CN103772294B - Phenoxy pyrimidine aminated compounds and purposes - Google Patents
Phenoxy pyrimidine aminated compounds and purposes Download PDFInfo
- Publication number
- CN103772294B CN103772294B CN201210412091.0A CN201210412091A CN103772294B CN 103772294 B CN103772294 B CN 103772294B CN 201210412091 A CN201210412091 A CN 201210412091A CN 103772294 B CN103772294 B CN 103772294B
- Authority
- CN
- China
- Prior art keywords
- acid
- hydrogen
- compound
- alkyl
- spp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 CCC1=C*C(N)=N1 Chemical compound CCC1=C*C(N)=N1 0.000 description 2
- SIUNBOQRQYAIJI-UHFFFAOYSA-N Cc1ncnc(Cl)c1Cl Chemical compound Cc1ncnc(Cl)c1Cl SIUNBOQRQYAIJI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/42—One nitrogen atom
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of phenoxy pyrimidine aminated compounds, structure is as shown in general formula I:
Description
Technical field
The invention belongs to agricultural bactericidal insecticidal/acaricidal agent field, be specifically related to a kind of novel phenoxy pyrimidine aminated compounds and purposes.
Background technology
Patent EP0370704 and JP2009161472 discloses following compound formula and particular compound CK1 (numbering in two patents is respectively compound 47 and compd A), has sterilization and insecticidal activity.This compound has now been developed as commercialization sterilant, popular name fluorine mepanipyrim (English popular name diflumetorim).Pesticide Science.1999,55:896-902 also disclose above-claimed cpd (being numbered compound 5 in document), and raw result of surveying shows to have certain activity to wheat rust and barley powdery mildew.
Patent JP11012253, JP11049759, EP0665225 disclose the preparation method of following Compound C K2 (being numbered compound 7 in JP11012253), the English popular name Flufenerim of this compound, the phonetic worm amine of Universal Chinese character name.
Patent EP264217, DE3786390, US4895849, US4985426, JP63225364 disclose the pyrimidine benzylamine compound general formula shown in following general formula and particular compound CK3 and CK4 (in EP264217, numbering is respectively compound 77 and compound 74), as the application of agricultural bactericidal, Insecticidal and acaricidal agent etc.
EP0665225, JP10036355, US5498612 report the preparation method of following pyrimidinamine compound general formula and particular compound CK5, CK6, CK7 and CK8 (in EP0665225, numbering is respectively compound 83, compound 87, compound 101 and compound 41), have desinsection, sterilization, acaricidal activity.
Carry out online information retrieval by Scifinder, retrieve Compound C K9 (CAS No.203734-18-3) and CK10 (CAS No.203734-22-9), but without concrete bibliographical information, also inactive report.
WO9728133 discloses following general formula and particular compound CK11 (being numbered 26 in patent), has sterilization, desinsection, acaricidal activity:
Patent US5227387 discloses following general formula and particular compound CK12 (being numbered 81 in patent), has eelworm-killing activity.
US5326766 discloses following general formula and particular compound CK13 (being numbered 29 in patent), has sterilization, insecticidal activity:
Patent US5925644 discloses following general formula and particular compound CK14 (being numbered 447 in patent), has desinsection, kills mite, eelworm-killing activity.
Patent US5468751, EP470600 disclose following general formula and particular compound CK15 (being numbered compound 2.50 in US5468751), have sterilization, desinsection, acaricidal activity.
Patent WO9507278 discloses the compound shown in following general formula and has certain sterilization, kills mite and/or insecticidal activity, and wherein TABLE 1 the 209th row is referred to Compound C K16, CK17, CK18, but reports without any biological activity;
Document Bioorganic & Medicinal Chemistry Letters, 2007.17:260-265 report following general formula compound and use as novel human immunodeficiency's virus HIV-1 (Human Immunodeficiency Virus) inhibitor.
Patent EP534341 discloses following general formula and particular compound CK19 (being numbered compound 98 in patent), CK20 (being numbered compound 271 in patent), CK21 (being numbered compound 117 in patent), has certain sterilization, insecticidal activity.
In prior art, the phenoxy pyrimidine aminated compounds of structure as shown in general formula I of the present invention has no report.
Summary of the invention
The object of the present invention is to provide a kind of phenoxy pyrimidine aminated compounds that just can control multiple germ, insect evil mite under very little dosage, it can be used for the medicine of preparation control germ and insect evil mite in agricultural or other field.
Technical scheme of the present invention is as follows:
The invention provides a kind of phenoxy pyrimidine aminated compounds, as shown in general formula I:
In formula:
R
1be selected from C
1-C
12alkyl or C
3-C
8cycloalkyl;
R
2be selected from halogen;
R
3be selected from hydrogen, halogen, hydroxyl, C
1-C
12alkyl or C
1-C
12alkoxyl group; M is selected from the integer of 0 to 4; When m is greater than 1, R
3may be the same or different;
R
4be selected from hydrogen, halogen, hydroxyl, amino, cyano group, nitro, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
3-C
12cycloalkyl, C
1-C
12alkylamino, halo C
1-C
12alkylamino, two (C
1-C
12alkyl) amino, halo two (C
1-C
12alkyl) amino, C (=O) NR
8r
9, C
1-C
12alkylthio, halo C
1-C
12alkylthio, 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
12alkyl sulphonyl, halo C
1-C
12alkyl sulphonyl, C
1-C
12alkyl-carbonyl, halo C
1-C
12alkyl-carbonyl, C
1-C
12alkoxy carbonyl, halo C
1-C
12alkoxy carbonyl, 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
12alkoxy carbonyl C
1-C
12alkyl, halo C
1-C
12alkoxy carbonyl C
1-C
12alkyl, C
1-C
12alkylthiocarbonyl C
1-C
12alkyl, halo C
1-C
12alkylthiocarbonyl C
1-C
12alkyl, C
1-C
12alkyl-carbonyl oxygen base, halo C
1-C
12alkyl-carbonyl oxygen base, C
1-C
12alkoxy-carbonyl oxy, halo C
1-C
12alkoxy-carbonyl oxy, C
1-C
12alkyl amino carbonyl oxy, halo C
1-C
12alkyl amino carbonyl oxy, C
1-C
12alkyl sulphonyl oxygen base, halo C
1-C
12alkyl sulphonyl oxygen base, C
1-C
12alkoxy C
1-C
12alkoxyl group, halo C
1-C
12alkoxy C
1-C
12alkoxyl group, C
1-C
12alkoxy carbonyl C
1-C
12alkoxyl group or halo C
1-C
12alkoxy carbonyl C
1-C
12alkoxyl group; N is selected from the integer of 0 to 5; When n is greater than 1, R
4may be the same or different;
R
5, R
6may be the same or different, be selected from hydrogen, halogen, C respectively
1-C
12alkyl, C
1-C
12alkoxyl group or C
3-C
12cycloalkyl; Or R
5, R
6c is formed with the carbon be connected
3-C
8ring;
R
7be selected from hydrogen, hydroxyl, formyl radical, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
3-C
12cycloalkyl, C
1-C
12alkylthio, C
2-C
12enylsulfanyl, C
2-C
12thiazolinyl, C
2-C
12alkynyl, halo C
2-C
12thiazolinyl, halo C
2-C
12alkynyl, 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
12alkyl amino sulfonyl, two (C
1-C
12alkyl) amino-sulfonyl, C
1-C
12alkylsulfonyl aminocarbonyl, C
1-C
12alkyl-carbonyl-amino alkylsulfonyl, C
3-C
12cycloalkyloxycarbonyl, C
1-C
12alkyl-carbonyl, halo C
1-C
12alkyl-carbonyl, C
1-C
12alkoxy carbonyl, halo C
1-C
12alkoxy carbonyl, C
1-C
12alkyl-carbonyl C
1-C
12alkyl, C
1-C
12alkoxy carbonyl C
1-C
12alkyl, C
1-C
12alkyl amino-carbonyl, two (C
1-C
12alkyl) aminocarboxyl, C
2-C
12allyloxycarbonyl, C
2-C
12alkynyloxycar bonyl, C
1-C
12alkoxy C
1-C
12alkoxy carbonyl, C
1-C
12alkylamino sulfenyl, two (C
1-C
12alkyl) amino sulfenyl, (mixing) aryl carbonyl C that is unsubstituted or that replaced further by the following group of 1-5
1-C
6alkyl, (mixing) aryl carbonyl, (mixing) aryloxycarbonyl, (mixing) aryl C
1-C
6alkyloxycarbonyl, (mixing) aryl C
1-C
6alkyl: halogen, nitro, cyano group, C
1-C
6alkyl, halo C
1-C
6alkyl, C
1-C
6alkoxyl group or halo C
1-C
6alkoxyl group;
R
8, R
9may be the same or different, be selected from hydrogen, C respectively
1-C
12alkyl or halo C
1-C
12alkyl;
A is selected from-CH
2-or-CH
2cH
2-;
W is selected from hydrogen or methyl;
Or the salt of compound of Formula I.
In the present invention, comparatively preferred compound is: in general formula I
R
1be selected from C
1-C
6alkyl or C
3-C
6cycloalkyl;
R
2be selected from halogen;
R
3be selected from hydrogen, halogen, hydroxyl, C
1-C
6alkyl or C
1-C
6alkoxyl group; M is selected from the integer of 0 to 4; When m is greater than 1, R
3may be the same or different;
R
4be selected from hydrogen, halogen, hydroxyl, amino, cyano group, nitro, 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
1-C
6alkylamino, halo C
1-C
6alkylamino, two (C
1-C
6alkyl) amino, halo two (C
1-C
6alkyl) amino, C (=O) NR
8r
9, C
1-C
6alkylthio, halo C
1-C
6alkylthio, 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
6alkyl sulphonyl, halo C
1-C
6alkyl sulphonyl, C
1-C
6alkyl-carbonyl, halo C
1-C
6alkyl-carbonyl, C
1-C
6alkoxy carbonyl, halo C
1-C
6alkoxy carbonyl, 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
6alkoxy carbonyl C
1-C
6alkyl, halo C
1-C
6alkoxy carbonyl C
1-C
6alkyl, C
1-C
6alkylthiocarbonyl C
1-C
6alkyl, halo C
1-C
6alkylthiocarbonyl C
1-C
6alkyl, C
1-C
6alkyl-carbonyl oxygen base, halo C
1-C
6alkyl-carbonyl oxygen base, C
1-C
6alkoxy-carbonyl oxy, halo C
1-C
6alkoxy-carbonyl oxy, C
1-C
6alkyl amino carbonyl oxy, halo C
1-C
6alkyl amino carbonyl oxy, C
1-C
6alkyl sulphonyl oxygen base, halo C
1-C
6alkyl sulphonyl oxygen base, C
1-C
6alkoxy C
1-C
6alkoxyl group, halo C
1-C
6alkoxy C
1-C
6alkoxyl group, C
1-C
6alkoxy carbonyl C
1-C
6alkoxyl group or halo C
1-C
6alkoxy carbonyl C
1-C
6alkoxyl group; N is selected from the integer of 0 to 5; When n is greater than 1, R
4may be the same or different;
R
5, R
6may be the same or different, be selected from hydrogen, halogen, C respectively
1-C
6alkyl, C
1-C
6alkoxyl group or C
3-C
6cycloalkyl; Or R
5, R
6c is formed with the carbon be connected
3-C
6ring;
R
7be selected from hydrogen, hydroxyl, formyl radical, C
1-C
6alkyl, C
1-C
6alkyl sulphonyl or C
1-C
6alkyl-carbonyl;
R
8, R
9may be the same or different, be selected from hydrogen, C respectively
1-C
6alkyl or halo C
1-C
6alkyl;
A is selected from-CH
2-or-CH
2cH
2-;
W is selected from hydrogen or methyl;
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid, phenylformic acid, phthalic acid, toxilic acid, Sorbic Acid, oxysuccinic acid or citric acid are formed.
The present invention further preferred compound is: in general formula I
R
1be selected from C
1-C
4alkyl or C
3-C
4cycloalkyl;
R
2be selected from halogen;
R
3be selected from hydrogen, halogen, hydroxyl, C
1-C
4alkyl or C
1-C
4alkoxyl group; M is selected from the integer of 0 to 4; When m is greater than 1, R
3may be the same or different;
R
4be selected from hydrogen, halogen, hydroxyl, amino, cyano group, nitro, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
3-C
4cycloalkyl, C
1-C
4alkylamino, halo C
1-C
4alkylamino, two (C
1-C
4alkyl) amino, halo two (C
1-C
4alkyl) amino, C (=O) NR
8r
9, C
1-C
4alkylthio, halo C
1-C
4alkylthio, C
2-C
4thiazolinyl, C
2-C
4alkynyl, C
2-C
4alkene oxygen base, halo C
2-C
4alkene oxygen base, C
2-C
4alkynyloxy group, halo C
2-C
4alkynyloxy group, 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
4alkoxy carbonyl, halo C
1-C
4alkoxy carbonyl, 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
4alkoxy carbonyl C
1-C
4alkyl, halo C
1-C
4alkoxy carbonyl C
1-C
4alkyl, C
1-C
4alkylthiocarbonyl C
1-C
4alkyl, halo C
1-C
4alkylthiocarbonyl C
1-C
4alkyl, C
1-C
4alkyl-carbonyl oxygen base, halo C
1-C
4alkyl-carbonyl oxygen base, C
1-C
4alkoxy-carbonyl oxy, halo C
1-C
4alkoxy-carbonyl oxy, C
1-C
4alkyl amino carbonyl oxy, halo C
1-C
4alkyl amino carbonyl oxy, C
1-C
4alkyl sulphonyl oxygen base, halo C
1-C
4alkyl sulphonyl oxygen base, C
1-C
4alkoxy C
1-C
4alkoxyl group, halo C
1-C
4alkoxy C
1-C
4alkoxyl group, C
1-C
4alkoxy carbonyl C
1-C
4alkoxyl group or halo C
1-C
4alkoxy carbonyl C
1-C
4alkoxyl group; N is selected from the integer of 0 to 5; When n is greater than 1, R
4may be the same or different;
R
5, R
6may be the same or different, be selected from hydrogen, halogen, C respectively
1-C
4alkyl, C
1-C
4alkoxyl group or C
3-C
6cycloalkyl; Or R
5, R
6c is formed with the carbon be connected
3-C
4ring;
R
7be selected from hydrogen, hydroxyl, formyl radical, C
1-C
4alkyl, C
1-C
4alkyl sulphonyl or C
1-C
4alkyl-carbonyl;
R
8, R
9may be the same or different, be selected from hydrogen, C respectively
1-C
4alkyl or halo C
1-C
4alkyl;
A is selected from-CH
2-or-CH
2cH
2-;
W is selected from hydrogen or methyl;
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid, phenylformic acid, toxilic acid, Sorbic Acid, oxysuccinic acid or citric acid are formed.
