solid inert carrier, also contains the dispersion agent of 3-10% weight, and if needs to add stablizer and/or other additive such as the permeate agent or the tackiness agent of 0-10% weight.Pulvis may be molded to the pulvis enriching agent that has the composition similar to wettable powder but do not have dispersion agent usually, further with the solid carrier dilution, is contained the composition of 0.5-10% weight active ingredient usually again.Granula is prepared into usually has 10 to 100 order (1.676-0.152mm) sizes, and available agglomerating or implantttion technique preparation.Usually granula contains the activeconstituents of 0.5-75% weight and 0-10% weight additive such as stablizer, tensio-active agent, slowly-releasing modifying agent.So-called " dry powder can flow " is by the relatively little granulometric composition with relative high density activeconstituents.Outside but emulsion concentrate desolventizes, when needs, contain cosolvent usually, 1-50%W/V activeconstituents, other additives of 2-20%W/V emulsifying agent and 0-20%W/V such as stablizer, permeate agent and corrosion inhibitor.The suspension enriching agent contains the activeconstituents of 10-75% weight, the dispersion agent of 0.5-15% weight, other additive such as defoamer, corrosion inhibitor, stablizer, permeate agent and the tackiness agent of 0.1-10% weight usually.
Water dispersant and emulsion, for example by dilute with water according to the composition that wettable powder of the present invention or enriched material obtain, also list the scope of the invention in.Said emulsion can have water-in-oil or two types of oil-in-water.
By in composition, adding other one or more sterilant, make it can have the more activity of wide spectrum than independent compound of Formula I.In addition, but the fungicidal activity of other sterilant mutual-through types I compound has synergism.Also compound of Formula I and other sterilants can be used with, or use with another kind of sterilant and other sterilants simultaneously.
Embodiment
Following specific embodiment is used for further specifying the present invention.
Synthetic embodiment
The preparation of example 1 compound 5
Figure A20051004651400121
At room temperature, the sodium hydride of 0.2 gram 60% is added in the reaction flask, after petroleum ether, to wherein adding 30 milliliters of exsiccant N, dinethylformamide stirs half an hour, add 0.5 and digest compound (III-1), continue to be stirred to no gas and emit, add 0.8 and digest compound (II-1), continue to stir 3 hours.Reaction mixture is poured in the frozen water, ethyl acetate extraction 3 times, combining extraction liquid, with saturated common salt washing 3 times, drying is filtered, and concentrating under reduced pressure gets oily liquids 5 grams.Column chromatography obtains title compound 0.68 gram faint yellow solid product, yield 68%.Fusing point: 131-133 ℃.
Nuclear magnetic data ( 1HNMR, 300MHz, interior mark TMS, solvent C DCl 3) 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 compounds 49
Figure A20051004651400122
At room temperature, to contain 0.85 gram Anhydrous potassium carbonate, 0.6 digests compound (III-2), 0.93 and digests compound (II-1) in the mixed solution reflux stirring reaction of 20 milliliters of butanone 5 hours, reaction mixture is poured in the frozen water, ethyl acetate extraction 3 times, combining extraction liquid, saturated common salt washing 3 times, dry, filter, concentrating under reduced pressure, getting yellow solid is thick product.Mixed solution (1: 2) column chromatography with ethyl acetate and sherwood oil obtains title compound 0.89 gram solid, yield 75%.Fusing point: 83-85 ℃.
Nuclear magnetic data ( 1HNMR, 300MHz, interior mark TMS, solvent C DCl 3) 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 compounds 106
At room temperature, to contain 0.3 gram Anhydrous potassium carbonate, 0.22 digests compound (III-3), 0.30 and digests compound (II-2) in the mixed solution reflux stirring reaction of 10 milliliters of butanone 5 hours, reaction mixture is poured in the frozen water, ethyl acetate extraction 3 times, combining extraction liquid, saturated common salt washing 3 times, dry, filter, concentrating under reduced pressure, getting yellow solid is thick product.Mixed solution (1: 2) column chromatography with ethyl acetate and sherwood oil obtains title compound 0.18 gram solid.
