CN102827033B - Compound containing o-dicyanoaniline and application thereof - Google Patents
Compound containing o-dicyanoaniline and application thereof Download PDFInfo
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- CN102827033B CN102827033B CN201110163460.2A CN201110163460A CN102827033B CN 102827033 B CN102827033 B CN 102827033B CN 201110163460 A CN201110163460 A CN 201110163460A CN 102827033 B CN102827033 B CN 102827033B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/34—Nitriles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
Abstract
The invention discloses a compound containing o-dicyanoaniline, shown as a general formula I, wherein a definition of each substituent is seen in the specification. The compound shown as the general formula I has a broad-spectrum bactericidal activity in the field of agriculture, has a good prevention effect for various pathogens such as cucumber downy mildew, wheat powdery mildew, corn rust disease, rice blast of rice, cucumber gray mold and the like, and particularly, has a good control efficiency at lower dosage for the corn rust disease, the rice blast of rice, the cucumber gray mold and the cucumber downy mildew. Meantime, a part of the compound provided by the invention also has a better insecticidal activity and can be used for controlling aphids, tetranychus cinnabarinus and the like. Moreover, the compound has the advantages of available raw materials, simple synthetic method, and low cost compared with the known bactericides, and has a broad application prospect.
Description
Technical field
The invention belongs to agricultural bactericidal, field of pesticides.Relate to a kind of containing adjacent dicyanobenzenes aminated compounds and application thereof particularly.
Background technology
Pentanoic (diphenylamine) and fluazinam (fluazinam) are known sterilant, and the former is mainly used in water prevention fruit vegetable storage disease, and the latter is mainly used in field crop and prevents and treats multiple diseases.
Vestnik Moskovskogo Universiteta, Seriya 2:Khimiya (1990) 31 (2), 180-5 reports the intermediate A of metal complex; Russian Journal of General Chemistry (2008), 78 (9), 1794-1801 report phthalic nitrile and related compound B, C, D, but all not relevant biological activity report.Pesticide Science (1988), 24 (2), 111-21 discloses the compound that code name is XXX, and report this compound at high doses to about disease as Plasmopara viticola (Plasmopora viticola) etc. has certain activity.
In prior art, the compound of structure as shown in general formula I of the present invention has no report.
Summary of the invention
Modern agricultural production needs the novel pesticide continually developing out novel structure, excellent performance.The object of the present invention is to provide a kind of just can control under very little dosage multiple germ containing adjacent dicyanobenzenes aminated compounds, it can be used for the medicine preparing controlling disease and insect in agricultural or other field.
Technical scheme of the present invention is as follows:
The invention provides a kind of containing adjacent dicyanobenzenes aminated compounds, as shown in general formula I:
In formula:
R
1be selected from hydrogen, C
1-C
12alkyl, C
3-C
12cycloalkyl, halo C
1-C
12alkyl, C
1-C
12alkyl-carbonyl, halo C
1-C
12alkyl-carbonyl, C
1-C
12alkoxy carbonyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphonyl, C
1-C
12alkoxy C
1-C
12alkyl, C
1-C
12alkoxy C
1-C
12alkyl-carbonyl, C
1-C
12alkoxy carbonyl C
1-C
12alkyl, C
2-C
12thiazolinyl, C
2-C
12alkynyl, halo C
2-C
12thiazolinyl, halo C
2-C
12alkynyl, C (=O) NR
6r
7or CO-X-CO
2r
6, wherein X is selected from (CHR
6) m, CR
6=CR
7or C
6h
4, m=0-6;
R
2, R
3, R
4be selected from halogen, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, NR
6r
7, C
1-C
12alkylthio, halo C
1-C
12alkylthio, C
1-C
12alkyl sulphinyl, halo C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphonyl, 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
12alkyl-carbonyl oxygen base, C
1-C
12alkyl-carbonyl-amino, C
1-C
12alkyl sulphonyl oxygen base, C
1-C
12alkoxy C
1-C
12alkoxyl group or C
1-C
12alkoxy carbonyl C
1-C
12alkoxyl group;
Q is selected from phenyl or nitrogenous six membered heteroaryl, and separately optionally by (R
5) n replacement, wherein R
5be selected from halogen, nitro, cyano group, sulfydryl, C
1-C
12alkyl, C
1-C
12haloalkyl, C
3-C
8cycloalkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
1-C
12alkylthio, halo C
1-C
12alkylthio, C
2-C
12thiazolinyl, halo C
2-C
12thiazolinyl, C
2-C
12alkynyl, halo 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
12alkyl sulphinyl, halo C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphonyl, 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
12alkyl sulphonyl oxygen base, C
1-C
12alkoxy carbonyl, C
1-C
12alkoxy C
1-C
12alkoxyl group, C
1-C
12alkoxy carbonyl C
1-C
12alkyl, C
1-C
12alkoxycarbonyl amino, C
1-C
12alkoxy carbonyl C
1-C
12alkoxyl group, CHO, CO
2h, CO
2na, CO
2nH
4, NR
6r
7, C (=O) NR
6r
7, OC (=O) NR
6r
7, C (=S) NR
6r
7or SO
2nR
6r
7; N=0-5;
And when Q is selected from phenyl, R
2, R
3, R
4when being F or Cl simultaneously, n ≠ 0;
R
6, R
7may be the same or different, be selected from hydrogen, C respectively
1-C
6alkyl, halo C
1-C
6alkyl or C
3-C
6cycloalkyl;
Or the salt of compound of Formula I.
The comparatively preferred compound of the present invention is: in general formula I
R
1be selected from hydrogen, C
1-C
8alkyl, C
3-C
8cycloalkyl, halo C
1-C
8alkyl, C
1-C
8alkyl-carbonyl, halo C
1-C
8alkyl-carbonyl, C
1-C
8alkoxy carbonyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphonyl, C
1-C
8alkoxy C
1-C
8alkyl, C
1-C
8alkoxy C
1-C
8alkyl-carbonyl, C
1-C
8alkoxy carbonyl C
1-C
8alkyl, C
3-C
8thiazolinyl, C
3-C
8alkynyl, halo C
3-C
8thiazolinyl, halo C
3-C
8alkynyl, C (=O) NR
6r
7or CO-X-CO
2r
6, wherein X is selected from (CHR
6) m, CR
6=CR
7or C
6h
4, m=0-6;
R
2, R
3, R
4be selected from halogen, C
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, NR
6r
7, C
1-C
8alkylthio, halo C
1-C
8alkylthio, C
1-C
8alkyl sulphinyl, halo C
1-C
8alkyl sulphinyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphonyl, C
3-C
8alkene oxygen base, halo C
3-C
8alkene oxygen base, C
3-C
8alkynyloxy group, halo C
3-C
8alkynyloxy group, C
1-C
8alkyl-carbonyl oxygen base, C
1-C
8alkyl-carbonyl-amino, C
1-C
8alkyl sulphonyl oxygen base, C
1-C
8alkoxy C
1-C
8alkoxyl group or C
1-C
8alkoxy carbonyl C
1-C
8alkoxyl group;
Q is selected from phenyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, cyanuro or inclined triazinyl, and separately optionally by (R
5) n replacement, wherein R
5be selected from fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfydryl, C
1-C
8alkyl, halo C
1-C
8alkyl, C
3-C
6cycloalkyl, C
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, C
1-C
8alkylthio, halo C
1-C
8alkylthio, C
2-C
8thiazolinyl, halo C
2-C
8thiazolinyl, C
2-C
8alkynyl, halo C
2-C
8alkynyl, C
3-C
8alkene oxygen base, halo C
3-C
8alkene oxygen base, C
3-C
8alkynyloxy group, halo C
3-C
8alkynyloxy group, 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
8alkyl-carbonyl, halo C
1-C
8alkyl-carbonyl, C
1-C
8alkyl-carbonyl oxygen base, C
1-C
8alkyl-carbonyl-amino, C
1-C
8alkyl sulphonyl oxygen base, C
1-C
8alkoxy carbonyl, C
1-C
8alkoxy C
1-C
8alkoxyl group, C
1-C
8alkoxy carbonyl C
1-C
8alkyl, C
1-C
8alkoxycarbonyl amino, C
1-C
8alkoxy carbonyl C
1-C
8alkoxyl group, CHO, CO
2h, CO
2na, CO
2nH
4, NR
6r
7, C (=O) NR
6r
7, OC (=O) NR
6r
7, C (=S) NR
6r
7or SO
2nR
6r
7; N=0-5;
And when Q is phenyl, R
2, R
3, R
4when being F or Cl simultaneously, n ≠ 0;
R
6, R
7may be the same or different, be selected from hydrogen, C respectively
1-C
6alkyl, halo C
1-C
6alkyl or C
3-C
6cycloalkyl;
Or the salt of compound of Formula I.
