CN103087041B - Use of diarylether-containing pyrazole-amide compounds as agricultural bactericide - Google Patents
Use of diarylether-containing pyrazole-amide compounds as agricultural bactericide Download PDFInfo
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- CN103087041B CN103087041B CN201110342469.XA CN201110342469A CN103087041B CN 103087041 B CN103087041 B CN 103087041B CN 201110342469 A CN201110342469 A CN 201110342469A CN 103087041 B CN103087041 B CN 103087041B
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Abstract
The invention discloses a use of diarylether-containing pyrazole-amide compounds having a structure represented by a general formula shown in the specification as an agricultural bactericide. Each substituent in the general formula is defined in the specification. The compounds have good bactericidal activities and have excellent control effects on diseases comprising cucumber downy mildew, rice blast and the like.
Description
Technical field
The invention belongs to disinfectant use in agriculture field, relate to particularly a kind of pyrazol acid amide compounds of two aryl oxides that contains as the purposes of disinfectant use in agriculture.
Background technology
Patent WO2009117421A2 discloses following N-benzyl pyrazole acidamide derivative cardiovascular and metabolic trouble has been had to therapeutic activity.
Patent WO2008073825A1 discloses following pyrazole amide analog derivative and has medically used as receptor modulators.
Patent WO2006069155A2 discloses following compound and has been used for treating the diseases such as inflammation infection as medicine.
Structure has no bibliographical information as the purposes of disinfectant use in agriculture as the pyrazol acid amide compounds that contains two aryl oxides of the present invention.
Summary of the invention
In order to obtain the novel germicide of preventing and treating various crop disease of new mechanism of action uniqueness, the present invention is studied the pyrazol acid amide compounds containing two aryl oxides shown in following general formula, find that first this compounds has fungicidal activity, especially has good preventive effect to the disease such as cucumber downy mildew, rice blast.
The pyrazol acid amide compounds containing two aryl oxides as disinfectant use in agriculture provided by the invention has following general structure:
In formula:
R
1be selected from hydrogen, halogen, cyano group, cyano group C
1-C
12alkyl, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, cyano group C
1-C
12alkoxyl group, C
1-C
12alkylthio, halo C
1-C
12alkylthio, C
1-C
12alkoxy C
1-C
12alkyl, halo C
1-C
12alkoxy C
1-C
12alkyl, C
1-C
12alkylthio C
1-C
12alkyl, halo C
1-C
12alkylthio C
1-C
12alkyl, C
1-C
12alkyl sulphinyl, halo C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphonyl or C
3-C
6cycloalkyl;
R
2be selected from hydrogen, halogen, nitro, cyano group, SCN, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
2-C
12thiazolinyl, C
2-C
12alkynyl, C
2-C
12alkene oxygen base, halo C
2-C
12alkene oxygen base, C
2-C
12alkynyloxy group, halo C
2-C
12alkynyloxy group, C
1-C
12alkylthio, C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphinyl, halo C
1-C
12alkyl sulphonyl, halo C
1-C
12alkylthio, C
1-C
12alkoxy C
1-C
12alkyl, halo C
1-C
12alkoxy C
1-C
12alkyl, C
1-C
12alkylthio C
1-C
12alkyl or halo C
1-C
12alkylthio C
1-C
12alkyl;
R
3, R
4can be identical or different, be selected from respectively hydrogen, halogen, cyano group, nitro, hydroxyl, amino, sulfydryl, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
3-C
6cycloalkyl, C
2-C
12thiazolinyl, C
2-C
12alkynyl, C
2-C
12alkene oxygen base, halo C
2-C
12alkene oxygen base, C
2-C
12alkynyloxy group, halo C
2-C
12alkynyloxy group, C
1-C
12alkylthio, halo C
1-C
12alkylthio, C
1-C
12alkoxy C
1-C
12alkyl, halo C
1-C
12alkoxy C
1-C
12alkyl, C
1-C
12alkylthio C
1-C
12alkyl, halo C
1-C
12alkylthio C
1-C
12alkyl, C
1-C
12alkyl sulphinyl, halo C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphonyl, C
1-C
12alkylamino, halo C
1-C
12alkylamino, C
2-C
12dialkyl amido, C
1-C
12alkyl-carbonyl, halo C
1-C
12alkyl-carbonyl, C
1-C
12alkyl-carbonyl oxygen base, C
1-C
12alkyl-carbonyl-amino, C
1-C
12alkoxy carbonyl or C
1-C
12alkyl amino-carbonyl;
R
5be selected from halogen, cyano group, nitro, hydroxyl, amino, sulfydryl, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
3-C
6cycloalkyl, C
2-C
12thiazolinyl, C
2-C
12alkynyl, C
2-C
12alkene oxygen base, halo C
2-C
12alkene oxygen base, C
2-C
12alkynyloxy group, halo C
2-C
12alkynyloxy group, C
1-C
12alkylthio, halo C
1-C
12alkylthio, C
1-C
12alkoxy C
1-C
12alkyl, halo C
1-C
12alkoxy C
1-C
12alkyl, C
1-C
12alkylthio C
1-C
12alkyl, halo C
1-C
12alkylthio C
1-C
12alkyl, C
1-C
12alkyl sulphinyl, halo C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphonyl, C
1-C
12alkylamino, halo C
1-C
12alkylamino, C
2-C
12dialkyl amido, C
1-C
12alkyl-carbonyl, halo C
1-C
12alkyl-carbonyl, C
1-C
12alkyl-carbonyl oxygen base, C
1-C
12alkyl-carbonyl-amino, C
1-C
12alkoxy carbonyl or C
1-C
12alkyl amino-carbonyl; M is the integer of 0-5;
R
6be selected from halogen, cyano group, nitro, hydroxyl, amino, sulfydryl, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
3-C
6cycloalkyl, C
2-C
12thiazolinyl, C
2-C
12alkynyl, C
2-C
12alkene oxygen base, halo C
2-C
12alkene oxygen base, C
2-C
12alkynyloxy group, halo C
2-C
12alkynyloxy group, C
1-C
12alkylthio, halo C
1-C
12alkylthio, C
1-C
12alkoxy C
1-C
12alkyl, halo C
1-C
12alkoxy C
1-C
12alkyl, C
1-C
12alkylthio C
1-C
12alkyl, halo C
1-C
12alkylthio C
1-C
12alkyl, C
1-C
12alkyl sulphinyl, halo C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphonyl, C
1-C
12alkylamino, halo C
1-C
12alkylamino, C
2-C
12dialkyl amido, C
1-C
12alkyl-carbonyl, halo C
1-C
12alkyl-carbonyl, C
1-C
12alkyl-carbonyl oxygen base, C
1-C
12alkyl-carbonyl-amino, C
1-C
12alkoxy carbonyl or C
1-C
12alkyl amino-carbonyl; N is the integer of 0-5;
Be selected from-CH of A
2-,-(CH
2)
2-,-(CH
2)
3-,-CH (CH
3)-,-C (CH
3)
2-,-C (CN) (CH
3)-,-CH (CN)-or-C (CH
2cH
3) (CH
3)-;
X, Y can be identical or different, are selected from respectively C-R
7or N;
R
7be selected from hydrogen, halogen, cyano group, nitro, hydroxyl, amino, C
1-C
6alkyl, halo C
1-C
6alkyl, C
1-C
6alkoxyl group, halo C
1-C
6alkoxyl group, C
3-C
6cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6alkynyl, C
2-C
6alkene oxygen base, halo C
2-C
6alkene oxygen base, C
2-C
6alkynyloxy group, halo C
2-C
6alkynyloxy group, C
1-C
6alkylthio, halo C
1-C
6alkylthio, C
1-C
6alkoxy C
1-C
6alkyl, halo C
1-C
6alkoxy C
1-C
6alkyl, C
1-C
6alkylthio C
1-C
6alkyl, halo C
1-C
6alkylthio C
1-C
6alkyl, C
1-C
6alkyl sulphinyl, halo C
1-C
6alkyl sulphinyl, C
1-C
6alkyl sulphonyl, halo C
1-C
6alkyl sulphonyl, C
1-C
6alkylamino, halo C
1-C
6alkylamino or C
2-C
6dialkyl amido.