The preparation of example 4 compounds 110
Figure A20051004651400131
With 0.52 methylamine stirred overnight at room temperature in 50 ml methanol of digesting compound 106 and twice as high molar ratio, concentrate the back with ethyl acetate extraction 2 times, the extract of merging washes with water 3 times, with saturated common salt washing 2 times, drying is filtered again, concentrate, get title compound 0.48 gram.Yield 92%.
Other compounds are synthetic with reference to aforesaid method.
The rerum natura of part of compounds and nuclear magnetic data ( 1HNMR, 300MHz, interior mark TMS, solvent C DCl 3) as follows:
Compound 6: fusing point is 144-146 ℃.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: fusing point is 139-141 ℃.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: oily matter δ ppm 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), and 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: fusing point is 177-179 ℃.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: fusing point is 150-151 ℃.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: fusing point is 160-161 ℃.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: fusing point is 167-169 ℃.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: fusing point is 140-142 ℃.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: fusing point is 190-192 ℃.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: fusing point is 114-116 ℃.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: fusing point is 170-172 ℃.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)。
Example of formulations (add-on of active ingredient is metered into after rolling over hundred in the prescription, and all percentage compositions are weight percentage)
Example 5 40% missible oil
Compound 5 (content 97.6%) 40%
Phosphorous acid 10%
Ethoxylated glycerol three acid esters 15%
Pimelinketone complements to 100%
Phosphorous acid is dissolved in the pimelinketone, adds compound 5 and ethoxylated glycerol three acid esters then, obtains transparent solution.
Example 6 60% wettable powders
Compound 6 (content 98.4%) 60%
Dodecyl sodium naphthalene sulfonate 2%
Sodium lignosulfonate 9%
Kaolin complements to 100%
Each component (being solid) mixes, and pulverizes in pulverizer, reaches standard up to particle.
Example 7 40% aq suspensions
Compound 26 (content 97.6%) 40%
Dodecyl sodium naphthalene sulfonate 4%
Hemicellulose 2%
Propylene oxide 8%
Water complements to 100%
Compound 26 is pulverized in (1mm pearl) in ball mill with 80% water that should add and dodecyl sodium naphthalene sulfonate.Other components dissolved stirs other component of adding then in remaining water.
Example 8 25% suspension-emulsion enriched materials
Compound 98 (content 96.2%) 25%
Dodecyl alcohol polyoxyethylene glycol phosphoric acid ester (emulsifying agent 1) 4%
Oxyethyl group tri-glyceride (emulsifying agent 2) 2%
Calcium dodecylbenzene sulphonate (emulsifying agent 3) 1.5%
The epoxy first and second alkane epoxy propane copolymers (dispersion agent) 2.5%
Pimelinketone (solvent 1) 30%
Alkylaryl cut (boiling point＞200 ℃) (solvent 2) complements to 100%
Compound 98 is dissolved in 80% the solvent, adds emulsifying agent and dispersion agent then, and mixture is thoroughly stirred.Mixture is pulverized in ball mill (1mm pearl), adds remaining solvent then.
Biological activity determination
Example 9 fungicidal activities are measured
With The compounds of this invention the various fungus diseases of plant are tested.The method of test is as follows:
Adopt the potted plant measuring method of live body.The former medicinal small amount of acetone dissolving of testing compound is diluted to required concentration with the water that contains 0.1% tween 80.Spray pesticide carries out the disease inoculation after 24 hours to plant examination material.After the inoculation, plant is placed in the fixed temperature and humidity incubator, makes to infect and continue, wait to contrast abundant morbidity back (being generally week age) and carry out assessment surveys.
The partial test result is as follows:
During 400ppm, to cucumber downy mildew (Pseudoperonospora cubenis) preventive effect be 100% compound 5,99,101 etc. arranged; Preventive effect greater than 90% compound 6,10 etc. arranged; Preventive effect greater than 80% compound 96,98 etc. arranged.
During 400ppm, to gray mold of cucumber (Botrytis cinerea) preventive effect be 100% compound 97,99 etc. arranged; Preventive effect greater than 85% compound 101 etc. arranged.