Preferred compound is further: in general formula I
R
1be selected from hydrogen, C
1-C
4alkyl, C
3-C
6cycloalkyl, halo C
1-C
4alkyl, C
1-C
4alkyl-carbonyl, halo C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl, C
1-C
4alkyl sulphonyl, halo C
1-C
4alkyl sulphonyl, C
1-C
4alkoxy C
1-C
4alkyl, C
1-C
4alkoxy C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl C
1-C
4alkyl, C
3-C
6thiazolinyl, C
3-C
6alkynyl, halo C
3-C
6thiazolinyl, halo C
3-C
6alkynyl, C (=O) NR
6r
7or CO-X-CO
2r
6, wherein X is selected from (CHR
6) m, CR
6=CR
7or C
6h
4, m=0-3;
R
2, R
3, R
4be selected from chlorine, bromine, iodine, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, NR
6r
7, C
1-C
4alkylthio, halo C
1-C
4alkylthio, C
1-C
4alkyl sulphinyl, halo C
1-C
4alkyl sulphinyl, C
1-C
4alkyl sulphonyl, halo C
1-C
4alkyl sulphonyl, C
3-C
6alkene oxygen base, halo C
3-C
6alkene oxygen base, C
3-C
6alkynyloxy group, halo C
3-C
6alkynyloxy group, C
1-C
4alkyl-carbonyl oxygen base, C
1-C
4alkyl-carbonyl-amino, C
1-C
4alkyl sulphonyl oxygen base, C
1-C
4alkoxy C
1-C
4alkoxyl group or C
1-C
4alkoxy carbonyl C
1-C
4alkoxyl group;
Q is selected from phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrazinyl, 2-cyanuro, the inclined triazinyl of 3-, the inclined triazinyl of 5-or the inclined triazinyl of 6-, and separately optionally by (R
5) n replacement, wherein R
5be selected from fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfydryl, C
1-C
4alkyl, halo C
1-C
4alkyl, C
3-C
6cycloalkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkylthio, halo C
1-C
4alkylthio, C
2-C
6thiazolinyl, halo C
2-C
6thiazolinyl, C
2-C
6alkynyl, halo C
2-C
6alkynyl, C
3-C
6alkene oxygen base, halo C
3-C
6alkene oxygen base, C
3-C
6alkynyloxy group, halo C
3-C
6alkynyloxy group, 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
4alkyl-carbonyl, halo C
1-C
4alkyl-carbonyl, C
1-C
4alkyl-carbonyl oxygen base, C
1-C
4alkyl-carbonyl-amino, C
1-C
4alkyl sulphonyl oxygen base, C
1-C
4alkoxy carbonyl, C
1-C
4alkoxy C
1-C
4alkoxyl group, C
1-C
4alkoxy carbonyl C
1-C
4alkyl, C
1-C
4alkoxycarbonyl amino, C
1-C
4alkoxy carbonyl C
1-C
4alkoxyl group, CHO, CO
2h, CO
2na, CO
2nH
4, NR
6r
7, C (=O) NR
6r
7, OC (=O) NR
6r
7, C (=S) NR
6r
7or SO
2nR
6r
7; N=0-5;
And when Q is phenyl, R
2, R
3, R
4when being Cl simultaneously, n ≠ 0;
R
6, R
7may be the same or different, be selected from hydrogen, C respectively
1-C
4alkyl, halo C
1-C
4alkyl or C
3-C
6cycloalkyl;
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, trifluoroacetic acid, methylsulfonic acid, tosic acid, oxysuccinic acid, citric acid, lithium, sodium or potassium are formed.
The present invention further preferred compound is: in general formula I
R
1be selected from hydrogen, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkyl-carbonyl, halo C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl, C
1-C
4alkyl sulphonyl, halo C
1-C
4alkyl sulphonyl or C
1-C
4alkoxy C
1-C
4alkyl;
R
2, R
3, R
4be selected from fluorine, chlorine, bromine, iodine, C
1-C
4alkoxyl group or halo C
1-C
4alkoxyl group;
Q is selected from phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl, 3-pyridazinyl, 4-pyridazinyl or 2-pyrazinyl, and separately optionally by (R
5) n replacement, wherein R
5be selected from fluorine, chlorine, bromine, iodine, nitro, cyano group, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group or C
1-C
4alkoxy carbonyl;
n＝1-4；
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, methylsulfonic acid, acetic acid, tosic acid, sodium or potassium are formed.
The present invention further preferred compound is: in general formula I
R
1be selected from H;
R
2, R
3, R
4be selected from chlorine;
Q is selected from phenyl ring, 2-pyridyl, 3-pyridyl or 4-pyridyl, and separately optionally by (R
5) n replacement, wherein R
5be selected from fluorine, chlorine, bromine, nitro, cyano group, CH
3, OCH
3, CF
3, OCF
3or CO
2cH
3;
n＝1-3。
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, methylsulfonic acid, acetic acid, tosic acid, sodium or potassium are formed.
In the definition of the compound of Formula I provided, collect the following substituting group of term general proxy used above:
Halogen: refer to fluorine, chlorine, bromine or iodine.
Alkyl: straight or branched alkyl, such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl or the tertiary butyl.
Cycloalkyl: substituted or unsubstituted cyclic alkyl, such as 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 replace by halogen atom, such as, chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl etc.
Alkoxyl group: straight or branched alkyl, is connected in structure through Sauerstoffatom key.
Halogenated alkoxy: straight or branched alkoxyl group, the hydrogen atom on these alkoxyl groups can partly or entirely replace by halogen atom.Such as, chlorine methoxyl group, dichloro methoxyl group, trichloromethoxy, 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.
Halogenated alkylthio: straight or branched alkylthio, the hydrogen atom on these alkyl can partly or entirely replace by halogen atom.Such as, chloromethane sulfenyl, dichloromethane sulfenyl, trichloro-methylthio, fluorine methylthio group, difluoro methylthio group, trifluoromethylthio, chlorine fluorine methylthio group etc.
Alkylamino: straight or branched alkyl, is connected in structure through nitrogen-atoms key.
Haloalkylamino: straight or branched alkylamino, the hydrogen atom on these alkyl can partly or entirely replace by halogen atom.
Thiazolinyl: straight or branched alkene class, such as vinyl, 1-propenyl, 2-propenyl and different butenyls, pentenyl and hexenyl isomers.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 replace by halogen atom.