In the above-mentioned pyrazol acid amide compounds that contains two aryl oxides during as the purposes of disinfectant use in agriculture comparatively preferably: in general formula (I)
R
1be selected from hydrogen, halogen, cyano group, cyano group C
1-C
8alkyl, C
1-C
8alkyl, halo C
1-C
8alkyl, C
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, cyano group C
1-C
8alkoxyl group, C
1-C
8alkylthio, halo C
1-C
8alkylthio, C
1-C
8alkoxy C
1-C
8alkyl, halo C
1-C
8alkoxy C
1-C
8alkyl, C
1-C
8alkylthio C
1-C
8alkyl, halo C
1-C
8alkylthio C
1-C
8alkyl, C
1-C
8alkyl sulphinyl, halo C
1-C
8alkyl sulphinyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphonyl or C
3-C
6cycloalkyl;
R
2be selected from hydrogen, halogen, nitro, cyano group, SCN, C
1-C
8alkyl, halo C
1-C
8alkyl, C
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, C
2-C
8thiazolinyl, C
2-C
8alkynyl, C
2-C
8alkene oxygen base, halo C
2-C
8alkene oxygen base, C
2-C
8alkynyloxy group, halo C
2-C
8alkynyloxy group, C
1-C
8alkylthio, C
1-C
8alkyl sulphinyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphinyl, halo C
1-C
8alkyl sulphonyl, halo C
1-C
8alkylthio, C
1-C
8alkoxy C
1-C
8alkyl, halo C
1-C
8alkoxy C
1-C
8alkyl, C
1-C
8alkylthio C
1-C
8alkyl or halo C
1-C
8alkylthio C
1-C
8alkyl;
R
3, R
4can be identical or different, be selected from respectively hydrogen, halogen, cyano group, nitro, hydroxyl, amino, sulfydryl, C
1-C
8alkyl, halo C
1-C
8alkyl, C
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, C
3-C
6cycloalkyl, C
2-C
8thiazolinyl, C
2-C
8alkynyl, C
2-C
8alkene oxygen base, halo C
2-C
8alkene oxygen base, C
2-C
8alkynyloxy group, halo C
2-C
8alkynyloxy group, C
1-C
8alkylthio, halo C
1-C
8alkylthio, C
1-C
8alkoxy C
1-C
8alkyl, halo C
1-C
8alkoxy C
1-C
8alkyl, C
1-C
8alkylthio C
1-C
8alkyl, halo C
1-C
8alkylthio C
1-C
8alkyl, C
1-C
8alkyl sulphinyl, halo C
1-C
8alkyl sulphinyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphonyl, C
1-C
8alkylamino, halo C
1-C
8alkylamino, C
2-C
8dialkyl amido, C
1-C
8alkyl-carbonyl, halo C
1-C
8alkyl-carbonyl, C
1-C
8alkyl-carbonyl oxygen base, C
1-C
8alkyl-carbonyl-amino, C
1-C
8alkoxy carbonyl or C
1-C
8alkyl amino-carbonyl;
R
5be selected from halogen, cyano group, nitro, hydroxyl, amino, sulfydryl, C
1-C
8alkyl, halo C
1-C
8alkyl, C
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, C
3-C
6cycloalkyl, C
2-C
8thiazolinyl, C
2-C
8alkynyl, C
2-C
8alkene oxygen base, halo C
2-C
8alkene oxygen base, C
2-C
8alkynyloxy group, halo C
2-C
8alkynyloxy group, C
1-C
8alkylthio, halo C
1-C
8alkylthio, C
1-C
8alkoxy C
1-C
8alkyl, halo C
1-C
8alkoxy C
1-C
8alkyl, C
1-C
8alkylthio C
1-C
8alkyl, halo C
1-C
8alkylthio C
1-C
8alkyl, C
1-C
8alkyl sulphinyl, halo C
1-C
8alkyl sulphinyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphonyl, C
1-C
8alkylamino, halo C
1-C
8alkylamino, C
2-C
8dialkyl amido, C
1-C
8alkyl-carbonyl, halo C
1-C
8alkyl-carbonyl, C
1-C
8alkyl-carbonyl oxygen base, C
1-C
8alkyl-carbonyl-amino, C
1-C
8alkoxy carbonyl or C
1-C
8alkyl amino-carbonyl; M is the integer of 1-5;
R
6be selected from halogen, cyano group, nitro, hydroxyl, amino, sulfydryl, C
1-C
8alkyl, halo C
1-C
8alkyl, C
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, C
3-C
6cycloalkyl, C
2-C
8thiazolinyl, C
2-C
8alkynyl, C
2-C
8alkene oxygen base, halo C
2-C
8alkene oxygen base, C
2-C
8alkynyloxy group, halo C
2-C
8alkynyloxy group, C
1-C
8alkylthio, halo C
1-C
8alkylthio, C
1-C
8alkoxy C
1-C
8alkyl, halo C
1-C
8alkoxy C
1-C
8alkyl, C
1-C
8alkylthio C
1-C
8alkyl, halo C
1-C
8alkylthio C
1-C
8alkyl, C
1-C
8alkyl sulphinyl, halo C
1-C
8alkyl sulphinyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphonyl, C
1-C
8alkylamino, halo C
1-C
8alkylamino, C
2-C
8dialkyl amido, C
1-C
8alkyl-carbonyl, halo C
1-C
8alkyl-carbonyl, C
1-C
8alkyl-carbonyl oxygen base, C
1-C
8alkyl-carbonyl-amino, C
1-C
8alkoxy carbonyl or C
1-C
8alkyl amino-carbonyl; N is the integer of 1-4;
Be selected from-CH of A
2-,-(CH
2)
2-,-(CH
2)
3-,-CH (CH
3)-,-C (CH
3)
2-,-C (CN) (CH
3)-,-CH (CN)-or-C (CH
2cH
3) (CH
3)-;
X, Y can be identical or different, are selected from respectively C-R
7or N;
R
7be selected from hydrogen, halogen, cyano group, nitro, amino, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
3-C
6cycloalkyl, C
2-C
6thiazolinyl, C
2-C
6alkynyl, C
2-C
6alkene oxygen base, halo C
2-C
6alkene oxygen base, C
2-C
6alkynyloxy group, halo C
2-C
6alkynyloxy group, C
1-C
4alkylthio, halo C
1-C
4alkylthio, C
1-C
4alkoxy C
1-C
4alkyl, halo C
1-C
4alkoxy C
1-C
4alkyl, C
1-C
4alkylthio C
1-C
6alkyl, halo C
1-C
4alkylthio C
1-C
4alkyl, C
1-C
4alkyl sulphinyl, halo C
1-C
4alkyl sulphinyl, C
1-C
4alkyl sulphonyl, halo C
1-C
4alkyl sulphonyl, C
1-C
4alkylamino, halo C
1-C
4alkylamino or C
2-C
6dialkyl amido.
Further in preferred general formula (I) compound as disinfectant use in agriculture:
R
1be selected from hydrogen, halogen, cyano group, cyano group C
1-C
4alkyl, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, cyano group C
1-C
4alkoxyl group, C
1-C
4alkylthio, halo C
1-C
4alkylthio, C
1-C
4alkoxy C
1-C
8alkyl, halo C
1-C
4alkoxy C
1-C
4alkyl, C
1-C
4alkylthio C
1-C
4alkyl, halo C
1-C
4alkylthio C
1-C
4alkyl, C
1-C
4alkyl sulphinyl, halo C
1-C
4alkyl sulphinyl, C
1-C
4alkyl sulphonyl, halo C
1-C
4alkyl sulphonyl or C
3-C
6cycloalkyl;
R
2be selected from hydrogen, halogen, nitro, cyano group, SCN, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkylthio, C
1-C
4alkyl sulphinyl, C
1-C
4alkyl sulphonyl, halo C
1-C
4alkyl sulphinyl, halo C
1-C
4alkyl sulphonyl, halo C
1-C
4alkylthio, C
1-C
4alkoxy C
1-C
4alkyl, halo C
1-C
4alkoxy C
1-C
4alkyl, C
1-C
4alkylthio C
1-C
4alkyl or halo C
1-C
4alkylthio C
1-C
4alkyl;
R
3, R
4can be identical or different, be selected from respectively hydrogen, halogen, cyano group, nitro, amino, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group or halo C
1-C
4alkoxyl group;
R
5be selected from halogen, cyano group, nitro, amino, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkylthio, halo C
1-C
4alkylthio, C
1-C
4alkoxy C
1-C
4alkyl, halo C
1-C
4alkoxy C
1-C
4alkyl, C
1-C
4alkylthio C
1-C
4alkyl, halo C
1-C
4alkylthio C
1-C
4alkyl, C
1-C
4alkyl sulphinyl, halo C
1-C
4alkyl sulphinyl, C
1-C
4alkyl sulphonyl, halo C
1-C
4alkyl sulphonyl, C
1-C
4alkylamino, halo C
1-C
4alkylamino, C
2-C
6dialkyl amido, C
1-C
4alkyl-carbonyl, halo C
1-C
4alkyl-carbonyl, C
1-C
4alkyl-carbonyl oxygen base, C
1-C
4alkyl-carbonyl-amino, C
1-C
4alkoxy carbonyl or C
1-C
4alkyl amino-carbonyl; M is the integer of 1-5;
R
6be selected from halogen, cyano group, nitro, amino, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group; N is the integer of 1-4;
Be selected from-CH of A
2-,-(CH
2)
2-,-(CH
2)
3-,-CH (CH
3)-,-C (CH
3)
2-,-C (CN) (CH
3)-or-CH (CN)-;
X, Y can be identical or different, are selected from respectively CH, C-Cl or N.
