CN106187893B - A kind of pyrazol acid amide compounds and application thereof - Google Patents
A kind of pyrazol acid amide compounds and application thereof Download PDFInfo
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- CN106187893B CN106187893B CN201510226412.1A CN201510226412A CN106187893B CN 106187893 B CN106187893 B CN 106187893B CN 201510226412 A CN201510226412 A CN 201510226412A CN 106187893 B CN106187893 B CN 106187893B
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Abstract
The invention belongs to fungicide fields.It is related to a kind of pyrazol acid amide compounds and its sterilizing use.Pyrazol acid amide compounds are as shown in general formula I:
Description
Technical field
The invention belongs to fungicide fields.It is related to a kind of pyrazol acid amide compounds and its sterilizing use.
Background technique
In use for some time due to fungicide, disease can generate resistance to it, novel therefore, it is necessary to constantly invent
With improved compound and composition with bactericidal activity.
The bactericidal activity of pyrazole amide compound has been reported.As JP62249975 discloses compound K C1、KC2、KC3With
KC4(respectively compound 3,2,10 and 4 in patent) and its bactericidal activity
In the prior art, structure pyrazol acid amide compounds as shown in general formula I of the present invention have not been reported.
Summary of the invention
The purpose of the present invention is to provide a kind of better pyrazol acid amide compounds of bactericidal activity, it can be applied to agricultural
The prevention and treatment of upper disease.
Technical scheme is as follows:
The present invention provides pyrazol acid amide compounds, as shown in general formula I:
In formula:
R1Selected from C1-C3Alkyl, C1-C3Halogenated alkyl or C3-C6Naphthenic base；
R2Selected from hydrogen, halogen or methyl；
Wherein, work as R1When selected from difluoromethyl, R2It is not hydrogen；
R3Selected from C1-C6Alkyl, C1-C6Halogenated alkyl, C3-C6Naphthenic base, C3-C6Halogenated cycloalkyl, C2-C6's
Alkenyl, C2-C6Alkynyl, hydroxyl-C1-C6Alkyl, C1-C6Alkoxy -C1-C6Alkyl, C1-C6Halogenated alkoxy-C1-
C6Alkyl, C3-C6Naphthenic base-C1-C6Alkyl oxy-C1-C6Alkyl, C3-C8Alkenyl oxygroup-C1-C6Alkyl, C3-
C8Alkynyl oxygroup-C1-C6Alkyl, by most 6 identical or different R8Substituted aryl C1-C6Alkoxy -C1-C6Alkane
Base, C1-C6Alkoxy carbonyl, C1-C6Haloalkoxycarbonyl, C3-C6Cyclo alkoxy carbonyl, C3-C6Halogenated cycloalkanes oxygen carbonyl
Base, C3-C6Naphthenic base-C1-C6Alkoxy carbonyl, aryloxy carbonyl, C1-C6Alkylaminocarbonyl, C3-C6Cycloalkanes amido
Carbonyl, C3-C6Naphthenic base-C1-C6Alkylaminocarbonyl, arylamine group carbonyl, aryl-C1-C6Alkylaminocarbonyl；
Wherein aryl is selected from phenyl ring, has 1-3 heteroatomic 5 with 1-3 heteroatomic 5 or 6 circle heterocyclic rings or benzo
Or 6 circle heterocyclic ring；
R4、R5And R6Separately it is selected from hydrogen, halogen, cyano, C3-C6Naphthenic base, C2-C6Alkenyl, C2-C6Alkynes
Base, C1-C12Alkoxy, C1-C12Halogenated alkyl or C1-C12Alkyl；
R7Selected from C1-C12Alkyl；
R8Selected from halogen, nitro, cyano, C1-C6Alkyl or C1-C6Halogenated alkyl.