Alkynyl: straight or branched alkynes class, such as ethynyl, 1-proyl, 2-propynyl and different butynyl, pentynyl and hexynyl isomers.Alkynyl also comprises the group be made up of multiple triple bond, as 2,5-hexadiyne base.
Halo alkynyl: straight or branched alkynes class, the hydrogen atom on these alkynyls can partly or entirely replace 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 replace 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 replace by halogen atom.
Alkyl sulphinyl: straight or branched alkyl is connected in structure, as methylsulfinyl through sulfinyl (-SO-).
Alkylsulfinyl: straight or branched alkyl sulphinyl, the hydrogen atom on its alkyl can partly or entirely replace 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 replace by halogen atom.
Aryl comprises phenyl or naphthyl etc.
Nitrogenous six membered heteroaryl is containing the heteroatomic hexa-atomic aromatic ring of one or more N.Such as pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazinyl etc.
Table 1, table 2, table 3 list R in general formula I respectively
1, R
2, R
3, R
4, and R
5the concrete substituting group of part, but they are not limited only to these substituting groups.In table, each substituent selection meets aforementioned condition simultaneously, that is: when Q is phenyl, and R
2, R
3, R
4when being Cl simultaneously, n ≠ 0;
Table 1 R
1substituting group
Table 2 R
2(R
3, R
4) substituting group
Table
3r
5substituting group
Part of compounds of the present invention can illustrate with the compound listed in table 4 to table 17, but does not limit the present invention.
Work as R
1=H, CH
3, C
2h
5, n-C
4h
9, COCH
3, COCH
2cH
3, COC (CH
3)
3, COCH
2cH
2cl, CO
2cH
3, SO
2cH
3, SO
2cF
3, CH
2cH
2oCH
3, CH
2cH=CH
2or CON (CH
3)
2, R
2, R
3=Cl, R
4=Cl, OMe, OEt, O-n-C
4h
9, SMe, SEt, S-n-C
4h
9, NHMe, NHEt, NH-n-C
4h
9, SOMe, SOEt, SO-n-C
4h
9, SO
2me, SO
2et or SO
2-n-C
4h
9time, (R
5) n is respectively as shown in table 4 to table 17:
Table 4
| (R 5)n | (R 5)n | (R 5)n |
| 2-F | 2-Br | 2-CH 3-4-Cl-6-CON(CH 3) 2 |
| 2，4-2F | 2，6-2Br-4-NO 2 | 2-CH 3-4-Cl-6-CONHCH(CH 3) 2 |
| 2，6-2F | 2，6-2Br-4-OCF 3 | 2-CH 3-4-Cl-6-CONHC(CH 3) 3 |
| 2-F-5-CH 3 | 3-Br-4-CN | 2-CH 3-4-Br-6-CO 2CH 3 |
| 2-F-5-NO 2 | 4-Br | 2-CH 3-4-Br-6-CONH 2 |
| 2-F-4-CN | 2-I | 2-CH 3-4-Br-6-CON(CH 3) 2 |
| 2，3，4-3F | 4-I | 2-CH 3-4-NO 2-6-F |
| 2-F-4-NO 2 | 2-NO 2 | 2-CH 3-4-NO 2-6-Cl |
| 2，6-2F-4-CF 3 | 2-NO 2-4-Cl | 2-CH 3-4-NO 2-6-Br |
| 2，5-2F-4-CO 2C 2H 5 | 2-NO 2-4-CN | 2-CH 3-4-NO 2-6-CN |
| 2，6-2F-4-NO 2 | 2-NO 2-5-Cl | 2-CH 3-4-NO 2-6-CF 3 |
| 2，6-2F-4-OCF 3 | 2，6-2NO 2-4-Cl | 2-CH 3-4-NO 2-6-OCH 3 |
| 2-F-4-NO 2-6-Cl | 2，6-2NO 2-4-SOCH 3 | 2-CH 3-4-NO 2-6-SO 2CH 3 |
| 2-F-4-CN-5-CO 2CH 3 | 2，6-2NO 2-4-SO 2CH 3 | 2-CH 3-4-NO 2-6-CO 2H |
| 2-F-4-CN-5-NO 2 | 2-NO 2-4，6-2Cl- | 2-CH 3-4-NO 2-6-CO 2CH 3 |
| 2-F-4-CN-6-OCH 3 | 2-NO 2-4-Cl-6-F | 2-CH 3-4，6-2CN |
| 2-F-4-NO 2-6-Cl | 2-NO 2-4-CN-6-Cl | 2-CH 3-4-CN-6-NO 2 |
| 2-F-4-NO 2-6-Br | 2-NO 2-3-C 2H 5-6-CO 2CH 3 | 2-CH 3-4-CN-6-CF 3 |
| 2-F-4-CN-6-Cl | 2-NO 2-4-CO 2CH 3-6-SCH 3 | 4-CH 3 |
| 3-F-6-CN | 2-NO 2-4-CO 2CH 3-6-SOCH 3 | 2-CH 3-4-CN-6-SO 2CH 3 |
| 3-F-4-CN | 2-NO 2-4-CO 2CH 3-6-SO 2CH 3 | 2-CH 3-4-CN-6-CO 2CH 3 |
| 4-F | 2-NO 2-4-CO 2CH 3-6-OCH 3 | 2-CH 3-4-CN-6-CONH 2 |
| 2-Cl | 2-NO 2-4-CO 2CH 3-6-OCH 2CH＝CH 2 | 2-CH 3-4-CN-6-CONHCH 3 |
| 2，3-2Cl | 2，6-2NO 2-3-Cl-4-CF 3 | 2-CH 3-4-CN-6-CONHCH(CH 3) 2 |
| 2，4-2Cl | 2，6-2NO 2-3-SCH 3-4-CF 3 | 2-CH 3-4-CF 3-6-Br |
| 2，4，5-3Cl | 2，6-2NO 2-3-SOCH 3-4-CF 3 | 2-CH 3-4-CF 3-6-NO 2 |
| 2，4，6-3Cl | 2，6-2NO 2-3-SO 2CH 3-4-CF 3 | 2-CH 3-4-CF 3-6-CN |
| 2，5-2Cl | 2，6-2NO 2-4-OCH 3 | 2-CH 3-4-CF 3-6-OCH 3 |
| 2，6-2Cl | 2，6-2NO 2-3-OCH 3-4-CF 3 | 2-CH 3-4-CF 3-6-CO 2CH 3 |
| 2-Cl-4-NO 2 | 3-NO 2 | 2-CH 3-4-CO 2C 2H 5-6-F |
| 2-Cl-5-NO 2 | 4-NO 2 | 2-CH 3-4-CO 2CH 3-6-Cl |
| 2-Cl-5-CN | 2-CN-5-Cl | 2-CH 3-4-CO 2CH 3-6-NO 2 |
| 2-Cl-5-CH 3 | 2-CN-4，6-2Cl | 2-CH 3-4-CO 2CH 3-6-CN |
| 2-Cl-3-CH 3 | 2-CN-4-NO 2-6-Br | 2-CH 3-4-CO 2CH 3-6-CF 3 |
| 2-Cl-3，5-2t-Bu | 2-CN-4-Cl-6-NO 2 | 3-CH 3 |
| 2-Cl-4-CF 3 | 2-CN-4-Cl-6-CF 3 | 3，4-2CH 3 |
| 2-Cl-5-CF 3 | 2-CN-4，6-2NO 2 | 2，6-2C 2H 5-4-Cl |
| 2-Cl-4-CH＝CH 2 | 2-CN-4-OCH 3-6-CF 3 | 2-C 2H 5-6-Br-4-NO 2 |
| 2，6-2Cl-4-CN | 2-CN-4-SCH 3-6-NO 2 | 2-C 2H 5-4，6-2NO 2 |
| 2，6-2Cl-4-CF 3 | 2-CN-4-SO 2CH 3-6-NO 2 | 2-C 2H 5-4-NO 2-6-CN |
| 2，6-2Cl-3-CH 3 | 2-CN-4-SO 2CH 3-6-CF 3 | 2-C 2H 5-4-NO 2-6-Cl |
| 2，6-2Cl-4-NO 2 | 2-CN-4-OCOCH 3-6-CF 3 | 2-C 2H 5-4-NO 2-6-COCH 3 |
| 2，6-2Cl-4-C≡CH | 2-CN-4-OCOCH 2CH 3-6-CF 3 | 4-C 2H 5 |
| 2，6-2Cl-4-CO 2H | 2-CN-4-NHCOCH 3-6-CF 3 | 2-(CH 2) 2CH 3-4-NO 2-6-OC 2H 5 |
| 2，6-2Cl-4-CO 2CH 3 | 2-CN-4-NHCOCH 2CH 3-6-CF 3 | 2-(CH 2) 2CH 3-4-NO 2-6-CF 3 |
| 2，6-2Cl-4-CONH 2 | 3-CN-5-NO 2 | 2-(CH 2) 2CH 3-4-NO 2-6-CO 2CH 3 |
| 2，6-2Cl-4-CON(CH 3) 2 | 3-CN-5-OCH 3 | 2-(CH 2) 2CH 3-4-NO 2-6-SO 2CH 3 |
| 2，6-2Cl-4-CONHC(CH 3) 3 | 4-CN | 2-n-C 3H 7-4-CN |
| 2，6-2Cl-4-SO 2NH 2 | 2-CH 3 | 2-n-C 4H 9-4-CN |
| 2，6-2Cl-4-SO 2NHCH 3 | 2，5-2CH 3 | 2-t-Bu-4-NO 2-6-Cl |
| 2-Cl-4-NO 2-5-t-Bu | 2，4，6-3CH 3 | 4-t-Bu |
| 2-Cl-4-NO 2-5-CF 3 | 2-CH 3-3-Cl | 2-CH 2Cl-4-CN |
| 2-Cl-4-NO 2-6-Br- | 2-CH 3-4-CN | 2-CF 3-4，6-2Cl |
| 2-Cl-4-NO 2-6-SCH 3 | 2-CH 3-4-Cl | 2-CF 3-4-CN |
| 2-Cl-4-CN-5-Br- | 2，6-2CH 3-4-Cl | 2-CF 3-4-Cl-6-NO 2 |
| 2-Cl-4-CN-6-CON(CH 3) 2 | 2-CH 3-4-Br | 3-CF 3 |
| 3-Cl | 2-CH 3-5-Cl | 3-CF 3-4-CN |
| 3，4-2Cl | 2-CH 3-4-OCF 3 | 3，5-2CF 3 |
| 3，5-2Cl | 2-CH 3-4-CO 2H | 4-CF 3 |
| 3-Cl-4-CN | 2-CH 3-4-CO 2Na | 2-OCH 3-4-NO 2 |
| 3-Cl-4-NHCO 2CH 3 | 2-CH 3-4-CO 2CH 3 | 2-OCH 3-4-NO 2-6-Cl |
| 3-Cl-4-NHBoc | 2-CH 3-4-CO 2C 2H 5 | 2-OCH 3-4-CN-6-Cl- |
| 3，5-2Cl-4-CH 3 | 2-CH 3-4-SO 2CH 3 | 3，4-2OCH 3 |
| 3，5-2Cl-4-OCH 2CH＝CCl 2 | 2-CH 3-6-CO 2CH 3 | 4-OCH 3 |
| 3，5-2Cl-4-OCH 2C≡CH | 2-CH 3-6-CO 2H | 4-OCF 3 |