Further in preferred general formula (I) compound as disinfectant use in agriculture:
R
1be selected from chlorine, bromine, methyl, ethyl or trifluoromethyl;
R
2be selected from hydrogen, chlorine, bromine, cyano group, methyl or ethyl;
R
3, R
4can be identical or different, be selected from respectively hydrogen, chlorine, bromine, cyano group, nitro, methyl, ethyl, trifluoromethyl, methoxyl group or trifluoromethoxy;
R
5be selected from chlorine, bromine, cyano group, nitro, amino, methyl, ethyl, a chlorodifluoramethyl-, trifluoromethyl, methoxyl group, trifluoromethoxy, methylthio group, methylsulfinyl, methyl sulphonyl or amino-carbonyl; M is the integer of 1-5;
R
6be selected from chlorine, bromine, cyano group, nitro, methyl, ethyl, methoxyl group or trifluoromethoxy; N is the integer of 1-3;
Be selected from-CH of A
2-,-(CH
2)
2-or-(CH
2)
3-;
X, Y can be identical or different, are selected from respectively CH, C-Cl or N.
Again in further preferred general formula (I) compound as disinfectant use in agriculture:
R
1be selected from chlorine, bromine or ethyl;
R
2be selected from hydrogen or chlorine;
R
3, R
4be selected from hydrogen;
R
5be selected from chlorine, cyano group, nitro, a chlorodifluoramethyl-, trifluoromethyl or amino-carbonyl; M is the integer of 1-5;
R
6be selected from chlorine; N is 1 or 2;
Be selected from-CH of A
2-or-(CH
2)
2-;
X, Y can be identical or different, are selected from respectively CH, C-Cl or N.
In the definition of the compound (I) providing, collect the following substituting group of term general proxy used above:
Halogen: refer to fluorine, chlorine, bromine or iodine.Alkyl: straight or branched alkyl, for example methyl, ethyl, propyl group, sec.-propyl, normal-butyl or the tertiary butyl.Cycloalkyl: replace or unsubstituted cyclic alkyl, for example cyclopropyl, cyclopentyl or cyclohexyl.Substituting group is as methyl, halogen etc.Haloalkyl: straight or branched alkyl, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen atom, for example, chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl etc.Alkoxyl group: straight or branched alkyl, is connected in structure through Sauerstoffatom key.Alkoxyalkyl: alkoxyl group is connected in structure through alkyl.As CH
3oCH
2-, CH
3cH
2oCH
2-.Halogenated alkoxy alkyl: the hydrogen atom on the alkyl of alkoxyalkyl can partly or entirely be replaced by halogen atom.As ClCH
2cH
2oCH
2-.Halogenated alkoxy: straight or branched alkoxyl group, the hydrogen atom on these alkoxyl groups can partly or entirely be replaced by halogen atom.For example, chlorine methoxyl group, dichloro methoxyl group, trichlorine methoxyl group, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, chlorine fluorine methoxyl group, trifluoro ethoxy etc.Alkylthio: straight or branched alkyl, is connected in structure through sulphur atom key.Alkylthio alkyl: alkylthio is connected in structure through alkyl.As CH
3sCH
2-.Halogenated alkylthio: straight or branched alkylthio, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen atom.For example, chloromethane sulfenyl, dichloromethane sulfenyl, trichloro-methylthio, fluorine methylthio group, difluoro methylthio group, trifluoromethylthio, chlorine fluorine methylthio group etc.Halogenated alkylthio alkyl: halogenated alkylthio is connected in structure through alkyl, as ClCH
2sCH
2-.Alkylamino: straight or branched alkyl, is connected in structure through nitrogen-atoms key.Haloalkyl amino: straight or branched alkylamino, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen atom.Thiazolinyl: straight or branched alkene class, for example vinyl, 1-propenyl, 2-propenyl and different butenyl, pentenyl and hexenyl isomer.Thiazolinyl also comprises polyenoid class, as 1,2-propadiene base and 2,4-hexadienyl.Haloalkenyl group: straight or branched alkene class, the hydrogen atom on these thiazolinyls can partly or entirely be replaced by halogen atom.Alkynyl: straight or branched alkynes class, for example ethynyl, 1-proyl, 2-propynyl and different butynyl, pentynyl and hexin base isomer.Alkynyl also comprises the group being made up of multiple triple bonds, as 2,5-hexadiyne base.Halo alkynyl: straight or branched alkynes class, the hydrogen atom on these alkynyls can partly or entirely be replaced by halogen atom.Alkene oxygen base: straight or branched alkene class, is connected in structure through Sauerstoffatom key.Haloalkene oxygen base: straight or branched alkene oxygen base, the hydrogen atom on these alkene oxygen bases can partly or entirely be replaced by halogen atom.Alkynyloxy group: straight or branched alkynes class, is connected in structure through Sauerstoffatom key.Halo alkynyloxy group: straight or branched alkynyloxy group, the hydrogen atom on these alkynyloxy groups can partly or entirely be replaced by halogen atom.Alkyl sulphinyl: straight or branched alkyl is connected in structure through sulfinyl (SO-), as methylsulfinyl.Haloalkyl sulfinyl: straight or branched alkyl sulphinyl, the hydrogen atom on its alkyl can partly or entirely be replaced by halogen atom.Alkyl sulphonyl: straight or branched alkyl is through alkylsulfonyl (SO
2-) be connected in structure, as methyl sulphonyl.Halogenated alkyl sulfonyl: straight or branched alkyl sulphonyl, the hydrogen atom on its alkyl can partly or entirely be replaced by halogen atom.Alkyl-carbonyl: alkyl is connected in structure through carbonyl, as CH
3cO-, CH
3cH
2cO-.Halogenated alkyl carbonyl: the hydrogen atom on the alkyl of alkyl-carbonyl can partly or entirely be replaced by halogen atom, as CF
3cO-.Alkyl amino-carbonyl: as CH
3nHCO-, CH
3cH
2nHCO-.Alkoxy carbonyl: alkoxyl group is connected in structure through carbonyl.As CH
3oCO-, CH
3cH
2oCO-.Alkyl-carbonyl oxygen base: as CH
3cOO-, CH
3cH
2nHCOO-.Alkyl-carbonyl-amino: as CH
3cONH-, CH
3cH
2nHCONH-.
The preparation of the compound shown in general formula of the present invention (I) can divide following three kinds of situations:
The first situation, works as A-CH
2in-time, preparation method is as shown in reaction scheme below:
In formula, L is leavings group, is halogen, methanesulfonate ester or p-toluenesulfonic esters.Other each group definition are the same.
In suitable solvent, under suitable alkali exists, general formula (V-1) reacts with (VI), processes and obtain (IV-1).Concrete preparation can be with reference to fine chemistry industry, and 2005,22 (12): the method for describing in 944-960 is carried out.Reaction is carried out to solvent boiling point temperature range in room temperature conventionally, and more suitable temperature of reaction is 20～100 ℃.Reaction times is 30 minutes to 20 hours, common 1～10 hour.The optional acetone freely of suitable solvent, butanone, tetrahydrofuran (THF), acetonitrile, toluene, dimethylbenzene, benzene, DMF, methyl-sulphoxide, methyl alcohol or ethanol etc.The optional potassium hydroxide freely of suitable alkali, sodium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, triethylamine, pyridine or sodium hydride etc.
In suitable solvent, (IV-1) under suitable catalyzer and ammoniacal liquor existence, obtain (II-1) through hydrogenating reduction.Concrete preparation can reference literature J.Am.Chem.Soc, and 70,3788 (1948); 82,681 (1960); 82,2386 (1960); Can.J.Chem, 49,2990 (1971); J.Org.Chem, 37,335 (1972); Organic Syntheses, Coll.Vol.3, p.229, p.720 (1955), and Vol.23, p.71 (1943) or Vol.27, method of p.18 describing in (1947) is carried out.Reaction is carried out to solvent boiling point temperature range in room temperature conventionally, and more suitable temperature of reaction is 20～100 ℃.Reaction times is 30 minutes to 20 hours, common 1～10 hour.Suitable solvent can be selected from methyl alcohol, ethanol, Virahol, benzene,toluene,xylene, acetone, methylethylketone, mibk, chloroform, methylene dichloride, methyl acetate, ethyl acetate, tetrahydrofuran (THF), diox, DMF, N-Methyl pyrrolidone or methyl-sulphoxide etc.Suitable catalyzer can be selected from Raney's nickel, palladium carbon or platinum oxide etc.