The present invention further preferred compound is: in general formula I
R
1be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, cyclopropyl or cyclobutyl;
R
2be selected from fluorine, chlorine or bromine;
R
3be selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy or tert.-butoxy; M is selected from the integer of 1 to 2;
R
4be selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano group, amino, nitro, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, trifluoromethyl, trichloromethyl, difluoro chloromethyl, dichloro one methyl fluoride, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, trifluoromethoxy, trifluoro ethoxy, methoxycarbonyl, ethoxy carbonyl, CONH
2, CONHCH
3, CONHC
2h
5or CONH (CH
3)
2; N is selected from the integer of 0 to 5;
R
5, R
6may be the same or different, be selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy or tert.-butoxy respectively;
R
7be selected from hydrogen;
A is selected from-CH
2-or-CH
2cH
2-;
W is selected from hydrogen or methyl;
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid or phenylformic acid are formed.
The present invention more preferred compound of a step is: in general formula I
R
1be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, cyclopropyl or cyclobutyl;
R
2be selected from fluorine, chlorine or bromine;
R
3be selected from hydrogen, fluorine, chlorine or bromine independently of one another respectively; M is selected from the integer of 1 to 2;
R
4be selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano group, nitro, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, trifluoromethyl, trichloromethyl, difluoro chloromethyl or dichloro one methyl fluoride; N is selected from the integer of 1 to 5;
R
5, R
6may be the same or different, be selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, sec.-propyl, methoxyl group, oxyethyl group, positive propoxy or isopropoxy respectively;
R
7be selected from hydrogen;
A is selected from-CH
2-or-CH
2cH
2-;
W is selected from hydrogen or methyl;
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid or phenylformic acid are formed.
Further, the preferred compound of the present invention is: in general formula I
R
1be selected from methyl or ethyl;
R
2be selected from chlorine;
R
3, R
5, R
6, R
7, W is selected from hydrogen;
R
4be selected from hydrogen, chlorine, cyano group, nitro, methyl or trifluoromethyl; N is selected from the integer of 1 to 5;
A is selected from-CH
2-;
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid or trifluoroacetic acid are formed.
The concrete preferred compound of the present invention is: in general formula I
R
1be selected from methyl, R
2be selected from chlorine, R
3, R
5, R
6, R
7, W is selected from hydrogen, (R
4) n is selected from the chloro-4-nitro of 2,6-bis-, A is selected from-CH
2-; Or
R
1be selected from ethyl, R
2be selected from chlorine, R
3, R
5, R
6, R
7, W is selected from hydrogen, (R
4) n is selected from the chloro-4-trifluoromethyl of 4-chlorine, 3,5-dichloros, 4-trifluoromethyl or 2-, A is selected from-CH
2-;
Or the salt that above-claimed cpd and hydrochloric acid are formed.
In the definition of the compound of Formula I provided above, collect term used and be generally defined as follows:
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.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.Halogenated alkyl sulfonyl: straight or branched alkyl sulphonyl, the hydrogen atom on its alkyl can partly or entirely replace by halogen atom.
Alkylamino sulfenyl: as CH
3nHS-, C
2h
5nHS-.Dialkyl amido sulfenyl: as (CH
3)
2nS-, (C
2h
5)
2nS-.Alkyl amino sulfonyl: alkyl-NH-SO
2-.Dialkyl amino sulfonyl: (alkyl)
2-N-SO
2-.
Alkylsulfonyl aminocarbonyl: alkyl-SO
2-NH-CO-.Alkyl-carbonyl-amino alkylsulfonyl: alkyl-CO-NH-SO
2-.Alkylcarbonylalkyl: alkyl-CO-alkyl-.Alkyl sulphonyl oxygen base: alkyl-S (O)
2-O-.Alkoxy carbonyl: alkyl-O-CO-, as CH
3oCO-, C
2h
5oCO-.Cycloalkyloxycarbonyl: as ring propoxycarbonyl, cyclohexyloxy carbonyl 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.Halo alkoxy carbonyl: the hydrogen atom on the alkyl of alkoxy carbonyl can partly or entirely replace by halogen atom, as ClCH
2cH
2oCO-, CF
3cH
2oCO-etc.Alkoxyalkyl: alkyl-O-alkyl-, such as CH
3oCH
2-.Halogenated alkoxy alkyl: the hydrogen atom on the alkyl of alkoxyalkyl can partly or entirely replace by halogen atom, as ClCH
2cH
2oCH
2-, CF
3cH
2oCH
2-etc.Alkoxy carbonyl alkyl: alkoxy carbonyl-alkyl-, such as CH
3oCOCH
2-.Alkoxyalkoxycarbonyl: as CH
3o CH
2cH
2oCO-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.Alkylthio alkyl: alkyl-S-alkyl-, such as CH
3sCH
2-.Haloalkylthioalkyl: the hydrogen atom on the alkyl of alkylthio alkyl can partly or entirely replace by halogen atom, as ClCH
2cH
2sCH
2-, CF
3cH
2sCH
2-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.Dialkyl amido: as (CH
3)
2n-, (CH
3cH
2)
2n-.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.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.Enylsulfanyl: straight or branched alkene class, is connected in structure through sulphur atom key.As CH
2=CHCH
2s-.Allyloxycarbonyl: as CH
2=CHCH
2oCO-etc.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.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.Alkynyloxycar bonyl: as CH ≡ CCH
2oCO-etc.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.Alkyl-carbonyl: alkyl is connected in structure, as CH through carbonyl
3cO-, CH
3cH
2cO-.Halogenated alkyl carbonyl: the hydrogen atom on the alkyl of alkyl-carbonyl can partly or entirely replace by halogen atom, as CF
3cO-.Alkoxy carbonyl: alkoxyl group is connected in structure through carbonyl.As CH
3oCO-, CH
3cH
2oCO-.Alkyl amino-carbonyl: alkyl-NH-CO-, such as CH
3nHCO-, CH
3cH
2nHCO-.Dialkyl amino carbonyl: as (CH
3)
2nCO-, (CH
3cH
2)
2nCO-.Aryl moiety in (mixing) arylalkyl, (mixing) aryl carbonyl, (mixing) aryl alkyl carbonyl, (mixing) aryloxycarbonyl, (mixing) arylalkyl oxygen base carbonyl comprises phenyl or naphthyl etc.Heteroaryl is containing the heteroatomic five-ring of one or more N, O, S or six-ring.Such as furyl, pyrazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazinyl, quinolyl etc.(mixing) arylalkyl: as phenmethyl, styroyl, to chlorophenylmethyl,
deng.(mixing) aryl carbonyl: as benzoyl, 4-chlorobenzene formacyl etc.(mixing) aryl alkyl carbonyl: as PhCOCH
2-.(mixing) aryloxycarbonyl: as phenyloxycarbonyl, 4-cHorophenoxycarbonyl, 4-nitrophenoxy carbonyl, naphthoxycarbonyl etc.Arylalkyl oxygen base carbonyl: as benzyloxycarbonyl, 4-chlorobenzyl oxygen base carbonyl, 4-trifluoromethyl benzyl oxygen base carbonyl etc.(mixing) arylalkyl oxygen base carbonyl: as PhCH
2oCO-, 4-Cl-PhCH
2oCO-etc.
Table 1, table 2, table 3, table 4, table 5, table 6 list R in general formula I respectively
1, R
2, R
3, R
4, R
5, R
6, R
7the concrete substituting group of part, but they are not limited only to these substituting groups.
Table 1 R
1substituting group
Table 2 R
2substituting group
Table 3 R
3substituting group
Table 4 (R
4) n substituting group
Table 5 R
5(R
6) substituting group
Table 6 R
7substituting group
Part of compounds of the present invention can illustrate by the particular compound listed in table 7-table 47, and wherein showing 7-table 38 is general formula I A compound, and table 39-table 47 is general formula I B compound, but the present invention is only limitted to absolutely not these compounds.
In general formula I A, as W=H, R
1=CH
3, R
2=Cl, R
3=R
5=R
6during=H, (R
4) n be different substituting group in table 7, representation compound is numbered 1-278.
Table 7
Table 8: in general formula I A, as W=H, R
1=C
2h
5, R
2=Cl, R
3=R
5=R
6during=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 279-556, is corresponding in turn to the 1-278 of table 7.
Table 9: in general formula I A, as W=H, R
1=CH
3, R
2=R
3=Cl, R
5=R
6during=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 557-834, is corresponding in turn to the 1-278 of table 7.
Table 10: in general formula I A, as W=H, R
1=C
2h
5, R
2=R
3=Cl, R
5=R
6during=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 835-1112, is corresponding in turn to the 1-278 of table 7.
Table 11: in general formula I A, as W=H, R
1=CH
3, R
2=Cl, R
3=Br, R
5=R
6during=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 1113-1390, is corresponding in turn to the 1-278 of table 7.
Table 12: in general formula I A, as W=H, R
1=C
2h
5, R
2=Cl, R
3=Br, R
5=R
6during=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 1391-1668, is corresponding in turn to the 1-278 of table 7.
Table 13: in general formula I A, as W=H, R
1=CH
3, R
2=Cl, R
3=OCH
3, R
5=R
6during=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 1669-1946, is corresponding in turn to the 1-278 of table 7.
Table 14: in general formula I A, work as W=H, R
1=C
2h
5, R
2=Cl, R
3=OCH
3, R
5=R
6during=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 1947-2224, is corresponding in turn to the 1-278 of table 7.
Table 15: in general formula I A, as W=H, R
1=CH
3, R
2=Cl, R
3=R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 2225-2502, is corresponding in turn to the 1-278 of table 7.
Table 16: in general formula I A, as W=H, R
1=C
2h
5, R
2=Cl, R
3=R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 2503-2780, is corresponding in turn to the 1-278 of table 7.
Table 17: in general formula I A, as W=H, R
1=CH
3, R
2=Cl, R
3=Cl, R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 2781-3058, is corresponding in turn to the 1-278 of table 7.
Table 18: in general formula I A, as W=H, R
1=C
2h
5, R
2=Cl, R
3=Cl, R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 3059-3336, is corresponding in turn to the 1-278 of table 7.
Table 19: in general formula I A, as W=H, R
1=CH
3, R
2=Cl, R
3=Br, R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 3337-3614, is corresponding in turn to the 1-278 of table 7.
Table 20: in general formula I A, as W=H, R
1=C
2h
5, R
2=Cl, R
3=Br, R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 3615-3892, is corresponding in turn to the 1-278 of table 7.
Table 21: in general formula I A, as W=H, R
1=CH
3, R
2=Cl, R
3=OCH
3, R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 3893-4170, is corresponding in turn to the 1-278 of table 7.
Table 22: in general formula I A, as W=H, R
1=C
2h
5, R
2=Cl, R
3=OCH
3, R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 4171-4448, is corresponding in turn to the 1-278 of table 7.
Table 23: in general formula I A, work as W=CH
3, R
1=CH
3, R
2=Cl, R
3=Cl, R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 4449-4726, is corresponding in turn to the 1-278 of table 7.
Table 24: in general formula I A, work as W=CH
3, R
1=C
2h
5, R
2=Cl, R
3=R
5=R
6during=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 4727-5004, is corresponding in turn to the 1-278 of table 7.
Table 25: in general formula I A, work as W=CH
3, R
1=CH
3, R
2=R
3=Cl, R
5=R
6during=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 5005-5282, is corresponding in turn to the 1-278 of table 7.
Table 26: in general formula I A, work as W=CH
3, R
1=C
2h
5, R
2=R
3=Cl, R
5=R
6during=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 5283-5560, is corresponding in turn to the 1-278 of table 7.
Table 27: in general formula I A, work as W=CH
3, R
1=CH
3, R
2=Cl, R
3=Br, R
5=R
6during=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 5561-5838, is corresponding in turn to the 1-278 of table 7.
Table 28: in general formula I A, work as W=CH
3, R
1=C
2h
5, R
2=Cl, R
3=Br, R
5=R
6during=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 5839-6116, is corresponding in turn to the 1-278 of table 7.
Table 29: in general formula I A, work as W=CH
3, R
1=CH
3, R
2=Cl, R
3=OCH
3, R
5=R
6during=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 6117-6394, is corresponding in turn to the 1-278 of table 7.
Table 30: in general formula I A, work as W=CH
3, R
1=C
2h
5, R
2=Cl, R
3=OCH
3, R
5=R
6during=H, substituting group (R
4) n is consistent with table 7, representation compound is numbered 6395-6672, is corresponding in turn to the 1-278 of table 7.
Table 31: in general formula I A, work as W=CH
3, R
1=CH
3, R
2=Cl, R
3=R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 6673-6950, is corresponding in turn to the 1-278 of table 7.
Table 32: in general formula I A, work as W=CH
3, R
1=C
2h
5, R
2=Cl, R
3=R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 6951-7228, is corresponding in turn to the 1-278 of table 7.
Table 33: in general formula I A, work as W=CH
3, R
1=CH
3, R
2=Cl, R
3=Cl, R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 7229-7506, is corresponding in turn to the 1-278 of table 7.
Table 34: in general formula I A, work as W=CH
3, R
1=C
2h
5, R
2=Cl, R
3=Cl, R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 7507-7784, is corresponding in turn to the 1-278 of table 7.
Table 35: in general formula I A, work as W=CH
3, R
1=CH
3, R
2=Cl, R
3=Br, R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 7785-8062, is corresponding in turn to the 1-278 of table 7.
Table 36: in general formula I A, work as W=CH
3, R
1=C
2h
5, R
2=Cl, R
3=Br, R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 8063-8340, is corresponding in turn to the 1-278 of table 7.
Table 37: in general formula I A, work as W=CH
3, R
1=CH
3, R
2=Cl, R
3=OCH
3, R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 8341-8618, is corresponding in turn to the 1-278 of table 7.