Preferred technical solution is in the present invention, in general formula I:
R1Selected from C1-C3Alkyl, C1-C3Halogenated alkyl or C3-C6Naphthenic base；
R2Selected from hydrogen, halogen or methyl；
Wherein, work as R1When selected from difluoromethyl, R2It is not hydrogen；
R3Selected from C1-C3Alkyl, C1-C3Halogenated alkyl, C3-C6Naphthenic base, C3-C6Halogenated cycloalkyl, C2-C6's
Alkenyl, C2-C6Alkynyl, hydroxyl-C1-C3Alkyl, C1-C3Alkoxy -C1-C3Alkyl, C1-C3Halogenated alkoxy-C1-
C3Alkyl, C3-C6Naphthenic base-C1-C3Alkyl oxy-C1-C3Alkyl, C3-C6Alkenyl oxygroup-C1-C3Alkyl, C3-
C6Alkynyl oxygroup-C1-C3Alkyl, by most 6 identical or different R8Substituted aryl C1-C3Alkoxy -C1-C3Alkane
Base, C1-C3Alkoxy carbonyl, C1-C3Haloalkoxycarbonyl, C3-C6Cyclo alkoxy carbonyl, C3-C6Halogenated cycloalkanes oxygen carbonyl
Base, C3-C6Naphthenic base-C1-C3Alkoxy carbonyl, aryloxy carbonyl, C1-C3Alkylaminocarbonyl, C3-C6Cycloalkanes amido
Carbonyl, C3-C6Naphthenic base-C1-C3Alkylaminocarbonyl, arylamine group carbonyl, aryl-C1-C3Alkylaminocarbonyl；
Wherein aryl is selected from phenyl ring, has 1-3 heteroatomic 5 with 1-3 heteroatomic 5 or 6 circle heterocyclic rings or benzo
Or 6 circle heterocyclic ring；
R4、R5And R6Separately it is selected from hydrogen, halogen, cyano, C3-C6Naphthenic base, C2-C6Alkenyl, C2-C6Alkynes
Base, C1-C6Alkoxy, C1-C6Halogenated alkyl or C1-C6Alkyl；
R7Selected from C1-C6Alkyl；
R8Selected from hydrogen, halogen, nitro, cyano, C1-C3Alkyl or C1-C3Halogenated alkyl.
Further preferred technical solution is in the present invention, in general formula I:
R1Selected from C1-C3Alkyl, trifluoromethyl, difluoromethyl or cyclopropyl；
R2Selected from hydrogen, fluorine, chlorine, bromine, iodine or methyl；
Wherein, work as R1When selected from difluoromethyl, R2It is not hydrogen；
R3Selected from C1-C3Alkyl, hydroxyl-C1-C3Alkyl, C1-C3Alkoxy -C1-C3Alkyl, C1-C3It is halogenated
Alkoxy -C1-C3Alkyl, C3-C6Naphthenic base-C1-C3Alkyl oxy-C1-C3Alkyl, C3-C6Alkenyl oxygroup-C1-C3
Alkyl, C3-C6Alkynyl oxygroup-C1-C3Alkyl, by most 6 identical or different R8Substituted aryl C1-C3Alcoxyl
Base-C1-C3Alkyl, C1-C3Alkoxy carbonyl, C1-C3Haloalkoxycarbonyl, C3-C6Cyclo alkoxy carbonyl, C3-C6's
Halogenated cycloalkoxycarbonyl, C3-C6Naphthenic base-C1-C3Alkoxy carbonyl, aryloxy carbonyl, C1-C3Alkylaminocarbonyl, C3-
C6Cycloalkanes amino-carbonyl, C3-C6Naphthenic base-C1-C3Alkylaminocarbonyl, arylamine group carbonyl, aryl-C1-C3Alkanamine
Base carbonyl；
Wherein aryl is selected from phenyl ring, furans, thiophene, pyrroles, pyrazoles, oxazole, isoxazole, thiazolyl, pyridine, pyrazine, phonetic
Pyridine, pyridazine, benzoxazoles, benzothiazole, quinoxaline, quinazolyl；
R4、R5And R6Separately it is selected from hydrogen, fluorine, cyano, C3-C6Naphthenic base, C2-C6Alkenyl, C2-C6Alkynyl,
C1-C3Alkoxy, C1-C3Halogenated alkyl or C1-C3Alkyl；
R7Selected from C1-C6Alkyl；
R8Selected from hydrogen, fluorine, chlorine, bromine, iodine, nitro, cyano, C1-C3Alkyl or C1-C3Halogenated alkyl.
Technical solution in the present invention still more preferably is, in general formula I:
R1Selected from methyl, ethyl, isopropyl, trifluoromethyl, difluoromethyl or cyclopropyl；
R2Selected from hydrogen, fluorine or chlorine；
Wherein, work as R1When selected from difluoromethyl, R2It is not hydrogen；
R3Selected from C1-C3Alkyl；
R4、R5And R6It is respectively selected from hydrogen；
R7Selected from C1-C6Alkyl.