The compound of general formula (I-1) representative can be by the pyrazol formyl chloride shown in the amine shown in general formula (II-1) and general formula (III) in suitable solvent, and under suitable alkali exists, (also can without alkali) condensation makes.Concrete preparation method is with reference to EP0365925A1, US5264448A.Suitable solvent can be selected from benzene,toluene,xylene, acetone, methylethylketone, mibk, tetrahydrofuran (THF), acetonitrile, diox, DMF, N-Methyl pyrrolidone, methyl-sulphoxide, pyridine, methylene dichloride, chloroform, ethylene dichloride, methyl acetate or ethyl acetate etc.The optional potassium hydroxide freely of suitable alkali, sodium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, triethylamine, pyridine or sodium hydride etc.Temperature of reaction can, in room temperature between solvent boiling point temperature, be generally 20～100 ℃.Reaction times is 30 minutes to 20 hours, common 1～10 hour.
The second situation, as A-(CH
2)
2-,-(CH
2)
3in-time, preparation method is as shown in reaction scheme below:
In formula, A
1for than the counter structure of the few carbon atom of A.Other each group definition are the same.
By (V-2) and (VI) reaction, make the reaction conditions of (I-2) and the selection of solvent, alkali and metal catalyst through intermediate (IV-2), (II-2) and be all same as in the first situation by (V-1) and (VI) reaction, make the corresponding steps of (I-1) through intermediate (IV-1), (II-1).
The third situation, when A is-CH (CH
3)-,-C (CH
3)
2-,-C (CN) (CH
3)-,-CH (CN)-or-C (CH
2cH
3) (CH
3)-time, preparation method is as shown in reaction scheme below:
In formula, Boc
2o refers to tert-Butyl dicarbonate.Other each group definition are the same.
First,, in suitable solvent, under the existence of suitable alkali, tert-Butyl dicarbonate and corresponding amino-phenol react in 0～100 ℃, first make the amino-phenol (VII) of Boc protection.Preferably 0～50 ℃ of temperature of reaction; Reaction times is 30 minutes to 20 hours, preferably 0.5～10 hour.Suitable solvent is selected from benzene,toluene,xylene, chloroform, methylene dichloride, tetrahydrofuran (THF), acetonitrile, diox, DMF, N-Methyl pyrrolidone or methyl-sulphoxide etc.; Suitable alkali is selected from alkaline carbonate for example sodium carbonate, sodium bicarbonate, salt of wormwood or saleratus.
Then, by (VII) with (VI) in suitable solvent, under the existence of suitable alkali, obtain (VIII) in 0～100 ℃ of condensation reaction.30 minutes to 20 hours reaction times, preferably 0.5～10 hour.Suitable solvent is selected from benzene,toluene,xylene, chloroform, methylene dichloride, acetone, butanone, tetrahydrofuran (THF), acetonitrile, diox, DMF, N-Methyl pyrrolidone or methyl-sulphoxide etc.; Suitable alkali is selected from such as sodium hydride of metal hydride, for example sodium hydroxide of alkali metal hydroxide or potassium hydroxide, for example sodium carbonate of alkaline carbonate or salt of wormwood, for example pyridine of organic amine or triethylamine.
(VIII) in suitable solvent, obtain corresponding salt through suitable sour deprotection, then alkalize to obtain (II-3).Preferably 0～50 ℃ of temperature of reaction; Reaction times is 30 minutes to 20 hours, preferably 0.5～10 hour.Suitable solvent is selected from ethyl acetate, methyl acetate, methyl-formiate, benzene,toluene,xylene, chloroform, methylene dichloride, water, tetrahydrofuran (THF), acetonitrile, diox, DMF, N-Methyl pyrrolidone or methyl-sulphoxide etc.; Suitable acid is selected from hydrochloric acid, trifluoroacetic acid, sulfuric acid, acetic acid, propionic acid, butyric acid, oxalic acid, hexanodioic acid, dodecanedioic acid, lauric acid, stearic acid, fumaric acid, toxilic acid, phenylformic acid or phthalic acid etc.; Described alkali is selected from such as sodium hydride of metal hydride, for example sodium hydroxide of alkali metal hydroxide or potassium hydroxide; For example sodium carbonate of alkaline carbonate or salt of wormwood, for example pyridine of organic amine or triethylamine.Concrete preparation method is referring to WO2004093800A.
The compound of general formula (I-3) representative can be by the pyrazol formyl chloride shown in the amine shown in general formula (II-3) and general formula (III) in suitable solvent, and under suitable alkali exists, (also can without alkali) condensation makes.The selection of reaction conditions and solvent, alkali is all same as in the first situation reacts and makes (I-1) by (II-1) with (III).
Raw material sources related in the preparation method of above-mentioned general formula (I) compound are as follows:
General formula (V-1), (V-2) and (VI) shown in compound all have commercially available, (V-3) compound shown in or have commercially available or according to known references as JP61024550, US4843160, US4746754, US2396580, JP02017164, Afinidad, 42 (397), 270-2; The method preparation of 1985 reports such as grade.General formula (III) compound is commercially available, also can be according to known references as Annalen der Chemie Justus Liebig ' s, 536,97 (1938), Bull.Soc.Chim.France, 293 (1966), the method preparation of the report such as US4950668, JP2292263, JP2053776, JP4069361, JP4069379, US2004171649A1 or US2005215798A1.
Can the present invention be described with the compound of listing in table 1 below, but not limit the present invention.
Table 1 general formula (I) part of compounds
| Numbering | X | (R 6)n | R 1 | R 2 | A | R 3 | R 4 | Y | (R 5)m |
| 1 | N | 3-Cl | Br | H | -CH 2- | H | H | C-Cl | 6-Cl-4-NO 2 |
| 2 | N | 3，5-di-Cl | Br | H | -CH 2- | H | H | C-Cl | 6-Cl-4-NO 2 |
| 3 | N | 3，5，6-triCl | Br | H | -CH 2- | H | H | C-Cl | 6-Cl-4-NO 2 |
| 4 | CH | 2-CH 3-4-Cl | Br | H | -CH 2- | H | H | C-Cl | 6-Cl-4-NO 2 |
| 5 | CH | 2-CH 3-4-CN | Br | H | -CH 2- | H | H | C-Cl | 6-Cl-4-NO 2 |
| 6 | CH | 2，4-diCl | Br | H | -CH 2- | H | H | C-Cl | 6-Cl-4-NO 2 |
| 7 | N | 3-Cl | Br | H | -CH 2- | H | H | CH | 4-CF 3 |
| 8 | N | 3，5-di-Cl | Br | H | -CH 2- | H | H | CH | 4-CF 3 |
| 9 | N | 3，5，6-triCl | Br | H | -CH 2- | H | H | CH | 4-CF 3 |
| 10 | CH | 2-CH 3-4-Cl | Br | H | -CH 2- | H | H | CH | 4-CF 3 |