Table 38: in general formula I A, work as W=CH
3, R
1=C
2h
5, R
2=Cl, R
3=OCH
3, R
5=H, R
6=CH
3time, substituting group (R
4) n is consistent with table 7, representation compound is numbered 8619-8896, is corresponding in turn to the 1-278 of table 7.
In general formula I B, work as R
1=CH
3, R
2=Cl, (R
4) n=4-CF
3time, substituent R
7for different substituting groups is in table 39, representation compound is numbered 8897-9036.
Table 39
Table 40: in general formula I B, work as R
1=C
2h
5, R
2=Cl, (R
4) n=4-CF
3time, substituent R
7consistent with table 39, representation compound is numbered 9037-9176, is corresponding in turn to the 8897-9036 of table 39.
Table 41: in general formula I B, work as R
1=CH
3, R
2=Cl, (R
4) n=4-Cl time, substituent R
7consistent with table 39, representation compound is numbered 9177-9316, is corresponding in turn to the 8897-9036 of table 39.
Table 42: in general formula I B, work as R
1=C
2h
5, R
2=Cl, (R
4) n=4-Cl time, substituent R
7consistent with table 39, representation compound is numbered 9317-9456, is corresponding in turn to the 8897-9036 of table 39.
Table 43: in general formula I B, work as R
1=CH
3, R
2=Cl, (R
4) n=2,4-2Cl time, substituent R
7consistent with table 39, representation compound is numbered 9457-9596, is corresponding in turn to the 8897-9036 of table 39.
Table 44: in general formula I B, work as R
1=C
2h
5, R
2=Cl, (R
4) n=2,4-2Cl time, substituent R
7consistent with table 39, representation compound is numbered 9597-9736, is corresponding in turn to the 8897-9036 of table 39.
Table 45: in general formula I B, work as R
1=CH
3, R
2=Cl, (R
4) n=2,6-2Cl-4-NO
2time, substituent R
7consistent with table 39, representation compound is numbered 9737-9876, is corresponding in turn to the 8897-9036 of table 39.
Table 46: in general formula I B, work as R
1=C
2h
5, R
2=Cl, (R
4) n=2,6-2Cl-4-NO
2time, substituent R
7consistent with table 39, representation compound is numbered 9877-10016, is corresponding in turn to the 8897-9036 of table 39.
The salt of part of compounds of the present invention can illustrate with the salt of the particular compound listed in table 47, but does not limit the present invention.
Table 47 part of compounds salt
The compounds of this invention is prepared in accordance with the following methods (in formula, each group unless otherwise indicated defines ditto):
The first situation, works as R
7during=H, the preparation of general formula (I-1) compound can adopt the following two kinds method:
Method one: the pyrimidine chlorine of replacement reacts with corresponding replacement amine, and reaction formula is as follows.Synthetic method is with reference to EP0370704, EP0356158, EP0264217, EP0665225, JP10036355, US4985426.
Compound representated by general formula of the present invention (I-1) can be obtained by the condensation in suitable solvent of the amine shown in the substituted pyrimidines chlorine shown in general formula (II) and general formula (III).React and carry out in suitable solvent, 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.Reaction can be carried out under having alkali or alkali-free to exist, and when reacting under having alkali to exist, can accelerated reaction carry out.Described alkali can be selected from alkalimetal hydride, as sodium hydride; Alkali metal hydroxide, as sodium hydroxide or potassium hydroxide; Alkaline carbonate, as sodium carbonate or salt of wormwood; Organic amine, as pyridine or triethylamine.Temperature of reaction between room temperature to solvent boiling point temperature, can be generally 20 ~ 110 DEG C.Reaction times is 30 minutes to 20 hours, usual 1 ~ 10 hour.
Substituted pyrimidines cl part shown in general formula (II) has commercially available, or can according to US4977264, Journal of the American Chemical Society, 79,1455 (1957), the method synthesis described in Journal of Chemical Society, pp.3478-3481 (1955).
Aminated compounds shown in general formula (III) or its salt are the key intermediates of preparation general formula of the present invention (I-1) compound, available following several method preparation: corresponding raw material or have commercially available or reference literature US4895849, JP10036355, EP665225, US20070093498, WO2007046809, US5783522A, WO02083647A1, CN1927860A, Organic Syntheses, Coll.Vol.10, p.501 (2004); Vol.75, p.61 (1998) or Organic Syntheses, Coll.Vol.10, p.102 (2004); Vol.75, p.53 (1998) preparation.
(1) cyano reduction method preparation:
In formula, L is leavings group, is halogen, boric acid, methanesulfonate ester or p-toluenesulfonic esters, and M is the alkyl chain of a carbon fewer than A.
In suitable solvent, under suitable alkali exists, general formula (IV) and (V) react, and process and obtain (VI).Concrete preparation can with reference to fine chemistry industry, and 2005, the method described in 22 (12): 944-960 is carried out.Reaction is carried out usually in room temperature to solvent boiling point temperature range, and comparatively suitable temperature of reaction is 20 ~ 100 DEG C.Reaction times is 30 minutes to 20 hours, usual 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, (VI) obtains (III) through hydrogenating reduction under suitable catalyzer and ammoniacal liquor exist.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); Vol.23, p.71 (1943) or Vol.27, the method p.18 described in (1947) is carried out.Reaction is carried out usually in room temperature to solvent boiling point temperature range, and comparatively suitable temperature of reaction is 20 ~ 100 DEG C.Reaction times is 30 minutes to 20 hours, usual 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.
(2) with the Uteramin replaced for raw material prepares amine and salt thereof:
In formula, Boc
2o refers to tert-Butyl dicarbonate.
First, in suitable solvent, under the existence of suitable alkali, tert-Butyl dicarbonate and corresponding Uteramin (VII) reacts in 0 ~ 100 DEG C, first obtain the Uteramin (VIII) that Boc protects.Temperature of reaction preferably 0 ~ 50 DEG C; 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 such as sodium carbonate, sodium bicarbonate, salt of wormwood or saleratus.
Then, by (VIII) and (V) in suitable solvent, under the existence of suitable alkali, obtain (IX) in 0 ~ 100 DEG C 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 alkalimetal hydride such as sodium hydride, alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, alkaline carbonate such as sodium carbonate or salt of wormwood, organic amine such as pyridine or triethylamine.
(IX) in suitable solvent, obtain corresponding salt (X) through suitable sour deprotection, Re-boostering test obtains (III).Temperature of reaction preferably 0 ~ 50 DEG C; 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 alkalimetal hydride such as sodium hydride, alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; Alkaline carbonate such as sodium carbonate or salt of wormwood, organic amine such as pyridine or triethylamine.Concrete preparation method is see WO2004093800A and US20050096485.
Method two: the pyrimidine chlorine of replacement reacts with corresponding replacement Uteramin, and then with intermediate (V) condensation, can obtain object (I-1), reaction formula is as follows:
Compound representated by general formula (I-1) by the condensation obtained (XI) in suitable solvent of the Uteramin shown in the substituted pyrimidines chlorine shown in general formula (II) and general formula (VII), then can obtain (I-1) by (XI) and intermediate (V) condensation under the effect of alkali.Other each group definition are the same.
(II) carry out in suitable solvent with the condensation reaction of (VII), 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.Reaction can be carried out under having alkali or alkali-free to exist, and when reacting under having alkali to exist, can accelerated reaction carry out.Described alkali can be selected from alkalimetal hydride, as sodium hydride; Alkali metal hydroxide, as sodium hydroxide or potassium hydroxide; Alkaline carbonate, as sodium carbonate or salt of wormwood; Organic amine, as pyridine or triethylamine.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.
The condensation reaction of (XI) and (V) that obtain is carried out in suitable solvent, 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.React and carry out under having alkali to exist, described alkali can be selected from alkalimetal hydride, as sodium hydride; Alkali metal hydroxide, as sodium hydroxide or potassium hydroxide; Alkaline carbonate, as sodium carbonate or salt of wormwood; Organic amine, as pyridine or triethylamine.Temperature of reaction between room temperature to solvent boiling point temperature, can be generally 20 ~ 200 DEG C.Reaction times is 30 minutes to 20 hours, usual 1 ~ 10 hour.Concrete preparation method is see JP11049759, EP0370704, EP0196524, US4895849.
Substituted pyrimidines chlorine (II), part has commercially available, or can synthesize to literature method according in method one.
Other raw material sources involved in the preparation method of above-mentioned general formula (I-1) compound are as follows: general formula (IV), (V), (VII) and Boc
2compound shown in O is commercially available.
The second situation, works as R
7be not hydrogen, i.e. R
7during for other substituting groups, general formula (I-2) compound can with reference to the preparation of such as Publication about Document: JP08269021, JP3543411, JP1995-72621, JP1995-96669, JP3511729, JP08291149, EP530149, WO9208704.
The preparation method of general formula (I) compound salt is as follows:
The preparation of PYRIMITHAMINE salify:
Compound of Formula I and organic acid or inorganic acid reaction obtain corresponding salt I-A, and reaction formula is as follows.
In addition, in general formula (I) compound, also can salify on pyrimidine ring N, preparation method can reference DE19647317, JP2001504473, US5925644, WO9822446, ZA9710187 etc.
General formula I and organic acid or inorganic acids react and usually carry out in room temperature to solvent boiling point temperature range, and comparatively suitable temperature of reaction is 20 ~ 100 DEG C.Reaction times is 30 minutes to 20 hours, usual 1 ~ 10 hour.Suitable solvent can be selected from water, 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.
Can comprise with the acid of compound of Formula I salify of the present invention: carboxylic acid is acetic acid, propionic acid, butyric acid, oxalic acid, trifluoroacetic acid, hexanodioic acid, dodecanedioic acid, lauric acid, stearic acid, trifluoroacetic acid, fumaric acid, toxilic acid, oxysuccinic acid, citric acid, phenylformic acid, p-methylbenzoic acid or phthalic acid etc. such as; Sulfonic acid is methylsulfonic acid, 1,3-third disulfonic acid, tosic acid or Witco 1298 Soft Acid etc. such as; And mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or carbonic acid etc.Preferred hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid or phenylformic acid etc. further.
Although some compound all belongs to pyrimidinamine compound disclosed in compound of Formula I of the present invention and prior art, but constitutional features still exists remarkable difference, and compound of the present invention is made to have better sterilization and/or pesticide and miticide actility due to these structural differences.
Compound of Formula I all demonstrates excellent activity to the multiple germ in agricultural or other field, insect evil mite.Therefore, technical scheme of the present invention also comprises the purposes that compound of Formula I is used as to prepare sterilant, Insecticiding-miticiding agent 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:
Coleoptera (Coleoptera) (beetle): bean weevil belongs to kind of (Acanthoscelides spp.) (curculionid), acanthoscelides obtectus (Acanthoscelides obtectus) (common pea weevil), Emerald ash borer (Agrilus planipennis) (emerald ash borer, Agrilus planipennis), acupuncture needle Eimeria kind (Agriotes spp.) (wireworm), Anoplophora glabripenis (Anoplophora glabripennis) (Asia psacotheahilaris), cotton boll resembles and belongs to kind of (Anthonomus spp.) (Culculionidae), Mexico's cotton boll resembles (Anthonomus grandis) (bollworm), cocoon honeybee belongs to kind of (an Aphidius spp.), weevil belongs to kind of (Apion spp.) (curculionid), sugarcane cockchafer belongs to kind of (Apogonia spp.) (grub), black suede cockchafer (Atacnius sprctulus) (smaller velvety chafer), Atomaria linearis (Atomaria linearis) (little beet beetle (pygmy mangold beetle), cucumber beetle belongs to kind of (an Aulacophore spp.), beet resembles (Bothynoderes punctiventris) (beet tails curculionid), bean weevil belongs to kind of (Bruchus spp.) (curculionid), pea weevil (Bruchus pisorum) (pea weevil), Cacoesia belongs to kind of (a Cacoesia spp.), Callosobruchus maculatus (Callosobruchus maculatus) (southern cowpea curculionid), pineapple bug (Carpophilus hemipteras) (dried-frait beetle), beet tortoise beetle (Cassida vittata), it Bos kind (Ccrostcrna spp.), Ccrotoma belongs to kind of (Ccrotoma spp.) (chrysomonad (chrysomcids)), beans chrysomelid (Cerotoma trifur cata) (the chrysomelid worm of beans), tortoise resembles and belongs to kind of (Ceutorhynchus spp.) (curculionid), Chinese cabbage seed tortoise resembles (Ceutorhynchus assimilis) (Chinese cabbage weevil (cabbage seedpod weevil)), turnip tortoise resembles (Ceutorhynchus napi) (Caulis et Folium Brassicae capitatae curculionid (cabbage curculio)), phyllotreta kind (Chaetocnema spp.) (chrysomonad), Colaspis belongs to kind of (Colaspis spp.) (a native beetle), Conoderus scalaris, Conoderus stigmosus, Lee resembles (Conotrachelus nenuphar) (plum cone weevil), Cotinus nitidis (Green june beetle (Green June beetle)), officinalis scotellaris (Crioceris asparagi) (officinalis beetle), rusty grain beetle (Cryptolestes ferrugincus) (rust paddy beetle (rusty grainbeetle)), Cryptolestes pusillus (Cryptolestes pusillus) (flat ostomatid), Cryptolestes turcicus Grouville (Cryptolestes turcicus) (Turkey paddy beetle (Turkish grain beetle)), Ctenicera belongs to kind of (Ctenicera spp.) (nematode), Curculio kind (Curculio spp.) (curculionid), round end rhinoceros cockchafer belongs to kind of (Cyclocephala spp.) (grub), close some withe resembles (Cylindrocpturus adspersus) (Sunflower Receptacle grass curculionid (sunflower stem weevil)), mango leaf-cutting resembles (Deporaus marginatus) (mango leaf-cutting curculionid (mango leaf-cutting weevil)), lader beetle stupid (Dermestes lardarius) (lader beetle is stupid), white abdomen skin stupid (Dermestes maculates) (white abdomen skin is stupid), chrysomelid genus kind of (Diabrotica spp.) (chrysomelid), mexican bean ladybird (Epilachna varivcstis) (Mexico beans beetle), moth stem weevil (raustinus cubae), pale collar resembles (Hylobius pales) (pales weevil (pales weevil)), Phytonomus kind (Hypera spp.) (curculionid), alfalfa leaf resembles (Hypera postica) (alfalfa weevil), Hyperdoes belongs to kind of (Hyperdoes spp.) (Argentinian stem weevil (a Hyperodes weevil)), coffee cherry little stupid (Hypothenemus hampei) (coffee cherry beetle), little stupid genus kind of (Ips spp.) (sour jujube shin little stupid (engravers)) of tooth, lasioderma serricorne (Lasioderma serricorne) (cigarette beetle), colorado potato bug (Leptinotarsa decemlineata) (Colorado potato beetle), Liogenys fuscus, Liogenys suturalis, rice water weevil (Lissorhoptrus oryzophilus) (rice water weevil), the stupid genus of powder kind of (Lyctus spp.) (the stupid beetle of wooden stupid moth/powder (powder post beetles)), Maecolaspis joliveti, Megascelis belong to kind of (a Megascelis spp.), corn click beetle (Melanotus communis), nitidulid belongs to kind of (a Meligethes spp.), rape nitidulid (Meligethes aeneus) (brevitarsis (blossom beetle)), May beetle (Melolontha melolontha) (typical European chafer), Oberea brevis, linear cylinder longicorn (Oberea linearis), coconut palm moth rhinoceros cockchafer (Oryctes rhinoceros) (date palm beetle (date palm beetle)), trade saw-toothed grain beetle (Oryzaephilus mercator) (market saw-toothed grain beetle (merchant grain beetle)), saw-toothed grain beetle (Oryzaephilus surinamensis) (sawtooth paddy beetle (sawtoothcd grain bcctlc)), beak weevil belongs to kind of (Otiorhynchus spp.) (curculionid), black angle scotellaris (Oulema melanopus) (cereal leaf beetle (cereal leafbeetle)), Oulema oryzae (Oulema oryzae), the short beak of rose resembles and belongs to kind of (Pantomorus spp.) (curculionid), food phyllobranchia cockchafer belongs to kind of (a Phyllophaga spp.) (May/June chafer), Phvllophaga cuyabana, striped flea beetle kind (Phyllotreta spp.) (chrysomonad), apple tiger resembles and belongs to kind of (a Phynchites spp.), Japan popillia flavosellata fairmaire (Popillia japonica) (Japanese beetle), large space between muscles stupid (Prostephanus truncates) (large space between muscles long stupid (larger grain borer)), paddy stupid (Rhizopertha dominica) (the little moth of paddy (lesser grain borer)), root gill cockchafer belongs to kind of (Rhizotrogus spp.) (European chafer (an Eurpoean chafer)), Rhynchophorus kind (Rhynchophorus spp.) (curculionid), little stupid genus kind of (Scolytus spp.) (wooden stupid moth), Shenophorus belongs to kind of (Shenophorus spp.) (grain weevil), pea leaf resembles (Sitona lincatus) (pealeaf weevil (pca leaf weevil)), Sitophilus kind (Sitophilus spp.) (grain weevil first), grain weevil (Sitophilus granaries) (paddy worm (granary weevil)), rice weevil (Sitophilus oryzae) (rice weevil first (rice weevil)), medicinal material ostomatid (Stegobium paniceum) (Stegobium paniceum (drugstore beetle)), Tribolium kind (Tribolium spp.) (flour beetle), red flour beetle (Tribolium castaneum) (red flour beetle (red flour beetle)), assorted plan paddy moistens (Tribolium confusum) (confused flour beetle (confused flour beetle)), piebald skin stupid (Trogoderma variabile) (warehouse skin stupid (warehouse beetle)) and Zabrus tenebioides.