Particularly preferred technical solution is in the present invention, in general formula I:
R1Selected from difluoromethyl；
R2Selected from fluorine or chlorine；
R3Selected from C1-C3Alkyl；
R4、R5And R6It is respectively selected from hydrogen；
R7Selected from C1-C6Alkyl.
In the definition of compound of Formula I given above, collects term used and is generally defined as follows:
Alkyl refers to linear chain or branched chain form, such as methyl, ethyl, n-propyl, isopropyl etc..Naphthenic base includes cyclopropyl
Base, cyclobutyl, Cvclopropvlmethvl, methylcyclopropyl groups etc..Halogenated alkyl refers to the base that alkyl is optionally substituted with one or more halogen atoms
Group, such as chloroethyl, trifluoromethyl, difluoromethyl, hepta-fluoroiso-propyl.Alkenyl refers to linear chain or branched chain alkenyl, as 1- acrylic,
2- acrylic etc..Alkynyl refers to linear chain or branched chain alkynyl, such as 1- propinyl, 2-propynyl.Alkoxy refers to that alkyl end connects
There are group of oxygen atom, such as methoxyl group, ethyoxyl, positive propoxy, isopropoxy etc..Halogen refers to fluorine, chlorine, bromine, iodine.
The technology of the present invention feature further includes the preparation method of compound of Formula I, outer except as otherwise indicating, each group in reaction equation
It is as defined above.
Method one:
In suitable solvent, temperature is -10 DEG C of boiling points for arriving suitable solvent for Compounds of formula II and compound of formula III
0.5-48 hours obtained target compound I of lower reaction.
Suitable solvent is selected from methylene chloride, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydro
Furans, dioxane, N,N-dimethylformamide or dimethyl sulfoxide etc..
Suitable alkali is added to reacting advantageous, suitable alkali includes the alkali metal such as hydrogen compound of lithium, sodium or potassium as hydrogenated
Sodium, the alkali metal such as hydroxide of lithium, sodium or potassium such as sodium hydroxide, can also be the carbonate such as sodium carbonate of alkali metal, can also
To be organic base such as triethylamine, sodium tert-butoxide etc..
Compounds of formula II can refer to following documents preparation: CN101979375A.
Compound of formula III can refer to following documents preparation: Bioorganic&Medicinal Chemistry, and 2012,
20(3):1213-1221；Pesticide, 2007,46 (5): 307-309.
Method two:
In formula, L represents leaving group, X represents halogen.
Compounds of formula II and compound of Formula IV (commercially available) in suitable solvent, in the presence of suitable alkali, temperature is-
0.5-48 hours obtained compound V are reacted under 10 DEG C of boiling points to suitable solvent.
Suitable solvent is selected from methylene chloride, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydro
Furans, dioxane, N,N-dimethylformamide or dimethyl sulfoxide etc..
Suitable alkali includes the alkali metal such as hydrogen compound of lithium, sodium or potassium such as sodium hydride, the alkali metal such as hydrogen of lithium, sodium or potassium
Oxide such as sodium hydroxide can also be the carbonate such as sodium carbonate of alkali metal, be also possible to organic base such as triethylamine, the tert-butyl alcohol
Sodium etc..
Compounds of formula V and compound of formula VI (commercially available) in suitable solvent, in the presence of suitable alkali, temperature is-
0.5-48 hours obtained target compounds I are reacted under 10 DEG C of boiling points to suitable solvent.
Suitable solvent is selected from methylene chloride, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydro
Furans, dioxane, N,N-dimethylformamide or dimethyl sulfoxide etc..
Suitable alkali includes the alkali metal such as hydrogen compound of lithium, sodium or potassium such as sodium hydride, the alkali metal such as hydrogen of lithium, sodium or potassium
Oxide such as sodium hydroxide can also be the carbonate such as sodium carbonate of alkali metal, be also possible to organic base such as triethylamine, the tert-butyl alcohol
Sodium etc..
Compound of Formula IV is commercial reagent.
Table 1 lists the structure and physical property of partial Formula Compound I.