| 11 | CH | 2-CH 3-4-CN | Br | H | -CH 2- | H | H | CH | 4-CF 3 |
| 12 | CH | 2，4-diCl | Br | H | -CH 2- | H | H | CH | 4-CF 3 |
| 13 | N | 3-Cl | Br | H | -CH 2- | H | H | CH | 4-OCF 3 |
| 14 | N | 3，5-di-Cl | Br | H | -CH 2- | H | H | CH | 4-OCF 3 |
| 15 | N | 3，5，6-triCl | Br | H | -CH 2- | H | H | CH | 4-OCF 3 |
| 16 | CH | 2-CH 3-4-Cl | Br | H | -CH 2- | H | H | CH | 4-OCF 3 |
| 17 | CH | 2-CH 3-4-CN | Br | H | -CH 2- | H | H | CH | 4-OCF 3 |
| 18 | CH | 2，4-diCl | Br | H | -CH 2- | H | H | CH | 4-OCF 3 |
| 19 | N | 3-Cl | Br | H | -CH 2- | H | H | CH | 2-CH 3-4-Cl |
| 20 | N | 3，5-di-Cl | Br | H | -CH 2- | H | H | CH | 2，4-diCl |
| 21 | N | 3，5，6-triCl | Br | H | -CH 2- | H | H | CH | 5-CF 3 |
| 22 | N | 3-Cl | Cl | H | -CH 2- | H | H | CH | 3-Cl-5-CF 3 |
| 23 | N | 3-Cl | Cl | H | -CH 2- | H | H | CH | 2-CH 3-4-Cl |
| 24 | N | 3-Cl | Cl | H | -CH 2- | H | H | CH | 2，4-diCl |
| 25 | N | 3-Cl | Cl | H | -CH 2- | H | H | CH | 5-CF 3 |
| 26 | N | 3-Cl | CF 3 | H | -CH 2- | H | H | CH | 3-Cl-5-CF 3 |
| 27 | N | 3-Cl | CF 3 | H | -CH 2- | H | H | CH | 2-CH 3-4-Cl |
| 28 | N | 3-Cl | CF 3 | H | -CH 2- | H | H | CH | 2，4-diCl |
| 29 | N | 3-Cl | CF 3 | H | -CH 2- | H | H | CH | 5-CF 3 |
| 30 | N | 3-Cl | CH 3 | H | -CH 2- | H | H | CH | 3-Cl-5-CF 3 |
| 31 | N | 3-Cl | CH 3 | H | -CH 2- | H | H | CH | 2-CH 3-4-Cl |
| 32 | N | 3-Cl | CH 3 | H | -CH 2- | H | H | CH | 2，4-diCl |
| 33 | N | 3-Cl | CH 3 | H | -CH 2- | H | H | CH | 5-CF 3 |
| 34 | N | 3-Cl | C 2H 5 | H | -CH 2- | H | H | CH | 3-Cl-5-CF 3 |
| 35 | N | 3-Cl | C 2H 5 | H | -CH 2- | H | H | CH | 2-CH 3-4-Cl |
| 36 | N | 3-Cl | C 2H 5 | H | -CH 2- | H | H | CH | 2，4-diCl |
| 37 | N | 3-Cl | C 2H 5 | H | -CH 2- | H | H | CH | 5-CF 3 |
| 38 | N | 3-Cl | Cl | Cl | -CH 2- | H | H | CH | 3-Cl-5-CF 3 |
| 39 | N | 3-Cl | Cl | Cl | -CH 2- | H | H | CH | 2-CH 3-4-Cl |
| 40 | N | 3-Cl | Cl | Cl | -CH 2- | H | H | CH | 2，4-diCl |
| 41 | N | 3-Cl | Cl | Cl | -CH 2- | H | H | CH | 5-CF 3 |
| 42 | N | 3-Cl | CF 3 | Cl | -CH 2- | H | H | CH | 3-Cl-5-CF 3 |
| 43 | N | 3-Cl | CF 3 | Cl | -CH 2- | H | H | CH | 2-CH 3-4-Cl |
| 44 | N | 3-Cl | CF 3 | Cl | -CH 2- | H | H | CH | 2，4-diCl |
| 45 | N | 3-Cl | CF 3 | Cl | -CH 2- | H | H | CH | 5-CF 3 |
| 46 | N | 3-Cl | CH 3 | Cl | -CH 2- | H | H | CH | 3-Cl-5-CF 3 |
| 47 | N | 3-Cl | CH 3 | Cl | -CH 2- | H | H | CH | 2-CH 3-4-Cl |
| 48 | N | 3-Cl | CH 3 | Cl | -CH 2- | H | H | CH | 2，4-diCl |
| 49 | N | 3-Cl | CH 3 | Cl | -CH 2- | H | H | CH | 5-CF 3 |
| 50 | N | 3-Cl | C 2H 5 | Cl | -CH 2- | H | H | CH | 3-Cl-5-CF 3 |
| 51 | N | 3-Cl | C 2H 5 | Cl | -CH 2- | H | H | CH | 2-CH 3-4-Cl |
| 52 | N | 3-Cl | C 2H 5 | Cl | -CH 2- | H | H | CH | 2，4-diCl |
| 53 | N | 3-Cl | C 2H 5 | Cl | -CH 2- | H | H | CH | 5-CF 3 |
| 54 | N | 3-Cl | Br | H | -CH 2- | H | H | N | 2-CH 3-4-Cl |
| 55 | N | 3，5-di-Cl | Br | H | -CH 2- | H | H | N | 2，4-diCl |
| 56 | N | 3，5，6-triCl | Br | H | -CH 2- | H | H | N | 5-CF 3 |
| 57 | N | 3-Cl | Cl | H | -CH 2- | H | H | N | 3-Cl-5-CF 3 |
| 58 | N | 3-Cl | Cl | H | -CH 2- | H | H | N | 2-CH 3-4-Cl |
| 59 | N | 3-Cl | Cl | H | -CH 2- | H | H | N | 2，4-diCl |
| 60 | N | 3-Cl | Cl | H | -CH 2- | H | H | N | 5-CF 3 |
| 61 | N | 3-Cl | CF 3 | H | -CH 2- | H | H | N | 3-Cl-5-CF 3 |
| 62 | N | 3-Cl | CF 3 | H | -CH 2- | H | H | N | 2-CH 3-4-Cl |
| 63 | N | 3-Cl | CF 3 | H | -CH 2- | H | H | N | 2，4-diCl |
| 64 | N | 3-Cl | CF 3 | H | -CH 2- | H | H | N | 5-CF 3 |
| 65 | N | 3-Cl | CH 3 | H | -CH 2- | H | H | N | 3-Cl-5-CF 3 |
| 66 | N | 3-Cl | CH 3 | H | -CH 2- | H | H | N | 2-CH 3-4-Cl |
| 67 | N | 3-Cl | CH 3 | H | -CH 2- | H | H | N | 2，4-diCl |
| 68 | N | 3-Cl | CH 3 | H | -CH 2- | H | H | N | 5-CF 3 |
| 69 | N | 3-Cl | C 2H 5 | H | -CH 2- | H | H | N | 3-Cl-5-CF 3 |
| 70 | N | 3-Cl | C 2H 5 | H | -CH 2- | H | H | N | 2-CH 3-4-Cl |
| 71 | N | 3-Cl | C 2H 5 | H | -CH 2- | H | H | N | 2，4-diCl |
| 72 | N | 3-Cl | C 2H 5 | H | -CH 2- | H | H | N | 5-CF 3 |
| 73 | N | 3-Cl | Br | Cl | -CH 2- | H | H | N | 2-CH 3-4-Cl |
| 74 | N | 3，5-di-Cl | Br | Cl | -CH 2- | H | H | N | 2，4-diCl |
| 75 | N | 3，5，6-triCl | Br | Cl | -CH 2- | H | H | N | 5-CF 3 |
| 76 | N | 3-Cl | Cl | Cl | -CH 2- | H | H | N | 3-Cl-5-CF 3 |
| 77 | N | 3-Cl | Cl | Cl | -CH 2- | H | H | N | 2-CH 3-4-Cl |
| 78 | N | 3-Cl | Cl | Cl | -CH 2- | H | H | N | 2，4-diCl |
| 79 | N | 3-Cl | Cl | Cl | -CH 2- | H | H | N | 5-CF 3 |
| 80 | N | 3-Cl | CF 3 | Cl | -CH 2- | H | H | N | 3-Cl-5-CF 3 |
| 81 | N | 3-Cl | CF 3 | Cl | -CH 2- | H | H | N | 2-CH 3-4-Cl |
| 82 | N | 3-Cl | CF 3 | Cl | -CH 2- | H | H | N | 2，4-diCl |
| 83 | N | 3-Cl | CF 3 | Cl | -CH 2- | H | H | N | 5-CF 3 |
| 84 | N | 3-Cl | CH 3 | Cl | -CH 2- | H | H | N | 3-Cl-5-CF 3 |
| 85 | N | 3-Cl | CH 3 | Cl | -CH 2- | H | H | N | 2-CH 3-4-Cl |
| 86 | N | 3-Cl | CH 3 | Cl | -CH 2- | H | H | N | 2，4-diCl |
| 87 | N | 3-Cl | CH 3 | Cl | -CH 2- | H | H | N | 5-CF 3 |
| 88 | N | 3-Cl | C 2H 5 | Cl | -CH 2- | H | H | N | 3-Cl-5-CF 3 |
| 89 | N | 3-Cl | C 2H 5 | Cl | -CH 2- | H | H | N | 2-CH 3-4-Cl |
| 90 | N | 3-Cl | C 2H 5 | Cl | -CH 2- | H | H | N | 2，4-diCl |
| 91 | N | 3-Cl | C 2H 5 | Cl | -CH 2- | H | H | N | 5-CF 3 |
| 92 | N | 3-Cl | Br | H | -(CH 2) 2- | H | H | CH | 4-CF 3 |
| 93 | N | 3-Cl | Br | H | -(CH 2) 2- | H | H | C-Cl | 6-Cl-4-NO 2 |
| 94 | N | 3-Cl | Br | H | -(CH 2) 2- | H | H | CH | 2，3，5-3Cl-4，6-2CN |
| 95 | N | 3-Cl | Br | H | -(CH 2) 2- | H | H | N | 2-CH 3-4-Cl |
| 96 | N | 3，5-di-Cl | Br | H | -(CH 2) 2- | H | H | N | 2，4-diCl |
| 97 | N | 3，5，6-triCl | Br | H | -(CH 2) 2- | H | H | N | 5-CF 3 |
| 98 | N | 3-Cl | Br | H | -(CH 2) 2- | H | H | N | 5-CF 3 |
| 99 | N | 3-Cl | Cl | H | -(CH 2) 2- | H | H | N | 3-Cl-5-CF 3 |
| 100 | N | 3-Cl | Cl | H | -(CH 2) 2- | H | H | N | 2-CH 3-4-Cl |
| 101 | N | 3-Cl | Cl | H | -(CH 2) 2- | H | H | N | 2，4-diCl |
| 102 | N | 3-Cl | Cl | H | -(CH 2) 2- | H | H | N | 5-CF 3 |
| 103 | N | 3-Cl | CF 3 | H | -(CH 2) 2- | H | H | N | 3-Cl-5-CF 3 |
| 104 | N | 3-Cl | CF 3 | H | -(CH 2) 2- | H | H | N | 2-CH 3-4-Cl |
| 105 | N | 3-Cl | CF 3 | H | -(CH 2) 2- | H | H | N | 2，4-diCl |
| 106 | N | 3-Cl | CF 3 | H | -(CH 2) 2- | H | H | N | 5-CF 3 |
| 107 | N | 3-Cl | CH 3 | H | -(CH 2) 2- | H | H | N | 3-Cl-5-CF 3 |