Dermaptera (Dcrmaptcra) (earwig).
Neuroptera (Dictyoptera) (cockroach): Groton bug (Blattella germanica) (Groton bug (German cockroach)), oriental cockroach (Blatta orientalis) (Blatta seu periplaneta), Pennsylvania wood Lian (Parcoblatta pennylvanica), periplaneta americana (Periplaneta americana) (America roach consumptive disease (American cockroach)), Australian cockroach (Periplaneta australoasiae) (Australian cockroach (Australian cockroach)), periplaneta brunnea (Pcriplancta brunnca) (periplaneta brunnea (brown cockroach)), smoke Perilpaneta americana (Periplaneta fuliginosa) (Peroplaneta fluligginosa (smokybrown cockroach)), the green blattaria of sugarcane (Pyncoselus suninamensis) (sugarcane Lian (Surinam cockroach)) and long palpus blattaria (Supella longipalpa) (brown band blattaria (brownbanded cockroach)).
Diptera (Diptera) (fly): Aedes kind (Aedes spp.) (mosquito), alfalfa is dived fly (Agromyza frontella) (alfalfa dive fly (alfalfa blotch leafminer)), Hippelates kind ((Agromyza spp.) (Liriomyza), by Anastrepha kind (Anastrepha spp.) (fruit bat), Caribbean is by trypetid (Anastrepha suspensa) (Caribbean is by trypetid (Caribbean fruit fly)), Anopheles kind (Anopheles spp.) (mosquito), Bactrocera kind (Batrocera spp.) (fruit bat), melon trypetid (Bactrocera cucurbitae) (melon fly), citrus fruit fly (Bactrocera dorsalis) (oriental fruit fly), little bar Anastrepha kind (Ceratitis spp.) (fruit bat), the little bar trypetid in Mediterranean Sea (Ceratitis capitata) (medfly), Chrysops kind (Chrysops spp.) (deer horsefly), Callitroga's kind (Cochliomyia spp.) (screw worm fly larva), Ying uranotaenia kind (Contarinia spp.) (Ying mosquito), Culex kind (Culex spp.) (mosquito), Ye Ying uranotaenia kind (Dasineura spp.) (Ying mosquito), You Cai Ye Ying mosquito (Dasineura brassicae) (Juan Xin Cai Ying mosquito), Delia kind (Delia spp.), delia platura (Delia platura) (root maggot (seedcorn maggot)), Drosophila kind (Drosophila spp.) (vinegar fly), Fannia kind (Fannia spp.) (housefly), anthomyia canicularis (Fannia canicularis) (Fannia canicularis (little house fly)), anthomyia scalaris (Fannia scalaris) (anthomyia scalaris), large horse botfly (Gasterophilus intestinalis) (horse botfly), Gracillia perseae, Haematobia irritans (Haematobia irritans) (horn fly), Hylemyia kind (Hylemyia spp.) (root maggot (root maggot)), heel fly (Hypoderma lineatum) (laiu wire rope torsalo (common cattle grub)), Liriomyza kind (Liriomyza spp.) (Liriomyza), wild cabbage liriomyza bryoniae (Liriomyza brassica) (Liriomyza that crawls (serpentine leafminer)), sheep hippoboscid (Melophagus ovinus) (sheepked), fly belongs to kind of (Musca spp.) (housefly (a muscid fly)), face fly (Musca autumnalis) (face fly (face fly)), housefly (Vusca domestica) (housefly (house fly)), Oestrus ovis (Oestrus ovis) (sheep nose fly (sheep bot fly)), Europe frit fly (Oscinella frit) (Oscinella frit), beet spring fly (Pegomyia betae) (spinach leaf miner (beet leafminer)), wheat fly belongs to kind of (a Phorbia spp.), carrot fly (Psila rosae) (Radix Dauci Sativae rust fly (carrotrust fly)), cherry fruit bat (Rhagoletis cerasi) (cherry fruit bat (cherry fruit fly)), Rhagoletis pomonella (Rhagoletis pomonella) (apple maggots (apple maggot)), wheat midge (Sitodiplosis mosellana) (orange wheat flower mosquito (orange wheat blossom midge)), tatukira (stomoxys calcitruns) (tatukira (stable fly)), the gadfly belongs to kind of (Tahanus spp.) (horse botfly) and a large uranotaenia kind (Tipula spp.) (daddy-longlegs).
Hemiptera (Hemiptera) (stinkbug): intend green stinkbug (Acrosternum hilare) (green stinkbug (green stink bug)), America paddy chinch bug (Blissus leucopterus) (chinch bug (chinch bug)), potato pretty fleahopper (Calocoris norvegicus) (potato fleahopper (potato mirid)), cimex hemipterus (Cimex hemipterus) (cimex hemipterus (tropical bed bug)), bedbug (Cimex lectularius) (bedbug (bed hug)), Daghertus fasciatus, Dichelops furcatus, cotton the red stinkbug of black wing (Dysdercus suturellus) (red cotton bug (cotton stainer)), Edessa meditabunda, Europe Eurygasterspp (Eurygaster maura) (paddy worm (cereal bug)), Euschi stus heros, brown smelly stinkbug (Euschi stus servus) (brown stinkbug (brown stink bug)), iS-One angle fleahopper (Helopeltis antonii), tea angle fleahopper (Helopeltis theivora) (tea blight plantbug), stinkbug belongs to kind of (Lagynotomus spp.) (stinkbug), large Leptocorisa spp (Leptocorisa oratorius), different Leptocorisa spp (Leptocorisa varicornis), Lygus Hahn kind (Lygus spp.) (fleahopper (plant bug)), beanpod lygus bug (Lygus hesperus) (western tarnished plant bug), the graceful powder stinkbug of the rose of Sharon (Maconellicoccus hirsutus), Neurocolpus longirostris, Nezara viridula smaragdula Fabricius. (Nezara viridula) (southern green stink bug), Phytocoris kind (PhyLocoris spp.) (fleahopper), fleahopper (Phytocoris californicus) is planted in California, Phytocoris relativus, Piezodorus guildingi, four line fleahoppers (Poecilocapsus lineatus) (fourlined plant bug), Psallus vaccinicola, Pseudacysta perseae, Scaptocoris castanea and Triatoma kind (Triatoma spp.) (cone nose worm (bloodsuckingconenose bug) of sucking blood/hunt stinkbug (kissing bug)).
Homoptera (Homoptera) (aphid, a red-spotted lizard, aleyrodid, leafhopper): acyrthosiphum pisim (Acrythosiphonpisum) (acyrthosiphum pisim (pea aphid)), adelgid belongs to kind of (Adelges spp.) (adelgids), wild cabbage aleyrodid (Aleurodes proletella) (Caulis et Folium Brassicae capitatae aleyrodid), Aleurodicus dispersus (Aleurodicus disperses), velvet aleyrodid (Aleurothrixus flccosus) (whitefly in bt cotton (woolly whitefly)), white wheel armored scale belongs to kind of (an Aluacaspis spp.), Amrasca bigutella bigutella, froghopper belongs to kind of (Aphrophora spp.) (leafhopper (leafhopper)), California red scale (Aonidiella aurantii) (the red a red-spotted lizard in California (California red scale)), Aphis kind (Aphis spp.) (aphid), cotten aphid (Aphis gossypii) (cotton aphid), apple aphid (Aphis pomi) (apple aphid), eggplant is without net aphid (Aulacorthitm solani) (foxglove aphid (foxglove aphid)), Aleyrodes kind (Bemisia spp.) (aleyrodid), Bemisia argentifolii (Bemisia argentifolii), sweet potato whitefly (Bemisia tabaci) (sweetpotato whitefly), Diuraphis noxia (Brachycolus noxius) (Russian aphid (Russian aphid)), officinalis tubule aphid (Brachycorynclia asparagi) (officinalis aphid (asparagus aphid)), Brevennia rehi, brevicoryne brassicae (Brevicoryne brassicae) (Caulis et Folium Brassicae capitatae aphid), lecanium belongs to kind of (Ceroplastes spp.) (a red-spotted lizard), ceroplastes rubens (Ceroplastes rubens) (red wax scale), snow armored scale belongs to kind of (Chionaspis spp.) (a red-spotted lizard), Aspidiotus belongs to kind of (Chrysomphalus spp.) (a red-spotted lizard), soft wax a red-spotted lizard belongs to kind of (Coccus spp.) (a red-spotted lizard), the pink bad aphid of apple (Dysaphis plantaginea) (rosy apple aphid), green jassids belongs to kind of (Empoasca spp.) (leafhopper), apple aphid (Eriosoma lanigerum) (woolly apple aphid), blow cotton a red-spotted lizard (Icerya purchasi) (cottony cushion scale), mango yellow line leafhopper (Idioscopus nitidulus) (mango leafhopper), small brown rice planthopper (Laodelphax striatellus) (smaller brown planthopper), lepidosaphes shimer kind (Lepidosaphes spp.), long tube Aphis kind (Macrosiphum spp.), root of Beijing euphorbia Macrosiphus spp (Macrosiphum euphorbiae) (potato aphid (potato aphid)), grain aphid (Macrosiphum granarium) (Britain's wheat aphid (English grain aphid)), rose aphid (Macrosiphum rosae) (rose aphid (rose aphid)), four line leafhopper (Macrosteles quadrilineatus) (Aster tataricus leafhopper (aster leafhopper)), Mahanarva frimbiolata, Acyrthosiphon dirhodum (Metopolophium dirhodum) (rose wheat aphid (rose grain aphid)), Midis longicornis, black peach aphid (Myzus persicae) (black peach aphid (green peach aphid)), rice green leafhopper belongs to kind of (Nephotettix spp.) (leafhopper), rice green leafhopper (Nephotettix cinctipes) (greenery cicada (green leafhopper)), brown paddy plant hopper (Nilaparvata lugens) (brown planthopper), chaff sheet armored scale (Parlatoria pergandii) (chaff scale), ebony armored scale (Parlatoria ziziphi) (ebony scale), popcorn wing plant hopper (Peregrinus maidis) (corn delphacid), froghopper belongs to kind of (Philaenus spp.) (spittle insects), grape phylloxera (Phylloxera vitifoliae) (grape phylloxera), Physokermes piceae (Physokermes piceae) (spruce bud scale), stern line mealybug belongs to kind of (Planococcus spp.) (mealybug), mealybug belongs to kind of (Pseudococcus spp.) (mealybug), the clean mealybug of pineapple (Pscudococcus brcvipcs) (pinc apple mcalybug), theatre armored scale (Quadraspidiotus perniciosus) (san jose scale (San Jose scale)), aphid a red-spotted lizard belongs to kind of (Rhapalosiphum spp.) (aphid), corn tree louse (Rhapalosiphum maida) (corn leaf aphids (corn leaf aphid)), rhopalosiphum padi (Rhapalosiphum padi) (oatbird-cherry aphid), pearl lecanium belongs to kind of (Saissetia spp.) (a red-spotted lizard), olive pearl lecanium (Saissetia oleae) (black a red-spotted lizard), green bugs (Schizaphis graminum) (green bugs (gr eenbug)), grain aphid (Sitobion avenge) (Britain's wheat aphid), white backed planthopper (Sogatella furcifera) (white-backed planthopper), variegation Aphis kind (Therioaphis spp.) (aphid), line lecanium belongs to kind of (Toumeyella spp.) (a red-spotted lizard), sound Aphis kind (Toxoptera spp.) (aphid), trialeurodes vaporariorum belongs to kind of (Trialeurodes spp.) (aleyrodid), Trialeurodes vaporariorum Westwood (Trialeurodes vaporariorum) (greenhouse whitefly (greenhouse whitefly)), knot wing trialeurodes vaporariorum (Trialeurodes abutiloneus) (bandedwing whitefly), point armored scale belongs to kind of (Unaspis spp.) (a red-spotted lizard), vow sharp clam (Unaspis yanonensis) (arrow a red-spotted lizard (arrowhead scale)) and Zulia entreriana.