The structure and physical property of 1 partial Formula Compound I of table
Part of compounds1H NMR(300MHz,CDCl3) data are as follows:
Compound 2:7.70 (s, 1H), 7.47 (d, 1H), 7.15-7.18 (m, 2H), 6.70 (d, 1H), 4.35-4.38 (m,
1H),3.89(s,3H),3.45-3.55(m,1H),2.16(s,3H),1.56-1.75(m,2H),1.28-1.46(m,13H),
0.88-0.96(m,3H)。
Compound 4:7.72 (s, 1H), 7.59 (d, 1H), 7.17 (t, 1H), 6.71 (d, 1H), 4.33-4.40 (m, 1H),
3.84(s,3H),2.52(s,3H),2.19(s,3H),1.57-1.80(m,2H),1.26-1.47(m,7H),0.88-0.97(m,
3H)。
Compound 5:7.73 (s, 1H), 7.58 (d, 1H), 7.16 (t, 1H), 6.71 (d, 1H), 4.30~4.40 (m, 1H),
3.86 (s, 3H), 2.96 (q, 2H), 2.20 (s, 3H), 1.25~1.80 (m, 6H), 1.29 (d, 3H), 1.28 (t, 3H), 0.91
(t,3H)。
Compound 8:7.58 (d, 1H), 7.32~7.33 (m, 1H), 7.15 (t, 1H), 6.70 (d, 1H), 4.30~4.40
(m, 1H), 3.74 (s, 3H), 2.49 (s, 3H), 2.16 (s, 3H), 1.23~2.05 (m, 6H), 1.27 (d, 3H), 0.91 (t,
3H)。
Compound 11:7.89 (s, 1H), 7.58 (d, 1H), 7.21 (t, 1H), 7.19 (t, 1H), 6.76 (d, 1H), 4.38-
4.42(m,1H),3.99(s,3H),2.22(s,3H),1.60-1.80(m,2H),1.32-1.47(m,7H),0.94-1.00(m,
3H)。
Compound 12:7.58 (s, 1H), 7.52 (d, 1H), 7.15 (t, 1H), 7.05 (t, 1H), 6.72 (d, 1H), 4.15
~4.21 (m, 1H), 3.85 (s, 3H), 2.16 (s, 3H), 1.50~1.80 (m, 2H), 1.27~1.50 (m, 4H), 1.28 (d,
3H),0.93(t,3H)。
Compound 13:8.02 (s, 1H), 7.61 (s, 1H), 7.45 (d, 1H), 7.15 (t, 1H), 6.73 (d, 1H), 4.31-
4.36(m,1H),3.97(s,3H),2.15(s,3H),1.56-1.75(m,2H),1.28-1.44(m,7H),0.91-0.94(m,
3H)。
Compound 15:7.72 (s, 1H), 7.59 (d, 1H), 7.16 (t, 1H), 6.70 (d, 1H), 4.32-4.36 (m, 1H),
3.85(s,3H),2.52(s,3H),2.19(s,3H),1.65-1.79(m,2H),1.27-1.58(m,9H),0.86-0.94(m,
3H)。
Compound 16:7.73 (s, 1H), 7.58 (d, 1H), 7.16 (t, 1H), 6.71 (d, 1H), 4.30~4.40 (m,
1H), 3.86 (s, 3H), 2.96 (q, 2H), 2.20 (s, 3H), 1.25~1.80 (m, 8H), 1.29 (d, 3H), 1.28 (t, 3H),
0.89(t,3H)。
Compound 17:7.59 (d, 1H), 7.31~7.33 (m, 1H), 7.15 (t, 1H), 6.70 (d, 1H), 4.30~4.40
(m, 1H), 3.75 (s, 3H), 2.49 (s, 3H), 2.16 (s, 3H), 1.27~1.80 (m, 8H), 1.28 (d, 3H), 0.89 (t,
3H)。
Compound 18:7.87 (s, 1H), 7.54 (d, 1H), 7.15 (t, 1H), 7.12~7.17 (m, 1H), 6.72 (d,
1H), 4.32~4.38 (m, 1H), 3.93 (s, 3H), 2.18 (s, 3H), 1.32 (d, 3H), 1.23~2.03 (m, 8H), 0.89
(t,3H)。
Compound 19:7.58 (s, 1H), 7.52 (d, 1H), 7.14 (t, 1H), 7.05 (t, 1H), 6.72 (d, 1H), 4.32
~4.38 (m, 1H), 3.83 (s, 3H), 2.18 (s, 3H), 1.31~1.76 (m, 8H), 1.28 (d, 3H), 0.89 (t, 3H).