During 200ppm, to rice sheath blight disease (Rhizoctonia solani) preventive effect greater than 85% compound 6,26 etc. arranged.
During 200ppm, be 100% compound 5,101 etc. to be arranged to wheat powdery mildew (BLumeria graminis) preventive effect; Greater than 95% compound 10 etc. arranged.
Biological activity determination
Example 10 pesticide and miticide actilities are measured
With The compounds of this invention several insects and mite class have been carried out the insecticidal activity assay test.Method for measuring is as follows:
After the mixed solvent dissolving of new compound with acetone/methanol (1: 1), be diluted to required concentration with the water that contains 0.1% tween 80.
With mythimna separata (Leucania separata), small cabbage moth (Plutella xylostella) and culex pipiens pollens (Culex pippenspallens) 2 instar larvaes, black peach aphid (Myzus persicae), carmine spider mite (Tetranychus cinnabarinus) is target, adopt airbrush spray method and immersion method (culex pipiens pallens larvae) to carry out insecticidal activity assay, the pressure that the airbrush spraying is handled is that 10psi (is roughly equal to 0.7kg/cm 2), spouting liquid is 0.5ml.Handle the mortality ratio that 2-3 day is investigated target in the back.
The partial test result is as follows:
When liquor strength was 600ppm, compound 99 grades were to reaching 100% for examination target culex pipiens pollens mortality ratio.
When liquor strength is 600ppm, 98 pairs of mythimna separatas of compound, small cabbage moth, black peach aphid also show suitable activity, greater than 50%.

Claims (8)

1, a kind of coumarin kind compound, shown in general formula I:
In the formula:
Q is selected from one of following group:
Work as Q=Q 1, Q 2Or Q 3The time, R 1Be selected from hydrogen or chlorine, R 2Be selected from the pyridine of replacement, or R 1With R 2Be connected to five yuan or six-ring; R 3Be selected from hydrogen, halogen, cyano group, nitro, C 1-C 12Alkyl, C 2-C 12Thiazolinyl, C 2-C 12Alkynyl, C 1-C 12Haloalkyl, C 1-C 12Alkoxyl group, C 1-C 12Alkylthio, C 1-C 12Alkane alkylsulfonyl, C 1-C 12Alkyl-carbonyl, C 1-C 12Alkoxy C 1-C 12Alkyl, C 1-C 12Alkoxy carbonyl, C 1-C 12Alkoxy carbonyl C 1-C 12Alkyl, C 1-C 12Halogenated alkoxy C 1-C 12Alkyl, any substituted amido C 1-C 12Alkyl, the aryloxy that replaces arbitrarily, any fragrant C that replaces 1-C 12Alkyl oxy, the aryl that replaces arbitrarily, heteroaryl, any aryl C that replaces 1-C 12Alkyl, heteroaryl C 1-C 12Alkyl, heteroaryl C 1-C 12Alkoxyl group;
Work as Q=Q 4The time, R 1, R 2, R 3Can be identical or different, be selected from hydrogen, halogen, cyano group, nitro, C respectively 1-C 12Alkyl, C 2-C 12Thiazolinyl, C 2-C 12Alkynyl, C 1-C 12Haloalkyl, C 1-C 12Alkoxyl group, C 1-C 12Alkylthio, C 1-C 12Alkane alkylsulfonyl, C 1-C 12Alkyl-carbonyl, C 1-C 12Alkoxy C 1-C 12Alkyl, C 1-C 12Alkoxy carbonyl, C 1-C 12Alkoxy carbonyl C 1-C 12Alkyl, C 1-C 12Halogenated alkoxy C 1-C 12Alkyl, any substituted amido C 1-C 12Alkyl, the aryloxy that replaces arbitrarily, any fragrant C that replaces 1-C 12Alkyl oxy, the aryl that replaces arbitrarily, heteroaryl, any aryl C that replaces 1-C 12Alkyl, heteroaryl C 1-C 12Alkyl, heteroaryl C 1-C 12Alkoxyl group, or R 1With R 2Be connected to five yuan or six-ring;
And steric isomer.