| 3，5-2Cl-4OCONHCH 3 | 2-CH 3-4，6-2NO 2 | 2-OCH 2CF 3-4-NO 2-6-Br |
| 3，5-2Cl-4OCON(CH 3) 2 | 2-CH 3-4-Cl-6-CN | 2-SOCH 3-4-NO 2-6-Cl |
| 3，5-2Cl-4OCON(n-C 3H 7) 2 | 2-CH 3-4-Cl-6-CO 2CH 3 | 2-SO 2CH 3-4-NO 2-6-Cl |
| 3，5-2Cl-4-NHBoc | 2-CH 3-4-Cl-6-CONH 2 | 2-COCH 3 |
| 4-Cl | 2-CH 3-4-Cl-6-CONHCH 3 | 2-CO 2CH 3-4-F |
Table 5
| (R 5)n | (R 5)n | (R 5)n | (R 5)n |
| H | 5-COCH 3 | 3-Br-5-CH 3 | 3-CONH 2-5-Cl |
| 3-F | 5-CO 2CH 3 | 3-Br-6-CH 3 | 3-CONH 2-6-CF 3 |
| 3-Cl | 3-CHO | 3-Br-5-CF 3 | 4-CONH 2-6-CH 3 |
| 3-Br | 4-CHO | 5-Br-6-C 2H 5 | 4-CONH 2-6-OCH 3 |
| 3-I | 5-CHO | 4-I-5-CH 3 | 3，5-2F-4-CF 3 |
| 4-Cl | 3-NH 2 | 4-I-5-CF 3 | 3，6-2F-4-CF 3 |
| 4-Br | 4-NH 2 | 5-I-6-C 2H 5 | 3-F-5-CN-6-Cl |
| 4-I | 5-NH 2 | 3-NO 2-4-Cl | 3-F-5-CO 2CH 3-6-Cl |
| 5-Cl | 6-NH 2 | 3-NO 2-4-CH 3 | 3-F-5-CONH 2-6-Cl |
| 5-Br | 3-CONH 2 | 3-NO 2-5-Cl | 3-F-5-CONHCH(CH 3) 2-6-Cl |
| 5-I | 4-CONH 2 | 3-NO 2-5-Br | 3，5-2Cl-4-CH 3 |
| 6-Cl | 5-CONH 2 | 3-NO 2-5-I | 3，5-2Cl-6-CH 3 |
| 6-Br | 3-F-5-Cl | 3-NO 2-6-Cl | 3，5-2Cl-4，6-2CH 3 |
| 3-NO 2 | 3-F-5-CN | 3-NO 2-6-CH 3 | 3，5-2Cl-6-OCH 2CO 2Me |
| 4-NO 2 | 3-F-4-CF 3 | 3-NO 2-6-OCH 3 | 3，6-2Cl-5-CF 3 |
| 5-NO 2 | 3-F-5-CF 3 | 4-NO 2-6-CH 3 | 3，5，6-3Cl |
| 6-NO 2 | 3-F-4-CHO | 5-NO 2-6-Cl | 3-Br-5-CF 3-6-Cl |
| 3-CN | 4，6-2F | 5-NO 2-6-CH 3 | 3，5-2Br-4-CH 3 |
| 4-CN | 5-F-6-CH 3 | 5-NO 2-6-NHCOCH 3 | 3，5-2Br-6-CH 3 |
| 5-CN | 3，5-2Cl | 3-CN-6-CH 3 | 3-Br-5，6-2CH 3 |
| 6-CN | 4，6-2Cl | 3-CN-4-OCH 3 | 3-NO 2-4-CH 3-5-Br |
| 3-CH 3 | 3，5-2Br | 3-CH 3-5-CN | 3，5-2CN-6-Cl |
| 4-CH 3 | 3-Cl-5-Br | 4-CH 3-5-Br | 3-CN-5-F-6-Cl |
| 5-CH 3 | 3-Cl-5-NO 2 | 4-CH 3-5-NO 2 | 3-CN-4-CF 3-6-Cl |
| 4-C 2H 5 | 3-Cl-5-CN | 4-CH 3-5-NH 2 | 3，5-2CN-6-CH 3 |
| 3-CF 3 | 3-Cl-5-CF 3 | 4，6-2CH 3 | 3-CN-4-CH 3-6-Cl |
| 4-CF 3 | 3-Cl-5-CO 2CH 3 | 4-CH 2Cl-6-Cl | 4-CH 3-5-CN-6-Cl |
| 5-CCl 3 | 3-Cl-5-CONH 2 | 3-CF 3-5-Cl | 3-CF 3-5-Br-6-Cl |
| 5-CF 3 | 3-Cl-5-CON(CH 3) 2 | 3-CF 3-5-Br | 3-CO 2CH 3-5-F-6-Cl |
| 3-OCH 3 | 3-Cl-5-SO 2NH 2 | 3-CF 3-6-Cl | 3-CO 2C 2H 5-4-Cl-6-CH 3 |
| 4-OCH 3 | 4-Cl-5-NO 2 | 4-CF 3-5-CO 2CH 3 | 3-CONH 2-4-CF 3-6-Cl |
| 5-OCH 3 | 4-Cl-6-CH 3 | 4-CH 2CO 2CH 3-6-Cl | 3-CONH 2-5-F-6-Cl |
| 6-OCH 3 | 5-Cl-6-CH 3 | 3-CHO-4-I | 3-CONHCH(CH 3) 2-5-F-6-Cl |
| 6-OC(CH 3) 3 | 3-Br-5-F | 4-CHO-6-Cl | 3-CN-4，6-2CH 3-5-Br |
| 3-NHCOCH 3 | 3-Br-5-Cl | 4-CO 2CH 3-6-CH 3 | 3-CSNH 2-4-CF 3-6-Cl |
| 3-CO 2CH 3 | 3-Br-5-NO 2 | 4-CO 2CH 3-6-OCH 3 | 3-CSNH 2-5-F-6-Cl |
| 4-CO 2C 2H 5 | 3-Br-5-CN | 3-CONH 2-6-CH 3 | 3-CSNHCH(CH 3) 2-5-F-6-Cl |
Table 6
| (R 5)n | (R 5)n | (R 5)n | (R 5)n |
| H | 2-CH 3 | 2-Cl-5-CH 3 | 5-CO 2H-6-Cl |
| 2-F | 4-CH 3 | 2-Cl-5-CF 3 | 5-CO 2CH 3-6-Cl |
| 2-Br | 4-CF 3 | 2-Cl-4-CHO | 5-CONH 2-6-Cl |
| 2-Cl | 5-CF 3 | 2-Cl-5-SO 2NH 2 | 2，5，6-3F |
| 2-I | 6-CF 3 | 5-Cl-6-CN | 2，6-2F-5-Cl |
| 4-F | 2-OCH 3 | 2，6-2Br | 2，6-2F-4-CF 3 |
| 4-Cl | 6-OCH 3 | 2-Br-4，CH 3 | 2，5-2F-4-CF 3 |
| 4-I | 6-OC 2H 5 | 2-Br-6-OCH 3 | 2，5，6-3Cl |
| 5-F | 6-NH 2 | 5-Br-6-OCH 3 | 2，6-2Cl-4-CF 3 |
| 5-Cl | 6-CHO | 5-NO 2-6-Cl | 2，6-2Cl-5-CN |
| 5-Br | 4-CO 2CH 3 | 5-NO 2-6-Br | 2，6-2Br-4-CH 3 |
| 5-I | 5-CO 2CH 3 | 2，6-2CH 3 | 2，6-2Cl-5-CO 2CH 3 |
| 6-F | 6-CO 2CH 3 | 2-CH 3-6-F | 2，6-2Cl-5-CONH 2 |
| 6-Br | 5-CONH 2 | 2-CH 3-6-Cl | 4-CF 3-5，6-2F |
| 6-I | 6-CONH 2 | 2-CH 3-6-NH 2 | 2-CO 2H-4，5，6-3Cl |
| 2-NO 2 | 2-OCH 2CO 2CH 3 | 4-CH 3-6-Cl | 2，5，6-3F-4-Br |
| 4-NO 2 | 2-F-5-CH 3 | 4-CH 3-6-OCH 3 | 2，5，6-3F-4-CN |
| 5-NO 2 | 2-F-5-CF 3 | 5-CH 3-6-Br | 2，5，6-3F-4-CO 2H |
| 6-NO 2 | 2，5-2Cl | 2-OCH 3-5-Br | 2，4，6-3Br-5-F |
| 2-CN | 2，6-2Cl | 2-OCH 3-6-Br | 2，4-2CH 3-5-CN-6-Cl |
| 4-CN | 2-Cl-4-CH 3 | 2-OCH 3-5-CF 3 | 5-CSNH 2-6-Cl |
| 5-CN | 2-Cl-4-CF 3 | 2，6-2(OCH 3) 2 | 5-CSNHCH 3-6-Cl |
| 6-CN | 2-Cl-5-NO 2 | 4-CHO-5-Cl | 5-CSN(CH 3) 2-6-Cl |
Table 7
| (R 5)n | (R 5)n | (R 5)n | (R 5)n |
| H | 2-CF 3 | 3，5-2Cl | 2，6-2NO 2 |
| 2-F | 3-CF 3 | 3，5-2Br | 3，5-2CH 3 |
| 3-F | 5-CF 3 | 3，5-2I | 2，6-2CH 3 |
| 2-Cl | 2-OCH 3 | 2-F-5-CH 3 | 3-CH 3-2-Cl |
| 2-Br | 3-OCH 3 | 2-F-3-CHO | 3，6-2Cl-5-CF 3 |
| 2-I | 3-CHO | 2-Cl-3-NO 2 | 2-Cl-3-CO 2C 2H 5-6-CH 3 |
| 3-Cl | 2-CO 2CH 3 | 2-Cl-5-CF 3 | 2，6-2CH 3-3-CO 2C 2H 5 |
| 3-Br | 2-CONH 2 | 2-Cl-3-CHO | 2，3，5，6-4F |
| 3-I | 3-CO 2CH 3 | 2-Cl-5-CO 2C 2H 5 | 3，5-2F-2，6-2Br |
| 3-NO 2 | 3-SO 2NH 2 | 3-Cl-5-NO 2 | 3，5-2F-2，6-2Br |
| 2-CH 3 | 2，6-2F | 3-Cl-5-CF 3 | 2-CSNH 2 |
| 3-CH 3 | 2，6-2Cl | 3-Br-5-CN | 2-CSNHCH 3 |
Table 8
| (R 5)n | (R 5)n | (R 5)n | (R 5)n |
| H | 5-CO 2C 2H 5 | 4-Cl-5-NO 2 | 4-CF 3-5-CO 2C 2H 5 |
| 4-F | 5-CO 2C(CH 3) | 4-Cl-5-CN | 4-CF 3-5-CONH 2 |
| 4-Cl | 5-CHO | 4-Cl-5-CH 3 | 4-OCH 3-5-Br |
| 4-CN | 5-NH 2 | 4-Cl-6-CH 3 | 4，6-2OCH 3 |
| 4-NO 2 | 5-CONH 2 | 4-Cl-6-CH(CH 3) 2 | 4-CO 2CH 3-6-Cl |
| 4-CH 3 | 5-CONHCH 3 | 4-Cl-5-CF 3 | 4-CO 2C 2H 5-6-Cl |
| 4-CF 3 | 5-CONHC 2H 5 | 4-Cl-5-OCH 3 | 4-CO 2CH 3-6-CH 3 |
| 4-OCH 3 | 5-CONHCH(CH 3) 2 | 4-Cl-6-OCH 3 | 4-CO 2C 2H 5-6-CH 3 |
| 4-SCH 3 | 5-CSNH 2 | 4-Cl-5-CO 2CH 3 | 5-CO 2C 2H 5-6-CH 3 |
| 4-NH 2 | 5-CSNHCH 3 | 4-Cl-5-CONHCH 3 | 4-N(CH 3) 2-5-F |
| 5-F | 4-F-5-Cl | 4-CN-6-CH 3 | 4，6-2F-5-Cl |
| 5-Br | 4-Cl-5-F | 4，6-2CH 3 | 4，6-2F-5-Br |
| 5-I | 4，5-2Cl | 4-CH 3-5-CO 2C 2H 5 | 4，6-2Cl-5-Br |
| 5-CN | 4，6-2Cl | 4-CH 3-5-CO 2H | 4，5-2Cl-6-CH 3 |
| 5-C 2H 5 | 4-Cl-5-Br | 4-CH 3-5-CONH 2 | 4，6-2Cl-5-CHO |
| 5-CH 2CH 2CH 3 | 4-Cl-5-I | 4-C(CH 3) 3-6-CF 3 | 4-Cl-5-NO 2-6-CH 3 |
| 5-CO 2CH 3 | 4，6-2Br | 4-CF 3-5-CO 2CH 3 | 4-Cl-5-NO 2--6-CO 2C 2H 5 |
Table 9
| (R 5)n | (R 5)n | (R 5)n | (R 5)n |
| H | 2，5-2Cl | 2-CH 3-6-Cl | 2-SCH 3-5-CONH 2 |
| 2-F | 2，6-2Cl | 5-CH 3-6-Cl | 2-SO 2CH 3-6-Cl |
| 2-Cl | 2-Cl-5-Br | 2-CH 3-5-CN | 2-SO 2CH 3-5-Br |
| 2-OC 2H 5 | 2-Cl-5-I | 2-CH 3-5-C(CH 3) 3 | 2-SO 2CH 3-6-OCH 3 |
| 2-SCH 3 | 2-Cl-5-NO 2 | 2-CF 3-5-CO 2C 2H 5 | 5-CHO-6-Cl |
| 2-SOCH 3 | 2-Cl-5-CN | 2-OCH 3-6-Cl | 5-CHO-6-NH 2 |