Compound 22:7.73 (s, 1H), 7.60 (d, 1H), 7.16 (t, 1H), 6.71 (d, 1H), 4.32-4.36 (m, 1H),
3.85(s,3H),2.52(s,3H),2.20(s,3H),1.60-1.74(m,2H),1.27-1.61(m,11H),0.86-0.94
(m,3H)。
Compound 23:7.72 (s, 1H), 7.58 (d, 1H), 7.16 (t, 1H), 6.71 (d, 1H), 4.30~4.40 (m,
1H), 3.86 (s, 3H), 2.96 (q, 2H), 2.20 (s, 3H), 1.25~1.80 (m, 10H), 1.29 (d, 3H), 1.28 (t, 3H),
0.88(t,3H)。
Compound 26:7.58 (d, 1H), 7.31~7.33 (m, 1H), 7.15 (t, 1H), 6.70 (d, 1H), 4.30~4.40
(m, 1H), 3.74 (s, 3H), 2.49 (s, 3H), 2.16 (s, 3H), 1.27~1.80 (m, 10H), 1.28 (d, 3H), 0.88 (t,
3H)。
Compound 27:7.87 (s, 1H), 7.55 (d, 1H), 7.16 (t, 1H), 7.13~7.18 (s, 1H), 6.73 (d,
1H), 4.32~4.38 (m, 1H), 3.94 (s, 3H), 2.19 (s, 3H), 1.29 (d, 3H), 1.23~1.80 (m, 10H), 0.90
(t,3H)。
Compound 28:7.57 (s, 1H), 7.53 (d, 1H), 7.15 (t, 1H), 7.05 (t, 1H), 6.72 (d, 1H), 4.34
~4.36 (m, 1H), 3.85 (s, 3H), 2.16 (s, 3H), 1.28 (d, 3H), 1.23~1.60 (m, 10H), 0.88 (t, 3H)
Compound 29:8.04 (s, 1H), 7.58 (s, 1H), 7.46 (d, 1H), 7.17 (t, 1H), 6.73 (d, 1H), 4.32-
4.36(m,1H),3.99(s,3H),2.15(s,3H),1.65-1.79(m,2H),1.23-1.61(m,11H),0.86-0.90
(m,3H)。
Compound 30:7.53-7.56 (m, 2H), 7.17 (t, 1H), 6.73 (d, 1H), 4.32-4.36 (m, 1H), 3.96
(s,3H),2.16(s,3H),1.65-1.79(m,2H),1.27-1.58(m,11H),0.86-0.90(m,3H)。
Compound 31:7.73 (s, 1H), 7.58 (d, 1H), 7.15 (t, 1H), 6.69 (d, 1H), 4.17-4.21 (m, 1H),
3.85(s,3H),2.46(s,3H),2.21(s,3H),1.63-1.70(m,4H),1.28-1.36(m,4H),0.87-0.97(m,
6H)。
Compound 33:7.87 (s, 1H), 7.53 (d, 1H), 7.15 (t, 1H), 7.13~7.18 (s, 1H), 6.71 (d,
1H), 4.18~4.21 (m, 1H), 3.94 (s, 3H), 2.19 (s, 3H), 1.61~2.04 (m, 4H), 1.26~1.42 (m, 4H),
0.95(t,3H),0.90(t,3H)。
Compound 34:7.59 (s, 1H), 7.50 (d, 1H), 7.14 (t, 1H), 7.05 (t, 1H), 6.70 (d, 1H), 4.18
~4.20 (m, 1H), 3.83 (s, 3H), 2.19 (s, 3H), 1.64~1.70 (m, 4H), 1.27~1.38 (m, 4H), 0.95 (t,
3H),0.90(t,3H)
Compound 35:8.04 (s, 1H), 7.58 (s, 1H), 7.46 (d, 1H), 7.15 (t, 1H), 6.71 (d, 1H), 4.17-
4.21(m,1H),3.99(s,3H),2.16(s,3H),1.63-1.70(m,4H),1.26-1.38(m,4H),0.87-0.97(m,
6H)。
Compound 36:7.54-7.61 (m, 2H), 7.15 (t, 1H), 6.71 (d, 1H), 4.17-4.21 (m, 1H), 3.96
(s,3H),2.17(s,3H),1.63-1.72(m,4H),1.28-1.41(m,4H),0.83-0.97(m,6H)。
Compound 41:7.89 (s, 1H), 7.59 (d, 1H), 7.10 (t, 1H), 7.08~7.13 (m, 1H), 6.54 (d,
1H), 4.58~4.62 (m, 1H), 4.18 (q, 2H), 3.91 (s, 3H), 2.25 (s, 3H), 1.93~1.98 (m, 2H), 1.47~
1.54 (m, 2H), 1.23 (t, 3H), 1.21~1.37 (m, 6H), 0.87 (t, 3H).