2, compound according to claim 1 is characterized in that: in the general formula I
Work as Q=Q 1, Q 2Or Q 3The time, R 1Be selected from hydrogen or chlorine, R 2Be selected from the pyridine of replacement, or R1 and R2 are connected to five yuan or six-ring; R3 is selected from hydrogen, halogen, C 1-C 6Alkyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6Alkoxy C 1-C 6Alkyl, C 1-C 6Alkoxy carbonyl, C 1-C 6), alkoxy carbonyl C 1-C 6Alkyl, C 1-C 6Halogenated alkoxy C 1-C 6Alkyl;
Work as Q=Q 4The time, R 1, R 2, R 3Can be identical or different, be selected from hydrogen, halogen, cyano group, nitro, C respectively 1-C 6Alkyl, C 2-C 6Thiazolinyl, C 2-C 6Alkynyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6Alkane alkylsulfonyl, C 1-C 6Alkyl-carbonyl, C 1-C 6Alkoxy C 1-C 6Alkyl, C 1-C 6Alkoxy carbonyl, C 1-C 6Alkoxy carbonyl C 1-C 6Alkyl, C 1-C 6Halogenated alkoxy C 1-C 6Alkyl, any substituted amido C 1-C 6Alkyl, the aryloxy that replaces arbitrarily, any fragrant C that replaces 1-C 6Alkyl oxy, the aryl that replaces arbitrarily, heteroaryl, any aryl C that replaces 1-C 6Alkyl, heteroaryl (C 1-C 6) alkyl, heteroaryl C 1-C 6Alkoxyl group, or R 1With R 2Be connected to five yuan or six-ring.
3, compound according to claim 2 is characterized in that: in the general formula I
Work as Q=Q 1, Q 2Or Q 3The time, R 1Be selected from hydrogen or chlorine, R 2Be selected from the pyridine of replacement, or R 1With R 2Be connected to five yuan or six-ring, R 3Be selected from hydrogen, halogen, C 1-C 6Alkyl;
Work as Q=Q 4The time, R 1, R 2, R 3Can be identical or different, be selected from hydrogen, chlorine, bromine, fluorine, C respectively 1-C 6Alkyl, C 1-C 6Haloalkyl, C 1-C 6Alkyl-carbonyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6Alkane alkylsulfonyl, C 1-C 6Alkoxy C 1-C 3Alkyl, C 1-C 3Halogenated alkoxy C 1-C 3Alkyl, substituted amido C 1-C 3Alkyl, phenyl or substituted-phenyl, benzyl or substituted benzyl, substituted pyridines, or R 1With R 2Be connected to five yuan or six-ring.
4, compound according to claim 3 is characterized in that: in the general formula I
Work as Q=Q 1, Q 2Or Q 3The time, R 1Be selected from hydrogen, R 2Be selected from chloro-pyridine or chlorinated alkoxy pyridine, or R 1With R 2Be connected to five yuan or six-ring, R 3Be selected from hydrogen or methyl;
Work as Q=Q 4The time, R 1, R 2, R 3Can be identical or different, be selected from hydrogen, chlorine, bromine, fluorine, C respectively 1-C 6Alkyl, C 1-C 6Haloalkyl, or R 1With R 2Be connected to five yuan or six-ring.
5, according to any described compound among the claim 1-4, it is characterized in that: the compound of general formula I is reacted under alkaline condition by the coumarin kind compound of the hydroxyl shown in benzyl halogen shown in the formula II and the formula III and makes:
Figure A2005100465140003C1
In the formula, Z is a leavings group, is selected from chlorine, bromine or iodine.
6, the described compound of claim 1 is in the application of control pest on crop.
7, the application of the described compound of claim 1 germ on the control crop.
8, a kind of desinsection, fungicidal composition is characterized in that: contain the described compound of Formula I of claim 1 in the composition, the weight percentage of active ingredient is 0.1-99%.
CNA2005100465141A 2005-05-26 2005-05-26 Coumarin kind compound and its preparation and application Pending CN1869032A (en)

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CN101368003B (en) * 2007-08-15 2011-09-14 中国科学院理化技术研究所 Pyrazoline pyridine-fluorescent coumarin dye derivant, synthesis and uses thereof
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