| 2-SO 2CH 3 | 2-Cl-5-CH 3 | 2-SCH 3-6-Cl | 5-CO 2H-6-Cl |
| 2-NHCH 3 | 2-Cl-6-CH 3 | 2-SCH 3-5-Br | 2-NH 2-6-CH(CH 3) 2 |
| 5-F | 2-Cl-5-CF 3 | 2-SCH 3-5-CN | 2，6-2F-5-Cl |
| 6-Cl | 2-Cl-5-OCH 3 | 2-SCH 3-6-CH 3 | 2，6-2Cl-5-NO 2 |
| 6-NHCH 3 | 2-Cl-6-CO 2CH 3 | 2-SCH 3-6-CF 3 | 2，6-2Br-5-NO 2 |
| 6-CH 3 | 2，6-2Br | 2-SCH 3-5-OCH 3 | 2-Cl-5-NO 2-6-CO 2C 2H 5 |
| 6-CF 3 | 2-Br-5-CN | 2-SCH 3-6-OCH 3 | 2-Cl-5-NO 2-6-CH 3 |
| 5，6-2F | 2-NO 2-6-NH 2 | 2-SCH 3-5-CO 2C 2H 5 | 2-CF 3-5，6-2CH 3 |
| 2-F-5-Cl | 5-NO 2-6-Cl | 2-SC 2H 5-5-CO 2C 2H 5 | 2-SCH 3-5-CN-6-Cl |
| 2-Cl-5-F | 5-CN-6-CH 3 | 2-SCH 3-5-CO 2H | 2-SO 2CH 3-5-CN-6-Cl |
Table 10
| (R 5)n | (R 5)n | (R 5)n | (R 5)n |
| H | 4-Cl | 2，4-2Br | 2-SCH 3-4-CO 2CH 3 |
| 2-F | 4-Br | 4，6-2Br | 2-SCH 3-4-CO 2H |
| 2-Cl | 2，4-2F | 2-OCH 3-4-Cl | 2-SCH 3-4-CONH 2 |
| 2-Br | 4，6-2F | 2-OCH 3-4-Br | 2-SCH 3-4-CSNH 2 |
| 2-I | 2，4，6-3F | 2，4-OCH 3 | 2-SO 2CH 3-4-Cl |
| 2-CN | 2，4-2Cl | 4，6-OCH 3 | 2-CH 3-4，6-2Cl |
| 2-OCH 3 | 4，6-2Cl | 2-OC 2H 5-4-Cl | 2-Cyclopropyl-4-Cl |
| 2-SCH 3 | 2-Cl-4-OCH 3 | 2-OC 2H 5-4-Br | 2-Cyclopropyl-4，6-2Cl |
| 2-NH 2 | 2-Cl-4-N(Me) 2 | 2-SCH 3-4-Cl | 2-Cyclopropyl-4，6-2OCH 3 |
Table 11
| (R 5)n | (R 5)n | (R 5)n | (R 5)n |
| H | 6-CO 2CH 3 | 6-CON(CH 3) 2 | 4-Cl-6-CO 2CH 3 |
| 6-Cl | 6-CO 2C 2H 5 | 6-CON(C 2H 5) 2 | 4-Cl-6-CONHCH 3 |
| 6-Br | 6-CO 2C(CH 3) 3 | 6-CSNH 2 | 5，6-2Cl |
| 6-CN | 6-CO 2H | 6-CSNHCH 3 | 4-Br-6-CN |
| 6-CH 3 | 6-NH 2 | 4-F-6-CN | 4-Br-6-CO 2CH 3 |
| 6-OCH 3 | 6-N(CH 3) 2 | 4-F-6-CO 2CH 3 | 4-Br-6-CONHCH 3 |
| 6-SCH 3 | 6-CONH 2 | 4-F-6-CONHCH 3 | 4-CH 3-6-CN |
| 6-SOCH 3 | 6-CONHCH 3 | 3-Cl-5-NHCOCH 3 | 4-CH 3-6-CO 2CH 3 |
| 6-SO 2CH 3 | 6-CONHC 2H 5 | 4-Cl-6-CN | 4-CH 3-6-CONHCH 3 |
Table 12
| (R 5)n | (R 5)n | (R 5)n | (R 5)n |
| H | 5，6-2Cl | 5-Cl-6-OCH 3 | 3-Cl-5-NHCOCH 3 |
| 3-Cl | 3-Cl-6-OCH 3 | 5-Cl-6-SCH 3 | 3-Cl-5-NHCO 2CH 3 |
| 6-Cl | 3-Cl-6-SCH 3 | 5-Cl-6-SOCH 3 | 5，6-2OCH 3 |
| 3，6-2Cl | 5-Cl-6-N(CH 3) 2 | 5-Cl-6-SO 2CH 3 | 5，6-2SCH 3 |
Table 13
| (R 5)n | (R 5)n | (R 5)n | (R 5)n |
| H | 6-CO 2CH 3 | 6-CONHCH 3 | 4-CH 3-6-CN |
| 6-Cl | 6-CO 2C 2H 5 | 6-CONHC 2H 5 | 4-F-6-CO 2CH 3 |
| 6-Br | 6-CO 2C(CH 3) 3 | 6-CON(CH 3) 2 | 4-Cl-6-CO 2CH 3 |
| 6-CN | 6-CO 2H | 6-CSNH 2 | 4-Br-6-CO 2CH 3 |
| 6-CH 3 | 6-CO 2Na | 6-CSNHCH 3 | 4-CH 3-6-CO 2CH 3 |
| 6-OCH 3 | 6-CO 2NH 4 | 5，6-2Cl | 4-F-6-CONHCH 3 |
| 6-SCH 3 | 6-NH 2 | 4-F-6-CN | 4-Cl-6-CONHCH 3 |
| 6-SOCH 3 | 6-N(CH 3) 2 | 4-Cl-6-CN | 4-Br-6-CONHCH 3 |
| 6-SO 2CH 3 | 6-CONH 2 | 4-Br-6-CN | 4-CH3-6-CONHCH 3 |
Table 14
| (R 5)n | (R 5)n | (R 5)n | (R 5)n |
| 4-Cl | 4-OCH 3-6-NHCH 3 | 4-N(CH 3) 2 | 4-NH-i-Pr-6-NHCOCH 3 |
| 4-CN | 4，6-2SCH 3 | 4-NH 2-6-Cl | 4-NH-i-Pr-6-NH 2 |
| 4-SCH 3 | 4-SCH 3-6-Cl | 4-NH 2-6-OCH 3 | 4-NH-i-Pr-6-NHCH 3 |
| 4-SOCH 3 | 4-SCH 3-6-NHCH 3 | 4-NH 2-6-SCH 3 | 4-NH-t-Bu-6-Cl |
| 4-SO 2CH 3 | 4-SOCH 3-6-Cl | 4-NH 2-6-SOCH 3 | 4-NH-t-Bu-6-CN |
| 4，6-2Cl | 4-SO 2CH 3-6-Cl | 4-NH 2-6-SO 2CH 3 | 4-NH-t-Bu-6-OCH 3 |
| 4-CN-6-Cl | 4-NHCOCH 3-6-Cl | 4-NH-i-Pr-6-Cl | 4-NH-t-Bu-6-SCH 3 |
| 4，6-2CH 3 | 4-NHCOCH 3-6-OCH 3 | 4-NH-i-Pr-6-CN | 4-NH-t-Bu-6-NH 2 |
| 4，6-2OCH 3 | 4-NHCOCH 3-6-SCH 3 | 4-NH-i-Pr-6-OCH 3 | 4-NH-t-Bu-6-NHCH 3 |
| 4-OCH 3-6-Cl | 4-NHCOCH 3-6-SO 2CH 3 | 4-NH-i-Pr-6-SCH 3 | 4-NH-t-Bu-6-NHCOCH 3 |
Table 15
| (R 5)n | (R 5)n | (R 5)n | (R 5)n |
| 5-F-6-CN | 5-Br-6-CO 2CH 3 | 6-CO 2CH 3 | 6-CON(C 2H 5) 2 |
| 5-Cl-6-CN | 5-F-6-CONHCH 3 | 6-CO 2H | 6-CSNH 2 |
| 5-Br-6-CN | 5-Cl-6-CONHCH 3 | 6-CONH 2 | 6-CSNHCH 3 |
| 5-CH 3-6-CN | 5-Br-6-CONHCH 3 | 6-CONHCH 3 | 6-CSNHC 2H 5 |
| 5-F-6-CO 2CH 3 | 5-CH 3-6-CO 2CH 3 | 6-CONHC 2H 5 | 6-CSN(CH 3) 2 |
| 5-Cl-6-CO 2CH 3 | 6-CN | 6-CON(CH 3) 2 | 6-CSN(C 2H 5) 2 |
Table 16
| (R 5)n | (R 5)n | (R 5)n | (R 5)n |
| 3-CN | 3-CONHCH 3 | 3-CSN(CH 3) 2 | 3-CO 2CH 3-6-Cl |
| 3-CO 2CH 3 | 3-CONHC 2H 5 | 3-CSN(C 2H 5) 2 | 3-CO 2CH 3-6-Br |
| 3-CO 2C 2H 5 | 3-CON(CH 3) 2 | 3-CN-6-F | 3-CO 2CH 3-6-CH 3 |
| 3-CO 2H | 3-CON(C 2H 5) 2 | 3-CN-6-Cl | 3-CONHCH 3-6-F |
| 3-CO 2Na | 3-CSNH 2 | 3-CN-6-Br | 3-CONHCH 3-6-Cl |
| 3-CO 2NH 4 | 3-CSNHCH 3 | 3-CN-6-CH 3 | 3-CONHCH 3-6-Br |
| 3-CONH 2 | 3-CSNHC 2H 5 | 3-CO 2CH 3-6-F | 3-CONHCH 3-6-CH 3 |
Table 17
| (R 5)n | (R 5)n | (R 5)n | (R 5)n |
| 3-CN | 3-CONH 2 | 3-CSNHC 2H 5 | 3-CO 2CH 3-5-Cl |
| 3-CO 2CH 3 | 3-CONHCH 3 | 3-CSN(CH 3) 2 | 3-CO 2CH 3-5-Br |
| (R 5)n | (R 5)n | (R 5)n | (R 5)n |
| 3-CO 2C 2H 5 | 3-CONHC 2H 5 | 3-CN-5-F | 3-CO 2CH 3-5-CH 3 |
| 3-CO 2C(CH 3) 3 | 3-CON(CH 3) 2 | 3-CN-5-Cl | 3-CONHCH 3-5-F |
| 3-CO 2H | 3-CON(C 2H 5) 2 | 3-CN-5-Br | 3-CONHCH 3-5-Cl |
| 3-CO 2Na | 3-CSNH 2 | 3-CN-5-CH 3 | 3-CONHCH 3-5-Br |
| 3-CO 2NH 4 | 3-CSNHCH 3 | 3-CO 2CH 3-5-F | 3-CONHCH 3-5-CH 3 |
Part of compounds of the present invention can illustrate by the particular compound listed in table 18, but does not limit the present invention.
Table 18
The compounds of this invention is prepared in accordance with the following methods, and reaction formula is as follows, and in formula, each group unless otherwise indicated defines ditto:
Intermediate II and III are obtained by reacting R in general formula I in the basic conditions
1=H, R
2, R
3, R
4be the Compound I-a of Cl; By itself and Z-R
1reaction, can obtain R in general formula I
1≠ H, R
2, R
3, R
4be the Compound I-b of Cl; By I-a and W-R
3(R
3≠ Cl) reaction or by I-b and W-R
3(R
3≠ Cl) reaction can obtain R in general formula I
2, R
4be Cl, R
3compound I-the c of ≠ Cl; By I-c again with W-R
4(R
4≠ Cl) react to obtain R in I
2=Cl, R
3≠ Cl, R
4compound I-the d of ≠ Cl; By I-d and W-R
2(R
2≠ Cl) reaction can obtain R in general formula I
2, R
3, R
4be not all Compound I-the e of Cl.
In formula: X with Y is different, be selected from halogen atom or amino respectively; Z is selected from halogen atom; W is selected from basic metal or hydrogen.