| 108 | N | 3-Cl | CH 3 | H | -(CH 2) 2- | H | H | N | 2-CH 3-4-Cl |
| 109 | N | 3-Cl | CH 3 | H | -(CH 2) 2- | H | H | N | 2，4-diCl |
| 110 | N | 3-Cl | CH 3 | H | -(CH 2) 2- | H | H | N | 5-CF 3 |
| 111 | N | 3-Cl | C 2H 5 | H | -(CH 2) 2- | H | H | N | 3-Cl-5-CF 3 |
| 112 | N | 3-Cl | C 2H 5 | H | -(CH 2) 2- | H | H | N | 2-CH 3-4-Cl |
| 113 | N | 3-Cl | C 2H 5 | H | -(CH 2) 2- | H | H | N | 2，4-diCl |
| 114 | N | 3-Cl | C 2H 5 | H | -(CH 2) 2- | H | H | N | 5-CF 3 |
| 115 | N | 3-Cl | Br | Cl | -(CH 2) 2- | H | H | N | 2-CH 3-4-Cl |
| 116 | N | 3，5-di-Cl | Br | Cl | -(CH 2) 2- | H | H | N | 2，4-diCl |
| 117 | N | 3，5，6-triCl | Br | Cl | -(CH 2) 2- | H | H | N | 5-CF 3 |
| 118 | N | 3-Cl | Cl | Cl | -(CH 2) 2- | H | H | N | 3-Cl-5-CF 3 |
| 119 | N | 3-Cl | Cl | Cl | -(CH 2) 2- | H | H | N | 2-CH 3-4-Cl |
| 120 | N | 3-Cl | Cl | Cl | -(CH 2) 2- | H | H | N | 2，4-diCl |
| 121 | N | 3-Cl | Cl | Cl | -(CH 2) 2- | H | H | N | 5-CF 3 |
| 122 | N | 3-Cl | CF 3 | Cl | -(CH 2) 2- | H | H | N | 3-Cl-5-CF 3 |
| 123 | N | 3-Cl | CF 3 | Cl | -(CH 2) 2- | H | H | N | 2-CH 3-4-Cl |
| 124 | N | 3-Cl | CF 3 | Cl | -(CH 2) 2- | H | H | N | 2，4-diCl |
| 125 | N | 3-Cl | CF 3 | Cl | -(CH 2) 2- | H | H | N | 5-CF 3 |
| 126 | N | 3-Cl | CH 3 | Cl | -(CH 2) 2- | H | H | N | 3-Cl-5-CF 3 |
| 127 | N | 3-Cl | CH 3 | Cl | -(CH 2) 2- | H | H | N | 2-CH 3-4-Cl |
| 128 | N | 3-Cl | CH 3 | Cl | -(CH 2) 2- | H | H | N | 2，4-diCl |
| 129 | N | 3-Cl | CH 3 | Cl | -(CH 2) 2- | H | H | N | 5-CF 3 |
| 130 | N | 3-Cl | C 2H 5 | Cl | -(CH 2) 2- | H | H | N | 3-Cl-5-CF 3 |
| 131 | N | 3-Cl | C 2H 5 | Cl | -(CH 2) 2- | H | H | N | 2-CH 3-4-Cl |
| 132 | N | 3-Cl | C 2H 5 | Cl | -(CH 2) 2- | H | H | N | 2，4-diCl |
| 133 | N | 3-Cl | C 2H 5 | Cl | -(CH 2) 2- | H | H | N | 5-CF 3 |
| 134 | N | 3-Cl | Br | H | -(CH 2) 2- | H | H | N | 3-Cl-5-CF 2Cl |
| 135 | N | 3-Cl | Br | H | -(CH 2) 2- | H | H | N | 3-CONHCH 3 |
| 136 | N | 3，5-diCl | Br | H | -(CH 2) 2- | H | H | N | 5-CF 3 |
| 137 | N | 3，5-diCl | Br | H | -(CH 2) 2- | H | H | N | 3-Cl-5-CF 3 |
| 138 | N | 3-Cl | Br | Cl | -(CH 2) 2- | H | H | N | 5-CF 3 |
| 139 | N | 3-Cl | Br | Cl | -(CH 2) 2- | H | H | N | 3-Cl-5-CF 2Cl |
| 140 | N | 3-Cl | Br | Cl | -(CH 2) 2- | H | H | N | 3-CONHCH 3 |
| 141 | N | 3-Cl | Br | Cl | -(CH 2) 2- | H | H | N | 5-CF 3 |
| 142 | N | 3-Cl | Br | Cl | -(CH 2) 2- | H | H | N | 3-Cl-5-CF 3 |
| 143 | N | 3-Cl | Br | H | -CH(CN)- | H | H | N | 5-CF 3 |
| 144 | N | 3-Cl | Br | H | -C(CH 3) 2- | H | H | N | 3-Cl-5-CF 3 |
| 145 | N | 3-Cl | Br | H | -C(CN)(CH 3)- | H | H | N | 3-CONHCH 3 |
Because having found the pyrazol acid amide compounds containing two aryl oxides as shown in general formula (I) first, the present invention there is good fungicidal activity, this compounds can be applied to the disease on various crops in the agricultural fields such as control agricultural, gardening and flower culture, be particularly suitable for preventing and treating following plants disease: cucumber downy mildew, rice blast etc.The phytopathogen that compound of the present invention can be prevented and treated is not limited to foregoing.Therefore technical scheme of the present invention is the purposes of this compounds as disinfectant use in agriculture.
The pyrazol acid amide compounds containing two aryl oxides shown in the general formula (I) that the present invention proposes also comprises a kind of fungicidal composition is provided as the purposes of disinfectant use in agriculture, in composition, contain general formula (I) compound with fungicidal activity as active ingredient, in composition, the weight percentage of active ingredient is 0.1-99%.In composition, also contain the upper acceptable carrier of agricultural and tensio-active agent.Above-mentioned composition can be prepared into required formulation according to currently known methods, for example wettable powder, pulvis, granule and solution, emulsible enriching agent, emulsion, suspension enriching agent, aerosol and smoke substance.In preparation, the selection of carrier and tensio-active agent is appreciated by those skilled in the art.
By add other one or more sterilant in composition, can there is the more activity of wide spectrum than independent general formula (I) compound.In addition the fungicidal activity that, other sterilant can mutual-through type (I) compound has synergism.Also can be by general formula (I) compound and other Mixture Use of Insecticides, or simultaneously and another kind of sterilant and other Mixture Use of Insecticides.
Embodiment
Concrete example can further illustrate the present invention below, but the present invention only limits to absolutely not these examples (except specified otherwise, all raw materials all have commercially available).
Synthetic example
The preparation of embodiment 1 intermediate (4-(5-5-flumethiazine-2-base oxygen base) phenyl) methylamine
1) preparation of 4-(5-(trifluoromethyl) pyridine-2-oxygen base) cyanophenyl
18.15g (0.1mol) 2-chloro-5-trifluoromethylpyridine and 14.28g (0.12mol) para hydroxybenzene nitrile add in 200ml butanone, add 27.60g (0.2mol) salt of wormwood, under stirring, be heated to reflux, reaction 4-5 hour, TLC monitors after completion of the reaction, remove solvent under reduced pressure, add the extraction of 300ml ethyl acetate, successively with 5% aqueous sodium hydroxide solution, the each 50ml washing of saturated aqueous common salt, after precipitation, resistates obtains white solid 21.90g by column chromatography for separation, yield 83.0%, fusing point 84-85 ℃.
1H NMR(300MHz，CDCl
3)：δppm 7.13(1H，d)，7.29(2H，d)，7.47(2H，d)，7.99(1H，d)，8.44(1H，d)。
2) preparation of (4-(5-5-flumethiazine-2-base oxygen base) phenyl) methylamine
By mixture stirring reaction 3-10 hour under hydrogen atmosphere, room temperature of 2.64g (0.01mol) 4-(5-(trifluoromethyl) pyridine-2-oxygen base) cyanophenyl, Raney nickel (1.0g), 25% ammoniacal liquor 10ml and ethanol 50ml composition, TLC monitors after completion of the reaction, filtering Raney nickel, remove solvent under reduced pressure and obtain viscous liquid (4-(5-5-flumethiazine-2-base oxygen base) phenyl) methylamine, after cooling, obtain white solid 2.00g, yield 75.8%, fusing point 88-89 ℃.