Hymenoptera (Hymenoptera) (ant, wasp and honeybee): Myrmecina kind (Acromyrrmex spp.), Xinjiang cabbage sawfly (Athalia rosae), leaf ant belongs to kind of (Atta spp.) (an Ieafcutting ants), black ant belongs to kind of (Camponotus spp.) (carpented ant (a carpenter ant)), Diprion kind (Diprion spp.) (sawfly (sawfly)), ant belongs to kind of (Formica spp.) (ant), Argentine ant (Iridomyrmex humilis) (Argentineant), Monomorium subspecies (Monomorium ssp.), MonomoriumMayr (Monomorium minumum) (little black ant), kitchen ant (Monomorium pharaonis) (little red ant (Pharaoh ant)), Neodiprion kind (Neodiprion spp.) (sawfly), Pogonomyrmex kind (Pogonomyrmex spp.) (harvester ant), hornet belongs to kind of (Polistes spp.) (wasp (a paper wasp)), Solenopsis kind (Solenopsis spp.) (fiery ant), odorous antenna (Tapoinoma sessile) (odorous antenna (odorous house ant)), Tetramorium kind (Tetranomorium spp.) (Pavement Ant (pavement ant)), Vespula kind (Vespula spp.) (yellow jacket (yellowjacket)) and Xylocopa kind (Xylocopa spp.) (carpenter bee (carpenter bee)).
Isoptera (Isoptera) (termite): formosanes belongs to kind of (a Coptotcrmcs spp.), bent jaw termite (Coptotermes curvignathus), France termite (Coptotermes frenchii), Coptotermes formosanus Shtrari． (Coptotermes formosanus) (Formosan subterranean termite), angle Cryptotermes kind (Cornitermes spp.) (proboscis termite (nasute termite)), sand Cryptotermes kind (Cryptotermes spp.) (dry-wood termite), different Cryptotermes kind (Heterotermes spp.) (desert Soil termites (desert subterranean termite)), golden yellow different termite ((IIeterotermes aureus), kalotermitid belongs to kind of (Kalotermes spp.) (dry-wood termite), principal columns of a hall Cryptotermes kind (Incistitermes spp.) (dry-wood termite), Macrotermes kind (Macrotermes spp.) (cultivation termite (fungus growing termite)), edge kalotermitid belongs to kind of ((Marginitermes spp.) (dry-wood termite), saw Cryptotermes kind (Microcerotermes spp.) (careless termite (harvester termite)), the little termite of rice wheat (Microtermes obesi), former angle Cryptotermes kind (Procornitermes spp.), Reticulitermes kind (Reticulitermes spp.) (Soil termites), Reticulitermes banyulensis, meadow reticulitermes flavipe (Reticulitermes grassei), yellow limb reticulitermes flavipe (Reticulitermes flavipes) (east Soil termites), beautiful little Huang reticulitermes flavipe (Reticulitermes hageni), west reticulitermes flavipe (Reticulitermes hesperus) (west Soil termites), Sang Te reticulitermes flavipe (Reticulitermes santonensis), dwell northern reticulitermes flavipe (Reticulitermes speratus), U.S. black shin reticulitermes flavipe (Reticulitermes tibialis), U.S. little black reticulitermes flavipe (Reticulitermes virginicus), proboscis Reticulitermes kind (Schedorhinotermes spp.) and ancient Cryptotermes kind (Zootermopsis spp.) (rotten kalotermitid).
Lepidopteran (Lepidoptera) (moth and butterfly): Achoea janata, Adoxophyes spp belongs to kind of (an Adoxophyes spp.), adoxophyes moth (Adoxophyes orana), tiger belongs to kind of (Agrotis spp.) (cutworm) on ground, little cutworm ((Agrotis ipsilon) (black cutworm), cotton leaf ripple noctuid (Alabama argillacea) (cotton leafworm (cotton leafworm)), Amorbia cuneana, Amyelosis transitella (navel orangeworm), Anacamptodes defectaria, sliver gelechiid (Anarsia lineatella) (peach twig borer), jute bridge night high (Anomis sabulijera) (jute looper), Anticarsia (Anticarsia gemmatalis) (velvetbean caterpillar), fruittree leafroller (Archips argyrospila) (fruit tree leafroller), rose leaf roller (Archips rosana) (rose leaf roller), moth belongs to kind of (Ar gyrotaenia spp.) (a tortricid moths) volume, tangerine Argyrotaenia spp (Argyrotaenia citrana) (citrus leaf-roller (orange tortrix)), Autographa gamma, Bonagota cranaodcs, Cnaphalocrocis medinali(rice leaf roller) (Borbo cinnara) (rice leaf folder), cotton leaf lyonetid (Bucculatrix thurberiella) (cotton leafperforator), thin moth belongs to kind of (Caloptilia spp.) (leaf miner), Capua reticulana, peach fruit moth (Carposina niponensis) (peach fruit moth (peach fruit moth)), straw borer spp kind (Chilo spp.), Chlumetia transversa Walker (Chlumetia transversa) (mango shoot borer), rose Choristoneura spp (Choristoneura rosaceana) (oblique banded leaf roller), Noctua kind (Chrysodeixis spp.), cnaphalocrocis medinalls guenee (Cnaphalocerus medinalis) (meadow leaf roller (grass leafroller)), beans Pier kind (Colias spp.), lichee litchi (Conpomorpha cramerella), fragrance wooden stupid moth (Cossus cossus) (wooden stupid moth), Crambus Fabricius kind (Crambus spp.) (Sod webworms), Lee's small kernel-eating insect (Cydia funebrana) (Li Guoe (plum fruit moth)), oriental fruit months (Cydia molesta) (east heart-eating worm (oriental fruit moth)), pea moth pod high (Cydia nignicana) (pea moth), the stupid moth of apple (Cydia pomonella) (codling moth (codling moth)), Darna diducta, Diaphania kind (Diaphania spp.) (stem borer (stem borer)), snout moth's larva belongs to kind of (Diatr aea spp.) (stem borer (a stalk bor er)), little sugarcane borer (Diatraea saccharalis) (sugarcane borer), Diatraea grandiosella (Diatraea graniosella) (southwester corn borer), Earias kind (Earias spp.) (bollworm), earias insulana (Earias insulata) (Egyptian bollworm), earias fabia (Earias vit.ella) (rough northern bollworm), Ecdytopopha aurantianum, South America maize seedling phycitid (Elasmopalpus lignosellus) (lesser cornstalk borer), shallow brown apple moth (Epiphysias postruttana) (light brown apple moth), meal moth belongs to kind of (Ephestia spp.) (a powder snout moth's larva), meal moth (Ephestia cautella) (almond moth), tobacco powder sp (Ephestia elutella) (tobacco snout moth's larva (tobbaco moth)), Mediterranean flour moth (Ephestia kuehniella) (Mediterranean flour moth), Epimeces belongs to kind of (an Epimeces spp.), steinernema at night (Epinotia aporema), Skipper of plantains (Erionota thrax) (banana skipper), ligustrum fine tortricidae (Eupoecilia ambiguella) (grape berry moth (grape berry moth)), former cutworm (Euxoa auxiliaris) (army cutworm), Agrotis kind (Feltia spp.) (cutworm), angle sword Noctua kind (Gortyna spp.) (stem borer), east moth fruit moth (Grapholita molesta) (peach (apricot) sub-heart-eating worm (oriental fruit moth)), treble cut snout moth (Hedylepta indicata) (bean pyralid (bean leaf webber)), blue or green Eimeria kind (Helicoverpa spp.) (noctuid), bollworm (Helicoverpa armigera) (cotton bollworm), paddy real noctuid (Helicoverpa zea) (Pyrausta nubilalis (Hubern). ridge (snout moth's larva ridge worm/bollworm)), Heliothis kind (Heliothis spp.) (noctuid), Heliothis virescens (Heliothis virescens) (tobacco budworm), Hellula undalis (Hellula undalis) (cabbage webworm), Indarbela belongs to kind of (Indarbela spp.) (a root moth), the stupid moth of tomato (Keiferia lycopersicella) (tomato pinworm), the white wing of eggplant wild snout moth's larva (Leucinodes orbonalis) (eggplant fruit borer), pear leaf blister moth (Leucoptera malifoliella), thin moth belongs to kind of (a Lithocollectis spp.), grape olethreutid (Lobesia botrana) (grape fruit moth), Loxagrotis belongs to kind of (Loxagrotis spp.) (noctuid), beans white line cutworm (Loxagrotis albicosta) (western bean cutworm), gypsymoth (Lymantria dispar) (gypsy moth), apple leaf miner (Lyonetiaclerkella) (apple leaf miner (apple leafminer)), oil palm bag moth (Mahasena corbetti) (oil palm bagworm), Malacosoma kind (Malacosoma spp.) (tent caterpillars), lopper worm (Mamestra brassicae) (dish march moth (cabbage armyworm)), the wild snout moth's larva (Maruca testulalis) of beanpod (the wild snout moth's larva of beans), bag moth (Metisa plana) (bagworm), Mythimna unipuncta (true armyworm), Neoleucinodes elegantalis (little tomato moth (small tomato borer)), 3 water snout moth's larvas (Nymphula depunctalis) (Cnaphalocrocis medinali(rice leaf roller) (rice caseworm)), winter looper (Operophthera brumata) (winter moth), European corn borer (Ostrinia nubilalis) (European corn borer (European corn borer)), Oxydia vesulia, the brown volume moth of boundary (Pandemis cerasana) (common glucose leaf roller (common currant tortrix)), apple brown bortrix (Pandemis heparana) (brown apple tortrix), Africa Bodhidharma swallowtail butterfly (Papilio demodocus), Pectinophora gossypiella (Pectinophora gossypiella) (pink bollworm (pink bollworm)), boundary Noctua kind (Peridroma spp.) (cutworm), variegated cutworm (Peridroma saucia) (variegated cutworm), coffee leafminer (Perileucoptera coffeella) (white coffee leafminer), phthorimaea operculella (Phthorimaea operculella) (potato tuber moth), citrus leaf lyonetid (Phyllocnisitis citrella), thin moth belongs to kind of (Phyllonorycter spp.) (leaf miner), small white (Pieris rapae) (external cabbage caterpillar (imported cabbageworm)), the first green noctuid of mat (Plathypena scabra), India paddy spot moth (Plodia interpunctella) (Indian meal moth), diamond-back moth (Plutella xylostella) (diamondback moth), grape berry moth (Polychrosis viteana) (grape berry moth), tangerine fruit ermine moth (Prays endocarps), Fructus oleae europaeae ermine moth (Prsys oleae) (olive moth), mythimna separata belongs to kind of (Pseudaletia spp.) (noctuid), Pseudaletia unipunctata (armyworm), soybean noctuid (Pseudoplusia includens) (soybean looper), looper (Rachiplusia nu), yellow rice borer (Scirpophaga incertulas), high genus at moth stem night kind of (Sesamia spp.) (stem borer), Sesamia inferens (Sesamia inferens) (pink rice stemborer), powder stem snout moth's larva (Sesamia nonagrioides), the brown slug moth of copper stain (Setora nitens), gelechiid (Sitotroga cerealella) (Angoumois grain moth), pilleriana (Sparganothis pilleriana), Spodoptera kind (Spodoptera spp.) (armyworm), beet armyworm (Spodoptera exigua) (beet armyworm (beet armyworm)), noctuid (Spodoptcra fugipcrda) (armyworm in autumn (fall armyworm)) is coveted on meadow, south spodoptera (Spodoptera oridania) (southern armyworm (southern armyworm)), emerging Noctua kind (Synanthedon spp.) (root moth), Thecla basilides, Thermisia gemmatalis, casemaking clothes moth (Tineola bisselliella) (webbing clothes moth), cabbage looper (Trichoplusia ni) (cabbage looper), Liriomyza brponiae (Tuts absoluta), Yponomeuta kind (Yponomeuta spp.), the stupid moth of coffee leopard (Zeuzeracoffeae) (red branch borer) and Zeuzera pyrina (the stupid moth of pears leopard (leopard moth)).
Mallophaga ((Mallophaga) poultry louse (chewing lice)): sheep poultry louse (Bovicola ovis) (sheep biting louse), fiery menopon gallinae (Menacanthus stramineus) (chick poultry louse (chicken body louse)) and shaft louse (Menopon gallinea) (common hen house (common hen house)).
Orthoptera (Orthoptera) (grasshopper, locust and cricket): blackspot arna Zhong (Anabrus simplex) (katydid that rubs (Mormon cricket)), mole cricket (Gryllotalpidae) (mole cricket (mole cricket)), Asiatic migrotory locust (Locusta migratoria), grasshopper belongs to kind of (Melanoplus spp.) (grasshopper), guiding principle wing spinelet Zhong (Microcentrum retinerve) (angle wing katydid (angular winged katydid)), Pterophylla belongs to kind of (Pterophylla spp.) (katydid), chistocerca gregaria, fork-tail katydid (Scudderia furcata) (fork-tail shrubbery tree Zhong (fork tailed bush katydid)) and black angle oncus locust (Valanga nigricorni).
Anoplura (Phthiraptera) (sucking lice (sucking louse)): sucking louse belongs to kind of (Haematopinus spp.) (ox louse and a pig lice), sheep jaw lice (Linognathus ovillus) (sheep lice (sheep louse)), head louse (Pediculus humanus capitis) (body louse), pediculus humanus corporis (Pediculus humanus humanus) (body louse) and crab louse (Pthirus pubis) (crab louse (crab louse)).