The suitable optional potassium hydroxide freely of alkali, sodium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, triethylamine, pyridine, sodium methylate, sodium ethylate, sodium hydride, potassium tert.-butoxide or sodium tert-butoxide etc.
React and carry out in suitable solvent, the suitable optional tetrahydrofuran (THF) freely of solvent, Isosorbide-5-Nitrae-dioxane, acetonitrile, toluene, dimethylbenzene, benzene, DMF, N-Methyl pyrrolidone, methyl-sulphoxide, acetone or butanone etc.
Temperature of reaction between room temperature to solvent boiling point temperature, can be generally 20-100 DEG C.
Reaction times is 30 minutes to 20 hours, usual 1-10 hour.
Intermediate II mostly is commercial goods, can commercial goods be that raw material is conventionally obtained by substituent simple transformation individually without commercially available intermediate.
When Y is chlorine, intermediate III is commercial goods.
When Y is amino, preparation method's reference Pesticide Science (1988) of intermediate III, 24 (2), 116-117.
R in general formula I
2, R
3, R
4for the compound of alkylamino, alkoxyl group, alkylthio etc., can by corresponding R
2, R
3, R
4prepare for the compound of Formula I of halogen atom and amine, alcohol or mercaptan (or its salt) etc. react, or with reference to Journal ofMedicinalChemistry, prepared by the method described in 1978,21 (9), 906-913.
R in general formula I
2, R
3, R
4for the compound of alkyl sulphinyl, alkyl sulphonyl, alkyl-carbonyl oxygen base etc., can refer to Journalof Medicinal Chemistry, 1978,21 (9), the method preparation described in 906-913.
The salt of compound of Formula I can be obtained with corresponding acid or alkali according to a conventional method by compound of Formula I.Suitable acid can be selected from hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, methylsulfonic acid, acetic acid or tosic acid etc., and suitable alkali can be selected from lithium, sodium, potassium or triethylamine etc.
Although some compound all belongs to diaryl-amine compounds disclosed in compound of Formula I of the present invention and prior art, still there is remarkable difference in constitutional features.And make compound of the present invention have better fungicidal activity due to these structural differences.Meanwhile, part of compounds of the present invention also has good insecticidal activity.And, due to the raw material synthesizing this compounds be easy to get, method is easy, thus compare with known biocides, compound of the present invention is with low cost, has more wide application prospect.
Compound of Formula I demonstrates excellent activity to the multiple germ in agricultural or other field, also demonstrates good activity to insect.Therefore, technical scheme of the present invention also comprises the purposes that compound of Formula I is used as to prepare sterilant and/or sterilant medicine in agricultural or other field.
The example of the disease mentioned below is only used for the present invention is described, but never limits the present invention.
Compound of Formula I can be used for preventing and treating following disease: oomycetes diseases, as oidium (cucumber downy mildew, oilseed rape downy mildew, downy mildew, beet oidium, downy mildew of sugarcane, tobacco downy mildew, pea oidium, sponge gourd oidium, wax gourd oidium, muskmelon downy mildew, cabbage oidium, downy mildew of spinach, radish oidium, downy mildew of garpe, onion mildew), white rust (white rust of colza, cabbage white blister), samping off (rape samping off, Tobacco seedling diseases, tomato samping off, capsicum samping off, eggplant samping off, cucumber samping off, cotton seedling samping off), phytophthora rot (capsicum phytophthora rot, sponge gourd phytophthora rot, wax gourd phytophthora rot), epidemic disease (broad bean epidemic disease, Cucumber Blight, pumpkin epidemic disease, wax gourd epidemic disease, watermelon epidemic disease, muskmelon blight, capsicum epidemic disease, leek epidemic disease, garlic epidemic disease, Cotton blight), late blight (the late blight of potato, tomato late blight) etc., imperfect fungi disease, as blight (sweet potato blight, cotton wilt, sesame blight, castor-oil plant blight, tomato wilt, Kidney bean blight, cucumber fusarium axysporum, sponge gourd blight, pumpkin blight, wax gourd blight, watermelon blight, Muskmelon Fusarium wilt, capsicum wilt, faba bean Fusarium wilt, rape blight, soybean Fusariuming disease), root rot (Fusarium solani, Fructus Solani melongenae root maize ear rot, Bean Root maize ear rot, cucumber root rot, Root of Balsampear maize ear rot, cotton black root rot, root rot of Vicia faba), damping-off (cotton seedling blight, sesame damping-off, capsicum damping-off, cucumber rhizoctonia rot, Chinese cabbage damping-off), anthrax (anthracnose of sorghum, cotton anthracnose, bluish dogbane anthrax, jute anthrax, anthracnose of flax, Colletotricum destructivum, mulberry anthrax, pepper anthracnose, eggplant anthracnose, bean anthracnose, cucumber anthracnose, balsam pear anthrax, summer squash anthrax, wax gourd anthrax, watermelon anthrax, muskmelon anthrax, lichee anthrax), verticillium (cotton verticillium wilt, Sunflower Receptacle verticillium, tomato verticillium, capsicum verticillium, eggplant verticillium wilt), black spot (summer squash black spot, wax gourd black spot, muskmelon black spot), gray mold (cotton boll gray mold, bluish dogbane gray mold, graw mold of tomato, Botrytis cinerea, Kidney bean gray mold, celery gray mold, spinach gray mold, Kiwifruit gray mold), brown spot (cotton brown spot, jute brown spot, beet cercospora leaf spot, the cercospora brown spot of peanut, capsicum brown spot, wax gourd brown spot, Soybean Brown Spot pinta, septorial brown spot of sunflower, pea brown spot, broad bean brown spot), black spot (the false black spot of flax, alternaria stem rot of colza, sesame black spot, Sunflower Receptacle black spot, castor-oil plant black spot, tomato black spot, capsicum black spot, eggplant black spot, Kidney bean black spot, cucumber black spot, celery black spot, carrot black rot, black rot of carrot, melanose or canker of apple, the cercospora black spot of peanut), spot blight (spotted wilt of tomato, cayenne pepper spots rot, celery septoria disease), early blight (early blight of tomato, capsicum early blight, eggplant early blight, target, early blight of celery), ring spot (soybean ring spot, sesame ring spot, Kidney bean ring spot), leaf blight (sesame leaf rot, Sunflower Leaf rot, watermelon leaf rot, Muskmelon leaf rot), base rot disease (tomato base rot disease, Kidney bean base rot disease), and other (Helminthosporium carbonum, bluish dogbane waist folding is sick, rice blast, the black sheath of chestnut is sick, sugarcane eye spot, cotton boll aspergillosis, peanut crown rot, soybean stem rot, soybean diplostomiasis, muskmelon leaf blight, Peanut Web Blotch Disease, the red leaf spot of tea, pepper white star disease, Leaf of Chinese Waxgourd pinta, celery Black Rotten, spinach heartrot, bluish dogbane leaf mold, bluish dogbane spot disease, jute stem pinta, purple spot of soybean, Alternaria sesami, castor-oil plant graywall, dark brown leaf spot, cercospora leaf spot of egg plant, Kidney bean red spot disease, balsam pear leukodermia, watermelon spot disease, jute withered rotten disease, Sunflower Root stem rot, Kidney bean charcoal rot, soybean target spot is sick, eggplant rod spore leaf spot, Leaf Spot Caused by Corynespora cassiicola on Cucumber, leaf muld of tomato, eggplant leaf mold, broad bean reddish macules etc.) etc., basidiomycetes disease, as rust (stripe rust of wheat, the stem rust of wheat, wheat leaf rust, Peanut Rust, rust of sunflower, sugarcane rust, leek rust, rust of onion, chestnut rust, soybean rust), smut (maize head smut, corn smut, head smut of sorghum, sorghum loose smut, covered kernel smut of kaoliang, high beam column smut disease, chestnut kernel smut, smut of sugarcane, Bean rust disease) and other (as wheat hypochnus, rice sheath blight diseases etc.) etc., ascomycetes disease, as Powdery Mildew (wheat powdery mildew, rape Powdery Mildew, sesame Powdery Mildew, Sunflower Receptacle Powdery Mildew, beet powdery mildew, eggplant Powdery Mildew, powdery mildew of pea, sponge gourd Powdery Mildew, squash marble dust, Pumpkin powdery mildew, wax gourd Powdery Mildew, melon powdery mildew, uncinula necator, broad bean Powdery Mildew), sclerotium disease (flax sclerotium disease, sclerotinia rot of colza, soybean sclerotinia crown rot, peanut sclerotium disease, tobacco sclerotium disease, capsicum sclerotium disease, eggplant sclerotium disease, bean sclerotinia rot, pea sclerotium disease, cucumber timberrot, balsam pear sclerotium disease, wax gourd sclerotinia, watermelon sclerotium disease, celery sclerotium disease), black spot (scab of apple, pear scab) etc.Especially, to corn rust, rice blast, gray mold of cucumber and cucumber downy mildew, at lower doses still there is good prevention effect.
Compound of Formula I can be used for preventing and treating following insect: striped rice borer, Cnaphalocrocis medinali(rice leaf roller), Pyrausta nubilalis (Hubern)., tobacco leaf moth, small kernel-eating insect, small cabbage moth, mythimna separata, beet armyworm, prodenia litura, carmine spider mite etc.Especially, to aphid, carmine spider mite, at lower doses still there is good prevention effect.
Due to the characteristic that it is positive, above-claimed cpd can be advantageously used in protecting agriculture and the important crop of horticulture, domestic animal and breeding stock, and the environment that often goes of the mankind avoids the injury of germ, insect.
For obtaining ideal effect, the consumption of compound changes because of various factors, the formulation of the crop of such as compound used therefor, pre-protection, the type of harmful organism, gradient of infection, weather condition, application method, employing.
The compound dosage of per hectare 10 grams-5 kilograms can provide sufficient control.
Another object of the present invention also relates to by using compound of Formula I, the insect in the environment that control agricultural and the important crop of horticulture and/or domestic animal and breeding stock and/or the mankind often go and/or the method for plant pathogenic fungi.Especially, the consumption of compound changes in per hectare 10 grams-5 kilograms.
In order to be applied to agricultural, use the composition containing one or more compound of Formula I normally useful.
Therefore, another technical scheme of the present invention also comprises a kind of sterilization, insect-killing composition, and containing as the compound of Formula I of active ingredient and agriculturally acceptable carrier, in composition, the weight percentage of active ingredient is 0.5-90%.