Compound 42:7.60 (s, 1H), 7.58 (d, 1H), 7.11 (t, 1H), 7.03 (t, 1H), 6.54 (d, 1H), 4.58
~4.60 (m, 1H), 4.19 (q, 2H), 3.83 (s, 3H), 2.25 (s, 3H), 1.93~2.03 (m, 2H), 1.47~1.54 (m,
2H), 1.24 (t, 3H), 1.21~1.37 (m, 6H), 0.88 (t, 3H).
Compared with known pyrazol acid amide compounds, pyrazol acid amide compounds of the invention have unexpected height
Bactericidal activity.Therefore, the invention also includes the purposes that compound of Formula I is used to control disease, to prevent and treat Oomycete
(Oomycetes), Ascomycetes (Ascomycetes), Basidiomycetes (Basidiomycetes), deuteromycetes
(Deuteromycetes), Plasmodiophoromycetes (Plasmodiophoromycetes), Chytridiomycetes (Chytridiomycetes) and knot
Combined bacteria subclass (Zygomycetes) disease.
What the example of the certain diseases of the guiding principle being listed above under one's name can be mentioned that includes but is not limited to:
Wheat rust, wheat powdery mildew, wheat scab, root rotof flax, wheat sharp eyespot, take-all, wheat
Glume blight, cucumber downy mildew, cucumber anthracnose, cucumber fusarium axysporum, gray mold of cucumber, downy mildew of garpe, early blight of tomato, tomato
Late blight, rice sheath blight disease, rice blast, watermelon grafting, Peanut Scab, the cercospora black spot of peanut, citrus scab, capsicum
Root rot, cotton verticillium wilt, cotton wilt, rape black stem, sclerotinia sclerotiorum, pear scab, ginseng rust rot, corn rust
Disease, Curvularia disease, the leaf blight of corn, mango blossom-end rot, ring rot of apple, the rotten disease of apple corruption bacterium, sigatoka.
The invention also includes the bactericidal compositions using compound of Formula I as active component.Conduct in the bactericidal composition
The weight percentage of the compound of Formula I of active component is between 1-99%.It further include agriculturally may be used in the bactericidal composition
The carrier of receiving.
Composition of the invention can be applied in the form of preparation.Compound of Formula I is dissolved or dispersed in as active component
In carrier or be configured to preparation so as to as sterilization use when it is more readily dispersible.Such as: these chemicals can be made into wettable
Property pulvis or missible oil.In these compositions, a kind of liquid or solid carrier is at least added, and can be added when needed suitable
When surfactant.
Technical solution of the present invention further includes the method for controlling disease: bactericidal composition of the invention is imposed on to the disease
On harmful or its somatomedin.The more suitable effective quantity generally selected is 10 grams to 1000 grams of per hectare.
For certain applications, such as one or more others can agriculturally be added in bactericidal composition of the invention
Thus insecticide, fungicide, herbicide, plant growth regulator or fertilizer etc. can produce additional advantage and effect.
Specific embodiment
Following synthetic example, biological activity determination embodiment can be used to further illustrate the present invention, but not mean that limit
The system present invention.
Synthetic example
The synthesis of 1 compound 28 of embodiment
2- methyl -3- (2- octyloxy) aniline (240 milligrams, 1.03 mMs), triethylamine (110 millis are added in reaction flask
Gram, 1.09 mMs) and 10 milliliters of methylene chloride, lower dropwise addition 1- methyl -3- difluoromethyl -5- fluorine pyrazoles -4- first is stirred at room temperature
10 milliliters of dichloromethane solution of acyl chlorides (210 milligrams, 0.99 mM).Drop finishes, and reacts at room temperature, end of reaction after 3 hours.
Reaction solution is poured into 30 milliliters of water, takes organic layer, and organic layer uses saturated sodium bicarbonate aqueous solution, saturated common salt washing respectively
It washs, anhydrous magnesium sulfate is dry, and solvent to the greatest extent is steamed in decompression.Residue by column chromatography purify (leacheate: ethyl acetate: petroleum ether=
1:2), 250 milligrams of compounds 28, yield 60.8% are obtained.