Siphonaptera (Siphonaptera) (flea): ctenocephalides canis (Ctenocephal ides canis) (dog flea), ctenocephalides felis (Ctenocephalides felis) (cat flea) and Pulex irritans (Pulex irritans) (human flea).
Thysanoptera (thrips): cigarette brown thrip (Frankliniella fusca) (tobacco thrip), western classical architecture (Frankliniella occidentalis) (western flower thrips), Frankliniella shultzei, Williams flower thrips (Frankliniella williamsi) (corn thrips (corn thrip)), greenhouse thrips (IIeliothrips haemorrhaidalis) (greenhouse thrip), Riphiphorothrips cruentatus, hard Thrips kind (Scirtothrips spp), balloonflower root thrips (Scirtothrips cirri) (citrus thrip), Scirothrips dorsalis (Scirtothrips dorsalis) (yellow tea thrips), Taeniothrips rhopalantennalis and Thrips kind (Thrips spp.).
Thysanura (Thysanura) (moth (bristletail)): silverfish belongs to kind of (Lepisma spp.) (stupid worm (silverfish)) and special mess silverfish belongs to kind of (Thermobia spp.) (a special mess fish).
Acarina (Acarina) (mite (mite) and cicada (tick)): Wu Shi honeybee shield mite (Acarapsis woodi) (honeybee Tracheal mite (tracheal mite of honeybee)), Tyroglyphus kind (Acarus spp.) (food mites), Acarus siro (Acarus siro) (paddy mite (grain mite)), mango bud mite (Aceria mangiferae) (mango bud mite), peronium Eriophyes kind (Aculops spp.), Aculops lycopersici (Aculops lycopersici) (tomato russet mite), Aculops pelekasi, tangerine peronium goitre mite (Aculus pelekassi), Si Shi stings goitre mite (Aculus schlechtendali) (apple thorn goitre mite (apple rust mite)), lone star tick (Amblyomma amcricanum) (lone star tick), Boophilus kind (Boophilus spp.) (tick), avette short hairs tick (Brevipalpus obovatus) (privet mite), purplish red short hairs mite (Brevipalpus phoenicis) (red and black flat mite), fat tick belongs to kind of (Demodex spp.) (a mange mites), Dermacentor kind (Dermacentorspp.) (hard tick), America dog tick (Dermacentor variabilis) (american dog tick), dermatophagoides pteronyssinus (Dermatophagoides pteronyssinus) (house dust mite), Eotetranychus kind (Eotetranycus spp.), Eotetranychus carpini (Eotetranychus carpini) (yellow spider mite (yellow spider mite)), Epitrimerus kind (Epitimerus spp.), Eriophyes kind (Eriophyes spp.), hard tick belongs to kind an of (work, odes spp.) (tick), Panonychus citri belongs to kind of ((a Metatetranycus spp.), notoedres cati (Notoedres cati), Oligonychus kind (Oligonychus spp.), coffee unguiculus mite (Oligonychus coffee), ilex Oligonychus (Oligonychus ilicus) (southernred mi te), Panonychus citri belongs to kind of (a Panonychus spp.), Jie-Li enzyme-SQ (Panonychus cirri) (orange spider (citrus red mite)), panonychus ulmi (Panonychus ulmi) (European red spider (European red mite)), tangerine wrinkle leaf thorn goitre (Phyllocoptruta oleivora) (citrus rust mite), Polyphagotarsonemus latus Banks (Polyphagotarsonemun latus) (broad mite (broad mite)), brown dog tick (Rhipicephalus sanguineus) (brown dog tick (brown dog tick)), root mite belongs to kind of (Rhizoglyphus spp.) (root mite (a bulb mite)), itch mite (Sarcoptes scabiei) (itch mite), avocado apical cap goitre mite (Tegolophus perseaflorae), Tetranychus kind (Tetranychus spp.), T.urticae Koch (Tetranychus urticae) (2 spider mites (twospotted spider mite)) and Di Shi watt of mite (Varroa destructor) (honeybee mite).
Nematoda (nematode): Aphelenchoides kind (Aphelenchoides spp.) (bud and leaf and pine wood nematode (bud and leaf & pine wood nematode)), thorn Turbatrix kind (Belonolaimus spp.) (sting nematodes), little loop wire Eimeria kind (Criconemella spp.) (ring nematodes), heart worm (Dirofilaria immitis) (dog heartworm), Ditylenchus kind (Ditylenchus spp.) (stem and bulb eelworm), sour jujube rubber-insulated wire Eimeria kind (Heterodera spp.) (cyst nematode), corn Cyst nematode (Heterodera zeae) (corn cyst nematode), Hirschmanniella kind (Hirschmanniella spp.) (root nematodes), tie Turbatrix kind (Hoplolaimus spp.) (lance nematodes), Meloidogyne kind (Meloidogyne spp.) (root knot nematode), Meloidogyne incognita ((Meloidogyne incognita) (root knot nematode), Onchocerca caecutiens (Onchocerca volvulus) (hook-tail worm), Pratylenchidae belongs to kind of (PraLylenchus spp.) (rotten nematode (a lesion nematode)), perforation line Eimeria kind (Radopholus spp.) (similes thorne (burrowing nematode)) and banana reniform nematode (Rotylenchus reniformis) (kidney-shaped nematode).
Symphyla (comprehensive insects): kahikatea worm (Scutigerella immaculata).
Especially, to black peach aphid, small cabbage moth, mythimna separata, 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 evil mite.
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.
The present invention also comprises sterilization using compound of Formula I as active ingredient, insecticide acaricide composition.In this sterilization, insecticide acaricide composition, the weight percentage of active ingredient is between 0.5-99%.Acceptable carrier in agricultural, forestry, health is also comprised in this sterilization, insecticide acaricide composition.
Composition of the present invention can the form of preparation be used.Compound of Formula I is dissolved or dispersed in carrier as active ingredient or is mixed with preparation to be easier to dispersion as sterilization, desinsection when using.Such as: these chemicals can be made into wettable powder, oil suspending agent, aqueous suspension, aqueous emulsion, aqua or missible oil etc.In these compositions, at least add a kind of liquid or solid carrier, and suitable tensio-active agent can be added when needed.
Technical scheme of the present invention also comprises the method for control germ, insect evil mite: sterilization of the present invention, insecticide acaricide composition are imposed on described germ or its growth medium.The comparatively suitable effective amount of usual selection is per hectare 10 grams to 1000 grams, and preferably having effective amount is per hectare 20 grams to 500 grams.
For some application, such as, one or more other sterilant, insecticidal/acaricidal agent, weedicide, plant-growth regulator or fertilizer etc. agriculturally can be added in sterilization of the present invention, insecticide acaricide composition, additional advantage and effect can be produced thus.
Should it is clear that, in claim limited range of the present invention, can various conversion and change be carried out.
Embodiment
Following specific embodiment is used for further illustrating the present invention, but the present invention be only limitted to absolutely not these examples (except as otherwise indicate outside, raw materials used all have commercially available).
Synthetic example
Embodiment 1: the preparation of the chloro-6-methylpyrimidine of intermediate 4,5-bis-
1) preparation of the chloro-6-methylpyrimidine of 4-hydroxyl-5-
In the 50ml methanol solution of 11.30g (0.11mol) FORMAMIDINE ACETATE, slowly drip the methanol solution of 8.80g (0.16mol) sodium methylate under stirring at room temperature, drip complete room temperature and continue to stir 2h.Then in above-mentioned solution, drip 11.17g (0.068mol) intermediate 2-chloroacetyl acetacetic ester, continue stirring at room temperature reaction 5-7 hour, TLC monitoring after completion of the reaction, remove solvent under reduced pressure, pH=5 ~ 6 are adjusted with hydrochloric acid, suction filtration obtains orange/yellow solid, aqueous phase (3 × 50ml) extraction into ethyl acetate, anhydrous magnesium sulfate drying, filtration, precipitation.Resistates is dissolved in 50ml ethyl acetate, and placement is spent the night, and filters to obtain orange/yellow solid 6.48g.Yield 66%, fusing point 181 ~ 184 DEG C.
2) preparation of 4,5-bis-chloro-6-methylpyrimidines
The chloro-6-methylpyrimidine of 14.5g (0.1mol) 4-hydroxyl-5-is dissolved in 50ml toluene solution, under stirring, in anti-bottle, instills 50ml phosphorus oxychloride, drip the reaction of complete temperature rising reflux 5-7 hour, TLC monitoring after completion of the reaction.Remove toluene and excessive phosphorus oxychloride under reduced pressure, by reactant impouring frozen water under stirring, aqueous phase (3 × 50ml) extraction into ethyl acetate, merges organic phase, anhydrous magnesium sulfate drying, filtration, precipitation.Resistates column chromatography (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C), and volume ratio is 1: 5) is separated to obtain yellow liquid 14.43g, yield 88.5%.
Embodiment 2: the preparation of intermediate 4-(2-chloro-trifluoromethyl phenoxy) phenylethylamine
1) preparation of 4-(2-chloro-trifluoromethyl phenoxy) benzyl cyanide
By 25.8g (0.12mol) 3, 4-bis-chloro-trifluoromethyl benzene, 13.3g (0.1mol) p-hydroxybenzylcyanide and 27.60g (0.2mol) salt of wormwood add 150mlN, in dinethylformamide, backflow is heated under stirring, reaction is spent the night, TLC monitoring after completion of the reaction, remove solvent under reduced pressure, add 300ml extraction into ethyl acetate, organic phase uses 5% aqueous sodium hydroxide solution successively, the each 50ml washing of saturated aqueous common salt, after precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1: 4) obtain white solid 14.55g, yield 46.2%, fusing point 66.2 DEG C.
2) preparation of 4-(2-chloro-trifluoromethyl phenoxy) phenethylamine hydrochloride
Under room temperature, the mixture that 3.12g (0.01mol) intermediate 4-(2-chloro-trifluoromethyl phenoxy) benzyl cyanide, Raney nickel (1.0g), 25% ammoniacal liquor 10ml and ethanol 50ml form is reacted 3 hours under high-pressure hydrogenation condition.After completion of the reaction, filtering Raney nickel, removes solvent under reduced pressure and obtains viscous liquid in TLC monitoring.In viscous liquid, add 15ml ethyl acetate, stirring at room temperature, drip 5ml concentrated hydrochloric acid, stir 30min afterwards, occur white solid.Filter to obtain white solid 3.45g, yield 97.9%, fusing point 155.7 DEG C.
Embodiment 3: the preparation of intermediate 4-(the chloro-4-nitrophenoxy of 2,6-bis-) phenethylamine hydrochloride
1) preparation of N-Boc-4-hydroxyphenethylamine
11.3g (0.1mol) 4-hydroxyphenethylamine is dissolved in 80ml tetrahydrofuran (THF), add 10.08g (0.12mol) sodium bicarbonate successively, 50ml water, 21.80g (0.1mol) tert-Butyl dicarbonate is dripped under stirring at room temperature, drip and finish, continue reaction 4-10 hour, TLC monitoring after completion of the reaction, remove solvent under reduced pressure, add (3 × 50ml) extraction into ethyl acetate, organic phase saturated aqueous common salt 50ml washs, after precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1: 3) obtain colourless oil liquid 23.37g, yield 98.6%.
2) preparation of N-Boc-4-(the chloro-4-nitrophenoxy of 2,6-bis-) phenylethylamine
By 2.10g (0.01mol) N-Boc-4-hydroxyphenethylamine and 2.33g (0.01mol) 3, 5-bis-chloro-4-fluorine nitromethyla benzene adds in 50ml butanone, add 2.76g (0.02mol) salt of wormwood, backflow is heated under stirring, reaction 4-10 hour, TLC monitoring after completion of the reaction, remove solvent under reduced pressure, add (3 × 50ml) extraction into ethyl acetate, organic phase saturated aqueous common salt 50ml washs, after precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1: 4) obtain white solid 3.73g, yield 87.3%, fusing point 149-151 DEG C.
3) preparation of 4-(the chloro-4-nitrophenoxy of 2,6-bis-) phenylethylamine
By 4.27g (0.01mol) N-Boc-4-(2, the chloro-4-nitrophenoxy of 6-bis-) phenylethylamine adds in 50ml ethyl acetate, drips 6ml trifluoroacetic acid, dissolution of solid under stirring at room temperature, continue to stir 4-5 hour, TLC monitoring after completion of the reaction, removes solvent under reduced pressure, adds (3 × 50ml) extraction into ethyl acetate, organic phase saturated aqueous common salt 50ml washs, precipitation obtains 3.03g white solid, yield 92.8%, fusing point 107-109 DEG C.
Embodiment 4: the preparation of intermediate 4-(4-4-trifluoromethylphenopendant) phenethylamine hydrochloride
1) preparation of N-Boc-4-(4-4-trifluoromethylphenopendant) phenylethylamine
4.56g (0.024mol) is added in 50ml methylene dichloride to trifluoromethylbenzene boronic acid, under stirring at room temperature, to add porphyrize successively
molecular sieve powder, 3.82g (0.021mol) Salicylaldoxime, 10.1g (0.1mol) triethylamine, 7.9g (0.1mol) pyridine, reaction is spent the night.TLC monitoring after completion of the reaction, filter and remove solvent under reduced pressure, add (3 × 50ml) extraction into ethyl acetate, organic phase saturated aqueous common salt 50ml washs, after precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1: 4) obtain white solid 5.95g, yield 65.1%.
2) preparation of 4-(4-4-trifluoromethylphenopendant) phenethylamine hydrochloride
3.81g (0.01mol) N-Boc-4-(4-trifluoromethyl) phenylethylamine is added in 50ml ethyl acetate, under stirring at room temperature, drips 12ml concentrated hydrochloric acid, continue to stir 4-5 hour generation white solid.TLC monitoring after completion of the reaction, removes solvent under reduced pressure, adds (3 × 50ml) ethyl acetate stirring at room temperature 30min, filter to obtain 2.92g white solid, yield 91.9%.