The type of service of composition can be dry powder, wettable powder, missible oil, microemulsion, paste, granule, solution, suspension agent etc.: concrete application is depended in the selection of types of compositions.
Composition is prepared in a known way, such as optional under the existence of tensio-active agent, by with solvent medium and/or solid diluent or lytic activity material.
Available solid diluent or carrier are such as: silicon-dioxide, kaolin, wilkinite, talcum, diatomite, rhombspar, calcium carbonate, magnesium oxide, chalk, clay, synthetic silicate, attapulgite, sepiolite.
Than water, available liquid diluent is such as aromatic organic solvent (mixture, chlorobenzene etc. of dimethylbenzene or alkylbenzene), paraffin (petroleum fractions), alcohols (methyl alcohol, propyl alcohol, butanols, octanol, glycerine), ester class (ethyl acetate, isobutyl acetate etc.), ketone (pimelinketone, acetone, methyl phenyl ketone, isophorone, ethyl pentyl group ketone etc.), amides (DMF, N-Methyl pyrrolidone etc.).
Available tensio-active agent is sodium, calcium, triethylamine or the triethanolamine salt of polyoxyethylene ester, sulfonated lignin etc. of alkylsulfonate, alkylaryl sulphonate, polyoxyethylene alkylphenol, sorbyl alcohol.
Composition also can be used for specific object containing special additive, and such as tackiness agent is as gum arabic, polyvinyl alcohol, polyvinylpyrrolidone etc.
In above-mentioned composition, the concentration of activeconstituents can change in wide region according to the preparation type of activeconstituents, its application target, envrionment conditions and employing.Usually, the concentration range of activeconstituents is 1-90%, preferred 5-50%.
If need, can add in composition can with other activeconstituentss of compound of Formula I compatibility, such as other mycocides, insecticide/miticide, plant-growth regulator, microbiotic, weedicide, fertilizer.
The compound method of several formulation is exemplified below:
The preparation of suspension agent: in common prescription, active component content is 5%-35%.Take water as medium, former medicine, dispersion agent, suspending agent and antifreezing agent etc. are added in sand mill, grinds, make suspension agent.
The preparation of aqueous emulsion: former medicine, solvent and emulsifying agent are added together, makes to be dissolved into homogeneous oil phase.Water, antifreezing agent etc. are mixed, become homogeneous aqueous phase.Under high velocity agitation, aqueous phase joined oil phase or oil phase is joined aqueous phase, forming the aqueous emulsion of favorable dispersity.Aqueous emulsion active component content of the present invention is generally 5%-15%.For preparation emulsifiable concentrate, compound being soluble solution of the present invention in one or several mixed solvents, then adds emulsifying agent to strengthen the dispersion effect of compound in water.
The preparation of wettable powder: by recipe requirements, by the fully mixing such as former medicine, various tensio-active agent and solid diluent, after ultra-fine pulverizer disintegrating, namely obtains the wettable powder product of predetermined content (such as 10%-40%).For preparation is suitable for the wettable powder of sprinkling, compound of the present invention can with the pressed powder of porphyrize as clay, inorganic silicate, carbonate and wetting agent, tackiness agent and/or dispersion agent composition mixture.
The preparation of water-dispersible granules: former medicine and powdered solid diluents, wetting spreader-sticker and tackiness agent etc. are carried out co-grinding; add water after mediating again; add in the tablets press that 10 to 100 eye mesh screens are housed and carry out granulation, and then drying, screening (by screen cloth scope).Also can add in sand mill by former medicine, dispersion agent, disintegrating agent and wetting agent and solid diluent, take water as medium milling, make suspension agent, then carry out spray drying granulation, usual formulation content is 20%-30% granular product.
Embodiment
Following specific embodiment is used for further illustrating the present invention, but the present invention is limited to absolutely not these examples.(except as otherwise indicate outside, raw materials used all have commercially available)
Synthetic example
Embodiment 1: the preparation of Compound I-A-8
To 1.64g (0.0075mol) 2, the N of the 40ml of 6-Dichloro-4-nitroaniline, sodium hydroxide 0.60g (0.015mol) is added in dinethylformamide solution, slowly 3 are added under stirring, 4, 5, 6-tetra-chloro-1, 4-benzene dicarbonitrile 2g (0.0075mol), add rear continuation stirring at room temperature reaction 5h, TLC monitoring after completion of the reaction, reaction solution is poured into water, extraction into ethyl acetate, organic phase is successively through washing, saturated salt is washed, dry, filter, precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1: 4) purifying obtains product 2.8g, i.e. Compound I-A-8.Yellow solid, fusing point 188-190 DEG C.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3), δ (ppm): 6.76 (s, 1H, NH), 8.31 (s, 2H, Ph-3,5-2H).
Embodiment 2: the preparation of Compound I-B-1
To the N of the 40ml of the bromo-PA of 1.3g (0.0075mol) 5-, sodium hydroxide 0.60g (0.015mol) is added in dinethylformamide solution, slowly 3 are added under stirring, 4, 5, 6-tetra-chloro-1, 4-benzene dicarbonitrile 2g (0.0075mol), add rear continuation stirring at room temperature reaction 5h, TLC monitoring after completion of the reaction, reaction solution is poured into water, extraction into ethyl acetate, organic phase is successively through washing, saturated salt is washed, dry, filter, precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1: 3) purifying obtains product 2.3g, i.e. Compound I-B-1.Yellow solid, fusing point 164-166 DEG C.
1h-NMR (300MHz, interior mark TMS, solvent DMSO), δ (ppm): 6.73 (s, 1H, NH), 6.96 (d, 1H, Py-3-1H), 7.84 (dd, 1H, Py-4-1H), 8.27 (d, 1H, Py-6-1H).
Other compounds of the present invention can be prepared with reference to above example.
The physical data of part of compounds and nuclear magnetic data (
1hNMR, 300MHz, interior mark TMS, ppm) as follows:
Compound I-A-1: fusing point 200-202 DEG C.δ(DMSO)：6.82-6.90(m，1H，Ph-6-1H)，7.12-7.22(m，1H，Ph-5-1H)，9.08(s，1H，NH)。
Compound I-A-2: fusing point 210-212 DEG C.δ(CDCl
3)：6.58(b r，1H，NH)，6.65(t，1H，Ph-6-1H)，8.05-8.16(m，2H，Ph-3，5-2H)。
Compound I-A-3: fusing point 166-168 DEG C.δ(CDCl
3)：6.65(s，1H，NH)，6.71(d，1H，Ph-6-1H)，7.10-7.15(m，1H，Ph-4-1H)，7.20-7.25(m，1H，Ph-5-1H)，7.46(d，1H，Ph-3-1H)。
Compound I-A-4: fusing point 68-70 DEG C.δ(CDCl
3)：6.52(d，1H，Ph-6-1H)，6.88(br，1H，NH)，8.07(d，1H，Ph-5-1H)，8.40(s，1H，Ph-3-1H)。
Compound I-A-5: fusing point 210-212 DEG C.δ(CDCl
3)：6.67(br,1H，NH)，7.37(d，1H，Ph-6-1H)，7.65(d，1H，Ph-3-1H)，7.94(s，1H，Ph-4-1H，)。
Compound I-A-6: fusing point 156-158 DEG C.δ(CDCl
3)：6.61(d，1H，Ph-6-1H，J＝8.4)，6.72(br,1H，NH)，7.46(d，1H，Ph-5-1H)，7.73(s，1H，Ph-3-1H)。
Compound I-A-7: fusing point 156-158 DEG C.δ(CDCl
3)：6.69(s，1H，NH)，6.82(d，1H，Ph-6-H)，7.37(dd，1H，Ph-5-H)，7.60(d，1H，Ph-3-H)。
Compound I-A-9: fusing point 146-148 DEG C.δ(CDCl
3)：6.63(s，1H，NH)，8.48(s，2H，Ph-3，5-2H)。
Compound I-A-10: fusing point 172-174 DEG C.δ(CDCl
3)：6.47(d，1H，Ph-6-1H，J＝9.0)，7.48(dd，1H，Ph-5-1H)，8.40(d，1H，Ph-3-1H)，9.36(s，1H，NH)。
Compound I-A-11: fusing point 248-250 DEG C.δ(CDCl
3)：6.64(s，1H，NH)，6.86(d，2H，Ph-2，6-2H)，7.63(d，2H，Ph-3，5-2H)。
Compound I-A-12: fusing point 124-126 DEG C.δ(CDCl
3)：1.89(s，3H，CH
3)，3.90(s，3H，OCH
3)，7.29(t，1H，Ph-4-1H，)，7.36(d，1H，Ph-5-1H)，7.87(d，1H，Ph-3-1H)，8.89(s，1H，NH)。
Compound I-A-13: fusing point 152-154 DEG C.δ(CDCl
3)：6.89(dd，1H，Ph-6-1H)，7.22(d，1H，Ph-2-1H，J＝1.8)，7.74(d，1H，Ph-5-1H，J＝8.1)。
Compound I-A-14: fusing point 224-226 DEG C.δ(CDCl
3)：4.07(s，3H，O-CH
3)，6.66(d，1H，Ph-6-1H)，6.91(br，1H，NH)，7.82-7.89(m，2H，Ph-3，5-2H)。
Compound I-A-15: fusing point 176-178 DEG C.δ(CDCl
3)：6.67(s，1H，NH)，6.93(d，2H，Ph-2，6-2H)，7.21(d，2H，Ph-3，5-2H)。
Compound I-B-2: fusing point 124-126 DEG C.δ(CDCl
3)：2.40(s，3H，CH
3)，3.66(br，1H，NH)，6.54(s，1H，Py-3-1H)，6.90(d，1H，Py-5-1H)，8.03(d，1H，Py-6-1H)。
Example of formulations
Each component add-on is weight percentage, and active compound is metered into after rolling over hundred.
Embodiment 3:30% wettable powder
Compound and other components are fully mixed, after ultra-fine pulverizer disintegrating, namely obtains the wettable powder product of 30%.
Embodiment 4:40% suspension concentrates
Compound and other components fully mix, the suspension concentrates obtained thus, and dilute with water gained suspension agent can obtain the diluent of any desired concn.
Embodiment 5:60% water-dispersible granules
By compound and other component co-grindings, then add water mediate after, add in the tablets press of 10-100 eye mesh screen and carry out granulation, and then drying, screening (by screen cloth scope).
Biological activity determination
The compounds of this invention all shows good activity to the multiple germ in agriculture field, also demonstrates good insecticidal activity.