The synthesis of 2 compound 41 of embodiment
2- (2- methyl -3- amino-benzene oxygen)-ethyl caprilate (290 milligrams, 0.99 mM), three second are added in reaction flask
Lower dropwise addition 1- methyl -3- difluoromethyl -5- chlorine pyrrole is stirred at room temperature in amine (110 milligrams, 1.09 mMs) and 10 milliliters of methylene chloride
10 milliliters of dichloromethane solution of azoles -4- formyl chloride (230 milligrams, 1.00 mMs).Drop finishes, and reacts at room temperature, anti-after 3 hours
It should finish.Reaction solution is poured into 30 milliliters of water, takes organic layer, and organic layer uses saturated sodium bicarbonate aqueous solution, saturation food respectively
Salt water washing, anhydrous magnesium sulfate is dry, and solvent to the greatest extent is steamed in decompression.Residue purifies (leacheate: ethyl acetate: stone by column chromatography
Oily ether=1:2), obtain 190 milligrams of compounds 41, yield 72.0%.
Other compound of Formula I of the invention can refer to above method synthesis.
Biological activity determination embodiment
The measurement of 3 bactericidal activity of embodiment
It is tested with multiple diseases of the compounds of this invention to plant.The method of test is as follows:
Using living body potting measuring method, i.e., by test compound sample a small amount of solvent (type of solvent such as acetone, first
Alcohol, DMF etc. are selected according to its solvability to sample, and the volume ratio of quantity of solvent and spouting liquid is equal to or less than 0.05.)
Dissolution is diluted with the water containing 0.1% Tween 80, is configured to required concentration prepare liquid.It is dense according to designing with the compounds of this invention
Degree carries out foliar spray processing.Separately set the blank control of spray clear water, 3 repetitions, progress disease inoculation in second day after processing.Inoculation
Afterwards, plant is placed on moisturizing culture in phjytotron (temperature: 25 DEG C of daytime, 20 DEG C of night, relative humidity: 95-99%).Test material
After material culture for 24 hours, dislocation hot-house culture directly in warm indoor inoculation and cultivates the plant for not needing moisturizing culture.Wait compare
(usually week age) carries out the assessment of compound protection effect after the onset of sufficiently.As a result investigation can write referring to U.S.'s pathology of plants
" A Manual of Assessment Keys for Plant Diseases ", indicated with 100~0, with " 100 " grade generation
Table is disease-free and " 0 " grade represents the occurring degree of most serious.
Partial test result is as follows:
To the preventive effect of cucumber anthracnose:
According to the above test method, partially in the compound of examination, following compounds prevention and treatment when concentration is 400ppm is imitated
Fruit is preferable, preventive effect >=80%: compound 4.
To the preventive effect of cucumber downy mildew:
According to the above test method, partially in the compound of examination, following compounds prevention and treatment when concentration is 400ppm is imitated
Fruit is preferable, preventive effect >=80%: compound 2,4,11,13,36.
According to the above test method, the compounds of this invention 2, compound 4, compound 11 and compound 13 and knownization are chosen
Close object KC1、KC2、KC3And KC4Carrying out the active parallel determination of prevention and treatment cucumber downy mildew, (control compound is self-control, structure warp
Nuclear magnetic resonance spectroscopy confirmation is consistent with the description of existing open source literature), test result is shown in Table 2.
Table 2: part the compounds of this invention is compared with known compound is to cucumber downy mildew
To the preventive effect of corn rust:
According to the above test method, partially in the compound of examination, following compounds are when concentration is 400ppm to corn
The control efficiency of rust is preferable, preventive effect >=80%: compound 2,4,11,13.
According to the above test method, compound 13 and known compound KC are chosen1It is active prevention and treatment corn rust has been carried out
It is measured in parallel.Test result is shown in Table 3.
Table 3: part the compounds of this invention is compared with known compound is to corn rust preventive effect
According to the above test method, compound 11 and known compound KC are chosen2It is active prevention and treatment corn rust has been carried out
It is measured in parallel.Test result is shown in Table 4.