The preparation of embodiment 2 intermediate 2-(4-(the chloro-5-of 3-(difluoro chloromethyl) pyridine-2-base oxygen base) phenyl) ethamine
1) preparation of 2-(4-(the chloro-5-of 3-(difluoro chloromethyl) pyridine-2-base oxygen base) phenyl) acetonitrile
23.24g (0.1mol) 2,3-bis-chloro-5-difluoro chloromethylpyridine and 15.96g (0.12mol) p-hydroxybenzylcyanide add in 200ml butanone, add 27.60g (0.2mol) salt of wormwood, under stirring, be heated to reflux, reaction 4-10 hour, TLC monitors after completion of the reaction, remove solvent under reduced pressure, add the extraction of 300ml ethyl acetate, successively with 5% aqueous sodium hydroxide solution, the each 50ml washing of saturated aqueous common salt, after precipitation, resistates obtains white solid 27.4g by column chromatography for separation, yield 83.2%.
2) preparation of 2-(4-(the chloro-5-of 3-(difluoro chloromethyl) pyridine-2-base oxygen base) phenyl) ethamine
By mixture stirring reaction 3-15 hour under hydrogen atmosphere, room temperature of 3.29g (0.01mol) intermediate 2-(4-(the chloro-5-of 3-(difluoro chloromethyl) pyridine-2-base oxygen base) phenyl) acetonitrile, Raney nickel (1.0g), 25% ammoniacal liquor 10ml and ethanol 50ml composition, TLC monitors after completion of the reaction, filtering Raney nickel, remove solvent under reduced pressure and obtain viscous liquid, after cooling, obtain white solid 2.66g, yield 80.1%.
1H NMR(300MHz，CDCl
3)：δppm 2.90-3.02(2H，m)，3.09-3.22(2H，m)，4.84(2H，s)，7.07(2H，d)，7.26(2H，d)，7.97(1H，s)，8.21(1H，s)。
The preparation of embodiment 3 intermediate 2-(4-(2-amino-ethyl) phenoxy group)-N-methylnicotinamide
1) preparation of the chloro-N-methylnicotinamide of 2-
First in the mixing solutions of 2-chlorine apellagrin 1.74g (0.01mol) and 15mL sherwood oil, add 15mL sulfur oxychloride, and then add 2 N, dinethylformamide, heating reflux reaction 2 hours, excessive sulfur oxychloride and solvent are removed in underpressure distillation, obtain intermediate 2-chloronicotinoyl chloride.Then, 0.68g (0.01mol) methylamine hydrochloride and 2.12g (0.21mol) triethylamine are added in 20mL methylene dichloride, ice bath stirs the 10mL dichloromethane solution of the lower 1.94g (0.011mol) of dropping 2-chloronicotinoyl chloride, then continue stirring at room temperature reaction 1 hour, TLC monitors after completion of the reaction, by in reaction mixture impouring 20mL water, separate organic layer, organic layer is successively through 5% dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, the each 10mL washing of saturated aqueous common salt, anhydrous magnesium sulfate drying, decompression precipitation, resistates obtains sterling 1.58g through column chromatography for separation, white solid, yield 92.7%.
2) preparation of 2-(4-(cyano methyl) phenoxy group)-N-methylnicotinamide
The chloro-N-methylnicotinamide of 17.1g (0.1mol) 2-and 15.96g (0.12mol) p-hydroxybenzylcyanide add in 200ml butanone, add 27.60g (0.2mol) salt of wormwood, under stirring, be heated to reflux, reaction 4-10 hour, TLC monitors after completion of the reaction, remove solvent under reduced pressure, add the extraction of 300ml ethyl acetate, successively with 5% aqueous sodium hydroxide solution, the each 50ml washing of saturated aqueous common salt, after precipitation, resistates obtains white solid 22.8g by column chromatography for separation, yield 85.2%.
3) preparation of 2-(4-(the chloro-5-of 3-(difluoro chloromethyl) pyridine-2-base oxygen base) phenyl) ethamine
By mixture stirring reaction 3-15 hour under hydrogen atmosphere, room temperature of 2.67g (0.01mol) intermediate 2-(4-(cyano methyl) phenoxy group)-N-methylnicotinamide, Raney nickel (1.0g), 25% ammoniacal liquor 10ml and ethanol 50ml composition, TLC monitors after completion of the reaction, filtering Raney nickel, remove solvent under reduced pressure and obtain viscous liquid, after cooling, obtain white solid 2.28g, yield 84.8%.
1H NMR(300MHz，CDCl
3)：δppm 2.93-3.02(2H，m)，3.06(3H，d)，3.73-3.84(2H，s)，7.15(2H，d)，7.36(2H，d)，7.84(1H，s)，8.19(1H，dd)，8.46(1H，dd)，8.63(1H，dd)。
The preparation of embodiment 4 compounds 7
(4-(5-5-flumethiazine-2-base oxygen base) phenyl) methylamine 0.27g (0.001mol) and triethylamine 0.12g (0.0012mol) are added in 20mL methylene dichloride, under stirring at room temperature, drip the 10mL dichloromethane solution of the bromo-1-of 0.35g (0.0011mol) 3-(3-chloro-2-pyridyl)-1H-pyrazoles-5-formyl chloride, then continue stirring at room temperature reaction 1 hour, TLC monitors after completion of the reaction, by in reaction mixture impouring 20mL water, separate organic layer, organic layer is successively through 5% dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, the each 10mL washing of saturated aqueous common salt, anhydrous magnesium sulfate drying, decompression precipitation, resistates obtains sterling 0.45g through column chromatography for separation, colorless oil, yield 81.4%.
The preparation of embodiment 5 compounds 93
By 2-(4-(the chloro-5-of 3-(difluoro chloromethyl) pyridine-2-base oxygen base) phenyl) ethamine (4-(2, the chloro-4-nitrophenoxy of 6-bis-) phenyl) methylamine 0.31g (0.001mol) and triethylamine 0.12g (0.0012mol) add in 20mL methylene dichloride, under stirring at room temperature, drip the 10mL dichloromethane solution of the bromo-1-of 0.35g (0.0011mol) 3-(3-chloro-2-pyridyl)-1H-pyrazoles-5-formyl chloride, then continue stirring at room temperature reaction 1 hour, TLC monitors after completion of the reaction, by in reaction mixture impouring 20mL water, separate organic layer, organic layer is successively through 5% dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, the each 10mL washing of saturated aqueous common salt, anhydrous magnesium sulfate drying, decompression precipitation, resistates obtains sterling 0.49g through column chromatography for separation, colorless oil, yield 82.5%.
The preparation of embodiment 6 compounds 134
2-(4-(the chloro-5-of 3-(difluoro chloromethyl) pyridine-2-base oxygen base) phenyl) ethamine 0.27g (0.001mol) and triethylamine 0.12g (0.0012mol) are added in 20mL methylene dichloride, under stirring at room temperature, drip the 10mL dichloromethane solution of the bromo-1-of 0.35g (0.0011mol) 3-(3-chloro-2-pyridyl)-1H-pyrazoles-5-formyl chloride, then continue stirring at room temperature reaction 1 hour, TLC monitors after completion of the reaction, by in reaction mixture impouring 20mL water, separate organic layer, organic layer is successively through 5% dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, the each 10mL washing of saturated aqueous common salt, anhydrous magnesium sulfate drying, decompression precipitation, resistates obtains sterling 0.53g through column chromatography for separation, colorless oil, yield 85.8%.
The preparation of embodiment 7 compounds 135
By 2-(4-(the chloro-5-of 3-(difluoro chloromethyl) pyridine-2-base oxygen base) phenyl) ethamine 2-(4-(2-amino-ethyl) phenoxy group)-N-methylnicotinamide (synthetic method with reference in example 1 1), 2)) 0.27g (0.001mol) and triethylamine 0.12g (0.0012mol) add in 20mL methylene dichloride, under stirring at room temperature, drip the 10mL dichloromethane solution of the bromo-1-of 0.35g (0.0011mol) 3-(3-chloro-2-pyridyl)-1H-pyrazoles-5-formyl chloride, then continue stirring at room temperature reaction 1 hour, TLC monitors after completion of the reaction, by in reaction mixture impouring 20mL water, separate organic layer, organic layer is successively through 5% dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, the each 10mL washing of saturated aqueous common salt, anhydrous magnesium sulfate drying, decompression precipitation, resistates obtains sterling 046g through column chromatography for separation, colorless oil, yield 80.3%.
The preparation of embodiment 8 compounds 136
2-(4-(5-5-flumethiazine-2-base oxygen base) phenyl) ethamine 0.28g (0.001mol) and triethylamine 0.12g (0.0012mol) are added in 20mL methylene dichloride, under stirring at room temperature, drip the chloro-1-(3 of 0.34g (0.0011mol) 3-, 5-dichloro-2-pyridyl base) the 10mL dichloromethane solution of-1H-pyrazoles-5-formyl chloride, then continue stirring at room temperature reaction 1 hour, TLC monitors after completion of the reaction, by in reaction mixture impouring 20mL water, separate organic layer, organic layer is successively through 5% dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, the each 10mL washing of saturated aqueous common salt, anhydrous magnesium sulfate drying, decompression precipitation, resistates obtains sterling 0.45g through column chromatography for separation, light yellow oil, yield 80.8%.