Embodiment 6: fungicidal activity measures
Antifungal Activity in Vitro or the test of live body protected effect has been carried out with the multiple fungal disease of the compounds of this invention sample to plant.Fungicidal activity measurement result is shown in following example.
(1) in vitro fungicidal activity measures
Measuring method is as follows:
Adopt high-throughput screening method, by test compound sample, with the solvent be applicable to, (kind of solvent as acetone, methyl alcohol, DMF etc., and is selected the dissolving power of sample according to it.) dissolve, be mixed with desired concn liquid to be measured.Under ultra-clean Working environment, joined by liquid to be measured in the micropore of 96 well culture plates, then add wherein by pathogenic bacteria propagulum suspension, the culture plate after process is placed in constant incubator to be cultivated.Investigate after 24 hours, estimate pathogenic bacteria propagulum during investigation and sprout or growing state, and according to the sprouting of control treatment or growing state, assessing compound bacteriostatic activity.
Antifungal Activity in Vitro (representing with the inhibiting rate) test result of part of compounds is as follows:
Inhibiting rate to rice blast fungus:
When liquor strength is 25mg/L, the inhibiting rate of Compound I-A-6, I-A-8, I-A-13, I-B-1 etc. is 100%; The inhibiting rate of Compound I-B-2 is 80%.
When liquor strength is 8.3mg/L, the inhibiting rate of Compound I-A-6, I-A-8, I-A-13, I-B-1 etc. is 100%.
When liquor strength is 2.8mg/L, the inhibiting rate of Compound I-A-6, I-A-8 etc. is 100%; The inhibiting rate of Compound I-A-13 is 80%.
When liquor strength is 0.9mg/L, the inhibiting rate of Compound I-A-8 is 100%; The inhibiting rate of Compound I-A-7 is 80%.
When liquor strength is 0.1mg/L, the inhibiting rate of Compound I-A-8 is 100%.
When liquor strength is 0.03mg/L, the inhibiting rate of Compound I-A-8 is 80%.
Inhibiting rate to botrytis cinerea pers:
When liquor strength is 25mg/L, the inhibiting rate of Compound I-A-8 is 100%; The inhibiting rate of Compound I-A-13 is 50%.
When liquor strength is 8.3mg/L, the inhibiting rate of Compound I-A-8 is 100%.
When liquor strength is 2.8mg/L, the inhibiting rate of Compound I-A-8 is 100%.
When liquor strength is 0.9mg/L, the inhibiting rate of Compound I-A-8 is 100%.
(2) live body prolection measures
Measuring method is as follows:
Adopt the potted plant measuring method of live body, by test compound sample, with a small amount of solvent, (kind of solvent is as acetone, methyl alcohol, DMF etc., and according to it, dissolving power of sample is selected, the volume ratio of quantity of solvent and spouting liquid is equal to or less than 0.05) dissolve, dilute with the water containing 0.1% tween 80, be mixed with desired concn liquid to be measured.On crops sprayer, liquid to be measured is sprayed on disease host plant (host plant is the standard Potted orchard at warm indoor cultivation), after 24 hours, carry out disease inoculation.According to disease feature, cultivate being placed in phytotron after the disease plant inoculating needing temperature control moisturizing to cultivate, after disease completes and infects, immigration hot-house culture, the disease plant cultivated not needing moisturizing is directly cultivated at warm indoor inoculation.After contrasting fully morbidity, (being generally week age) carries out the assessment of compound protection effect.
The live body prolection test result of part of compounds is as follows:
Live body prolection to cucumber downy mildew:
When liquor strength is 400mg/L, the prolection of Compound I-A-1, I-A-6, I-A-8, I-A-13, I-B-1, I-B-2 etc. is 100%.
When liquor strength is 100mg/L, the prolection of Compound I-A-8, I-B-1, I-B-2 etc. is 100%; The prolection of Compound I-A-1, I-A-13 etc. is all greater than 95%.
When liquor strength is 50mg/L, the prolection of Compound I-A-8, I-B-1 etc. is all greater than 95%; The prolection of Compound I-A-1, I-A-13 etc. is all greater than 80%.
When liquor strength is 25mg/L, the prolection of Compound I-A-8, I-B-1 etc. is all greater than 90%..
Live body prolection to corn rust:
When liquor strength is 400mg/L, the prolection of Compound I-A-8 etc. is 98%; The prolection of Compound I-A-6 etc. is 80%; The prolection of Compound I-A-13 etc. is 70%.
Embodiment 7: pesticide and miticide actility measures
With the compounds of this invention, insecticidal activity assay test is carried out to several insect.Measuring method is as follows:
Testing compound is diluted to required concentration with the water containing 0.1% (wt) tween 80 after dissolving with the mixed solvent of acetone/methanol (1: 1).
With aphid, carmine spider mite for target, airbrush spray method is adopted to carry out insecticidal activity assay.
(1), the determination of activity of killing aphis
Measuring method: cut-off footpath 6cm culture dish, covers one deck filter paper at the bottom of ware, and drips appropriate tap water moisturizing.Clip suitable size (diameter is about 3cm) from the cabbage plant cultivating black peach aphid and the long cabbage leaves having 15 ~ 30 aphids, remove the aphid of alatae and face of blade, blade back is upwards placed in culture dish.The pressure of airbrush spraying process is that 10psi (is roughly equal to 0.7kg/cm
2), spouting liquid is 0.5ml, often processes 3 times and repeats.Put into 25 DEG C, relative humidity 60 ~ 70% observation indoor cultivation after process, 48 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio.
As follows to the partial test result of aphid:
When liquor strength is 600mg/L, to aphid lethality rate be 100% have Compound I-A-8 etc.
(2) determination of activity of carmine spider mite, is killed
Measuring method: get two panels true leaf Kidney bean seedling, connects carmine spider mite and becomes mite and after investigating radix, carry out whole strain process with airbrush atomizer, pressure is that 10psi (is roughly equal to 0.7kg/cm
2), spouting liquid is 0.5ml.Often process and repeat for 3 times, process is placed on standard sight room, and 72 hours " Invest, Then Investigate " survival mite numbers, calculate mortality ratio.
When liquor strength is 600mg/L, to carmine spider mite lethality rate be all greater than 80% have Compound I-A-8 etc.
Claims (5)
1. an adjacent dicyanobenzenes aminated compounds, as shown in general formula I:
In formula:
R
1be selected from hydrogen;
R
2, R
3, R
4be selected from fluorine, chlorine, bromine or iodine;
Q is selected from phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl, and separately optionally by (R
5) n replacement, wherein R
5be selected from fluorine, chlorine, bromine, iodine, nitro, cyano group, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group or C
1-C
4alkoxy carbonyl;
n＝1-4；
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, methylsulfonic acid, acetic acid, tosic acid, sodium or potassium are formed.
2. compound according to claim 1, is characterized in that: in general formula I
R
1be selected from H;
R
2, R
3, R
4be selected from chlorine;
Q is selected from phenyl ring, 2-pyridyl, 3-pyridyl or 4-pyridyl, and separately optionally by (R
5) n replacement, wherein R
5be selected from fluorine, chlorine, bromine, nitro, cyano group, CH
3, OCH
3, CF
3, OCF
3or CO
2cH
3;
n＝1-3；
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, methylsulfonic acid, acetic acid, tosic acid, sodium or potassium are formed.
3. one kind is used as the purposes preparing sterilant medicine according to compound of Formula I according to claim 1 in agricultural or other field.
4. one kind is used as the purposes preparing sterilant medicine according to compound of Formula I according to claim 1 in agricultural or other field.
5. a Fungicidal insecticidal composition, is characterized in that: containing as the compound of Formula I as claimed in claim 1 of active ingredient and agriculturally acceptable carrier, and in composition, the weight percentage of active ingredient is 0.5-90%.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110163460.2A CN102827033B (en) | 2011-06-17 | 2011-06-17 | Compound containing o-dicyanoaniline and application thereof |
| EP12800201.1A EP2757092A4 (en) | 2011-06-17 | 2012-06-15 | Substituted cyanoaniline compounds, preparation and use thereof |
| PCT/CN2012/077011 WO2012171484A1 (en) | 2011-06-17 | 2012-06-15 | Substituted cyanoaniline compounds, preparation and use thereof |
| US14/118,509 US8937072B2 (en) | 2011-06-17 | 2012-06-15 | Substituted cyanoaniline compounds, preparation and use thereof |
| JP2014515051A JP5931187B2 (en) | 2011-06-17 | 2012-06-15 | Substituted cyanoaniline compounds, their preparation and use |
| CN201280024754.XA CN103547565B (en) | 2011-06-17 | 2012-06-15 | Substituted cyanoaniline compounds, preparation and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110163460.2A CN102827033B (en) | 2011-06-17 | 2011-06-17 | Compound containing o-dicyanoaniline and application thereof |
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| Publication Number | Publication Date |
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| CN102827033B true CN102827033B (en) | 2015-04-01 |
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| CN103254144B (en) * | 2013-04-12 | 2015-10-28 | 武汉工程大学 | A kind of cyanuric chloride derivant and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1383306A (en) * | 1971-03-19 | 1974-02-12 | Ici Ltd | Diphenylamine derivatives and compositions thereof |
| US3965109A (en) * | 1971-03-19 | 1976-06-22 | Imperial Chemical Industries Limited | Certain aryl amino pyridines |
| US3974276A (en) * | 1971-03-19 | 1976-08-10 | Imperial Chemical Industries Limited | Certain diazines as plant pesticides |
| US4614742A (en) * | 1985-08-29 | 1986-09-30 | S.D.S. Biotech K.K. | Fluorinated isophthalonitrile compound and nonmedical fungicide containing the same |
-
2011
- 2011-06-17 CN CN201110163460.2A patent/CN102827033B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1383306A (en) * | 1971-03-19 | 1974-02-12 | Ici Ltd | Diphenylamine derivatives and compositions thereof |
| US3965109A (en) * | 1971-03-19 | 1976-06-22 | Imperial Chemical Industries Limited | Certain aryl amino pyridines |
| US3974276A (en) * | 1971-03-19 | 1976-08-10 | Imperial Chemical Industries Limited | Certain diazines as plant pesticides |
| US4614742A (en) * | 1985-08-29 | 1986-09-30 | S.D.S. Biotech K.K. | Fluorinated isophthalonitrile compound and nonmedical fungicide containing the same |
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|---|---|
| CN102827033A (en) | 2012-12-19 |
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Effective date of registration: 20160128 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 |