Embodiment 5: the preparation of compound 69
Add in 50ml toluene by chloro-for 1.63g (0.01mol) 4,5-bis-6-methylpyrimidine and 3.18g (0.01mol) 4-(4-4-trifluoromethylphenopendant) phenethylamine hydrochloride, stirring at room temperature is to dissolving completely.Add 4.45g (0.022mol) triethylamine, be heated to backflow, reaction 4-10 hour, TLC monitoring after completion of the reaction, removes solvent under reduced pressure, adds (3 × 50ml) extraction into ethyl acetate, organic phase saturated aqueous common salt 50ml washs, after precipitation, resistates column chromatography (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C), and volume ratio is 1: 2) obtains colorless oil 2.76g, yield 72.6%.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (ppm): 2.46 (3H, s), 2.94 (2H, t), 3.77 (2H, q), 5.42 (1H, s), 702 (4H, m), 7.25 (2H, m), 7.56 (2H, d), 8.39 (1H, s).
Embodiment 6: the preparation of compound 165
Add in 50ml toluene by chloro-for 1.63g (0.01mol) 4,5-bis-6-methylpyrimidine and 3.26g (0.01mol) 4-(the chloro-4-nitrophenoxy of 2,6-bis-) phenethylamine hydrochloride, stirring at room temperature is to dissolving completely.Add 4.45g (0.022mol) triethylamine, be heated to backflow, reaction 4-10 hour, TLC monitoring after completion of the reaction, removes solvent under reduced pressure, add (3 × 50ml) extraction into ethyl acetate, organic phase saturated aqueous common salt 50ml washs, and after precipitation, resistates column chromatography (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C), and volume ratio is 1: 2) obtains red brown solid 3.23g, yield 71.2%, fusing point 118-120 DEG C.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (ppm): 2.45 (3H, s), 2.91 (2H, t), 3.70-3.85 (2H, q), 5.42 (1H, t), 6.80 (2H, d), 7.18 (2H, d), 8.31 (2H, s), 8.38 (1H, s).
Embodiment 7: the preparation of compound 297
By 1.77g (0.01mol) 4, the chloro-6-ethyl-pyrimidine of 5-bis-(preparation method's reference as above embodiment 1, difference is that starting raw material 2-chloroacetyl acetacetic ester is replaced with 2-chlorine Propionylacetic acid ethyl ester) and 2.84g (0.01mol) 4-(4-chlorophenoxy) phenethylamine hydrochloride (preparation method's reference as above embodiment 4, difference is replaced with chlorophenylboronic acid trifluoromethylbenzene boronic acid by starting raw material) add in 50ml toluene, 4.45g (0.022mol) triethylamine is added under stirring at room temperature, be heated to backflow, reaction 4-10 hour, TLC monitoring after completion of the reaction, remove solvent under reduced pressure, add (3 × 50ml) extraction into ethyl acetate, organic phase saturated aqueous common salt 50ml washs, after precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1: 2) obtain red brown solid 3.16g, yield 81.6%, fusing point 84.7 DEG C.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (ppm): 1.26 (3H, t), 2.78 (2H, dd), 2.92 (2H, t), 3.75 (2H, dd), 5.45 (1H, t), 6.84-7.00 (4H, m), 7.20 (2H, d), 7.29 (2H, d), 8.44 (1H, s).
Embodiment 8: the preparation of compound 303
By 1.77g (0.01mol) 4, the chloro-6-ethyl-pyrimidine of 5-bis-and 3.19g (0.01mol) 4-(3,5-dichlorophenoxy) phenethylamine hydrochloride (preparation method's reference as above embodiment 4, difference is that starting raw material is replaced with 3 to trifluoromethylbenzene boronic acid, 5-dichlorobenzene boric acid) add in 50ml toluene, stirring at room temperature is to dissolving completely.Add 4.45g (0.022mol) triethylamine, be heated to backflow, reaction 4-10 hour, TLC monitoring after completion of the reaction, removes solvent under reduced pressure, adds (3 × 50ml) extraction into ethyl acetate, organic phase saturated aqueous common salt 50ml washs, after precipitation, resistates column chromatography (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C), and volume ratio is 1: 2) obtains pale red brown oil 3.17g, yield 75.1%.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (ppm): 1.26 (3H, t), 2.78 (2H, dd), 2.95 (2H, t), 3.72-3.84 (2H, q), 5.45 (1H, t), 6.85 (2H, d), 7.00 (2H, d), 7.25 (2H, d), 8.45 (1H, s).
Embodiment 9: the preparation of compound 347
Add in 50ml toluene by chloro-for 1.77g (0.01mol) 4,5-bis-6-ethyl-pyrimidine and 3.18g (0.01mol) 4-(4-4-trifluoromethylphenopendant) phenethylamine hydrochloride, stirring at room temperature is to dissolving completely.Add 4.45g (0.022mol) triethylamine, be heated to backflow, reaction 4-10 hour, TLC monitoring after completion of the reaction, removes solvent under reduced pressure, add (3 × 50ml) extraction into ethyl acetate, organic phase saturated aqueous common salt 50ml washs, and after precipitation, resistates column chromatography (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C), and volume ratio is 1: 2) obtains white solid 3.15g, yield 74.8%, fusing point 52.6 DEG C.
1h-NMR (300MHz, interior mark TMS, solvent C DCl
3) δ (ppm): 1.27 (3H, t), 2.78 (2H, q), 2.95 (2H, t), 3.78 (2H, q), 5.42 (1H, s), 7.01 (4H, m), 7.24 (2H, m), 7.58 (2H, d), 8.45 (1H, s).
Embodiment 10: the preparation of compound 10018
0.42g (0.01mol) compound 347 is dissolved in 20mL ethanol, under room temperature, drip 10mL concentrated hydrochloric acid, drip and finish, reflux 4-10 hour, TLC detection reaction to terminal, remove solvent under reduced pressure, residual brownish solid with ethyl acetate (3 × 10mL) washs to obtain white solid 0.36g, yield 78.1%, fusing point 120.5 DEG C.
1h-NMR (300MHz, interior mark TMS, solvent DMSO) δ (ppm): 1.27 (3H, t), 2.80-3.09 (4H, m), 3.80 (2H, d), 6.92-7.18 (4H, d), 7.31 (2H, d), 7.67 (2H, d), 8.71 (1H, d), 9.28 (1H, s).
Other compounds of the present invention can be prepared with reference to above embodiment.
The physical data of part of compounds and nuclear magnetic data (
1hNMR, 300MHz, interior mark TMS, ppm) as follows:
Compound 19: δ (CDCl
3): 2.52 (3H, s), 2.92 (2H, t), 3.75 (2H, dd), 5.43 (1H, t), 6.81-7.01 (4H, m), 7.19 (2H, d), 7.28 (2H, d), 8.39 (1H, s).
Compound 25: δ (CDCl
3): 2.45 (3H, s), 2.95 (2H, t), 3.70-3.83 (2H, q), 5.44 (1H, t), 6.84 (2H, d), 7.00 (2H, d), 7.06 (1H, s), 7.26 (2H, d), 8.40 (1H, s).
Compound 53: fusing point 140-142 DEG C.δ(CDCl
3)：2.65(3H，s)，3.13(2H，t)，3.65-3.76(2H，q)，6.93(1H，d)，7.17(2H，d)，7.35(2H，d)，8.31(1H，d)，8.47(1H，s)，8.62(1H，t)，9.14(1H，d)。
Compound 154: δ (CDCl
3): 2.46 (3H, s), 2.95 (2H, t), 3.77 (2H, dd), 5.42 (1H, t), 6.92 (1H, d), 7.00 (2H, d), 7.25 (2H, d), 7.43 (1H, d), 7.75 (1H, s), 8.39 (1H, s).
Compound 235: fusing point 140-142 DEG C.δ(CDCl
3)：1.25(3H，s)，2.45(3H，s)，2.86(2H，t)，3.72(2H，q)，5.41(1H，s)，6.79(2H，d)，7.08(2H，d)，8.39(2H，m)。
Compound 236: δ (CDCl
3): 2.25 (3H, s), 2.45 (3H, s), 2.90 (2H, t), 3.62-3.81 (2H, q), 5.43 (1H, t), 6.74 (2H, d), 7.14 (2H, d), 7.40 (1H, d), 7.77 (1H, d), 8.38 (1H, s).
Compound 254: fusing point 183-185 DEG C.δ(CDCl
3)：2.45(3H，s)，2.86(2H，t)，3.66-3.83(2H，q)，5.43(1H，t)，6.80(2H，d)，7.08(2H，d)，8.39(1H，s)。
Compound 274: fusing point 130-132 DEG C.δ(CDCl
3)：2.929-2.953(t，2H)，3.744-3.765(q，2H)，5.65(s，1H)，6.830-7.230(dd，4H)，8.392(s，1H)。
Compound 432: δ (CDCl
3): 1.26 (3H, t), 2.78 (2H, dd), 2.95 (2H, t), 3.77 (2H, dd), 5.44 (1H, t), 6.92 (1H, d), 7.00 (2H, d), 7.25 (2H, d), 7.42 (1H, d), 7.73 (1H, s), 8.44 (1H, s).
Compound 443: fusing point 101.0 DEG C.δ(CDCl
3)：1.25(3H，t)，2.77(2H，dd)，2.92(2H，t)，3.74(2H，dd)，5.42(1H，t)，6.79(2H，d)，7.18(2H，d)，8.32(2H，s)，8.43(1H，s)。
Biological activity determination embodiment
The compounds of this invention all shows good activity to the multiple germ in agriculture field, insect evil mite.
Control compound, except the CK1 to CK21 (known compound) described in background parts, has also synthesized following CK22-CK64 in contrast with reference to prior art file:
Table 48 control compound
Embodiment 11: 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 embodiment.
(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 is as acetone, methyl alcohol, DMF etc., and according to it, dissolving power of sample is selected) 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 Pyricularia oryzae:
Under 25ppm dosage, have the compound of inhibiting rate more than 80% of rice blast: 19,25,53,69,165,274,347 etc., wherein the inhibiting rate of 53,165,274 is 100%; It is 50% to the inhibiting rate of rice blast that control compound CK3, CK5, CK6, CK7, CK10, CK11, CK12, CK19, CK21 inhibiting rate to rice blast is 0, CK4, CK8, CK9, CK14, CK18;
Under 8.3ppm dosage, have the compound of inhibiting rate more than 80% of rice blast: 53,165,274 etc., wherein the inhibiting rate of 53,165 is 100%; Control compound CK1, CK20 are 0, CK15 to the inhibiting rate of rice blast is 50% to the inhibiting rate of rice blast;
Under 2.8ppm dosage, have the compound of inhibiting rate more than 80% of rice blast: 53,165,274 etc., wherein the inhibiting rate of 53,165 is 100%; Control compound CK15 is 0 to the inhibiting rate of rice blast;
Under 0.9ppm dosage, the inhibiting rate of compound 53 and 165 pairs of rice blast is 100%;
Under 0.3ppm dosage, the inhibiting rate of compound 53 and 165 pairs of rice blast is 100%;
Under 0.1ppm dosage, the inhibiting rate of compound 165 pairs of rice blast is 100%;
Under 0.03ppm dosage, the inhibiting rate of compound 165 pairs of rice blast is 100%.
Inhibiting rate to botrytis cinerea pers:
Under 25ppm dosage, the compound of inhibiting rate more than 80% has: 69,303,347 etc., and wherein the inhibiting rate of 303 is 100%; Control compound CK1, CK2, CK3, CK4, CK5, CK6, CK7, CK8, CK11, CK16, CK17, CK18, CK19, CK20, CK21 are 0, CK9, CK10 to the inhibiting rate of gray mold is 50% to the inhibiting rate of gray mold.
(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:
Under 400ppm dosage, have the compound of cucumber downy mildew more than 80%: 25,69,154,235,236,254,274,297,303,347,432,10018 etc., wherein 25,69,154,236,254,297,303,347,432 preventive effects are 100%;
Under 100ppm dosage, have the compound of cucumber downy mildew more than 80%: 25,69,236,297,303,347 etc., wherein 236 and 297 preventive effects are 100%;
Under 50ppm dosage, have the compound of cucumber downy mildew more than 80%: 25,236,297 etc., wherein 236 and 297 preventive effects are 100%;
Under 25ppm dosage, have the compound of cucumber downy mildew more than 80%: 25,236,297 etc., wherein 236 and 297 preventive effects are 100%;
Under 12.5ppm dosage, compound 297 pairs of cucumber downy mildew are 100%;
Under 6.25ppm dosage, compound 297 pairs of cucumber downy mildew are 100%;
Under 3.125ppm dosage, compound 297 pairs of cucumber downy mildew are 98%.
Live body prolection to wheat powdery mildew:
Under 400ppm dosage, have the compound of wheat powdery mildew preventive effect more than 80%: 19,25,53,69,154,297,303,347,432,10018 etc., wherein 19,25,69,154,297,303,347,432,10018 preventive effects are 100%;
Under 100ppm dosage, have the compound of wheat powdery mildew preventive effect more than 80%: 19,25,154,297,303,347,432,10018 etc., wherein 154,297,303,347,432,10018 preventive effects are 100%;
Under 25ppm dosage, have the compound of wheat powdery mildew preventive effect more than 80%: 19,297,303,347,432,10018 etc., wherein 297,303,347,432,10018 preventive effects are 100%;
Under 6.25ppm dosage, have the compound of wheat powdery mildew preventive effect more than 80%: 19,297,303,432,10018, wherein 432 and 10018 preventive effects are 100%;
Under 1.6ppm dosage, the preventive effect of compound 303,432 pairs of wheat powdery mildews is 80%;
Live body prolection to corn rust:
Under 400ppm dosage, have the compound of corn rust preventive effect more than 80%: 19,25,53,69,154,165,236,254,297,303,347,432,10018 etc., wherein 19,53,69,154,165,297,303,347,432,10018 preventive effects are 100%;
Under 100ppm dosage, have the compound of corn rust preventive effect more than 80%: 19,69,154,165,297,303,347,432,10018 etc., wherein 69,154,297,303,347,432 preventive effects are 100%;
Under 25ppm dosage, have the compound of corn rust preventive effect more than 80%: 69,154,297,303,347,432 etc., wherein 69,154,303,432 preventive effects are 100%;
Under 6.25ppm dosage, have the compound of corn rust preventive effect more than 80%: 154,297,303,347,432 etc., wherein 154,303,432 preventive effects are 100%;
Under 1.6ppm dosage, the preventive effect of compound 303 pairs of wheat powdery mildews is 80%.
(3) test result of part of compounds and contrast medicament
Carried out part of compounds and the active simultaneous test contrasting medicament, test result is in Table 49-table 51 (in table " ///" represent do not test).