Table 4: part the compounds of this invention is compared with known compound is to corn rust preventive effect
Claims (6)
1. a kind of pyrazol acid amide compounds, as shown in general formula I:
In formula:
R1Selected from C1-C3Alkyl；
R2Selected from hydrogen or chlorine；
R3Selected from C1-C3Alkyl
R4、R5And R6It is respectively selected from hydrogen；
R7Selected from C1-C6Alkyl.
2. compound described in accordance with the claim 1, which is characterized in that in general formula I:
R1Selected from methyl；
R2Selected from hydrogen or chlorine；
R3Selected from C1-C3Alkyl；
R4、R5And R6It is respectively selected from hydrogen；
R7Selected from methyl.
3. a kind of preparation method of compound of Formula I described in accordance with the claim 1, reaction equation are as follows:
Or
In formula:
L leaving group, X represent halogen；R1、R2、R3、R4、R5、R6And R7As defined in claim 1.
4. a kind of compound of Formula I described in accordance with the claim 1 is as being used as the use for preparing fungicide drug in agriculture field
On the way.
5. a kind of bactericidal composition is active component containing compound shown in general formula I as described in claim 1 and agriculturally may be used
The carrier of receiving, the weight content in composition as the compound of Formula I of active component are 1-99%.
6. a kind of method for controlling germ, it is characterised in that: by composition described in claim 5 with 10 grams to 1000 of per hectare
Gram effective dose impose on the medium for needing the germ that controls or its growth.
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| CN201510226412.1A CN106187893B (en) | 2015-05-06 | 2015-05-06 | A kind of pyrazol acid amide compounds and application thereof |
| US15/551,401 US10315998B2 (en) | 2015-05-06 | 2016-05-04 | Amide compound and the preparation method and use thereof |
| EP16789312.2A EP3293179A4 (en) | 2015-05-06 | 2016-05-04 | Amide compound and the preparation method and use thereof |
| PCT/CN2016/080952 WO2016177318A1 (en) | 2015-05-06 | 2016-05-04 | Amide compound and the preparation method and use thereof |
| CN201680004319.9A CN107108515B (en) | 2015-05-06 | 2016-05-04 | A kind of amides compound and its preparation method and application |
| BR112017014498-0A BR112017014498B1 (en) | 2015-05-06 | 2016-05-04 | Amide compound and the method of preparation and use thereof |
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| CN109867628A (en) * | 2017-12-02 | 2019-06-11 | 沈阳中化农药化工研发有限公司 | Substituted aryl pyrazole carboxylic acid compound and application thereof |
| CN111285807B (en) * | 2018-12-07 | 2023-06-23 | 沈阳中化农药化工研发有限公司 | Pyrazole amide compound and application thereof |
| CN111285815A (en) * | 2018-12-07 | 2020-06-16 | 沈阳中化农药化工研发有限公司 | Pyrazinamide compound and application thereof |
| CN112390727B (en) * | 2019-08-16 | 2021-12-07 | 沈阳中化农药化工研发有限公司 | Oxime carboxylate compound and application thereof |
| WO2021031984A1 (en) * | 2019-08-16 | 2021-02-25 | 沈阳中化农药化工研发有限公司 | Carboxylic acid oxime ester compound and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1078234A (en) * | 1991-12-06 | 1993-11-10 | 孟山都公司 | Pyrazole carboxanilide fungicide |
| CN103391925A (en) * | 2010-11-15 | 2013-11-13 | 拜耳知识产权有限责任公司 | 5-halogenopyrazolecarboxamides |
| CN103524419A (en) * | 2013-10-18 | 2014-01-22 | 孙家隆 | Group of 3-trifluoromethyl pyrazole compounds |
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| JPS62249975A (en) * | 1986-04-22 | 1987-10-30 | Sumitomo Chem Co Ltd | Anilide derivative and germicide containing said derivative as active ingredient |
| JP4378855B2 (en) * | 2000-06-05 | 2009-12-09 | 宇部興産株式会社 | 5- (1-Fluoroethyl) -1-methylpyrazole-4-carboxylic acid amide derivatives and pest control agents for agriculture and horticulture |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1078234A (en) * | 1991-12-06 | 1993-11-10 | 孟山都公司 | Pyrazole carboxanilide fungicide |
| CN103391925A (en) * | 2010-11-15 | 2013-11-13 | 拜耳知识产权有限责任公司 | 5-halogenopyrazolecarboxamides |
| CN103524419A (en) * | 2013-10-18 | 2014-01-22 | 孙家隆 | Group of 3-trifluoromethyl pyrazole compounds |
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