Other compounds of general formula (I) can make by preparation method provided by the invention, or part known compound can be prepared according to currently known methods.
Part of compounds fusing point and nuclear magnetic data (
1hNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows:
Compound 7: colorless oil.δppm 4.44(2H，d)，6.71(1H，s)，6.80(1H，t)，6.86-7.18(4H，m)，7.24(2H，d)，7.40(1H，dd)，7.57(2H，d)，7.89(1H，dd)，8.40(1H，d)。
Compound 92: fusing point 58-59 ℃.δppm 2.84(2H，t)，3.56-3.58(2H，m)，6.30(1H，s)，6.63(1H，s)，7.01(1H，s)，6.98-7.04(4H，m)，7.18(2H，d)，7.56-7.59(2H，m)，7.89(1H，d)，8.43(1H，d)。
Compound 93: yellow oil.δppm 2.77-2.87(2H，t)，3.45-3.62(2H，q)，6.17-6.23(1H，t)，6.60(1H，s)，6.79(2H，d)，7.13(2H，d)，7.35-7.46(1H，q)，7.89(1H，d)，8.32(2H，s)，8.38-8.49(1H，q)。
Compound 94: fusing point 154-156 ℃.δppm 2.65-2.85(2H，t)，3.26-3.45(2H，q)，6.96(2H，d)，7.06(1H，s)，7.21(2H，d)，7.52-7.62(1H，q)，8.07(1H，d)，8.46(1H，d)，8.70(1H，s)。
Compound 98: fusing point 165-166 ℃.δppm 2.82-2.88(2H，t)，3.54-3.62(2H，q)，6.35-6.44(1H，t)，6.54(1H，s)，7.03(1H，d)，7.10(2H，d)，7.22(2H，d)，7.40(1H，dd)，7.88-7.94(2H，m)，8.42(1H，s)，8.44(1H，d)。
Compound 134: colorless oil.δppm 2.83-2.89(2H，t)，3.54-3.63(2H，q)，6.28-6.41(1H，t)，6.63(1H，s)，7.12(2H，d)，7.23(2H，d)，7.37-7.43(1H，q)，7.87-7.92(1H，q)，8.00(1H，d)，8.28(1H，d)，8.40-8.44(1H，t)。
Compound 135: fusing point 150-152 ℃.δppm 2.75-2.79(2H，t)，2.83(3H，d)，3.32-3.39(2H，q)，7.06(2H，d)，7.13(1H，s)，7.14-7.19(1H，q)，7.23(2H，d)，7.55-7.64(1H，m)，8.05-8.29(4H，m)，8.48(1H，d)，8.76-8.84(1H，t)。
Compound 136: light yellow oil.δppm 2.83-2.89(2H，t)，3.54-3.62(2H，q)，6.27-6.40(1H，t)，6.54(1H，s)，7.03(1H，d)，7.10(2H，d)，7.23(2H，d)，7.90(1H，d)，7.93(1H，d)，8.38(1H，d)，8.42(1H，d)。
Compound 137: reddish-brown oily matter.δppm 2.85-2.91(2H，t)，3.56-3.64(2H，q)，6.20-6.36(1H，t)，6.54(1H，s)，7.13(2H，d)，7.23(2H，d)，7.91(1H，d)，7.99(1H，d)，8.26(1H，d)，8.38(1H，d)。
In FORMULATION EXAMPLE formula, each component add-on by weight, is metered into after active compound folding hundred.
Embodiment 960% wettable powder
Each component (being solid) mixes, and pulverizes, until particle reaches standard in pulverizer.
Embodiment 1030% aq suspension
By compound 135 with should add the water yield 80% with dodecyl sodium naphthalene sulfonate in ball mill in (1mm pearl) together with pulverize.Other components dissolved, in remaining water, then stirs and adds other component.
Embodiment 1125% suspend-emulsion enriched material
Compound 136 is dissolved in solvent (should add hold metering 80%), then adds emulsifying agent and dispersion agent, and mixture is thoroughly stirred.Mixture is pulverized in ball mill (1mm pearl), then adds remaining solvent.
Biological activity determination embodiment
Embodiment 12 fungicidal activities are measured
The test method of measuring general formula of the present invention (I) compound fungicidal activity is as follows:
Measure cucumber downy mildew and adopt potted plant seedling assay method.Select the consistent potted plant cucumber seedling of growth, cut off vegetative point and retain two true leaves, as test materials.Carry out foliar spray processing according to design concentration with the compounds of this invention, separately establish the blank of spray clear water, repeat for 3 times.Process latter second day inoculation cucumber downy mildew sporangia suspension, then be positioned over phytotron (temperature: 25 ℃ of daytimes, 20 ℃ of nights, relative humidity: 95～100%) moisturizing is cultivated, after 24 hours, be positioned over greenhouse (25 ± 2 ℃) normal management, 5 days " Invest, Then Investigate " prevention effect.Disease scale, with reference to State Standard of the People's Republic of China " pesticide field efficacy medicine test criterion ", calculates prevention effect with disease index.
Measure rice blast fungus and adopt spore germination method.Add in 96 well culture plates according to design concentration with the compounds of this invention, then add rice blast spore suspension, separately establish the blank that adds clear water, repeat for 3 times.Culture plate after treatment is positioned over incubator (temperature: 24 ℃-26 ℃) and cultivates, 1 day " Invest, Then Investigate " test-results, and calculate inhibition of germination.
Partial test result is as follows:
When liquor strength is 400ppm, compound 134,136 etc. to the preventive effect of cucumber downy mildew more than 80%.
When liquor strength is 25ppm, the inhibition of germination of 93,134,135 pairs of rice blast fungus of compound is all more than 80%.
Claims (5)
1. the purposes as disinfectant use in agriculture containing the pyrazol acid amide compounds of two aryl oxides, described compound structure is as general formula (I):
In formula:
R
1be selected from halogen or C
1-C
8alkyl;
R
2be selected from hydrogen or halogen;
R
3, R
4be selected from hydrogen;
R
5be selected from halogen, nitro, halo C
1-C
8alkyl or C
1-C
8alkyl amino-carbonyl; M is the integer of 1-5;
R
6be selected from halogen; N is the integer of 1-4;
Be selected from-CH of A
2-or-(CH
2)
2-;
X, Y can be identical or different, are selected from respectively C-R
7or N;
R
7be selected from hydrogen or halogen.
2. purposes according to claim 1, is characterized in that: in general formula (I)
R
1be selected from halogen;
R
2be selected from hydrogen;
R
3, R
4be selected from hydrogen;
R
5be selected from halogen, nitro, halo C
1-C
4alkyl or C
1-C
4alkyl amino-carbonyl; M is the integer of 1-5;
R
6be selected from halogen; N is the integer of 1-4;
Be selected from-CH of A
2-or-(CH
2)
2-;
X, Y can be identical or different, are selected from respectively C-Cl or N.
3. purposes according to claim 2, is characterized in that: in general formula (I)
R
1be selected from chlorine or bromine;
R
2be selected from hydrogen;
R
3, R
4be selected from hydrogen;
R
5be selected from chlorine, nitro, a chlorodifluoramethyl-, trifluoromethyl or amino-carbonyl; M is the integer of 1-5
R
6be selected from chlorine; N is the integer of 1-3;
Be selected from-CH of A
2-or-(CH
2)
2-;
X is selected from N; Y is selected from C-Cl or N.
4. purposes according to claim 3, is characterized in that: in general formula (I)
R
1be selected from bromine;
R
2be selected from hydrogen;
R
3, R
4be selected from hydrogen;
R
5be selected from chlorine, nitro, a chlorodifluoramethyl-, trifluoromethyl or amino-carbonyl; M is the integer of 1-5;
R
6be selected from chlorine; N is 1 or 2;
Be selected from-(CH of A
2)
2-;
X is selected from N; Y is selected from C-Cl or N.
5. purposes according to claim 1, is characterized in that: the active ingredient using the pyrazol acid amide compounds containing two aryl oxides shown in general formula (I) as composition, in composition, the weight percentage of active ingredient is 0.1-99%.
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Effective date of registration: 20160125 Address after: 110021 Liaodong Road, Tiexi District, Liaoning, No. 8-1, No. Patentee after: SHENYANG SINOCHEM PESTICIDE CHEMICAL RESEARCH AND DEVELOPMENT CO., LTD. Address before: 100031 Beijing, Xicheng District, the door of the revitalization of the main street, No. 28 Patentee before: Sinochem Corporation Patentee before: Shenyang Research Institute of Chemical Industry |