The live body prolection of table 49 pair cucumber downy mildew
The live body prolection of table 50 pair wheat powdery mildew
The live body prolection of table 51 pair corn rust
Embodiment 12: 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 small cabbage moth, mythimna separata, black peach aphid, carmine spider mite for target, airbrush spray method is adopted to carry out insecticidal activity assay.
(1) determination of activity of small cabbage moth, is killed
Measuring method: leaf dish cabbage leaves punch tool being broken into diameter 2cm, the pressure of airbrush spraying process is that 10psi (is roughly equal to 0.7kg/cm
2), every leaf dish pros and cons spraying, spouting liquid is 0.5ml.Often process access after drying in the shade and try worm 10 2 ages, often process 3 times and repeat.Put into 25 DEG C, relative humidity 60 ~ 70% observation indoor cultivation after process, 72 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio.
As follows to the partial test result of small cabbage moth:
Under 600ppm dosage, have 19,154,274,297,303,347,432,10018 etc. to the compound of lethality rate more than 80% of small cabbage moth, wherein the lethality rate of 19,154,297,347 and 10018 is 100%;
Under 100ppm dosage, the lethality rate of compound 19 and 10018 pairs of small cabbage moths is 100%.
(2) determination of activity of mythimna separata, is killed
Measuring method: leaf section maize leaf being cut into long 2cm, the pressure of airbrush spraying process is that 10psi (is roughly equal to 0.7kg/cm
2), every leaf section pros and cons spraying, spouting liquid is 0.5ml.Often process access after drying in the shade and try worm 10 2 ages, often process 3 times and repeat.Put into 25 DEG C, relative humidity 60 ~ 70% observation indoor cultivation after process, 72 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio.
As follows to the partial test result of mythimna separata:
Under 600ppm dosage, have 19,69,297,303,347,432,10018 etc. to the compound of lethality rate more than 80% of mythimna separata, wherein 19,69,297,347,10018 lethality rate be 100%;
Under 100ppm dosage, have 69,297,10018 etc. to the compound of lethality rate more than 80% of mythimna separata.
(3) determination of activity of black peach aphid, is killed
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 10psi (being roughly equal to 0.7kg/cm2), and 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.
Under 600ppm dosage, compound 19,25,69,154,236,297,303,347,432,443,10018 etc. is 100% to the lethality rate of black peach aphid;
Under 100ppm dosage, have 19,25,69,154,297,303,347,432,443,10018 etc. to the compound of lethality rate more than 80% of black peach aphid, wherein the lethality rate of 19,69,154,297,303,347,432,443,10018 is 100%;
Under 10ppm dosage, the lethality rate of compound 19,69,297,347,10018 pairs of black peach aphids is 100%;
Under 5ppm dosage, the lethality rate of compound 69,297,347 pairs of black peach aphids is 100%, and the lethality rate of compound 10018 pairs of black peach aphids is 96%;
Under 2.5ppm dosage, have 69,297,347,10018 etc. to the compound of lethality rate more than 80% of black peach aphid, wherein the lethality rate of 297 and 347 is 100%;
Under 1.25ppm dosage, have 297,347 etc. to the compound of lethality rate more than 80% of black peach aphid.
(4) 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.
As follows to the partial test result of carmine spider mite:
Under 600ppm dosage, more than 80%, have 19,69,154,165,297,303,347,432,443,10018 etc. to the lethality rate of carmine spider mite, wherein 19,69,154,297,303,347,432,443,10018 lethality rate be 100%;
Under 100ppm dosage, the lethality rate of compound 19,69,154,297,347,432,443,10018 pairs of carmine spider mite is 100%;
Under 10ppm dosage, more than 80%, have 69,347,443,10018 etc. to the lethality rate of carmine spider mite, wherein 347 and 10018 lethality rate be 100%;
Under 5ppm dosage, the lethality rate of compound 10018 pairs of carmine spider mite is 100%, and the lethality rate of compound 347 pairs of carmine spider mite is 90%;
Under 2.5ppm dosage, the lethality rate of compound 10018 pairs of carmine spider mite is 87%, and the lethality rate of compound 347 pairs of carmine spider mite is 75%.
(5), the test result of part of compounds and contrast medicament
Carried out part of compounds and the active simultaneous test contrasting medicament, test result is in Table 52-table 55 (in table " ///" represent do not test).
The preventive effect of table 52 pair small cabbage moth
The preventive effect of table 53 pair mythimna separata
The preventive effect of table 54 pair black peach aphid
The preventive effect of table 55 pair carmine spider mite
Claims (10)
1. a phenoxy pyrimidine aminated compounds, as shown in general formula I:
In formula:
R
1be selected from C
1-C
12alkyl;
R
2be selected from halogen;
R
3be selected from hydrogen; M is selected from the integer of 0 to 4;
R
4be selected from hydrogen, halogen, cyano group, nitro, C
1-C
12alkyl, halo C
1-C
12alkyl; N is selected from the integer of 0 to 5; When n is greater than 1, R
4may be the same or different;
R
5, R
6be selected from hydrogen;
R
7be selected from hydrogen;
A is selected from-CH
2-;
W is selected from hydrogen;
Or the salt of compound of Formula I.
2. phenoxy pyrimidine aminated compounds according to claim 1, is characterized in that: in general formula I
R
1be selected from C
1-C
6alkyl;
R
2be selected from halogen;
R
3be selected from hydrogen; M is selected from the integer of 0 to 4; R
4be selected from hydrogen, halogen, cyano group, nitro, C
1-C
6alkyl, halo C
1-C
6alkyl; N is selected from the integer of 0 to 5; When n is greater than 1, R
4may be the same or different;
R
5, R
6be selected from hydrogen;
R
7be selected from hydrogen;
A is selected from-CH
2-;
W is selected from hydrogen;
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid, phenylformic acid, phthalic acid, toxilic acid, Sorbic Acid, oxysuccinic acid or citric acid are formed.
3. compound according to claim 2, is characterized in that: in general formula I
R
1be selected from C
1-C
4alkyl;
R
2be selected from halogen;
R
3be selected from hydrogen; M is selected from the integer of 0 to 4;
R
4be selected from hydrogen, halogen, cyano group, nitro, C
1-C
4alkyl, halo C
1-C
4alkyl; N is selected from the integer of 0 to 5; When n is greater than 1, R
4may be the same or different;
R
5, R
6be selected from hydrogen;
R
7be selected from hydrogen;
A is selected from-CH
2-;
W is selected from hydrogen;
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid, phenylformic acid, toxilic acid, Sorbic Acid, oxysuccinic acid or citric acid are formed.
4. compound according to claim 3, is characterized in that: in general formula I
R
1be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-or the tertiary butyl;
R
2be selected from fluorine, chlorine or bromine;
R
3be selected from hydrogen; M is selected from the integer of 1 to 2;
R
4be selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano group, nitro, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, trifluoromethyl, trichloromethyl, difluoro chloromethyl, dichloro one methyl fluoride; N is selected from the integer of 0 to 5;
R
5, R
6be selected from hydrogen;
R
7be selected from hydrogen;
A is selected from-CH
2-;
W is selected from hydrogen;
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid or phenylformic acid are formed.
5. compound according to claim 4, is characterized in that: in general formula I
R
1be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-or the tertiary butyl;
R
2be selected from fluorine, chlorine or bromine;
R
3be selected from hydrogen; M is selected from the integer of 1 to 2;
R
4be selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano group, nitro, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, trifluoromethyl, trichloromethyl, difluoro chloromethyl or dichloro one methyl fluoride; N is selected from the integer of 1 to 5;
R
5, R
6be selected from hydrogen;
R
7be selected from hydrogen;
A is selected from-CH
2-;
W is selected from hydrogen;
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, tosic acid or phenylformic acid are formed.
6. compound according to claim 5, is characterized in that: in general formula I
R
1be selected from methyl or ethyl;
R
2be selected from chlorine;
R
3, R
5, R
6, R
7, W is selected from hydrogen;
R
4be selected from hydrogen, chlorine, cyano group, nitro, methyl or trifluoromethyl; N is selected from the integer of 1 to 5;
A is selected from-CH
2-;
Or the salt that compound of Formula I and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid or trifluoroacetic acid are formed.
7. compound according to claim 6, is characterized in that: in general formula I
R
1be selected from methyl, R
2be selected from chlorine, R
3, R
5, R
6, R
7, W is selected from hydrogen, (R
4) n is selected from the chloro-4-nitro of 2,6-bis-, A is selected from-CH
2-; Or
R
1be selected from ethyl, R
2be selected from chlorine, R
3, R
5, R
6, R
7, W is selected from hydrogen, (R
4) n is selected from the chloro-4-trifluoromethyl of 4-chlorine, 3,5-dichloros, 4-trifluoromethyl or 2-, A is selected from-CH
2-;
Or the salt that above-claimed cpd and hydrochloric acid are formed.
8. a compound of Formula I according to claim 1 or its salt are used as the purposes preparing sterilant, Insecticiding-miticiding agent medicine in agricultural, forestry or health field.
9. a sterilization and disinsection miticide composition, is characterized in that: containing, for example compound of Formula I according to claim 1 or its salt as active ingredient, in composition, the weight percentage of active ingredient is 0.5-99%.
10. prevent and treat a method for germ, insect evil mite, it is characterized in that: the composition according to claim 9 of significant quantity is imposed on described germ, insect evil mite or its growth medium.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210412091.0A CN103772294B (en) | 2012-10-25 | 2012-10-25 | Phenoxy pyrimidine aminated compounds and purposes |
| PCT/CN2013/085879 WO2014063642A1 (en) | 2012-10-25 | 2013-10-24 | Substituted pyrimidine compound and uses thereof |
| EP13849899.3A EP2913325B1 (en) | 2012-10-25 | 2013-10-24 | Substituted pyrimidine compound and uses thereof |
| CN201380051597.6A CN104684900B (en) | 2012-10-25 | 2013-10-24 | Substituted pyrimidine compound and uses thereof |
| EP20184845.4A EP3760617B1 (en) | 2012-10-25 | 2013-10-24 | Substituted pyrimidine compound and uses thereof |
| US14/423,953 US9770026B2 (en) | 2012-10-25 | 2013-10-24 | Substituted pyrimidine compound and uses thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210412091.0A CN103772294B (en) | 2012-10-25 | 2012-10-25 | Phenoxy pyrimidine aminated compounds and purposes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103772294A CN103772294A (en) | 2014-05-07 |
| CN103772294B true CN103772294B (en) | 2015-09-09 |
Family
ID=50565114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210412091.0A Active CN103772294B (en) | 2012-10-25 | 2012-10-25 | Phenoxy pyrimidine aminated compounds and purposes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103772294B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417682A (en) * | 2017-09-12 | 2017-12-01 | 山东省联合农药工业有限公司 | A kind of substituted benzo isothiazole compound and purposes |
| CN114516868B (en) * | 2020-11-20 | 2024-02-27 | 湖南海利常德农药化工有限公司 | N-heteroaryl methyl difluoromethyl pyrimidine amine compound, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5498612A (en) * | 1994-02-01 | 1996-03-12 | Ube Industries, Ltd. | 4-phenethylaminopyrimidine derivative, and agricultural and horticultural chemical for controlling noxious organisms containing the same |
| US5925644A (en) * | 1996-11-15 | 1999-07-20 | Hoechst Schering Agrevo Gmbh | Substituted nitrogen heterocycles, processes for their preparation and their use as pesticides |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1036355A (en) * | 1996-07-19 | 1998-02-10 | Ube Ind Ltd | Production of 4-amino-5-chloro-6-(1-fluoroehyl)pyrimidine derivative |
-
2012
- 2012-10-25 CN CN201210412091.0A patent/CN103772294B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5498612A (en) * | 1994-02-01 | 1996-03-12 | Ube Industries, Ltd. | 4-phenethylaminopyrimidine derivative, and agricultural and horticultural chemical for controlling noxious organisms containing the same |
| US5925644A (en) * | 1996-11-15 | 1999-07-20 | Hoechst Schering Agrevo Gmbh | Substituted nitrogen heterocycles, processes for their preparation and their use as pesticides |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103772294A (en) | 2014-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105722837B (en) | Pyrazolyl pyrimidines aminated compounds and purposes | |
| CN103772369B (en) | Homopiperony lamine compounds and application thereof | |
| CN106167484A (en) | Substituted pyrazolecarboxylic compounds containing pyrimidine and its production and use | |
| KR20230023001A (en) | Isoxazoline substituted benzamide-based derivatives and their preparation methods and uses | |
| CN103772293B (en) | Fluorine-containing pyrimidines and purposes | |
| CN104684900B (en) | Substituted pyrimidine compound and uses thereof | |
| CN108623562A (en) | A kind of quinolinone alkaloid class compound and its preparation method and application | |
| CN107964007A (en) | Pyridazinone compound and its application | |
| TW201519769A (en) | Synergistic pesticidal compositions and related methods | |
| CN109776427A (en) | Double aminated compounds of pyrimidine and application thereof | |
| CN107778298A (en) | Substituted azole compounds containing pyrimidine and application thereof | |
| CN104292169B (en) | Substituted pyrimidinamine compound and application thereof | |
| CN106467538B (en) | A kind of substituted tetrahydro isoquinoline compound and purposes | |
| TW201519775A (en) | Synergistic pesticidal compositions and related methods | |
| CN103772357A (en) | Substituted pyrimidine compound and use thereof | |
| CN108017628A (en) | Substituted uracil compound and application thereof | |
| CN109836418A (en) | Substituted pyrazolecarboxylic class compound and preparation method thereof and purposes as insecticidal/acaricidal agent | |
| TW201519776A (en) | Synergistic pesticidal compositions and related methods | |
| CN103772294B (en) | Phenoxy pyrimidine aminated compounds and purposes | |
| CN104974136B (en) | Pyrazol acid amide compounds and application thereof | |
| CN108069973A (en) | Substitution hexa-member heterocycle class compound of the ring containing pyrimido and its preparation method and application | |
| CN108617661A (en) | A kind of application of alkaloid compound in agricultural drugs | |
| CN105753791B (en) | Substituted uracil compound and application thereof | |
| CN105315296B (en) | Substitute fragrant oxy picolinate class compound and application thereof | |
| CN103772356A (en) | Substituted aryloxy pyridine compound and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160118 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 |